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Use of marker ion and cationic surfactant plastic membrane electrode for potentiometric titration of cationic polyelectrolytes.
A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to stearyltrimethylammonium (STA) ion is applied to the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by potentiometric titration, using a potassium poly (vinyl sulfate) (PVSK) solution as a titrant. The end-point of the titration is detected as the potential change of the plasticized PVC membrane electrode caused by decrease in the concentration of STA ion added to the sample solution as a marker ion due to the ion association reaction between the STA ion and PVSK. The effects of the concentration of STA ion, coexisting electrolytes in the sample solution and pH of the sample on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2x10(-5) to 4x10(-4) N for Cat-floc, glycol chitosan, and methylglycol chitosan. PMID:18969090
Masadome, Takashi; Imato, Toshihiko
Modeling potentiometric titration behavior of glauconite
Microsoft Academic Search
Potentiometric titration behavior and the effects of dissolution on the titration experiment of a complex natural clay mineral, glauconite, were investigated and interpreted according to surface complexation theory. Considerable dissolution was detected in the time frame of the titration experiments, with the amount of individual cations released from glauconite a function of solution variables and dissolution kinetics. Dissolution effects can
Weiping Lu; Edward H. Smith
Potentiometric titration of free acid in uranium solutions.
National Technical Information Service (NTIS)
Hydrolysis properties of metal cations and fundamental principles of the potentiometric titration of free acid in aqueous solutions containing metal cations were described. The published papers and reports for the alkalimetric and acidimetric titration of...
M. Suh W. Kim J. Kim S. Sohn T. Eom
Potentiometric titration of calcium in seawater
NASA Astrophysics Data System (ADS)
By using calcium ion selective electrode (Ca ISE) as indicating electrode, saturated calomel electrode (SCE) as reference electrode and EGTA as titrant, calcium in seawater was determined by potentiometric titration in borate buffer solution. This method can reduce observation errors in the determination of the endpoint, and thus provide better analytical precision (<0.08%) than present complexometric titration.
Xie, Shi-Nan; Ji, Hong; Wu, Ai-Qin; Chen, Guo-Hua
On potentiometric titration curves in complexometry.
An equation is given which describes the potential change during complexometric titration of metals with potentiometric end-point detection. The potential of the indicator electrode (e.g., silver or mercury electrode) depends on the equilibrium of the reaction MY + W right harpoon over left harpoon WY + M, where W represents the indicator metal ion, and M the metal ion determined by titration with the ligand Y, forming 1:1 chelates. Introduction of the conditional stability constants and corresponding side-reaction coefficients facilitates the prediction of the limits of application of this type of titration as well as the optimum conditions for the determination. PMID:18960490
Hulanicki, A; Trojanowicz, M
Potentiometric titrations of rutile suspensions to 250 C
SciTech Connect
A stirred hydrogen electrode concentration cell was used to conduct potentiometric titrations of rutile suspensions from 25 to 250 C in NaCl and tetramethylammonium chloride media (0.03 to 1.1 m). Hydrothermal pretreatment of the rutile improved titration reproducibility, decreased titration hysteresis, and facilitated determination of the point of zero net proton charge (pHznpc). These pHznpc values are 5.4, 5.1, 4.7, 4.4, 4.3 ({+-} 0.2 pH units), and 4.2 ({+-} 0.3 pH units) at 25, 50, 100, 150, 200, and 250 C, respectively. The difference between these pHznpc values and 1/2 pK{sub w} (the neutral pH of water) is rather constant between 25 and 250 C ({minus} 1.45 {+-} 0.2). This constancy is useful for predictive purposes and, more fundamentally, may reflect similarities between the hydration behavior of surface hydroxyl groups and water. A three-layer, 1pKa surface complexation model with three adjustable parameters (two capacitance values and one counterion binding constant) adequately described all titration data. The most apparent trend in these data for pH values greater than the pHznpc was the increase in proton release (negative surface charge) with increasing temperature. This reflects more efficient screening by Na{sup +} relative to Cl{sup {minus}}. Replacing Na{sup +} with the larger tetramethylammonium cation for some conditions resulted in decreased proton release due to the less efficient screening of negative surface charge by this larger cation.
Machesky, M.L. [Illinois State Water Survey, Champaign, IL (United States)] [Illinois State Water Survey, Champaign, IL (United States); Wesolowski, D.J.; Palmer, D.A. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.] [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.; Ichiro-Hayashi, Ken [Tohoku Univ., Sendai (Japan). Inst. of Mineralogy, Petrology and Economic Geology] [Tohoku Univ., Sendai (Japan). Inst. of Mineralogy, Petrology and Economic Geology
Automatic Stepwise Potentiometric Titration in a Monosegmented Flow System
.��?An automatic stepwise potentiometric titration carried out in a monosegmented flow system is proposed. A tubular hydrogen\\u000a ion-selective electrode without inner reference solution was employed as sensor. The titration procedure was implemented by\\u000a exploiting continuous variations in volumetric fractions achieved by inserting different sample and titrant aliquots into\\u000a the analytical path and maintaining the sample zone volume. Every sample plug
Eduardo P. Borges; Patr�cia B. Martelli; Boaventura F. Reis
Potentiometric titration and equivalent weight of humic acid
USGS Publications Warehouse
The "acid nature" of humic acid has been controversial for many years. Some investigators claim that humic acid is a true weak acid, while others feel that its behaviour during potentiometric titration can be accounted for by colloidal adsorption of hydrogen ions. The acid character of humic acid has been reinvestigated using newly-derived relationships for the titration of weak acids with strong base. Re-interpreting the potentiometric titration data published by Thiele and Kettner in 1953, it was found that Merck humic acid behaves as a weak polyelectrolytic acid having an equivalent weight of 150, a pKa of 6.8 to 7.0, and a titration exponent of about 4.8. Interdretation of similar data pertaining to the titration of phenol-formaldehyde and pyrogallol-formaldehyde resins, considered to be analogs for humic acid by Thiele and Kettner, leads to the conclusion that it is not possible to differentiate between adsorption and acid-base reaction for these substances. ?? 1960.
Pommer, A. M.; Breger, I. A.
Logarithmic diagrams and gran-curves as an aid in potentiometric titrations in complexometry.
A detailed exposition is given of the use of logarithmic diagrams and Gran plots to construct titration curves and to determine accurately the equivalence point in potentiometric complexometric titrations. PMID:18961242
Johansson, A
Simultaneous potentiometric determination of cationic and ethoxylated nonionic surfactants in liquid cleaners and disinfectants.
A sensitive potentiometric surfactant sensor based on a highly lipophilic 1,3-didecyl-2-methyl-imidazolium cation and a tetraphenylborate (TPB) antagonist ion was used as the end-point detector in ion-pair potentiometric surfactant titrations using sodium TPB as a titrant. Several analytical and technical grade cationic and ethoxylated nonionic surfactants (EONS) and mixtures of both were potentiometrically titrated. The sensor showed satisfactory analytical performances within a pH range of 3-10 and exhibited satisfactory selectivity for all CS and EONS investigated. Ionic strength did not influence the titration except at 0.1M NaCl, in which a slight distortion of the second inflexion corresponded with the nonionic surfactant. Two-component combinations of four CS and three EONS were potentiometrically titrated using the sensor previously mentioned as the end-point detector. The quantities of the surfactants varied between 2 and 6 ?mol for CS and 2.50 and 7.50 ?mol for EONS. The known addition methodology was used for determination of the surfactant with considerably lower concentration in the mixture. Three commercial products containing cationic surfactants as disinfectants and nonionic surfactants were potentiometrically titrated, and the results for both type of surfactants were compared with those obtained with standard conventional methods. PMID:21147321
Samard�i?, Mirela; Sak-Bosnar, Milan; Maduni?-?a?i?, Dubravka
Application of various electrodes in potentiometric titration of calcium.
In complexometric titrations various indicator electrodes may be employed for monitoring the course of titration and for detection of the end-point. Several of them, including the silver, mercury, bivalent cation membrane, calcium membrane and manganese dioxide electrodes were investigated and compared in their usefulness. As titrant, EDTA was mostly used, but results with similar chelating titrants were also obtained. The practical utility of the electrodes in titrations depends on their selectivity, magnitude of the end-point break and precision in determination of the end-point. For the electrodes studied, in some instances there is good correlation between the theoretical and experimental titration curves, but it is not always possible to predict the electrode response in the low activity range. In other cases poor correlation does not mean that reasonably good analytical results may not be obtained. PMID:18961322
Nonaqueous potentiometric titration and elemental analysis were used to study basic and nonbasic functionalities present in high-boiling distillates of four Saudi Arabian crude oils. Model nitrogen compounds were titrated under similar titration conditions to differentiate them into strong, weak and nonbasic species. The strong bases titrated were due to the presence of pyridine and its benzologs like acridines, phe-nanthridines and
Mohammad Farhat Ali; Mohammed Ashraf Ali
Charge characteristics of humic and fulvic acids: comparative analysis by colloid titration and potentiometric titration with continuous pK-distribution function model.
Charge characteristics of humic and fulvic acids of a different origin (inshore soils, peat, marine sediments, and soil (lysimetric) waters) were evaluated by means of two alternative methods - colloid titration and potentiometric titration. In order to elucidate possible limitations of the colloid titration as an express method of analysis of low content of humic substances we monitored changes in acid-base properties and charge densities of humic substances with soil depth, fractionation, and origin. We have shown that both factors - strength of acidic groups and molecular weight distribution in humic and fulvic acids - can affect the reliability of colloid titration. Due to deviations from 1:1 stoichiometry in interactions of humic substances with polymeric cationic titrant, the colloid titration can underestimate total acidity (charge density) of humic substances with domination of weak acidic functional groups (pK>6) and high content of the fractions with molecular weight below 1kDa. PMID:18657293
Bratskaya, S; Golikov, A; Lutsenko, T; Nesterova, O; Dudarchik, V
Characterization of Sea Lettuce Surface Functional Groups by Potentiometric Titrations
In pursuit of our ultimate goal to better understand the prodigious capacity of the marine macroalga Ulva lactuca (sea lettuce) for adsorbing a broad range of dissolved trace metals from seawater, we performed an initial characterization of its surface functional groups. Specifically, the number of distinct functional groups as well as their individual bulk concentrations and acid dissociation constants (pKas) were determined by potentiometric titrations in NaCl solutions of various ionic strengths (I = 0.01-5.0 M), under inert nitrogen atmosphere at 25�C. Depending on the ionic strength, Ulva samples were manually titrated down to pH 2 or 3 with 1 N HCl and then up to pH 10 with 1 N NaOH in steps of 0.1-0.2 units, continuously monitoring pH with a glass combination electrode. Titrations of a dehydrated Ulva standard reference material (BCR-279) were compared with fresh Ulva tissue cultured in our laboratory. A titration in filtered natural seawater was also compared with one in an NaCl solution of equal ionic strength. Equilibrium constants for the ionization of water in NaCl solutions as a function of ionic strength were obtained from the literature. Fits to the titration data ([H]T vs. pH) were performed with the FITEQL4.0 computer code using non-electrostatic 3-, 4-, and 5-site models, either by fixing ionic strength at its experimental value or by allowing it to be extrapolated to zero, while considering all functional group pKas and bulk concentrations as adjustable parameters. Since pKas and bulk concentrations were found to be strongly correlated, the latter were also fixed in some cases to further constrain the pKas. Whereas these calculations are currently ongoing, preliminary results point to three, possibly four, functional groups with pKas of about 4.1, 6.3, and 9.5 at I = 0. Bulk concentrations of the three groups are very similar, about 5-6�10-4 mol/g based on dry weight, which suggests that all are homogeneously distributed over the surface and probably part of a single macromolecular scaffold. Fresh Ulva tissue appears to contain the same three functional groups but at lower concentrations, based on wet weight. The titration in natural seawater was largely dominated by the non-carbonate alkalinity of the solution and could not be robustly modeled. Results of fits with ionic strengths fixed at their experimental values indicate that the pKas of all three groups display prominent Debije-H�ckel-type behavior, hence that these acid dissociation reactions involve a different mechanism than metal-proton exchange reactions on mineral surfaces, whose distribution coefficients (i.e., equilibrium constants) generally show a weak ionic strength dependence.
Ebling, A. M.; Schijf, J.
Signal processing with a summing operational amplifier in multicomponent potentiometric titrations.
It has been proved that application of two indicator electrodes connected to the ordinary titration apparatus through an auxiliary electronic device (a summing operational amplifier) significantly extends the scope of multicomponent potentiometric titrations in which the analytes are determined simultaneously from a single titration curve. For each analyte there is a corresponding potential jump on the titration curve. By application of the proposed auxiliary device, the sum of the electrode potentials is measured. The device also enables the relative sizes of the potential jumps at the end-points on the titration curve to be varied. The advantages of the proposed signal processing are exemplified by complexometric potentiometric titrations of Fe(III) and Cu(II) in mixtures, with a platinum electrode and a copper ion-selective electrode as the indicator electrodes. PMID:18964366
Parczewski, A
Simple home-made sensors for potentiometric titrations. [Nitroform CH(NO/sub 2/)/sub 3/
A sensor for potentiometric titrations was prepared by coating a spectroscopic graphite rod with a solution of poly(vinyl chloride) and dioctyphthalate in tetrahydrofuran. The reference electrode was an Ag/AgCl single-junction electrode. The sensor was used in precipitation, acid-base, compleximetric, and redox titrations. Preparation of the coated-graphite sensor is simple and rapid. Moreover, it is quite inexpensive. A limitation is its applicability in aqueous media only, because organic solvents will dissolve the membrane. Various uncoated types of graphite have also been investigated as sensors, particularly in two applications of interest in the analysis of propellants: the titration of nitroform and perchlorate. Obviously, these sensors can be used also in nonaqueous, or partially nonaqueous media. These sensors may also find use in the potentiometric titration of fluoride vs La(III) or Th(IV).
Selig, W.
Pulsating potentiometric titration technique for assay of dissolved oxygen in water at trace level
A simple but high performance potentiometric titration technique using pulsating sensors has been developed for assay of dissolved oxygen (DO) in water samples down to 10.0?gL?1 levels. The technique involves Winkler titration chemistry, commonly used for determination of dissolved oxygen in water at mgL?1 levels, with modification in methodology for accurate detection of end point even at 10.0?gL?1 levels DO
P. Sahoo; R. Ananthanarayanan; N. Malathi; M. P. Rajiniganth; N. Murali; P. Swaminathan
A novel approach for high precision rapid potentiometric titrations: application to hydrazine assay.
We propose a high precision rapid personal computer (PC) based potentiometric titration technique using a specially designed mini-cell to carry out redox titrations for assay of chemicals in quality control laboratories attached to industrial, R&D, and nuclear establishments. Using this technique a few microlitre of sample (50-100 ?l) in a total volume of ~2 ml solution can be titrated and the waste generated after titration is extremely low comparing to that obtained from the conventional titration technique. The entire titration including online data acquisition followed by immediate offline analysis of data to get information about concentration of unknown sample is completed within a couple of minutes (about 2 min). This facility has been created using a new class of sensors, viz., pulsating sensors developed in-house. The basic concept in designing such instrument and the salient features of the titration device are presented in this paper. The performance of the titration facility was examined by conducting some of the high resolution redox titrations using dilute solutions--hydrazine against KIO(3) in HCl medium, Fe(II) against Ce(IV) and uranium using Davies-Gray method. The precision of titrations using this innovative approach lies between 0.048% and 1.0% relative standard deviation in different redox titrations. With the evolution of this rapid PC based titrator it was possible to develop a simple but high precision potentiometric titration technique for quick determination of hydrazine in nuclear fuel dissolver solution in the context of reprocessing of spent nuclear fuel in fast breeder reactors. PMID:22128994
Sahoo, P; Malathi, N; Ananthanarayanan, R; Praveen, K; Murali, N
Sodium and lithium chlorides are titrated potentiometrically with silver ; nitrate following two extractions of the lithium chloride with 2-ethyl-1-hexanol. ; Using glass and silver- silver chloride electrodes, the detection of the end ; point is enhanced in the organic medium. For 17 determinations, an average of ; 99.99% was obtained for lithium, with a standard deviation of 0.16%, and
G. R. Waterbury; E. H. Van Kooten; Bruno Morosin
DETERMINATION OF CONDITIONAL STABILITY CONSTANTS OF METAL-Trichoderma viride COMPLEXES BY THE POTENTIOMETRIC TITRATION METHOD
SUMMARY In this paper the binding ability of functional groups present in the cell walls of an ubiquitous soil fungus, Trichoderma viride Pers.: Fr., towards some divalent heavy metals, Cd, Co, Cu, Pb and Zn, was studied. Proc- essing the data from potentiometric titrations of T. viride by the McCallum, Midgley and Gran's combined meth- ods, the surface of the
Giovanna SANNA; Guido ALBERTI; Paola CASTALDI; Pietro MELIS
Potentiometric titration of gold, platinum, and some other precious metals.
Gold, platinum, and several other platinum metals can be determined by titration with cetylpyridinium chloride (CPC). CPC forms a precipitate with AuCl(sub 4)(sup (minus)) and PtCl(sub 6)(sup 2(minus)). Differentiation of AuCl(sub 4(minus)) and PtCl(sub 6...
W. S. Selig
Nonaqueous potentiometric titration and elemental analysis of high-boiling distillates of Saudi Arabian crude oils
Nonaqueous potentiometric titration and elemental analysis were used to study basic and nonbasic functionalities present in high-boiling distillates of four Saudi Arabian crude oils. Model nitrogen compounds were titrated under similar titration conditions to differentiate them into strong, weak and nonbasic species. The strong bses titrated were due to the presence of of pyridine and its benzologs like acridines, phenanthridines and quionolines. The weak bases titrated were due to phenazxines and amides whereas the pyrroles, indoles and carbazoles were found to be nonbasic in nature. The total nitrogen and the total basic nitrogen compounds were generally found to be in very low concentration in the four crude oil distillates. A gradual decrease in the basicity of the distillates was found from Arab Heavy to Arab Extra Light through Arab Medium and Arab Light crude oils.
Ali, M.F.; Ali, M.A. (Dept. of Chemistry, King Fahd Univ. of Petroleum and Minerals, Dhahran 31261 (SA))
Determination of Hydrogen Fluoride and Uranium (VI) in Crude Uranium Hexafluoride by Hydrolysis and Potentiometric Titration
A simple method for determining HF and U(VI) in a hydrolyzed solution of UF6 by alkalimetry is described.About 1 g of UF6 was taken in a polytrifluoromonochloroethylene tube, and hydrolyzed with about 50 ml of water in a closed polyethylene bottle. Using a glass electrode, HF in the hydrolyzed solution was titrated potentiometrically with an alkali solution, after the U(VI)
Haruka SHINOHARA; Kimie IZAWA; Shigeo TSUJIMURA; Kenji MOTOJIMA
Protein-salt binding data from potentiometric titrations of lysozyme in aqueous solutions containing KCl
An existing method for potentiometric titrations of proteins was improved, tested and applied to titrations of the enzyme hen-egg-white lysozyme in aqueous solutions containing KCl at ionic strengths from 0.1 M to 2.0 M at 25 C. Information about the protein`s net charge dependence on pH and ionic strength were obtained and salt binding numbers for the system were calculated using a linkage concept. For the pH range 2.5--11.5, the net charge slightly but distinctly increases with increasing ionic strength between 0.1 M and 2.0 M. The differences are most distinct in the pH region below 5. Above pH 11.35, the net charge decreases with increasing ionic strength. Preliminary calculation of binding numbers from titration curves at 0.1 M and 1.0 M showed selective association of chloride anions and expulsion of potassium ions at low pH. Ion-binding numbers from this work will be used to evaluate thermodynamic properties and to correlate crystallization or precipitation phase-equilibrium data in terms of a model based on the integral-equation theory of fluids which is currently under development.
Engmann, J.; Blanch, H.W.; Prausnitz, J.M. [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.
Potentiometric Titrations and Nickel(II) Complexes of Four Topologically Constrained Tetraazamacrocycles
The novel high spin Ni complexes of the topologically constrained tetraazamacrocycles (1�4) [4,11-dimethyl-1,4,8,11 - tetraazabicyclo[6.6.2]hexadecane (1); 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane (2); 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (3); racemic-4,5,7,7,11,12,14,14-octamethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (4)] show striking properties. Potentiometric titrations of the ligands 2 and 4 revealed them to be proton sponges, as reported earlier for 1 [1]. Ligand 3 is less basic, losing its last proton with a pK = 11.3(2). Despite
Timothy J. Hubin; Nathaniel W. Alcock; Howard J. Clase; Daryle H. Busch
Determination of phosphorous in titanium bearing minerals by potentiometric titration using Pb-ion selective electrode.
A method for phosphorous determination in titanium bearing minerals by potentiometric titration using a Pb-ion selective electrode has been developed. Sample decomposition is achieved by means of K(2)CO(3) fusion in a platinum crucible at 800 degrees C for 30 min in a muffle furnace, and subsequent leaching with water of the fused melt. The aqueous leachate is neutralised with HClO(4) and subsequent boiling. The obtained solution is used for titration with Pb(ClO(4))(2), and the Pb-ion selective electrode detects the end point. The lowest concentration determinable is 0.02% P(2)O(5) in a solid sample. The method was applied on in-house titanium bearing mineral samples and on IGS-31 ilmenite sample (British Geological Survey, UK). Synthetic samples were prepared and analysed, and phosphorous recovery is in the range 98-106%. The recovery and accuracy of the present method have been validated by spiking experiments and by comparing with the spectrophotometric values, respectively. The precision of the proposed method in terms of relative standard deviation is 2.0%. PMID:18967837
Ramadoss, K; Murty, D S; Mahanta, P L; Gomathy, B; Rangaswamy, R
Micellar acid-base potentiometric titrations of weak acidic and/or insoluble drugs.
The effect of various surfactants [the cationics cetyl trimethyl ammonium bromide (CTAB) and cetyl pyridinium chloride (CPC), the anionic sodium dodecyl sulphate (SDS), and the nonionic polysorbate 80 (Tween 80)] on the solubility and ionization constant of some sparingly soluble weak acids of pharmaceutical interest was studied. Benzoic acid (and its 3-methyl-, 3-nitro-, and 4-tert-butyl-derivatives), acetylsalicylic acid, naproxen and iopanoic acid were chosen as model examples. Precise and accurate acid-base titrations in micellar systems were made feasible using a microcomputer-controlled titrator. The response curve, response time and potential drift of the glass electrode in the micellar systems were examined. The cationics CTAB and CPC were found to increase considerably the ionization constant of the weak acids (delta pKa ranged from -0.21 to -3.57), while the anionic SDS showed negligible effect and the nonionic Tween 80 generally decreased the ionization constants. The solubility of the acids in aqueous micellar and acidified micellar solutions was studied spectrophotometrically and it was found increased in all cases. Acetylsalicylic acid, naproxen, benzoic acid and iopanoic acid could be easily determined in raw material and some of them in pharmaceutical preparations by direct titration in CTAB-micellar system instead of using the traditional non-aqueous or back titrimetry. Precisions of 0.3-4.3% RSD and good correlation with the official tedious methods were obtained. The interference study of some excipients showed that a preliminary test should be carried out before the assay of formulations. PMID:8466957
Gerakis, A M; Koupparis, M A; Efstathiou, C E
Comparison of a miniaturized shake-flask solubility method with automated potentiometric acid/base titrations and calculated solubilities.
Solubility is one of the most important parameters for lead selection and optimization during drug discovery. Its determination should therefore take place as early as possible in the process. Because of the large numbers of compounds involved and the very low amounts of each compound available in the early development stage, it is highly desirable to measure the solubility with as little compound as possible and to be able to improve the throughput of the methods used. In this work, a miniaturized shake-flask method was developed and the solubility results were compared with those measured by semiautomated potentiometric acid/base titrations and computational methods for 21 poorly soluble compounds with solubilities mostly in the range 0.03-30 microg/mL. The potentiometric method is very economical (approximately 100 microg of a poorly soluble compound is needed) and is able to create a pH/solubility profile with one single determination, but is limited to ionizable compounds. The miniaturized shake-flask method can be used for all compounds and a wide variety of media. Its precision and throughput proved superior to the potentiometric method for very poorly soluble compounds. Up to 20 compounds a week can be studied with one set-up. Calculated solubility data seem to be sufficient for a first estimate of the solubility, but they cannot currently be used as a substitute for experimental measurements at key decision points in the development process. PMID:15761925
Glomme, A; M�rz, J; Dressman, J B
NSDL National Science Digital Library
The purpose of this project is to construct a mathematical model describing the effects of titration, and then to use that model to determine the concentration and the identity of an acid in a solution by fitting the model to real titration data.
Smith, David
Concentration determination of methyl magnesium chloride and other Grignard reagents by potentiometric titration with in-line characterization of reaction species by FTIR spectroscopy
A potentiometric titration method for methyl magnesium chloride and other Grignard reagents based on the reaction with 2-butanol in THF has been developed and validated. The method employs a commercially available platinum electrode, using an electrolyte compatible with non-aqueous solvents. Well-defined titration curves were obtained, along with excellent method precision. The endpoint was precisely determined based on the first derivative
Yadan Chen; Tao Wang; Roy Helmy; George X. Zhou; Rosario LoBrutto
Determination of Fe(II)Fe(III) and Fe(III)Ni(II) by the two-component potentiometric complexometric titration
The two-component complexometric potentiometric titration has been applied to the simultaneous determination of Fe(III) and Fe(II), and of Fe(III) and Ni(II) in solution. In each case the two analytes were determined by reading the end-points directly from the titration curve. The end-points are determined in a sense arbitrarily, but they are repeatable and easy to be detected precisely. However, the
Jolanta Kochana; Katarzyna Madej; Andrzej Parczewski
Potentiometric behavior of ion-selective electrodes to large cationic species modulated by decyl alcohol
The effect of 1-decanol on the potentiometric response of three ion-selective electrodes to large cationic species is analyzed. The electrodes were constructed with plasticized PVC membranes. The results suggest that 1-decanol alters the ionic transport through the membrane\\/water interface to an extent that depends on the strength of the active ion pair. The water solubility of the cation, its molecular
Walton J. Cabrera; Marianne A. Kaempfe; Marcela D. Urz�a; Hern�n E. R�os
Application of modified Gran functions and derivative methods to potentiometric acid titration studies of the distribution of inorganic carbon species in cultivation medium of marine microalgae
This paper presents an evaluation of the modified Gran functions (MGFs) and derivative methods for assessing the concentrations of inorganic carbon species, CO2, HCO3? and CO32?, in the cultivation medium of the marine microalgae Tetraselmis gracilis. Both methods were applied to simulated and experimental potentiometric titration data and were able to detect small variations of inorganic carbon species during 10
Marilda Rigobello-Masini; Jorge C. Masini
Determination of sulphated glycosaminoglycans by automated potentiometric titration with simple coated-wire electrodes.
A method for the determination of sulphated glycosaminoglycans is based on their precipitation with (1-ethoxycarbonyl)pentadecyltrimethylammonium bromide (Septonex), the excess of which is back-titrated with sodium tetraphenylborate. The titration is monitored by a simple coated-wire ion-selective electrode with a plasticized poly(vinyl chloride) membrane on aluminium wire. Under certain conditions the results are almost independent of the relative molecular mass of glycosaminoglycans. The method has been applied to the determination of the active ingredient in the pharmaceutical preparation, heparon injection. PMID:2490091
Dohnal, J; Vytras, K; Roubal, Z; Zemanov�, I
Concentration determination of methyl magnesium chloride and other Grignard reagents by potentiometric titration with in-line characterization of reaction species by FTIR spectroscopy.
A potentiometric titration method for methyl magnesium chloride and other Grignard reagents based on the reaction with 2-butanol in THF has been developed and validated. The method employs a commercially available platinum electrode, using an electrolyte compatible with non-aqueous solvents. Well-defined titration curves were obtained, along with excellent method precision. The endpoint was precisely determined based on the first derivative of the titration curve. Different solvents such as THF, diethyl ether and methylene chloride provided similar results with regard to sharpness of the endpoint and method precision. The method was applied to a wide array of Grignard reagents including methyl magnesium bromide, ethyl magnesium chloride, propyl magnesium chloride, vinyl magnesium chloride, phenyl magnesium chloride, and benzyl magnesium chloride with similar precision and accuracy. Application of in-line FTIR was demonstrated for in situ monitoring of the titration reaction, allowing characterization of the reaction species. An authentic spectrum of the MeMgCl-THF complex was obtained using spectral subtraction and the vibrational absorbance bands were identified. FTIR also provided an alternative for detecting the titration endpoint, and the titration results so obtained, provided a cross-validation of the accuracy of the potentiometric titration. PMID:12062641
Chen, Yadan; Wang, Tao; Helmy, Roy; Zhou, George X; LoBrutto, Rosario
Thermodynamics of Cationic Lipid-DNA Complex Formation as Studied by Isothermal Titration Calorimetry
The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual
Edwin Pozharski; Robert C. MacDonald
Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches
To provide constraints on the speciation of bacterial surface functional groups, we have conducted potentiometric titrations using the gram-positive aerobic species Bacillus subtilis, covering the pH range 2.1 to 9.8. Titration experiments were conducted using an auto-titrator assembly, with the bacteria suspended in fixed ionic strength (0.01 to 0.3 M) NaClO 4 solutions. We observed significant adsorption of protons over the entire pH range of this study, including to the lowest pH values examined, indicating that proton saturation of the cell wall did not occur under any of the conditions of the experiments. Ionic strength, over the range studied here, did not have a significant effect on the observed buffering behavior relative to experimental uncertainty. Electrophoretic mobility measurements indicate that the cell wall is negatively charged, even under the lowest pH conditions studied. These experimental results necessitate a definition of the zero proton condition such that the total proton concentration at the pH of suspension is offset to account for the negative bacterial surface charge that tends towards neutrality at pH <2. The buffering intensity of the bacterial suspensions reveals a wide spread of apparent pKa values. This spread was modeled using three significantly different approaches: a Non-Electrostatic Model, a Constant Capacitance Model, and a Langmuir-Freundlich Model. The approaches differ in the manner in which they treat the surface electric field effects, and in whether they treat the proton-active sites as discrete functional groups or as continuous distributions of related sites. Each type of model tested, however, provides an excellent fit to the experimental data, indicating that titration data alone are insufficient for characterizing the molecular-scale reactions that occur on the bacterial surface. Spectroscopic data on the molecular-scale properties of the bacterial surface are required to differentiate between the underlying mechanisms of proton adsorption inherent in these models. The applicability and underlying conceptual foundation of each model is discussed in the context of our current knowledge of the structure of bacterial cell walls.
Fein, Jeremy B.; Boily, Jean-Fran�ois; Yee, Nathan; Gorman-Lewis, Drew; Turner, Benjamin F.
Determination of chlorine and dissolved oxygen in waters and of ascorbic acid in pharmaceuticals by iodimetric potentiometric titration using a plasticized poly(vinyl chloride) membrane electrode
The response to triiodide of an electrode based on a membrane containing poly(vinyl chloride) and 2-nitrophenyl octyl ether as plasticizer in a 1:2 (ww) ratio is studied. The electrode is suitable for the automatic potentiometric titration of triiodide in the concentration range 10?5�10?3 mol l?1 with thiosulphate. The electrode has been satisfactorily applied to the determination of chlorine and dissolved
Concepci�n S�nchez-Pedre�o; Joaqu�n A. Ortu�o; J. Hern�ndez
Organic-inorganic composite cation-exchanger: poly-o-toluidine Zr(IV) phosphate-based ion-selective membrane electrode for the potentiometric determination of mercury.
A new heterogeneous precipitate of an organic-inorganic composite cation-exchanger poly-o-toluidine Zr(IV) phosphate was utilized for the preparation of a Hg(II) ion-sensitive membrane electrode for the determination of Hg(II) ions in real aqueous as well as in real samples. The electrode showed good potentiometric response characteristics, and displayed a linear log[Hg(2+)] versus EMF response over a wide concentration range of 1 x 10(-1) - 1 x 10(-6) M with a Nernstian slope of 30 mV per decade change in concentration with a detection limit of 1 x 10(-6). The membrane electrode showed a very fast response time of 5 s and could be operated well in the pH range 2 - 8. The selectivity coefficients were determined by the mixed-solution method, and revealed that the electrode was selective in the presence of interfering cations; however most of these did not show significant interference in the concentration range of 1 x 10(-1) - 1 x 10(-4) M. The lifetime of the membrane electrode was observed to be 120 days. The analytical utility of this electrode was established by employing it as an indicator electrode in the potentiometric titrations of Hg(2+) ions from a synthetic mixture as well as drain water. PMID:18614830
Khan, Asif Ali; Inamuddin; Akhtar, Tabassum
Determination of cationic polyelectrolytes using a photometric titration with crystal violet as a color indicator.
The reaction of the cationic dye, crystal violet (CV) with the anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) results in a decrease of the absorbance of CV at the maximum absorption wavelength (590 nm). This change of the absorption spectra of the CV has been already applied to the determination of anionic polyelectrolytes using flow injection analysis method. In this paper, CV was applied to the indicator for the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by photometric titration, using a PVSK solution as a titrant. The end-point of the titration is detected as the break point of the titration curve. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 0 to 5 x 10(-5) eq. mol dm(-3) for Cat-floc, glycol chitosan and methylglycol chitosan. The effects of the concentration of CV and coexisting electrolytes in the sample solution and the effect of pH of the sample solution on the degree of the change of absorbance at the end-point were also examined. PMID:18968953
Masadome, Takashi
New approach in the treatment of data from an acid-base potentiometric titrationI. Monocomponent systems of monofunctional acids and bases.
Based on precise analysis of the acid-base equilibrium, a new approach in the treatment of experimental data from a potentiometric titration is proposed. A new general formula giving explicitly the relation V=f([H(+)]) is derived, valid for every acid-base titration, which includes mono- and polyfunctional protolytes and their mixtures. The present study is the first practical application of this formula for the simplest case, the analysis of one monofunctional protolyte. The collected mV data during the titration are converted into pH-values by means of an auto pH-calibration procedure, thus avoiding preliminary preparation of the measuring system. The mentioned pH-calibration method is applicable also in water-organic mixtures and allows the quantitative determination of sparingly soluble substances (particularly pharmaceuticals). The treatment of the data is performed by means of ready-to-use software products, which makes the proposed approach accessible for a wide range of applications. PMID:12560965
Maslarska, Vania; Tencheva, Jasmina; Budevsky, Omortag
Humic substance charge determination by titration with a flexible cationic polyelectrolyte
The anionic charge of humic substances (HS) plays a major role in the interaction of HS with other components. Therefore, the potential of the polyelectrolyte titration technique to obtain the charge density of HS in simple 1-1 electrolyte solutions has been investigated. Titrations are carried out with an automatic titrator combined with the "M�tek particle charge detector" which allows determination of the M�tek potential and the pH as a function of the added amount of titrant which is a solution of poly-diallyldimethylammonium chloride (polyDADMAC), a cationic strong polyelectrolyte. When the M�tek potential reverses its sign the iso-electric point (IEP) of the polyDADMAC-HS complex is reached. The polyDADMAC/HS mass ratio at the IEP gives information on the HS charge density and from the pH changes in solution an estimate of the charge regulation in the HS-polyDADMAC complex can be obtained. In general, for polyDADMAC-HS complexes an increase in the dissociation of the acid groups of HS is found (charge regulation). The charge regulation decreases with increasing concentration of 1-1 background electrolyte. Cation incorporation can be neglected at 1-1 electrolyte concentrations ? 1 mmol L -1 and a 1-1 stoichiometry exists between the polyDADMAC and HS charge. However, at these low salt concentrations the charge regulation is substantial. A detailed analysis of purified Aldrich humic acid (PAHA) at pH 5 and a range of KCl concentrations reveals that the anionic charge of PAHA in the complex increases at 5 mmol L -1 KCl by 30% and at 150 mmol L -1 KCl by 12%. On the other hand, increasing amounts of K + become incorporated in the complex: at 5 mmol L -1 KCl 5% and at 150 mmol L -1 KCl 24% of the PAHA charge is balanced by K +. By comparing at pH 5 the mass ratios polyDADMAC/PAHA in the complex at the IEP with the theoretical mass ratios of polyDADMAC/PAHA required to neutralize PAHA in the absence of charge regulation and K + incorporation, it is found that at 50 mmol L -1 KCl the extra negative charge due to the interaction between polyDADMAC and PAHA is just compensated by K + incorporation in the complex. Therefore, a pseudo 1-1 stoichiometry exists at about 50 mmol L -1 1-1 electrolyte concentration and only at this salt concentration polyDADMAC titrations and conventional proton titrations give identical results. Most likely this is also true for other HA samples and other pH values. For FA further study is required to reveal the conditions for which polyDADMAC and proton titrations give identical results.
Tan, Wen-Feng; Norde, Willem; Koopal, Luuk K.
The Determination of the pKaof Multiprotic, Weak Acids by Analyzing Potentiometric Acid Base Titration Data with Difference Plots
This paper discusses the pKa determination of mono-, di-, and triprotic weak acids with the help of difference (Bjerrum) plots, and the effect of strong acid base concentration errors, ligand weight errors, and nonlinear electrode response. Experimental examples are given for the titration of an acidic heterocycle, as well as glycine, ethylenediamine, and tris(2-aminoethyl)amine (the last two after addition of excess HCl to ensure complete protonation) with standarized NaOH. The analysis procedure makes use of Microsoft Excel spreadsheets and nonlinear least squares curve fitting of the experimental data to the theoretical Bjerrum function. In addition to providing pKa values for mono- and multiprotic acids, this approach has been found suitable for detecting small errors in parameters, such as strong acid and ligand concentration, and corrections can often become necessary to achieve the best fit. Difference plots allow the pKa values of monoprotic and multiprotic weak acids to be determined rapidly and with good precision.
Kraft, Arno
Novel antagonists acting at the P2Y(1) purinergic receptor: synthesis and conformational analysis using potentiometric and nuclear magnetic resonance titration techniques.
The human P2Y(1) receptor is widely distributed in many tissues and has a classical structure of a G protein-coupled receptor. Activated by adenosine-5'-diphosphate (ADP), this receptor is essential for platelet aggregation. In the present paper, we describe the synthesis of novel P2Y(1) antagonists that could be of interest at least as tools to define the physiological roles of the P2Y(1) receptor, at best as new antithrombotic agents. Thus, we prepared the 2,N(6)-dimethyl-2'-deoxyadenosine-3',5'-bisphosphate derivative, 1e. The biological activity was demonstrated by the ability of compound 1e to inhibit ADP-induced platelet aggregation, shape change, and intracellular calcium rise. This compound was a full antagonist at the P2Y(1) receptor with a pA(2) value of 7.11 +/- 0.11 and was found to be 4-fold more potent than the reference N(6)-methyl-2'-deoxyadenosine-3',5'-bisphosphate (1a, pA(2) = 6.55 +/- 0.05), revealing the potency-enhancing effects of the 2-methyl group. The better activity of 1e as compared to 1a was analyzed using both potentiometric and nuclear magnetic resonance titration techniques, which highlighted specific conformational features of this compound. These results clearly indicate the preference for both compounds for an anti conformation at the N-glycosyl linkage. Furthermore, the percentage of S conformer of 1e is close to that of 1a, which is nearly 70% at pH = 2.8 and increases dramatically when pH increases. From the macroprotonation constants, it can be noted that compound 1e is significantly more basic than 1a. This is indeed expected for the N1 adenine nitrogen due to the electron-donating character of the methyl moiety. By considering the microconstants of the phosphate groups, the higher basicity of P3 and P5 for 1e may be due to the decrease in the local dielectric constant induced by the substitution of the hydrogen atom by a more lipophilic methyl group. Thus, it may be suggested that the gain in activity of 1e when compared to the reference compound 1a would result from its gain in basicity rather than steric and conformational modifications. The synthesis of the first selective radioligand acting at the P2Y(1) receptor ([(33)P]-N(6)-methyl-2'-deoxyadenosine-3',5'-bisphosphate, 17) is also reported and will be used in the future for efficient screening needed for drug optimization. PMID:11831909
Raboisson, Pierre; Baurand, Anthony; Cazenave, Jean-Pierre; Gachet, Christian; Retat, Myriam; Spiess, Bernard; Bourguignon, Jean-Jacques
Report: Determination of pKa values of new phenacyl-piperidine derivatives by potentiometric titration method in aqueous medium at room temperature (25�0.5oC).
Dissociation constant (pKa) of ten novel phenacyl derivatives of piperidine were determined by potentiometric titration method in aqueous medium at room temperature (25 �0.5�C). The sample solutions were prepared in deionized water with ionic strength 0.01M and titrated with 0.1M NaOH solution. In addition, ?G values were also calculated. Different prediction software programs were used to calculate pKa values too and compared to the experimentally observed pKa values. The experimental and theoretical values were found in close agreement. The results obtained in this research would help to predict the good absorption of the studied compounds and can be selected as lead molecules for the synthesis of CNS active agents because of their lipophilic nature especially compound VII. PMID:25015461
Zafar, Shaista; Akhtar, Shamim; Tariq, Talat; Mushtaq, Noushin; Akram, Arfa; Ahmed, Ahsaan; Arif, Muhammad; Naeem, Sabahat; Anwar, Sana
Spectrophotometric titration of bimetallic metal cation binding in polyamido(amine) dendrimer templates.
Spectrophotometric titration and a binding isotherm were used to accurately assess the loading capacity of generation four polyamido(amine) (PAMAM) dendrimer templates with terminal alcohol groups (G4-OH). Preparation of bimetallic G4-OH dendrimer-encapsulated metal nanoclusters (DENs) necessitates knowledge of the precise metal-ion binding capacity. The binding of metal ions such as Pt(2+) and Pd(2+) has proven difficult to assess via UV-vis spectroscopy because the absorbance shifts associated with metal-ion binding within the dendrimer template are masked by the absorbance of the PAMAM dendrimer itself. In contrast, the binding of Cu(2+) to G4-OH PAMAM dendrimer results in a strong, distinct absorption band at 300 nm, making UV-vis spectrophotometric titration with copper straightforward. Here we use copper binding as a means to assess the number of binding sites remaining within the PAMAM G4-OH dendrimer after the complexation of a specified molar excess of Pd(2+) or Pt(2+). In addition, we use a binding isotherm to mathematically estimate the loading capacity of the dendrimer in each case. The loading capacities for M(2+) in the G4-OH dendrimer were found to be ?16 for copper alone, ?21 for copper combined with palladium, and ?25 for copper combined with platinum. PMID:22587595
Marvin, Katherine A; Johnson, Justin A; Rodenbusch, Stacia E; Gong, Lucy; Vanden Bout, David A; Stevenson, Keith J
A deuterium-palladium electrode as a new sensor in non-aqueous solutions: potentiometric titration of weak acids in acetonitrile and benzonitrile
A deuterium-palladium electrode was employed as a new indicator electrode for the titration of weak acids in acetonitrile\\u000a and benzonitrile. The investigated electrode showed a linear dynamic response for p-toluenesulfonic acid in the concentration\\u000a range from 0.001 M to 0.1 M with a Nernstian slope of 48 mV in acetonitrile. Sodium methylate, potassium hydroxide and tetrabutylammonium\\u000a hydroxide proved to be
Ivan ?. Panti?; Ran?el P. Mihajlovi?; Ljiljana V. Mihajlovi?
Determination of total fluoride in HF/HNO3/H2SiF6 etch solutions by new potentiometric titration methods.
In the photovoltaic industry the etching of silicon in HF/HNO(3) solutions is a decisive process for cleaning wafer surfaces or to produce certain surface morphologies like polishing or texturization. With regard to cost efficiency, a maximal utilisation of etch baths in combination with highest quality and accuracy is strived. To provide an etch bath control realised by a replenishment with concentrated acids the main constituents of these HF/HNO(3) etch solutions including the reaction product H(2)SiF(6) have to be analysed. Two new methods for the determination of the total fluoride content in an acidic etch solution based on the precipitation titration with La(NO(3))(3) are presented within this paper. The first method bases on the proper choice of the reaction conditions, since free fluoride ions have to be liberated from HF and H(2)SiF(6) at the same time to be detected by a fluoride ion-selective electrode (F-ISE). Therefore, the sample is adjusted to a pH of 8 for total cleavage of the SiF(6)(2-) anion and titrated in absence of buffers. In a second method, the titration with La(NO(3))(3) is followed by a change of the pH-value using a HF resistant glass-electrode. Both methods provide consistent values, whereas the analysis is fast and accurate, and thus, applicable for industrial process control. PMID:19071540
Weinreich, Wenke; Acker, J�rg; Gr�ber, Iris
Automatic potentiometric determination of dissolved oxygen
Commercially available automatic titration systems were tested in 1988 for potentiometric titration of liberated iodine by the Winkler method of oxygen determination. The potentiometric equivalence point was also compared to the manual starch end point. Finally the automatic method was used in order to estimate belowhalocline respiration in the Kattegat, Sweden. Standard deviations of 0.007 ml O2 l-1 or 0.1
W. Gran�li; E. Gran�li
Going Beyond, Going Further: Knives, Forks, and Beer Cans as Potentiometric Sensors.
ERIC Educational Resources Information Center
Background information, materials needed, and procedures used are provided for potentiometric fluoride, halide, orthophosphate, and sulfate titrations. Typical results obtained are also provided for each type of titration. (JN)
Selig, Walter S.
Structure of the S. aureus PI-specific phospholipase C reveals modulation of active site access by a titratable ?-cation latched loop�
PubMed Central
Staphylococcus aureus secretes a phosphatidylinositol-specific phospholipase C (PIPLC) as a virulence factor that is unusual in exhibiting higher activity at acidic pH values than other enzymes in this class. We have determined the crystal structure of this enzyme at pH 4.6 and pH 7.5. Under slightly basic conditions, the S. aureus PI-PLC structure closely follows the conformation of other bacterial PI-PLCs. However, when crystallized under acidic conditions, a large section of mobile loop at the ??-barrel rim in the vicinity of the active site shows ~10 � shift. This loop displacement at acidic pH is the result of a titratable intramolecular ?-cation interaction between His258 and Phe249. This was verified by a structure of the mutant protein H258Y crystallized at pH 4.6, which does not exhibit the large loop shift. The intramolecular ?-cation interaction for S. aureus PI-PLC provides an explanation for the activity of the enzyme at acid pH and also suggests how phosphatidylcholine, as a competitor for Phe249, may kinetically activate this enzyme.
Goldstein, Rebecca; Cheng, Jiongjia; Stec, Boguslaw; Roberts, Mary F.
1. The usefulness of the radiomicrometer in titration work has been pointed out. The authors suggest that light titration may also be used where a reaction mixture changes its absorption in the (near) infra-red. 2. The applicability of this method to the starch-iodine reaction has been demonstrated.
Field, John; Baas-Becking, Lourens G. M.
Reduction of water wettability of nanofibrillated cellulose by adsorption of cationic surfactants
Adsorption isotherms of single and double chain cationic surfactants with different chain length (cetyltrimethyl-, didodecyl-\\u000a and dihexadecyl ammonium bromide) onto cellulose nanofibrils were determined. Nanofibrillated cellulose, also known as microfibrillated\\u000a cellulose (MFC), with varying contents of carboxyl groups (different surface charge) was prepared by TEMPO-mediated oxidation\\u000a followed by mechanical fibrillation. The fibril charge was characterized by potentiometric and conductometric titration.
Klodian Xhanari; Kristin Syverud; Gary Chinga-Carrasco; Kristofer Paso; Per Stenius
Potentiometric Determination of Free Nitric-Acid in Trilaurylamine Solutions Containing Plutonium Nitrate (Dosage Potentiometrique de L 'Acidite Nitrique Libre Dans les Solutions Organiques de Trilaurylamine).
