text:
More Topics
Creator's Hub
Collect Leads
Get Started
Tips & Tricks
For Business
Your SlideShare is downloading.
Application of double pulse theory for hemispherical microelectrodes to theexperimental study of slow charge transfer processes
Upcoming SlideShare
Loading in...
Like this document? Why not share!
Introduction to electrochemistry 2 ...
by Toru Hara
524 views
Share SlideShare
Email sent successfully!
Size (px)
Start on
Show related SlideShares at end
WordPress Shortcode
Application of double pulse theory for hemispherical microelectrodes to theexperimental study of slow charge transfer processes
Martin Bezdomny
Published on
Apr 02, 2013
0 Comments
Full Name
Comment goes here.
12 hours ago
Are you sure you want to
Your message goes here
Be the first to comment
Be the first to like this
No Downloads
Total Views
On Slideshare
From Embeds
Number of Embeds
No embeds
Report content
Flagged as inappropriate
Flag as inappropriate
Copyright Complaint
No notes for slide
Transcript of "Application of double pulse theory for hemispherical microelectrodes to theexperimental study of slow charge transfer processes"
1. Electrochimica Acta 55 (2010) 6577–6585 Contents lists available at ScienceDirect Electrochimica Acta journal homepage: www.elsevier.com/locate/electactaApplication of double pulse theory for hemispherical microelectrodes to theexperimental study of slow charge transfer processesEduardo Laborda a , Emma I. Rogers b , Francisco Martínez-Ortiz a , Ángela Molina a,∗ ,Richard G. Compton b,∗a Departamento de Química Física, Universidad de Murcia, Espinardo 30100, Murcia, Spainb Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ, United Kingdoma r t i c l e i n f o a b s t r a c tArticle history: Differential Pulse Voltammetry and Reverse Pulse Voltammetry are applied to the study of the electrodeReceived 20 May 2010 kinetics of slow charge transfer processes at hemispherical microelectrodes of ca. 25 m radius. TheReceived in revised form 31 May 2010 electrochemical reversibility of three redox systems: 3-nitrophenolate−/2− • , 3-nitrophthalate2−/3− • andAccepted 5 June 2010 europium3+/2+ , are evaluated with both techniques by determining the heterogeneous rate constant, theAvailable online 15 June 2010 electron transfer coefficient as well as the formal potential for each. The experimental results show the value of these techniques for the characterization of the electrodeKeywords: kinetics by means of simple diagnostic criteria and single-point fit to general working curves. Further,Reverse Pulse VoltammetryDifferential Pulse Voltammetry theory developed for double potential pulse under radial diffusion conditions is validated.Heterogeneous rate constant © 2010 Elsevier Ltd. All rights reserved.Electron transfer coefficientMicroelectrodes1. Introduction ering a wide range of electrode kinetics (k0 ∼ 10−2 –10−4 cm s−1 ): 3-nitrophenolate−/2−• [10], 3-nitrophthalate2−/3−• [10] and Eu3+/2+ Differential Pulse Voltammetry (DPV) and Reverse Pulse [11–14].Voltammetry (RPV) are double potential pulse techniques with sev- Simple criteria for the evaluation of the electrode kineticseral valuable advantages for electrochemical studies, such as min- are applied, based on the shape of the responses recorded inimization of the capacitative effects and reduction of background both techniques. In DPV, the appearance of a tail in the peak ofcurrents [1,2]. Their application to the study of the kinetics of elec- 3-nitrophthalate2−/3−• is indicative of a small electron transfertrode reactions is expected to be both precise and sensitive [3–8]. coefficient. Regarding RPV, a split into a cathodic and an anodic Recently, explicit analytical solutions have been obtained for the wave of the RPV curve is obtained for Eu3+/2+ as a result of theDPV and RPV techniques at spherical electrodes of any size and for sluggish charge transfer process. This technique is much moreany degree of reversibility of the electrode reaction [7,8]. The ana- advantageous than Normal Pulse Voltammetry (NPV) because twolytical expression for the RPV curve is rigorously valid whatever separate irreversible waves in NPV are only seen when both twothe lengths of either potential pulse, which is important since the species of the redox couple of interest are initially present, andcorresponding theory for a spherical diffusion field had never been also because the RPV technique is susceptible to the existence ofdeveloped [8,9]. Moreover, from these solutions diagnosis criteria any subsequent chemical reactivity of the reduced species. It is alsoand working curves were established, demonstrating that the char- more accurate than the cyclic voltammetry due to the minimizationacterization of the electrode kinetics is possible from DPV and RPV of capacitive effects.experiments. Finally, for each case the values of the heterogeneous rate con- In this paper, the experimental application of the DPV and stant, the electron transfer coefficient and the formal potential areRPV techniques to the characterization of the electrochemical determined from DPV and RPV experiments by means of single-reversibility and the validation of the previous theoretical results point fit to the theoretical working curves.are carried out. For this purpose, three redox systems are studied onmercury hemispherical microelectrodes of ca. 25 m radius, cov- 2. Experimental 2.1. Chemical reagents ∗ Corresponding authors. E-mail addresses: email@example.com (Á. Molina), Ferrocene (Fe(C5 H5 )2 , Aldrich, 98%), email@example.com (R.G. Compton). nium(III) chloride ([Ru(NH3 )6 ]Cl3 , Aldrich, 98%), europium(III)0013-4686/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.doi:10.1016/j.electacta.2010.06.017
6578 E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585chloride dihydrate (EuCl3 , Aldrich, 99.99%), 3-nitrophthalicacid (Ph(COOH)2 NO2 , Aldrich, 95%), 3-nitrophenol (Ph(OH)NO2 ,Aldrich, 99%), mercury(I) nitrate dihydrate (Hg2 (NO3 )2 , Aldrich,>97%), acetonitrile (MeCN, Fischer Scientific, dried and distilled,99%), dimethylsulfoxide (DMSO, Aldrich, anhydrous, 99.9%),tetra-n-butylammonium perchlorate (TBAP, Fluka, Puriss electro-chemical grade, 99%), sodium perchlorate (NaClO4 , Sigma–Aldrich,98+%), tetra-n-butylammonium hexafluorophosphate (Bu4 NPF6 ,Aldrich, 98%), potassium nitrate (KNO3 , Aldrich, 99+% ACSreagent, 0.10 M), tetra-n-butylammonium hydroxide (Bu4 NOH,Sigma–Aldrich, 40 wt.% in water), perchloric acid (HClO4 , Aldrich,70%) and nitric acid (HNO3 , Fisher Scientific, 70%, 0.15 M) were allused as received without further purification. For DPV and RPV experiments a 1 mM solution of the oxidizedspecies of the corresponding redox couple was prepared. The pHof Eu3+ solutions was adjusted to 4.5 by addition of HClO4. The3-nitrophenolate monoanion and 3-nitrophthalate dianion solu-tions were prepared in the electrochemical cell by adding anexcess of base (Bu4 NOH) to the corresponding 3-nitrophenol and3-nitrophthalic acid solutions [10].2.2. Working electrode Mercury was electrodeposited by holding the potential at−0.245 V on Pt disc electrodes with r0 = 25 m from a 10 mMsolution of Hg2 (NO3 )2 with 0.1 M KNO3 as supporting electrolyte Fig. 1. Differential Pulse Voltammetry: (a) potential-time function; (b) DPV signal. Reverse Pulse Voltammetry: (c) potential–time function; (d) RPV signal.(acidified with 0.5% of HNO3 ), as described in literature [16,17]. The platinum electrode radius was calibrated by analyzing thesteady-state voltammetry of a 2 mM solution of Fc in acetonitrile ing the uncompensated solution resistance (Ru ) [19], its effect oncontaining 0.1 M TBAP, adopting a value of diffusion coefficient of the DPV and RPV signals was studied by numerical simulation (seeferrocene in MeCN of D = 2.3 × 10−9 m2 s−1 at 25 ◦ C [18]. Appendix A), demonstrating that this is negligible for our working Before the mercury deposition the platinum electrode was pol- conditions. At least three experiments were performed with eachished using 3.0, 1.0, and 0.1 m diamond spray on soft lapping system, a good reproducibility of results being found.pads (Kemet, U.K.). The mercury nitrate solution was bubbled withnitrogen gas (BOC, Guildford, Surrey, U.K.) for 30 min to remove 3. Results and discussionatmospheric oxygen, and nitrogen atmosphere was maintainedduring the deposition. 3.1. Theory The size of the hemisphere was controlled by means of theamount of charge transferred, which for a 25 m radius electrode 3.1.1. Differential Pulse Voltammetry (DPV)corresponds to 213.7 C. Next, it was confirmed electrochemically In the DPV technique successive double potential pulses arefrom the steady-state voltammetry of reduction of [Ru(NH3 )6 ]3+ , applied, with a constant pulse height ( E) and the second pulsedemonstrating that the ratio of limiting steady-state currents being much shorter than the first one (t2 t1 , see the schemebefore and after deposition was close to /2 [16]. shown in Fig. 1a). The current is measured at the end of each poten- tial pulse, (I1 (t1 )) and (I2 (t2 )), and the DPV signal is a plot of the2.3. Instrumentation difference between the two current samples ( I = I2 (t2 ) − I1 (t1 )) vs. the arithmetic average of both potential values (E1,2 = (E1 + E2 )/2, A computer-controlled -Autolab potentiostat Type II (Eco- see Fig. 1b). The initial equilibrium conditions are restored beforeChemie, Netherlands) was used to undertake the mercury the application of each double pulse, by renewal of the electrodedeposition, the calibration of the mercury hemispherical electrodes (mercury drop electrode), by open circuiting the working electrodeas well as the DPV and RPV experiments. [20] or by setting the applied potential at the adequate value [21]. For DPV and RPV experiments a three-electrode set-up was An explicit analytical solution for the DPV response of a chargeemployed, with a 25 m radius Hg electrode as working electrode transfer processes with finite electrode kinetics has been recentlyand a coiled Pt wire as the counter electrode. For measurements deduced [7], valid for spherical electrodes of any size (includingin aqueous solution a Saturated Calomel Electrode (SCE) was planar electrodes and hemispherical ultramicroelectrodes):employed as a reference electrode; for experiments in DMSO, a ksmicro · K −˛ · f ( I 2 1 /2) micro −˛ 2commercial 'no leak' reference electrode comprising Ag/Ag+ in a = 1 + ks · K2 · (1 + K2 ) · F Id (∞) 1 + ksmicro K −˛ (1 + K ) 2PEEK barrel fitted with a membrane junction (66-EE009, Cypress 2 2 (1)electrodes) was used. Solutions were bubbled with N2 before the experiments and where all the variables and functions are given in Table 1 andpositive pressure of N2 was maintained throughout. Before the Appendix B. This expression is fully applicable under the typicalapplication of each double pulse, equilibrium conditions were conditions of the DPV technique (t1 ≥ 50·t2 ).restored by open circuiting the working electrode for 10 s. Chronoamperograms were recorded under identical conditions 3.1.2. Reverse Pulse Voltammetryof DPV and RPV experiments in the absence of the electroactive According to the RPV waveform (Fig. 1c), the applied poten-species, confirming in all cases that the background currents were tial is set at a value corresponding to diffusion limiting conditionsnegligible in the scales of potential and time of interest. Regard- (E1 → −∞ for a reduction process) in the interval 0 ≤ t ≤ t1 and
E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585 6579Table 1Definitions. r0 Radius of the electrode tj , j ≡ 1, 2 Duration of the jth potential pulse D Diffusion coefficient of the electroactive species ci∗ , i ≡ O, R Bulk concentration of species i c∗ = R c∗ Ratio of the bulk concentrations of the electroactive O species (j) ci , i ≡ O, R; j ≡ 1, 2 Concentration profile of species i for the jth potential pulse kf , kb Heterogeneous rate constants of reduction, oxidation processes k0 Standard heterogeneous rate constant k0 ·r0 micro ks = D Dimensionless rate constant at microelectrodes under steady-state conditions ˛ Electron transfer coefficient E0 Formal potential of the electroactive couple Ej , j ≡ 1, 2 Potential applied during the jth pulse E1 +E2 E1,2 = 2 Abscissa potentialstepped from E1 to E2 for t ≥ t1 . The current is measured at the endof the second pulse (t = t1 + t2 ) and plotted vs. the second potentialvalue (see Fig. 1d). As in DPV, after each double pulse the initialequilibrium conditions are re-established. The analytical solution for this technique at spherical electrodesfor processes of any reversibility degree is given by [8]: p Id (t2 )IRPV = Id,DC + micro K −˛ (1 + K ) 1 + ks 2 2 √ micro −˛ Z 2 − ˇ1/2 + ks K2 (1 + K2 ) 2 [Z · F( 2) + Y · H( 2 , ˇ)] (2) Fig. 2. (a) Experimental DPV curves obtained for 3-nitrophenolate−/2− • (᭹), 3- nitrophthalate2−/3− • ( ) and Eu3+/2+ ( ); t1 = 0.5 s, t1 /t2 = 50, E = −50 mV. (b)with all the variables and functions given in Table 1 and Appendix Experimental RPV curves for the above systems; t1 = 0.5 s, t1 /t2 = 20. a vs. SCE refer-B. ence electrode for Eu 3+/2+ ; vs. Ag/Ag reference electrode for 3-nitrophenolate−/2− • + and 3-nitrophthalate2−/3− • . Solutions: 1 mM 3-nitrophenolate− , 0.1 M Bu4 NPF6 in This solution is rigorously valid whatever the lengths of either DMSO; 1 mM 3-nitrophthalate2− , 0.1 M Bu4 NPF6 in DMSO; 1 mM Eu3+ , 0.1 M NaClO4potential pulse (t1 , t2 ), which is significant since the RPV problem is in H2 O (pH = 4.5).usually tackled by assuming a much shorter second pulse (t2 t1 ),otherwise it presents a considerable difficulty even under lineardiffusion conditions [9]. will be seen, from the direct visual inspection of the shape of the experimental responses, qualitative kinetic information about the3.2. Experimental results systems can be easily extracted (Figs. 2–4). Also quantitative data were determined by means of the theory [7,8] from single-point The experimental verification of the theory as well as the fitting of the experimental results to theoretical working curvesdemonstration of the value of the DPV and RPV techniques in (Figs. 6 and 7), the values obtained for the kinetic parameters andkinetic studies is carried out from three one-electron reduction the formal potential being indicated in Tables 2 and 3.processes for which very different electrochemical reversibility has In Fig. 2 the experimental DPV and RPV curves for all the redoxbeen reported [10–14]: system are plotted. In Fig. 2a, the effect of the electrode kinetics on the position and shape of DPV curves is clearly observed. The- 3-nitrophenolate−/2−• position of the peak with respect to the formal potential (E0 ) is greatly affected by the electrochemical reversibility of the system − k0 ,˛ 2− • [Ph(O− )NO2 ] + e− [Ph(O− )NO2 ] (I) so that the more irreversible the electrochemical process is, the greater the shift of the peak potential with respect to the formal- 3-nitrophthalate2−/3−• potential [7]. Thus, in the case of Eu3+/2+ (grey points) there is a sig- 2− k0 ,˛ 3− • nificant shift of the peak potential towards more negative values, [Ph(COO− )2 NO2 ] + e− [Ph(COO− )2 NO2 ] (II) related with the small heterogeneous rate constant of the sys-- Eu3+/2+ tem (see Tables 2 and 3). The DPV curve of 3-nitrophthalate2−/3−• (white points) is slightly shifted with respect to E0 whereas for k0 ,˛ Eu3+ + e− Eu2+ (III) 3-nitrophenolate−/2−• (black points) the peak potential and the for- mal potential coincide. So, from the position of the DPV response The experimental application of the DPV and RPV techniques the reversibility of the redox systems is qualitative determined,to the kinetic study of these three redox systems was performed finding that this decreases in the order: 3-nitrophenolate−/2−• > 3-on mercury hemispherical microelectrodes of ca. 25 m radius. As nitrophthalate2−/3−• > Eu3+/2+ .
6580 E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585Fig. 3. Experimental DPV curves with positive ( E = +50 mV, triangularpoints) and negative ( E = −50 mV, circular points) pulse height values for p Fig. 4. Experimental Id,RPV /Id (t2 ) vs. t2 /(t1 + t2 ) curves obtained for 3-3-nitrophenolate−/2− • (black points), 3-nitrophthalate2−/3− • (white points) and −/2− •Eu3+/2+ (grey points). t1 = 1 s, t1 /t2 = 100. a vs. SCE reference electrode for Eu3+/2+ ; vs. nitrophenolate (᭹), 3-nitrophthalate2−/3− • ( ) and Eu3+/2+ ( ). Straight linesAg/Ag+ reference electrode for 3-nitrophenolate−/2− • and 3-nitrophthalate2−/3− • . corresponding to the linear regression of the experimental results are also plottedOther experimental conditions as in Fig. 2. for each case, the values of the correlation coefficient (R), the slope and the intercept given in the table imbedded. t1 = 0.5 s. Other experimental conditions as in Fig. 2. Information about the electrode kinetics can also be inferred of the former having a greater heterogeneous rate constant (seefrom the shape of DPV curves. As is well known [7], for given Fig. 6).˛ value and experimental conditions (r0 , t2 and t1 values) the According to the above discussed, the DPV technique is a goodDPV peak becomes smaller and broader as the heterogeneous rate method to determine the kinetic parameters by single-point fit ofconstant decreases. Thus, in the case of 3-nitrophenolate−/2−• a the peak current and the peak potential, which are strongly depen-much greater and sharper DPV peak is obtained, which points dent on the kinetics of the electrode process.out the greater reversible behaviour of this system. On the other In Fig. 2b the experimental RPV curves obtained are shown. Thehand, the DPV curves of 3-nitrophthalate2−/3−• and Eu3+/2+ show effect of the electrode kinetics on the shape of the RPV curves isbroader and smaller peaks, characteristic of more sluggish charge very significant so that the morphology of the responses enables thetransfer processes. The peak of 3-nitrophthalate2−/3−• is espe- estimation of the electrode kinetics from simple visual inspection.cially interesting (see graph imbedded in Fig. 2a) since it shows Thus, a gradual split of the RPV curve into two waves is found as thea remarkable asymmetry with a 'tail' at the more negative poten- system becomes more irreversible. Thus, for 3-nitrophenolate−/2−•tials. This feature of the DPV curve is indicative of a small value of (black points) a well-shaped sigmoidal signal is obtained, charac-the electron transfer coefficient (˛). The smaller ˛ value together teristic of fast charge transfer. On the other hand, the RPV curvewith the smaller diffusion coefficient (therefore, smaller spheric- obtained for Eu3+/2+ (grey points) clearly shows a split of the RPVity) of 3-nitrophthalate also explains that the peak height obtained curve into a cathodic and an anodic wave, showing that the chargefor 3-nitrophthalate2−/3−• is smaller than that of Eu3+/2+ in spite transfer process is much more sluggish. An intermediate behaviourTable 2Heterogeneous rate constant (k0 ), electron transfer coefficient (˛) and formal potential (E0 ) corresponding to the best fit of theoretical working curves (Eq. (1)) to the DPVexperimental results (Fig. 6). Redox couple Mediuma D × 106 /cm2 s−1 b k0 /cm s−1 ˛ E0 /V 3- Nitrophenolate−/2− • 0.1 M Bu4 NPF6 , DMSO 3.30 ± 0.03 1.4 × 10−2 0.45 −1.415c 3-Nitrophthalate2−/3− • 0.1 M Bu4 NPF6 , DMSO 1.88 ± 0.06 1.5 × 10−3 0.37 −1.503c Eu3+/2+ 0.1 M NaClO4 , H2 O (pH = 4.5) 6.11 ± 0.05 1.7 × 10−4 0.69 −0.643d , e a Concentration substrate: 1 mM of 3-nitrophenolate− , 3-nitrophthalate2− , Eu3+ . b Calculated from several repeat potential step chronoamperograms. c vs. Ag/Ag+ reference electrode. d vs. SCE reference electrode. e Value taken from the data determined from RPV experiments (Table 3).Table 3Heterogeneous rate constant (k0 ), electron transfer coefficient (˛) and formal potential (E0 ) corresponding to the best fit of theoretical working curves (Eq. (2)) to the RPVexperimental results (Fig. 7). Redox couple Mediuma k0 /cm s−1 ˛ E0 /V −/2− • −2 3-Nitrophenolate 0.1 M Bu4 NPF6 , DMSO 1.6 × 10 0.46 b −1.410c , b 3-Nitrophthalate2−/3− • 0.1 M Bu4 NPF6 , DMSO 1.7 × 10−3 0.40 −1.515c Eu3+/2+ 0.1 M NaClO4 , H2 O (pH = 4.5) 1.4 × 10−4 0.72 −0.643d a Concentration substrate: 1 mM of 3- nitrophenolate− , 3-nitrophthalate2− , Eu3+ . b Values calculated from the fit of the complete RPV curve. c vs. Ag/Ag+ reference electrode. d vs. SCE reference electrode.