A potentiometric method of determination of the free nitric acid in trilaurylamine solutions containing plutonium or thorium nitrates is described. The potentiometric titration is carried out in a mixtrue of benzene and 1, 2-dichloro ethane with a standar...
J. J. Perez J. C. Saey
Studies on the complexation of Pr(III) and Nd(III) with glycyl-glycine (gly-gly) using spectral analysis of 4f-4f transitions and potentiometric titrations
The interaction of gly-gly with Pr(III) and Nd(III) have been studied in different aquated organic solvents like CH3OH, CH3CN, dioxane and DMF by using 4f-4f transitions spectra. Various energy interaction parameters like Slater Condon (Fk), Racah (Ek), Lande (?4f), nephelauxetic effect (?), bonding (b1/2) and percent covalency (?) parameters have been calculated to explain the nature of complexation. The intensity parameters like oscillator strength (P) and Judd-Ofelt parameters (T?, ? = 2, 4, 6) also support the mode of binding of gly-gly to metal ions. The results show that Pr(III) and Nd(III) with gly-gly form complexes by ionic linkages with carboxylate anion with weak covalency. The protonation constants and metal-ligand stability constants have also been determined by potentiometric measurements in aqueous medium at different temperatures (290, 300 and 310 K) at constant ionic strength, 0.1 mol dm-1. The results show the formation of metal-ligand complexes in the stoichiometric ratio 1:1. The stability of complexes is more in Nd(III) complexes as compared to Pr(III) complexes. Thermodynamic parameters (?G, ?H and ?S) of complexes were also calculated and the negative values of ?G and ?H show that the complex reactions are spontaneous and exothermic. The positive values of ?S indicate high stability of complex reactions which are enthalpy-driven.
Ranjana Devi, N.; Huidrom, Bimola; Rajmuhon Singh, N.
Thermometric titration in investigation of the formation of polyanions of molybdenum(VI), tungsten(VI), vanadium(V), and chromium(VI). III. Titration of molybdic acid with sodium hydroxide solution
To define the propenties of molybdenum-containing species which appear ; in the acidification of neutral molybdate solution with mineral acid, the reverse ; process (i.e., the titration of molybdic acid of acidified molybdate solution ; with sodium hydroxide) was examined and the titration curves were obtained ; thermometrically as well as potentiometrically. In the thermometric titration ; curves there are
Nobutoshi Kiba; Tsugio Takeuchi
Potentiometric determination of cetylpyridinium chloride using a new type of screen-printed ion selective electrodes.
A new type of screen-printed ion-selective electrode for the determination of cetylpyridinium chloride (CPC) is presented. These new electrodes involve in situ, modified and unmodified screen-printed ion-selective electrodes for the determination of CPC. The screen-printed electrodes (SPEs) show a stable, near-Nernstian response for 1 x 10(-2) to 1 x 10(-6) M CPC at 25 degrees C over the pH range 2-8 with cationic slope 60.66+/-1.10. The lower detection limit is found to be 8 x 10(-7) M and response time of about 3s and exhibit adequate shelf-life (6 months). The fabricated electrodes can be also successfully used in the potentiometric titration of CPC with sodium tetraphenylborate (NaTPB). The analytical performances of the SPEs are compared with those for carbon paste electrode (CPE) and polyvinyl chloride (PVC) electrodes. The method is applied for pharmaceutical preparations with a percentage recovery of 99.60% and R.S.D.=0.53. The frequently used CPC of analytical and technical grade as well as different water samples has been successfully titrated and the results obtained agreed with those obtained with commercial electrode and standard two-phase titration method. The sensitivity of the proposed method is comparable with the official method and ability of field measurements. PMID:20630181
Mohamed, Gehad G; Ali, Tamer Awad; El-Shahat, M F; Al-Sabagh, A M; Migahed, M A; Khaled, Elmorsy
Simultaneous determination of mixtures of metal ions by complexometric titration and multivariate calibration
A new complexometric titration method for the determination of mixtures of metal ions with multivariate calibration was developed. The principle of this method is described and a linear complexometric titration equation is derived. In this work, a mercury film electrode (MFE) was used as indicator electrode for potentiometric measurements, and a double junction Ag\\/AgCl electrode as reference electrode. The mixtures
Yongnian Ni; Yingliang Wu
The potentiometric and spectrophotometric determination of dissociation constants for same 2-mercapto-5-R-amino-1,3,4-thiadiazole derivatives.
In order to establish the dissociation constants of organic compounds, the spectrophotometric and potentiometric methods are the most precise and useful ones. Comparing the results, we used both methods for three derivatives of 2-mercapto-5-R-amino-1,3,4-thiadiazole. For the pKa determination by the spectrophotometric method we measured the ratio between the concentration of dissociated and undissociated forms. The ratio was calculated from spectral data. The potentiometric method for pKa consists of measuring the pH values within a potentiometric titration with 0.1 M NaOH. The results proved a very low acid character of the derivatives. The pKa values were influenced by the properties of the amino group substituents, and the results confirm the theoretical considerations. The study confirms the thion-thiolic tautometry of the 2-mercapto-5-R-amino-1,3,4-thiadiazole derivates and their property of being ligands for the coordination of the cations of some representative and transitional metals, with application in the preconcentration, in the detection and the quantitative determination of polluting and toxic cations in environmental analysis. PMID:9863951
Roman, L; Mirel, S; Florean, E; Oprean, R
Potentiometric monitoring DNA hybridization.
The usual procedure to monitor the ion exchange of small ions utilizes a potentiometer with a selective membrane as part of the working electrode. As the next step, we have applied polyaniline electrodes to the monitoring the activity macromolecular ions during DNA hybridization. Single-strand oligonucleotide (ssODN) probes were immobilized using a nucleophilic substitution reaction of the thiolated ssODN molecules with polyaniline. The anionic phosphate groups of the probe molecules also interacted with the cationic-doped polyaniline surface. Three useful findings were observed with the potentiometric experiments. First, the binding of the complimentary target molecules with the immobilized probes revealed a substantial potential change. Further, potential change was observed neither with the non-complimentary targets nor with the samples with a mutation in the sequence. The last two experiments were important for the future evaluation of the impact of medium and potential interfering compounds: anionic groups and hydrogen bonding groups in the non-complimentary samples did not cause any interactions. PMID:19477628
Zhou, Y; Yu, B; Guiseppi-Elie, A; Sergeyev, V; Levon, K
Titrations using an apparatus for recording the antilogarithm of pH or pM.
A titration apparatus plotting either the concentration of sample ion or the concentration of titrant ion has been tested. An antilog apparatus, converting measured e.m.f. values into concentrations is connected to ordinary titration equipment. The instrument has been tested by means of acid-base titrations (titrations of mixtures of weak acids and of a weak and a strong acid), precipitation titrations (determination of the chloride concentration in tap-water, titration of mixtures of halides), titrations with ion-selective electrodes (determination of the fluoride content of toothpaste) and complexometric titrations (determination of copper with EDTA, using mercuric ion as indicator ion and amalgamated silver rod as indicator electrode, or using a copper-selective indicator electrode). The method considerably simplifies the evaluation of the results as compared to conventional potentiometric titrations. PMID:18961596
PVC matrix membrane sensor for potentiometric determination of metoclopramide hydrochloride in some pharmaceutical formulations.
The construction and characteristic performance of metoclopramide (MCP)-polyvinyl chloride (PVC) membrane sensor are described. The sensor is based on the use of MCP-tetraiodomercurate ion pair as electroactive material in PVC matrix in presence of dioctylphthalate (DOP) as solvent mediator. MCP membrane sensor shows a stable, near Nernstian response over the concentration range 1 x 10(-2)-6 x 10(-5) M of MCP at 25 degrees C in the pH range 3-7 with cationic slope of 53.0+/-0.5. The detection limit of 4 x 10(-5) M and the response time of 30-60 s have been attained. Selectivity coefficient data for some common ions show negligible intereferences. Direct potentiometric determination of 15-3540 microg/ml MCP show an average recovery of 98.5% and a mean relative standard deviation (R.S.D.) of 1.6% at 100.0 microg/ml. The determination of MCP in Primperan tablets, injection, and syrup gave results that compare favorably with those obtained by the British pharmacopoeia method. Precipitation titrations involving MCP as titrant are monitored with the MCP sensor for some potentiometric precipitation reaction, e.g. sodium tetraphenylborate (STPB) and phosphomolybdic acid (PMA). PMID:12615239
Mostafa, G A E
Thermodynamic analysis of Bacillus subtilis endospore protonation using isothermal titration calorimetry
Bacterial proton and metal adsorption reactions have the capacity to affect metal speciation and transport in aqueous environments. We coupled potentiometric titration and isothermal titration calorimetry (ITC) analyses to study Bacillus subtilis spore-proton adsorption. We modeled the potentiometric data using a four and five-site non-electrostatic surface complexation model (NE-SCM). Heats of spore surface protonation from coupled ITC analyses were used to determine site specific enthalpies of protonation based on NE-SCMs. The five-site model resulted in a substantially better model fit for the heats of protonation but did not significantly improve the potentiometric titration model fit. The improvement observed in the five-site protonation heat model suggests the presence of a highly exothermic protonation reaction circa pH 7 that cannot be resolved in the less sensitive potentiometric data. From the log Ks and enthalpies we calculated corresponding site specific entropies. Log Ks and site concentrations describing spore surface protonation are statistically equivalent to B. subtilis cell surface protonation constants. Spore surface protonation enthalpies, however, are more exothermic relative to cell based adsorption suggesting a different bonding environment. The thermodynamic parameters defined in this study provide insight on molecular scale spore-surface protonation reactions. Coupled ITC and potentiometric titrations can reveal highly exothermic, and possibly endothermic, adsorption reactions that are overshadowed in potentiometric models alone. Spore-proton adsorption NE-SCMs derived in this study provide a framework for future metal adsorption studies.
Harrold, Zo� R.; Gorman-Lewis, Drew
Flow injection potentiometric determination of pipazethate hydrochloride.
New plastic membrane electrodes for pipazethate hydrochloride based on pipazethatium phosphotungstate, pipazethatium phosphomolybdate and a mixture of the two were prepared. The electrodes were fully characterized in terms of composition, life span, pH and temperature and were then applied to the potentiometric determination of the pipazethate ion in its pure state and pharmaceutical preparations under batch and flow injection conditions. The selectivity of the electrodes towards many inorganic cations, sugars and amino acids was also tested. PMID:11205518
Abdel-Ghani, N T; Shoukry, A F; el Nashar, R M
Titration curves in complexometric titrations with the redox system Fe(III)/Fe(II).
Potentiometric titrations of metal ions with EDTA have been carried out with a platinum or graphite electrode and the Fe(III)/Fe(II) redox system. In the absence of oxygen and for pH < 2 the titration curves may be described by an equation similar to that given previously for titrations with silver and mercury electrodes. Titration curves for bismuth and indium, which are more strongly complexed than iron, are asymmetrical and useful for analytical purposes. When the titrated ions are complexed less strongly than iron(III) ions the kinetics of metal complexation have a pronounced effect. The titration curves of thorium and copper, which react more rapidly than iron, are analytically useful. The curves recorded rapidly after titrant additions have a better end-point break than those which correspond to thermodynamic equilibrium. When a metal, e.g., nickel, is weakly bound by EDTA, and reacts more slowly than iron, a very small end-point break or none at all is observed. PMID:18960880
Hulanicki, A; Karwowska, R
Potentiometric butyrylcholine sensor for organophosphate pesticides
A highly sensitive potentiometric butyrylcholine (BuCh) sensor based on plasticized poly(vinyl chloride) membrane was fabricated using tetrakis (3,5-bis[2-methoxy-hexafluoro-methyl] phenyl) borate (HFPB) as a cation exchanger. The sensor showed a Nernstian response from 10?1 M to 10?6 M for BuCh. The detection limit of the BuCh-sensor were improved in comparison with corresponding parameters of BuCh-sensors using prepared other cation exchangers. This
Toshihiko Imato; Nobuhiko Ishibashi
Potentiometric study on critical micellization concentrations (CMC) of sodium salts of bile acids and their amino acid derivatives
The critical micellization concentration (CMC)s of a group of sodium salts of bile acids, i.e., cholic acid (abbreviated as C), deoxycholic acid (DC), chenodeoxycholic acid (CDC), ursodeoxycholic acid (UDC), glycocholic acid (GC), glycodeoxycholic acid (GDC), glycochenodeoxycholic acid (GCDC), and some amino acid derivatives of C and DC were determined by potentiometric titration. An automatic titration system has been established to
Toshio Nakashima; Tomoyuki Anno; Hiroshi Kanda; Yuka Sato; Tatsuaki Kuroi; Hironari Fujii; Shigemi Nagadome; Gohsuke Sugihara
Titanium (III) cation selective electrode based on synthesized tris(2pyridyl) methylamine ionophore and its application in water samples
The introduction of low detection limit ion selective electrodes (ISEs) may well pave the way for the determination of trace targets of cationic compounds. This research focuses on the detection of titanium (III) cation using a new PVC-membrane sensor based on synthesized tris(2pyridyl) methylamine (tpm) ionophore. The application and validation of the proposed sensor was done using potentiometric titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). The membrane sensor exhibited a Nernstian response to the titanium (III) cation over a concentration range of 1.0 � 10?6�1.0 � 10?2?M and pH range from 1�2.5. The Nernstian slope, the lower of detection (LOD), and the response time (t95%) of the proposed sensor were 29.17 � 0.24?mV/dec, 7.9 � 10?7?M, and 20?s, respectively. The direct determination of 4�39??g/ml of titanium (III) standard solution showed an average recovery of 94.60 and a mean relative standard deviation of 1.8 at 100.0??g/ml. Finally, the utilization of the electrodes as end-point indicators for potentiometric titration with EDTA solutions for titanium (III) sensor was successfully carried out.
Rezayi, Majid; Karazhian, Reza; Abdollahi, Yadollah; Narimani, Leila; Sany, Seyedeh Belin Tavakoly; Ahmadzadeh, Saeid; Alias, Yatimah
The introduction of low detection limit ion selective electrodes (ISEs) may well pave the way for the determination of trace targets of cationic compounds. This research focuses on the detection of titanium (III) cation using a new PVC-membrane sensor based on synthesized tris(2pyridyl) methylamine (tpm) ionophore. The application and validation of the proposed sensor was done using potentiometric titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). The membrane sensor exhibited a Nernstian response to the titanium (III) cation over a concentration range of 1.0 � 10-6-1.0 � 10-2 M and pH range from 1-2.5. The Nernstian slope, the lower of detection (LOD), and the response time (t95%) of the proposed sensor were 29.17 +/- 0.24 mV/dec, 7.9 � 10-7 M, and 20 s, respectively. The direct determination of 4-39 ?g/ml of titanium (III) standard solution showed an average recovery of 94.60 and a mean relative standard deviation of 1.8 at 100.0 ?g/ml. Finally, the utilization of the electrodes as end-point indicators for potentiometric titration with EDTA solutions for titanium (III) sensor was successfully carried out.
Titanium (III) cation selective electrode based on synthesized tris(2pyridyl) methylamine ionophore and its application in water samples.
The introduction of low detection limit ion selective electrodes (ISEs) may well pave the way for the determination of trace targets of cationic compounds. This research focuses on the detection of titanium (III) cation using a new PVC-membrane sensor based on synthesized tris(2pyridyl) methylamine (tpm) ionophore. The application and validation of the proposed sensor was done using potentiometric titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). The membrane sensor exhibited a Nernstian response to the titanium (III) cation over a concentration range of 1.0 � 10(-6)-1.0 � 10(-2) M and pH range from 1-2.5. The Nernstian slope, the lower of detection (LOD), and the response time (t95%) of the proposed sensor were 29.17 � 0.24 mV/dec, 7.9 � 10-7 M, and 20 s, respectively. The direct determination of 4-39 ?g/ml of titanium (III) standard solution showed an average recovery of 94.60 and a mean relative standard deviation of 1.8 at 100.0 ?g/ml. Finally, the utilization of the electrodes as end-point indicators for potentiometric titration with EDTA solutions for titanium (III) sensor was successfully carried out. PMID:24722576
Modern Directions for Potentiometric Sensors
This paper gives an overview of the newest developments of polymeric membrane ion-selective electrodes. A short essence of the underlying theory is given, emphasizing how the electromotive force may be used to assess binding constants of the ionophore, and how the selectivity and detection limit are related to the underlying membrane processes. The recent developments in lowering the detection limits of ISEs are described, including recent approaches of developing all solid state ISEs, and breakthroughs in detecting ultra-small quantities of ions at low concentrations. These developments have paved the way to use potentiometric sensors as in ultra-sensitive affinity bioanalysis in conjunction with nanoparticle labels. Recent results establish that potentiometry compares favorably to electrochemical stripping analysis. Other new developments with ion-selective electrodes are also described, including the concept of backside calibration potentiometry, controlled current coulometry, pulsed chronopotentiometry, and localized flash titration with ion-selective membranes to design sensors for the direct detection of total acidity without net sample perturbation. These developments have further opened the field for exciting new possibilities and applications.
Bakker, Eric; Chumbimuni-Torres, Karin
Determination of the point-of-zero, charge of manganese oxides with different methods including an improved salt titration method
Manganese (Mn) oxides are important components in soils and sediments. Points-of-zero charge (PZC) of three synthetic Mn oxides (birnessite, cryptomelane, and todorokite) were determined by using three classical techniques (potentiometric titration or PT, rapid PT or R-PT, and salt titration or ST) and a modified salt titration method with a prolonged equilibration time (ST method with a prolonged equilibration time
Wen-feng Tan; Si-jun Lu; Fan Liu; Xiong-han Feng; Ji-zheng He; Luuk K. Koopal
A scandium solution containing copper(IV) can be titrated ; photometrically in acid solution with (ethylenedinitrilo)tetraacetic acid (EDTA) ; in the presence of up to 60 times as much rare earth (on a molar basis). The ; absorbance of copper(IV)-EDTA at745 m mu is used a follow the course of the ; titration. Large amounts of aluminum (III), calcium (II), magnesium
James Fritz; Donald Pietrzyk
Potentiometric determination of acid dissociation constants (p K a) for human and veterinary antibiotics
This work determined the acid dissociation constants (pKa) of 26 common human and veterinary antibiotics by potentiometric titration. Selected antibiotics consisted of sulfonamides, macrolides, tetracyclines, fluoroquinolones, and other miscellaneous antibiotics. After validation of analysis methods using phosphoric acid as a model compound, a second-derivative (?2pH\\/?V2) method was primarily applied to determining pKa's from titration curves for most antibiotics due to
Zhimin Qiang; Craig Adams
An automated precise Winkler titration for determining dissolved oxygen on board ship
An automated titration for the Winkler method is presented for measuring primary productivity in the ocean. The system is based on a microcomputer-controlled titration with potentiometric endpoint detection. By the use of 0.005-N sodium thiosulfate as a titrant and a program designed to shorten the time for measuring, the method achieves a precision of 0.04% coefficient of variation with a
Ken Furuya; Kazutoshi Harada
Potentiometric Determination of Ketotifen Fumarate in Pharmaceutical Preparations and Urine Using Carbon Paste and PVC Membrane Selective Electrodes
This study compares between unmodified carbon paste (CPE; the paste has no ion pair) and polyvinyl chloride (PVC) membrane selective electrodes that were used in potentiometric determination of ketotifen fumarate (KTF), where sodium tetraphenylborate (NaTPB) was used as titrant. The performance characteristics of these sensors were evaluated according to IUPAC recommendations which reveal a fast, stable, and linear response for KTF over the concentration range of 10?7 to 10?2?mol?L?1. The electrodes show Nernstian slope value of 52.51 � 0.20 and 51.51 � 0.25?mV?decade?1 for CPE and PVC membrane electrodes at 30�C, respectively. The potential is nearly stable over the pH range 3.0�6.0 and 2.0�7.0 for CPE and PVC membrane electrodes, respectively. Selectivity coefficient values towards different inorganic cations, sugars, and amino acids reflect high selectivity of the prepared electrodes. The electrodes responses at different temperatures were also studied, and long operational lifetime of 12 and 5 weeks for CPE and PVC membrane electrodes, respectively, were found. These are used for determination of ketotifen fumarate using potentiometric titration, calibration, and standard addition methods in pure samples, its pharmaceutical preparations (Zaditen tablets), and biological fluid (urine). The direct potentiometric determination of KTF using the proposed sensors gave recoveries % of 98.97 � 0.53 and 98.62 � 0.74 with RSD 1.42 and 0.63% for CPE and PVC membrane selective electrodes, respectively. Validation of the method shows suitability of the proposed sensors for use in quality control assessment of KTF. The obtained results were in a good agreement with those obtained using the reported spectrophotometric method.
Frag, Eman Y. Z.; Mohamed, Gehad G.; Khalil, Mohamed M.; Hwehy, Mohammad M. A.
Potentiometric determination of ketotifen fumarate in pharmaceutical preparations and urine using carbon paste and PVC membrane selective electrodes.
This study compares between unmodified carbon paste (CPE; the paste has no ion pair) and polyvinyl chloride (PVC) membrane selective electrodes that were used in potentiometric determination of ketotifen fumarate (KTF), where sodium tetraphenylborate (NaTPB) was used as titrant. The performance characteristics of these sensors were evaluated according to IUPAC recommendations which reveal a fast, stable, and linear response for KTF over the concentration range of 10(-7) to 10(-2)?mol?L(-1). The electrodes show Nernstian slope value of 52.51 � 0.20 and 51.51 � 0.25?mV?decade(-1) for CPE and PVC membrane electrodes at 30�C, respectively. The potential is nearly stable over the pH range 3.0-6.0 and 2.0-7.0 for CPE and PVC membrane electrodes, respectively. Selectivity coefficient values towards different inorganic cations, sugars, and amino acids reflect high selectivity of the prepared electrodes. The electrodes responses at different temperatures were also studied, and long operational lifetime of 12 and 5 weeks for CPE and PVC membrane electrodes, respectively, were found. These are used for determination of ketotifen fumarate using potentiometric titration, calibration, and standard addition methods in pure samples, its pharmaceutical preparations (Zaditen tablets), and biological fluid (urine). The direct potentiometric determination of KTF using the proposed sensors gave recoveries % of 98.97 � 0.53 and 98.62 � 0.74 with RSD 1.42 and 0.63% for CPE and PVC membrane selective electrodes, respectively. Validation of the method shows suitability of the proposed sensors for use in quality control assessment of KTF. The obtained results were in a good agreement with those obtained using the reported spectrophotometric method. PMID:22013443
Frag, Eman Y Z; Mohamed, Gehad G; Khalil, Mohamed M; Hwehy, Mohammad M A
Potentiometric propranolol-selective sensor based on molecularly imprinted polymer.
A novel potentiometric sensor based on molecularly imprinted polymer (MIP) for propranolol, an adrenergic-blocking drug, was designed. The influence of molecularly imprinted polymer particle content and sodium tetraphenylborate additives in polyvinylchloride membrane was shown. The electrodes show near-Nernstian responses down to 10(-4)-10(-5) M propranolol concentration. The potentiometric response of MIP-based sensor for propranolol in mixed nonaqueous medium was shown at first. Sensor selectivity relative to various inorganic cations, atenolol and metoprolol, was reported. Direct potentiometry was used to determine propranolol in aqueous modeling solutions and pharmaceutical preparations with good results. PMID:23104313
Gurtova, O; Ye, L; Chmilenko, F
The possibility of using Chromeazurol S for the titration of Th, Ni, Ce, ; La, and other rare earth elements was investigated. The interfering ions were ; determined, and the means of eliminating them were studied. (J.S.R.);
M. Malat; M. Tenorova
Metal oxide electrodes as sensors in complexometric titrations.
EDTA titrations of lead and manganese, and of some other ions by using these as indicator ions, have been followed potentiometrically with PbO(2) and MnO(2) electrodes. Explanations are put forward for the anomalies observed in the titration curves. With the MnO(2) electrode, formation of an Mn(III)-EDTA complex is responsible for the diminished potential breaks. With the PbO(2) electrode the decrease in the potential break and the distortion of the curves in acid solution may be due to reaction between electrode coating and titrant. The MnO(2) electrode has been used for titrations of Ba(2+) Ca(2+), Cd(2+) and Cu(2+) with errors < 1%. PMID:18961911
A method based on the quantitative reaction of uranyl nitrate with ; hydrogen peroxide to release nitric acid is presented for the determination of ; uranyl nitrate in nitric acid solution. The hydrogen peroxide is added to the ; uranyl nitrate solution and the total nitric acid determined by visual or ; potentiometric titration with sodium hydroxide. The free nitric
J. Cepelak; Maly; V. J. f Vesely
Surfactant/detergent titration analysis method and apparatus for machine working fluids, surfactant-containing wastewater and the like
The present invention is an improved method and related apparatus for quantitatively analyzing machine working fluids and other aqueous compositions such as wastewater which contain various mixtures of cationic, neutral, and/or anionic surfactants, soluble soaps, and the like. The method utilizes a single-phase, non-aqueous, reactive titration composition containing water insoluble bismuth nitrate dissolved in glycerol for the titration reactant. The chemical reaction of the bismuth ion and glycerol with the surfactant in the test solutions results in formation of micelles, changes in micelle size, and the formation of insoluble bismuth soaps. These soaps are quantified by physical and chemical changes in the aqueous test solution. Both classical potentiometric analysis and turbidity measurements have been used as sensing techniques to determine the quantity of surfactant present in test solutions. This method is amenable to the analysis of various types of new, in-use, dirty or decomposed surfactants and detergents. It is a quick and efficient method utilizing a single-phase reaction without needing a separate extraction from the aqueous solution. It is adaptable to automated control with simple and reliable sensing methods. The method is applicable to a variety of compositions with concentrations from about 1% to about 10% weight. It is also applicable to the analysis of waste water containing surfactants with appropriate pre-treatments for concentration. 1 fig.
Smith, D.D.; Hiller, J.M.
The present invention is an improved method and related apparatus for quantitatively analyzing machine working fluids and other aqueous compositions such as wastewater which contain various mixtures of cationic, neutral, and/or anionic surfactants, soluble soaps, and the like. The method utilizes a single-phase, non-aqueous, reactive titration composition containing water insoluble bismuth nitrate dissolved in glycerol for the titration reactant. The chemical reaction of the bismuth ion and glycerol with the surfactant in the test solutions results in formation of micelles, changes in micelle size, and the formation of insoluble bismuth soaps. These soaps are quantified by physical and chemical changes in the aqueous test solution. Both classical potentiometric analysis and turbidity measurements have been used as sensing techniques to determine the quantity of surfactant present in test solutions. This method is amenable to the analysis of various types of new, in-use, dirty or decomposed surfactants and detergents. It is a quick and efficient method utilizing a single-phase reaction without needing a separate extraction from the aqueous solution. It is adaptable to automated control with simple and reliable sensing methods. The method is applicable to a variety of compositions with concentrations from about 1% to about 10% weight. It is also applicable to the analysis of waste water containing surfactants with appropriate pre-treatments for concentration.
Smith, Douglas D. (Knoxville, TN); Hiller, John M. (Oak Ridge, TN)
Sorption modelling on illite Part I: Titration measurements and the sorption of Ni, Co, Eu and Sn
In this study the physico-chemical, titration and sorption characteristics of Na-illite du Puy (Na-illite) have been measured and modelled. Samples of illite, collected in the region of le Puy-en-Velay, France, were purified and conditioned to the Na-form and physico-chemically characterised. Potentiometric titrations on suspensions of the Na-illite were carried out using a batch backtitration technique in 0.01, 0.1 and 0.5 M NaClO 4 background electrolytes from pH�3 to �11.5 in an inert atmosphere glove box. The supernatant solutions from each titration experiment in each series were analysed for K, Mg, Ca, Sr, Si, Al, Fe and Mn. The titration data were modelled in terms of the protolysis of two amphoteric edge sites ( tbnd S W1OH and tbnd S W2OH) without an electrostatic term. Sorption edges (solid/liquid distribution ratios versus pH at trace sorbate concentrations and constant ionic strength) were determined for the transitions metals Ni(II) and Co(II), the lanthanide Eu(III), and the heavy metal Sn(IV) on Na-illite with NaClO 4 as the background electrolyte under anoxic conditions (CO 2 ? 2 ppm, O 2 ? 2 ppm). The study thus encompasses a broad range of metals with different thermodynamic characteristics and with valence states ranging from II to IV. The results from the modelling of the titration data, in combination with a non electrostatic surface complexation and cation exchange sorption model were applied to quantitatively describe the uptake characteristics of the metals listed above on Na-illite. Since sorption edges were measured at trace concentrations, metal uptake was modelled as occurring on strong type sites ( tbnd S SOH) only. This sorption model, the two site protolysis non electrostatic surface complexation and cation exchange model (2SPNE SC/CE model) had been previously developed and used to describe metal uptake on montmorillonite.
Bradbury, M. H.; Baeyens, B.
Acid-base equilibria in ethylene glycol--III: selection of titration conditions in ethylene glycol medium, protolysis constants of alkaloids in ethylene glycol and its mixtures.
Theoretical titration curves are used for the selection of appropriate conditions for the acid-base volumetric determination of weak bases in ethylene glycol medium. The theoretical curves for titration of some alkaloids are deduced graphically on the basis of the logarithmic concentration diagram. The acid-base constants used for the construction of the theoretical titration curves were determined by potentiometric titration in a cell without liquid junction, equipped with a glass and a silver-silver chloride electrode. It is shown that the alkaloids investigated can be determined accurately by visual or potentiometric titration. The same approach for the selection of titration conditions seems to be applicable to other non-aqueous amphiprotic solvents. PMID:18961934
Zikolov, P; Zikolova, T; Budevsky, O
Dual potentiometric and UV\\/Vis spectrophotometric disposable sensors with dispersion cast polyaniline
Simple conducting polymer�polyaniline-based sensors\\/biosensors, working either in potentiometric or UV\\/Vis spectrophotometric\\u000a mode, are proposed. Disposable sensors were produced by coating polyaniline layers, cast from aqueous dispersion of the polymer\\u000a nanoparticles, on a transparent plastic polyacetate foil. In the potentiometric mode, polyaniline layers are sensitive to\\u000a a number of metal cations, while in UV\\/Vis mode, changes of absorbance were recorded only
Pawe? Malinowski; Iwona Grzegrz�?ka; Agata Michalska; Krzysztof Maksymiuk
Aluminum(III) selective potentiometric sensor based on morin in poly(vinyl chloride) matrix.
Al(3+) selective sensor has been fabricated from poly(vinyl chloride) (PVC) matrix membranes containing neutral carrier morin as ionophore. Best performance was exhibited by the membrane having composition as morin:PVC:sodium tetraphenyl borate:tri-n-butylphosphate in the ratio 5:150:5:150 (w/w, mg). This membrane worked well over a wide activity range of 5.0x10(-7) to 1.0x10(-1)M of Al(3+) with a Nernstian slope of 19.7+/-0.1mV/decade of Al(3+) activity and a limit of detection 3.2x10(-7)M. The response time of the sensor is approximately 5s and membrane could be used over a period of 2 months with good reproducibility. The proposed sensor works well over a pH range (3.5-5.0) and demonstrates good discriminating power over a number of mono-, di- and trivalent cations. The sensor can also be used in partially non-aqueous media having up to 20% (v/v) methanol, ethanol or acetone content with no significant change in the value of slope or working activity range. The sensor has also been used in the potentiometric titration of Al(3+) with EDTA and for its determination in zinc plating mud and red mud. PMID:19071785
Gupta, Vinod K; Jain, Ajay K; Maheshwari, Gaurav
Filtrates & Residues: Olfactory Titration.
Presents an experiment that uses a unique acid-base indicator--the odor of raw onion--to indicate the end point of the titration of sodium hydroxide with hydrochloric acid. Allows the student to detect the completion of the neutralization reaction by olfaction rather than sight. (JRH)
Wood, John T.; Eddy, Roberta M.
Characteristics of new composite- and classical potentiometric sensors for the determination of pioglitazone in some pharmaceutical formulations.
The construction and electrochemical response characteristics of poly(vinyl chloride) membrane sensors for pioglitazone HCl (PG) are described. The sensing membranes incorporate ion association complexes of pioglitazone cation and sodium tetraphenylborate (NaTPB) (sensor 1) or phosphomolybdic acid (PMA) (sensor 2) or phosphotungstic acid (PTA) (sensor 3) as electroactive materials. The sensors display a fast, stable and near-Nernstian response over a relative wide pioglitazone concentration range (1x10(-2) to 10(-6) M), with cationic slopes of 55.0+/-0.5, 58.0+/-0.5 and 53.0+/-0.5 mV per concentration decade over a pH range of 1.0-5.0. The sensors show good discrimination of pioglitazone from several inorganic and organic compounds. The direct determination of 2.5-3900.0 microg/ml of pioglitazone show an average recovery of 98.5, 99.0 and 98.4% and a mean relative standard deviation of 1.6, 1.5 and 1.7% at 100.0 microg/ml for sensors 1, 2 and 3, respectively. The proposed sensors have been applied for direct determination of pioglitazone in some pharmaceutical preparations. The results obtained by determination of pioglitazone in tablets using the proposed sensors are comparable favorably with those obtained using the HPLC method. The sensors have been used as indicator electrodes for potentiometric titration of pioglitazone. PMID:18555633
Mostafa, Gamal A E; Al-Majed, A
Neutron absorptiometric titration.
A method is outlined for detection of two-phase titration end-points by means of an abrupt change in the neutron-absorption characteristics of one of the phases. One of the components of the precipitate must have a large neutron absorption cross-section, and the disappearance or appearance of neutron absorption by the supernatant liquid from the precipitation reaction then marks the completion of precipitation. PMID:18960115
T�lgyessy, J; Varga, S; Dillinger, P
Titration Curves: Fact and Fiction.
Discusses ways in which datalogging equipment can enable titration curves to be measured accurately and how computing power can be used to predict the shape of curves. Highlights include sources of error, use of spreadsheets to generate titration curves, titration of a weak acid with a strong alkali, dibasic acids, weak acid and weak base, and�
Chamberlain, John
Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model
Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.
Tonkin, J. W.; Balistrieri, L. S.; Murray, J. W.
Septonex-tetraphenylborate screen-printed ion selective electrode for the potentiometric determination of Septonex in pharmaceutical preparations.
A screen-printed electrode (SPE) was fabricated for the determination of 1-(ethoxycarbonyl)pentadecyltrimethylammonium bromide (Septonex) based on the use of Septonex-tetraphenylborate as the electroactive substance, and o-nitrophenyloctylether (o-NPOE) as the plasticizing agent. The electrode passes a near-Nernstian cationic slope of 59.33 � 0.85 mV from activity between pH values of 2 to 9 with a lower detection limit of 9�10(-7) M and response time of about 5 s and exhibits an adequate shelf-life of 6 months. The method was applied for the determination of Septonex in pharmaceutical preparations. A percentage recovery of 99.88% was obtained with RSD=1.24%. The electrode was successfully applied in the determination of Septonex in laboratory-prepared samples by direct potentiometric, calibration curve and standard addition methods. Potentiometric titration of Septonex with sodium tetraphenylborate and phosphotungstic acid as a titrant was monitored with the modified screen-printed electrode as an end-point indicator electrode. Selectivity coefficients for Septonex relative to a number of potential interfering substances were determined. The sensor was highly selective for Septonex over a large number of compounds. Selectivity coefficient data for some common ions show negligible interference; however, cetyltrimethylammonium bromide and iodide ions interfere significantly. The analytical usefulness of the proposed electrode was evaluated by its application in the determination of Septonex in laboratory-prepared pharmaceutical samples with satisfactory results. The results obtained with the fabricated sensor are comparable with those obtained by the British Pharmacopeia method. PMID:21286616
Mohamed, Gehad G; El-Shahat, M F; Al-Sabagh, A M; Migahed, M A; Ali, Tamer Awad
Micromechanical potentiometric sensors
A microcantilever potentiometric sensor utilized for detecting and measuring physical and chemical parameters in a sample of media is described. The microcantilevered spring element includes at least one chemical coating on a coated region, that accumulates a surface charge in response to hydrogen ions, redox potential, or ion concentrations in a sample of the media being monitored. The accumulation of surface charge on one surface of the microcantilever, with a differing surface charge on an opposing surface, creates a mechanical stress and a deflection of the spring element. One of a multitude of deflection detection methods may include the use of a laser light source focused on the microcantilever, with a photo-sensitive detector receiving reflected laser impulses. The microcantilevered spring element is approximately 1 to 100 .mu.m long, approximately 1 to 50 .mu.m wide, and approximately 0.3 to 3.0 .mu.m thick. An accuracy of detection of deflections of the cantilever is provided in the range of 0.01 nanometers of deflection. The microcantilever apparatus and a method of detection of parameters require only microliters of a sample to be placed on, or near the spring element surface. The method is extremely sensitive to the detection of the parameters to be measured.
Thundat, Thomas G. (Knoxville, TN) [Knoxville, TN
Luminescence Titrations of Polyelectrolytes.
When an anionic polyelectrolyte is added to a solution of a cationic lumophore (the probe), binding of the probe ions to the anionic sites on the polymer chain can occur. We have found that in some cases, this binding results in an increase in the probe's...
E. R. Alvarez-Roa N. E. Prieto C. R. Martin
Potentiometric Determination of Acids and Bases using Silicone Rubber Based Graphite Electrode
A silicone rubber based graphite electrode has been used as an indicator electrode for potentiometric acid-base titrations. The electrode potential changes an average of 30 mV per pH-unit. If the electrodes are pretreated with a solution of an oxidant before use, the pH-sensitivity is increased. The electrode can be used in both aqueous and non-aqueous solutions. A measuring cell, composed
E. Szepesvary; E. Pungor
Thermometric titration of polysulfides
A novel calorimetric approach has been developed for analyzing mixtures of sulfides and polysulfides in aqueous solution, where the moieties HS/sup -/, S/sub 2//sup 2 -/, S/sub 3//sup 2 -/, S/sub 4//sup 2 -/, and S/sub 5//sup 2 -/ are in dynamic equilibrium. Advantage is taken of their Lewis base reactivities with the organomercury Lewis acid zwitterion /sup -/OOCPhHg/sup +/. On the basis of judicious thermochemical considerations, samples are titrated to thermometric end points with standard p-hydroxymercuribenzoate. Quantitation of sulfidic and polysulfidic sulfur concentrations is feasible in a single experiment. Sulfidic sulfur can be estimated at concentration levels as low as 0.0001 M. Polysulfidic sulfur is amenable to determination even in the presence of a more than 40-fold excess of sulfide. Capabilities of the method are documented by the analysis of synfuel process stream specimens. Precision and accuracy of 1-3% were attained.
Stahl, J.W.; Jordan, J.
A novel cobalt(II)-selective potentiometric sensor based on p-(4-n-butylphenylazo)calix[4]arene.
A new poly(vinyl chloride)-based membranes containing p-(4-n-butylphenylazo)calix[4]arene (I) as an electroactive material along with sodiumtetraphenylborate (NaTPB), and dibutyl(butyl)phosphonate in the ratio 10:100:1:200 (I:DBBP:NaTPB:PVC) (w/w) was used to fabricate a new cobalt(II)-selective sensor. It exhibited a working concentration range of 9.2 x 10(-6) to 1.0 x 10(-1)M, with a Nernstian slope of 29.0+/-1.0 mV/decade of activity and the response time of 25s. This sensor shows the detection limit of 4.0 x 10(-6)M. Its potential response remains unaffected of pH in the range, 4.0-7.2, and the cell assembly can be used successfully in partially non-aqueous medium (up to 10%, v/v) without significant change in the slope of working concentration range. The sensor has a lifetime of about 3 months and exhibits excellent selectivity over a number of mono-, bi-, and tri-valent cations including alkali, alkaline earth metal, heavy and transition metal ions. It can be used as an indicator electrode for the end point determination in the potentiometric titration of cobalt ions against ethylenediaminetetraacetic acid (EDTA) as well as for the determination of cobalt ion concentration in real samples. PMID:19064091
Kumar, Pankaj; Shim, Yoon-Bo
A new Zn(II)-selective potentiometric sensor based on 4-tert-butylcalix[4]arene in PVC matrix.
Poly(vinyl chloride) (PVC) based membranes containing 4-tert-butylcalix[4]arene (I) as an electroactive material along with anion excluder sodiumtetraphenylborate (NaTPB) and plasticizer tri-butylphosphate (TBP) have been developed to fabricate a new zinc-selective sensor. Out of various compositions, the best performance was exhibited by the membrane having I, NaTPB, TBP and PVC in the ratio 8:5:100:200 (w/w). The sensor works well in the concentration range 9.8 x 10(-6) to 1.0 x 10(-1) mol dm(-3) with a near-Nernstian slope of 28.0+/-1.0 mV/decade of activity. The detection limit is down to 5.0 x 10(-7) mol dm(-3). The working pH range of this sensor is 2.5-4.3 and it works well in partially non-aqueous medium up to 15% (v/v) (methanol, ethanol and acetone). It exhibits a fast response time of 30s and could be used for more than four months without any considerable change in response characteristics. It has excellent selectivity for Zn(II) over other mono-, bi- and trivalent cations which have been reported to cause interference in the working of other sensors. It has been successfully used as an indicator electrode in the potentiometric titration of Zn(II) against EDTA and also to estimate zinc ions in industrial waste waters. PMID:18970696
Gupta, V K; Goyal, R N; Al Khayat, M; Kumar, P; Bachheti, N
Acid-Base Titration Applet
Acid-Base titration applet that plots pH changes as student adds acid or base. Gives choice of indicators (only two right now). Compares plots for titration of traditional solution and a buffered solution (several choices for comparison). Can alter starting concentrations.
Peptide-lanthanide cation equilibria in aqueous phase. I. Bound shifts for L-carnosine-praseodymium complexes
L-Carnosine complexes of Pr 3+ were characterized in aqueous solution by 1H NMR and potentiometric titration. A rigorous treatment of chemical shifts and pH variation data with lanthanide concentration is presented. Two different forms of the peptide ligand, forming simultaneously two complexes, were taken into account. At low pH values the cation is only coordinated at the carboxylate site of the ligand in a weak complex ( ?2 = 6) whereas in neutral solution a stronger complex ( ?1 = 37) is present as a consequence of the deprotonation of the imidazole ring. The computation of induced bound shifts � 2 and ?1 for resonating nuclei of the peptide in both forms yields consistent figures. These provide the experimental basis for a conformational model which is usually not obtainable for labile complexes with low stability constants.
Mossoyan, J.; Asso, M.; Benlian, D.
Iodine losses during Winkler titrations
An experiment designed to measure iodine loss during the aliquot version of the Winkler titration for dissolved oxygen in seawater shows that 0.01-0.03 ml l -1 equivalent oxygen is lost at typical oceanic concentrations in the method presently used. A standardization technique, which mimics that employed during the titration of seawater samples, compensates for this iodine loss throughout the oceanic range. This result, contradicting an earlier report by GREEN and CARRITT (1966, Analyst, 91, 207-208), demonstrates that the whole-bottle method of oxygen titration is not to be preferred over the aliquot method.
Knapp, George P.; Stalcup, Marvel C.; Stanley, Robert J.
Complexometric photometric titrations without an indicator.
Calculations of titration curves in advance with the aid of conditional constants saves some experimental work. The limits of a conventional titration curve are determined, the titration of lead with EDTA being used as an example. PMID:18962641
von Haartman, C
Acid Strong Base Titrations Model
The Acid Strong Base Titrations model show how to estimate the concentration of the acid in a given sample. If one follows the titration by a visual indicator, the neutralization is detected through a sudden change of that indicator color. This model shows the titration curve as a strong monofunctional base (sodium hydroxide, for example), is added to an aqueous solution of a monoprotic acid. The Acid Strong Base Titrations model was developed using the Easy Java Simulations (EJS) modeling tool. It is distributed as a ready-to-run (compiled) Java archive. Double clicking the jar file will run the program if Java is installed. You can modify this simulation if you have EJS installed by right-clicking within the map and selecting "Open Ejs Model" from the pop-up menu item.
Fernandes, Fernando S.
Galvanic cell without liquid junction for potentiometric determination of copper.
This paper describes potentiometric measurements in an integrated galvanic cell with both indicator and reference electrodes. Both electrodes are conducting polymer-based. The copper-sensitive indicator electrode is made by using poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 2-(o-arsenophenylazo)-1,8-dihydroxynaphthalene-3,6-disulphonic sodium salt (Arsenazo-I) as the electroactive substance in the film, while the reference electrode is based on PEDOT doped by 2-morpholineoethanesulfonic acid (MES). It is shown that the galvanic cell can be used for determination of copper both in non-aqueous media (where all PVC-based membranes failed) and in the presence of chloride ions, which disturb the signal of conventional copper ion-selective electrodes with solid-state membranes. It is further shown that the titration of copper ions can be successfully monitored using the described electrochemical cell. PMID:17586116
Migdalski, Jan; B?az, Teresa; Zra?ka, Barbara; Lewenstam, Andrzej
Potentiometric studies at ORNL with hydrogen electrode concentration cells
The absence of suitably stable reference electrodes for and to 300 C led ORNL to develop hydrogen electrode concentration cells for studies of equilibria of interest in reactor and steam generator systems to about 300 C during the late 1960`s and seventies. During the intervening two dozen years over twenty scientists have participated in potentiometric studies at Oak Ridge and much of that work will be summarized in this paper. A description of hydrogen electrode concentration cells developed in the late sixties and currently in use at Oak Ridge is given. The method of measurement, data interpretation, and published results are reviewed for studies of acid-base ionization, metal ion hydrolysis, and metal complexation reactions using principally such cells in titration or flow modes. 41 refs.
Mesmer, R.E.; Palmer, D.A.; Wesolowski, D.J. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.
Construction and performance characterization of screen printed and carbon paste ion selective electrodes for potentiometric determination of naphazoline hydrochloride in pharmaceutical preparations.
This paper describes the development of screen-printed (SPE) and carbon paste (CPE) sensors for the rapid and sensitive quantification of naphazoline hydrochloride (NPZ) in pharmaceutical formulations. This work compares the electroactivity of conventional carbon paste and screen-printed carbon paste electrodes towards potentiometric titration of NPZ. The repeatability and accuracy of measurements performed in the analysis of these pharmaceutical matrices using new screen printed sensors were evaluated. The influence of the electrode composition, conditioning time of the electrode and pH of the test solution, on the electrode performance were investigated. The drug electrode showed Nernstain responses in the concentration range from 1 � 10(-6) to 1 � 10(-2) mol L(-1) with slopes of 57.5 � 1.3 and 55.9 � 1.6 mV per decade for SPE and CPE, respectively, and was found to be very precise and usable within the pH range 3-8. These sensors exhibited a fast response time (about 3 s for both SPE and CPE, respectively), a low detection limit (3.5 � 10(-6) and 1.5 � 10(-6) M for SPE and CPE, respectively), a long lifetime (3 and 2 months for SPE and CPE, respectively) and good stability. The selectivity of the electrode toward a large number of inorganic cations, sugars and amino acids was tested. It was applied to potentiometric determination of NPZ in pure state and pharmaceutical preparation under batch conditions. The percentage recovery values for the assay of NPZ in tablets (relative standard deviations ?0.3% for n = 4) were compared well with those obtained by the official method. PMID:20959926
Frag, Eman Y Z; Mohamed, Gehad G; El-Dien, F A Nour; Mohamed, Marwa E
Flow injection potentiometric determination of clobutinol hydrochloride.