E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585 6581 p Fig. 6. Experimental values of (a) Ip /Id (t2 ) and (b) Ep vs. log( 2) for 3-Fig. 5. Typical shape of the signals recorded in (a) DPV and (b) RPV techniques −/2− • 2−/3− • nitrophenolate (᭹), 3-nitrophthalate ( ) and Eu3+/2+ ( ) and theoreticalindicating the points of the curves from which they can be easily characterized: working curves (from Eq. (1), solid lines) corresponding to the best fit to experimen-(a) DPV: peak current ( Ip ) and peak potential (Ep ); (b) RPV: cathodic and anodic tal results. t1 /t2 = 50. a vs. SCE reference electrode for Eu3+/2+ ; vs. Ag/Ag+ referencelimiting currents (Id,DC and Id,RPV , respectively) and cathodic and anodic half-wave electrode for 3-nitrophenolate−/2− • and 3-nitrophthalate2−/3− • . The value of the cat anpotentials (E1/2 and E1/2 , respectively). sum of the squared residuals (S) obtained from the fitting is indicated on each 2 curve: S = (experimental value − theoretical value) . Other experimental con- ditions as in Fig. 2.is observed for the RPV curve obtained with 3-nitrophthalate2−/3−•(white points), in which the split starts to appear but it is not The RPV technique is also very useful for the full analysis offully developed. It can be inferred that the RPV technique is very the electrode reaction since the anodic branch of the RPV curve isappropriate for the study of the product of the electrode reac- strongly affected by the behaviour of the reaction product. In partic-tion in comparison with single-pulse techniques (like Normal Pulse ular, from the anodic limiting current of the RPV curve (Id,RPV = IRPVVoltammetry) where obtaining two separate irreversible waves is (E2 → +∞)) the existence of any process involving the reactiononly possible when both electroactive species comprising the redox product can be inferred such as, for example, a coupled subse-couple are initially present. quent chemical reaction (EC mechanism). These complications can In DPV, an alternative simple way for the elucidation of electrode be discarded by taking into account that for a simple charge trans-kinetics is by doing DPV experiments with positive and negative fer process (E mechanism) the expression of Id,RPV when only the E values, and studying the symmetry of the peaks obtained. The oxidized species is initially present ( = 0) is [22]:asymmetry between both peaks increases as the system becomesmore irreversible [7]. Id,RPV t2 p = −1 (3) In Fig. 3, the experimental DPV curves obtained with Id (t2 ) t1 + t2 E = −50 mV (normal mode) and E = +50 mV (reverse mode) areplotted for the three redox systems considered. The asymmetry of which is valid for any electrode radius and for any reversibil- pthe peaks corresponding to positive and negative E values is very ity degree. As a result, if the plot Id,RPV /Id (t2 ) vs. t2 /(t1 + t2 ) isapparent in the case of Eu3+/2+ reduction, for which a notably larger a straight line with slope = 1 and intercept = −1 the system underpeak is obtained when E < 0. On the other hand, the peaks corre- study corresponds to an E mechanism, since if the reduced speciessponding to 3-nitrophenolate−/2−• are almost symmetrical, which is involved in a following chemical reaction deviation from theagain points out a more rapid charge transfer process. An interme- above linear relationship is obtained as well as smaller anodicdiate situation is found for 3-nitrophthalate2−/3−• , a slightly larger currents.peak for E < 0 being obtained. So, this type of analysis also allows In Fig. 4, this simple diagnostic test is applied to the experi-us to easily classify the reversibility degree of the electrode pro- mental systems here studied. In all cases, very good correlationcesses. coefficients (R) are obtained for the linear regression of the plots
6582 E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585Fig. 7. Experimental values of (a) E1/2 (= E1/2 − E1/2 ), and (b) and (c) an cat E1/2 (= E1/2 + E1/2 ) vs. log( an cat 2) for 3-nitrophenolate−/2− • (᭹), 3-nitrophthalate2−/3− • ( ) and Eu3+/2+( ) and theoretical working curves (from Eq. (2), solid lines) corresponding to the best fit to experimental results. t1 /t2 = 20. a vs. SCE reference electrode for Eu3+/2+ ; vs.Ag/Ag+ reference electrode for 3-nitrophenolate−/2− • and 3-nitrophthalate2−/3− • . The value of the sum of the squared residuals (S) obtained from the fitting is indicated on 2each curve: S = (experimental value − theoretical value) . Other experimental conditions as in Fig. 2. p is directly related to the duration of the double pulse so that theId,RPV /Id (t2 ) vs. t2 /(t1 + t2 ), with slope and intercepts values veryclose to 1 and −1, respectively, as required for an E mechanism. greater 2 , the longer t1 + t2 . DPV and RPV curves can be described by the characteristic As can be observed in Fig. 6b, the duration of the doubleparameters shown in Fig. 5. Thus, DPV curves can be character- pulse slightly affects the position of the DPV peaks of 3-ized by the peak current ( Ip ) and the peak potential (Ep ) (see nitrophenolate−/2−• , which is characteristic of rapid electrode pro-Fig. 5a), and RPV curves by the cathodic and anodic limiting cur- cesses [7]. On the other hand, for Eu3+/2+ and 3-nitrophthalate2−/3−•rents (Id,DC and Id,RPV , respectively) and the cathodic and anodic the peak potential shifts towards less negative values when the cat anhalf-wave potentials (E1/2 and E1/2 , respectively) (see Fig. 5b). double pulse duration increases (i.e., when 2 increases), as cor- This allows a straightforward way of analysis of the experimen- responds to slower charge transfer reactions [7]. In all cases, the ptal response by single-point fit to theoretical results, instead of the normalized peak current Ip /Id (t2 ) increases with 2 (see Fig. 6a).more complex fit of the whole curve. Thus, from the experimental The solid lines in Fig. 6 are the theoretical working curves cor-values of the above parameters for different lengths of the double responding to the best fit to the experimental results. Thus, frompulse (t1 + t2 ) (keeping the ratio t1 /t2 constant), the quantitative the simultaneous fitting of the variation of the peak current and thecharacterization of the electrode kinetics can be performed [7,8]. peak potential, the values of the heterogeneous rate constant, theFor this purpose, general working curves can be easily obtained transfer coefficient and the formal potential are determined (valuesfrom Eqs. (1) and (2): Ip and Ep vs. log( 2 ) for DPV (Fig. 6), and given in Table 2). The fitting was done by computerized minimum an cat E1/2 (= E1/2 − E1/2 ) and an cat E1/2 (= E1/2 + E1/2 ) vs. log( 2 ) for RPV least square procedure of theoretical and experimental results. The value of the sum of the squared residuals (S) is shown on the curves(Fig. 7). as an indicator of the goodness of the fitting. Regarding DPV technique, in Fig. 6 the variation of the normal- p For very slow charge transfer processes, as is the case of Eu3+/2+ized peak current ( Ip /Id (t2 ), Fig. 6a) and the peak potential (Ep , redox system, the peak current is not sensitive to k0 value [7]. Nev-Fig. 6b) obtained for each system are plotted vs. log( 2 ). The exper- ertheless, if the formal potential of the system is known, the kineticimental points correspond to DPV experiments undertaken with parameters can be extracted from the working curves considereddifferent t1 + t2 values, being t1 /t2 = 50 in all cases. Note that given in Fig. 6. Thus, from the variation of the normalized peak currentthat the ratio t1 /t2 is kept constant, the parameter 2 (= 2 Dt2 /r0 ) p ( Ip /Id (t2 )) with log( 2 ) the ˛ value is determined and, once ˛ and
E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585 6583Table 4Data reported in the literature for the diffusion coefficient (D), heterogeneous rate constant (k0 ) and electron transfer coefficient (˛) of the systems under study at mercuryelectrodes. Redox couple Medium D × 106 /cm2 s−1 k0 /cm s−1 ˛ Methoda Reference −/2− • −2 3-Nitrophenolate 0.1 M Bu4 NPF6 , DMSO 4.0 2.1 × 10 0.43 DCV [10] 3-Nitrophthalate2−/3− • 0.1 M Bu4 NPF6 , DMSO 1.3 1.1 × 10−3 0.34 DCV [10] Eu3+/2+ 1 M NaClO4 , H2 O (pH = 3.0) 7.0 2.5 × 10−4 0.60 d.c. polarography [11] 0.5 M NaClO4 , H2 O ∼7.5 9.3 × 10−5 0.68 Chrono-coulometry [12] 1 M KCl, H2 O – 2.6 × 10−4 0.54 DPP [13] 0.1 M NaClO4 , H2 O (pH = 2.0) – 10−3 0.76 SWV [14] 1 M NaClO4 , H2 O 5.7 – – Chrono-potentiometry [15] a DCV: Derivative Cyclic Voltammetry; DPP: Differential Pulse Polarography; SWV: Square Wave Voltammetry.E0 values are known, the heterogeneous rate constant is obtained behaviours of E1/2 with 2 are obtained for ˛ > 0.5 (Eu3+/2+ ) andfrom the plot of the peak potential (Ep ) vs. log( 2 ). ˛ < 0.5 (3-nitrophthalate2−/3−• ) (see Fig. 7b). Thus, from the curves In Fig. 7 the results obtained from RPV experiments for t1 /t2 = 20 E1/2 vs. log( 2 ) the ˛ value is immediately obtained and onceare shown. The parameter E1/2 is related to the separation of this is determined, the value of the heterogeneous rate constant isthe cathodic and anodic branches of RPV curves and so with the extracted from the curve E1/2 vs. log( 2 ) (Fig. 7a). Finally, oncereversibility of the system. Hence, the greater the E1/2 value, the ˛ and k0 values are known, the value of the formal potential isthe more irreversible the process, so that the greatest E1/2 determined from E1/2 vs. log( 2 ) curves.values are obtained for Eu3+/2+ and the smallest ones for 3- From the comparison of the fitting procedures carried out innitrophenolate−/2−• (see Fig. 7a). Figs. 6 and 7 we deduce that, although both DPV and RPV techniques The parameter E1/2 informs about the relative symmetry are useful for the study of the electrode kinetics, the RPV tech-of the cathodic and anodic branches and it is strongly dependent nique is more powerful for the case of irreversible systems sinceon the value of the electron transfer coefficient. Thus, contrasting the separation of the cathodic and anodic branches (i.e., E1/2 ) is always sensitive to k0 value [8], E1/2 increasing as k0 decreases. On the other hand, as was previously indicated, the peak current in DPV becomes independent of k0 value for very slow charge transfer processes [7]. In Fig. 8 the experimental and theoretical DPV and RPV curves for t1 = 0.5 s are plotted. In all cases, the agreement between theory and experiments is quite satisfactory which validates the analy- sis of the curves by single-point fit, much easier than the fit of the whole curve, as well as the theory for double potential pulse recently developed [7,8]. Moreover, the data of the kinetic parame- ters here obtained from DPV and RPV experiments show a good or reasonable concordance with those reported in the literature with different electrochemical techniques (see Table 4), which validates the applicability of both double pulse techniques for kinetic studies. 4. Conclusions The value of Differential Pulse Voltammetry and Reverse Pulse Voltammetry for the characterization of the electrode kinetics of the electrode process has been experimentally demonstrated by studying three redox systems with notably different electrode kinetics at mercury hemispherical microelectrodes. Simultane- ously, the applicability of a recent theory for double pulse at spherical electrodes has been validated. The qualitative analysis of the electrochemical reversibility of these systems has been performed by visual analysis of DPV and RPV responses, as well as from the symmetry of DPV peaks obtained with positive and negative pulse heights. In addition, sim- ple methodology for the detection of following coupled chemical reactions from the time behaviour of the anodic limiting current of the RPV curve is described. Finally, the kinetic parameters and the formal potential of the redox couples under study are determined by simple fit of exper- imental responses obtained with different values of the length of the double potential pulse.Fig. 8. Fit of the experimental (points) and theoretical (solid line) (a) DPV and (b) RPVcurves for 3-nitrophenolate−/2− • (᭹), 3-nitrophthalate2−/3− • ( ) and Eu3+/2+ ( ). AcknowledgementsThe theoretical curves correspond to the k0 , ˛ and E0 values obtained from the fit toworking curves shown in Figs. 6 and 7 (values given in Tables 2 and 3). a vs. SCE refer-ence electrode for Eu3+/2+ ; vs. Ag/Ag+ reference electrode for 3-nitrophenolate−/2− • A.M., F.M.-O. and E.L. greatly appreciate the financial supportand 3-nitrophthalate2−/3− • . Other experimental conditions as in Fig. 2. provided by the Dirección General de Investigación (MEC) (Project
6584 E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585Number CTQ2009-13023) and by the Fundación SENECA (Project the relevant dimensionless parameter to take into account iR-dropNumber 08813/PI/08). Also, E.L. thanks the Ministerio de Ciencia e effect isInnovacion for the grant received. ∗ F 2 r0 cO D1/2 ς= (A2) RT t 1/2Appendix A. 1 The evaluation of the effects of the uncompensated solution In Fig. A.1 DPV and RPV curves for different values of ς areresistance (Ru ) on the DPV and RPV responses has been performed plotted considering a hemispherical electrode with r0 = 25 m. Theby digital simulation with a homemade program. response expected with no iR-drop effects is also shown (circle In this program, we have used an exponentially expanding grid points).with high expansion factors and four-point formulae for the dis- It is clearly demonstrated that for ς ≤ 2 × 10−2 (– – – –) the DPVcretisation of spatial derivatives (as shown in Ref. [23]). Under these and RPV responses are almost indistinguishable from that corre-conditions, a Thomas-like algorithm is feasible and the u–v method sponding to no iR-drop effects. So, under the working conditions[24] for boundary conditions fully applicable. In this way, the sur- of this paper (ς < 5 × 10−3 ) the effect of the solution resistance isface concentration of both species and their surface gradient are negligible and it can be ignored.very simply related, and the implicit calculation of surface con- It is worth to highlight the tolerance of the RPV technique to thecentrations with the inclusion of iR-drop effects is reduced to the solution resistance so that the signal is only significantly affectedsolution of one-unknown equation. For time-integration we have for large ς values (see Fig. A.1b).used EXTRAP4 algorithm taking 5-time intervals [23] in each poten-tial step (which gives rise to very fast calculations). Appendix B. Being the resistivity of the solution, with the assumption thatfor a hemispherical electrode uncompensated resistance can be ∗ FAcO Devaluated as [19] Id (∞) = (B1) r0Ru = (A1) 2 r0 p ∗ D Id (t) = FAcO (B2) t r0 Id,DC = Id (∞) 1+ (B3) D(t1 + t2 ) F Kj = exp (E − E 0 ) j ≡ 1, 2 (B4) RT j 2 Dt2 2 = (B5) r0 t2 ˇ= (B6) t1 + t2 t2 0 −˛ 2 = 2 +2 k K2 (1 + K2 ) (B7) D 2 (t1 + t2 ) 0 −˛ 1 = +2 k K1 (1 + K1 ) (B8) ˇ D 1+kmicro K1−␣ (1 + ) s 2 Z=− (B9) 1 + kmicro K−˛ (1 + K2 ) s 2 2 ␤ Y=− (B10) 2 ˛ micro K −˛ (1 + K ) 1 + ks K2 2 2 f (x) = 1 − K2 − (1 − K1 ) K1 micro K −˛ (1 + K ) 1 + ks 1 1 micro K −˛ (1 + K ) 1 + ks 2 2 + 1− · F(x) (B11) micro K −˛ (1 + K ) 1 + ks 1 1Fig. A.1. Influence of the uncompensated solution resistance (Ru ) on the (a) DPVand (b) RPV responses. Several values of ς parameter are considered: ς = 2 × 10−3 ∞ √(working conditions, —), ς = 2 × 10−2 (– – – –), ς = 0.1 (· · ·) and ς = 0.2 (– · · – · · – ·). (−1)i xi+1 x 2 xCircle points (᭹) correspond to the response obtained with no solution resistance. F(x) = = x · exp · erfc (B12) i p 2 2 2r0 = 25 m, t1 = 2.5 s, t1 /t2 = 100, D = 10−5 cm2 s−1 ; (a) E = −50 mV. i=0 l=0 l
E. Laborda et al. / Electrochimica Acta 55 (2010) 6577–6585 6585for 2 < 10 H( 2 , ˇ) [7] A. Molina, F. Martínez-Ortiz, E. Laborda, R.G. Compton, Electrochim. Acta 55 ∞ i i+1 ∞ (2010) 5163. (−1) 2 (2k − 1)!iˇk [8] A. Molina, F. Martínez-Ortiz, E. Laborda, R.G. Compton, J. Electroanal. Chem. In = 1+ Press. i p 22k−1 k!(k − 1)!(i + 2k) i=0 l=0 l k=1 [9] L. Camacho, J.J. Ruiz, C. Serna, A. Molina, F. Martínez-Ortiz, Can. J. Chem. 72 (1994) 2369. [10] H. Wang, O. Hammerich, Acta Chem. Scand. 46 (1992) 563.for 2 > 10 H( 2 , ˇ) (B13) [11] B. Timmer, M. Sluyters-Rehbach, J.H. Sluyters, J. Electroanal. Chem. 14 (1967) ∞ ∞ 181. √ (−1)k−1 (2k − 1)!ˇk (−1)i 2(2i − 1)! = 1−ˇ+ + [12] M. Cetnarska, J. Stroka, J. Electroanal. Chem. 234 (1987) 263. 2k−1 (i − 1)! 2i (k − 1)! 2 2 [13] J.W. Dillard, K.W. Hanck, Anal. Chem. 48 (1976) 218. k=1 i=1 [14] M. Zelic, Croat. Chem. Acta 79 (1) (2006) 49. ∞ 21–2k (2k − 1)!(2i + 1)ˇk [15] T. Rabockai, Electrochim. Acta 22 (1977) 489. × 1− [16] J. Mauzeroll, E.A. Hueske, A.J. Bard, Anal. Chem. 75 (2003) 3880. k!(k − 1)!(2k − 2i − 1) [17] J.G. Limon-Petersen, N.V. Rees, I. Streeter, A. Molina, R.G. Compton, J. Elec- k=1 troanal. Chem. 623 (2008) 165. [18] K.N. Marsh, A. Deev, A.C.-T. Wu, E. Tran, A. Klamt, Kor. J. Chem. Eng. 19 (2002) 357.References [19] S.H. Hong, C. Kraiya, M.W. Lehmann, D.H. Evans, Anal. Chem. 72 (2000) 454. [20] A. Molina, E. Laborda, E.I. Rogers, F. Martínez-Ortiz, C. Serna, J.G. Limon- Petersen, N.V. Rees, R.G. Compton, J. Electroanal. Chem. 634 (2009) 73.[1] A.J. Bard, L.R. Faulkner, Electrochemical Methods, Fundamental and Applica- [21] M. Lovric, J.J. O'Dea, J. Osteryoung, Anal. Chem. 55 (1983) 704. tions, 2nd ed., Wiley, New York, 2001. [22] A. Molina, R.G. Compton, C. Serna, F. Martínez-Ortiz, E. Laborda, Electrochim.[2] R.G. Compton, C.E. Banks, Understanding Voltammetry, World Scientific, 2007. Acta 54 (2009) 2320.[3] J. Osteryoung, E. Kirowa-Eisner, Anal. Chem. 52 (1980) 62. [23] F. Martínez-Ortiz, N. Zoroa, A. Molina, C. Serna, E. Laborda, Electrochim. Acta[4] K.B. Oldham, E.P. Parry, Anal. Chem. 42 (1970) 229. 54 (2009) 1042.[5] R.L. Birke, Anal. Chem. 50 (1978) 1489. [24] D. Britz, Digital Simulation in Electrochemistry, 3rd ed., Springer, Berlin, 2005.[6] R.L. Birke, M.-H. Kim, M. Strassfeld, Anal. Chem. 53 (1981) 852.