New clobutinol (Clob) ion-selective polyvinyl chloride (PVC) membrane electrodes, based on the ion-associates of Clob with phosphotungstic acid or phosphomolybdic acid were prepared using dibutyl phthalate as plasticizing solvent. The electrodes were characterized in terms of membrane composition, temperature and pH. The sensors showed a near-Nernstian response over the concentration ranges (6.31 x 10(-6))-(1.00 x 10(-2)) and (5.01 x 10(-5))-(1.00 x 10(-2))M in the case of clobutinol-phosphotungstate ((Clob)(3)-PT) applying batch and flow injection (FI) analysis, respectively, and (1.58 x 10(-5))-(1.00 x 10(-2)) and (5.01 x 10(-5))-(1.00 x 10(-2))M in case of clobutinol-phosphomolybdate ((Clob)(3)-PM) for batch and FI analysis systems, respectively. The electrodes were successfully applied for the potentiometric determination of ClobCl in pharmaceutical preparation and urine in steady state and flow injection conditions. The electrodes exhibit good selectivity for Clob with respect to a large number of inorganic cations, sugars and amino acids. PMID:18970592
Issa, Y M; Zayed, S I M
Amperometric, Bipotentiometric, and Coulometric Titration.
Reviews literature on amperometric, bipotentiometric, and coulometric titration methods examining: apparatus and methodology; acid-base reactions; precipitation and complexing reactions (considering methods involving silver, mercury, EDTA or analogous reagents, and other organic compounds); and oxidation-reduction reactions (considering methods�
Stock, John T.
Potentiometric studies of complex formation between methylmercury(II) and EDTA.
The protonation of EDTA (ethylenediaminetetra-acetic acid) and its complex formation with methylmercury(II) ions was studied by a potentiometric method at 25 degrees in 1.0M NaNO(3). The protonation constants of EDTA and the equilibrium constants for the complexation reactions between methylmercuric ions and EDTA were evaluated by analysing the experimental data with the ETITR version of the general error-minimizing program LETAGROP. The results were used to develop an analytical method, based on complexometric titration and ion-exchange separation, for the determination of inorganic and organic mercury in the presence of one another. PMID:18962242
Jawaid, M
Primary methods of measurement are essential in the realization of the SI units. In 1995, the CCQM (Comit� Consultatif pour la Quantit� de Mati�re) identified titrimetry as a primary method of measurement. Titrimetry is a method that has wide range of applications for amount of substance measurements and can be applied at primary level and at working level depending on
Molecular Weight Measurement of Biobased Furan Polyamides via Non- Aqueous Potentiometric Titration.
The U.S. Department of Defense (DOD) has increased the use of polymers due to their lightweight nature and high performance in composite materials, body armor, and military vehicles. Unfortunately, traditional polymers are petroleum-derived, thus creating...
G. Fountzoulas J. J. La Scala L. T. Cureton
Titration of an Unknown Acid or Base
This website contains a JAVA applet that simulates the titration of an unknown acid or base, and provides a graphical output of the titration curve. The unknown compounds are taken from a list of amino acids. Students set up the parameters of the titration, and then create a simulated pH curve. From this they are able to identify the unknown compound from the list, and determine the acid dissociation constant(s) from the titration data.
Blauch, David N.
Endosomal escape and siRNA delivery with cationic shell crosslinked knedel-like nanoparticles with tunable buffering capacities
Cationic shell crosslinked knedel-like nanoparticles (cSCKs) have emerged as a highly efficient transfection agent for nucleic acids delivery. In this study, a new class of cSCKs with tunable buffering capacities has been developed by altering the amounts of histamines and primary amines incorporated into their crosslinked shell regions. The effect of histamine content of these nanoparticles with a hydrodynamic diameter of ca. 20 nm, on the siRNA-binding affinity, cytotoxicity, immunogenicity, and transfection efficiency was investigated. The modification of cSCKs with histamine was found to reduce the siRNA-binding affinity and cellular binding. On the other hand, it significantly reduced the toxicity and immunogenicity of the nanoparticles with subsequent increase in the transfection efficiency. In addition, escape from endosomes was facilitated by having two species of low and high pKas (i.e. histamine and primary amine groups, respectively), as demonstrated by the potentiometric titration experiments and the effect of bafilomycin A1, an inhibitor of the endosomal acidification, on the transfection efficiency of cSCKs. Histamine modification of 15 mol% was a threshold, above which cSCKs with higher histamine content completely lost the ability to bind siRNA and to transfect cells. This study highlights the potential of histamine incorporation to augment the gene silencing activity of cationic nanoparticles, reduce their toxicity, and increase their biocompatibility, which is of particular importance in the design of nucleic acids delivery vectors.
Shrestha, Ritu; Elsabahy, Mahmoud; Florez-Malaver, Stephanie; Samarajeewa, Sandani; Wooley, Karen L.
Complexometric Titrations: Competition of Complexing Agents in the Determination of Water Hardness with EDTA
The competition of complexing agents for the same metal ion and the formation of colored metal-ion complexes is demonstrated with the use of an overhead projector. This demonstration can be used to emphasize both the relevance of the relative values of formation constants in the complexation of metal cations and the applicability of complexometric titrations in quantitative chemical analysis. The
M. Cecilia Yappert; Donald B. Dupre
Direct complexometric titration of calcium phosphates.
Calcium was determined in calcium phosphate samples by dissolving the sample in hydrochloric acid, adding hydroxynaphthol blue indicator and triethanolamine, adjusting the pH to 12.3--12.5 with potassium hydroxide solution, and titrating with standard disodium ethylenediaminetetraacetate solution. Time can be saved and the formation of a precipitate (which dissolves readily during the titration) can be avoided by adding at least 85% of the amount of complexing agent required for titration before adjusting the pH. PMID:903881
Tuckerman, M M; Sanchez de Ramos, M E
Potentiometric determination of hydrogen peroxide with permanganate in presence of fluoride, with iron as a catalyst: Application to the titanium-fluoride-peroxide mixed complex.
A potentiometric permanganate titration has been developed for the determination of hydrogen peroxide in the presence of fluoride, as well as of the peroxide content in the titanium-fluoride-peroxide mixed complex. It is based on the stabilization of manganese(III) with an excess of fluoride in a moderately acidic medium (pH close to 3) and on the use of iron(III) as catalyst. Errors are less than 0.5%. PMID:18963036
Diez, L P; Mendez, J H; Parra, M J
Isothermal Titration Calorimetry of RNA
Isothermal titration calorimetry (ITC) is a fast and robust method to study the physical basis of molecular interactions. A single well-designed experiment can provide complete thermodynamic characterization of a binding reaction, including Ka, ?G, ?H, ?S and reaction stoichiometry (n). Repeating the experiment at different temperatures allows determination of the heat capacity change (?CP) of the interaction. Modern calorimeters are sensitive enough to probe even weak biological interactions making ITC a very popular method among biochemists. Although ITC has been applied to protein studies for many years, it is becoming widely applicable in RNA biochemistry as well, especially in studies which involve RNA folding and RNA-interactions with small molecules, proteins and with other RNAs. This review focuses on best practices for planning, designing, and executing effective ITC experiments when one or more of the reactants is an RNA.
Salim, Nilshad N.; Feig, Andrew L.
An efficient ab initio DFT and PCM assessment of the potentiometric selectivity of a salophen type Schiff base.
As a neutral carrier component for the preparation of a potentiometric membrane sensor, the affinity and selectivity of the salophen type Schiff base ligand obtained by 1:2 condensation of 2.3-diaminopyridine with salicylaldehyde toward a series of common cations has been fully examined by DFT/B3LYP and integral equation formalism polarizable continum model (IEF-PCM or only given with PCM as default input in the computations) in combination with the experimental data. Both the potentiometric measurements and DFT calculations have exhibited that the ionophore shows appreciable selectivity for Cu(2+) ion over other cations. Four different approaches where the last three are the modified version of each other have been evaluated and compared with potentiometric data. Based upon the results of comparison among the approaches suggested to verify the selective behavior of ionophore toward Cu(2+), PCM implemented approach having a whole computational groundwork has given well-matched results with the observed data and with the method augmented with experimental hydration energies. The foremost interferences were detected by determining potentiometric selectivity coefficients for each metal ion relative to Cu(2+) and compared to the results obtained by the DFT calculations. PMID:24839211
Demir, Serkan; Yilmaz, Hakan; Dilimulati, Maowulidan; Anda�, M�berra
Simple Potentiometric Determination of Reducing Sugars
In this article a potentiometric method for reducing sugar quantification is described. Copper(II) ion reacts with the reducing sugar (glucose, fructose, and others), and the excess is quantified using a copper wire indicator electrode. In order to accelerate the kinetics of the reaction, working conditions such as pH and temperature must be�
Moresco, Henry; Sanson, Pedro; Seoane, Gustavo
An integrator for multichannel potentiometric recorders
An integrator is described which is accurate to 1% of full scale and is suitable for use with a multiple channel recorder. The pen travel of a multipoint potentiometric recorder is digitized by a non-contact device and the pulses fed to appropriate high speed counters through relay contacts. The relays are controlled, via a phase conscious rectifier, by the pen-drive
J P Funk; D G Dowe
In situ dissolution testing using potentiometric sensors.
Potentiometric sensors can be used to determine the amount of API dissolved in the dissolution medium in function of time by measuring directly in the dissolution vessel of a Paddle (USP type 2) and Basket (USP type 1) apparatus. The prototype potentiometric sensor instrumentation showed very promising results for a selection of APIs with different physico-chemical properties. The applicability, benefits and limitations of the prototype were explored. The applicability of the measurement technique strongly depends on the log(P) of the API. Here, it is shown that measurements can easily be performed for APIs with a log(P)>4. Electrode performance however decreases with decreasing logP of the APIs due to decreased drug selectivity in comparison to the excipients and ionic strength of the applied dissolution medium. The potentiometric sensors are shown to be insensitive towards undissolved particles and air bubbles as opposed to UV spectrometric measurement where these can lead to severe light scattering. For the tested APIs, the obtained dissolution profiles are very reproducible and show a low variation compared to the measurements using manual sampling and UV or HPLC analysis. The measurements demonstrate that potentiometric sensors are a very promising technology that can become a standard for in situ dissolution measurements. PMID:18539443
Peeters, Karl; De Maesschalck, Roy; Bohets, Hugo; Vanhoutte, Koen; Nagels, Luc
Potentiometric determination of molybdenum as silver molybdate
Silver molybdate was first prepared by SCribbLE aS a white or yellowishwhite amorphous precipitate by adding a silver salt to the solution of a molybdate. The salt is precipitated in colloidal form if the solutions are very dilute. It decomposes on heating and is soluble in nitric acid. The reaction has been successfully followed potentiometrical ly using silver as an
G. C. Shivahare
Potentiometric responses of ion-selective electrodes after galvanostatically controlled incorporation of primary ions.
A new method of quantitative incorporation of primary cations into ion-selective membrane by means of galvanostatic cathodic polarization/conditioning, before measurement step, was proposed and tested on the example of potassium-selective electrode with ionophore - valinomycin in poly(vinyl chloride) based membrane and with polypyrrole solid contact. Open circuit potential values recorded after polarization can be quantitatively explained by changes of primary cations and ionophore concentration in the surface part of the membrane. The influence of potassium ions concentration in the membrane (in relation to ion exchange sites amount) on the shape of potentiometric calibration plots was also observed. Improved characteristics, with extended linear range, can be obtained for membrane of minor loading with primary cations (around 25%), the responses are relatively stable in course of following calibrations. PMID:21482287
Paw?owski, Pawe?; Kisiel, Anna; Michalska, Agata; Maksymiuk, Krzysztof
Potentiometric determination of free acidity in presence of hydrolysable ions and a sequential determination of hydrazine.
A simple potentiometric method for the determination of free acidity in presence of hydrolysable ions and sequential determination of hydrazine is developed and described. Both free acid and hydrazine are estimated from the same aliquot. In this method, free acid is titrated with standard sodium carbonate solution after the metal ions in solutions are masked with EDTA. Once the end point for the free acid is determined at pH 3.0, an aliquot of formaldehyde is added to liberate the acid equivalent to hydrazine which is then titrated with the same standard sodium carbonate solution using an automatic titration system. The described method is simple, accurate and reproducible. This method is especially applicable to all ranges of nitric acid and heavy metal ion concentration relevant to Purex process used for nuclear fuel reprocessing. The overall recovery of nitric acid is 98.9% with 1.2% relative standard deviation. Hydrazine content has also been determined in the same aliquot with a recovery of nitric acid is 99% with 2% relative standard deviation. The major advantage of the method is that generation of corrosive analytical wastes containing oxalate or sulphate is avoided. Valuable metals like uranium and plutonium can easily be recovered from analytical waste before final disposal. PMID:21726724
Ganesh, S; Khan, Fahmida; Ahmed, M K; Pandey, S K
Actinide cation-cation complexes
The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO{sub 2}{sup +}) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO{sub 2}{sup +}; therefore, cation-cation complexes indicate something unique about AnO{sub 2}{sup +} cations compared to actinide cations in general. The first cation-cation complex, NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO{sub 2}{sup +} species, the cation-cation complexes of NpO{sub 2}{sup +} have been studied most extensively while the other actinides have not. The only PuO{sub 2}{sup +} cation-cation complexes that have been studied are with Fe{sup 3+} and Cr{sup 3+} and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, NpO{sub 2}{sup +}{center_dot}Th{sup 4+}, PuO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, and PuO{sub 2}{sup +}{center_dot}Th{sup 4+} at an ionic strength of 6 M using LIPAS are 2.4 {plus_minus} 0.2, 1.8 {plus_minus} 0.9, 2.2 {plus_minus} 1.5, and {approx}0.8 M{sup {minus}1}.
Stoyer, N.J. [Lawrence Berkeley Lab., CA (United States); Seaborg, G.T. [Lawrence Livermore National Lab., CA (United States)
Surface Complexation of Neodymium at the Rutile-Water Interface: A Potentiometric and Modeling Study in NaCl Media to 250�C
The adsorption of Nd{sup 3+} onto rutile surfaces was examined by potentiometric titration from 25 to 250 C, in 0.03 and 0.30m NaCl background electrolyte. Experimental results show that Nd{sup 3+} sorbs strongly, even at low temperature, with adsorption commencing below the pHznpc of rutile. In addition, there is a systematic increase in Nd{sup 3+} adsorption with increasing temperature. The experimental results were rationalized and described using surface oxygen proton affinities computed from the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three-layer description of the oxide/water interface. Moreover, molecular-scale information was incorporated successfully into the surface complexation model, providing a unique geometry for the adsorption of Nd{sup 3+} on rutile. The primary mode of Nd{sup 3+} adsorption was assumed to be the tetradentate configuration found for Y{sup 3+} adsorption on the rutile (110) surface from previously described in situ X-ray standing wave experiments, wherein the sorbing cations bond directly with two adjacent ''terminal'' and two adjacent ''bridging'' surface oxygen atoms. Similarly, the adsorption of Na{sup +} counterions was also assumed to be tetradentate, as supported by MD simulations of Na{sup +} interactions with the rutile (110) surface, and by analogous X-ray standing wave results for Rb{sup +} adsorption on rutile. Fitting parameters for Nd{sup 3+} adsorption included binding constants for the tetradentate adsorption complex and capacitance values for the inner-sphere binding plane. In addition, hydrolysis of the tetradentate adsorption complex was permitted and resulted in significantly improved model fits at higher temperature and pH values. The modeling results indicate that the Stern-based MUSIC surface-complexation model adequately accommodates molecular-scale information to uniquely rationalize and describe multivalent ion adsorption systematically into the hydrothermal regime.
Ridley, Mora K. [Texas Tech University, Lubbock; Machesky, Michael L. [Illinois State Water Survey, Champaign, IL; Wesolowski, David J [ORNL; Palmer, Donald [ORNL
Sequential potentiometric complexometric redox determination of iron(III) and cobalt(II) with application to alloys.
A simple potentiometric method is presented for successive determination of iron(III) and cobalt(II) by complexometric titration of the iron(III) with EDTA at pH 2 and 40 degrees , followed by redox titration of the cobalt(II) complex with 1,10-phenanthroline or 2,2'-bipyridyl at pH 4-5 and 40 degrees , with gold(III). There is no interference in either determination from common metal ions other than copper(II), which severely affects the cobalt determination but can be removed by electrolysis. The method has been successfully applied to determination of iron and cobalt in Kovar and Alnico magnet alloys. PMID:18964822
Rao, B V; Gopinath, R
Chloride selective potentiometric sensor based on a newly synthesized hydrogen bonding anion receptor
A new potentiometric chloride sensor based on the use of anion receptor 2-(1-H-imidazo [4,5-f][1,10]phenanthroline-2-yl)-6methoxyphenol (HIPM) in poly(vinyl chloride) (PVC) matrix is reported. Effect of various plasticizers: 2-nitrophenyloctylether (o-NPOE), di-n-butylphthalate (DBP), diethyl phthalate (DEP), dioctylpthalate (DOP), tri-n-butyl phosphates (TBP), chloronapthalene (CN) and cation excluder, cetryltrimethylammoniumbromide (CTAB) was studied. The best performance was obtained with a membrane composition of PVC: o-NPOE:HIPM: CTAB
Vinod K. Gupta; R. N. Goyal; Ram A. Sharma
Prediction of aluminum, uranium, and co-contaminants precipitation and adsorption during titration of acidic sediments.
Batch and column recirculation titration tests were performed with contaminated acidic sediments. A generic geochemical model was developed combining precipitation, cation exchange, and surface complexation reactions to describe the observed pH and metal ion concentrations in experiments with or without the presence of CO2. Experimental results showed a slow pH increase due to strong buffering by Al hydrolysis and precipitation and CO2 uptake. The cation concentrations generally decreased at higher pH than those observed in previous tests without CO2. Using amorphous Al(OH)3 and basaluminite precipitation reactions and a cation exchange selectivity coefficient K(Na\\Al) of 0.3, the model approximately described the observed (1) pH titration curve, (2) Ca, Mg, and Mn concentration by cation exchange, and (3) U concentrations by surface complexation with Fe hydroxides at pH < 5 and with liebigite (Ca2UO2(CO3)3�10H2O) precipitation at pH > 5. The model indicated that the formation of aqueous carbonate complexes and competition with carbonate for surface sites could inhibit U and Ni adsorption and precipitation. Our results suggested that the uncertainty in basaluminite solubility is an important source of prediction uncertainty and ignoring labile solid phase Al underestimates the base requirement in titration of acidic sediments. PMID:23641798
Tang, Guoping; Luo, Wensui; Watson, David B; Brooks, Scott C; Gu, Baohua
Titration Calculations -- A Problem-Solving Approach.
A problem-solving network (flow chart) constructed for use in calculating titration is described. Points out that use of the network has greatly improved student confidence and skill in performing these calculations. (Author/JN)
Waddling, Robin E. L.
Potentiometric biosensors based on polyaniline semiconductor films
Application of polyaniline (PAn) semiconductor films for potentiometric biosensor development provides certain advantages compared with the known systems. For enzyme immobilisation a pH sensitive matrix was used, which could improve sensor sensitivity. Indeed the limiting response value of the PAn based trypsin electrode in 1 mM buffer was 270 mV. The maximal slope of the calibration curve in semilogarithmic coordinates
Arkady A. Karyakin; Oksana A. Bobrova; Lylia V. Lukachova; Elena E. Karyakina
Effect of condensation phenomena on potentiometric measurements
Results of potentiometric analysis, namely those of pH measurements, depend on temperature control of the experimental setup, as it is expressed in the analytical law, the Nernst equation, starting from the primary level, where reference values are conventionally assigned to standard solutions, through the whole traceability chain, down to the service laboratory.Fundamental studies of pH standards, based on the measurement
M. J. Guiomar H. M. Lito; M. Filomena Cam�es; Catarina M. Vi�oso
Potentiometric Sensors for High Temperature Liquids
The purpose of this chapter is to present a brief overview of the potentiometric sensors available for applications in high\\u000a temperature liquids. The topics addressed include: the calculation rules of the e.m.f. of the electrochemical chain, with\\u000a special emphasis on sources of errors, a discussion on the reference electrodes of the cells according to the temperature\\u000a and the types of
J. Fouletier; V�ronique Ghetta
Lead-selective membrane potentiometric sensor based on a recently synthesized bis(anthraquinone) sulfide derivative
The need for monitoring of toxic heavy metal ions in environmental samples has prompted the development of ion-selective electrodes for these ions. A new PVC membrane electrode for lead ions, based on bis[(1-hydroxy-9,10-anthraquinone)-2-methyl]sulfide as membrane carrier, was prepared. The sensor exhibits a Nernstian response for Pb{sup 2+} over a wide concentration range (5.6 {times} 10{sup {minus}3}--4.0 {times} 10{sup {minus}6} M). It has a response time of about 30 s and can be used for at least 3 months without any divergence in potentials. The proposed membrane sensor revealed good selectivities for Pb{sup 2+} over a wide variety of other metal ions. It was used as an indicator electrode in potentiometric titration of lead ion.
Pouretedal, H.R.; Forghaniha, A.; Sharghi, H. [Shiraz Univ. (Iran, Islamic Republic of). Dept. of Chemistry; Shamsipur, M. [Razi Univ., Kermanshah (Iran, Islamic Republic of). Dept. of Chemistry
Contributions to the theory of catalytic titrations--I: Complexometric catalytic titrations.
Complexometric catalytic titrations with both volumetric and coulometric addition of the titrant have been simulated. By taking into consideration the equilibrium concentration of the catalyst during the titration, general mathematical equations have been set up. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed. The work also deals with the conditions under which the approximate mathematical expressions (equilibrium concentration of the catalyst being neglected) can be applied to simulate the catalytic titration curves with a satisfactory accuracy. PMID:18963705
Ga�l, F F; Abramovi?, B F
Potentiometric Zinc Ion Sensor Based on Honeycomb-Like NiO Nanostructures
In this study honeycomb-like NiO nanostructures were grown on nickel foam by a simple hydrothermal growth method. The NiO nanostructures were characterized by field emission electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) techniques. The characterized NiO nanostructures were uniform, dense and polycrystalline in the crystal phase. In addition to this, the NiO nanostructures were used in the development of a zinc ion sensor electrode by functionalization with the highly selective zinc ion ionophore 12-crown-4. The developed zinc ion sensor electrode has shown a good linear potentiometric response for a wide range of zinc ion concentrations, ranging from 0.001 mM to 100 mM, with sensitivity of 36 mV/decade. The detection limit of the present zinc ion sensor was found to be 0.0005 mM and it also displays a fast response time of less than 10 s. The proposed zinc ion sensor electrode has also shown good reproducibility, repeatability, storage stability and selectivity. The zinc ion sensor based on the functionalized NiO nanostructures was also used as indicator electrode in potentiometric titrations and it has demonstrated an acceptable stoichiometric relationship for the determination of zinc ion in unknown samples. The NiO nanostructures-based zinc ion sensor has potential for analysing zinc ion in various industrial, clinical and other real samples.
Abbasi, Mazhar Ali; Ibupoto, Zafar Hussain; Hussain, Mushtaque; Khan, Yaqoob; Khan, Azam; Nur, Omer; Willander, Magnus
Combinatorial screening of potentiometric Pb(II) sensors from polysulfoaminoanthraquinone solid ionophore.
A potentiometric Pb(II)-selective sensor was fabricated by a combinatorial screening of electrically conducting polysulfoaminoanthraquinone (PSA) nanoparticles as a solid ionophore, ion exchangers (oleic acid (OA) and NaTPB), plasticizers in a polyvinyl chloride (PVC) matrix, membrane thickness, inner filling ion species, and concentration. The membrane sensor with the composition of PSA/PVC/DOP (dioctyl phthalate)/OA (1.0:33:61:5.0) exhibited the best performance, including a slope of 29.3 mV decade(-1) in the concentration range 10(-6.3)-10(-1.6) M, detection limit of 1.6 � 10(-7) M, response time of 16 s, lifetime of five months, and good response reversibility. The proposed sensor has demonstrated good selectivity for Pb(II) over other monovalent, divalent and trivalent interfering ions, and could be used in a pH range of 3.62-5.22. The Pb(II) sensor has been successfully applied for the determination of Pb(II) concentration in real-world samples and also as an indicator electrode for potentiometric titration of lead ions. PMID:24512280
Huang, Mei-Rong; Ding, Yong-Bo; Li, Xin-Gui
[Determination of the sulfate ion content in antibiotic sulfate salts by a complexometric titration method].
A possibility of assaying antibiotic sulfates, such as gentamicin, kanamycin, monomycin, neomycin, ristomycin, streptomycin, florimycin and polymyxin M sulfates for sulfate ions by titration with barium chloride in the presence of chlorphosphonaso-III, a metal indicator immediately in the salt solutions or after elimination of the cation by means of ion exchange (sulfocation exchange resins in H+-form) was tested. The procedure was shown to be adequate to the classical weight method. PMID:7469396
Kartseva, V D; Lokshin, G B; Libinson, G S; Kruzhkova, N G
Potentiometric, ESI MS and AM1d studies of lasalocid esters silver(I) complexes
Eight lasalocid esters (L) were synthesised and their complex formation with Ag + cations in propylene carbonate was studied by the potentiometric, ESI MS and AM1d semiempirical methods. The stability constants of AgL +, AgL2+ and Ag 2L 2+ complexes were determined indicating the favourable formation of the 1:1 complexes (AgL +). ESI MS spectra of the Lasalocid esters complexes with Ag + cations demonstrated also the formation of the 1:1 complexes. The formation of AgL2+ and Ag 2L 2+ complexes under the ESI MS conditions was not detected. The ?HOF values calculated by the AM1d semiempirical method show that the formation of the 1:1 complexes is favourable and this result is in very good agreement with the experimental data. The structures of AgL +, and Ag 2L 2+ complexes of Las3 and Las7 are visualised and discussed.
Pankiewicz, Rados?aw; Kira, Jaromir; Schroeder, Grzegorz; Ossowski, Tadeusz; Brzezinski, Bogumi?
Potentiometric flow injection analysis of mebeverine hydrochloride in serum and urine.
Four PVC membrane electrodes for the determination of mebeverine hydrochloride (MvCl) were fabricated and fully characterized in terms of composition, life span, usable pH range, working concentration range and temperature. The membranes of these electrodes consist of mebeverinium-silicotungstate (Mv-ST), silicomolybdate (Mv-SM), phosphotungstate (Mv-PT), or phosphomolybdate (Mv-PM) ion-associations dispersed in PVC matrix with dibutyl phthalate plasticizer. The electrodes showed near-Nernstian response over the concentration range of 4.0 x 10(-6) to 1.0 x 10(-2)M MvCl and were applied to the potentiometric determination of mebeverinium ion in pharmaceutical preparations, serum and urine in steady state and flow injection (FI) conditions with average recoveries of 96.4-102 % and relative standard deviations of 0.132-1.86%. The electrodes exhibit good selectivity for MvCl with respect to a large number of inorganic cations, organic cations, sugars and amino acids. The sensitivities of these electrodes are high enough to measure as low as 1.86 microg/ml of MvCl which permit the determination of the Ksp values of the ion-associates used. The proposed potentiometric methods offer the advantages of simplicity, accuracy, automation feasibility and applicability to turbid and colored sample solutions. PMID:15620532
Ibrahim, Hosny; Issa, Yousry M; Abu-Shawish, Hazem M
An ultrasensitive and stable potentiometric immunosensor.
We describe a novel quantitative polypyrrole based potentiometric biosensor that provides broad-spectrum assay capability. The biosensor allows for capture of analytes of interest from complex real samples such as serum and whole blood, and subsequent measurement in a controlled matrix environment. The technology is rapid (<15 min), ultrasensitive (<50 fM) and reproducible (CV<5% at 0.1 ng/ml). In addition the system has shown a wide dynamic range (four to five orders of magnitude), and good stability, 37 degrees C for at least 4 months. This potentiometric biosensor detects enzyme labelled immuno-complexes formed at the surface of a polypyrrole coated, screenprinted gold electrode. Detection is mediated by a secondary reaction that produces charged products (a 'charge-step' procedure). A shift in potential is measured at the sensor surface, caused by local changes in redox state, pH and/or ionic strength. The magnitude of the difference in potential is related to the concentration of the formed receptor-target complex. The potentiometric sensing technology has been demonstrated in assays for hepatitis B surface antigen (HBsAg) (Mw>300 kDa), Troponin I (Mw approximately 23 kDa), Digoxin (Mw 780 Da) and tumour necrosis factor (hTNF-alpha) (Mw approximately 23 kDa). These model targets were chosen to represent analytes of a range of molecular weights, and because of their requirement for assays of high analytical sensitivity and precision. All these assays were performed using complex fluid samples and the presence of any non-specific binding has no significant effect on the final measurement. New assays can be transferred and optimised readily. PMID:12896840
Purvis, D; Leonardova, O; Farmakovsky, D; Cherkasov, V
Potentiometric-scanning ion conductance microscopy.
We detail the operation mechanism and instrumental limitations for potentiometric-scanning ion conductance microscopy (P-SICM). P-SICM makes use of a dual-barrel probe, where probe position is controlled by the current measured in one barrel and the potential is measured in a second barrel. Here we determine the interaction of these two barrels and resultant effects in quantitation of signals. Effects due to the size difference in pipet tip opening are examined and compared to model calculations. These results provide a basis for quantitation and image interpretation for P-SICM. PMID:24773406
Zhou, Yi; Chen, Chiao-Chen; Weber, Anna E; Zhou, Lushan; Baker, Lane A
A new method for determining the acid number of biodiesel based on coulometric titration.
A new method is proposed for determining the acid number (AN) of biodiesel using coulometric titration with potentiometric detection, basically employing a potentiostat/galvanostat and an electrochemical cell containing a platinum electrode, a silver electrode, and a combination pH electrode. The method involves a sequential application of a constant current between the platinum (cathode) and silver (anode) electrodes, followed by measuring the potential of the combination pH electrode, using an isopropanol/water mixture as solvent and LiCl as the supporting electrolyte. A preliminary evaluation of the new method, using acetic acid for doping a biodiesel sample, showed an average recovery of 100.1%. Compared to a volumetric titration-based method for determining the AN of several biodiesel samples (ranging from about 0.18 to 0.95 mg g(-1)), the new method produced statistically similar results with better repeatability. Compared to other works reported in the literature, the new method presented an average repeatability up to 3.2 times better and employed a sample size up to 20 times smaller. PMID:22841067
Barbieri Gonzaga, Fabiano; Pereira Sobral, Sidney
A practical method for the separation and amperometric determination of ; thorium in monazite sands is proposed. The attack is carried out with sulfuric ; acid on 10-gram samples; thorium and the rare earths are separated by a single ; precipitation with oxalic acid, and the final amperometric titration is made with ; ammonium paramolybdate as titrant. The composition of
J. J. Burastero; R. W. Martres
Isothermal Titration Calorimetry in the Student Laboratory
Isothermal titration calorimetry (ITC) is the measurement of the heat produced by the stepwise addition of one substance to another. It is a common experimental technique, for example, in pharmaceutical science, to measure equilibrium constants and reaction enthalpies. We describe a stirring device and an injection pump that can be used with a�
Wadso, Lars; Li, Yujing; Li, Xi
Determination of traces of zinc by fluorimetrically indicated complexometric titrations.
Zinc forms fluorescent complexes with 8-hydroxyquinoline-5-sulphonic acid (HQS) in the pH region 7-10. The stability of these complexes is such that two different titration procedures are possible: the titration of zinc with HQS and the titration of zinc with EDTA in the presence of HQS. For both procedures the choice of the titration conditions is described. Also two separation procedures for zinc are described, especially suitable in connection with the EDTA titration. The practical results show that zinc in concentrations larger than 10(-6)M (0.05 mug/ml) can be titrated with good precision. PMID:18961340
van Slageren, R; den Boef, G; van der Linden, W E
Analysis of Various Very Slightly Water-Soluble Drugs in Micellar Medium. I. Potentiometric and Visual Determination of Non-Steroidal Anti-Inflammatory Therapeutic Agents
Each one of four very slightly water-soluble to practically water-insoluble, non-steroidal anti-inflammatory, antipyretic and analgesic drugs, such as indomethacin(I), aspirin(II), ibuprofen(III) and flurbiprofen(IV) were dissolved in a N-hexadecyl-N, N, N-trimethylammonium bromide (CTAB) micellar medium and the resulting solutions were titrated with a carbonate-free 2.5 mmol\\/L NaOH solution. The end point determined potentiometrically by the convetional manner, using the second derivative
Prodromos B. Issopoulos
Quantification of hydrolytic charge loss of DMAEA-Q-based polyelectrolytes by proton NMR spectroscopy and implications for colloid titration.
Copolymers of acrylamide and quaternised dimethylaminoethyl acrylate (DMAEA-Q) constitute an economically important range of cationic polyelectrolytes used in sludge conditioning. The latter treatment involves charge neutralisation and bridging induced by these polymers. Since both of these phenomena rely on charge-driven sorption onto the negatively charged colloidal particles, the accurate assessment of their charge density is of primary importance in polyelectrolyte characterisation. The experimental determination of this characteristic generally relies on colloidal charge titration, in which the cationic polymer is titrated against an anionic polymer. Hereby, one of the requirements to have a stoichiometric reaction between the oppositely charged polymers is a sufficiently low polymer concentration. In this study, it is shown that such a low polymer concentration may entail a pronounced hydrolysis effect for DMAEA-Q-based polymers, which leads to a release of the cationic side groups and hence causes considerable errors on the charge titration results. Proton nuclear magnetic resonance spectroscopy was applied to investigate the fast hydrolysis kinetics of DMAEA-Q polymers together with time-dependent charge titration measurements. Diffusion NMR spectroscopy was used to assist in establishing the nature of the hydrolysis compounds. The results from both techniques indicate that a high degree of hydrolysis is reached within minutes after dilution of a concentrated polymer stock solution into aqueous solutions of slightly acidic to neutral pH values. Therefore, a modification to the classic colloid titration procedure is proposed, using a buffered dilution liquid to avoid polymer hydrolysis. It is shown that a buffer pH value of 4.5 avoids not only polymer hydrolysis effects but also possible protonation of the anionic titrant, thereby avoiding overestimation of the charge density. By means of this procedure, reproducible and time-independent charge titration results are obtained. PMID:18295818
Saveyn, Hans; Hendrickx, Pieter M S; Dentel, Steven K; Martins, Jos� C; Van der Meeren, Paul
Ionization constants of water insoluble arylpropionic acids in aqueous N, N-dimethylformamide mixtures from potentiometric pH-titrations
The ionization constants of five water insoluble anti-inflammatory arylpropionic acids were evaluated in 80% V\\/V N,N-dimethylformamide aqueous mixture. From these values, data on proton dissociation constants in water have been computed and compared with the results previously reported by using different approaches.
A. Gustavo Gonz�lez; M. Angeles Herrador
Convergence-optimized procedure for applying the NICA-Donnan model to potentiometric titrations of humic substances.
Despite the high success of the NICA-Donnan (N-D) model to describe the interaction of protons and metal ions with natural organic matter, the large number of fit parameters is a major hindrance to its capacity to provide unique numerical solutions. This well-known difficulty is reflected in the unusually low value of the generic proton binding constant for carboxylic-type groups of fulvic acid (pK(H1) = 2.34), and to some extent of humic acid (2.93), and by the considerable covariance of the other generic N-D parameters. In some studies, the number of parameters obtained by regression is reduced by estimating some values independently with other techniques. Alternatively, the applicability of the model can be improved by devising a rigorous simulation procedure, which constrains the model-fit to converge toward chemically and physically realistic values. A procedure based on three successive iterations is proposed, and the solution is shown to be stable and invariant with the initial set of parameter values. The new generic parameters, in particular pK(H1)(FA) = 3.54 and pK(H1)(HA) = 3.87, derived from the same data set as the previous generic parameters, are in better agreement with literature data. PMID:20704219
Lenoir, Thomas; Matynia, Anthony; Manceau, Alain
Potentiometric studies of the rutile�water interface: hydrogen-electrode concentration-cell versus glass-electrode titrations
This paper represents a comparison of surface protonation studies of rutile in NaCl media obtained using a conventional glass-electrode autotitrator system from 10 to 50�C, and hydrogen-electrode concentration cells from 25 to 250�C [J. Colloid Interface Sci., 200 (1998) 298]. Experimental conditions were matched as closely as possible between the two techniques, permitting a direct comparison of the results. Values
Moira K. Ridley; Michael L. Machesky; Donald A. Palmer; David J. Wesolowski
Cation exchange resins from chemically modified poly(vinyl chloride)
Poly(vinyl chloride) has been modified chemically to a cation exchange resin by halogen displacement reactions with phenol sulfonic acid, bisphenol-A sulfonic acid and phenolpthalein sulfonic acid. Ion-exchange capacity, salt-splitting capacity and pH-titration characteristics of these resins have been evaluated. pH-titration behaviour of these resins is consistent with that of a polyfunctional cation-exchanger having pK1=2 and pK2=9�10 corresponding to -SO3H and
Subrata Moitra; Mukul Biswas
Coulometric titration of urea with electrogenerated hypobromite.
A definitive method is described for the indirect assay of several tens of milligrams of urea by coulometric titration. Urea was decomposed in concentrated sulfuric acid using a Kjeldahl flask. Subsequently, the formed ammonium ion was titrated with electrogenerated hypobromite ion in a sodium bromide-sodium tetraborate medium of pH 8.6, with amperometric end-point detection. Parameters affecting the pretreatment procedure were evaluated. The optimized conditions included the heating of 2 g of urea at around 300�C for 2 h with 10 cm(3) of sulfuric acid. Under the proposed conditions, the assay value with expanded uncertainty (k = 2), 99.870 � 0.026%, agreed well with the certified value of NIST SRM 912a urea, 99.9 � 0.1%. PMID:23842420
Kato, Jun; Koseki, Takuma; Aoki, Yukie; Yamada, Ayako; Tanaka, Tatsuhiko
Graphical evaluation of complexometric titration curves.
A graphical method, based on logarithmic concentration diagrams, for construction, without any calculations, of complexometric titration curves is examined. The titration curves obtained for different kinds of unidentate, bidentate and quadridentate ligands clearly show why only chelating ligands are usually used in titrimetric analysis. The method has also been applied to two practical cases where unidentate ligands are used: (a) the complexometric determination of mercury(II) with halides and (b) the determination of cyanide with silver, which involves both a complexation and a precipitation system; for this purpose construction of the diagrams for the HgCl(2)/HgCl(+)/Hg(2+) and Ag(CN)(2)(-)/AgCN/CN(-) systems is considered in detail. PMID:18963841
Guinon, J L
Coulometrische titration von hypochloriten und chloraten.
Hypochlorite was determined by direct coulometric titration with iron(II) in an acetate buffered solution. Chlorate was titrated with titanium(III) in 2M hydrochloric acid. Amperometric indication with one and two electrodes, respectively, was used. Mixtures of hypochlorites and chlorates, e.g., in industrial electrolytes, may be analysed. On a d�termin� l'hypochlorite par titrage coulom�trique direct avec le fer(II) dans une solution tamponn�e � l'ac�tate. On a titr� le chlorate avec le titane(III) en acide chlorhydrique 2M. On a utilis� l'indication amp�rom�trique une et deux �lectrodes respectivement. On peut analyser des m�langes d'hypochlorites et de chlorates, par exemple dans des �lectrolytes industriels. PMID:18960728
Gr�ndler, P; Holzapfel, H
[Estimation of sulfhydryl groups by laboratory titrator T-201].
A method for estimating sulfhydryl groups by laboratory titrator T-201 is proposed. It consists in culonometric titration of SH-groups by silver ions. The method is highly sensitive and reproducible. PMID:7378573
Aleksidze, N G; Koshoridze, N I
Spectrophotometric titration of zirconium in siliceous materials.
An accurate and selective complexometric titration procedure based upon a spectrophotometrically detected end-point has been developed for the determination of zirconium in glasses, glass-ceramics and refractories. A p-bromomandelic acid separation step for zirconium imparts excellent selectivity to the procedure. The method is particularly important for the 1-5% concentration range where a simple, accurate and selective method for the determination of zirconium has been lacking. PMID:18962344
Sugawara, K F; Su, Y S; Strzegowski, W R
Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.
Thermodynamic dissociation constants of the Br�nsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-H�ckel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions. PMID:24720707
Chen, Yuehua; Wang, Huiyong; Wang, Jianji
Simple and Automated Coulometric Titration of Acid Using Nonisolated Electrodes
Coulometric titrations involve the quantification of analyte by measurements of current and time. In most coulometric titrations, the anode and cathode are placed in isolated cells that are connected by a salt bridge. By contrast, the experiments described here involve coulometric titrations (of acidic protons in solution) using a silver anode and�
Kuntzleman, Thomas S.; Kenney, Joshua B.; Hasbrouck, Scott; Collins, Michael J.; Amend, John R.
Amperometric complex-formation titration of traces of thorium.
Thorium has been determined in the microgram range by complexometric titration with EDTA. The end-point was detected by following the anodic wave of EDTA at a rotating mercury electrode. It has been shown that thorium can be titrated in the presence of large amounts of other metals. Following electrolysis at a mercury pool electrode the titration is selective for thorium. PMID:18960984
Freese, F; Oostervink, R; Den Boef, G
Potentiometric Urea Biosensor Based on an Immobilised Fullerene-Urease Bio-Conjugate
A novel method for the rapid modification of fullerene for subsequent enzyme attachment to create a potentiometric biosensor is presented. Urease was immobilized onto the modified fullerene nanomaterial. The modified fullerene-immobilized urease (C60-urease) bioconjugate has been confirmed to catalyze the hydrolysis of urea in solution. The biomaterial was then deposited on a screen-printed electrode containing a non-plasticized poly(n-butyl acrylate) (PnBA) membrane entrapped with a hydrogen ionophore. This pH-selective membrane is intended to function as a potentiometric urea biosensor with the deposition of C60-urease on the PnBA membrane. Various parameters for fullerene modification and urease immobilization were investigated. The optimal pH and concentration of the phosphate buffer for the urea biosensor were 7.0 and 0.5 mM, respectively. The linear response range of the biosensor was from 2.31 � 10?3 M to 8.28 � 10?5 M. The biosensor's sensitivity was 59.67 � 0.91 mV/decade, which is close to the theoretical value. Common cations such as Na+, K+, Ca2+, Mg2+ and NH4+ showed no obvious interference with the urea biosensor's response. The use of a fullerene-urease bio-conjugate and an acrylic membrane with good adhesion prevented the leaching of urease enzyme and thus increased the stability of the urea biosensor for up to 140 days.
Saeedfar, Kasra; Heng, Lee Yook; Ling, Tan Ling; Rezayi, Majid
Potentiometric biosensors using immobilized enzyme layers mixed with hydrophilic polyurethane
Potentiometric biosensors using asymmetric type polyurethane (PU) membranes are reported. The proposed membrane system consists of a thin hydrophilic polyurethane (HPU) film directly mixed with an enzyme that is coated over an underlying plasticized PU-based ion-selective membrane. It is shown that the intrinsic potentiometric response of the basic ion-selective PU membrane is not influenced significantly by the HPU\\/enzyme film coated
Jae Ho Shin; Sang Yong Yoon; In Jun Yoon; Sung Hyuk Choi; Sung Dong Lee; Hakhyun Nam; Geun Sig Cha
A Novel Potentiometric Glucose Biosensor Based on Polyaniline Semiconductor Films
Application of polyaniline semiconductor films to potentiometric biosensor development provides certain advantages comparing with the known systems. Using self-doped polyaniline instead of common polymer as pH transducer the stable potentiometric response of 70 mV\\/pH was obtained. Taking as an example glucose biosensor we showed that polyaniline based electrode possessed three-four fold increased potential shift than glucose-sensitive field-effect transistor did. One
Elena E. Karyakina; Lylia V. Neftyakova; Arkady A. Karyakin
Potentiometric sensors enabling fast screening of the benign prostatic hyperplasia drug alfuzosin in pharmaceuticals, urine and serum.
The construction and characterization of potentiometric membrane electrodes are described for the quantification of alfuzosin, a drug used in a mono- and combined therapy of benign prostatic hyperplasia (BPH). The membranes of these electrodes consist of alfuzosin hydrochloride-tetraphenyl borate, (Az-TPB), chlorophenyl borate (Az-ClPB), and phosphotungstate (Az(3)-PT) ion associations as molecular recognition reagent dispersed in PVC matrix with dioctylpthalate as plasticizer. The performance characteristics of these electrodes, which were evaluated according to IUPAC recommendations, revealed a fast, stable and liner response for alfuzosin over the concentration ranges of 8.3 x 10(-6) to 1.0 x 10(-2) M, 3.8 x 10(-6) to 1.0 x 10(-2) M, 7.5 x 10(-7) to 1.0 x 10(-2) M AzCl with cationic slopes of 57.0, 56.0 and 58.5 mV/decade, respectively. The solubility product of the ion-pair and the formation constant of the precipitation reaction leading to the ion-pair formation were determined conductometrically. The electrodes, fully characterized in terms of composition, life span and usable pH range, were applied to the potentiometric determination of alfuzosin hydrochloride ion in different pharmaceutical preparations and biological fluids without any interference from excipients or diluents commonly used in drug formulations. The potentiometric method was also used in the determination of alfuzosin hydrochloride in pharmaceutical preparations in four batches with different expiration dates. Validation of the method showed suitability of the proposed electrodes for use in the quality control assessment of alfuzosin hydrochloride. This potentiometric method offers the advantages of high-throughput determination, simplicity, accuracy, automation feasibility, and applicability to turbid and colored sample solutions. PMID:17979639
Gupta, Vinod K; Singh, Ashok K; Gupta, Barkha
Choice of ion-selective electrodes in potentiometric determination of mercaptans and hydrogen sulfide in condensates
Ion-selective electrodes for the potentiometric analysis of sulfur content of high-sulfur gas condensates from fields in the Caspian lowlands and West Siberia were evaluated. The membrane electrodes are based on silver sulfide in combination with tungsten, copper, cadmium, lead, zirconium, and platinum. Tests were also conducted for titrants that form stable compounds with mercaptans as well as for solvents that would be compatible with the condensates and not stratify when the titrants were added. Anion-selective electrodes included iodine-selective, sulfide-selective, and thiocyanate-selective; cation-selective electrodes were cadmium-selective, copper-selective, and lead-selective. The preferred titrant was found to be either a solution of ammoniacal silver nitrate in isopropanol or a solution of silver nitrate in DMFA. Reduction and poisoning behavior along with service life and sensitivity were assessed. The electrodes were field tested and the procedure has been implemented at the Karachaganak field.
Kiyanskii, V.V.; Burakhta, V.A.
Fibre-optic titrations-IV Direct complexometric titration of aluminium(III) with DCTA.
The end-point of the direct complexometric titration of Al(3+) in pH 4.6 solution can be determined by monitoring the fluorescence intensity of the aluminium-morin complex, by use of a bifurcated fibre-optic light guide. The method allows the determination of aluminium in the 1-800 ppm range with good precision. The procedure is applicable even when the solutions are strongly coloured or turbid, but because of the slow complexation kinetics requires a titration time of about 20 min. PMID:18964217
Wolfbeis, O S; Schaffar, B P; Chalmers, R A
Modeling complexometric titrations of natural water samples.