text:
OSI-Approved Open Source (897)
- GNU General Public License version 2.0 (507)
- GNU Library or Lesser General Public License version 2.0 (117)
- GNU General Public License version 3.0 (107)
- BSD License (82)
- MIT License (34)
- Mozilla Public License 1.1 (29)
- Apache License V2.0 (22)
- GNU Library or Lesser General Public License version 3.0 (20)
- Affero GNU Public License (16)
- Apache Software License (15)
- zlib/libpng License (14)
- Academic Free License (11)
- Artistic License (11)
- Common Public License 1.0 (10)
- Eclipse Public License (10)
- Public Domain (59)
- Creative Commons Attribution License (25)
- Windows (2,372)
- Linux (1,902)
- Mac (1,322)
- Modern (736)
- Other Operating Systems (178)
Top Apps
- Audio & Video
- Business & Enterprise
- Communications
- Development
- Home & Education
- Games
- Graphics
- Science & Engineering
- Security & Utilities
- System Administration
In this project, we expect to build supporting libraries to develop applications on top, and as many open standards we can. Use tracker to request libraries and enhancements. Visit our home page at http://nmatrix.com.ar23 weekly downloads
Z-Bar: Managed .NET for Barcode Printers
A collection of MS VS.NET (C++, C#, VB.NET) components, controls and class libraries (Win32/64 and WinCE/WM) to aid development of printing functionality in .NET applications that make use of some barcode printers (Zebra, O'Neil, etc.).23 weekly downloads
RedCast Playout
License: Creative Commons - Attribution-NoDerivatives 4.0 International (CC BY-ND 4.0) RedCast is a free Playout Software proven for 24/7 use. RedCast is the perfect CasparCG Client with Scheduling! It's free and easy to use! Get your Copy now! System requirements - Windows 7 64bit - Windows 8.1 is NOT supported! - Microsoft .Net 4.5 Framework - Microsoft Visual C++ 2010 Redistributable Package - Microsoft Visual Basic Power Packs 10 Installation Guide Installation of RedCast Stable Version V1 1. Windows 7 64bit is required. 2. Install Microsoft .net 4.5 (RedCast use it) 3. Install Microsoft Visual C++ 2010 Redistributable Package. (CasparCG use it) 4. Install Microsoft Visual Basic Power Packs 10 (RedCast CG use it) 5. Reboot your Machine. 6. Download the Setup-Pack 7. Unzip Administrator rights required Communication Port: 5250 (Firewall)41 weekly downloads
Cloudium OS
Cloudium OS is being written in pure ASM with cloud computing in mind.10 weekly downloads
UFFS: Ultra-low-cost Flash File System, designed for NAND flash working in embedded system. UFFS typically consumes less then 200K ram for 1Gb(page 512)/4Gb(page 2K) NAND flash. It supports direct flash interface, works with or without OS.14 weekly downloads
An OpenGL port of ZDoom 2.0!22 weekly downloads
LightWallet is a open source lightweight J2ME personal finance management application for mobile phones.7 weekly downloads
Total Commander eXtensions
A set of eXtensions for Total Commander file manager.39 weekly downloads
A mod for Civilization 4: Beyond the Sword, depicting the sengoku jidai (warring states) period of feudal Japan.11 weekly downloads
Windows XP ported to Nintendo DS38 weekly downloads
( pro ping )pinger network alert monitor
Pinger alert, STATICTICAL TABLES, send EMAILs or SMS by SMS GATEWAY21 weekly downloads
UltraTools - Tools for ultrastar songs
Ultratools is a suite of freeware for ultrastar songs. -The first freeware is Ultratools - Editor a really great editor, with a new song creation tool.21 weekly downloads
Cobos Project
the disruptive IDE for COBOL developers30 weekly downloads
Camp Smalltalk ANSI Tests
A test suite that tests for conformance to the ANSI standard for Smalltalk.20 weekly downloads
Shadows Rising RPG
openXpertya solución empresarial global
Solución de Gestión Empresarial en Software Libre20 weekly downloads
Implementation of the PowerWatershed algorithm (q=2) described in the following paper (ICCV 2009) http://www.esiee.fr/~najmanl/papers/couprie2009iccv.pdf12 weekly downloads
Python PyGame Tower Defense
A tower defense game written in Python with PyGame12 weekly downloads
exploit.co.il Vulnerable Web App
exploit.co.il Vulnerable Web app designed as a learning platform to test various SQL injection Techniques This is a fully functional web site with a content management system based on fckeditor. You can download it as source code or a pre configured34 weekly downloads
ORSEE is a web-based Online Recruitment System for Economic Experiments. Key features: attribute query selection, random recruitment, experiment calendar, reputation system, automated mailing, pdf output, complete documentation.18 weekly downloads
A collection of Java ports of open source terrain and solar system generation packages. Code has been extensively refactored, extended and documented. GPL License with exception for required libraries.18 weekly downloads
PHP installer, plus GTK installer, plus PHP-GTK installer : all in one - although each one may be installed separately - for MS-Windows users.9 weekly downloads
Open Utlity
Open Utlity is series of unix utlity just like gnu for linux / windows11 weekly downloads
InfoNode Docking Windows
InfoNode Docking Windows is a Java Swing based docking windows framework. It also includes a highly flexible tabbed panel component and a slim Swing look and feel.31 weekly downloads
CAMFR (CAvity Modelling FRamework) is a fast, flexible, friendly full-vectorial Maxwell solver. Although it can tackle general electromagnetic problems, its main focus is on applications in the field of photonics.17 weekly downloads