Complexometric titrations are the primary source of metal speciation data for aquatic systems, yet their interpretation in waters containing humic and fulvic acids remains problematic. In particular, the accuracy of inferred ambient free metal ion concentrations and parameters quantifying metal complexation by natural ligands has been challenged because of the difficulties inherent in calibrating common analytical methods and in modeling the diverse array of ligands present. This work tests and applies a new method of modeling titration data that combines calibration of analytical sensitivity (S) and estimation of concentrations and stability constants for discrete natural ligand classes ([Li]T and Ki) into a single step using nonlinear regression and a new analytical solution to the one-metal/two-ligand equilibrium problem. When applied to jointly model data from multiple titrations conducted at different analytical windows, it yields accurate estimates of S, [Li]T, Ki, and [Cu2+] plus Monte Carlo-based estimates of the uncertainty in [Cu2+]. Jointly modeling titration data at low-and high-analytical windows leads to an efficient adaptation of the recently proposed "overload" approach to calibrating ACSV/CLE measurements. Application of the method to published data sets yields model results with greater accuracy and precision than originally obtained. The discrete ligand-class model is also re-parametrized, using humic and fulvic acids, L1 class (K1 = 10(13) M(-1)), and strong ligands (L(S)) with K(S) > K1 as "natural components". This approach suggests that Cu complexation in NW Mediterranean Sea water can be well represented as 0.8 +/- 0.3/0.2 mg humic equiv/L, 13 +/- 1 nM L1, and 2.5 +/- 0.1 nM L(S) with [CU]T = 3 nM. In coastal seawater from Narragansett Bay, RI, Cu speciation can be modeled as 0.6 +/- 0.1 mg humic equiv/L and 22 +/- 1 nM L1 or approximately 12 nM L1 and approximately 9 nM L(S), with [CU]T = 13 nM. In both waters, the large excess (approximately 10 nM) of high-affinity, Cu-binding ligands over [CU]T results in low equilibrium [Cu2+] of 10(-14.5 +/- 0.2) M and 10(-13.3 +/- 0.4) M, respectively. PMID:12731837
Hudson, Robert J M; Rue, Eden L; Bruland, Kenneth W
A "release" protocol for isothermal titration calorimetry.
Isothermal titration calorimetry (ITC) has become a standard method for investigating the binding of ligands to receptor molecules or the partitioning of solutes between water and lipid vesicles. Accordingly, solutes are mixed with membranes (or ligands with receptors), and the subsequent heats of incorporation (or binding) are measured. In this paper we derive a general formula for modeling ITC titration heats in both binding and partitioning systems that allows for the modeling of the classic incorporation or binding protocols, as well as of new protocols assessing the release of solute from previously solute-loaded vesicles (or the dissociation of ligand/receptor complexes) upon dilution. One major advantage of a simultaneous application of the incorporation/binding and release protocols is that it allows for the determination of whether a ligand is able to access the vesicle interior within the time scale of the ITC experiment. This information cannot be obtained from a classical partitioning experiment, but it must be known to determine the partition coefficient (or binding constant and stochiometry) and the transfer enthalpy. The approach is presented using the partitioning of the nonionic detergent C12EO7 to palmitoyloleoylphosphatidylcholine vesicles. The release protocol could also be advantageous in the case of receptors that are more stable in the ligand-saturated rather than the ligand-depleted state.
Heerklotz, H H; Binder, H; Epand, R M
Disposable potentiometric sensors for monitoring cholinesterase activity.
A highly sensitive disposable screen-printed butyrylcholine (BuCh) potentiometric sensor, based on heptakis (2,3,6-tri-o-methyl)-?-cyclodextrin (?-CD) as ionophore, was developed for butyrylcholinesterase (BuChE) activity monitoring. The proposed sensors have been characterized and optimized according to the constituents of homemade printing carbon ink including ?-CD, anionic sites, and plasticizer. The fabricated sensor showed Nernstian responses from 10(-6) to 10(-2)mol L(-1) with detection limit of 8 � 10(-7)mol L(-1), fast response time (1.6s) and adequate shelf-life (6 months). Improved selectivity towards BuCh with minimal interference from choline (Ch) was achieved and the sensor was used for determination of 0.06-1.25 U mL(-1) BuChE. The developed disposable sensors have been successfully applied for real-time intoxication monitoring through assaying cholinesterases (ChEs) activity in human serum. Determination of organophosphate pesticide was conducted by measuring their inhibition of BuChE with successful assaying of malathion in insecticide samples with high accuracy and precision. PMID:21111146
Khaled, Elmorsy; Hassan, H N A; Mohamed, Gehad G; Ragab, Fahem A; Seleim, Aly Eldin A
Alkaline Titrations of poly(dG-dC)�poly(dG-dC): Microemulsion Versus Solution Behavior
PolyGC was titrated with a strong base in the presence of increasing concentrations of NaCl (from 0.00 to 0.60M) either in water solution or with the polynucleotide solubilized in the aqueous core of reverse micelles, i.e., the cationic quaternary water-in-oil microemulsion CTAB\\/n-hexane\\/n-pentanol\\/water. The results for matched samples in the two media were compared. CD and UV spectroscopies and, for the
Marta Airoldi; Giuseppe Gennaro; Marcello Giomini; Anna Maria Giuliani; Mauro Giustini
Potentiometric Biosensor for Studying Hydroquinone Cytotoxicity in vitro
Many processes in living cells have electrochemical characteristics that are suitable for measurement by potentiometric biosensors. Potentiometric biosensors allow non invasive, real-time monitoring of the extracellular environment changes by measuring the potential at cell/sensor interface. This can be used as an indicator for overall cell cytotoxicity. The present work employs a potentiometric sensor array to investigate the cytotoxicity of hydroquinone to cultured mammalian V79 cells. Various electrode substrates (Au, PPy-HQ and PPy-PS) used for cell growth were designed and characterized. The controllable release of hydroquinone from PPy substrates was studied. Our results showed that hydroquinone exposure affected cell proliferation and delayed cell growth and attachment in a dose-dependent manner. Additionally, we have shown that exposure of V79 cells to hydroquinone at low doses (i.e 5?M) for more than 15 hours allows V79 cells to gain enhanced adaptability to survive exposure to high toxic HQ doses afterwards. Compared with traditional methods, the potentiometric biosensor not only provides non-invasive and real time monitoring of the cellular reactions but also is more sensitive for in vitro cytotoxicity study. By real time and non-invasive monitoring of the extracellular potential in vitro, the potentiometric sensor system represents a promising biosensor system for drug discovery.
Wang, Yanyan; Chen, Qiang; Zeng, Xiangqun
Amperometric complex-formation titration of traces of alkaline earths.
Alkaline earth metals were determined in microgram quantities by complexometric titration with EDTA, EGTA and DTPA. The end-point was detected by following the anodic wave of the chelating agent at the rotating mercury electrode. All the alkaline earths can be titrated at the microgram level with reasonable accuracy, and calcium may be titrated with EGTA in the presence of a 1000-fold excess of magnesium. PMID:18960827
den Boef, G; Freese, F; Kramer, M M; Poppe, H
Generalized theory for two- phase ion- pair and complexometric titrations
A systematic theoretical treatment of the two-phase titration based on ion-pair and metal-complex formation is presented. Equations for the titration curve, accuracy, equivalence point and choice of the indicator are derived. Much attention is paid to the parameters determining the �titratability�viz. extraction constant, distribution constant, phase volume ratio and the concentration of the analyte. Special attention is given to the
A. Bult; H. A. Dingjan; S. M. Dreijer-van der Glas; W. P. Van Bennekom
Direct potentiometric determination of diastase activity in honey.
A novel method for the determination of diastase activity is reported. The method is based on a direct potentiometric measurement of triiodide ion that is released when a starch-triiodide complex is hydrolysed by honey diastase. The increase of free triiodide ion concentration in a sample is found to be directly proportional to the diastase activity of the sample. A response mechanism of the platinum redox electrode is proposed, allowing a calculation of the diastase activity factor (F). The sensor and analyte parameters, including F, were obtained by least squares fitting of potentiometric data using the optimisation function of the Solver add-in of Microsoft Excel. The values of F obtained by the new direct potentiometric method were compared with those obtained using the standard Phadebas method (DN values), and the two values were found to agree within experimental error. Finally, the diastase activity of nine varieties of honey was determined using the novel method developed here. PMID:22868165
Sak-Bosnar, Milan; Saka?, Nikola
A potentiometric study on oxalate and citrate complexes of tin(II).
The formation of oxalate and citrate complexes of the Sn2+ ion in 1 M Na(ClO4) at 25 degrees C was investigated in the -log[H+] range 2 to 5 by potentiometric titrations using glass and tin amalgam electrodes. The tin concentration was varied from 0.5 to 5 mM and the concentration of the ligands from 1 to 40 mM. The experimental data have been explained by the formation of the oxalato complexes SnC2O4(aq) and Sn(C2O4)2(2-) and of the citrate complexes (C3H5O7(3-) = citrate ion) SnC3H5O7-, SnHC3H5O7(aq), SnH2C3H5O7+ and Sn(OH)C3H5O7(2-). The equilibrium constants were refined by the computer program SUPERQUAD. The final values of the constants on the medium scale and in the infinite dilution reference state are given in Table 2. PMID:11507832
Ciavatta, L; De Tommaso, G; Iuliano, M
Potentiometric determination of antimony in metal(II) hexafluoroantimonates(V).
The purpose of this study was to develop an accurate and precise analytical procedure for the determination of the content of antimony in coordination compounds of metal(II) hexafluoroantimonates(V) (M(SbF(6))(2) compounds, where M=Mg, Ca, Sr or Ba) synthesized in our laboratory. The major problem was to find an appropriate reagent for reductive decomposition of SbF(6)(-) to Sb(3+) required for the determination of antimony by redox titration. Effective reduction of Sb(5+) regardless of the metal M bound to SbF(6)(-) species was achieved using metallic aluminium powder in acidic medium. Precipitated Sb(0) was quantitatively reoxidized to Sb(3+) and determined potentiometrically with KBrO(3) or KMnO(4). Other metals were determined complexometrically with disodium ethylenediaminetetraacetic acid (EDTA). Highly accurate and reproducible results were obtained in the concentration range 5-25 mg Sb with an RSD smaller than 0.6%. Antimony-fluoro-hydroxo species and fluoride did not interfere with the complexometric determinations of other metals with EDTA. The developed method enabled, for the first time, complete elemental chemical analysis of M(SbF(6))(2) compounds in the bulk form. PMID:18968810
Ponikvar, M; Pihlar, B; Zemva, B
Automated titration method for use on blended asphalts
A system for determining parameters and compatibility of a substance such as an asphalt or other petroleum substance uses titration to highly accurately determine one or more flocculation occurrences and is especially applicable to the determination or use of Heithaus parameters and optimal mixing of various asphalt stocks. In a preferred embodiment, automated titration in an oxygen gas exclusive system and further using spectrophotometric analysis (2-8) of solution turbidity is presented. A reversible titration technique enabling in-situ titration measurement of various solution concentrations is also presented.
Pauli, Adam T. (Cheyenne, WY); Robertson, Raymond E. (Laramie, WY); Branthaver, Jan F. (Chatham, IL); Schabron, John F. (Laramie, WY)
Electrochemical titrations and reaction time courses monitored in situ by magnetic circular dichroism spectroscopy.
Magnetic circular dichroism (MCD) spectra, at ultraviolet-visible or near-infrared wavelengths (185-2000 nm), contain the same transitions observed in conventional absorbance spectroscopy, but their bisignate nature and more stringent selection rules provide greatly enhanced resolution. Thus, they have proved to be invaluable in the study of many transition metal-containing proteins. For mainly technical reasons, MCD has been limited almost exclusively to the measurement of static samples. But the ability to employ the resolving power of MCD to follow changes at transition metal sites would be a potentially significant advance. We describe here the development of a cuvette holder that allows reagent injection and sample mixing within the 50-mm-diameter ambient temperature bore of an energized superconducting solenoid. This has allowed us, for the first time, to monitor time-resolved MCD resulting from in situ chemical manipulation of a metalloprotein sample. Furthermore, we report the parallel development of an electrochemical cell using a three-electrode configuration with physically separated working and counter electrodes, allowing true potentiometric titration to be performed within the bore of the MCD solenoid. PMID:21864495
Bradley, Justin M; Butt, Julea N; Cheesman, Myles R
Direct spectrophotometric detection of the endpoint in metachromatic titration of polydiallyldimethylammonium chloride in water
Polydiallyldimethylammonium chloride (poly-DADMAC) is a water soluble polymer that easily ionizes when dissolved in water. This cationic polyelectrolyte is mainly used as a flocculant within the water treatment industry, but little is known of its toxicological properties or its fate in the environment. It is often assumed that the polyelectrolyte sorbs onto solid surfaces in the water treatment stream and may be removed with the sludge or by a sand bed filter; which may not always be the case. In any event, reliable analytical techniques are needed for the determination of poly-DADMAC in matrices of environmental relevance. Metachromatic polyelectrolyte titration was used to quantify poly-DADMAC in model and tap water samples. We compared a routine visual titration method with a direct spectrophotometric technique that uses a dip probe, spectrometer, and computer. The direct spectrophotometric technique allowed for the determination of titration curves at 634 nm and 510 nm, whereby the later value has never been successfully utilised in the literature. The method simplifies the data analysis, and our recovery and matrix interference experiments demonstrate that the method is accurate, precise, and robust. The detection limit for this method was 0.1 mg L-1 in model water and 0.5 mg L-1 in tap water. The limit of quantification for both water matrices was 0.5 mg L-1.
Gumbi, B.; Ngila, J. C.; Ndungu, P. G.
Generalized theory for two-phase ion-pair and complexometric titrations. II. Two-phase titrations with side reactions.
For the two-phase titration based on ion-pair and metal-complex formation full attention is given to side reactions in both phases. Their significance for the applicability of this type of titration is evaluated. Side reactions in the aqueous phase diminish and in the organic phase promote the 'titratability'. Equations for the calculation of the side reaction coefficients, the titration curve and the selection of the optimal pH and minimal side reaction interference (in the aqueous phase) are presented. Finally a full description is given of the two-phase titration including all parameters determining the 'titratability'. The merits of the developed theory are illustrated by literature examples. PMID:4080512
Bult, A; Dingjan, H A; Dreijer-van der Glas, S M; Van Bennekom, W P
Potentiometric sensing utilizing paper-based microfluidic sampling.
A new approach to potentiometric sensing utilizing paper-based microfluidic sampling is studied in this work. A solid-contact ion-selective electrode and a solid-contact reference electrode are pressed against a filter paper into which the sample solution is absorbed. The filter paper acts simultaneously as a sampling unit and as a sample container during potentiometric sensing. The paper substrates containing standard and sample solutions are disposable, while the sensors are used multiple times. The analytical method presented here opens new possibilities for economically and ecologically sound measurements of ions in various samples. PMID:24647405
Cui, Jingwen; Lisak, Grzegorz; Strzalkowska, Sylwia; Bobacka, Johan
Continuous on-line feedback based flow titrations. Complexometric titrations of calcium and magnesium.
The methodology of continuous feedback-based flow titrations and the principle of compensating errors [Anal. Chem. 72 (2000) 4713; Anal. Chim. Acta 435 (2001) 289] were applied to the determination of calcium and magnesium ions with EDTA. The flow of the titrant, EDTA, varied linearly in response to a controller output voltage while the total flow (F(T), the sum of the metal ion sample flow and the titrant flow) was held constant. The sample was pre-doped with a metal ion indicator; the status of the indicator color in the mixed stream was monitored by an optical detector and was used for governing the controller output as well as for interpreting the results of the titrations. The titrant flow initially ramped upward linearly. As a change in the color corresponding to the equivalence point was sensed by the detector, the controller output (instantaneous value V(H)) reversed its ramp direction, thus decreasing the titrant flow linearly at the same ramp rate. When the predefined absorbance corresponding to the equivalence point was sensed again, the controller voltage (instantaneous value V(L)) was ramped in reverse once more, going upward. Because of the lag time between a change in the controller output and its effect being sensed by the detector, the controller voltage corresponding to the actual equivalence point was the average of V(H) and V(L). Continuous sensor-governed operation of the controller resulted in a triangular waveform. The mean of this waveform during any cycle gives the equivalence point controller voltage V(E). This principle allowed true titrations with good reproducibility (0.2-0.7% R.S.D.) and throughput (33-42 s per titration). PMID:18969033
Jo, Kyoo Dong; Dasgupta, Purnendu K
Cationic magnetoliposomes.
Magnetoliposomes (MLs) consist of nanosized, magnetisable iron oxide cores (magnetite, Fe(3)O(4)) which are individually enveloped by a bilayer of phospholipid molecules. To generate these structures, the so-called water-compatible magnetic fluid is first synthesized by co-precipitation of Fe(2+) and Fe(3+) salts with ammonia and the resulting cores are subsequently stabilized with lauric acid molecules. Incubation and dialysis of this suspension with an excess of sonicated, small unilamellar vesicles, ultimately, results in phospholipid-Fe(3)O(4) complexes which can be readily captured from the solution by high-gradient magnetophoresis (HGM), reaching very high yields. Examination of the architecture of the phospholipid coat reveals the presence of a typical bilayered phospholipid arrangement. Cationic MLs are then produced by confronting MLs built up of zwitterionic phospholipids with vesicles containing the relevant cationic lipid, followed by fractionation of the mixture in a second HGM separation cycle. Data, published earlier by our group (Soenen et al., ChemBioChem 8:2067-2077, 2007) prove that these constructs are unequivocal biocompatible imaging agents resulting in a highly efficient labeling of biological cells. PMID:20072875
De Cuyper, Marcel; Soenen, Stefaan J H
Potentiometric sensors for the determination of trifluoperazine hydrochloride in pharmaceutical preparations.
Trifluoperazine is widely used in the treatment of psychotic patients for its neuroleptic and antidepressive action. In this study, the construction, evaluation and application of new potentiometric sensors for trifluoperazine hydrochloride (TFPH) are described. The sensing membranes incorporated either ion-pair complexes of the trifluoperazine cation and phosphotungstic acid (PTA) or phosphomolybdic acid (PMA) or sodium tetraphenyl borate (NaTPB) as electroactive materials in poly(vinyl chloride) matrix membrane. The plasticizers used were di-n-butyl phthalate (DBPH) and tri-n-butyl phosphate (TBP). After a series of experiments, the best electrodes were based on PTA or PMA as electroactive materials and DBPH as plasticizer. A linear concentration range between 1 x 10(-5)-1 x 10(-2) M with a near Nernstian slope of 28.43 and 32.11 mV decade(-1), respectively, was obtained. The electrodes were characterized in terms of the composition, usable pH range, life span and response time. The selectivity coefficient values were calculated for different inorganic cations and sugars. Validation of the method shows the suitability of the electrodes for the determination of TFPH in pharmaceutical formulations. PMID:19907085
Hassan, Ahmed K; Ameen, Suhaam T; Saad, Bahruddin; Al-Aragi, Suad M
Spectrophotometric Titration of a Mixture of Calcium and Magnesium.
Describes a spectrophotometric titration experiment which uses a manual titration spectrophotometer and manually operated buret, rather than special instrumentation. Identifies the equipment, materials, and procedures needed for the completion of the experiment. Recommends the use of this experiment in introductory quantitative analysis�
Fulton, Robert; And Others
pH Static Titration: A Quasistatic Approach
The pH-static titration is applicable to those systems where at least two types of reactions occur in comparable intensities. The commonalities in titrimetric procedure realized according to pH-static titration, irrespective of the kind of chemical processes occurring are discussed.
Michalowski, Tadeusz; Toporek, Marcin; Rymanowski, Maciej
Indirect complexometric titration of sodium and potassium with EDTA
Sodium is precipitated as sodium zinc uranyl acetate, filtered and dissolved in water, and zinc is titrated with EDTA using eriochrome black T as indicator. Potassium is precipitated as potassium sodium cobaltinitrite and dissolved in hot water containing little hydrochloric acid. The blue colored solution produced by cobalt in solution, with ammonium thiocyanate and acetone was titrated with EDTA until
Buddhadev Sen
Successive determination of praseodymium and ytterbium by coulometric complexometric titration
A method is described for the successive coulometric complexometric titration of microgram levels of light and heavy rare earth elements. The total amount of light and heavy rare earth elements is titrated by electrogenerating titrant EDTA on the mercury pool as a cathode. Then, the mercury pool is switched as an anode, electrogenerating Hg\\/sup 2 +\\/, and is used to
S. Chun-Nian; L. Jing-Ci; N. Qi-Dao; C. Mou-Sen
Quantitative Analysis of Sulfate in Water by Indirect EDTA Titration
The determination of sulfate concentration in water by indirect EDTA titration is an instructive experiment that is easily implemented in an analytical chemistry laboratory course. A water sample is treated with excess barium chloride to precipitate sulfate ions as BaSO[subscript 4](s). The unprecipitated barium ions are then titrated with EDTA.�
Belle-Oudry, Deirdre
A Closer Look at Acid-Base Olfactory Titrations
Olfactory titrations using raw onions and eugenol as acid-base indicators are reported. An in-depth investigation on olfactory titrations is presented to include requirements for potential olfactory indicators and protocols for using garlic, onions, and vanillin as acid-base olfactory indicators are tested.
Neppel, Kerry; Oliver-Hoyo, Maria T.; Queen, Connie; Reed, Nicole
Potentiometric Sensors Based on Fluorous Membranes Doped with Highly Selective Ionophores for Carbonate
Manganese(III) complexes of three fluorophilic salen derivatives were used to prepare ion-selective electrodes (ISEs) with ionophore-doped fluorous sensing membranes. Because of their extremely low polarity and polarizability, fluorous media are not only chemically very inert but also solvate potentially interfering ions poorly, resulting in a much improved discrimination of such ions. Indeed, the new ISEs exhibited selectivities for CO32? that exceed those of previously reported ISEs based on non-fluorous membranes by several orders of magnitude. In particular, the interference from chloride and salicylate was reduced by two and six orders of magnitude, respectively. To achieve this, the selectivities of these ISEs were fine-tuned by addition of non-coordinating hydrophobic ions (i.e., ionic sites) into the sensing membranes. Stability constants of the anion�ionophore complexes were determined from the dependence of the potentiometric selectivities on the charge sign of the ionic sites and the molar ratio of ionic sites and the ionophore. For this purpose, a previously introduced fluorophilic tetraphenylborate and a novel fluorophilic cation with a bis(triphenylphosphoranylidene)ammonium group, (Rf6(CH2)3)3PN+P(Rf6(CH2)3)3, were utilized. The optimum CO32? selectivities were found for sensing membranes composed of anionic sites and ionophore in a 1:4 molar ratio, which results in the formation of 2:1 complexes with CO32? with stability constants up to 4.1 � 1015. As predicted by established theory, the site-to-ionophore ratios that provide optimum potentiometric selectivity depend on the stoichiometries of the complexes of both the primary and the interfering ions. However, the ionophores used in this study give examples of charges and stoichiometries previously neither explicitly predicted by theory nor shown by experiment. The exceptional selectivity of fluorous membranes doped with these carbonate ionophores suggests their use not only for potentiometric sensing but also for other types of sensors, such as the selective separation of carbonate from other anions and the sequestration of carbon dioxide.
Chen, Li D.; Mandal, Debaprasad; Pozzi, Gianluca; Gladysz, John A.; Buhlmann, Philippe
Potentiometric sensors based on fluorous membranes doped with highly selective ionophores for carbonate.
Manganese(III) complexes of three fluorophilic salen derivatives were used to prepare ion-selective electrodes (ISEs) with ionophore-doped fluorous sensing membranes. Because of their extremely low polarity and polarizability, fluorous media are not only chemically very inert but also solvate potentially interfering ions poorly, resulting in a much improved discrimination of such ions. Indeed, the new ISEs exhibited selectivities for CO(3)(2-) that exceed those of previously reported ISEs based on nonfluorous membranes by several orders of magnitude. In particular, the interference from chloride and salicylate was reduced by 2 and 6 orders of magnitude, respectively. To achieve this, the selectivities of these ISEs were fine-tuned by addition of noncoordinating hydrophobic ions (i.e., ionic sites) into the sensing membranes. Stability constants of the anion-ionophore complexes were determined from the dependence of the potentiometric selectivities on the charge sign of the ionic sites and the molar ratio of ionic sites and the ionophore. For this purpose, a previously introduced fluorophilic tetraphenylborate and a novel fluorophilic cation with a bis(triphenylphosphoranylidene)ammonium group, (R(f6)(CH(2))(3))(3)PN(+)P(R(f6)(CH(2))(3))(3), were utilized (where R(f6) is C(6)F(13)). The optimum CO(3)(2-) selectivities were found for sensing membranes composed of anionic sites and ionophore in a 1:4 molar ratio, which results in the formation of 2:1 complexes with CO(3)(2-) with stability constants up to 4.1 � 10(15). As predicted by established theory, the site-to-ionophore ratios that provide optimum potentiometric selectivity depend on the stoichiometries of the complexes of both the primary and the interfering ions. However, the ionophores used in this study give examples of charges and stoichiometries previously neither explicitly predicted by theory nor shown by experiment. The exceptional selectivity of fluorous membranes doped with these carbonate ionophores suggests their use not only for potentiometric sensing but also for other types of sensors, such as the selective separation of carbonate from other anions and the sequestration of carbon dioxide. PMID:22070518
Chen, Li D; Mandal, Debaprasad; Pozzi, Gianluca; Gladysz, John A; B�hlmann, Philippe
Dissolved Oxygen: Method Comparison with Potentiometric Stripping Analysis
Three methods for determination of dissolved oxygen in samples of natural water are compared; patentiometric stripping analysis, PSA compares well with oxygen selective electrodes. Although potentiometric stripping analysis and oxygen selective electrode methods are found to be simple, rapid and of higher reproducibility than the usual Dinkier procedure, the use of oxygen selective electrodes has many disadvantages.
M. Fayyad; M. Tutunji; R. S. Ramakrishna; Z. Taha
Titration and hysteresis in epigenetic chromatin silencing.
Epigenetic mechanisms of silencing via heritable chromatin modifications play a major role in gene regulation and cell fate specification. We consider a model of epigenetic chromatin silencing in budding yeast and study the bifurcation diagram and characterize the bistable and the monostable regimes. The main focus of this paper is to examine how the perturbations altering the activity of histone modifying enzymes affect the epigenetic states. We analyze the implications of having the total number of silencing proteins, given by the sum of proteins bound to the nucleosomes and the ones available in the ambient, to be constant. This constraint couples different regions of chromatin through the shared reservoir of ambient silencing proteins. We show that the response of the system to perturbations depends dramatically on the titration effect caused by the above constraint. In particular, for a certain range of overall abundance of silencing proteins, the hysteresis loop changes qualitatively with certain jump replaced by continuous merger of different states. In addition, we find a nonmonotonic dependence of gene expression on the rate of histone deacetylation activity of Sir2. We discuss how these qualitative predictions of our model could be compared with experimental studies of the yeast system under anti-silencing drugs. PMID:23588040
Dayarian, Adel; Sengupta, Anirvan M
Potentiometric sensor for polyethoxylated nonionic surfactant determination
A new liquid membrane surfactant sensor based on a 1,3-didecyl-2-methylimidazolium�tetraphenylborate ion-exchange complex was tested in different ethoxylated nonionic surfactants (EONS) and polyethylene glycols. The sensor also responded to tetraphenylborate (slope=?56.1�0.8mV\\/decade of activity) in the 1�10?6 to 2�10?3M concentration range.The selectivity performance of the sensor toward alkaline, alkaline earth, and heavy metal cations was investigated. The sensor exhibited a fast response
Milan Sak-Bosnar; Dubravka Maduni?-?a?i?; Nikola Saka?; Olivera Galovi?; Mirela Samard�i?; Zorana Grabari?
Fluorescent cationic probes of mitochondria. Metrics and mechanism of interaction.
Mitochondria strongly accumulate amphiphilic cations. We report here a study of the association of respiring rat liver mitochondria with several fluorescent cationic dyes from differing structural classes. Using gravimetric and fluorometric analysis of dye partition, we find that dyes and mitochondria interact in three ways: (a) uptake with fluorescence quenching, (b) uptake without change in fluorescence intensity, and (c) lack of uptake. For dyes that quench upon uptake, the extent of quenching correlates with the degree of aggregation of the dye to dimers, as predicted by theory (Tomov, T.C. 1986. J. Biochem. Biophys. Methods. 13:29-38). Also predicted is the relationship observed between quenching and the mitochondria concentration when constant dye is titrated with mitochondria. Not predicted is the relationship observed between quenching and dye concentration when constant mitochondria are titrated with dye. Because a limit to dye uptake exists, in this case, the degree of quenching decreases as dye is added. A Langmuir isotherm analysis gives phenomenological parameters that predict quenching when it is observed as a function of dye concentration. By allowing for a decrease in membrane potential, caused by incorporation of cationic dye into the lipid bilayer, a modification of the Tomov theory predicts the dye titration data. We present a model of cationic dye-mitochondria interaction and discuss the use of these as probes of mitochondrial membrane potential.
Bunting, J R; Phan, T V; Kamali, E; Dowben, R M
Automatic photometric titrations of calcium and magnesium in carbonate rocks
Rapid nonsubjective methods have been developed for the determination of calcium and magnesium in carbonate rocks. From a single solution of the sample, calcium is titrated directly, and magnesium is titrated after a rapid removal of R2O3 and precipitation of calcium as the tungstate. A concentrated and a dilute solution of disodium ethylenediamine tetraacetate are used as titrants. The concentrated solution is added almost to the end point, then the weak solution is added in an automatic titrator to determine the end point precisely.
Shapiro, L.; Brannock, W. W.
Protein detection with potentiometric aptasensors: a comparative study between polyaniline and single-walled carbon nanotubes transducers.
A comparison study on the performance characteristics and surface characterization of two different solid-contact selective potentiometric thrombin aptasensors, one exploiting a network of single-walled carbon nanotubes (SWCNTs) and the other the polyaniline (PANI), both acting as a transducing element, is described in this work. The molecular properties of both SWCNT and PANI surfaces have been modified by covalently linking thrombin binding aptamers as biorecognition elements. The two aptasensors are compared and characterized through potentiometry and electrochemical impedance spectroscopy (EIS) based on the voltammetric response of multiply charged transition metal cations (such as hexaammineruthenium, [Ru(NH3)6](3+)) bound electrostatically to the DNA probes. The surface densities of aptamers were accurately determined by the integration of the peak for the reduction of [Ru(NH3)6](3+) to [Ru(NH3)6](2+). The differences and the similarities, as well as the transduction mechanism, are also discussed. The sensitivity is calculated as 2.97 mV/decade and 8.03 mV/decade for the PANI and SWCNTs aptasensors, respectively. These results are in accordance with the higher surface density of the aptamers in the SWCNT potentiometric sensor. PMID:23533345
D�zg�n, Ali; Imran, Hassan; Levon, Kalle; Rius, F Xavier
Geochemical reactions and dynamics during titration of a contaminated groundwater with high uranium, aluminum, and calcium
This study investigated possible geochemical reactions during titration of a contaminated groundwater with a low pH but high concentrations of aluminum, calcium, magnesium, manganese, and trace contaminant metals/radionuclides such as uranium, technetium, nickel, and cobalt. Both Na-carbonate and hydroxide were used as titrants, and a geochemical equilibrium reaction path model was employed to predict aqueous species and mineral precipitation during titration. Although the model appeared to be adequate to describe the concentration profiles of some metal cations, solution pH, and mineral precipitates, it failed to describe the concentrations of U during titration and its precipitation. Most U (as uranyl, UO 22+) as well as Tc (as pertechnetate, TcO 4-) were found to be sorbed and coprecipitated with amorphous Al and Fe oxyhydroxides at pH below �5.5, but slow desorption or dissolution of U and Tc occurred at higher pH values when Na 2CO 3 was used as the titrant. In general, the precipitation of major cationic species followed the order of Fe(OH) 3 and/or FeCo 0.1(OH) 3.2, Al 4(OH) 10SO 4, MnCO 3, CaCO 3, conversion of Al 4(OH) 10SO 4 to Al(OH) 3,am, Mn(OH) 2, Mg(OH) 2, MgCO 3, and Ca(OH) 2. The formation of mixed or double hydroxide phases of Ni and Co with Al and Fe oxyhydroxides was thought to be responsible for the removal of Ni and Co in solution. Results of this study indicate that, although the hydrolysis and precipitation of a single cation are known, complex reactions such as sorption/desorption, coprecipitation of mixed mineral phases, and their dissolution could occur simultaneously. These processes as well as the kinetic constraints must be considered in the design of the remediation strategies and modeling to better predict the activities of various metal species and solid precipitates during pre- and post-groundwater treatment practices.
Gu, Baohua; Brooks, Scott C.; Roh, Yul; Jardine, Philip M.
A Titration Technique for Demonstrating a Magma Replenishment Model.
Conductiometric titrations can be used to simulate subduction-setting volcanism. Suggestions are made as to the use of this technique in teaching volcanic mechanisms and geochemical indications of tectonic settings. (JN)
Hodder, A. P. W.
Complexometric Titration of Zinc: An Analytical Chemistry Laboratory Experiment
Complexometric titrations with EDTA have traditionally been performed in undergraduate analytical chemistry courses to determine the calcium or magnesium content of water. These titrations are performed at a basic pH, where the formation constants of Ca-EDTA and Mg-EDTA complexes are high. These types of problems are well-treated in the analytical chemistry textbooks. In contrast, treatment of metal ions whose EDTA complexes occur significantly at low pH (e.g., Zn2+, Fe3+, Cu2+, Ni2+, Pb2+, Al3+) is sparse. An incorrect conclusion can be reached by the student that practical EDTA titrations are only performed at high pH. In addition, widening the window of possible metal ions for complexometric titration affords the possibility of analyzing real world products, such as the cold lozenges discussed in the article.
Novick, S. G.
Complexometric Titration of Calcium and Magnesium by a Semiautomated Procedure
A semiautomatic procedure for the direct estimation of both serum calcium and magnesiumis described. The indicator used, Eriochromeblue SE (EBSE), has the advantageof stability and freedom from interference by naturally occurring sub- stances. The procedurerequires3-5 mm. per sampleand is very reproducible. The valuesobtainedagreewith thoseobtainedbyback-titration of excesschelator andare consistently0.3 mg.\\/100 ml. lessthan thoseobtainedbyastandardoxalateprecipita- tion method. C OMPLEXOMETRIC TITRATION s of calcium
James D. Jonesand; Warren F. McGuckin
Complexometric Titration of Metals Using a Lead Selective Electrode
A solid state lead selective electrode is used satisfactorily to indicate the end point eufing the complexometric titration of Ni, Co, Zn and V (IV) with EDTA, CDTA, and DTPA, in presence of a small amount of the corresponding lead complex. The optimum pH for the titration was in the range of 4.0 to 6.0. The quantity of lead complex
Maria L. Suarez; Alfredo Calvo; Luis E. Leon
Direct potentiometric determination of starch using a platinum redox sensor.
Here, we describe the development of a platinum redox sensor for the direct potentiometric quantification of starch in solution. The sensor measures the decrease in free triiodide ion after it complexes with starch to form a starch-triiodide complex. This decrease was, therefore, correlated with starch concentration, and the composition and stability of the potassium triiodide solution were optimised. The starch-triiodide complex was characterized potentiometrically at variable starch and triiodide concentrations. We also propose a response mechanism for the platinum redox sensor towards starch and an appropriate theoretical model. The optimised method exhibited satisfactory accuracy and precision and was in good agreement with a standard spectrophotometric method. The sensor was tested over a range of 0.4-9 mg starch, with recoveries ranging from 97.8% to 103.4% and a detection limit of 0.01 mg starch. PMID:23265448
Saka?, Nikola; Sak-Bosnar, Milan; Horvat, Marija
Groundwater potentiometric decline in the Springfield, Missouri area
The decline of the potentiometric surface of the Ozark aquifer underneath Springfield Missouri intensified during the 1980s and has been of concern since. From 1990 to the present, the shifting of population from urban to rural areas and water management changes to use more surface water created an opportunity for groundwater levels to recover. However, in 2002 private well owners reported low levels and water problems, which prompted mapping the new cone of depression. To this purpose, well data measured from private wells and data available elsewhere were mapped using GIS mapping tools. The results show a cone of depression extending towards the recently developed areas south of Springfield while the potentiometric levels of some areas within the city had recovered. The maps show that, compared to the 1987 conditions, the present cone of depression has changed significantly in extent and shape while its maximum depth has changed only slightly.
Dintelmann, D.; Guti�rrez, M.; Gouzie, D.
Comparison of enzyme immobilisation methods for potentiometric phosphate biosensors
The development of two phosphate biosensors is described and compared for potentiometric detection of phosphate. Purine nucleoside phosphorylase (PNP) and xanthine oxidase (XOD) were co-immobilised by chemical cross-linking with glutaraldehyde (GLA) and bovine serum albumin (BSA), and via entrapment into polypyrrole (PPy) films by galvanostatic polymerisation. The BSA-GLA film was made with 4.5% v\\/v GLA and 6.8% w\\/v BSA with
A. T. Lawal; S. B. Adeloju
Galvanic cell without liquid junction for potentiometric determination of copper
This paper describes potentiometric measurements in an integrated galvanic cell with both indicator and reference electrodes. Both electrodes are conducting polymer-based. The copper-sensitive indicator electrode is made by using poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 2-(o-arsenophenylazo)-1,8-dihydroxynaphthalene-3,6-disulphonic sodium salt (Arsenazo-I) as the electroactive substance in the film, while the reference electrode is based on PEDOT doped by 2-morpholineoethanesulfonic acid (MES). It is shown
Jan Migdalski; Teresa B?a?; Barbara ?ra?ka; Andrzej Lewenstam
Automated potentiometric electrolyte analysis system. [for use in weightlessness
NASA Technical Reports Server (NTRS)
The feasibility is demonstrated of utilizing chemical sensing electrode technology as the basis for an automatically-controlled system for blood gas and electrolyte analyses under weightlessness conditions. The specific measurements required were pH, pCO2, sodium, chloride, potassium ions, and ionized calcium. The general electrode theory, and ion activity measurements are described along with the fluid transport package, electronics unit, and controller for the automated potentiometric analysis system.
Microprocessor-controlled system for automatic acquisition of potentiometric data and their non-linear least-squares fit in equilibrium studies.
A microprocessor-controlled potentiometric titration apparatus for equilibrium studies is described. The microprocessor controls the stepwise addition of reagent, monitors the pH until it becomes constant and stores the constant value. The data are recorded on magnetic tape by a cassette recorder with an RS232 input-output interface. A non-linear least-squares program based on Marquardt's modification of the Newton-Gauss method is discussed and its performance in the calculation of equilibrium constants is exemplified. An HP 9821 desk-top computer accepts the data from the magnetic tape recorder. In addition to a fully automatic fitting procedure, the program allows manual adjustment of the parameters. Three examples are discussed with regard to performance and reproducibility. PMID:18962716
Gampp, H; Maeder, M; Zuberb�hler, A D; Kaden, T A
Potentiometric surface of the Ozark aquifer in northern Arkansas, 2004
The Ozark aquifer in northern Arkansas comprises dolomites, limestones, sandstones, and shales of Late Cambrian to Middle Devonian age, and ranges in thickness from approximately 1,100 feet to more than 4,000 feet. Hydrologically, the aquifer is complex, characterized by discrete and discontinuous flow components with large variations in permeability. The potentiometric-surface map, based on 59 well and 5 spring water-level measurements collected in 2004 in Arkansas and Missouri, indicates maximum water-level altitudes of about 1,188 feet in Benton County and minimum water-level altitudes of about 116 feet in Randolph County. Regionally, the flow within the aquifer is to the south and southeast in the eastern and central part of the study area and to the northwest and north in the western part of the study area. Comparing the 2004 potentiometric- surface map with a predevelopment potentiometricsurface map indicates general agreement between the two surfaces. Potentiometric-surface differences could be attributed to differences in pumping related to changing population from 1990 to 2000, change in source for public supplies, processes or water use outside the study area, or differences in data-collection or map-construction methods.
Schrader, T. P.
On the indirect polyelectrolyte titration of cellulosic fibers. Conditions for charge stoichiometry and comparison with ESCA.
The effect of electrolyte (NaHCO3) concentration on the adsorption of poly-DADMAC (poly-diallyldimethylammonium chloride) onto cellulosic fibers with different charge profiles was investigated. Surface carboxymethylated fibers were obtained by grafting carboxymethyl cellulose (CMC) onto the fiber surface and bulk carboxymethylated fibers were obtained by reacting the fibers with monochloroacetic acid. It was shown that nonionic interactions do not exist between cellulose and poly-DADMAC, rather electrostatic interactions govern the adsorption. Charge stoichiometry prevails under electrolyte-free conditions, whereas surface charge overcompensation occurs at higher electrolyte concentrations. It was shown that charge stoichiometry prevails if the thickness of the electric double layer kappa(-1) was larger than the mean distance between the charges on the fiber surface, as predicted by polyelectrolyte adsorption theories, taking lateral correlation effects into account. In a second set of experiments the ESCA technique served to independently calibrate the polyelectrolyte titrations for determining the surface charge of cellulosic fibers. Various molecular masses of poly-DADMAC were adsorbed to carboxymethylated fibers having different charge profiles. The adsorption of low M(w) poly-DADMAC (7.0 x 10(3)), analyzed by polyelectrolyte titration, was about 10 times higher than that of the high M(w) poly-DADMAC (9.2 x 10(5)). Despite the difference in accessibility of these two polyelectrolytes to the fiber cell wall, ESCA surface analysis showed, as expected, only slight differences between the two polyelectrolytes. This gives strong credibility to the idea that surface charge content of cellulosic fibers can be analyzed by means of adsorption of a high-molecular-mass cationic polymer, i.e., by polyelectrolyte titration. PMID:16401137
Horvath, A Elisabet; Lindstr�m, Tom; Laine, Janne
Total Acid Value Titration of Hydrotreated Biomass Fast Pyrolysis Oil: Determination of Carboxylic Acids and Phenolics with Multiple End-Point Detection
Total acid value titration has long been used to estimate corrosive potential of petroleum crude oil and fuel oil products. The method commonly used for this measurement, ASTM D664, utilizes KOH in isopropanol as the titrant with potentiometric end point determination by pH sensing electrode and Ag/AgCl reference electrode with LiCl electrolyte. A natural application of the D664 method is titration of pyrolysis-derived bio-oil, which is a candidate for refinery upgrading to produce drop in fuels. Determining the total acid value of pyrolysis derived bio-oil has proven challenging and not necessarily amenable to the methodology employed for petroleum products due to the different nature of acids present. We presented an acid value titration for bio-oil products in our previous publication which also utilizes potentiometry using tetrabutylammonium hydroxide in place of KOH as the titrant and tetraethylammonium bromide in place of LiCl as the reference electrolyte to improve the detection of these types of acids. This method was shown to detect numerous end points in samples of bio-oil that were not detected by D664. These end points were attributed to carboxylic acids and phenolics based on the results of HPLC and GC-MS studies. Additional work has led to refinement of the method and it has been established that both carboxylic acids and phenolics can be determined accurately. Use of pH buffer calibration to determine half-neutralization potentials of acids in conjunction with the analysis of model compounds has allowed us to conclude that this titration method is suitable for the determination of total acid value of pyrolysis oil and can be used to differentiate and quantify weak acid species. The measurement of phenolics in bio-oil is subject to a relatively high limit of detection, which may limit the utility of titrimetric methodology for characterizing the acidic potential of pyrolysis oil and products.
Christensen, E.; Alleman, T. L.; McCormick, R. L.
A potentiometric study of the hydrolysis of ethylenediaminetetraacetic acid to 150{degrees}C
Ethylenediaminetetraacetate anions, EDTA{sup 4-}, were titrated in a hydrogen-electrode concentration cell with an acidic titrant from 0 to 150{degrees}C at 25{degrees}C intervals. These titrations were carried out in the presence of 0. 1, 0.2, and 1.0 mol{center_dot}kg{sup -1} with the supporting electrolytes, sodium chloride, NaCl, and 1.0 mol{center_dot}kg{sup -1} tetramethylammonium trifluoromethylsulfonate, (CH{sub 3}){sub 4}N(F{sub 3}CSO{sub 3}) {l_brace}TMATFMS{r_brace} in order to assess the effect of both cation complexation by EDTA{sup 4-} and anion activity coefficient variations. The resulting hydrolysis quotients are discussed with reference to applications in boiler and heat exchanger chemical cleaning, as well as chemical and nuclear waste containment. Some recent diverse uses of this emf technique that also pertain to these applications will be mentioned briefly, e.g., surface absorption - zero-point-of-charge - measurements to high temperatures and in situ pH measurements in solubility and kinetic experiments.
Palmer, D.A. [Oak Ridge National Lab., TN (United States); Nguyen-Trung, Chinh [CREGU, Vandoeuvre les Nancy (France)
The competition of complexing agents for the same metal ion and the formation of colored metal-ion complexes is demonstrated with the use of an overhead projector. This demonstration can be used to emphasize both the relevance of the relative values of formation constants in the complexation of metal cations and the applicability of complexometric titrations in quantitative chemical analysis. The demonstration is based on the traditional determination of water hardness in which EDTA is used as the titrant that complexes Mg2+ and Ca2+ ions. The color change that signals the end of the titration represents the successful removal of the Mg2+ ions from the metallochromic indicator Calmagite. This removal is possible because the value of the formation constant of the [Mg(EDTA)]2- complex is about 3 orders of magnitude greater than that corresponding to the [Mg(Calmagite)]- complex. The color change from wine-red (metal-bound indicator) to blue (unbound indicator) can be seen clearly in a large classroom with the use of overhead projection.
Yappert, M. Cecilia; Dupre, Donald B.
Factors Governing the Assembly of Cationic Phospholipid-DNA Complexes
The interaction of DNA with a novel cationic phospholipid transfection reagent, 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (EDOPC), was investigated by monitoring thermal effects, particle size, vesicle rupture, and lipid mixing. By isothermal titration calorimetry, the heat of interaction between large unilamellar EDOPC vesicles and plasmid DNA was endothermic at both physiological and low ionic strength, although the heat absorbed was slightly larger at the
Michael T. Kennedy; Edvin V. Pozharski; Vera A. Rakhmanova; Robert C. MacDonald
Manganese(III) Porphyrin-based Potentiometric Sensors for Diclofenac Assay in Pharmaceutical Preparations
Two manganese(III) porphyrins: manganese(III) tetraphenylporphyrin chloride and manganese(III)-tetrakis(3-hydroxyphenyl)porphyrin chloride were tested as ionophores for the construction of new diclofenac�selective electrodes. The electroactive material was incorporated either in PVC or a sol�gel matrix. The effect of different plasticizers and additives (anionic and cationic) on the potentiometric response was studied. The best results were obtained for the PVC membrane plasticized with dioctylphtalate and having sodium tetraphenylborate as a lipophilic anionic additive incorporated. The sensor response was linear in the concentration range 3 � 10?6 � 1 � 10?2 M with a slope of ?59.7 mV/dec diclofenac, a detection limit of 1.5 � 10?6 M and very good selectivity coefficients. It was used for the determination of diclofenac in pharmaceutical preparations, by direct potentiometry. The results were compared with those obtained by the HPLC reference method and a good agreement was found between the two methods.
Vlascici, Dana; Pruneanu, Stela; Olenic, Liliana; Pogacean, Florina; Ostafe, Vasile; Chiriac, Vlad; Pica, Elena Maria; Bolundut, Liviu Calin; Nica, Luminita; Fagadar-Cosma, Eugenia
Manganese(III) porphyrin-based potentiometric sensors for diclofenac assay in pharmaceutical preparations.
Two manganese(III) porphyrins: manganese(III) tetraphenylporphyrin chloride and manganese(III)-tetrakis(3-hydroxyphenyl)porphyrin chloride were tested as ionophores for the construction of new diclofenac-selective electrodes. The electroactive material was incorporated either in PVC or a sol-gel matrix. The effect of different plasticizers and additives (anionic and cationic) on the potentiometric response was studied. The best results were obtained for the PVC membrane plasticized with dioctylphtalate and having sodium tetraphenylborate as a lipophilic anionic additive incorporated. The sensor response was linear in the concentration range 3 � 10(-6) - 1 � 10(-2) M with a slope of -59.7 mV/dec diclofenac, a detection limit of 1.5 � 10(-6) M and very good selectivity coefficients. It was used for the determination of diclofenac in pharmaceutical preparations, by direct potentiometry. The results were compared with those obtained by the HPLC reference method and a good agreement was found between the two methods. PMID:22163384
Determination of pethidine hydrochloride using potentiometric coated graphite and carbon paste electrodes.
A new approach for lowering the detection limit of a pethidine ion-selective electrode is presented. A coated graphite (CGE) and carbon paste (CPE) electrodes for pethidine ions based on pethidine-phosphotungstate (PD-PT) as ion-pair complex are described. The sensors exhibit a Nernstian slope of 58.1 and 54.2 mVdecade(-1) for pethidine ion over a wide concentration range from 2.6 � 10(-7) to 1.0 � 10(-2) M and 2.1 � 10(-6) to 1.0 � 10(-2) M with a detection limit of 1.8 � 10(-7) M and 7.3 � 10(-7) M for pethidine coated graphite (PD-CGE) and pethidine carbon paste electrode (PD-CPE), respectively. These sensors exhibited a fast response time (about 5-8 s) and good stability. The standard electrode potentials, E(o) , were determined at different temperatures and used to calculate the isothermal temperature coefficient (dE(o) /dT) of the PD-CGE and PD-CPE, which was 0.0062 and 0.0071 V/ �C, respectively. Selectivity coefficients, determined by matched potential method (MPM) and separate solution method (SSM), showed high selectivity for pethidine hydrochloride (PDCl) over a large number of inorganic cations, organic cations, sugars, urine components, and some common drug excipients. The sensors were applied for determination of PDCl in ampoule and in spiked urine samples using potentiometric determination, standard addition and the calibration curve methods. The results obtained were satisfactory with excellent percentage recovery comparable and sometimes better than those obtained by other routine methods for the assay. PMID:21538999
Abu-Shawish, Hazem M; Dalou, Ayoub A; Ghalwa, Nasser Abu; Khraish, Ghada I; Hammad, Jehad; Basheer, Abdel-Hakem
Complexometric determination of metal ions by microscopic diffusional titration.
Acid/base titrations of pico- and femtoliter microsamples have been performed previously using a diffusional microburet (DMB) for reagent delivery in a simple droplet-heptane system (Gratzl, M.; Yi, C. Anal. Chem. 1993, 65, 2085-2088). The lowest delivery rate achieved with a DMB was about 6 fmol/s, which would correspond to about a 1 microL/year volumetric flow rate with a hypothetical equivalent mechanical delivery scheme (Yi, C.; Gratzl, M. Anal. Chem. 1994, 66, 1976-1982). In this work, the feasibility of complexometric titrations in microscopic samples is explored. Stability of pH in the microdroplets required for different determinations and the effects of DMB shank geometry on titration characteristics are also studied. Diffusional microtitrations of Fe(III), Zn(II), and Cu(II) have been performed with EDTA. Xylenol orange and Eriochrome Black T provide clear color changes at the end point of the respective titrations, despite the microscopic size of the samples (between 16 and 1570 pL, corresponding to diameters between 30 and 144 microns). Random errors of the determinations relative to full scale were 6.6% for Fe(III), 5.8% for Cu(II), and 7.9% for Zn(II). The pH required for EDTA titrations of the individual metal ions stays stable in the acidic range. This makes the microscopic titration of a number of metal ions, such as Fe(III), Fe(II), Cu(II), and Pb(II), feasible in a simple droplet-heptane system without any modification. With a higher density of strongly alkaline buffer droplets (about 100 droplets/mm2) sprayed on the bottom of the Petri dish, or by flushing N2 above the heptane, the microscopic samples can also be kept alkaline despite ambient CO2 present. In this way, Zn(II) can also be titrated in microdroplets, requiring a pH around 10. This work renders it possible to perform a variety of complexometric titrations and other chemical manipulations in microdroplets even if they need to be kept alkaline. Similar titrations in single biological cells to assess intracellular buffer capacities of different metal ions, such as Ca(II) and Mg(II), are underway. PMID:8815747
Yi, C; Huang, D; Gratzl, M
Titrated oxygen requirement and prognostication in idiopathic pulmonary fibrosis
Background The supplemental oxygen flow rate is a common bedside measure of gas exchange impairment. We aimed to determine whether a titrated oxygen requirement predicted mortality in idiopathic pulmonary fibrosis. Methods We examined 104 adults with idiopathic pulmonary fibrosis enrolled in a prospective cohort study and a validation cohort of 151 adults with a variety of interstitial lung diseases. The titrated oxygen requirement was defined as the lowest oxygen flow rate required to maintain an oxyhemoglobin saturation of 96% while standing. Cox proportional hazards models and time-dependent receiver operating characteristic curves were used to examine survival time. Results A higher titrated oxygen requirement was associated with a greater mortality rate independent of forced vital capacity and six-minute walk test results in idiopathic pulmonary fibrosis (adjusted hazard ratio per 1 L/min = 1.10, 95% confidence interval 1.01 to 1.20). The titrated oxygen requirement was at least as accurate as pulmonary function and six-minute walk testing at predicting 1-year mortality. Findings were similar in other interstitial lung diseases. Conclusion The titrated oxygen requirement is a simple, inexpensive bedside measurement that aids prognostication in idiopathic pulmonary fibrosis.
Hook, Jaime L.; Arcasoy, Selim M.; Zemmel, David; Bartels, Matthew; Kawut, Steven M.; Lederer, David J.
Two-phase titration of cerium(III) by permanganate
This paper presents a method for the two-phase titrimetric determination of cerium(III) with permanganate which does not require an expenditure of sugar and preliminary removal of chlorides and nitrates. The interaction of cerium(III) with permanganate at room temperature was studied as a function of the pH, the concentration of pyrophosphate, tetraphenylphosphonium (TPP), permanganate, and extraneous compounds, the rate of titration, and the time of stay of the solution in air before titration. The investigations were conducted according to the following methodology: water, solution of cerium(III) pyrophosphate, and TPP were introduced into an Erlenmeyer flask with a side branch near the bottom for clearer observation of the color of the chloroform phase. The authors established the given pH value, poured the water into a volume of 50 ml, and added chloroform. The result was titrated with permanganate solutions of various concentrations until a violet color appeared in the chloroform phase.
Lazarev, A.I.; Lazareva, V.I.; Gerko, V.V.
Coulometric titration of D(+)-glucose using its enzymatic oxidation.
A definitive method is described for the indirect assay of milligram quantities of D(+)-glucose by coulometric titration. D(+)-Glucose was aerobically oxidized by glucose oxidase in an acetate buffer solution (pH 5.1). Subsequently, the enzymatically formed hydrogen peroxide was titrated coulometrically with electrogenerated hypobromite in sodium bromide-sodium tetraborate medium of pH 8.6, with biamperometric end-point detection. Parameters affecting the enzymatically catalyzed oxidation and coulometric titration were evaluated. The optimized conditions for the oxidation of up to 20 mg of D(+)-glucose include the addition of 4500 U of glucose oxidase and stirring over a 10-min interval at 25 degrees C. Under proposed conditions, the assay values of several commercial D(+)-glucose reagents were somewhat lower than the guaranteed minimum values, with RSDs (n = 5) of 0.071 - 0.106%. PMID:11990540
Tanaka, T; Shutto, E; Mizoguchi, T; Fukushima, K
Preliminary map showing the potentiometric surface of the Aquia Aquifer in southern Maryland, September 1984
The potentiometric map is highlighted with indications concerning: (1) outcrop areas of the Aquia aquifer; (2) the potentiometric contour of the aquifer; (3) observation and/or supply wells yielding < 10,000 gallons/day (gpd); and (4) other supply wells with yields > 10,000 gpd. (Lantz-PTT)
Mack, Frederick K.; Wheeler, Judith C.; Curtin, Stephen E.; Andreasen, David C.
The potentiometric surface of the Magothy Aquifer in southern Maryland, September 1984
The potentiometric map is highlighted with indications concerning: (1) outcrop areas of the Magothy aquifer; (2) the potentiometric contour of the aquifer; (3) observation and/or supply wells yielding < 10,000 gallons/day (gpd); and (4) other supply wells with yields > 10,000 gpd. (Lantz-PTT)
Mack, Frederick K.; Wheeler, Judith C.; Curtin, Stephen E.
The potentiometric surface of the Magothy Aquifer in southern Maryland, September 1985
The Potentiometric Surface of the Aquia Aquifer in Southern Maryland, September 1985
Development of a monoclonal antibody based potentiometric biosensor for terbuthylazine detection
In the present paper a new potentiometric biosensor for terbuthylazine (TBA, a herbicide widely utilized in agriculture) suitable for this determination in water samples is shown. As previously described, monoclonal antibody (mAb) showing high specificity for the analyte was utilized as biological element to perform the biosensor assay. A light addressable potentiometric sensor (LAPS), measuring NH3 ions concentration in term
Lucia Mosiello; Cristina Laconi; Maddalena Del Gallo; Claudia Ercole; Aldo Lepidi
A potentiometric biosensor for d-amygdalin based on a consolidated biocomposite membrane
A new potentiometric biosensor for d-amygdalin based on a consolidated biocomposite membrane has been designed. The manufacturing technique involved a simple compression of dry components presenting an ideal technology for the mass production of potentiometric biosensor devices. The effect of high pressures applied during the preparation of a d-amygdalin biosensor membrane was studied. The immobilisation of ?-glucosidase was improved by
Arben Merko�i; Susana Braga; Esteve F�bregas; Salvador Alegret
A novel potentiometric method for the determination of real crosslinking ratio of poly(aspartic acid) gels.
In order to obtain nontoxic functional polymer gels for biomedical applications, chemically crosslinked poly(aspartic acid) gels have been prepared using 1,4-diaminobutane as crosslinker. The presence of COOH and amino groups on the network chains renders these gels pH sensitive. Due to the specific hydrophobic-hydrophilic balance, these gels show a significant volume transition at a well-defined pH close to the pK value of uncrosslinked poly(aspartic acid). Since the magnitude of volume change critically depends on the degree of crosslinking, it is an important task to determine the topological characteristics of these networks. A novel method based on potentiometric acid-base titration has been developed to assess the crosslinking ratio, excluding physical crosslinks and entanglements. It turned out that only 25% of all crosslinker molecules forms real crosslinks between the poly(aspartic acid) chains; the rest react with one of its functional groups and forms short pendant side chains. At a nominal crosslinking ratio of 0.1, the number average molecular mass between crosslinks is found to be M(c) = 2300. PMID:19761876
Torma, Vikt�ria; Gyenes, Tam�s; Szak�cs, Zolt�n; Zr�nyi, Mikl�s
Potentiometric surface of Floridan aquifer May 1975, and change of potentiometric surface 1969 to 1975, Southwest Florida Water Management District and adjacent areas
Maps showing the potentiometric surface of the Floridan aquifer for May 1975, and changes of potentiometric surface from 1964 to 1975 were prepared for areas in southwest Florida. Contours and color codes describe water-level changes. The larger map, scale 1:500,000, reflects the water-level changes from 1969-75. The smaller map shows the changes from January 1964 to May 1969. (Woodard-USGS)
Mills, L. R.; Laughlin, C. P.
Generalized theory for two-phase ion-pair and complexometric titrations. I. Two-phase titrations without side reactions.
A systematic theoretical treatment of the two-phase titration based on ion-pair and metal-complex formation is presented. Equations for the titration curve, accuracy, equivalence point and choice of the indicator are derived. Much attention is paid to the parameters determining the 'titratability' viz. extraction constant, distribution constant, phase volume ratio and the concentration of the analyte. Special attention is given to the role of intermediate ion-pair and metal-complex formation in the aqueous phase. The ion-pair formation in aqueous solution is examined closer by means of the relationship between the association constant in water, the degree of dissociation of the ion pair (alpha) and the concentration of the counter ion. The merits of this theoretical treatment are illustrated with literature examples. PMID:4080511
Elucidation of ionic interactions in the protic ionic liquid solutions by isothermal titration calorimetry.
The strong hydrogen-bonded network noted in protic ionic liquids (PILs) may lead to stronger interactions of the ionic entities of PILs with solvents (water, methanol, ethylene glycol, dimethylsulfoxide (DMSO), N,N'-dimethylformamide (DMF)) as compared with those of aprotic ionic liquids (APILs). The PILs used in this work are 1-methylimidazolium tetrafluoroborate, 2-methylpyridinium tetrafluoroborate, and N-methylpyrrolodinium tetrafluoroborate in comparison to 1-butyl-3-methylimidazolium tetrafluoroborate, which is classified as an APIL. In this work, the excess partial molar enthalpy, H(E)IL obtained from isothermal calorimetric titrations at 298.15 K is used to probe the nature of interactions of the PIL cations with solvent molecules against those present in APIL-solvent systems. This work also reports interesting flip-flopping in the thermal behavior of these PIL-solvent systems depending upon the structure of the cationic ring of a PIL. In some cases, these flip-flops are the specific fingerprints for specific PILs in a common solvent environment. The excess partial molar enthalpy at infinite dilution, H(E,?)IL, of these PILs bears a critical dependence on the solvent properties. An analysis of relative apparent molar enthalpies, ?L, of the PIL solutions by the ion interaction model of Pitzer yields important information on ionic interactions of these systems. PMID:24650134
Rai, Gitanjali; Kumar, Anil
PbO2-based graphite-epoxy electrode for potentiometric determination of acids and bases in aqueous and aqueous-ethanolic media.
The construction and analytical evaluation of a PbO2-based graphite-epoxy electrode sensitive to H3O+, based on incorporation of lead(IV) oxide in a graphite-epoxy matrix, are described. The data obtained from a variety of acid-base titrations in aqueous and aqueous-ethanolic media were compared with those obtained by use of a glass electrode under the same conditions. The proposed electrode provides a linear response in the pH range from 1 to 11 with a slope of -58.7+/-0.3 mV pH(-1) and -60.8+/-0.2 mV pH(-1) in aqueous and ethanolic media, respectively. The response time was less than 15 s and the lifetime of the electrode was at least eight months (ca. 5000 determinations) and its performance is good in pH determination and end-point detection in potentiometric acid-base titrations in both aqueous and aqueous-ethanolic media. PMID:11495060
Teixeira, M F; Ramos, L A; Fatibello-Filho, O; Cavalheiro, E T
Direct measurement of protein binding energetics by isothermal titration calorimetry
Of all the techniques that are currently available to measure binding, isothermal titration calorimetry is the only one capable of measuring not only the magnitude of the binding affinity but also the magnitude of the two thermodynamic terms that define the binding affinity: the enthalpy (?H) and entropy (?S) changes. Recent advances in instrumentation have facilitated the development of experimental
Stephanie Leavitt; Ernesto Freire
Using Spreadsheets to Produce Acid-Base Titration Curves.
Describes two spreadsheets for producing acid-base titration curves, one uses relatively simple cell formulae that can be written into the spreadsheet by inexperienced students and the second uses more complex formulae that are best written by the teacher. (JRH)
Cawley, Martin James; Parkinson, John
A method is described for the successive coulometric complexometric titration of microgram levels of light and heavy rare earth elements. The total amount of light and heavy rare earth elements is titrated by electrogenerating titrant EDTA on the mercury pool as a cathode. Then, the mercury pool is switched as an anode, electrogenerating Hg/sup 2 +/, and is used to titrate EDTA which is displaced from its light rare earth elements complex by malic acid that has been added prior to the electrogenerating Hg/sup 2 +/. The heavy rare earth elements can be determined from the total rare earth elements minus the result of displacement titration of EDTA which is equivalent to the light rare earth elements. A 10-30 ..mu..g sample of light and heavy rare earth elements (Pr and Yb, La and Lu, Nd and Tm) can be determined successively. Errors and standard deviation are not more than 2.5% and 0.20, respectively. 2 tables, 5 figures.
Chun-Nian, S.; Jing-Ci, L.; Qi-Dao, N.; Mou-Sen, C.
Direct complexometric titration of thorium with versene using SPADNS
The existing volumetric methods for the determination of thorium are indirect and unsatisfactory. A direct titrimetric method for the estimation of thorium has been developed which involves the adjustment ofph, addition of 1 ml. of 0.02% SPADNS indicator, dilution to volume and titration with versene. It is based on the fact that thorium forms a coloured complex with SPADNS and
Gurupada Banerjee
Thermometric Titration Analysis of Seawater for Chlorinity, Sulfate, and Alkalinity.
Total sulfate, chlorinity, and total alkalinity in seawater solutions have been determined by thermometric titration. The precision of the analyses was 0.3% for sulfate, 0.04% for chlorinity, and 0.1% for total alkalinity. Because of their simplicity, spe...
F. J. Millero, S. R. Schrager, L. D. Hansen
Constant-Current Coulometric Titration of Hydrochloric Acid
The titration of a strong acid with a strong base and the electrolysis of water are two classic laboratory exercises that are either performed or demonstrated in secondary school classrooms in order to introduce two important areas of chemsitry: acid-base chemistry and electrochemistry. In this experiment we have combined these two classical experiments into one complete laboratory experience. Here we
James Swim; Edward Earps; Laura M. Reed; David Paul
A new potentiometric sensor for the determination of ?-amylase activity.
A platinum redox sensor for the direct potentiometric determination of ?-amylase concentration has been described. The sensor measured the amount of triiodide released from a starch-triiodide complex, which was correlated with the ?-amylase activity after biocatalytic starch degradation. The composition and stability of the potassium triiodide solution was optimized. The starch-triiodide complex was characterized potentiometrically at variable starch and triiodide concentrations. The response mechanism of the platinum redox sensor towards ?-amylase was proposed and the appropriate theoretical model was elaborated. The results obtained using the redox sensor exhibited satisfactory accuracy and precision and good agreement with a standard spectrophotometric method and high-sensitive fully automated descret analyser method. The sensor was tested on pure ?-amylase (EC 22.214.171.124, Fluka, Switzerland), industrial granulated ?-amylase Duramyl 120 T and an industrial cogranulate of protease and ?-amylase Everlase/Duramyl 8.0 T/60 T. The detection limit was found to be 1.944 mU for ?-amylase in the range of 0-0.54 U (0-15 ?g), 0.030 mKNU for Duramyl 120 T in the range of 0-9.6 mKNU (0-80 ?g) and 0.032 mKNU for Everlase/Duramyl 8.0 T/60 T in the range of 0-9.24 mKNU (0-140 ?g). PMID:21238759
Sakac, Nikola; Sak-Bosnar, Milan; Horvat, Marija; Maduni?-Caci?, Dubravka; Szechenyi, Aleksandar; Kovacs, Barna
A surface complex reaction model for the pH-dependence of corundum and kaolinite dissolution rates
Comparison of experimental and theoretical potentiometric titrations of kaolinite at 25�C indicates that the adsorption of H + and OH - ions to the mineral surface are metal cation specific and that the net adsorption can be modeled in terms of the constituent oxide components. We conclude, from the potentiometric, electrophoretic, and dissolution rate data presented in this paper, that
Susan A. Carroll-Webb; John V. Walther
Potentiometric surface of the Aquia Aquifer in southern Maryland during the fall of 1987
A map showing the potentiometric surface of the Aquia aquifer in the Paleocene Aquia Formation in southern Maryland during the fall of 1987 was prepared by using water level measurements from 80 observation wells. The potentiometric surface was above sea level near the northeastern boundary and outcrop area of the aquifer in topographically high areas of Anne Arundel and Prince Georges Counties. The potentiometric surface was below sea level in the remainder of the study area. The hydraulic gradient was generally to the southeast toward an extensive cone of depression, which is centered around well fields near Lexington Park. Much of the cone is more than 40 ft below sea level. (USGS)
Mack, Frederick K.; Andreasen, David C.; Curtin, Stephen E.; Wheeler, Judith C.
Potentiometric surface of the Floridan Aquifer, Southwest Florida Water Management District, September 1979
A September 1979 potentiometric-surface map of the Southwest Florida Water Management District depicts the annual high water-level period. Potentiometric levels increased 1 to 20 feet between May 1979 and September 1979, in the citrus and farming sections of southern Hillsborough, northern Hardee, southwestern Polk, northwestern DeSoto, and Manatee Counties. Water levels in these areas are widely affected by pumping for irrigation and have the greatest range in fluctuations. Water-level increases ranged from 0 to 7 feet in coastal, northern, and southern areas of the Water Management District. Generally, potentiometric levels were higher than previous September levels due to heavy rains in August and September. (USGS)
Yobbi, D. K.; Woodham, W. M.; Laughlin, Charles P.
The cation-? interaction.
The chemistry community now recognizes the cation-? interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author's perspective on the intellectual origins and fundamental nature of the cation-? interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with ? systems. Important gas phase studies established the fundamental nature of the cation-? interaction. The strength of the cation-? interaction (Li(+) binds to benzene with 38 kcal/mol of binding energy; NH4(+) with 19 kcal/mol) distinguishes it from the weaker polar-? interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-? interaction in gas phase studies, the cation-? interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-? interactions can enhance binding energies by 2-5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-? interaction includes a substantial electrostatic component. The six (four) C(?-)-H(?+) bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the ? system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li(+) > Na(+) > K(+) > Rb(+): as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane is more polarizable than benzene but a decidedly poorer cation binder. Many studies have documented cation-? interactions in protein structures, where lysine or arginine side chains interact with phenylalanine, tyrosine, or tryptophan. In addition, countless studies have established the importance of the cation-? interaction in a range of biological processes. Our work has focused on molecular neurobiology, and we have shown that neurotransmitters generally use a cation-? interaction to bind to their receptors. We have also shown that many drug-receptor interactions involve cation-? interactions. A cation-? interaction plays a critical role in the binding of nicotine to ACh receptors in the brain, an especially significant case. Other researchers have established important cation-? interactions in the recognition of the "histone code," in terpene biosynthesis, in chemical catalysis, and in many other systems. PMID:23214924
Dougherty, Dennis A
Determination of stoichiometry of Li 1+ y CoO 2 materials by flame atomic absorption spectrometry and automated potentiometric titration
A rapid, accurate and precise analytical method to determine the stoichiometry of pure, excess lithium and magnesium-doped Li1+yCoO2 materials is described. The method is based on the determination of lithium, cobalt and magnesium by flame atomic absorption spectrometry after dissolution of samples in dilute hydrochloric acid. Five-point calibration curves using aqueous standard solutions have been constructed for all the analytes.
Silvera Scaccia; Maria Carewska
Characterization of molecular interactions using isothermal titration calorimetry.
Isothermal titration calorimetry (ITC) is based on a simple titration of one ligand with another and the small heat changes caused by the molecular interaction are detected. From one ITC experiment the complete set of thermodynamic parameters of binding including association and dissociation constants as well as changes in enthalpy, entropy, and free energy can be derived. Using this technique almost any type of molecular interaction can be analyzed. Both ligands are in solution, and there is no need for their chemical derivatization. There are no limits as to the choice of the analysis buffer, and the analysis temperature can be set between 4 and 80 �C. This technique has been primarily applied to study the interaction between various proteins of Pseudomonas with small molecule ligands. In addition, ITC has been used to study the binding of Pseudomonas proteins to target DNA fragments. PMID:24818906
Krell, Tino; Lacal, Jes�s; Garc�a-Fontana, Cristina; Silva-Jim�nez, Hortencia; Rico-Jim�nez, Miriam; Lugo, Andr�s Corral; Darias, Jos� Antonio Reyes; Ramos, Juan-Luis
SBR on-line monitoring by set-point titration.
The applicability of set-point titration for monitoring biological processes has been widely demonstrated in the literature. Based on published and on-going experiences, some operating procedures have been specifically developed to be applied to SBRs, so that real-time information about the process and/or the influent can be obtained. This, in turn, would allow plant operators to select the most appropriate actions properly and timely. Five operating modes are described for the monitoring of (1) influent toxicity, (2) influent N-content, (3) nitrification capacity, (4) end of the nitrification reaction, and (5) nitrate effluent concentration, and are currently tested on the on-line titrator TITAAN (TITrimetric Automated ANalyser) which is in operation on a pilot scale SBR. PMID:16722107
Fiocchi, N; Ficara, E; Canziani, R; Luccarini, L; Ciappelloni, F; Ratini, P; Pirani, M; Mariani, S
Retention of Cationic Starch onto Cellulose Fibres
Three methods of cationic starch titration were used to quantify its retention on cellulose fibres, namely: (i) the complexation of CS with iodine and measurement of the absorbency of the ensuing blue solution by UV-vis spectroscopy; (ii) hydrolysis of the starch macromolecules followed by the conversion of the resulting sugars to furan-based molecules and quantifying the ensuing mixture by measuring their absorbance at a ? of 490 nm, using the same technique as previous one and; finally (iii) hydrolysis of starch macromolecules by trifluoro-acetic acid and quantification of the sugars in the resulting hydrolysates by high performance liquid chromatography. The three methods were found to give similar results within the range of CS addition from 0 to 50 mg per g of cellulose fibres.
Missaoui, Mohamed; Mauret, Evelyne; Belgacem, Mohamed Naceur
Role of titratable acidity in acid aerosol-induced bronchoconstriction
We evaluated the importance of pH, titratable acidity, and specific chemical composition in acid aerosol-induced bronchoconstriction in 8 asthmatic subjects. We administered aerosols of HCl and H/sub 2/SO/sub 4/ at pH 2.0 in an unbuffered state and buffered with glycine. The buffered acids were given in order of increasing titratable acidity (defined as the number of ml of 1 N NaOH required to neutralize 100 ml of acid solution to pH 7.0). Each set of buffered or unbuffered acid aerosols was given on a separate day and each aerosol was inhaled through a mouthpiece during 3 min of tidal breathing. Bronchoconstriction was assessed by measurement of specific airway resistance (SRaw) before and after inhalation of each aerosol. SRaw increased by more than 50% above baseline in 1 of 8 subjects after inhalation of unbuffered HCl and in no subjects after inhalation of unbuffered H/sub 2/SO/sub 4/, even at pH 2.0. In contrast, SRaw increased by greater than 50% in all 8 subjects after inhalation of HCl and glycine at pH 2.0 and 7 of 8 subjects after inhalation of H/sub 2/SO/sub 4/ and glycine at pH 2.0. The mean titratable acidity required to increase SRaw by 50% above baseline was calculated for each challenge by linear interpolation; these values for H/sub 2/SO/sub 4/ and glycine (5.1 ml of 1 N NaOH) and HCl and glycine (2.2 ml of 1 N NaOH) were slightly, but significantly, different (p = 0.01) and were considerably higher than the titratable acidity of the unbuffered acids at pH 2 (1.0 ml of 1 N NaOH).
Fine, J.M.; Gordon, T.; Thompson, J.E.; Sheppard, D.
Determination of berkelium by the method of spectrophotometric titration
The method that the authors propose consists of the following: berkelium is oxidized electrochemically, spectrophotometric titration of berkelium(IV) by a solution of the reducing agent is performed, and the amount of berkelium(IV) is determined according to the volume of the titrant, and considering the degree of oxidation of berkelium(III) to berkelium(IV), the total berkelium content in the sample is also
L. M. Frolova; V. M. Vityutnev; V. M. Vasilev
Suspension culture titration: A simple method for measuring baculovirus titers.
The baculovirus-insect cell expression system is an important technology for the production of recombinant proteins and baculovirus-based biopesticides. Budded virus titration is critical when scaling up baculovirus production processes in suspension cultures, to ensure reproducible infections, especially when a low multiplicity of infection (MOI) is applied. In this study, a simple suspension culture titration (SCT) assay was developed that involves accurate measurements of the initial cell densities (ICDs) and peak cell densities (PCDs) of an infected culture, from which the MOI and hence the virus inoculum infectious titer can be estimated, using the established Power-Nielsen baculovirus infection model. The SCT assay was assessed in parallel with two adherent culture-based assays (MTT and AlamarBlue) for the Heliothine baculovirus HaSNPV, and was shown to be more objective, time-efficient and reproducible. The model predicted a linear correlation between log(PCD/ICD) and log(MOI), hence an alternative model-independent SCT assay was also developed, which relies on a well-replicated standard curve relating suspension culture-derived PCD/ICD ratios with plaque or endpoint assay-derived MOIs. Standard curves with excellent linearity were generated for HaSNPV and the industrially significant rAcMNPV, demonstrating the feasibility of this simple titration approach, especially in terms of its applicability to a wide range of virus infection kinetics. PMID:22561639
Matindoost, Leila; Chan, Leslie C L; Qi, Ying Mei; Nielsen, Lars K; Reid, Steven
Generalized theory for two-phase ion-pair and complexometric titrations
For the two-phase titration based on ion-pair and metal-complex formation full attention is given to side reactions in both phases. Their significance for the applicability of this type of titration is evaluated. Side reactions in the aqueous phase diminish and in the organic phase promote the �titratability�. Equations for the calculation of the side reaction coefficients, the titration curve and
Revised potentiometric-surface map, Yucca Mountain and vicinity, Nevada
The revised potentiometric-surface map presented in this report updates earlier maps of the Yucca Mountain area using mainly 1988 average water levels. Because of refinements in the corrections to the water-level measurements, these water levels have increased accuracy and precision over older values. The small-gradient area to the southeast of Yucca Mountain is contoured with a 0.25-meter interval and ranges in water-level altitude from 728.5 to 731.0 meters. Other areas with different water levels, to the north and west of Yucca Mountain, are illustrated with shaded patterns. The potentiometric surface can be divided into three regions: 1) A small-gradient area to the southeast of Yucca Mountain, which may be explained by flow through high-transmissivity rocks or low ground-water flux through the area; 2) A moderate-gradient area, on the western side of Yucca Mountain, where the water-level altitude ranges from 775 to 780 meters, and appears to be impeded by the Solitario Canyon Fault and a splay of that fault; and 3) A large-gradient area, to the north-northeast of Yucca Mountain, where water level altitude ranges from 738 to 1,035 meters, possibly as a result of a semi-perched groundwater system. Water levels from wells at Yucca Mountain were examined for yearly trends (1986-89) using linear least-squares regression. Data from five wells exhibited trends which were statistically significant, but some of those may be a result of slow equilibration of the water level from drilling in less permeable rocks. Adjustments for temperature and density changes in the deep wells with long fluid columns were attempted, but some of the adjusted data did not fit the surrounding data and, thus, were not used.
Ervin, E. M.; Luckey, R. R.; Burkhardt, D. J.
Potentiometric map of the Coffee Sand Aquifer in northeastern Mississippi, October and November 1978
This potentiometric map of the Coffee Sand aquifer in northeastern Mississippi is the fourth in a series of maps, prepared by the U.S. Geological Survey in cooperation with the Mississippi Department of Natural Resources, Bureau of Land and Water Resources, delineating the potentiometric surfaces of the major aquifers in Mississippi. In the outcrop areas the potentiometric surface is strongly affected by recharge from precipitation, topography, and drainage of the aquifer by streams. The potentiometric surface slopes generally to the west away from the area of outcrop and is mildly affected by moderate ground-water withdrawals by wells in Tippah and Union County. Historically, water levels in or near the outcrop of the Coffee Sand have shown little or no long-term changes as shown by a hydrograph of one well in Alcorn County. In the downdip part of the aquifer water-level declines of 2 feet per year are common. (USGS)
Wasson, B. E.
Potentiometric surface of Floridan Aquifer, Southwest Florida Water Management District and adjacent areas, May 1979
A May 1979 potentiometric-surface map depicts the annual low water-level period. Potentiometric levels declined 4 to 21 feet between September 1978 and May 1979, in the citrus and farming sections of southern Hillsborough, northern Hardee, southwestern Polk, northwestern DeSoto, and Manatee Counties. Water levels in these areas are widely affected by pumping for irrigation and have the greatest range in fluctuations. Water-level declines ranged from 0 to 6 feet in coastal, northern, and southern areas of the Water Management District. Generally potentiometric levels were higher than previous May levels due to heavy rains in April and May. In parts of Hillsborough, Pasco, and Pinellas Counties, May 1979 potentiometric levels were 18 feet higher than those of September 1978. (USGS)
Wolansky, R. M.; Mills, L. R.; Woodham, W. M.; Laughlin, C. P.
Potentiometric Determination of the Tungsten Content of Tantalum--Tungsten Alloys with Chromium II.
A method was developed for the potentiometric determination of the tungsten content of tantalum-tungsten alloys of different compositions. These were dissolved under conditions that enabled the tungsten content to be determined with chromium (II). Phospho...
Z. Gavra S. Ronen R. Levin
Potentiometric-Level Monitoring Program, Mississippi and Louisiana: Annual Status Report for Fiscal Year 1985.
Potentiometric-level data presented in this report were collected at 82 wells in Mississippi and Louisiana from October 1984 through September 1985. These wells are located near Richton and Cypress Creek Domes in Mississippi and Vacherie dome in Louisiana...
Colloid Titration--A Rapid Method for the Determination of Charged Colloid.
"Colloid titration" is a volumetric method for determining charged polyelectrolytes in aqueous solutions. The principle of colloid titration, reagents used in the procedure, methods of endpoint detection, preparation of reagent solutions, general procedure used, results obtained, and pH profile of colloid titration are considered. (JN)
Ueno, Keihei; Kina, Ken'yu
The Acid-Base Titration of a Very Weak Acid: Boric Acid
A laboratory experiment based on the titration of boric acid with strong base in the presence of d-mannitol is described. Boric acid is a very weak acid and direct titration with NaOH is not possible. An auxiliary reagent that contributes to the release of protons in a known stoichiometry facilitates the acid-base titration. Students obtain the�
Celeste, M.; Azevedo, C.; Cavaleiro, Ana M. V.
Preliminary investigations on a glucose biosensor based on the potentiometric principle
In this study, an electron mediator and a simple immobilization process are adopted to fabricate a potentiometric glucose biosensor. The enzyme and the electron mediator are immobilized on the surface of tin oxide (SnO2)\\/indium tin oxide (ITO) glass using a covalent bond method to develop a disposable potentiometric glucose biosensor. The SnO2\\/ITO glass is a pH sensor fabricated by depositing
Cheng-Wei Liao; Jung-Chuan Chou; Tai-Ping Sun; Shen-Kan Hsiung; Jui-Hsiang Hsieh
Potentiometric urea biosensor based on immobilization of urease onto molecularly imprinted TiO 2 film
A novel potentiometric urea biosensor has been developed for selective and quantitative recognition of urea by immobilizing urease onto Ti\\/urease-imprinted TiO2 film and monitoring the potentiometric response caused by the immobilized urease\\/urea reaction system. Urease immobilization on TiO2 film was investigated using a potentiometer, and factors affecting its immobilization such as concentration of urease, pH and ionic strength were discussed
Xin Chen; Zhengpeng Yang; Shihui Si
Binding of Polycarboxylic Acids to Cationic Mixed Micelles: Effects of Polymer Counterion Binding and Polyion Charge Distribution
Mixed micelles of cetyltrimethylammonium chloride (CTAC) and n-dodecyl hexaoxyethylene glycol monoether (C12E8) bind to polyanions when the mole fraction of the cationic surfactant exceeds a critical value (Yc).Yccorresponds to a critical micelle surface charge density at which polyelectrolyte will bind to this colloidal particle. Turbidimetric titrations were used to determineYcfor such cationic-nonionic micelles in the presence of acrylic acid and
K. Yoshida; S. Sokhakian; P. L. Dubin
Comparative study of ZnO nanorods and thin films for chemical and biosensing applications and the development of ZnO nanorods based potentiometric strontium ion sensor
In this study, the comparative study of ZnO nanorods and ZnO thin films were performed regarding the chemical and biosensing properties and also ZnO nanorods based strontium ion sensor is proposed. ZnO nanorods were grown on gold coated glass substrates by the hydrothermal growth method and the ZnO thin films were deposited by electro deposition technique. ZnO nanorods and thin films were characterised by field emission electron microscopy [FESEM] and X-ray diffraction [XRD] techniques and this study has shown that the grown nanostructures are highly dense, uniform and exhibited good crystal quality. Moreover, transmission electron microscopy [TEM] was used to investigate the quality of ZnO thin film and we observed that ZnO thin film was comprised of nano clusters. ZnO nanorods and thin films were functionalised with selective strontium ionophore salicylaldehyde thiosemicarbazone [ST] membrane, galactose oxidase, and lactate oxidase for the detection of strontium ion, galactose and L-lactic acid, respectively. The electrochemical response of both ZnO nanorods and thin films sensor devices was measured by using the potentiometric method. The strontium ion sensor has exhibited good characteristics with a sensitivity of 28.65 � 0.52 mV/decade, for a wide range of concentrations from 1.00 � 10-6 to 5.00 � 10-2 M, selectivity, reproducibility, stability and fast response time of 10.00 s. The proposed strontium ion sensor was used as indicator electrode in the potentiometric titration of strontium ion versus ethylenediamine tetra acetic acid [EDTA]. This comparative study has shown that ZnO nanorods possessed better performance with high sensitivity and low limit of detection due to high surface area to volume ratio as compared to the flat surface of ZnO thin films.
Khun, K.; Ibupoto, Z. H.; Chey, C. O.; Lu, Jun.; Nur, O.; Willander, M.
Potentiometric and Relaxometric Properties of a Gadolinium-based MRI Contrast Agent for Sensing Tissue pH
The pH sensitive contrast agent, GdDOTA-4AmP (Gd1) has been successfully used to map tissue pH by MRI. Further studies now demonstrate that two distinct chemical forms of the complex can be prepared depending upon the pH at which Gd3+ is mixed with ligand 1. The desired pH sensitive form of this complex, referred to here as a Type II complex, is obtained as the exclusive product only when the complexation reaction is performed above pH 8. At lower pH values, a second complex is formed that, by analogy with an intermediate formed during preparation of GdDOTA, we tentatively assign this to a Type I complex where the Gd3+ is coordinated only by the appended side-chain arms of 1. The proportion of Type I complex formed is largely determined by the pH of the complexation reaction. The magnitude of pH dependent change in relaxivity of Gd1 was found to be less than earlier reported (S. Zhang, K. Wu, and A. D. Sherry, Angew. Chem., Int. Ed., 1999, 38, 3192), likely due to contamination of the earlier sample by an unknown amount of Type I complex. Examination of the NMRD and relaxivity temperature profiles, coupled with information from potentiometric titrations, shows that the amphoteric character of the phosphonate side-chains enables rapid prototropic exchange between the single bound water of the complex with those of the bulk water thereby giving Gd1 a unique pH dependent relaxivity that is quite useful for pH mapping of tissues by MRI.
Kalman, Ferenc K.; Woods, Mark; Caravan, Peter; Jurek, Paul; Spiller, Marga; Tircso, Gyula; Kiraly, Robert; Brucher, Erno; Sherry, A. Dean
Applications of Isothermal Titration Calorimetry in RNA Biochemistry and Biophysics
Isothermal titration calorimetry (ITC) has been applied to the study of proteins for many years. Its use in the biophysical analysis of RNAs has lagged significantly behind its use in protein biochemistry, however, in part because of the relatively large samples required. As the instrumentation has become more sensitive, the ability to obtain high quality data on RNA folding and RNA ligand interactions has improved dramatically. This review provides an overview of the ITC experiment and describes recent work on RNA systems that have taken advantage of its versatility for the study of small molecule binding, protein binding, and the analysis of RNA folding.
Feig, Andrew L.
Monitoring assembly of ribonucleoprotein complexes by isothermal titration calorimetry
Isothermal titration calorimetry (ITC) is a useful technique to study RNA-protein interactions, as it provides the only method by which the thermodynamic parameters of free energy, enthalpy, and entropy can be directly determined. This chapter presents a general procedure for studying RNA-protein interactions using ITC, and gives specific examples for monitoring the binding of Caenorhabditis elegans GLD-1 STAR domain to TGE RNA and the binding of Aquifex aeolicus S6:S18 ribosomal protein heterodimer to an S15-rRNA complex.
Recht, Michael I.; Ryder, Sean P.; Williamson, James R.
Potentiometric Surface of the Upper Floridan Aquifer in the St. Johns River Water Management District and Vicinity, Florida, September 2007
This map depicts the potentiometric surface of the Upper Floridan aquifer in the St. Johns River Water Management District and vicinity for September 2007. Potentiometric contours are based on water-level measurements collected at 554 wells during the period September 15-27, near the end of the wet season. Some contours are inferred from previous potentiometric-surface maps with larger well networks. The potentiometric surface of the carbonate Upper Floridan aquifer responds mainly to rainfall, and more locally, to ground-water withdrawals and spring flow. Potentiometric-surface highs generally correspond to topographic highs where the aquifer is recharged. Springs and areas of diffuse upward leakage naturally discharge water from the aquifer and are most prevalent along the St. Johns River. Areas of discharge are reflected by depressions in the potentiometric surface. Ground-water withdrawals locally have lowered the potentiometric surface. Ground water in the Upper Floridan aquifer generally flows from potentiometric highs to potentiometric lows in a direction perpendicular to the contours.
Kinnaman, Sandra L.; Dixon, Joann F.
Potentiometric Surface of the Upper Floridan Aquifer in the St. Johns River Water Management District and Vicinity, Florida, May 2007
Introduction This map depicts the potentiometric surface of the Upper Floridan aquifer in the St. Johns River Water Management District and vicinity for May 2007. Potentiometric contours are based on water-level measurements collected at 566 wells during the period May 4-June 11 near the end of the dry season, however most of the water level data for this map were collected by the U.S. Geological Survey during the period May 21-25, 2007. Some contours are inferred from previous potentiometric-surface maps with larger well networks. The potentiometric surface of the carbonate Upper Floridan aquifer responds mainly to rainfall, and more locally, to ground-water withdrawals and spring flow. Potentiometric-surface highs generally correspond to topographic highs where the aquifer is recharged. Springs and areas of diffuse upward leakage naturally discharge water from the aquifer and are most prevalent along the St. Johns River. Areas of discharge are reflected by depressions in the potentiometric surface. Ground-water withdrawals locally have lowered the potentiometric surface. Ground water in the Upper Floridan aquifer generally flows from potentiometric highs to potentiometric lows in a direction perpendicular to the contours.
Potentiometric surface of the Upper Floridan aquifer in the St. Johns River water management district and vicinity, Florida, September 2005
This map depicts the potentiometric surface of the Upper Floridan aquifer in the St. Johns River Water Management District and vicinity for September 2005. Potentiometric contours are based on water-level measurements collected at 643 wells during the period September 12-28, near the end of the wet season. Some contours are inferred from previous potentiometric-surface maps with larger well networks. The potentiometric surface of the carbonate Upper Floridan aquifer responds mainly to rainfall, and more locally, to ground-water withdrawals and springflow. Potentiometric-surface highs generally correspond to topographic highs where the aquifer is recharged. Springs and areas of diffuse upward leakage naturally discharge water from the aquifer and are most prevalent along the St. Johns River. Areas of discharge are reflected by depressions in the potentiometric surface. Ground-water withdrawals locally have lowered the potentiometric surface. Ground water in the Upper Floridan aquifer generally flows from potentiometric highs to potentiometric lows in a direction perpendicular to the contours.
Kinnaman, Sandra L.
Sorption and desorption of quaternary amine cations on clays
The authors have studied the sorption and desorption of three quaternary amines, namely, nonyltrimethylammonium, dodecyltrimethylammonium, and hexadecyltrimethylammonium, on homoionic Na- and K-montmorillonite using a titration procedure. More than 99% of all three of the quaternary amine cations studied were sorbed on the montmorillonite when the added amines were less than 70% of the cation-exchange capacity of the montmorillonite. Sorption of quaternary amine cations involves at least two types of reactions, namely, an exchange reaction and the adsorption of amines at nonexchangeable sites. The exchange reaction proceeded almost to completion when Na[sup +] was the exchangeable cation. Exchangeable K[sup +] was much more difficult to replace. The adsorbed quaternary amine cations were not easily desorbed in the presence of 0.1 M NaCl and KCl solutions. In addition, desorption of quaternary amines did not increase with prolonged equilibrium time, up to 180 days. Therefore, it appears that there is good promise in using quaternary amine-modified clays as effective sorbents for removing organic pollutants or mitigating their mobilities in the environment. 26 refs., 5 figs., 6 tabs.
Zhang, Z.Z.; Sparks, D.L. (Univ. of Delaware, Newark, DE (United States)); Scrivner, N.C. (DuPont Engineering, Newark, DE (United States))
A study of statistical error in isothermal titration calorimetry.
In isothermal titration calorimetry (ITC), the two main sources of random (statistical) error are associated with the extraction of the heat q from the measured temperature changes and with the delivery of metered volumes of titrant. The former leads to uncertainty that is approximately constant and the latter to uncertainty that is proportional to q. The role of these errors in the analysis of ITC data by nonlinear least squares is examined for the case of 1:1 binding, M+X right arrow over left arrow MX. The standard errors in the key parameters-the equilibrium constant Ko and the enthalpy DeltaHo-are assessed from the variance-covariance matrix computed for exactly fitting data. Monte Carlo calculations confirm that these "exact" estimates will normally suffice and show further that neglect of weights in the nonlinear fitting can result in significant loss of efficiency. The effects of the titrant volume error are strongly dependent on assumptions about the nature of this error: If it is random in the integral volume instead of the differential volume, correlated least-squares is required for proper analysis, and the parameter standard errors decrease with increasing number of titration steps rather than increase. PMID:12963058
Tellinghuisen, Joel
Common Standards of Basal Insulin Titration in T2DM
Type 2 diabetes mellitus has become a worldwide major health problem, and the number of people affected is steadily increasing. Thus, not all patients suffering from the disease can be treated by specialized diabetes centers or outpatient clinics, but by primary care physicians. The latter, however, might have time constraints and have to deal with many kinds of diseases or with multimorbid patients, so their focus is not so much on lowering high blood glucose values. Thus, the physicians, as well as the patients themselves, are often reluctant to initiate and adjust insulin therapy, although basal insulin therapy is considered the appropriate strategy after oral antidiabetic drug failure, according to the latest international guidelines. A substantial number of clinical studies have shown that insulin initiation and optimization can be managed successfully by using titration algorithms�even in cases where patients themselves are the drivers of insulin titration. Nevertheless, tools and strategies are needed to facilitate this process in the daily life of both primary health care professionals and patients with diabetes.
Arnolds, Sabine; Heise, Tim; Flacke, Frank; Sieber, Jochen
The method that the authors propose consists of the following: berkelium is oxidized electrochemically, spectrophotometric titration of berkelium(IV) by a solution of the reducing agent is performed, and the amount of berkelium(IV) is determined according to the volume of the titrant, and considering the degree of oxidation of berkelium(III) to berkelium(IV), the total berkelium content in the sample is also determined. In this case the necessity for preliminary determination of the molar extinction coefficient of berkelium(IV) under the experimental conditions falls away. Moreover, the radiometric method of determining the berkelium content is not used. Successful titration requires selection of a reagent which, on the one hand, would rapidly reduce berkelium(VI), but on the other hand, neither itself nor the reaction products would interfere with the measurement of the optical density of berkelium(IV). As is well known, berkelium(IV) is quantitatively and rapidly reduced by hydrogen peroxide (10, 11), hydroxylamine (11), and nitrous acid (9). After preliminary experiments, they selected hydrogen peroxide and sodium nitrite as the titrants.