subset: commoncrawl


text:
Gunman holed up in Canadian motel bar, possibly with hostages
The Associated Press
MONCTON, New Brunswick- An armed man was holed up in a motel bar and may have taken hostages, police and witnesses said Friday.
Royal Canadian Mounted Police constable Michel Mercier said a police negotiator was in contact with the man, but he could not confirm whether any hostages had been taken.
"The rest of the hotel has been evacuated, as well as the surrounding businesses," he said.
Kevin Campbell, an eyewitness from a neighboring business, said some of the people who fled the bar reported that the man entered with a gun and ordered everyone out. He apparently put a gun to the head of a patron who was playing a video lottery game.
"Other employees at the hotel said this gentleman was playing the (lottery) machines yesterday and lost quite a bit of money," Campbell told the CBC. "Some people are very shook up, and crying. it was very traumatic for them."
Copyright 2015 Associated Press. All rights reserved. This material may not be published, broadcast, rewritten, or redistributed.
Recommended Standoff Situations
Dallas police HQ attacker's mom: Officers should have tried harder not to kill him
Officer, suspect injured in shooting at Calif. apartment complex
Relatives: Man tied to Dallas shooting was mentally unstable
2 suspects dead after stealing police SUV, standoff with Texas cops
Join the discussion
PoliceOne top 5
- 1 Video: Police release full footage of Cincinnati OIS that led to murder charge
- 2 Ex-con Memphis cop killer turns himself in
- 3 Baltimore prosecutor won't cooperate with homicide panel
- 4 Memphis officer shot to death, manhunt underway for suspect
- 5 Slain Memphis cop was shy, atypical officer


text:
World Bulletin / News Desk
WikiLeaks founder Julian Assange has hired Spanish jurist Baltasar Garzon as a legal adviser as he seeks political asylum in Ecuador, the Andean country's foreign minister, Ricardo Patino, said on Tuesday.
Assange has been taking refuge in the Ecuadorean Embassy in London since June 19. The Australian anti-secrecy campaigner, who enraged Washington in 2010 when his WikiLeaks website published secret U.S. diplomatic cables, is wanted for questioning in Sweden over sex crime allegations.
Assange broke his bail terms and requested asylum in Ecuador. He denies any wrongdoing in Sweden and says he fears that if extradited there, he could be sent on to the United States, where he believes he could face criminal charges punishable by death.
The Ecuadorean government has said it will take as long as needed to make a thorough analysis of Assange's asylum application before making a decision.
"Mr. Assange has requested the services of lawyer Baltasar Garzon to deal with his case. ... Of course he has the right to hire and look for the legal advice that he needs or may need for the asylum request," Patino told reporters in Quito.
Human rights investigator Garzon is best known for ordering the arrest of former Chilean military leader Augusto Pinochet in 1998.
For three decades, Garzon has made a career of tackling the most complex and controversial of cases, winning notoriety as well as a clutch of powerful enemies in Spain's ruling class. Politicians across the spectrum have been implicated or targeted in his investigations over the years.
He also stirred up controversy with an attempt to order an investigation into the killing of tens of thousands of civilians during the dictatorship of General Francisco Franco, who died in 1975.
Patino said he welcomed Garzon's involvement in the Assange case because the Ecuadorean government had "a very good relationship" with the jurist. Garzon is part of an international panel that was set up to oversee the ongoing judicial overhaul in the OPEC-member country.
Neither the U.S. nor Swedish authorities have charged Assange with anything. Swedish prosecutors want to question him about allegations of rape and sexual assault made by two former WikiLeaks volunteers in 2010.
Italy says monetary fund needed to prevent members from crashing out of eurozone
About twenty people were also kidnapped by suspected Boko Haram men
According to International Organization for Migration, the death toll so far in 2015 has reconfirmed the Mediterranean route to reach Europe as deadliest
Ukrainian President called for National Security and Defense Council of Ukraine emergency session
The operation was conducted with assistance from FBI
Deal removes 99 per cent of tariffs on trade between EU and Vietnam, according to the European Commission
The Russian diplomats were expelled because of actions 'not in line with the Vienna Convention'
If the terms of EU summit are met a deal can be expected by the 18th of August
The murder of baby Ali Saad Dawabshe is a direct result of a 48 year military occupation which consistently uses violence to enforce that inequality that exists today.
An increase in attacks on Muslim clerics has many in Uganda searching for those who are responsible.
Soma Oil and Gas will be investigated for large amounts of money to the Somalian oil ministry. The company's London headquarters were raided last week.
Tornado fighter jets will be used to conduct strikes until at least March 2017
Russia's foreign minister Sergei Lavrov has met with Hamas leader Khaled Meshaal in Qatar and has extended an invitation to visit Moscow.
Ukraine will establish a new Crimean military unit made up primarily of Muslims to monitor transportation of goods between Ukraine and the peninsula.
A total of 16 aircraft fly as part of the Baltic Air Policing mission located in Estonia, Latvia and Lithuania
Turkish President promised to never recognize illegal annexation of Crimea


text:
by Mike Phillips
Posted on 10.23.2006
share this
Tomorrow, October 24, is the opening day for eComXpo, the online trade show featuring more than 450 exhibitors.
The show will run from October 24 - 26 and will include dozens of live presentations from such presenters as Chris Anderson (Author, The Long Tail), Steve Denton (President, LinkShare), Paul Botto and Nick Mihailovski (Google) and many more.
EComXpo is a great opportunity to attend a trade show from the comfort of your desk, couch or kitchen table. It's free to register and definitely worth a look around. You can certainly learn some new and interesting things to help your business succeed.
Website Magazine has a booth at eComXpo, so please drop by and say hello and share your thoughts!
Not already a part of our community? Sign up to participate in the discussion. It's free and quick.
hydrogen sulfide toxicity 07-05-2012 12:27 AM
Does this still release an updates to now.
Why Is Mobile Search Converting?
5 Best Practices For High-Performing Emails...
Social Snapshot: July 2015
View all...


text:
452 Country Club Dr, Morgantown, WV, 26505, United States of America, 855-239-9482
Travelodge Morgantown, Morgantown
Lowest price$67
Best Price Guarantee
We do not have Hotels.com photos for this hotel.
Within easy reach of West Virginia University
- Free continental breakfast, free WiFi, and free parking
- Airport within 5 mi/8 km: Morgantown, WV (MGW-Morgantown Municipal)
Main amenities
- 51 guestrooms
- Spa tub
- 24-hour front desk
- Air conditioning
What's around
- West Virginia University (1.6 mi / 2.6 km)
- Mylan Puskar Stadium (0.3 mi / 0.5 km)
This motel was within walking distance to Milan Puskar Stadium which was very convenient…
Good hotel, friendly staff
Enter dates to check prices
Hotel Info: 866-539-8117from $67
- Standard Room, 1 King Bed
- Double Room, 2 Double Beds
Recommended hotels
At a glance
Key facts
Hotel size
- This hotel has 51 rooms
- This hotel is arranged over 2 floors
Required at check in
- Credit card or cash deposit required
- Government-issued photo ID required
Travelling with others
- Pets not allowed
- Free WiFi in public areas
- Free WiFi in rooms
- Free self parking
- Accessible parking
- Free RV/bus/truck parking
Nearby Two Star Morgantown hotels
In the hotel
Food and drink
- Free continental breakfast daily
Things to do
- Spa tub
- 24-hour front desk
- Number of buildings/towers - 2
- Disabled parking
- Accessible path of travel
- Accessible bathroom
- In-room accessibility
In the room
Home comforts
- Air conditioning
- Coffee/tea maker
- Iron/ironing board (on request)
Freshen up
- Hair dryer
Stay connected
- Desk
- Free WiFi
Food and drink
- Refrigerator
- Microwave
- Connecting/adjoining rooms available
Top Morgantown hotels
Recently reviewed hotels in Morgantown
- Super 8 Uniontown PAFrom
"Large rooms, two queen beds, perfect for what our family needed. Breakfast included at the hotel includes waffles."Jul 25, 2015
- Park Inn by Radisson Uniontown, PAFrom
"We stayed on our way home from a long drive from the beach and the hotel was a really nice way to get some energy out for the kids from driving in the car all day. I really…"Jul 24, 2015
- The Preston County InnFrom
"We enjoyed our stay here a lot. The only down side was it was pretty warm in our room. The air conditioner unit didn't cool the room very much. However the owners were very…"Jul 21, 2015
- Microtel Inn & Suites by Wyndham WaynesburgFrom
"Good place to stay. Staff was very accommodating. We were in town for a funeral and we were well taken care of by the staff."Jul 8, 2015
Nearby hotels
Travelodge Morgantown, Morgantown's small print
Also known as
- Travelodge Hotel Morgantown
- Travelodge Morgantown
- Travelodge Morgantown
- Travelodge Morgantown Morgantown
The property has connecting/adjoining rooms, which are subject to availability and can be requested by contacting the property using the number on the booking confirmation.
We have included all charges provided to us by this hotel. However, charges can vary, for example, based on length of stay or the room you book.