Frolova, L.M.; Vityutnev, V.M.; Vasil'ev, V.M.
In silico concurrent multisite pH titration in proteins.
The concurrent proton binding at multiple sites in macromolecules such as proteins and nucleic acids is an important yet challenging problem in biochemistry. We develop an efficient generalized Hamiltonian approach to attack this issue. Based on the previously developed generalized-ensemble methods, an effective potential energy is constructed which combines the contributions of all (relevant) protonation states of the molecule. The effective potential preserves important phase regions of all states and, thus, allows efficient sampling of these regions in one simulation. The need for intermediate states in alchemical free energy simulations is greatly reduced. Free energy differences between different protonation states can be determined accurately and enable one to construct the grand canonical partition function. Therefore, the complicated concurrent multisite proton titration process of protein molecules can be satisfactorily simulated. Application of this method to the simulation of the pKa of Glu49, Asp50, and C-terminus of bovine pancreatic trypsin inhibitor shows reasonably good agreement with published experimental work. This method provides an unprecedented vivid picture of how different protonation states change their relative population upon pH titration. We believe that the method will be very useful in deciphering the molecular mechanism of pH-dependent biomolecular processes in terms of a detailed atomistic description. � 2014 Wiley Periodicals, Inc. PMID:24889139
Hu, Hao; Shen, Lin
Hydrophobically modified cationic polyelectrolytes
Cationic polyelectrolytes with hydrophilic\\/hydrophobic properties were synthesized by condensation polymerization of epichlorohydrin with dimethylamine, N,N-dimethyl-1,3-diaminopropane, and primary amines with nonpolar chains, hexyloxypropylamine and decyloxypropylamine. Viscometric measurements of these polymers in dilute aqueous solutions with and without salt revealed a typical polyelectrolyte behaviour. Thermal analyses of cationic polyelectrolytes showed that the relative thermal stability decreases with decreasing hydrophobic chain lengths and
Luminita Ghimici; I. Dranca; Stela Dragan; T. Lupascu; A. Maftuleac
New tobermorite cation exchangers
Tobermorite minerals, calcium silicate hydrates substituted with Al3+ and alkali, exhibit cation exchange and selectivity properties. The total cation exchange capacities of the Al3+ and alkali substituted tobermorites synthesized here range from 128 to 197 meq per 100g. These substituted tobermorites also have high selectivity for caesium and rubidium. For examples, a tobermorite synthesized from Na2SiO3, AlCl3 and CaO has
Sridhar Komarneni; Della M. Roy
Potentiometric polymeric membrane electrodes for mercury detection using calixarene ionophores.
It is here established that potentiometric polymeric membrane electrodes based on electrically neutral ionophores are a useful analytical tool for the detection of heavy metal ions from environmental and industrial waste water. PVC based membrane containing p-tert-butyl-calix[4]arenethioether derivative as active material along with sodiumtetraphenylborate (NaTPB) as solvent mediator and dibutylphthalate as a plasticizer in the ratio 45:9:460:310 (w/w%) (I:NaTPB:DBP:PVC) exhibits good properties with a Nernstian response of 29.50+/-1.0 mV per decade of activity and a working concentration range of 7.2 x 10(-8)-1.0 x 10(-1) M. The electrode gave more stable potential readings when used around pH 2.5-6.8 and exhibits fast response time of 14 s. The sensors were found to work satisfactorily in partially non-aqueous media up to 40% (v/v) content of acetone, methanol or ethanol and could be used over a period of 7-9 months. Excellent selectivity for Hg(2+) ions is indicated by match potential method and fixed interference method. The sensors could be used successfully in the estimation of mercury in different sample. PMID:20150706
Tyagi, Sonika; Agarwal, Himanshu; Ikram, Saiqa
Potentiometric enzyme immunoassay using miniaturized anion-selective electrodes for detection
An enzyme-linked immunosorbent assay (ELISA) for prostate specific antigen (PSA) detection in human serum was developed based on the potentiometric detection of 6,8-difluoro-4-methylumbelliferone (DiFMU). The assays were carried out in anti-human PSA capture-antibody modified microtiter plates (150 �l volume). After incubation in the PSA containing serum samples, ?-galactosidase-labeled PSA tracer antibody was added. The ?-galactosidase label catalyzed the hydrolysis of 6,8-difluoro-4-methylumbelliferyl-?-D-galactopyranoside (DiFMUG) and the resulting DiFMU? anion was detected by potentiometric microelectrodes with anion-exchanger membrane. The selectivity of the anion-exchanger electrode is governed by the lipophilicity of the anions in the sample. Since DiFMU? is much more lipophilic (log P = 1.83) than any of the inorganic anions normally present in the working buffers and occurs in its anionic form at the physiological pH (pKa = 4.19), it was chosen as the species to be detected. The potentiometric ELISA-based method detects PSA in serum with a linear concentration range of 0.1�50 ng/mL. These results confirm the applicability of potentiometric detection in diagnostic PSA assays. Owing to simple methodology and low cost, potentiometric immunoassays seem to offer a feasible alternative to the development of in vitro diagnostic platforms.
Szucs, Julia; Pretsch, Erno; Gyurcsanyi, Robert E.
Potentiometric anion selectivity of polymer-membrane electrodes based on cobalt, chromium, and aluminum salens.
Metallo-salens of cobalt(II) (Co-Sal), chromium(III) (Cr-Sal), and aluminum(III) (Al-Sal) are used as the active ionophores within plasticized poly(vinyl chloride) membranes. It is shown that central metal-ion plays a critical role in directing the ionophore selectivity. Polymer-membrane electrodes based on Co-Sal, Cr-Sal, and Al-Sal are demonstrated to exhibit enhanced responses and selectivity toward nitrite/thiocyanate, thiocyanate, and fluoride anions, respectively. The improved anion selectivity of the three ionophore systems is shown to deviate significantly from the classical Hofmeister pattern that is based only on ion lipophilicity. For example, optimized membrane electrodes for nitrite ion based on Co-Sal exhibit logK(Nitrite,Anion)(pot) values of -5.22, -4.66, -4.48, -2.5 towards bromide, perchlorate, nitrate, and iodide anions, respectively. Optimized membrane electrodes based on Co-Sal and Cr-Sal show near-Nernstian responses towards nitrite (-57.9+/-0.9 mV/decade) and thiocyanate (-56.9+/-0.8 mV/decade), respectively, with fast response and recovery times. In contrast, Al-Sal based membrane electrodes respond to fluoride ion in a super-Nernstian (-70+/-3 mV/decade) and nearly an irreversible mode. The operative response mechanism of Co-Sal, Cr-Sal, and Al-Sal membrane electrodes is examined using the effect of added ionic sites on the potentiometric response characteristics. It is demonstrated that addition of lipophilic anionic sites to membrane electrodes based on the utilized metallo-salens enhances the selectivity towards the primary ion, while addition of cationic sites resulted in Hofmeister selectivity patterns suggesting that the operative response mechanism is of the charged carrier type. Electron spin resonance (ESR) data indicates that Co(II) metal-ion center of Co-Sal ionophore undergoes oxidation to Co(III). This process leads to formation of a charged anion-carrier that is consistent with the response behavior obtained for Co-Sal based membrane electrodes. PMID:17723397
Badr, Ibrahim H A
The difference between the potentiometric surfaces of the Magothy Aquifer of September 1982 and September 1984 in southern Maryland
Potentiometric Surface of the Upper Floridan Aquifer in the St. Johns River Water Management District and Vicinity, Florida, September 2006
Introduction This map depicts the potentiometric surface of the Upper Floridan aquifer in the St. Johns River Water Management District and vicinity for September 2006. Potentiometric contours are based on water-level measurements collected at 571 wells during the period September 11-29, near the end of the wet season. Some contours are inferred from previouspotentiometric-surface maps with larger well networks. The potentiometric surface of the carbonate Upper Floridan aquifer responds mainly to rainfall, and more locally, to ground-water withdrawals and spring flow. Potentiometric-surface highs generally correspond to topographic highs where the aquifer is recharged. Springs and areas of diffuse upward leakage naturally discharge water from the aquifer and are most prevalent along the St. Johns River. Areas of discharge are reflected by depressions in the potentiometric surface. Ground-water withdrawals locally have lowered the potentiometric surface. Ground water in the Upper Floridan aquifer generally flows from potentiometric highs to potentiometric lows in a direction perpendicular to the contours.
Ultrasensitivity by molecular titration in spatially propagating enzymatic reactions.
Delineating design principles of biological systems by reconstitution of purified components offers a platform to gauge the influence of critical physicochemical parameters on minimal biological systems of reduced complexity. Here we unravel the effect of strong reversible inhibitors on the spatiotemporal propagation of enzymatic reactions in a confined environment in�vitro. We use micropatterned, enzyme-laden agarose gels which are stamped on polyacrylamide films containing immobilized substrates and reversible inhibitors. Quantitative fluorescence imaging combined with detailed numerical simulations of the reaction-diffusion process reveal that a shallow gradient of enzyme is converted into a steep product gradient by addition of�strong inhibitors, consistent with a mathematical model of molecular titration. The results confirm that ultrasensitive and threshold effects at the molecular level can convert a graded input signal to a steep spatial response at macroscopic length scales. PMID:23972857
Semenov, Sergey N; Markvoort, Albert J; Gevers, Wouter B L; Piruska, Aigars; de Greef, Tom F A; Huck, Wilhelm T S
Cationic Polystyrene Nanoparticles: Preparation and Characterization of a Model Drug Carrier System for Antisense Oligonucleotides
Polystyrene nanoparticles were prepared by surfactant-free emulsion polymerization using water-soluble cationic initiators to induce a positive surface charge. Reaction conditions were optimized to obtain monodisperse polymeric particles with mean diameters of 150�200 nm. The nanospheres were characterized by scanning electron microscopy, photocorrelation spectroscopy, conductometric titrations, zeta potential measurements, and investigations of their colloidal stability in different media. Sterically stabilized polymeric
Hans Fritz; Martin Maier; Ernst Bayer
Indophenol blue colorimetric method for measuring cation exchange capacity in sandy soils
In the determination of the cation exchange capacity (CEC) by the NH4-acetate-NaCl method, the evaluation of the quantity of ammonium exchanged by the soil is often carried out by steam distillation and titration. While this procedure gives reliable results when applied to soils with medium to high amounts of available sites for exchange, in the case of sandy or desert
Stefania Santoni; Eleonora Bonifacio; Ermanno Zanini
Novel approaches to analysis by flow injection gradient titration.
Two novel procedures for flow injection gradient titration with the use of a single stock standard solution are proposed. In the multi-point single-line (MP-SL) method the calibration graph is constructed on the basis of a set of standard solutions, which are generated in a standard reservoir and subsequently injected into the titrant. According to the single-point multi-line (SP-ML) procedure the standard solution and a sample are injected into the titrant stream from four loops of different capacities, hence four calibration graphs are able to be constructed and the analytical result is calculated on the basis of a generalized slope of these graphs. Both approaches have been tested on the example of spectrophotometric acid-base titration of hydrochloric and acetic acids with using bromothymol blue and phenolphthalein as indicators, respectively, and sodium hydroxide as a titrant. Under optimized experimental conditions the analytical results of precision less than 1.8 and 2.5% (RSD) and of accuracy less than 3.0 and 5.4% (relative error (RE)) were obtained for MP-SL and SP-ML procedures, respectively, in ranges of 0.0031-0.0631 mol L(-1) for samples of hydrochloric acid and of 0.1680-1.7600 mol L(-1) for samples of acetic acid. The feasibility of both methods was illustrated by applying them to the total acidity determination in vinegar samples with precision lower than 0.5 and 2.9% (RSD) for MP-SL and SP-ML procedures, respectively. PMID:17903467
W�jtowicz, Marzena; Kozak, Joanna; Ko?cielniak, Pawe?
Field-effect based attomole titrations in nanoconfinement.
This paper describes a novel capacitive method to change the pH in micro- and nanofluidic channels. A device with two metal gate electrodes outside an insulating channel wall is used for this purpose. The device is operated at high ionic strength with thin double layers. We demonstrate that gate potentials applied between the electrodes cause a release or uptake of protons from the silicon nitride surface groups, resulting in a pH shift in the channel and a titration of solution compounds present. Due to the high quality silicon nitride insulating layer, the effect is purely capacitive and electrolysis can be neglected. Fluorescein was employed as a fluorescent pH indicator to quantify the induced pH changes, and a maximum change of 1.6 pH units was calculated. A linear relationship was found between applied potential and fluorescein intensity change, indicating a linear relation between actuated proton amount and applied voltage. Since this pH actuation method avoids redox reactions and can be operated at physiological ionic strength, it can be very useful as a "soft" way to change the pH in very small volumes e.g. in bioassays or cell-based research. The sensitivity of the optical detection method poses the only limit to the detectable amount of substance and the observed volume. In a preliminary measurement we show one possible application, namely titration of 100 attomol of TRIS in a 7 pL detection volume. It is important to stress that this pH actuation principle fundamentally differs from the pH changes occurring in ionic transistors which are due to counterion enrichment and coion exclusion, because it does not rely on double-layer overlap. As a result it can be operated at high ionic strength and in channels of up to at least 1 microm height. PMID:20024025
Veenhuis, Rogier B H; van der Wouden, Egbert J; van Nieuwkasteele, Jan W; van den Berg, Albert; Eijkel, Jan C T
Potentiometric surface of the upper Patapsco aquifer in southern Maryland, September 1999
This report presents a map showing the potentiometric surface of the Upper Patapsco aquifer in the Patapsco Formation of Cretaceous age in Southern Maryland during September 1999. The map is based on water-level measurements in 49 wells. The potentiometric surface was 119 feet above sea level near the northern boundary and outcrop area of the aquifer in a topographically high area of Anne Arundel County, and 55 feet above sea level in a similar setting in Prince Georges County. From these high areas, the potentiometric surface declined to the southeast toward large well fields in the Annapolis area, and from all directions toward a cone of depression southwest of Waldorf. Ground-water levels declined to 20 feet below sea level in the Annapolis area, and 131 feet below sea level southwest of Waldorf.
Curtin, Stephen E.; Andreasen, David C.; Wheeler, Judith C.
Potentiometric surface of the Magothy Aquifer in southern Maryland during the fall of 1987
A map showing the potentiometric surface of the Magothy aquifer in the Cretaceous Magothy Formation in southern Maryland during the fall of 1987 was prepared by using water level measurements in 85 observation wells. The potentiometric surface was highest near the northwestern boundary and outcrop area of the aquifer in topographically high locations of Anne Arundel and Prince Georges Counties. The hydraulic gradient in the study area was generally southeastward or toward the centers of three cones of depression which have developed in response to pumping stresses. These cones formed around well fields in the Annapolis, Waldorf, and Chalk Point areas. The potentiometric surface of the Magothy aquifer was more than 40 ft below sea level in parts of the Waldorf and Chalk Point areas. (USGS)
Preliminary map showing the potentiometric surface of the Aquia Aquifer in southern Maryland, September 1982
A map was prepared that shows the potentiometric surface of the Aquia aquifer in southern Maryland in September 1982. The map is based on measurements from a network of 78 observation wells. The highest measured level of the potentiometric surface, 34 ft above sea level, was near the outcrop of the aquifer in a topographically high area of Anne Arundel County. The potentiometric surface slopes downward to the extensive cone of depression--much of it more than 40 ft below sea level--has developed around the well fields in the vicinity of Lexington Park. The network of observation wells was developed as part of the cooperative program between the U.S. Geological Survey, the Maryland Geological Survey, and the Maryland Energy Administration. (USGS)
Potentiometric surface of the Magothy Aquifer in southern Maryland during September 1988
A map showing the potentiometric surface of the Magothy aquifer in southern Maryland during the fall of 1988 was prepared from water-level measurements in 83 observation wells. The potentiometric surface was highest near the northwest boundary and outcrop area of the aquifer in topographically high locations of Anne Arundel and Prince Georges Counties. The hydraulic gradient in the study area was generally southeastward or toward the centers of three cones of depression that have developed in response to pumping stresses. These cones formed around well fields in the Annapolis, Waldorf, and Chalk Point areas. The potentiometric surface of the Magothy aquifer was more than 40 ft below sea level in parts of the Waldorf and Chalk Point areas. (USGS)
Potentiometric Surface of the Upper Patapsco Aquifer in Southern Maryland, September 2001
This report presents a map showing the potentiometric surface of the Upper Patapsco aquifer in the Patapsco Formation of Cretaceous age in Southern Maryland during September 2001. The map is based on water-level measurements in 49 wells. The potentiometric surface was highest at 118 feet above sea level near the northern boundary and outcrop area of the aquifer in northern Anne Arundel County. From this area, the potentiometric surface declined to the southeast toward large well fields in the Annapolis area, and from all directions toward a cone of depression located southwest of Waldorf. The ground-water level declined to 26 feet below sea level in the Annapolis area, and the lowest water level was 132 feet below sea level southwest of Waldorf.
Preparation of nano-structured Pt-YSZ composite and its application in oxygen potentiometric sensor
Nano-structured Platinum-Yttria Stabilized Zirconia (YSZ) composites for oxygen potentiometric sensors were directly prepared with carbon black and the precursors such as chloroplatinic acid, zirconyl nitrate and yttrium nitrate. The as-prepared Pt-YSZ composite consisted of cubic crystalline YSZ and Pt particles, and the particle sizes of Pt catalyst and YSZ electrolyte were about 25-35 and 5-10 nm, respectively. The Pt-YSZ composite electrodes exhibited excellent electrochemical performances when evaluated by EIS measurements. The introduction of the nano-structured Pt-YSZ composite into the oxygen potentiometric sensor can reduce sensor's operating temperature to be about 380 �C, and also can reduce sensor's response time to be about 5 s at 400 �C. The oxygen potentiometric sensors incorporating nano-structured Pt-YSZ composites exhibited longer lifetime than those employing pure Pt as the sensing electrodes.
ChaoYang, Xia; XuChen, Lu; Yan, Yan; TiZhuang, Wang; ZhiMin, Zhang; SuPing, Yang
Acidity constants in methanol/water mixtures of polycarboxylic acids used in drug salt preparations. Potentiometric determination of aqueous pKa values of quetiapine formulated as hemifumarate.
The acidic dissociation constants in a number of methanol/water mixtures of mono and polycarboxylic acids commonly used in the preparation of drug salts were determined. These solvent mixtures are usually used to determine the pKa of drugs of low aqueous solubility. However, when these drugs are prepared in salt form, the acid-base equilibria of both the basic drug and the counter-anion are involved in the potentiometric titration curves. In these instances, the inclusion of the pKa of acids as constant values in the curve fitting provides easy computation of the drug pKa without the need of any previous step to get the free base. As an application example, the aqueous pKa values of the quetiapine formulated as hemifumarate (Seroquel) were estimated by extrapolation from the experimental pKa in several methanol/water mixtures, which were then calculated according to the suitable constants of fumaric acid. The estimated aqueous pKa values of quetiapine are compared with those directly obtained in aqueous solution by potentiometry and by capillary electrophoresis. PMID:16488581
Garrido, Gemma; R�fols, Clara; Bosch, Elisabeth
Aluminum speciation and equilibria in aqueous solution: III. Potentiometric determination of the first hydrolysis constant of aluminum(III) in sodium chloride solutions to 125�C
The first molal hydrolysis quotient of aluminum(III) was measured potentiometrically from 25 to 125�C at 25� intervals at ionic strengths of 0.1, 0.3, 1.0 and 5 mol � kg -1 with sodium chloride as the supporting electrolyte. The experimental method involved using a hydrogen-electrode concentration cell modified to compensate for any intrinsic potential offset between the two electrodes. The initial concentration of Al 3+ was varied to test for the presence of multinuclear aluminum species while being kept to a maximum of 10 -3 mol � kg -1 to minimize their occurrence. Similarly, the maximum degree of hydrolysis of Al 3+ reached in each titration was ca. 30%, after which polymerization and/or precipitation became apparent. The equilibrium quotients obtained in this study and selected values from the literature were fitted by an empirical equation incorporating a linear dependence of log K1,1 on the reciprocal temperature (Kelvins) over the range 10-200�C and three ionic-strength-dependent parameters. Comparisons are made between the results of this study and the literature values.
Palmer, Donald A.; Wesolowski, David J.
Carbonic acid ionization and the stability of sodium bicarbonate and carbonate ion pairs to 200 �C - A potentiometric and spectrophotometric study
Carbonic acid ionization and sodium bicarbonate and carbonate ion pair formation constants have been experimentally determined in dilute hydrothermal solutions to 200 �C. Two experimental approaches were applied, potentiometric acid-base titrations at 10-60 �C and spectrophotometric pH measurements using the pH indicators, 2-napthol and 4-nitrophenol, at 25-200 �C. At a given temperature, the first and second ionization constants of carbonic acid (K1, K2) and the ion pair formation constants for NaHCO(aq)(K) and NaCO3-(aq)(K) were simultaneously fitted to the data. Results of this study compare well with previously determined values of K1 and K2. The NaHCO(aq) and NaCO3-(aq) ion pair formation constants vary between 25 and 200 �C having values of logK=-0.18 to 0.58 and logK=1.01 to 2.21, respectively. These ion pairs are weak at low-temperatures but become increasingly important with increasing temperature under neutral to alkaline conditions in moderately dilute to concentrated NaCl solutions, with NaCO3-(aq) predominating over CO32-(aq) in ?0.1 M NaCl solution at temperatures above 100 �C. The results demonstrate that NaCl cannot be considered as an inert (non-complexing) electrolyte in aqueous carbon dioxide containing solutions at elevated temperatures.
Stef�nsson, Andri; B�n�zeth, Pascale; Schott, Jacques
A mercury(II) selective sensor based on N,N'-bis(salicylaldehyde)-phenylenediamine as neutral carrier for potentiometric analysis in water samples.
Mercuric ions in water samples were determined by a new modified carbon paste electrode based on N,N'-bis(salicylaldehyde)-phenylenediamine (salophen) as a chemical modifier. The construction, performance, and applications of mercury carbon paste electrode are described. The electrode displays a linear log[Hg(2+)] versus EMF response over a wide concentration range of 3.2 x 10(-7) to 3.2 x 10(-4) with Nernstian slope of 58.8+/-0.3 mV/decade with limit of detection 1.5 x 10(-7) over the pH range 3.8-7.8; the presence of the complex Hg(OH)(+) ion explains the slope of the response curve. The proposed sensor shows a reasonable discrimination ability towards Hg(II) in comparison to some alkali, alkaline earth transition and heavy metal ions. The modified electrode was applied as indicator electrode in potentiometric titration and successfully used to determine mercury(II) in water samples with satisfactory results. PMID:19195781
Abu-Shawish, Hazem M
Characterization of the kinetic and thermodynamic landscape of RNA folding using a novel application of isothermal titration calorimetry.
A novel isothermal titration calorimetry (ITC) method was applied to investigate RNA helical packing driven by the GAAA tetraloop-receptor interaction in magnesium and potassium solutions. Both the kinetics and thermodynamics were obtained in individual ITC experiments, and analysis of the kinetic data over a range of temperatures provided Arrhenius activation energies (?H(�)) and Eyring transition state entropies (?S(�)). The resulting rich dataset reveals strongly contrasting kinetic and thermodynamic profiles for this RNA folding system when stabilized by potassium versus magnesium. In potassium, association is highly exothermic (?H(25�C) = -41.6 � 1.2 kcal/mol in 150 mM KCl) and the transition state is enthalpically barrierless (?H(�) = -0.6 � 0.5). These parameters are significantly positively shifted in magnesium (?H(25�C) = -20.5 � 2.1 kcal/mol, ?H(�) = 7.3 � 2.2 kcal/mol in 0.5 mM MgCl(2)). Mixed salt solutions approximating physiological conditions exhibit an intermediate thermodynamic character. The cation-dependent thermodynamic landscape may reflect either a salt-dependent unbound receptor conformation, or alternatively and more generally, it may reflect a small per-cation enthalpic penalty associated with folding-coupled magnesium uptake. PMID:22058128
Vander Meulen, Kirk A; Butcher, Samuel E
Potentiometric Surface of the Magothy Aquifer in Southern Maryland, September 2001
This report presents a map showing the change in the potentiometric surface of the Aquia aquifer in the Aquia Formation of Paleocene age in Southern Maryland for September 1982 and September 2001. The map, based on water level measurements in 58 wells, shows that the potentiometric surface during the 19-year period declined from zero in the northernmost part of the study area, which is the outcrop of the aquifer, to 120 feet at Lexington Park. Lexington Park is near the southeasternmost part of the study area and approaches the downdip boundary of the aquifer.
Potentiometric surface of the Magothy aquifer in southern Maryland, September 1999
This report presents a map showing the change in the potentiometric surface of the Lower Patapsco aquifer in the Lower Patapsco Formation of Cretaceous age in Southern Maryland for September 1990 and September 1999. The map, based on water?level measurements in 52 wells, shows that the change of the potentiometric surface during the 9- year period ranged from a rise of 13 feet at Indian Head and 6 feet near the outcrop area in Glen Burnie, to declines of 34 feet at Arnold, 30 feet at Waldorf, and 24 feet at Morgantown.
Potentiometric surface of Floridan aquifer, Southwest Florida Water Management District and adjacent areas, September 1977
A potentiometric-surface map of the Southwest Florida Water Management District depicts the annual high water-level period. Potentiometric levels increased 15 to 30 feet between May 1977 and September 1977 in the citrus and farming sections of southeastern Hillsborough, northern Hardee, and southwestern Polk Counties. These areas are widely affected by pumpage for irrigation and have the greatest range in water-level fluctuations between the low and high water-level periods. Water-level rises in coastal, northern, and southern areas of the Water Management District ranged from 0 to 15 feet. (Woodard-USGS)
Ryder, P. D.; Mills, L. R.; Laughlin, C. P.
Potentiometric surface of the Floridan Aquifer, Southwest Florida Water Management District and adjacent areas, September 1978
A September 1978 potentiometric-surface map depicts the annual high water-level period of the Floridan aquifer in the Southwest Florida Management District. Potentiometric levels increased 10 to 25 feet between May 1978 and September 1978, in the citrus and farming sections of southern Hillsborough, northern Hardee, southwestern Polk and Manatee Counties. These areas are widely affected by pumping for irrigation and have the greatest fluctuations in water-levels between the low and high water-level periods. Water-level rises in coastal, northern and southern areas of the Water Management District ranged from 0 to 10 feet. (Woodard-USGS)
Potentiometric Electronic Tongues for Foodstuff and Biosample Recognition--An Overview
Potentiometric sensors are attractive tools for the fabrication of various electronic tongues that can be used in wide area of applications, ranging from foodstuff recognition to environmental monitoring and medical diagnostics. Their main advantages are the ability to modify their selectivity (including cross-sensitivity effects) and the possibility of miniaturization using appropriate construction methods for the transducer part (e.g., with the use of solid-state technology). In this overview various examples of the design, performance, and applications of potentiometric electronic tongues are presented. The results summarize recent research in the field conducted in the Department of Microbioanalytics, Warsaw University of Technology (WUT).
Ciosek, Patrycja; Wroblewski, Wojciech
Design, Fabrication and Characterization of a Miniaturized Series-Connected Potentiometric Oxygen Sensor
Miniaturization of potentiometric sensors facilitates connecting many sensors in series to amplify the output. Miniaturized series-connected potentiometric sensors were developed on silicon (Si) wafer by microfabrication techniques. The sensors consist of a thin nickel-nickel oxide (Ni-NiO) mixture. The open circuit voltage (OCV) was tested in air at 300 C and was found to be lower than expected. The output of the net sensor increased almost linearly by connecting 10 sensors in series. Impedance spectroscopy was used to investigate the electrolyte and electrolyte-electrode interfaces using a two electrode configuration.
Radhakrishnan, Rajesh; Virkar, Anil V.; Singhal, Subhash C.; Dunham, Glen C.; Marina, Olga A.
Stability of Ultradisperse Copper in a Sulfo Cation Exchanger Matrix
The recrystallization of ultradisperse copper chemically deposited onto a sulfo cation exchanger matrix was studied by the potentiometric method. The stationary value of the electrode potential of the copper-sulfo cation exchanger composite was established during a long period of time, which depended on the ionic form of the composite (H+, Cu2+, or Na+), solution composition (CuSO4, H2SO4, and Na2SO4), and solution concentration. Recrystallization was favored by copper(II) counterions, which entered the composite as a result of ion exchange, nonexchange absorption of copper sulfate, or preliminary composite transformation into the Cu2+ form. In the quasi-equilibrium state, the concentration of copper(II) counterions was maintained at a high level by the Donnan interfacial potential. At all the copper(II) sulfate concentrations used, the potential of the Cu2+/Cu ion�metal pair in the ion-exchange matrix remained at virtually the same level, which was indicative of the stable state of copper particles. In the absence of an external source of copper ions, recrystallization was significantly hindered; therefore, the potential exhibited only a slight drift. Copper ions formed in the solution of small crystals were localized in the vicinity of ionogenic matrix centers, which decreased the mobility of these particles as counterions; therefore, the dispersity of particles remained unchanged.
Zolotukhina, E. V.; Polyanskii, L. N.; Peshkov, S. V.; Kravchenko, T. A.; Krysanov, V. A.
Potentiometric sensors for the selective determination of sulbutiamine
Five novel polyvinyl chloride (PVC) matrix membrane sensors for the selective determination of sulbutiamine (SBA) cation are described. These sensors are based on molybdate, tetraphenylborate, reineckate, phosphotun gestate and phosphomolybdate, as possible ion-pairing agents. These sensors display rapid near-Nernstian stable response over a relatively wide concentration range 1�10?2�1�10?6 M of sulbutiamine, with calibration slopes 28�32.6 mV decade?1 over a reasonable
Mona A Ahmed; Menna M Elbeshlawy
Map showing how the potentiometric surface of the Magothy Aquifer of August 1980 differed from the potentiometric surface of September 1977, in southern Maryland
The map is based on the differences between two sets of water-level measurements made in 65 observation wells. One set was made in 1977, a relatively dry year, and the other set was made in 1980, another relatively dry year. The map shows that the potentiometric surface was higher in 1980, by as much as 9 feet, than it was in 1977, in a band a few miles wide near the outcrop and subcrop areas of the aquifer in northern Prince Georges County and central Anne Arundel County. In the remainder of the map area, the 1980 potentiometric surface was lower than it had been in 1977, with declines as great as 20 feet measured in well fields at Waldorf and Chalk Point. The network of observation wells was developed and is operated and maintained as part of the cooperative program between the U.S. Geological Survey and agencies of the Maryland Department of Natural Resources. (USGS)
Mack, Frederick K., Jr.; Wheeler, J. C.; Curtin, Stephen E.
Map showing how the potentiometric surface of the Magothy Aquifer of September 1979 differed from the potentiometric surface of September 1977 in southern Maryland
This map is based on the differences between two sets of water-level measurements made in 63 observation wells. One set was made in 1977, a relatively dry year, and the other set was made in 1979, a relatively wet year. The map shows that the potentiometric surface in 1979, in northern Prince Georges County and southern Anne Arundel County, was higher than it was in 1977, with a maximum measured rise of 9 feet. In southern parts of the mapped area, the 1979 potentiometric surface was lower than the 1977 surface, with a maximum measured decline of 11 feet. The network of observation wells was developed and is operated and maintained as part of the cooperative program between the U.S. Geological Survey and agencies of the Maryland Department of Natural Resources. (USGS)
Mack, Frederick K.; Wheeler, J. C.; Curtin, Stephen E.
Complexation Effect on Redox Potential of Iron(III)-Iron(II) Couple: A Simple Potentiometric Experiment
A titration curve with multiple inflection points results when a mixture of two or more reducing agents with sufficiently different reduction potentials are titrated. In this experiment iron(II) complexes are combined into a mixture of reducing agents and are oxidized to the corresponding iron(III) complexes. As all of the complexes involve the�
Rizvi, Masood Ahmad; Syed, Raashid Maqsood; Khan, Badruddin
Effects of Acute and Chronic Cocaine Administration on Titrating-Delay Matching-to-Sample Performance
The effects of cocaine were examined under a titrating-delay matching-to-sample procedure. In this procedure, the delay between sample stimulus offset and comparison stimuli onset adjusts as a function of the subject's performance. Specifically, matches increase the delay and mismatches decrease the delay. Titrated delay values served as the�
Kangas, Brian D.; Branch, Marc N.
Binding of globular proteins to lipid membranes studied by isothermal titration calorimetry and fluorescence
The interactions of bovine serum albumin, lysozyme and cytochrome c with phosphatidylcholine liposomes in liquid crystalline phase have been investigated using isothermal titration calorimetry in combination with steady state, and fluorescence measurements. Calorimetric titration studies of the binding of liposomes to the protein species indicate in all cases exothermic processes with single binding sites in the protein molecule. Distinct saturation
Mariana N Dimitrova; Hideo Matsumura; Nelly Terezova; Vassil Neytchev
Selective Two-Step Titration of Thorium by Sulfate Displacement of the Diethylenetriaminepentaacetic Acid Complex.
Thorium and other metals are complexed with excess diethylenetriaminepentaacetic acid (DTPA) at pH 1.4, the excess DTPA is titrated with Bi(III) to a xylenol orange end point, sulfate is added to complex Th(IV), and the displaced DTPA again is titrated wi...
P. Kiefer
Quantification of the maleic anhydride grafted onto polypropylene by chemical and viscosimetric titrations, and FTIR spectroscopy
An acid�base titration method for an accurate and reproducible quantification of maleic anhydride grafted onto polyolefins is proposed. The use of an organic base (tetra-butylammonium hydroxide) enhances the base solubility in organic solvents and prevents phenomena like coarcervation. The titration goes on until the visual endpoint of a coloured indicator, corresponding to the neutralisation of the grafted functions. Bromothymol blue
M. Sclavons; P. Franquinet; V. Carlier; G. Verfaillie; I. Fallais; R. Legras; M. Laurent; F. C. Thyrion
A Laser-Pointer-Based Spectrometer for Endpoint Detection of EDTA Titrations
A laser spectrometer for the ethylenediaminetetra-acetic acid (EDTA) titration of magnesium or calcium ions that is designed around a handheld laser pointer as the source and a photoresistor as the detector is developed. Findings show that the use of the spectrometer reduces the degree of uncertainty and error in one part of the EDTA titrations,�
Dahm, Christopher E.; Hall, James W.; Mattioni, Brian E.
An estimated potentiometric surface of the Death Valley region, Nevada and California, developed using geographic information system and automated interpolation techniques
An estimated potentiometric surface was constructed for the Death Valley region, Nevada and California, from numerous, disparate data sets. The potentiometric surface was required for conceptualization of the ground-water flow system and for construction of a numerical model to aid in the regional characterization for the Yucca Mountain repository. Because accurate, manual extrapolation of potentiometric levels over large distances is difficult, a geographic-information-system method was developed to incorporate available data and apply hydrogeologic rules during contour construction. Altitudes of lakes, springs, and wetlands, interpreted as areas where the potentiometric surface intercepts the land surface, were combined with water levels from well data. Because interpreted ground-water recharge and discharge areas commonly coincide with groundwater basin boundaries, these areas also were used to constrain a gridding algorithm and to appropriately place local maxima and minima in the potentiometric-surface map. The resulting initial potentiometric surface was examined to define areas where the algorithm incorrectly extrapolated the potentiometric surface above the land surface. A map of low-permeability rocks overlaid on the potentiometric surface also indicated areas that required editing based on hydrogeologic reasoning. An interactive editor was used to adjust generated contours to better represent the natural water table conditions, such as large hydraulic gradients and troughs, or ``vees``. The resulting estimated potentiometric-surface map agreed well with previously constructed maps. Potentiometric-surface characteristics including potentiometric-surface mounds and depressions, surface troughs, and large hydraulic gradients were described.
D`Agnese, F.A.; Faunt, C.C.; Turner, A.K.
Condensate Polishing with Cation-Anion-Cation Filters.
A cation-anion-cation filter system was chosen instead of the cation-mixed bed filter system for condensate polishing in unit 25 of the PEN power station at Velsen. The principles of this ion-exchange system were tested. The results of the experiments are...
H. W. Venderbosch R. Fresen
Acid�base equilibria in systems involving substituted pyridines in polar aprotic protophobic media and in the amphiprotic methanol
Acid dissociation, as well as cationic homo- and heteroconjugation constants have been determined by potentiometric titration in systems involving substituted pyridines and conjugate cationic acids in the polar protophobic aprotic solvent acetone and in polar amphiprotic methanol. The values of the constant were compared with those previously determined in other polar protophobic aprotic solvents, acetonitrile, nitromethane and propylene carbonate. The
D Augustin-Nowacka; M Makowski; L Chmurzynski
Stepwise a.c. amperometric titration of cadmium and zinc with EGTA.
The theory of d.c. and a.c. amperometric titrations based on complexometric reactions is presented. It is shown that when E(1 2 )(M(I)) > E(1 2 )(M(II)) and log K(M(I)L) < log K(M(II)L), M(I) and M(II) can be sequentially determined by d.c. as well as a.c. amperometric titration. If, on the other hand E(1 2 )(M(I)) > E(1 2 )(M(II)) and log K(M(II)L), a stepwise titration can be performed only by a.c. amperometry. The effect of oxygen on an a.c. amperometric titration is also discussed. The stepwise a.c. amperometric titration of cadmium and zinc with EGTA at pH 6 in the presence of oxygen and an excess of 0.05 M acetate illustrates the theory. PMID:18961447
Asplund, J
[Simultaneous determination of calcium and magnesium by calculative spectrophotometric complexometric titration].
A new spectrophotometric complexometric titration method coupled with chemometrics for the determination of mixtures of metal ions has been developed. In the method described here, the titrant is a mixture of EDTA and two indicators. In the process of titration, both the volumetric addition of titrant and the progress of titration reaction can be characterized simultaneously by chemometric calculation with the absorption spectra, and then the titration curves can be obtained. With the titration curves, a matrix equation can be established, and thus the concentration of each component in the mixture of metal ions can be calculated with principal component regression. The method only needs the information of absorption spectra to obtain the analytical results, and is free of volumetric measurements. So the method is simple, convenient and precise, and has been applied to the simultaneous determination of mixtures of calcium and magnesium using malachite green and Cu-PAN as indicators with satisfactory results. PMID:18330321
Liao, Li-fu; Xiao, Xi-lin; Yang, Ming-hui; Yang, Jing
Molecularly imprinted polymer based potentiometric sensor for the determination of hydroxyzine in tablets and biological fluids
Molecular imprinting is a useful technique for the preparation of functional materials with molecular recognition properties. In this work, a biomimetic potentiometric sensor, based on a non-covalent imprinted polymer, was fabricated for the recognition and determination of hydroxyzine in tablets and biological fluids. The molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization, using hydroxyzine dihydrochloride as a template molecule,
Mehran Javanbakht; Solmaz Eynollahi Fard; Ali Mohammadi; Majid Abdouss; Mohammad Reza Ganjali; Parviz Norouzi; Leila Safaraliee
Map showing the potentiometric surface of the Magothy Aquifer in southern Maryland, September 1982
A map was prepared that shows the potentiometric surface of the Magothy aquifer in southern Maryland in September 1982. The map is based on measurements from a network of 83 observation wells. The highest levels of the potentiometric surface, 57 and 58 feet above sea level, were measured near the outcrop-subcrop of the aquifer in topographically high areas of Anne Arundel and Prince Georges Counties. The potentiometric surface slopes to the southeast to about sea level along much of the western shore of the Chesapeake Bay. Three distinct and extensive cones of depression have developed in the potentiometric surface around the well fields of the Annapolis area, Waldorf area, and Chalk Point. Several square miles of each cone are below sea level, and in some areas at Chalk Point and Waldorf, the cone is more than 50 feet below sea level. The network of wells was developed as part of the cooperative program between the U.S. Geological Survey, the Maryland Geological Survey, and the Maryland Energy Administration. (USGS)
Direct Determinationof Cadmiumand Lead in Whole Blood by Potentiometric Stripping Analysis
The commercially available equipment for potentiometric stripping analysis (PSA) was tested for routine lead and cadmium determination in whole-blood samples. In con- trast to anodic stripping voltammetry, PSA is not subject to background interferences from organic electroactive constituents in the sample or to the presence of dissolved oxygen (i.e., oxygen removal is not necessary). To deter- mine lead and cadmium
Peter Ostapczuk
Lead in Hair and in Red Wine by Potentiometric Stripping Analysis: The University Students' Design.
A new program for training upper secondary school chemistry teachers (SE 537 693) depends heavily on student project work. A project in which lead in hair and in red wine was examined by potentiometric stripping analysis is described and evaluated. (JN)
Josephsen, Jens
Measurements on fluoride-containing hafnium solutions in 3M perchlorate ; media at 25 deg C by precision potentiometry and by solvent extraction ; distribution using thenoyltrifluoroacetone (TTA) and tri-n-octylphosphine oxide ; (TOPO) were subjected to high-speed digital computer analysis and the results ; interpreted in terms of the nature and stabilities of complex hafnium fluoride ; species present. Potentiometric hydrogen ion
L. P. Varga; D. N. Hume
Hot biological catalysis: isothermal titration calorimetry to characterize enzymatic reactions.
Isothermal titration calorimetry (ITC) is a well-described technique that measures the heat released or absorbed during a chemical reaction, using it as an intrinsic probe to characterize virtually every chemical process. Nowadays, this technique is extensively applied to determine thermodynamic parameters of biomolecular binding equilibria. In addition, ITC has been demonstrated to be able of directly measuring kinetics and thermodynamic parameters (kcat, KM, ?H) of enzymatic reactions, even though this application is still underexploited. As heat changes spontaneously occur during enzymatic catalysis, ITC does not require any modification or labeling of the system under analysis and can be performed in solution. Moreover, the method needs little amount of material. These properties make ITC an invaluable, powerful and unique tool to study enzyme kinetics in several applications, such as, for example, drug discovery. In this work an experimental ITC-based method to quantify kinetics and thermodynamics of enzymatic reactions is thoroughly described. This method is applied to determine kcat and KM of the enzymatic hydrolysis of urea by Canavalia ensiformis (jack bean) urease. Calculation of intrinsic molar enthalpy (?Hint) of the reaction is performed. The values thus obtained are consistent with previous data reported in literature, demonstrating the reliability of the methodology. PMID:24747990
Mazzei, Luca; Ciurli, Stefano; Zambelli, Barbara
Calorimetric study of phenol adsolubilisation by cationic surfactants adsorbed on a flat silica surface or confined within small mesopores of powdered MCM-41 aluminosilicates
Adsolubilisation of phenol by cationic surfactants adsorbed on a flat silica surface or confined within small mesopores of powdered MCM-41 aluminosilicates has been studied at room temperature by means of titration calorimetry. In aqueous solution of dodecyltrimethylammonium bromide (DTAB), the transfer of phenol to the outer portions of the surfactant micelles was considered to account for the slight depression of
H Benalla; Jerzy Zajac; S Partyka; J Rozi�re
Potentiometric surface of the lower Cape Fear Aquifer in the central coastal plain of North Carolina, December 1986
Water level measurements were made in four wells open to the lower Cape Fear aquifer at the end of 1986 to determine the configuration of its potentiometric surface over an area of approximately 4,100 sq mi. Because of the scarcity of data, five earlier measurements were also used to help estimate the position of the potentiometric contours. These were one-time measurements in temporary observation wells. A broad cone of depression has formed in the area between Kinston and New Bern where the potentiometric surface is below sea level and seems likely related to large groundwater withdrawals from the aquifers overlying the lower Cape Fear in that area.
Winner, M. D., Jr.; Lyke, William L.; Brockman, Allen R.
Altitude and configuration of the potentiometric surface, Casey Village, Warminster and Upper Southampton townships, Bucks County, Pennsylvania, August 3, 1995
A map showing the potentiometric surface in Casey Village, Warminster and Upper Southampton Townships, Bucks County, was constructed from water levels measured on August 3, 1995. The potentiometric surface, measured in 17 wells screened between 18 and 64 feet below land surface, ranged from 321.99 to 344.80 feet above sea level. The potentiometric surface, measured in 12 wells screened between 48 and 108 feet below land surface, ranged from 321.95 to 337.50 feet above sea level.
Sloto, Ronald A.; Grazul, Kevin E.
Cation-selective electropreconcentration.
A cation-selective microfluidic sample preconcentration system is described. The cation sample was electropreconcentrated using a reversed-direction electroosmotic flow (EOF) and an anion-permselective filter, where an electric double layer (EDL) overlap condition existed. The anion-permselective filter between microchannels was fabricated by three different methods: 1) extending a positively charged, nanoporous, polymer membrane by photopolymerization of poly(diallyldimethylammonium chloride) (PDADMAC); 2) etching a nanochannel and then coating it with a positively-charged monomer, N-[3-(trimethoxysilyl)propyl]-N'-(4-vinylbenzyl)ethylenediamine hydrochloride (TMSVE); and, 3) etching a nanochannel and then coating it with a positively-charged, pre-formed polymer, polyE-323. The EOF direction in the microchannel was reversed by both TMSVE and polyE-323 coatings. The cation-selective preconcentration was investigated using charged fluorescent dyes and tetramethylrhodamine isothiocyanate (TRITC)-tagged peptides/proteins. The preconcentration in the three different systems was compared with respect to efficiency, dependence on buffer concentration and pH, tolerable flow rate, and sample adsorption. Both TMSVE- and polyE-323-coated nanochannels showed robust preconcentration at high flow rates, whereas the PDADMAC membrane maintained anion-permselectivity at higher buffer concentrations. The TMSVE-coated nanochannels showed a more stable preconcentration process, whereas the polyE-323-coated nanochannels showed a lower peptide sample adsorption and robust efficiency under a wide range of buffer pHs. The system described here can potentially be used for the preconcentration of cationic peptides/proteins on microfluidic devices for subsequent analyses. PMID:24733115
Shin, Il Hyung; Kim, Ki-Jung; Kim, Jiman; Kim, Hee Chan; Chun, Honggu
Cation diffusion in titanomagnetites
Interdiffusion couple experiments were performed with titanomagnetite single crystals at 1,000�C, 1,100� C and 1,200� C in various buffered atmospheres. The dependence of the interdiffusion coefficient on oxygen fugacity, composition and temperature was interpreted in terms of point defect structure. Estimates of the cation tracer diffusivities indicate that Fe migrates via a point defect mechanism, involving mixed tetrahedral-octahedral site jumps,
R. Aragon; R. H. McCallister; H. R. Harrison
Analysis of chromite by cation-exchange using ethylenediaminetetra-acetic acid.
A method for the separation and determination of five major elements in chromite ore (and chrome-bearing refractories), based on complexation of the metals with EDTA is described. After removal of silica, the cations are separated into two groups by passing the solution through a cation-exchange resin (Dowex 50W-X8, in Na-form) in the presence of an excess of the complexing agent. The optimum conditions for the separation are discussed on the basis of exchange constants that were either known or determined. The first group contains Cr and Fe, which emerge in the filtrate at pH between 1.5 and 2.1, whereas A1, Mg and Ca, which are adsorbed on the resin, form another group. Complexometric titrations are used for the subsequent determination of the cations in each group. The method is simpler and more rapid and accurate for routine analysis than the current methods. PMID:18961783
Jawaid, M; Ingman, F
The difference between the potentiometric surfaces of the Aquia Aquifer of September 1986 and September 1988 in southern Maryland
A map was prepared that shows the net change in the potentiometric surface of the Aquia aquifer (in the Paleocene Aquia Formation) in southern Maryland from the fall of 1986 to the fall of 1988. The map, based on water level measurements from 74 observation wells, shows that during the 2 year period the potentiometric surface declined less than 6 ft in most of southern Maryland but 10 ft or more in the Lexington Park and Solomons Island areas. (USGS)
Potentiometric Multisensor Based on Ruthenium Dioxide Thin Film With a Bluetooth Wireless and Web-Based Remote Measurement System
This study reports the preparation and analysis of a potentiometric multisensor for detecting pH, uric acid, and glucose levels. The pH sensor was based on a ruthenium dioxide (RuO2) sensing membrane. The potentiometric uric acid and glucose biosensors consisted of immobilized uricase and glucose oxidase (GOD) enzymes on the RuO2 sensing membrane. The ruthenium dioxide sensing membrane was first deposited
Yi-Hung Liao; Jung-Chuan Chou
Influence of decyl alcohol on the potentiometric behavior of three p-alkylbenzenesulfonate ion-selective electrodes
The influence of decyl alcohol on the potentiometric response of three para-alkylbenzenesulfonate (p-RBS) electrodes is analyzed. The results are clearly dependent on the membrane surface polarity due to the presence of the alcohol. The ionophore was the complex trioctylmethylammonium�p-RBS, (TOMA+)�p-RBS?, with R=H, CH3, and C2H5. The nature of the complex plays a fundamental role on the potentiometric behavior of the
Walton J. Cabrera; Marcela D. Urz�a; Hern�n E. R�os
A New Potentiometric Sensor for the Determination of Desipramine Based on N-(1Naphthyl)Ethylenediamine Dihydrochloride-Tetraphenyl Borate
A new fast and sensitive potentiometric sensor is introduced for the determination of desipramine. The membrane was prepared by incorporating of N-(1-naphthyl)ethylenediamine dihydrochloride with sodium tetraphenyl borate (as an ion-pair). In this study, different plasticized poly(vinyl chloride) (PVC) mem- branes with different compositions were tested to construct the potentiometric sensor. A membrane with an ion-pair:dioctylseba- cate:PVC ratio of 8.2:61.7:30.1 was
Ali A. Ensafi; Ali R. Allafchian
Potentiometric, spectrophotometric and density functional study of the interaction of N-hydroxyacetamide with oxovanadium(IV): the influence of ligand to the V(IV)/V(V) oxi-reduction reaction.
The interaction of N-hydroxyacetamide (acetohydroxamic acid, HL) with V(IV) in aqueous solution has been investigated using potentiometric and spectrophotometric experiments. Density functional method (DFT) has been used aiming to understand the ligand chelation at a molecular level. Stability constants have been estimated for species with the metal/ligand ratios 1:1 and 1:2 from spectrophotometric and potentiometric measurements. The stability of these V(IV) species toward oxidation has been investigated. Experiments carried out in an oxygen atmosphere led to the displacement of the titration curves with respect to the one obtained under inert atmosphere. Spectrophotometric evidence of the V(IV)/V(V) oxidation in the presence of N-hydroxyacetamide is presented. It has been shown that V(IV)/V(V) oxidation in the presence of N-hydroxyacetamide by the oxygen can be simulated using the standard programs for simulating the equilibrium in a multiligand/multimetal system. In this approach, the oxygen is considered a ligand and the log beta estimated from the standard oxidation potential. The structure and respective tautomers of the species have been optimized from DFT calculations. Geometrical and thermodynamical properties have been estimated for the most stable complexes. The VOL-->VOL(2) equilibrium constant has been theoretically estimated with a less than 1.5 logarithmic unit of error with respect to the experimental estimate. The oxidation process has also been investigated and it is adequately described by the equation: 4[VOL(2)]+2H(2)O+O(2)-->4[VO(OH)L(2)]. The calculated value of DeltaG for this reaction is about -46.2 kcal mol(-1), in excellent agreement with the experimental estimates. PMID:12706537
da Silva Santos, Jos� Mauro; Carvalho, Sandra; Paniago, Eucler B; Duarte, H�lio A
A Computer-Based Simulation of an Acid-Base Titration
Reviews the advantages of computer simulated environments for experiments, referring in particular to acid-base titrations. Includes pre-lab instructions and a sample computer printout of a student's use of an acid-base simulation. Ten references. (PR)
Boblick, John M.
Going Beyond, Going Further: The Preparation of Acid-Base Titration Curves.
Background information, list of materials needed, and procedures used are provided for a simple technique for generating mechanically plotted acid-base titration curves. The method is suitable for second-year high school chemistry students. (JN)
McClendon, Michael
Effect of Molecular Acid-Base Dissociation of Salts on Conductometric Titration Curves in Acetonitrile.
The main objectives of the paper are to calculate Kf and Kd from the characteristics of conductometric titration curves at different initial concentrations of acid. Equations were derived to find, under specified conditions, Kf from the location of and Kd...
I. M. Kolthoff M. K. Chantooni
Accuracy of an Unattended Home CPAP Titration in the Treatment of Obstructive Sleep Apnea
Treatment of sleep apnea-hypopnea syndrome (SAHS) by fixed continuous positive airway pressure (CPAP) requires an in-labora- tory titration procedure to determine the effective pressure level (Peff). We recently reported that one auto-CPAP machine can be used without titration study allowing Peff determination. The aim of this study was to evaluate the accuracy of an auto CPAP trial at home. A
Helix-coil transformation and titration curve of poly-L-glutamic acid
The titration curve of poly-L-glutamic acid was studied in connection with the helix-coil transformation. In aqueous solution the transformation has its origin in the ionization of the polar group COOH in the side chain. Conversely the ionization and the titration curve of this molecule are affected by the change of the electrostatic interaction produced by its transformation. It is shown
Akiyoshi Wada
Revisiting titration procedures for the determination of exchangeable acidity and exchangeable aluminum in soils
The use of 1 mol L ammonium chloride (NH4Cl) or ammonium nitrate (NH4NO3) solutions as alternative soil extractants were evaluated for the determination of the exchangeable acidity and exchangeable aluminum (Al) in twelve soil samples by the traditional titration\\/back?titration method. The exchangeable Al results were compared with those obtained by inductively coupled plasma emission spectrometry (ICP?AES) measurements while the exchangeable
Aline Ren�e Coscione; Jo�o Carlos de Andrade; Bernardo van Raij
Report of a patient chewing fentanyl patches who was titrated onto methadone
This case report discusses the clinical presentation and management of a patient presenting to substance misuse services reporting chewing fentanyl patches in addition to wearing them transdermally. The patient was successfully titrated onto methadone 30 mg. Only one previously reported case of an individual chewing fentanyl patches was found in the literature; no case reports were found where treatment involved titrating the patient onto methadone. The pharmacology and illicit use of fentanyl are also considered.
Dale, Eric; Ashby, Fleur; Seelam, Kalyan
The Softening of Hard Water and Complexometric Titrations. An Undergraduate Experiment
A 2-hour experiment for undergraduates is presented in which (i) water hardness is explained and demonstrated; (ii) ion-exchange resin properties are visually demonstrated and then used for softening water; (iii) complexometric titrations are used for evaluating water hardness before and after softening; and (iv) acid-base titration can be used to show that the Ca\\/Mg ions removed by the ion exchanger
Helena Ceretti; Enrique A. Hughes; Anita Zalts
Complexometric titration of copper (II) using chromotropic acid dioxime as a metal indicator
Chromotropic acid dioxime forms purple coloured complexes with copper in the pH ranges 5.82 to 6.45 and 7.25 to 8.05 respectively which are less stable than the CuII-EDTA complex. On titrating these solutions with EDTA, the purple coloured complexes turn colourless or yellow at the end point. These titrations give satisfactory results in the temperature ranges 20 to 70� C
A. B. Sen; T. S. Srivastava
Potentiometric Determination of CO2 Concentration in the Gaseous Phase: Applications in Different Laboratory Activities
Four simple experiments are described, in two laboratory sessions of 3 hours each. They provide high school students of a combined science course with the opportunity to review and integrate many topics while participating in a hands-on activity that resembles real industrial problems. The first lab comprises the calibration of a CO2 potentiometric detector with gas mixtures. The CO2 and CO2-free air required for the gaseous samples are produced in the lab by an inexpensive and simple apparatus. In the second lab, the CO2 potentiometric device is used to measure CO2uptake and release during different metabolic processes. The variation of CO2 production will be also estimated while changing the air/fuel proportion in a Bunsen burner.
Cort�n, Eduardo; Kocmur, Santiago; Haim, Liliana; Galagovsky, Lydia
Potentiometric strip cell based on carbon nanotubes as transducer layer: toward low-cost decentralized measurements.
In this study, we developed a potentiometric planar strip cell based on single-walled carbon nanotubes that aims to exploit the attributes of solid-contact ion-selective electrodes for decentralized measurements. That is, the ion-selective and reference electrodes have been simultaneously miniaturized onto a plastic planar substrate by screen-printing and drop-casting techniques, obtaining disposable strip cells with satisfactory performance characteristics (i.e., the sensitivity is 57.4 � 1.3 mV/dec, the response time is ?30 s within the linear range from log a(K+) = -5 to -2, and the limit of detection is -6.5), no need of maintenance during long dry storage, quick signal stabilization, and light insensitivity in short-term measurements. We also show how the new potentiometric strip cell makes it possible to perform decentralized and rapid determinations of ions in real samples, such as saliva or beverages. PMID:21961835
Rius-Ruiz, F Xavier; Crespo, Gast�n A; Bejarano-Nosas, Diego; Blondeau, Pascal; Riu, Jordi; Rius, F Xavier
Map showing the potentiometric surface of the Magothy Aquifer in southern Maryland, August 1980
This map is based on measurements made in a network of 77 observation wells. Highest levels of the potentiometric surface, 61 to 64 feet above sea level, were near the outcrop or subcrop of the aquifer in topographically high areas of Anne Arundel and northern Prince Georges Counties. The potentiometric surface slopes toward centers of pumpage near Annapolis, in northern Charles County, and southern Prince Georges County. Two separate , distinct, and extensive cones of depression have developed in the surface around the well fields of Waldorf, in northern Charles County, and the Chalk Point power plant, in southern Prince Georges County. The cone of depression in the Annapolis area has coalesced with a more shallow cone that includes the Broadneck Peninsula. The network of wells was developed and is operated and maintained as part of the cooperative program between the U.S. Geological Survey and agencies of the Maryland Department of Natural Resources. (USGS)
Potentiometric Surface of the Upper Patapsco Aquifer in Southern Maryland, September 2002
This report presents a map showing the potentiometric surface of the Upper Patapsco aquifer in the Patapsco Formation of Lower Cretaceous age in Southern Maryland during September 2002. The map is based on water-level measurements in 50 wells. The highest measured water level was 117 feet above sea level near the northern boundary and outcrop area of the aquifer in northern Anne Arundel County. From this area, the potentiometric surface declined to the southeast toward large well fields in Arnold and Annapolis, and from all directions toward a cone of depression located southwest of Waldorf. The measured ground-water level declined to 36 feet below sea level in Arnold, and to 23 feet below sea level in Annapolis. The lowest water level measured was 136 feet below sea level southwest of Waldorf.
Potentiometric Surface of the Aquia Aquifer in Southern Maryland, September 2001
This report presents a map showing the potentiometric surface of the Aquia aquifer in the Aquia Formation of Paleocene age in Southern Maryland during September 2001. The map is based on water-level measurements in 76 wells. The potentiometric surface was highest at 40 feet above sea level near the northern boundary and outcrop area of the aquifer in the central part of Anne Arundel County, and was below sea level in the remainder of the study area. The hydraulic gradient was directed southeastward toward an extensive cone of depression around well fields at Lexington Park and Solomons Island. A cone of depression formed in northern Calvert County due to pumpage at Chesapeake Beach and North Beach. The water level has declined to 44 feet below sea level in this area. The lowest measurement was 160 feet below sea level at the center of a cone of depression at Lexington Park.
Potentiometric surface map of the Magothy aquifer in southern Maryland, September, 2003
This report presents a map showing the potentiometric surface of the Magothy aquifer in the Magothy Formation of Upper Cretaceous age in Southern Maryland during September 2002. The map is based on water-level measurements in 79 wells. The highest measured water level was 83 feet above sea level near the northern boundary and outcrop area of the aquifer in the north-central part of Anne Arundel County. The potentiometric surface declined towards the south and east. Local gradients were directed toward the centers of two cones of depression that developed in response to pumping. These cones of depression were centered around well fields in the Waldorf area and at the Chalk Point power plant. Measured ground-water levels were as low as 81 feet below sea level in the Waldorf area and 75 feet below sea level at Chalk Point.
Potentiometric Surface of the Magothy Aquifer in Southern Maryland, September 2002
Potentiometric surface of the Aquia Aquifer in southern Maryland during September 1988
A map showing the potentiometric surface of the Aquia aquifer in the Paleocene Aquia Formation in southern Maryland during the fall of 1988 was constructed on the basis of water level measurements made at 84 observation wells. The potentiometric surface was above sea level near the northwestern boundary and outcrop area of the aquifer in topographically high areas of Anne Arundel and Prince Georges Counties; it was below sea level in the remainder of the study area. The hydraulic gradient generally was to the southeast toward an extensive cone of depression centered around well fields near Lexington Park and Solomons Island. Water levels were more than 60 ft below sea level in a 50 sq-mi area near the center of the cone and were more than 100 ft below sea level at two of the wells near the center of the cone. (USGS)
Rapid Detection of High Charge Density Polyanion Contaminants in Biomedical Heparin Preparations Using Potentiometric Polyanion Sensors
A very simple and inexpensive method to detect oversulfated chondroitin sulfate (OSCS) or other high charge density polyanionic structures as contaminants in heparin products using potentiometric polyanion sensors is described. In the potentiometric measurement, a greater change in the phase boundary equilibrium potential of polymeric membranes formulated with tridodecylmethylammonium (TDMA) anion exchange sites is observed for the contaminated heparin than for the untainted heparin due to the higher charge density of OSCS or other impurities compared to that of porcine heparin. Detection of 0.5 wt% OSCS impurity is readily achieved using only 1 mg/mL of final polyion concentration. Even lower detection limits for OSCS contamination may be possible if higher final concentrations of heparin preparations can be employed in the test procedure.
Wang, Lin; Buchanan, Stacey; Meyerhoff, Mark E.
Potentiometric Surface of the Magothy Aquifer in Southern Maryland, September 2007
This report presents a map showing the potentiometric surface of the Magothy aquifer in the Magothy Formation of Late Cretaceous age in Southern Maryland during September 2007. The map is based on water-level measurements in 69 wells. The highest measured water level was 85 feet above sea level near the northern boundary and outcrop area of the aquifer in the north-central part of Anne Arundel County. The potentiometric surface declined towards the south. Local gradients were directed toward the center of a cone of depression in the Waldorf area that developed in response to pumping. Measured ground-water levels were as low as 90 feet below sea level in the Waldorf area.
Curtin, Stephen E.; Andreasen, David C.; Staley, Andrew W.
Potentiometric Surface of the Patuxent Aquifer in Southern Maryland, September 2007
This report presents a map showing the potentiometric surface of the Patuxent aquifer in the Patuxent Formation of Early Cretaceous age in Southern Maryland during September 2007. The map is based on water-level measurements in 41 wells. The highest measured water level was 165 feet above sea level near the northwestern boundary and in the outcrop area of the aquifer in northern Prince George's County. From this area, the potentiometric surface declined south towards well fields at Glen Burnie, Bryans Road, the Morgantown power plant, and the Chalk Point power plant. The measured ground-water levels were 81 feet below sea level at Glen Burnie, 47 feet below sea level southwest of Bryans Road, 27 feet below sea level at the Morgantown power plant, and 24 feet below sea level at the Chalk Point power plant.
The adsorption of cationic and amphoteric copolymers on glass surfaces: zeta potential measurements, adsorption isotherm determination, and FT Raman characterization.
The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed. PMID:12909030
Tartakovsky, Alla; Drutis, Dane M; Carnali, Joseph O
Flow injection potentiometric determination of total antioxidant activity of plant extracts
A new flow injection potentiometric (FIP) method, rapid, reproducible and simple to apply, has been developed for the in vitro evaluation of antioxidative capacity of aqueous plant extracts. This method is based on the transient negative signal measurements with a flow-type platinum electrode detector due to the composition change of a [Fe(CN)6]3?\\/[Fe(CN)6]4? redox-reagent solution. The variables affecting the signal height
Liliya K. Shpigun; Marina A. Arharova; Khena Z. Brainina; Alla V. Ivanova
Isocitrate analysis using a potentiometric biosensor with immobilized enzyme in a FIA system
A potentiometric biosensor for the analysis of isocitrate was developed by using a CO32?-selective electrode and enzyme immobilization in flow injection analysis (FIA). The biosensor consisted of a peristaltic pump, injector, enzyme reactor, reference electrode, working electrode, pH\\/mV meter and record. The experimental parameters that influenced the sensitivity and selectivity of the biosensors were optimized in the FIA system. A
Meera Kim; Mi-Jung Kim
Urea potentiometric enzymatic biosensor based on charged biopolymers and electrodeposited polyaniline
A potentiometric biosensor based on urease was developed for the quantitative determination of urea concentration in aqueous solutions for biomedical applications. The urease was either physisorbed onto an electrodeposited polyaniline film (PANI), or immobilized on a layer-by-layer film (LbL) assembled over the PANI film, that was obtained by the alternate deposition of charged polysaccharides (carboxymethylpullulan (CMP) and chitosan (CHI)). In
Boris Lakard; Delphine Magnin; Olivier Deschaume; Guilhem Vanlancker; Karine Glinel; Sophie Demoustier-Champagne; Bernard Nysten; Alain M. Jonas; Patrick Bertrand; Sami Yunus
Rigorous Potentiometric Determination of Metal Complexes Stability Constants: An Undergraduate Laboratory Practice
In the present work an undergraduate laboratory practice is described corresponding to both experimental and computational methods used in potentiometric equilibrium constants determinations. As an example of these determinations the system formed by Cu(II) and D-galacturonic acid was selected. Both the deprotonation constant for the ligand and the equilibrium constants for the metal chelates were determined by using the program BEST.
Escandar, Graciela M.; Federico Sala, Luis
Potentiometric determination of cysteine with thiol sensitive silver-mercury electrode
A potentiometric procedure for cysteine thiol group concentration monitoring in media generat- ing free radicals was developed using a thiol specific silver-mercury electrode. Electrolytic depo - sition of mercury on a silver wire and treatment with 20 mM cysteine in 0.5 M NaOH were used to produce the electrode. A silver-chloride electrode in saturated KCl was the reference. A glass
Jerzy Naskalski; Anna Z?bek-Adamska
Detection of Zinc and Lead in Wine by Potentiometric Stripping on Novel Dental Amalgam Electrodes
A simple method for detection of zinc and lead in wine by use of potentiometric stripping analyses (PSA) on the dental amalgam electrode is introduced and demonstrated for 10 different wines, both red and white. The combination of PSA and the novel nontoxic electrode offers a fast and easy?to?use technique without matrix effects seen in, e.g., voltammetry. Concentrations of zinc
�yvind Mikkelsen; Camilla Nordhei; Silje M. Skogvold; Knut H. Schr�der
Determination of citric acid in soft drinks using flow injection with potentiometric detection
A flow injection analysis (FIA) system with potentiometric detection has been developed for the determination of citric acid\\u000a in commercial fruit juices using a copper-selective tubular electrode. It consists of the complexation of citrate ion with\\u000a copper (II) ion, monitoring the free copper (II) concentration. Linear relationships between the potential and log concentrations\\u000a of citric acid in the range of
Jos� L. F. C. Lima; Cristina Delerue-Matos; M. Carmo; M. C. V. F. Vaz; Jeanine Silva
Factors governing the assembly of cationic phospholipid-DNA complexes.
The interaction of DNA with a novel cationic phospholipid transfection reagent, 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (EDOPC), was investigated by monitoring thermal effects, particle size, vesicle rupture, and lipid mixing. By isothermal titration calorimetry, the heat of interaction between large unilamellar EDOPC vesicles and plasmid DNA was endothermic at both physiological and low ionic strength, although the heat absorbed was slightly larger at the higher ionic strength. The energetic driving force for DNA-EDOPC association is thus an increase in entropy, presumably due to release of counterions and water. The estimated minimum entropy gain per released counterion was 1.4 cal/mole- degrees K (about 0.7 kT), consistent with previous theoretical predictions. All experimental approaches revealed significant differences in the DNA-lipid particle, depending upon whether complexes were formed by the addition of DNA to lipid or vice versa. When EDOPC vesicles were titrated with DNA at physiological ionic strength, particle size increased, vesicles ruptured, and membrane lipids became mixed as the amount of DNA was added up to a 1.6:1 (+:-) charge ratio. This charge ratio also corresponded to the calorimetric end point. In contrast, when lipid was added to DNA, vesicles remained separate and intact until a charge ratio of 1:1 (+:-) was exceeded. Under such conditions, the calorimetric end point was 3:1 (+:-). Thus it is clear that fundamental differences in DNA-cationic lipid complexes exist, depending upon their mode of formation. A model is proposed to explain the major differences between these two situations. Significant effects of ionic strength were observed; these are rationalized in terms of the model. The implications of the analysis are that considerable control can be exerted over the structure of the complex by exploiting vectorial preparation methods and manipulating ionic strength.
Kennedy, M T; Pozharski, E V; Rakhmanova, V A; MacDonald, R C
Potentiometric Surface of the Lower Patapsco Aquifer in Southern Maryland, September 2001
This report presents a map showing the potentiometric surface of the Lower Patapsco aquifer in the Patapsco Formation of Cretaceous age in Southern Maryland during September 2001. The map is based on water-level measurements in 65 wells. The potentiometric surface was as high as 110 feet above sea level near the northwestern boundary and outcrop area of the aquifer in northern Anne Arundel County. From this area, the potentiometric surface declined towards large well fields at Severndale, Arnold, and Annapolis. The ground-water levels declined to 78 feet below sea level at Severndale, 38 feet below sea level at Arnold, and 31 feet below sea level a few miles west of Annapolis. There was also a cone of depression covering a large area in Charles County that includes Waldorf, LaPlata, Indian Head, and the Morgantown power plant. The ground-water levels were as low as 173 feet below sea level at Waldorf, 126 feet below sea level at LaPlata, 112 feet below sea level at Indian Head, and 92 feet below sea level at the Morgantown power plant.
Urea potentiometric enzymatic biosensor based on charged biopolymers and electrodeposited polyaniline.
A potentiometric biosensor based on urease was developed for the quantitative determination of urea concentration in aqueous solutions for biomedical applications. The urease was either physisorbed onto an electrodeposited polyaniline film (PANI), or immobilized on a layer-by-layer film (LbL) assembled over the PANI film, that was obtained by the alternate deposition of charged polysaccharides (carboxymethylpullulan (CMP) and chitosan (CHI)). In the latter case, the urease (Urs) enzyme was either physically adsorbed or covalently grafted to the LbL film using carbodiimide coupling reaction. Potentiometric responses of the enzymatic biosensors were measured as a function of the urea concentration in aqueous solutions (from 10(-6) to 10(-1) mol L(-1) urea). Very high sensitivity and short response time were observed for the present biosensor. Moreover, a stability study showed a higher stability over time for the potentiometric response of the sensor with the enzyme-grafted LbL film, testifying for the protective nature of the polysaccharide coating and the interest of covalent grafting. PMID:21536421
Lakard, Boris; Magnin, Delphine; Deschaume, Olivier; Vanlancker, Guilhem; Glinel, Karine; Demoustier-Champagne, Sophie; Nysten, Bernard; Jonas, Alain M; Bertrand, Patrick; Yunus, Sami
Man-tailored biomimetic sensor of molecularly imprinted materials for the potentiometric measurement of oxytetracycline.
A novel biomimetic sensor for the potentiometric transduction of oxytetracycline is presented. The artificial host was imprinted in methacrylic acid and/or acrylamide based polymers. Different amounts of molecularly imprinted and non-imprinted polymers were dispersed in different plasticizing solvents and entrapped in a poly(vinyl chloride) matrix. Only molecularly imprinted based sensors allowed a potentiometric transduction, suggesting the existence of host-guest interactions. These sensors exhibited a near-Nernstian response in steady state evaluations; slopes and detection limits ranged 42-63 mV/decade and 2.5-31.3 ?g/mL, respectively. Sensors were independent from the pH of test solutions within 2-5. Good selectivity was observed towards glycine, ciprofloxacin, creatinine, acid nalidixic, sulfadiazine, cysteine, hydroxylamine and lactose. In flowing media, the biomimetic sensors presented good reproducibility (RSD of �0.7%), fast response, good sensitivity (65 mV/decade), wide linear range (5.0�10(-5) to 1.0�10(-2) mol/L), low detection limit (19.8 ?g/mL), and a stable baseline for a 5�10(-3) M citrate buffer (pH 2.5) carrier. The sensors were successfully applied to the analysis of drugs and urine. This work confirms the possibility of using molecularly imprinted polymers as ionophores for organic ion recognition in potentiometric transduction. PMID:20688507
Moreira, Felismina T C; Kamel, Ayman H; Guerreiro, Joana R L; Sales, M Goreti F
Application of flow-injection potentiometric system for determination of total concentration of aliphatic carboxylic acids.
In this work, flow-injection system with potentiometric detection was tested for determination of total carboxylic acid concentration. Detection part of the examined system consists of ion-selective electrodes (ISEs) with polymer membranes of different compositions. First electrode is based on Zr(IV)-tetraphenylporphyrin as ionophore selective towards carboxylic acid anions, the membrane of second one contains only liphophilic anion exchanger - tridodecylmethylammonium chloride. Final response of the system is a result of combination of EMF signals from both electrodes. Combination of two detectors enables significant decrease of differences between potentiometric signals induced by mixtures of studied anions of various concentrations as compared to results obtained only with metalloporphyrin-based ISE. The use of anion-exchanger based detector allows for elimination of the influence of aliphatic carboxylic acids lipophilicity. Proposed potentiometric flow-injection system was employed for determination of short-chain aliphatic carboxylic acids (so-called VFA - volatile fatty acids) in samples originating from an anaerobic digester. Results obtained for these relatively complicated samples are in good agreement with results obtained with the use of reference colorimetric method. Linear response towards carboxylic acids was observed in the concentration range of 10(-4) to 10(-2)mold m(-3), with the slopes in the range of -110 to -150 mV dec(-1) (for acetate(-) and butyrate(-), respectively). System enables for determination of about 6 samples per hour. Life time of ISEs average about 2 months. PMID:21872056
Mroczkiewicz, Monika; G�rski, ?ukasz; Zamojska-Jaroszewicz, Anna; Szewczyk, Krzysztof W; Malinowska, El?bieta
Potentiometric Surface of the Upper Floridan Aquifer, West-Central Florida, May 2007
The Floridan aquifer system consists of the Upper and Lower Floridan aquifers separated by the middle confining unit. The middle confining unit and the Lower Floridan aquifer in west-central Florida generally contain highly mineralized water. The water-bearing units containing fresh water are herein referred to as the Upper Floridan aquifer. The Upper Floridan aquifer is the principal source of water in the Southwest Florida Water Management District and is used for major public supply, domestic use, irrigation, and brackish water desalination in coastal communities (Southwest Florida Water Management District, 2000). This map report shows the potentiometric surface of the Upper Floridan aquifer measured in May 2007. The potentiometric surface is an imaginary surface connecting points of equal altitude to which water will rise in tightly-cased wells that tap a confined aquifer system (Lohman, 1979). This map represents water-level conditions near the end of the dry season, when ground-water levels usually are at an annual low and withdrawals for agricultural use typically are high. The cumulative average rainfall of 41.21 inches for west-central Florida (from June 2006 through May 2007) was 11.63 inches below the historical cumulative average of 52.84 inches (Southwest Florida Water Management District, 2007). Historical cumulative averages are calculated from regional rainfall summary reports (1915 to most recent complete calendar year) and are updated monthly by the Southwest Florida Water Management District. This report, prepared by the U.S. Geological Survey in cooperation with the Southwest Florida Water Management District, is part of a semi-annual series of Upper Floridan aquifer potentiometric-surface map reports for west-central Florida. Potentiometric-surface maps have been prepared for January 1964, May 1969, May 1971, May 1973, May 1974, and for each May and September since 1975. Water-level data are collected in May and September each year to show the approximate annual low and high water-level conditions, respectively. Most of the water-level data for this map were collected by the U.S. Geological Survey during the period May 21-25, 2007. Supplemental water-level data were collected by other agencies and companies. A corresponding potentiometric-surface map was prepared for areas east and north of the Southwest Florida Water Management District boundary by the U.S. Geological Survey office in Orlando, Florida (Kinnaman and Dixon, 2007). Most water-level measurements were made during a 5-day period; therefore, measurements do not represent a 'snapshot' of conditions at a specific time, nor do they necessarily coincide with the seasonal low water-level condition.
Ortiz, A. G.
Potentiometric Surface of the Upper Floridan Aquifer, West-Central Florida, September 2007
The Floridan aquifer system consists of the Upper and Lower Floridan aquifers separated by the middle confining unit. The middle confining unit and the Lower Floridan aquifer in west-central Florida generally contain highly mineralized water. The water-bearing units containing fresh water are herein referred to as the Upper Floridan aquifer. The Upper Floridan aquifer is the principal source of water in the Southwest Florida Water Management District and is used for major public supply, domestic use, irrigation, and brackish water desalination in coastal communities (Southwest Florida Water Management District, 2000). This map report shows the potentiometric surface of the Upper Floridan aquifer measured in September 2007. The potentiometric surface is an imaginary surface connecting points of equal altitude to which water will rise in tightly-cased wells that tap a confined aquifer system (Lohman, 1979). This map represents water-level conditions near the end of the wet season, when ground-water levels usually are at an annual high and withdrawals for agricultural use typically are low. The cumulative average rainfall of 39.50 inches for west-central Florida (from October 2006 through September 2007) was 13.42 inches below the historical cumulative average of 52.92 inches (Southwest Florida Water Management District, 2007). Historical cumulative averages are calculated from regional rainfall summary reports (1915 to most recent complete calendar year) and are updated monthly by the Southwest Florida Water Management District. This report, prepared by the U.S. Geological Survey in cooperation with the Southwest Florida Water Management District, is part of a semi-annual series of Upper Floridan aquifer potentiometric-surface map reports for west-central Florida. Potentiometric-surface maps have been prepared for January 1964, May 1969, May 1971, May 1973, May 1974, and for each May and September since 1975. Water-level data are collected in May and September each year to show the approximate annual low and high water-level conditions, respectively. Most of the water-level data for this map were collected by the U.S. Geological Survey during the period September 17-21, 2007. Supplemental water-level data were collected by other agencies and companies. A corresponding potentiometric-surface map was prepared for areas east and north of the Southwest Florida Water Management District boundary by the U.S. Geological Survey office in Orlando, Florida (Kinnaman and Dixon, 2008). Most water-level measurements were made during a 5-day period; therefore, measurements do not represent a 'snapshot' of conditions at a specific time, nor do they necessarily coincide with the seasonal high water-level condition.
Molecular modelling of cation�? interactions
Cation�? interactions have long been considered a challenge for molecular modelling and a shortcoming of most of the commonly used biomolecular force fields. In this article, we provide an overview of current research on molecular modelling of cation�? interactions, with an emphasis on applications to proteins and on our recent polarisable models based on the classical Drude oscillator. We describe
Guillaume Lamoureux; Esam A. Orabi
Potentiometric surface of the upper Floridan Aquifer in the St. Johns River Water Management District and vicinity, May 1995
This map depicts the potentiometric surface of the Upper Floridan aquifer in the St. Johns River Water Management District and vicinity for May 1995. The map is based on water-level measurements made at more than 900 wells and springs. Approximately 30 new wells were added to better define the potentiometric surface mainly in the northwest area of the map. Data on the map were contoured using 5-foot contour intervals in most areas. Two new wells located north of Rainbow Springs indicate a slight northward extension of the depressed area surrounding the springs. Several new wells in Bradford County indicate a slight reduction in the size of the potentiometric-surface high along the northwest edge of the county. The potentiometric surface of this karstic aquifer generally reflects land surface topography. Potentiometric-surface highs often correspond to topographic highs, which are areas of recharge to the Upper Floridan aquifer. Springs within topographic lows along with areas of more diffuse upward leakage are natural zones of discharge. Municipal, agricultural, and industrial withdrawals have lowered the potentiometric surface in some areas. The potentiometric surface ranged from 127 feet above sea level in Polk County to 84 feet below sea level in southeast Georgia near the St. Marys River. Water levels measured in May 1995 generally were about 0 to 4 feet higher than those measured in May 1994 except in St. Lucie County and near Rainbow Springs, where levels were 1 to 3 feet lower. Generally, May 1995 water levels were 0 to 5 feet lower than levels in September 1994, except near Orlando, where levels were 6 to 12 feet lower, and across the northwest corner of the map area which includes Marion, Alachua, Bradford, Baker, and Nassau Counties, north and west Duval County, and south Georgia. (USGS)
Knowles, Leel, Jr.; O'Reilly, A. M.; Phelps, G. G.; Bradner, L. A.
Do nonmetallic superalkali cations exist?
In order to explore the possibility of using hydrogen atoms as ligands in creating superalkalies, a systematic investigation on the FH3+, OH5+, NH7+ and CH9+ cations has been carried out. These nonmetallic cations have pretty low electron affinities (EA) of 3.55-4.48 eV at the OVGF/6-311++G(3df, 3pd) level, and hence should be classified as superalkali cations. It is also worth mentioning that the weakly bound NH7+ and CH9+ cations exhibit even lower EA values than the ionization potential of Cs atom. In addition, the positive fragmentation energies indicate the stabilities of these cation species with respect to dissociation.
Hou, Na; Li, Ying; Wu, Di; Li, Zhi-Ru
Potentiometric detection of mercury(II) ions using a carbon paste electrode modified with substituted thiourea-functionalized highly ordered nanoporous silica.
A potentiometric sensor is reported for the mercury(II) detection, which uses substituted thiourea-functionalized nanoporous silica (FTU-LUS-1) as the sensitive material. Substituted thiourea (FTU) and FTU-LUS-1 were first prepared and then characterized by 1H NMR, 19F NMR, 13C NMR, FTIR, XRD, TG and CNS elemental analysis. The electrodes with FTU-LUS-1 proportion of 10.0 wt% demonstrated very stable potentials. The prepared electrodes exhibit a Nernstian slope of 28.4 +/- 1.0 mV decade(-1) for mercury(II) ion over a wide concentration range of 1.0 x 10(-7) to 1.0 x 10(-1) mol dm(-3). The electrode exhibited a detection limit of 7.0 x 10(-8) mol dm(-3). Moreover, the selectivity coefficient, response time, performance, sensitivity and stability of the modified electrode were investigated. The electrode presented a response time of about 35 s, a high performance and sensitivity in a wide range of cation activities as well as good long term stability (more than 9 months). The method was satisfactory and could also be used to monitor the mercury(II) ion concentration in waste water and fish samples. PMID:19531889
Javanbakht, Mehran; Divsar, Faten; Badiei, Alireza; Ganjali, Mohammad Reza; Norouzi, Parviz; Mohammadi Ziarani, Ghodsi; Chaloosi, Marzieh; Abdi Jahangir, Ali
Ascorbic Acid as a Standard for Iodometric Titrations. An Analytical Experiment for General Chemistry
Ascorbic acid is suggested as the weighable compound for the standardization of iodine solutions in an analytical experiment in general chemistry. The experiment involves an iodometric titration in which iodine reacts with ascorbic acid, oxidizing it to dehydroascorbic acid. The redox titration endpoint is determined by the first iodine excess that is complexed with starch, giving a deep blue-violet color. The results of the titration of iodine solution using ascorbic acid as a calibration standard were compared with the results acquired by the classic method using a standardized solution of sodium thiosulfate. The standardization of the iodine solution using ascorbic acid was accurate and precise, with the advantages of saving time and avoiding mistakes due to solution preparation. The colorless ascorbic acid solution gives a very clear and sharp titration end point with starch. It was shown by thermogravimetric analysis that ascorbic acid can be dried at 393 K for 2 h without decomposition. This experiment allows general chemistry students to perform an iodometric titration during a single laboratory period, determining with precision the content of vitamin C in pharmaceutical formulations.
Silva, Cesar R.; Simoni, Jose A.; Collins, Carol H.; Volpe, Pedro L. O.
Kinetic and chemical mechanisms for the effects of univalent cations on the spectral properties of aromatic amine dehydrogenase.
Univalent cations and pH influence the UV-visible absorption spectrum of the tryptophan tryptophylquinone (TTQ) enzyme, aromatic amine dehydrogenase (AADH). Little spectral perturbation was observed when pH was varied in the absence of univalent cations. The addition of alkali metal univalent cations (K+, Na+, Li+, Rb+ or Cs+) to oxidized AADH caused significant changes in its absorption spectrum. The apparent Kd for each cation, determined from titrations of the spectral perturbation, decreased with increasing pH. Transient kinetic studies involving rapid mixing of AADH with cations and pH jump revealed that the rate of the cation-induced spectral changes initially decreased with increasing cation concentration to a minimum value, then increased with increasing cation concentration. A kinetic model was developed to fit these data, determine the true pH-independent Kd values for K+ and Na+, and explain the pH-dependence of the apparent Kd. A chemical reaction mechanism, based on the kinetic data, is presented in which the metallic univalent cation facilitates the chemical modification of the TTQ prosthetic group to form an hydroxide adduct which gives rise to the spectral change. Addition of NH4(+)/NH3 to AADH caused changes in the absorption spectrum which were very different form those caused by addition of the metallic univalent cations. The kinetics of the reaction induced by addition of NH4+/NH3 were also different, being simple saturation kinetics. Another reaction mechanism is proposed for the NH4+/NH3-induced spectral change that involves nucleophilic addition of the unprotonated NH3 to TTQ. The general relevance of these data and models to the physiological reactions of TTQ-dependent enzymes and to the roles of univalent cations in modulating enzyme activity are discussed.
Zhu, Z; Davidson, V L
Potentiometric surface of the upper Floridan Aquifer in the St. Johns River Water Management District and vicinity, Florida, May 1994
This map depicts the potentiometric surface of the Upper Floridan aquifer in the St. Johns River Water Management District and vicinity for May 1994. The map is based on water-level measurements made at approximately 1,000 wells and several springs. Data on the map were contoured using 5-foot contour intervals in most areas. The potentiometric surface of this karstic aquifer generally reflects land surface topography. Potentiometric surface highs often correspond to topographic highs, which are areas of surficial recharge to the Upper Floridan aquifer. Springs within topographic lows along with areas of more diffuse upward leakage are natural zones of discharge. Municipal, agricultural, and industrial withdrawals have lowered the potentiometric surface in some areas. The potentiometric surface ranged from 125 feet above sea level in Polk County to 32 feet below sea level in Nassau County. Water levels in May 1994 generally were 0 to 3 feet lower than those measured in May 1993. Water levels in May 1994 in northeast Florida generally were 0 to 3 feet higher than in September 1993, except in the lower St. Johns River basin, where water levels were 0 to 4 feet lower than in September 1993. In the rest of the mapped area, water levels in May 1994 generally were 0 to 4 feet lower than those measured in September 1993.
Schiffer, D. M.; O'Reilly, A. M.; Phelps, G. G.; Bradner, L. A.; Halford, K. J.; Spechler, R. M.
Use of potentiometric detection in (ultra) high performance liquid chromatography and modelling with adsorption/desorption binding kinetics.
Observation of a potentiometric sensor's response behaviour after injection in flow injection analysis at different concentrations allowed studying "on" and "off" kinetics of the analyte's adsorption/diffusion behaviour. The alkaloid metergoline was mostly used as an example. k(on) and k(off) rate constant values were measured, and the association constant K(ass), and ?G values of the analyte-surface interaction were calculated with an adsorption-based model which proved to be fully applicable. k(on) increased by decreasing the sensor dimensions, while koff was unaffected by miniaturization. Increasing acetonitrile concentrations in the running buffer increased k(off), while k(on) was unaffected. The experimentally determined ?G values of the analyte-surface interaction showed a linear relation to the response of the sensor, in mV. This knowledge was applied to optimize the potentiometric detection of plant alkaloids in (U)HPLC. Sub-micromolar detection limits were obtained with the potentiometric detector/(U)HPLC combination. This is the first time that the response rates and the response itself can be modelled accurately for coated wire potentiometric sensors, and it is the first application of a potentiometric detector in UPLC. PMID:23622961
Daems, D; Van Camp, G; Fernandez, M; Guisez, Y; Prinsen, E; Nagels, L J
Studies on the interaction between alkali metal cations and polyion by sound velocity.
The sound velocities in polyelectrolyte solutions were measured at various concentrations of added salts. When aqueous solutions of tetra (n-butyl)ammonium polyacrylate were titrated with concentrated solutions of LiCl, NaCl, KCl or CsCl, the sound velocity, i.e., the adiabatic compressibility of the solution, did not change linearly with added salt concentration, but showed a breaking point. The degrees of counterion binding on polyacrylate ion estimated from the breaking points were 0.25-0.30, independent of cation species. In polystyrenesulfonate, moreover, no Na+ binding was detected from such sound velocity measurements. PMID:17007790
Koda, S; Nomura, H; Nagasawa, M
NMR spectroscopy for determination of cationic polymer concentrations.
Organic polyelectrolytes are utilized extensively in wastewater treatment, but their fate after use is poorly understood. Analytical methods used for polymer determination in less complex systems appear to fail in application to wastewater systems, contributing to the lack of knowledge. Thus, the development of 1H NMR spectroscopy is reported here for specifically quantitating certain cationic flocculant polymers in environmental samples. Proton observe frequencies of 250 or 400 MHz proton were used. A copolymer of acrylamide and acryloyloxyethyltrimethylammonium chloride was used, representative of cationic flocculant polymers possessing quaternary ammonium groups with terminal methyls that provide a sharp singlet at a chemical shift of approximately 3.06 ppm. A strong linear relationship was demonstrated between polymer concentration and either height or area of this peak. Recoveries were up to 96% at higher concentrations (250 mg/L), and were greater than when using viscosity or charge titration methods for polymer determination. Lesser recoveries at lower concentrations (70% at 5 mg/L) were attributed to adsorptive losses. The detection limit of this method was determined to be <0.5 mg/L. Use of the method was exemplified by analysis of anaerobically digested sludges for residual polymer following a range of dosages, showing the resulting isotherm. PMID:12108718
Chang, Lin-Li; Bruch, Martha D; Griskowitz, Nancy J; Dentel, Steven K
Synthetic cation-selective nanotube: Permeant cations chaperoned by anions
The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 A? long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 A?. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.
Hilder, Tamsyn A.; Gordon, Dan; Chung, Shin-Ho
Preliminary map showing the difference between the potentiometric surfaces of the Aquia Aquifer of September 1982 and September 1984 in southern Maryland
Rapid carvedilol up-titration in hospitalized patients with systolic heart failure.
To determine whether carvedilol can be safely up-titrated before hospital discharge, we studied 372 consecutive patients with systolic heart failure who were being treated with carvedilol. Carvedilol was initiated a median of 3 days after admission, with a mean starting dose of 12 mg. Up-titration was performed in 67% of patients, with a mean increase of 16 mg and a mean discharge daily dose of 23 +/- 17 mg. Mean daily dose at the end of follow-up was 35.3 +/- 25.3 mg and it increased with higher discharge dose. PMID:18656807
Mart�nez-Sell�s, Manuel; Datino, Tom�s; Alhama, Marta; Barrueco, Nelida; Castillo, Isabel; Fern�ndez-Avil�s, Francisco
Selective two-step titration of thorium by sulfate displacement of the diethylenetriaminepentaacetic acid complex
Thorium and other metals are complexed with excess diethylenetriaminepentaacetic acid (DTPA) at pH 1.4, the excess DTPA is titrated with Bi(III) to a xylenol orange end point, sulfate is added to complex Th(IV), and the displaced DTPA again is titrated with Bi(III). Of 61 metal ions and nonmetal anions tested, only Ga(III), Sc(III), tungstate, citrate, oxalate, and thiosulfate interfere seriously. Lesser interferences are In(III), Zr(IV), V(IV), and permanganate. The standard deviation is 2 ..mu..g for 56 to 840 ..mu..g Th.
Kiefer, P.
Specification of colour changes of metallochromic indicators in the titration of bismuth with EDTA.
The quality of the colour changes at the end-point in the complexometric titration of bismuth(III) with EDTA, using the indicators Hemotoxylin, PAN [1-(2-Pyridylazo)-Naphthol-2], PAR [4-(2-Pyridylazo)-Resorcinol], Xylenol Orange and Thoran is studied by means of the CIE 1931 trichromatic system, using specific colour discrimination (SCD) and colour difference (DeltaE*). The indicators are arranged in order of colour change quality. Of the indicators studied, Hemotoxylin is recommended as the most suitable for this titration. PMID:18965223
Prasad, K M; Raheem, S
Potentiometric surface of the upper Cape Fear Aquifer in the central coastal plain of North Carolina, December 1986
Water-level measurements were made in 84 wells open to the upper Cape Fear aquifer at the end of 1986 to determine the configuration of its potentiometric surface over an area of approximately 5,500 sq mi. The major feature of the potentiometric surface is the development of a large, almost circular cone of depression as a result of the merging of a number of smaller cones. The center of the large cone lies along an axis between Greenville and Kinston. The potentiometric surface in the upper Cape Fear is nearly 100 ft below sea level at Greenville; it is more than 100 ft above sea level south of the Neuse River near Colorado.
Novel potentiometric membrane sensor for selective determination of aluminum(III) ions
A poly(vinyl chloride) matrix membrane sensor incorporating 7-ethylthio-4-oxa-3-phenyl-2-thioxa-1,2-dihydropyrimido[4,5-d]pyrimidine (ETPTP) ionophore exhibits good potentiometric response for Al3+ over a wide concentration range (10?5 to 10?1M) with a slope of 19.5mV per decade. The sensor response is stable for at least 1 month. Good selectivity for Al3+ in comparison with alkali, alkaline earth, transition and heavy metal ions and minimal interference are
Mohamed B Saleh; Saad S. M Hassan; Ahmed A. Abdel Gaber; Nahed A. Abdel Kream
Quantitative Determination of High Charge Density Polyanion Contaminants in Biomedical Heparin Preparations Using Potentiometric Polyanion Sensors
Quantification of oversulfated chondroitin sulfate (OSCS) in biomedical heparin preparations is achieved using a recently described potentiometric polyanion sensor-based approach operated in a kinetic mode of analysis. This is accomplished by adjusting the concentration of the test sample to a range where the OSCS level is low enough for the sensor not to achieve a full and rapid equilibrium phase boundary potential change at the membrane/sample interface upon exposure to the heparin sample. Using this method, the OSCS wt% determined within heparin samples containing OSCS are shown to be in good agreement with those determined by an accepted NMR method.
Wang, Lin; Meyerhoff, Mark E.
A paper-based potentiometric cell for decentralized monitoring of Li levels in whole blood.