text:
Jodi Ayers Latest News hot news Breaking news - chicago tribune, Chicago breaking news from the chicago tribune. find chicago local news, illinois news and more.. Jodi Ayers Latest News hot news Six places study | campus, Picking a destination may be the hardest part of getting ready to study abroad. with 196 countries scattered across the globe, it's hard to pick just one. Jodi Ayers Latest News hot news Neil young times, Massive news!!! july 18, 2015 this is the only relevant study that unequivocally proves that the genetic modification, itself, independent of roundup, shocks the poor.
Snopes.: barack obama bill ayers, Claim: barack obama acquaintanceship bill ayers, domestic terrorist. status: partly true. origins: william (bill) ayers . snopes.com/politics/obama/ayers.asp U.. news | national news - abc news, Abc news reports united states politics, crime, education, legal stories, celebrities, weather, economy . abcnews.go.com/US News | american music therapy association (amta), The american music therapy association (amta) presents historic innovative research symposium, "improving access quality: music therapy research 2025. musictherapy.org/news/


text:
Liberal Loses His Job For Using Racial Slur Against Black Conservative
Liberal Dropped By Publishing House For Using Racial Slur Against Black Conservative
There are very few things that liberals and conservatives agree on, but one of them is that racial slurs are extraordinarily offensive.
A Minnesota-based publishing house has dropped one of its authors for calling a black conservative woman an "Aunt Tom" and "ignorant c—t" on Twitter.
Author Scott Colbert has since deleted the Friday tweet to Crystal Wright, known as "@GOPBlackChick," and locked his Twitter feed, but not before conservative commentator and bestselling author Brad Thor highlighted it on his own Twitter account. Thor, a frequent Glenn Beck television and radio guest, replied to Colbert: "Did you just hurl a racial slur at my friend?"
Thor then proceeded to tweet Colbert's publisher, KHP Publishers, Inc., and many of Colbert's followers a screenshot of his epithet.
By Saturday, KHP had posted a message on its website announcing it had terminated its contract with an author, whom it did not name, due to an "inexcusable" incident.
"[T]he author made a racial slur at the person with KHP material plastering his Twitter page's background. This involved the company, and we saw the results of this on our own Twitter page this morning," KHP wrote. "[W]e find this inexcusable. In sticking to our own 'zero tolerance' model, we terminated our contract with this author immediately and his book is in the process of being removed from stores."
The publisher noted that the decision was "not just a business issue" but a personal one as well – the company's CEO is white and married to a black woman: "They have two beautiful children and have dealt with racism often in their lives. It simply will not be tolerated by any of us here at KHP."
Racial slurs like Uncle Tom, Aunt Jemima, oreo & n*gger are incredibly offensive. Nobody should be hurling that kind of language at his political adversaries, including liberals.
Also see...
This dad punches the crap out of two girls attacking his daughter. Tell me you wouldn't do the same if a pack of thugs were beating on your child. I...Read More
John Hawkins
Related Articles
The Federal Government Teams Up With Mexico To Thwart The Minutemen
This is absolutely unbelievable! The Border Patrol is actually teaming up with the Mexican government to try to prevent the
A Look at the Satanic Statue to Be Erected at Oklahoma Statehouse
Literally. In January, the Satanic Temple announced plans to build a statue on the lawn of the Oklahoma State House–and
I Get Letters: Holding The President Accountable
I received an email from Phillip Bass who disagreed for the most part with my "Why Conservatives Should Vote For


text:
Ravi seeks upturning of hate crime conviction
New York: An Indian-origin student of Rutgers University, who was found guilty of bias intimidation for spying on his gay roommate`s sexual encounter, is seeking to have the conviction against him overturned and be granted a new trial in the case.
Lawyers for Dharun Ravi, 20, submitted a 33-page brief in Superior Court in New Brunswick requesting that the judge acquit him entirely or at least grant him a new trial.
The motion also requests that Ravi be allowed to remain free on bail after sentencing, pending the planned appeal.
Attorneys Steven Altman and Philip Nettl said in the motion that Ravi`s conviction be overturned as there is evidence that he did not intimidate or invade the privacy of his gay roommate Tyler Clementi, who had committed suicide in September 2010 after finding out Ravi had spied on him using a webcam.
Ravi was found guilty in March on charges of bias intimidation and invasion of privacy and faces up to 10 years in prison and possible deportation to India when he is sentenced on May 21.
The motion filed in court contends that evidence presented at trial showed Ravi was not guilty of invading the privacy or intimidating Clementi.
The attorneys argue that in the bias intimidation counts, which are the more serious of the charges that Ravi faces, the law was misapplied.
"To criminalise a defendant for a victim`s mistaken belief about the defendant`s motive would turn the bias intimidation statute into a mockery of itself," the lawyers said.
On some of those counts, the jury acquitted Ravi of intending to intimidate Clementi and his partner, but convicted him on grounds Clementi felt intimidated and felt Ravi`s actions were purposeful.
More from India
More from World
More from Sports
More from Entertaiment
- Political war of words erupts over Yakub Memon's execution
- Dr Subhash Chandra Show: How do you cope up with ever changing environment in life?
- Exclusive interview with APJ Abdul Kalam's aide Srijan Pal Singh
- Russian aircraft Mi-28 crashes during an aerobatics show
- Shravan month begins, devotees throng Shiva temples
- Yakub Memon's execution: Supreme Court Deputy Registrar quits over judgement
- Govt formalises strategies to counter ISIS threat, maintain internal security
- Manbir Kaur becomes first Sikh girl in Pakistan to top Class 10 exam
- Here's what Islamic State captors told Indian teachers
- 2nd T20: Shahid Afridi, Anwar Ali help Pakistan win thriller against Sri Lanka


text:
Related Pins
Scripture Post-Its - great LDS quotes to stick inside your scriptures at {my3monsters.com} #lds #quotes #printables
Names of Christ Advent Gifts - 24 scriptures to read each day in December. Each one talks about a different name of Christ. There are coordinating gifts to go with the scriptures to use for advent!
New Testament Scripture Mastery Flashcards
Memorizing Scripture with kids is fun, especially when you teach it through these 5 different methods.
Free LDS Printable. Alma 7:23,24. (Great scripture!)


text:
Winner by pin And New TNA Knockouts Champion: Mickie James
Velvet favors her knee on the mat as ODB tends to her and Mickie celebrates.
- A nice AJ Styles video package is shown about the question of his allegiance.
- Bully and Co. toast, in the back, to Anderson for beating Angle. They toast again to AJ Styles. We go to commercial.
- Aces & 8's makes their way to the ring, lead by Bully Ray. Anderson has a vest for AJ. Bully shuts the music off and cuts a promo about who they are. He says no member is more important than the other but when someone screws up, he gets dealt with like D-Lo. Bully praises Anderson for what he has done for the club.
Bully says that tonight is about one man. He calls out AJ Styles and he saunters to the ring. Devon opens the ropes for AJ to get in and Bully says that is the biggest sign of respect he could have shown him. Bully says everyone wants a piece of AJ but AJ knows where the power lies.
Bully hands AJ a beer and says it is no secret that AJ doesn't drink but he wants AJ to 'cheers' him and drink with him. He says AJ can give his heart to Jesus but his soul belongs to the club. AJ slams his beer with Bully and he guzzles it down. Bully is impressed and asks Anderson to give their brother his colors. The crowd chants, "You sold out."
AJ begins to don the vest and Anderson asks to help him put it on as Angle's music hits. Angle cuts a promo on his way down the ramp and he tells AJ to go ahead but he will see Angle at the PPV. AJ slips into the "cut" and he embraces all the members in the ring. Bully raises AJ's hand as Angle rushes the ring but is beaten down. They hold Angle for AJ and Bully hands him a hammer. AJ hits Angle in the knee with the hammer and throws Angle to the floor. They all pose, shoulder to shoulder, for the camera.
All the members of Aces & 8's turn around to pose to the crowd with their backs to the hard camera and AJ swings DOC around and clocks him in the head with the hammer and hits Garett in the gut before escaping to the ramp. Aces & 8's begin to give chase as we go off the air. Bully Ray is beside himself.
Got a news tip or correction? Send it to us by clicking here.
WrestlingInc.com is the largest independently owned wrestling website in the world (Source: Alexa).
Become a fan on Facebook, follow us (@WrestlingInc) on Twitter:
Follow @WrestlingInc
Paige Names Her New Divas Stable, More RAW Opening Segment Video, Jack Swagger On WWE Superstars
WWE's Roddy Piper Tribute Video, Photo And Clip From Tonight's Ten-Bell Salute At RAW
Huge Title Match Set For WWE SummerSlam
** SPOILERS ** WWE Superstars Results For This Week
Big Angle With Paul Heyman And Brock Lesnar On RAW
Stone Cold Arrives In San Jose, WWE Hypes Brock Lesnar, NXT - Samoa Joe Preview
Roddy Piper Tribute Confirmed For Tonight's WWE RAW, Big Six-Man Match Announced
Update On New Gimmicks For Several WWE Talents
WWE Star Takes Homeless Couple To Restaurant, Returns With Big Group Due To "Distant" Manager
Undertaker Rumor Killer, Early Brock Lesnar Vs. Undertaker Betting Odds, Mascot No-Sells Kevin Nash
Bret Hart Reacts To "Rowdy" Roddy Piper's Death
UFC 190: Rousey Vs. Correia Recap: Ronda Rousey Continues To Make History