A novel approach to monitor Li levels in blood in decentralized (out of the lab) settings is presented. The approach uses a potentiometric cell fully made with filter paper as a support. Electrodes were built using carbon nanotubes ink to create a conductive path and a suitable polymeric membrane. Solid-state ion-selective electrodes for Li and a reference electrode were built and optimized. The results obtained on real samples of serum and whole blood are comparable with those obtained by conventional standard approaches. This platform shows an outstanding performance for the direct, fast and low-cost monitoring of Li levels in blood. PMID:24513977
Novell, Marta; Guinovart, Tom�s; Blondeau, Pascal; Rius, F Xavier; Andrade, Francisco J
Thermodynamics of Substituted Rhodanine IV: Potentiometric Studies of 3-(P-Tolylsulphonamido)Rhodanine Transition Metal Complexes
Proton-ligand dissociation and metal-ligand stability constants of 3-(p-Tolylsulphonamido)rhodanine (TSR) with some transition metal ions were calculated potentiometrically in 0.1 M KC1 and 20% (v\\/v) ethanol-water mixture. The order of stability constants was found to be: Th>UO 2>Gd>Ce>La>MnZn The dissociation constants pK of TSR and the stability constants log K of their complexes were determined at different temperatures (303, 308 and
M. M. Ghoneim; A. A. El-Bindary; A. Z. El-Sonbati; S. A. Barakat
Virtual Instrument for an Automated Potentiometric e-Tongue Employing the SIA Technique
In this work we report the design, construction, and applications of an electronic tongue (abbreviated e-tongue) based on an array of potentiometric sensors employing the Sequential Injection Analysis technique (SIA) operated as a Virtual Instrument implemented in LabVIEW6.1�. The system can use transient and stationary responses as the measured input information for e-tongues. The new concepts applied, lead to different advantages to be obtained, such as complete automation, easy handling, saving time, reliability and modularity.
Duran, Alejandro; Cortina, Montserrat; Velasco, Lya; Rodriguez, Jose Antonio; Alegret, Salvador; del Valle, Manuel
The difference between the potentiometric surfaces of the Magothy Aquifer of September 1986 and September 1988 in southern Maryland
A map was prepared that shows the net change in the potentiometric surface of the Magothy aquifer (in the Cretaceous Magothy Formation) in southern Maryland from the fall of 1986 to the fall of 1988. The map, based on water level measurements from 79 observation wells, shows that during the 2 year period the potentiometric surface declined less than 5 ft in most of the northern part of the study area and more than 10 ft in a 4-sq-mi area in northern Charles County. Net water-level rises of as much as 2 ft were measured in central Charles County. (USGS)
The Difference Between the Potentiometric Surfaces of the Upper Patapsco Aquifer, September 1982 and September 2001 in Southern Maryland
This report presents a map showing the change in the potentiometric surface of the Upper Patapsco aquifer in the Upper Patapsco Formation of Cretaceous age in Southern Maryland for September 1990 and September 2001. The map, based on water level measurements in 35 wells, shows that during the 11-year period, the potentiometric surface ranged from an increase of 3 feet at Arnold, which is located just north of Annapolis, to a decline of 24 feet 5 miles south of LaPlata and 20 feet at both Waldorf and LaPlata.
The difference between the potentiometric surfaces of the Lower Patapsco Aquifer, September 1990 and September 2003 in Southern Maryland
This report presents a map showing the change in the potentiometric surface of the Lower Patapsco aquifer in the Lower Patapsco Formation of Cretaceous age in Southern Maryland for September 1990 and September 2003. The map, based on water level measurements in 45 wells, shows that the change of the potentiometric surface during the 13- year period ranged from rises of 17 feet at Indian Head and 9 feet near the outcrop area in Glen Burnie, to declines of 40 feet at Arnold, 44 feet at Severndale, 48 feet at Waldorf, 69 feet at LaPlata, and 31 feet at the Morgantown powerplant.
The difference between the potentiometric surfaces of the lower Patapsco aquifer, September 1990 and September 1999 in southern Maryland
The difference between the potentiometric surfaces of the Magothy aquifer, September 1975 and September 1999 in southern Maryland
This report presents a map showing the change in the potentiometric surface of the Magothy aquifer in the Magothy Formation of Cretaceous age in Southern Maryland for September 1975 and September 1999. The map, based on water level measurements in 61 wells, shows that the potentiometric surface during the 24-year period ranged from zero at the outcrop area, which is in the northernmost part of the study area, to a decline of 76 feet in Waldorf. Waldorf is located near the southwesternmost part of the study area, and approaches the downdip boundary of the aquifer.
The difference between the potentiometric surfaces of the Aquia Aquifer, September 1982 and September 2003 in southern Maryland
This report presents a map showing the change in the potentiometric surface of the Aquia aquifer in the Aquia Formation of Paleocene age in Southern Maryland for September 1982 and September 2003. The map, based on water level measurements in 56 wells, shows that the potentiometric surface during the 21-year period declined from zero in the northernmost part of the study area, which is the outcrop of the aquifer, to 108 feet at Lexington Park. Lexington Park is near the southeasternmost part of the study area and approaches the downdip boundary of the aquifer.
Curtin, Stephen E.; Andreason, David C.; Wheeler, Judith C.
The difference between the potentiometric surfaces of the Aquia aquifer, September 1982 and September 1999 in southern Maryland
This report presents a map showing the change in the potentiometric surface of the Aquia aquifer in the Aquia Formation of Paleocene age in Southern Maryland for September 1982 and September 1999. The map, based on water level measurements in 67 wells, shows that the change of the potentiometric surface during the 17-year period declined from zero in the northernmost part of the study area, which is the outcrop of the aquifer, to 101 feet at Lexington Park. Lexington Park is near the southeasternmost part of the study area and approaches the downdip boundary of the aquifer.
The Difference Between the Potentiometric Surfaces of the Aquia Aquifer, September 1982 and September 2001 in Southern Maryland
The difference between the potentiometric surfaces of the Magothy aquifer, September 1975 and September 2003 in southern Maryland
This report presents a map showing the change in the potentiometric surface of the Magothy aquifer in the Magothy Formation of Cretaceous age in Southern Maryland for September 1975 and September 2003. The map, based on water level measurements in 51 wells, shows that during the 28-year period, the potentiometric surface had no change at the outcrop area, which is in the northernmost part of the study area, but declined 71 feet at Waldorf. Waldorf is located near the southwesternmost part of the study area, and approaches the downdip boundary of the aquifer.
The difference between the potentiometric surfaces of the upper Patapsco aquifer, September 1990 and September 1999 in southern Maryland
This report presents a map showing the change in the potentiometric surface of the Upper Patapsco aquifer in the Upper Patapsco Formation of Cretaceous age in Southern Maryland for September 1990 and September 1999. The map, based on water?level measurements in 37 wells, shows that the potentiometric surface during the 9- year period ranged from a decline of 1 foot in the northernmost part of the study area, which is near the outcrop of the aquifer, to a decline of 22 feet at LaPlata, which is near the southwesternmost part of the study area.
The Difference Between the Potentiometric Surfaces of the Magothy Aquifer, September 1975 and September 2001 in Southern Maryland
This report presents a map showing the change in the potentiometric surface of the Magothy aquifer in the Magothy Formation of Cretaceous age in Southern Maryland for September 1975 and September 2001. The map, based on water level measurements in 54 wells, shows that during the 26-year period, the potentiometric surface ranged from zero at the outcrop area, which is in the northernmost part of the study area, to a decline of 75 feet at Waldorf. Waldorf is located near the southwesternmost part of the study area, and approaches the downdip boundary of the aquifer.
The difference between the potentiometric surfaces of the Upper Patasco Aquifer, September 1990 and September 2003 in southern Maryland
This report presents a map showing the change in the potentiometric surface of the Upper Patapsco aquifer in the Upper Patapsco Formation of Cretaceous age in Southern Maryland for September 1990 and September 2003. The map, based on water level measurements in 32 wells, shows that during the 13-year period, the potentiometric surface changed from an increase of 6 feet at Arnold, which is located just north of Annapolis, to a decline of 25 feet at Waldorf and Lexington Park and 20 feet at LaPlata and the Chalk Point powerplant.
The Difference Between the Potentiometric Surfaces of the Upper Patapsco Aquifer in Southern Maryland, September 1990 and September 2007
This report presents a map showing the change in the potentiometric surface of the upper Patapsco aquifer in the Patapsco Formation of Early Cretaceous age in Southern Maryland for September 1990 and September 2007. The map, based on water-level measurements in 33 wells, shows that during the 17-year period, the change in the potentiometric surface ranged from zero at the edge of the outcrop area in northern Anne Arundel County to a decline of 28 feet at Crofton Meadows, 38 feet at Arnold, 36 feet at Waldorf, 35 feet at the Chalk Point power plant, and 40 feet at Lexington Park.
The Difference Between the Potentiometric Surfaces of the Magothy Aquifer in Southern Maryland, September 1975 and September 2007
This report presents a map showing the change in the potentiometric surface of the Magothy aquifer in the Magothy Formation of Late Cretaceous age in Southern Maryland for September 1975 and September 2007. The map, based on water-level measurements in 51 wells, shows that during the 32-year period, the potentiometric surface had no change at the outcrop area, which is in the northernmost part of the study area, but declined 90 feet at Waldorf. Waldorf is located near the southwesternmost part of the study area, and approaches the downdip boundary of the aquifer.
The Difference Between the Potentiometric Surfaces of the Aquia Aquifer in Southern Maryland, September 1982 and September 2007
This report presents a map showing the change in the potentiometric surface of the Aquia aquifer in the Aquia Formation of Paleocene age in Southern Maryland for September 1982 and September 2007. The map, based on water-level measurements in 53 wells, shows that the potentiometric surface during the 25-year period declined from zero in the northernmost part of the study area, which is the outcrop of the aquifer, to 117 feet at Lexington Park. Lexington Park is near the southeasternmost part of the study area and approaches the downdip boundary of the aquifer.
Complexation of triptolide and its succinate derivative with cyclodextrins: affinity capillary electrophoresis, isothermal titration calorimetry and 1H NMR studies.
The complexation of the triptolide PG490 and its succinate derivative PG490-88Na with various cyclodextrins was studied using three complementary techniques: affinity capillary electrophoresis (ACE), isothermal titration calorimetry (ITC) and nuclear magnetic resonance (NMR). The apparent binding constants of the complexes formed between the drugs and 8 CDs (?-CD, ?-CD, ?-CD, HP-?-CD, HP-?-CD, HP-?-CD, CM-?-CD and amino-?-CD) were determined by ACE through linear Scott's plots. The apparent and averaged binding constants of the complexes formed between PG490-88 and ?-CD, ?-CD, HP-?-CD, HP-?-CD or HP-?-CD are contained in the narrow range 135-167 M(-1). For the anionic CM-?-CD and cationic amino-?-CD, these constants are 38 and 278 M(-1), respectively, which is in accordance with electrostatic repulsions or attractions with the succinate moiety. ITC and NMR investigations for the binding constants determinations were performed for 2 CDs allowing high complexation: HP-?-CD and amino-?-CD. The three techniques provided similar results. ITC and NMR, in contrast to ACE, allowed to study the complexes formed between the neutral compound PG490 and neutral cyclodextrins. A more advanced characterization of the PG 490-88Na/amino-?-CD complex, which displays the highest apparent binding constant, was undertaken using NMR spectroscopy. The 1:1 stoichiometry of the complex was established by (1)H NMR 1D and selective 1D TOCSY experiments using the continuous variation method. Moreover, the 1D and 2D ROESY experiments revealed the inclusion of the isopropyl moiety of the triptolide derivative in the hydrophobic CD cavity. Altogether, the data provide strong evidences that the two triptolide compounds can be efficiently complexed with CD. PMID:22033106
Danel, C�cile; Duval, C�cile; Azaroual, Nathalie; Vaccher, Claude; Bonte, Jean-Paul; Bailly, Christian; Landy, David; Goossens, Jean-Fran�ois
Exact Analysis of Competition Ligand Binding by Displacement Isothermal Titration Calorimetry
A rigorous method for the least-squares nonlinear regression analysis of displacement isothermal titration calorimetric data is presented. The method can fit the binding isotherm of a ligand which is competitively inhibited in its binding by another bound ligand to a molecule with n identical and independent binding sites. There are no other assumptions for the method and no approximations. Analysis
Bent W. Sigurskjold
Hydrogen-ion titrations of amino acids and proteins in solutions containing concentrated electrolyte.
This report describes a first attempt to quantify the net charge as a function of solution pH for lysozyme and (alpha)-chymotrypsin at 0.1 M, 1.0 M and 3.0 M ionic strength, (IS). The calculations are based on the residue (titratable group) pK(sub a)'s in...
F. Fergg D. E. Kuehner H. W. Blanch J. M. Prausnitz
Trace analysis of acids and bases by conductometric titration with multiparametric non-linear regression.
A chemometric method for analysis of conductometric titration data was introduced to extend its applicability to lower concentrations and more complex acid-base systems. Auxiliary pH measurements were made during the titration to assist the calculation of the distribution of protonable species on base of known or guessed equilibrium constants. Conductivity values of each ionized or ionizable species possibly present in the sample were introduced in a general equation where the only unknown parameters were the total concentrations of (conjugated) bases and of strong electrolytes not involved in acid-base equilibria. All these concentrations were adjusted by a multiparametric nonlinear regression (NLR) method, based on the Levenberg-Marquardt algorithm. This first conductometric titration method with NLR analysis (CT-NLR) was successfully applied to simulated conductometric titration data and to synthetic samples with multiple components at concentrations as low as those found in rainwater (approximately 10 micromol L(-1)). It was possible to resolve and quantify mixtures containing a strong acid, formic acid, acetic acid, ammonium ion, bicarbonate and inert electrolyte with accuracy of 5% or better. PMID:18970555
Coelho, L�cia H G; Gutz, Ivano G R
Performing Titration Analyses for Water Quality. Module 17. Vocational Education Training in Environmental Health Sciences.
This module, one of 25 on vocational education training for careers in environmental health occupations, contains self-instructional materials on performing titration analysis for water quality. Following guidelines for students and instructors and an introduction that explains what the student will learn are three lessons: (1) naming each part of�
Consumer Dynamics Inc., Rockville, MD.
Titration of a Solid Acid Monitored by X-Ray Diffraction
An experiment is described to introduce students to an important class of solid-state reactions while reinforcing concepts of titration by using a pH meter and a powder X-ray diffractometer. The experiment was successful in teaching students the abstract concepts of solid-state structure and diffraction by applying the diffraction concepts learned�
Dungey, Keenan E.; Epstein, Paul
Use of tetrabutylammonium tribromide for voltametric titration of unsaturation in vegetable oils and fatty acids
The use of tetrabutylammonium tribromide as reagent for bromination of carbon-carbon double bonds of fatty acids and vegetable\\u000a oils, followed by a voltametric titration of tribromide and bromide ions, has been studied. This method is easy and fast,\\u000a and results show good accuracy and high sensitivity.
J. Berthelota; P. L. Desb�ne; A. Desb�ne-Monvernay
Impairment and Deportment Responses to Different Methylphenidate Doses in Children With ADHD: The MTA Titration Trial
ObjectiveResults of the NIMH Collaborative Multisite Multimodal Treatment Study of Children With Attention-Deficit\\/Hyperactivity Disorder (MTA) were analyzed to determine whether a double-blind, placebo-controlled methylphenidate (MPH) titration trial identified the best MPH dose for each child with attention-deficit\\/hyperactivity disorder (ADHD).
Prednisone for chronic active liver disease: dose titration, standard dose, and combination with azathioprine compared
Among 120 consecutive patients with chronic active liver disease (CALD) randomized to different treatments, those receiving maintenance doses of prednisone 20 mg daily (Pred), prednisone in doses given on alternate days and titrated to secure resolution of clinical and biochemical abnormalities (Pred-Titrad), or a combination of prednisone 10 mg and azathioprine 50 mg daily (Comb) survived and underwent resolution of
W H Summerskill; M G Korman; H V Ammon; A H Baggenstoss
Charge Density Quantification of Polyelectrolyte Polysaccharides by Conductometric Titration: An Analytical Chemistry Experiment
An easy analytical method for determination of the charge density of polyelectrolytes, including polysaccharides and other biopolymers, is presented. The basic principles of conductometric titration, which is used in the pulp and paper industry as well as in colloid and interface science, were adapted to quantify the charge densities of a�
Farris, Stefano; Mora, Luigi; Capretti, Giorgio; Piergiovanni, Luciano
Surface characterization of plasma sprayed oxide materials: estimation of surface acidity using mass titration.
The aim of this study was to characterize the influence of plasma spraying on the point of zero charge (PZC) of Al2O3-, Cr2O3- and TiO2-based materials. PZC is one of the most important parameter, which describes the acidity of oxide material in aqueous environments. PZC values of several plasma sprayed oxides were determined using mass titration method. Studies were performed for initial spray powders and plasma sprayed coating materials. In addition, mass titration experiments were performed for water-washed and nonwashed samples. It was found that mass titration is a suitable method to estimate the surface acidity of relatively coarse sample powders. It was found for most of the studied materials that the limiting pH values (assumed to be close PZC) were close to those reported in literature for the PZC values of traditionally manufactured oxide materials. On the other hand, mass titration curves of some oxide samples showed unexpected deviation in curve shapes and limiting pH. These deviations were probably due to selective dissolution of sample contaminations or sample material. PMID:15271562
Harju, Mika; Lev�nen, Erkki; M�ntyl�, Tapio
Modification of a pH-Titration Standardization Method for Formaldehyde
Procedures for monitoring formaldehyde concentration in air ultimately require a standard solution with which to calibrate the response of the analytical method. Although formaldehyde solutions of nominal concentration may be prepared from a variety of sources, the solutions must be standardized. The sulfite-pH\\/ titration method was tested and found to give erratic results. This paper presents evidence to indicate that
Reimar R. W. Gaertner
Base-Induced 2,4,6-Trinitrotoluene Transformation, Titration Studies.
The removal of 2,4,6-trinitrotoluene (TNT) from solution by the addition of a base, sodium hydroxide (NaOH), was examined. TNT solutions were titrated to determine the required hydroxide concentration for the removal of TNT from solutions to proceed. It w...
L. D. Hansen D. D. Ringelberg D. R. Felt J. D. Davis
Solubility measurement of polymorphic compounds via the pH-metric titration technique.
In drug development, the thermodynamically most stable form of a compound is preferred because metastable forms are prone to transform to the stable form during processing, formulation, or storage [Guillory, J.K., 1999. Generation of polymorphs, hydrates, solvates, and amorphous solids. In: Brittain, H.G. (Ed.), Polymorphism in Pharmaceutical Solids. Marcel Dekker, New York, pp. 183-226]. It is therefore important to discover and characterize the stable form as early as possible. One of the most important properties to determine is thermodynamic solubility. However, due to compound and time constraints this solubility value is usually not determined until late in discovery. This report explores the ability of the pH-metric titration method to measure intrinsic solubility of the stable form of compounds that exist in one or more polymorphic forms. One metastable form and the stable form of eight compounds were examined. Intrinsic solubility was measured via pH-metric titration. The technique was performed on a larger scale in order to monitor polymorphic form changes by powder X-ray diffraction. Shake-flask solubility and corresponding X-ray diffraction data of each form was also determined. The results of this study indicate that, in general, when starting with a metastable polymorph, the pH-metric titration method is able to achieve the solubility of the stable form by the third titration, while the traditional shake-flask solubility method is unable to consistently determine the stable form solubility. PMID:17049191
Fioritto, Ann F; Bhattachar, Shobha N; Wesley, James A
Simultaneous multiple injection to perform titration and standard addition in mono-segmented flow analysis.
An automated system to perform titration and standard addition in monosegemented flow analysis by employing the simultaneous multiple injection is described. The system was controlled by aPC-AT-386 microcomputer through a home-made parallel interface, employing a diode array spectrophotometer as detector. Software was written in QuickBasic 4.5 to control the system and for data acquisition. A three-way solenoid valve was used in conjunction with a proportional injector to add the titrant solution or the standard solution to the sample, to carry out titration or standard addition, respectively. Only one standard solution was used in each procedure and different quantities of titrant or standard were added to the sample by controlling the time interval in which the solenoid valve was switched on. Titration and standard addition curves similar to those of the manual methods were obtained in both cases, since the sample dispersion was very low due to the air bubbles of the monosegment. The titration system was evaluated through the determination of Fe(II) with a KMnO4 standard solution in pharmaceutical preparations. The standard addition process was assessed by determining Cr(VI) in natural waters and domestic wastewater using the diphenylcarbazide method. The results obtained in both methodologies did not differ significantly from the reference methods at a 95% confidence level. PMID:18924880
Assali, M; Raimundo, I M; Facchin, I
A comparison was made of a number of direct complexometric titrations ; previously published ior the determination of yttrium and the lanthanons. ; Working and optimum pH ranges were obtained for what are considered to be the ; best indicators, Alizarin Red S screened with Methylene Blue, Eriochrome Black T, ; Copper-Naphthyl Azoxine, and Xylenol Orange. The precision and accuracy
S. J. Lyle
Complexometric titration of submicromole amounts of thorium(IV) with photometric end-point detection
Summary Thorium(IV) can be determined in the microgram range by photometric titration with EDTA in the presence of an approximately equivalent amount of the indicator Semi-Xylenol Orange at pH 2 (HClO4). Most other elements do not interfere. Interfering metal ions can be separated from thorium(IV) by electrolysis at a mercury pool cathode.
C. J. C. Pijpers; L. G. Decnop-Weever; G. den Boef; W. E. van der Linden
Coulometric Titration of Ethylenediaminetetraacetate (EDTA) with Spectrophotometric Endpoint Detection: An Experiment for the Instrumental Analysis Laboratory
Ethylenediaminetetraacetate (EDTA) is commonly used as an anticoagulant in blood-collection procedures. In this experiment for the instrumental analysis laboratory, students determine the quantity of EDTA in commercial collection tubes by coulometric titration with electrolytically generated Cu[superscript 2+]. The endpoint is detected�
Williams, Kathryn R.; Young, Vaneica Y.; Killian, Benjamin J.
Intravenous Nefopam Reduces Postherpetic Neuralgia during the Titration of Oral Medications
Background The recently known analgesic action mechanisms of nefopam (NFP) are similar to those of anticonvulsants and antidepressants in neuropathic pain treatment. It is difficult to prescribe high doses of oral neuropathic drugs without titration due to adverse effects. Unfortunately, there are few available intravenous analgesics for the immediate management of acute flare-ups of the chronic neuropathic pain. The aim of this study was to determine the additional analgesic effects for neuropathic pain of NFP and its adverse effects during the titration of oral medications for neuropathic pain among inpatients with postherpetic neuralgia (PHN). Methods Eighty inpatients with PHN were randomly divided into either the NFP or normal saline (NS) groups. Each patient received a 3-day intravenous continuous infusion of either NFP with a consecutive dose reduction of 60, 40, and 20 mg/d, or NS simultaneously while dose titrations of oral medications for neuropathic pain gradually increased every 3 days. The efficacy of additional NFP was evaluated by using the neuropathic pain symptom inventory (NPSI) score for 12 days. Adverse effects were also recorded. Results The median NPSI score was significantly lower in the NFP group from days 1 to 6 of hospitalization. The representative alleviating symptoms of pain after using NFP were both spontaneous and evoked neuropathic pain. Reported common adverse effects were nausea, dizziness, and somnolence, in order of frequency. Conclusions An intravenous continuous infusion of NFP reduces spontaneous and evoked neuropathic pain with tolerable adverse effects during the titration of oral medications in inpatients with PHN.
Joo, Young Chan; Ko, Eun Sung; Cho, Jae Geun; Ok, Young Min; Jung, Gyu Yong
Cation Diffusion in Xenotime
Xenotime is an important mineral in metamorphic paragenesis, and useful in isotopic dating, garnet-xenotime thermometry, and monazite-xenotime thermometry, so diffusion data for xenotime of cations of geochronological and geochemical importance are of some interest. We report here on diffusion of the rare earth elements Sm, Dy and Yb in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na2}CO{3}-MoO_{3 flux method. The source of diffusant for the experiments were REE phosphate powders, with experiments run with sources containing a single REE. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from thirty minutes to a month, at temperatures from 1000 to 1400C. The REE distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS). The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101): DSm = 1.7x10-4 exp(-442 kJ mol-1/RT) m2}sec{-1 DDy = 3.5x10-7 exp(-365 kJ mol-1/RT) m2}sec{-1 DYb = 7.4x10-7 exp(-371 kJ mol-1/RT) m2}sec{-1. Diffusivities of these REE do not differ greatly in xenotime, in contrast to the findings noted for the REE in zircon (Cherniak et al., 1997), where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE+3 - Y+3 exchange, without charge compensation as needed for REE+3 - Zr+4 exchange in zircon. This latter factor may also contribute to the large activation energies for diffusion of the REE in zircon (i.e., 691 - 841 kJ mol-1, Cherniak et al., 1997), in comparison for those for xenotime. Work has also begun on Pb diffusion in xenotime. Preliminary results suggest Pb diffusivities similar to those for Pb in monazite (Cherniak et al., 2004). Cherniak et al. (1997) Chem. Geol. 134, 289-301; Cherniak et al. (2004) GCA 68, 829-840.
Cherniak, D. J.
Potentiometric Surface of the Lower Patapsco Aquifer in Southern Maryland, September 2002
This report presents a map showing the potentiometric surface of the Lower Patapsco aquifer in the Patapsco Formation of Lower Cretaceous age in Southern Maryland during September 2002. The map is based on water-level measurements in 69 wells. The highest measured water level was 108 feet above sea level near the northwestern boundary and outcrop area of the aquifer in northern Anne Arundel County. From this area, the potentiometric surface declined towards large well fields at Severndale, Arnold, and Annapolis. The measured ground-water levels declined to 87 feet below sea level at Severndale, 39 feet below sea level at Arnold, and 43 feet below sea level a few miles west of Annapolis. There was also a cone of depression covering a large area in Charles County that includes Waldorf, LaPlata, Indian Head, and the Morgantown power plant. The ground-water levels measured were as low as 191 feet below sea level at Waldorf, 131 feet below sea level at LaPlata, 115 feet below sea level at Indian Head, and 86 feet below sea level at the Morgantown power plant.
Potentiometric Surface Map of the Lower Patapsco Aquifer in Southern Maryland, September, 2003
This report presents a map showing the potentiometric surface of the Lower Patapsco aquifer in the Patapsco Formation of Lower Cretaceous age in Southern Maryland during September 2003. The map is based on water-level measurements in 66 wells. The highest measured water level was 112 feet above sea level near the northwestern boundary and outcrop area of the aquifer in northern Prince Georges County. From this area, the potentiometric surface declined towards well fields at Severndale, Arnold, and Annapolis. The measured ground-water levels were 86 feet below sea level at Severndale, 41 feet below sea level at Arnold, and 39 feet below sea level a few miles west of Annapolis. There was also a cone of depression covering a large area in Charles County that includes Waldorf, LaPlata, Indian Head, and the Morgantown powerplant. The ground-water levels measured were as low as 165 feet below sea level at Waldorf, 135 feet below sea level at LaPlata, 114 feet below sea level at Indian Head, and 92 feet below sea level at the Morgantown powerplant.
Potentiometric Surface of the Aquia Aquifer in Southern Maryland, September 1999
This report presents a map showing the potentiometric surface of the Aquia aquifer in the Aquia Formation of Paleocene age in Southern Maryland during September 1999. The map is based on water-level measurements in 85 wells. The potentiometric surface was above sea level near the northern boundary and outcrop area of the aquifer in a topographically high area of Anne Arundel County, and was below sea level in the remainder of the study area. The hydraulic gradient was directed southeastward toward an extensive cone of depression around well fields at Lexington Park and Solomons Island. Ground-water levels were more than 80 feet below sea level in a 100-square-mile area surrounding the deepest part of the cone of depression. A cone of depression formed in northern Calvert County due to pumpage at Chesapeake Beach and North Beach. The water level has declined to 43 feet below sea level in this area. The lowest measurement was 164 feet below sea level in a well near the center of the cone of depression at Lexington Park.
A biomimetic potentiometric sensor based on molecularly imprinted polymer for the determination of memantine in tablets.
Memantine hydrochloride is one of the first novel class medications for treatment of Alzheimer's disease. In this work, a biomimetic potentiometric sensor, based on a non-covalent imprinted polymer, was fabricated for the recognition and determination of memantine in pure drug and tablet pharmaceutical form. The molecularly imprinted polymer was synthesized by precipitation polymerization, using memantine hydrochloride as a template molecule, methacrylic acid as a functional monomer, and ethylene glycol dimethacrylate as a cross-linking agent. The sensor was developed by dispersing the memantine imprinted polymer particles in dibutyl sebacate plasticizer and embedding in poly(vinyl chloride) matrix. The wide linear range (10(-5) -10(-1) ?M), with a near Nernstian response of 57.4?mV/decade, a limit of detection 6.0?�?10(-6) ?M, fast response time (~15?s) and a satisfactory long-term stability (4?months) are characterizations of the proposed sensor. The sensor showed a high selectivity and a sensitive response to the template in aqueous system. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the electrode. It was used as indicator electrode in potentiometric determination of memantine in pharmaceutical formulations. PMID:22514137
Arvand, Majid; Samie, Hedyeh Asadi
Potentiometric Surface of the Upper Patapsco Aquifer in Southern Maryland, September 2007
This report presents a map showing the potentiometric surface of the upper Patapsco aquifer in the Patapsco Formation of Early Cretaceous age in Southern Maryland during September 2007. The map is based on water-level measurements in 50 wells. The highest measured water level was 120 feet above sea level near the northern boundary and outcrop area of the aquifer in northern Anne Arundel County. From this area, the potentiometric surface declined to the south toward a well field in the Annapolis-Arnold area, and from all directions toward four cones of depression. These cones are located in the Waldorf-La Plata area, Chalk Point-Prince Frederick area, Swan Point subdivision in southern Charles County, and the Lexington Park-St. Inigoes area. The lowest measured ground-water level was 44 feet below sea level at Arnold, 106 feet below sea level south of Waldorf, 54 feet below sea level at Swan Point, 59 feet below sea level at Chalk Point, and 58 feet below sea level at Lexington Park.
Potentiometric Surface of the Lower Patapsco Aquifer in Southern Maryland, September 2007
This report presents a map showing the potentiometric surface of the lower Patapsco aquifer in the Patapsco Formation of Early Cretaceous age in Southern Maryland during September 2007. The map is based on water-level measurements in 65 wells. The highest measured water level was 111 feet above sea level near the northwestern boundary and outcrop area of the aquifer in northern Prince George's County. From this area, the potentiometric surface declined towards well fields at Severndale and Arnold. The measured ground-water levels were 87 feet below sea level at Severndale, and 42 feet below sea level at Arnold. There was also a cone of depression covering a large area in Charles County that includes Waldorf, La Plata, Indian Head, and the Morgantown power plant. The ground-water levels measured were as low as 219 feet below sea level at Waldorf, 187 feet below sea level at La Plata, 106 feet below sea level at Indian Head, and 89 feet below sea level at the Morgantown power plant.
Preliminary investigations on a new disposable potentiometric biosensor for uric acid.
In this paper, uricase, catalase, and electron mediator were coimmobilized on the surface of the tin oxide (SnO2)/indium tin oxide (ITO) glass, to develop a disposable potentiometric uric acid biosensor. The SnO2/ITO glass was employed as a pH sensor, fabricated by sputtering SnO2 thin films on the ITO glass. 3-Glycidyloxypropyltrimethoxysilane (GPTS) was utilized to immobilize uricase, catalase and the electron mediator (ferrocenecarboxylic acid, FcA) on the sensing window. The experimental results reveal that the optimal weight ratio of uricase, FcA to catalase (CAT) is 4:1:2. The sensor responds linearly between 2 mg/dl and 7 mg/dl at pH 7.5, in 20 mM of test solution, with a correlation coefficient of 0.99213. Accordingly, no significant interference was observed when interfering substances, glucose, urea and ascorbic acid, were added to the uric acid solution. Moreover, the recorded voltage was relatively constant during the first 28 days of measurement. Consequently, a potentiometric uric acid biosensor was realized with the advantages of low cost and simple fabrication. PMID:16830944
Liao, Cheng Wei; Chou, Jung Chuan; Sun, Tai Ping; Hsiung, Shen Kan; Hsieh, Jui Hsiang
Potentiometric urea biosensor utilizing nanobiocomposite of chitosan-iron oxide magnetic nanoparticles
The iron oxide (Fe3O4) magnetic nanoparticles have been fabricated through a simple, cheap and reproducible approach. Scanning electron microscope, x-rays powder diffraction of the fabricated nanoparticles. Furthermore, the fabrication of potentiometric urea biosensor is carried out through drop casting the initially prepared isopropanol and chitosan solution, containing Fe3O4 nanoparticles, on the glass fiber filter with a diameter of 2 cm and a copper wire (of thickness -500 ?m) has been utilized to extract the voltage signal from the functionalized nanoparticles. The functionalization of surface of the Fe3O4 nanoparticles is obtained by the electrostatically immobilization of urease onto the nanobiocomposite of the chitosan- Fe3O4 in order to enhance the sensitivity, specificity, stability and reusability of urea biosensor. Electrochemical detection procedure has been adopted to measure the potentiometric response over the wide logarithmic concentration range of the 0.1 mM to 80 mM. The Fe3O4 nanoparticles based urea biosensor depicts good sensitivity with ~42 mV per decade at room temperature. Durability of the biosensor could be considerably enhanced by applying a thin layer of the nafion. In addition, the reasonably stable output response of the biosensor has been found to be around 12 sec.
Ali, A.; AlSalhi, M. S.; Atif, M.; Ansari, Anees A.; Israr, M. Q.; Sadaf, J. R.; Ahmed, E.; Nur, O.; Willander, M.
Array of potentiometric sensors for the analysis of creatinine in urine samples.
The development of potentiometric biosensors for creatinine based on creatinine iminohydrolase (E.C. 22.214.171.124) immobilized on chitosan membranes coupled to a nonactin based ammonium ion selective electrode is described. The response characteristics of three types of biosensors with the enzyme immobilized by three different procedures were evaluated. The biosensors with better response characteristics were obtained by coupling the ammonium ion selective electrodes to chitosan membranes with the enzyme immobilized by adsorption. The linear response range of these biosensors to creatinine was 10(-4) to 10(-2) M, the response time was between 30 and 60 s, they showed an operational lifetime of 44 days and the slope of the response to creatinine in the first day varied between 50 and 52 mV decade-1. An array of six potentiometric sensors, constituted by two creatinine biosensors and four ion selective electrodes for potassium, sodium, ammonium and calcium was calibrated and a multivariate model based on PLS1 for the response to creatinine was obtained and validated. The array was used for the analysis of creatinine in urine samples and the results were compared with the results of a clinical analysis laboratory, based on the Jaff� reaction. PMID:12195948
Magalh�es, J�lia M C S; Machado, Ad�lio A S C
Generalized potentiometric surface of the aquifers in the Cockfield Formation, southeastern Arkansas, spring 1980
This map shows the generalized contours of the altitude of water levels in wells completed in the Cockfield Formation in southeastern Arkansas for 1980. Most water levels used in constructing the map were made in the spring of 1980. However, in parts of the State water levels from the spring of 1980 were unavailable. Where data indicated no long-term changes in nearby water levels, measurements from as early as 1952 and as late as 1983 were used. At a few locations the altitude of the water surface in a stream was used to define the potentiometric surface. Available water level data limited the interpretation of potentiometric surface primarily to the area of occurrence of the aquifers south of the Arkansas River. Water level data from Arkansas and adjacent states used in the construction of this map are from the groundwater file of the U.S. Geological Survey 's National Water Data Storage and Retrieval System. This map was prepared as part of the Gulf Coast Regional Aquifer-System Analysis study. (Lantz-PTT)
Ackerman, D. J.
Acid-base titration across the membrane system of rat-liver mitochondria
1. Pulsed acid�base titrations of suspensions of rat-liver mitochondria under anaerobic equilibrium conditions show fast and slow titration processes. 2. The fast process is the titration of the outer aqueous phase of the mitochondria, which is continuous with the suspension medium, and the slow process can be identified with the titration of the inner aqueous phase of the mitochondria, which is separated from the outer aqueous phase by the non-aqueous osmotic barrier or M phase of the cristae membrane system. 3. The buffering power of the outer and inner phases have been separately measured over a range of pH values. 4. The rate of titration of the inner aqueous phase under a known protonmotive force across the M phase has been characterized by an effective proton conductance coefficient, which, near pH7 and at 25�, is only 0�45?mho/cm.2 of the M-phase membrane. 5. The low effective proton conductance of the M phase will account quantitatively for the observed respiratory control in state 4, assuming that oxidoreduction and phosphorylation are coupled by a circulating proton current as required by the chemi-osmotic hypothesis. 6. The addition of 2,4-dinitrophenol (or carbonyl cyanide p-trifluoromethoxyphenylhydrazone) at normal uncoupling concentrations causes a large increase in the effective proton conductance of the M phase of the cristae membrane. 7. The increase of the effective proton conductance of the M phase by 2,4-dinitrophenol (or carbonyl cyanide p-trifluoromethoxyphenylhydrazone) will account quantitatively for the short-circuiting effect of the uncoupling agent on the proton current and for the observed rise of the rate of respiration to that characteristic of state 3 or higher.
Mitchell, Peter; Moyle, Jennifer
On-line titration method for monitoring buffer capacity and total volatile fatty acid levels in anaerobic digesters.
The construction and use of an automatic on-line titration unit for routine or event- initiated monitoring of alkalinity, buffer capacity, and volatile fatty acid (VFA) levels is presented. Under computer control a sample of digester liquor is pumped into the titration vessel and weighed. A sequence of titration, sparging, and back-titration operations are then initiated during which the pH and weight are recorded continuously and a titration curve constructed. From the curve, estimates of the alkalinity, buffer capacity to any desired pH endpoint, and total VFA levels are computed. The data is stored to disk and output as hard copy together with the titration curve itself. Monitoring and control of the titration apparatus is effected by a microcomputer via two analog input lines and eight digital output lines, respectively. The system is suitable for downloading to a small, inexpensive dedicated microprocessor-based system. The apparatus is constructed from standard and widely available equipment and the titration sequence, being under software control, is fully adaptable to particular requirements. The use of this facility in the on-line monitoring, control and optimization of the anaerobic digestion process is discussed. PMID:18587953
Powell, G E; Archer, D B
The Quantitative Resolution of a Mixture of Group II Metal Ions by Thermometric Titration with EDTA. An Analytical Chemistry Experiment.
Presents an experiment in thermometric titration used in an analytic chemistry-chemical instrumentation course, consisting of two titrations, one a mixture of calcium and magnesium, the other of calcium, magnesium, and barium ions. Provides equipment and solutions list/specifications, graphs, and discussion of results. (JM)
Smith, Robert L.; Popham, Ronald E.
Several Applications of Advanced Scientific Calculators: Nonlinear Least-Squares Analysis and Titration of a Weak Acid
Several advanced applications of scientific graphing calculators are demonstrated. These include (a) nonlinear least squares analysis and (b) construction of titration curves for weak acids with a strong base. Stepwise instructions for obtaining the titration curves with TI-80 Series Calculators are presented. Immediate display of graphical results of a solution from a quantitative chemical problem in a classroom setting is
Myung-Hoon Kim; Suw-Young Ly; Tae-Kee Hong
Cationic lipids containing protonated cyclen and different hydrophobic groups linked by uracil-PNA monomer: Synthesis and application for gene delivery
In this report, as candidates for non-viral gene vectors, cationic lipids L1, L2 and L3 based on protonated cyclen and different hydrophobic groups (cholesterol, dodecanol or diosgenin) linked by PNA monomer were designed and synthesized. Their liposomes were easily prepared by mixing the synthesized lipids with dioleoylphosphatidyl ethanolamine (DOPE) under appropriate mole ratios. Agarose gel retardation and fluorescent titration by
Jun-Liang Liu; Qing-Ping Ma; Qing-Dong Huang; Wei-Han Yang; Ji Zhang; Jing-Yi Wang; Wen Zhu; Xiao-Qi Yu
Synthesis, Characterization, and Analytical Applications of a New Composite Cation Exchange Material Acetonitrile Stannic(IV) Selenite: Adsorption Behavior of Toxic Metal Ions in Nonionic Surfactant Medium
A composite cation exchange material acetonitrile stannic(IV) selenite was prepared under different experimental conditions. The ion exchange capacity of the material was improved from 0.75 to 1.83�meq g in comparison to its inorganic counterpart, stannic selenite. The material was characterized on the basis of X-ray, TGA, FTIR, and SEM studies. Ion-exchange capacity, pH titration, elution behavior, and distribution studies were
S. A. Nabi; R. Bushra; Z. A. Al-Othman; Mu. Naushad
Cation Ordering in Layered Nickelates
The single layer Ruddlesden-Popper nickelates present a model system to understand how the effects of digital dopant cation ordering may affect the properties of 2-dimensional conducting sheets. We investigate the effects of aliovalent A-site cation order on LaSrNiO4 films. Using molecular beam epitaxy, we interleave full layers of SrO and LaO in a series of chemically equivalent films, varying the pattern of SrO and LaO layers relative to the NiO2 layers. Through synchrotron surface x-ray diffraction and Coherant Bragg Rod Analysis (COBRA), we directly investigate the A-site cation order and the resulting atomic displacements for each ordering pattern. We correlate these results with theoretical calculations and transport measurements of the layered nickelate films.
Nelson-Cheeseman, Brittany; Zhou, Hua; Cammarata, Antonio; Hoffman, Jason; Balachandran, Prasanna; Rondinelli, James; Bhattacharya, Anand
Mixed micellization of tetradecyltrimethylammonium bromide and Triton X-100 in water�ethanol mixtures, using potentiometric and surface tension techniques
The mixed micelles of tetradecyltrimethylammonium bromide (TTAB) and Triton X-100 (TX-100) in mixed solvent have been investigated using potentiometric and surface tension techniques. In order to estimate the interaction between the surfactants and ethanol, the cmc data were treated by using the conventional regular solution theory for mixed micelles. It was found that the interaction parameter values (?) varied with
Amir Abbas Rafati; Hamed Maleki
Cyclic arsenic-nitrogen cations.
A series of different cyclo-diarsa-diazenium salts bearing several bulky groups such as supermesityl (Mes* = 2,4,6-tBu(3)C(6)H(2)) and m-terphenyl (2,6-Mes(2)-C(6)H(3), Mes = 2,4,6-Me(3)C(6)H(2)) and anions such as triflate (OTf = SO(3)CF(3) = trifluoromethylsulfonate) and tetrachloridogallate (GaCl(4)(-)) were synthesized and fully characterized. The novel 1-chloro-cyclo-1,3-diarsa-2,4-diazenium cation represents the first example of a binary cyclic As(III)/N four-membered heterocyclic cation, with a di- and tricoordinated As atom and a delocalized pi bond along the NAs((+))N unit. The addition of excess Me(3)SiN(3) yields the fully characterized cationic arsenic azide, 1-azido-cyclo-1,3-diarsa-2,4-diazenium-mu-azido-hexachlorido-digallate. The Cl(-)/N(3)(-) exchange is triggered by the action of the Lewis acid GaCl(3). Depending on the Me(3)SiN(3) stoichiometry, different mu-azido-hexachlorido-digallate salts with either 1-chloro- or 1-azido-cyclo-1,3-diarsa-2,4-diazenium cations or even a mixture of both are observed. Moreover, it was of special interest to study the distances between the cationic arsenic center and the anion in cyclo-diarsa-diazenium salts. A correlation between the color of the salt and the anion/cation distance, ranging between 2 and 8 A in cyclo-diarsa-diazenium salts of the type [R(2)N(2)As(2)Y](+)X(-) depending on the bulky group R (R = Mes*, Ter), the substituent Y (Y = Cl, N(3), OTf), and the anion X(-) (X = OTf, GaCl(4), Cl(3)Ga-N(3)-GaCl(3)), was established. PMID:19586007
Schulz, Axel; Villinger, Alexander
Cationic liposomes for gene delivery.
Cationic liposome-DNA complexes (lipoplexes) constitute a potentially viable alternative to viral vectors for the delivery of therapeutic genes. This review will focus on various parameters governing lipoplex biological activity, from their mode of formation to in vivo behaviour. Particular emphasis is given to the mechanism of interaction of lipoplexes with cells, in an attempt to dissect the different barriers that need to be surpassed for efficient gene expression to occur. Aspects related to new trends in the formulation of lipid-based gene delivery systems aiming at overcoming some of their limitations will be covered. Finally, examples illustrating the potential of cationic liposomes in clinical applications will be provided. PMID:16296751
Sim�es, S�rgio; Filipe, Ana; Faneca, Henrique; Mano, Miguel; Penacho, Nuno; D�zg�nes, Nejat; de Lima, Maria Pedroso
Air Leak during CPAP Titration as a Risk Factor for Central Apnea
Objectives: Emergence of central sleep apnea has been described in the setting of continuous positive airway pressure (CPAP) initiation. The underlying mechanism is unclear; however, we postulate that air leak washing out anatomical dead space is a contributing factor. Design: Data were obtained from 310 patients with obstructive sleep apnea (OSA) who underwent either split-night or full-night CPAP titration during January to July of 2009. The majority (n = 245) underwent titration with a nasal mask. Average total leak and maximum total leak were measured at therapeutic CPAP level. Unintentional leak was calculated by subtracting manufacturer-defined intentional leak from maximum leak. Results: Subjects were divided into two groups: central apnea index (CAI) during titration < 5/hour and ? 5/hour. The groups were similar in terms of gender, age, BMI, and AHI. The CAI < 5 group had a median average leak of 45.5 L/min (IQR 20.8 L/min) versus 51.0 L/min (IQR 21.0 L/min) with CAI ? 5 (p = 0.056). Maximum leak was 59.5 L/min (IQR 27.0 L/min) with CAI < 5 and 75.0 L/min (IQR 27.8 L/min) with CAI ? 5 (p = 0.003). In the subset of subjects titrated using a nasal mask, median average leak was 42.0 L/min (IQR 17.0) in the CAI < 5 group and 50.0 L/min (IQR 16.8) in the CAI ? 5 group (p = 0.001). In the CAI < 5 group, median maximum leak was 57.0 L/min (IQR 23.0) versus 74.5 L/min (IQR 24.3) in the CAI ? 5 group (p < 0.001). Conclusions: Leak during CPAP titration is associated with the development of acute central apnea; these data may have mechanistic and therapeutic implications for complex apnea. Commentary: A commentary on this article appears in this issue on page 1193. Citation: Montesi SB; Bakker JP; Macdonald M; Hueser L; Pittman S; White DP; Malhotra A. Air leak during CPAP titration as a risk factor for central apnea. J Clin Sleep Med 2013;9(11):1187-1191.
Montesi, Sydney B.; Bakker, Jessie P.; Macdonald, Mary; Hueser, Lauren; Pittman, Stephen; White, David P.; Malhotra, Atul
Cation-cation interactions and cation exchange in a series of isostructural framework uranyl tungstates
The isotypical compounds (UO2)3(WO6)(H2O)5 (1), Ag(UO2)3(WO6)(OH)(H2O)3 (2), K(UO2)3(WO6)OH(H2O)4 (3), Rb(UO2)3(WO6)(OH)(H2O)3.5 (4), and Cs(UO2)3(WO6)OH(H2O)3 (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), ?=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), ?=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), ?=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), ?=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), ?=101.661 (4). Compounds 1-5 are a framework of uranyl and tungsten polyhedra containing cation-cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2-5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO2)2+ uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO6 octahedra. Chains are linked through cation-cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [-1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 �C.
Balboni, Enrica; Burns, Peter C.
The applicability of cation exchange between synthetic zeolites, such as ; Linde Molecular Sieve 4A, and molten salts, such as monovalent nitrates, was ; studied. It was found that sodium and silver nitrate were occluded in the ; cavities of the zeolite framework, wfth approximately nine to ten molecules ; occuluded per unit cell of the zeolite. No occlusion was
M. Liquornik; Y. Marcus