text: HVACR Contractors Battle Weather War Angela D. Harris June 23, 2011 One Comment It is summer. The season has officially begun and it's time to get out and enjoy the weather. For some this is difficult. Global warming - or was it global cooling? - is allegedly causing some rough weather. Read More


text:
Ebony Pussy contains gigabytes of exciting black porn! Do you want to relax examining some of the most exciting black porn videos you have ever watched in your life? If your answer is affirmative then you should just enter Ebony Pussy and you would get mouth water as well as penis rock-hard from the great view of everything what is taking place here. Hottest chocolate nymphs are showing everything they got, playing with dildos, having lesbian sex and get nailed by white or black men.
Ebony6089 movies
Ghetto307 movies
Teen647 movies
Compilation65 movies
Cute240 movies
Close Up39 movies
Shemale6 movies
Cum797 movies
Fat826 movies
Party92 movies
Anal402 movies
Big Ass551 movies
Granny22 movies
Blowjob425 movies
Riding179 movies
Masturbation62 movies
Mature92 movies
Lesbian512 movies
Homemade27 movies
Hairy91 movies
Wet234 movies
Black6202 movies
1885 movies
Creampie147 movies
Chubby159 movies
Teacher30 movies
Interracial437 movies
Clit45 movies
Threesome366 movies
African133 movies
Twins5 movies
Public55 movies
Upskirt19 movies
Dildo242 movies
Rough326 movies
Orgasm44 movies
Funny10 movies
Brutal15 movies
Kitchen41 movies
Babe1541 movies
Amateur537 movies
Cheerleader66 movies
Wife217 movies
Swallow127 movies
Big Cock5 movies
Tight140 movies
Solo46 movies
Massage24 movies
Shower96 movies
Hardcore996 movies
Muscle12 movies
Dogging401 movies
Whore271 movies
Brazil88 movies
Voyeur8 movies
Tease105 movies
Squirt101 movies
Latin211 movies
Pregnant24 movies
Beach39 movies
Babysitter2 movies
Glasses23 movies
6925 movies
Old220 movies
Gangbang96 movies
College42 movies
Pov221 movies
Cheating17 movies
Panties21 movies
Midget19 movies
Casting20 movies
Couple229 movies
Nipples34 movies
Surprise22 movies
Maid47 movies
Milf195 movies
Drunk6 movies
Asian94 movies
Office52 movies
Facial296 movies
Hidden28 movies
Deepthroat77 movies
Student14 movies
Indian16 movies
Nurse42 movies
Natural64 movies
Big Tits46 movies
Hd14 movies
Car377 movies
Cumshot176 movies
Gloryhole222 movies
German14 movies
Strapon51 movies
Girlfriend338 movies
Hooker60 movies
British16 movies
Bikini39 movies
Handjob70 movies
Oil199 movies
Strip223 movies
Feet131 movies
Outdoor79 movies
Boots16 movies
Spy20 movies
Celebs6 movies
Secretary13 movies
Beauty259 movies
Fetish29 movies
Orgy45 movies
Bathroom106 movies
Blonde127 movies
Kissing11 movies
Bisexual11 movies
Dress26 movies
Pantyhose9 movies
Audition19 movies
Group59 movies
Gagging36 movies
Prostitute21 movies
French68 movies
Footjob52 movies
Erotic16 movies
Titjob13 movies
Gay7 movies
Latex16 movies
Pool77 movies
Bondage4 movies
Retro22 movies
Stockings38 movies
Italian6 movies
Shaving7 movies
Swinger11 movies
Femdom14 movies
Bukkake39 movies
Vibrator28 movies
Spanking8 movies
Bdsm17 movies
Toys255 movies
Lingerie45 movies
Smoking24 movies
Tattoo31 movies
Japanese10 movies
Double Penetration21 movies
Fisting10 movies
Sperm58 movies


text:
Free Shipping
Product Information:
5-Cup(Uncooked)/10-Cup(Cooked) Microcomputer Controlled Fuzzy Logic Rice Cooker with 1 Touch Cooking
Slow cooking breakthrough innovation up to 4 times faster to bring to a boil than conventional slow cookers, then slowly simmer to gourmet perfection, sealing in flavor and retaining texture
Weights & Dimensions
6 cups Size
8 cups Size
Additional Weights & Dimensions
|Product Type: Rice cooker
|Shape: Round
|Finish: Silver
|Primary Material: Metal
|Number of Items Included: 6
|Pieces Included: Clay pot, clay lid, rice scoop, measuring cup, power cord, and water catcher
|Lid Included: Yes
|Steaming Basket Included: No
|Temperature Probe Included: No
|Gradations: Yes
|Timer: Yes
|Auto Shut-Off: Yes
|Locking: Yes
|Non-Stick: Yes
|Portable: No
|Removable Interior: Yes
|Warming Setting: Yes
|Operation Type: Programmable
|Number of Settings: 4
|Spoon Hanger Included: Yes
|Detachable Cord: Yes
|Dishwasher Safe: No
|Wattage: 500 Watts (W)
|Voltage: 110 Volts (V)
|Outdoor Use: Yes
|Eco-Friendly: Yes
|Country of Manufacture: China
|Capacity (6 cups Size): 1.5 Quarts
|Capacity (8 cups Size): 2 Quarts
|Rice Capacity (6 cups Size): 6 Cups
|Rice Capacity (8 cups Size): 8 Cups
|Assembly Required: No
|Installation Required: No
|FDA Approved: Yes
|UL Listed: Yes
About the ManufacturerVitaClay® was included in an article called "Top Rated Slow Cookers" by Good Housekeeping and has definitely lived up to its reputation. A brand you can trust, VitaClay® will not disappoint.
More About This Product
Free Shipping
Ships to:
Ships via: FedEx/UPS
Enter your shipping zip or postal code to calculate shipping estimatesGet Delivery Estimate
We want you to love it. If you don't, you may return your purchase within 30 days of delivery. All you need to do is visit our Self-Service Return Center for instructions. Return credits are issued within 24 hours once the item is received and inspected. Please note that shipping charges are non-refundable. The cost of return shipping will be deducted from your refund. 30-Day Return Policy
Average Overall Rating (based on 31 reviews)
Convenience & great results in clay! gmacfan from San Jose, CA on 03/09/2011
I use this product just about every day, from making rice and other grains (oatmeal, quinoa, millet), to cranberry sauce and stuffing for Thanksgiving, to soups and stews. The results from clay cooking are quite noticeably better than any other cooking medium I've used. Rice (brown especially) is the best I've ever made in this pot, and at the push of a button. Also it cooks faster, even for "slow" cooking, so it saves time and energy, and you don't end up with soggy food like sometimes happens in crock pots. I couldn't be happier! I've been using it for more than a year and the clay pot is very durable--I haven't broken it yet!
Good Value Shakil from New York on 10/25/2013 – Verified Buyer
I really like this rice cooker. It works well and is very easy to use. The only complaint I have is that the clay bowl and lid are very fragile. I had the lid crack a little bit and now have to try to find a replacement lid. It's still useable and overall I like it.
Nice looking! Clay Pot! Works well! Susan from Newport, Oregon on 08/05/2012 – Top 500 Reviewer
Have only used it a few times, but it works well. Instructions are vague, so the first round was just an experiment, but it came out great anyway. It's actually pretty easy to use. I love the fact that the pot is clay! The timer is great, and the keep warm feature is fabulous. I can throw something in at lunch time, and come home to a cooked, warm meal. Am thinking about getting one for the office as well.
Great product! PARISA from Holly Springs, NC on 05/13/2015 – Verified Buyer
Wanted a rice cooker without a non stick coating & this was it! Pros: Naturally non stick, easy to clean Cons: None
Great! Tracy from Nepean, ON on 06/02/2015 – Verified Buyer
Great! Meets all our expectations for a rice cooker! Cooks well, washes well and I would recommend it


text:
Jon Dodson Pushes a 10 Year Old Boy!!! Hilarious!!!! watch video >>
The biggest flyweight fight in the world will be heading to the MGM Grand Garden Arena in Las Vegas on Saturday, September 5, as Demetrious "Mighty Mouse" Johnson defends his UFC title for the sevent watch video >>
Demetrious Johnson and John Dodson rematch on Sept 5th at UFC 191 Dodson won the first fight by decision in January 2013. Eonda Rousey wins 2 ESPY awards and takes a shot at Floyd Mayweather. Franiki watch video >>
Demetrious Johnson will face off in a rematch against John Dodson at UFC 191 on September 5th. watch video >>
http://fightnetwork.com/ - Fight Network's John Pollock, John Ramdeen and Robin Black bring us the latest including Jose Aldo diagnosed with bruised rib; Aldo vs. Conor McGregor still on at UFC 189; watch video >>
Ariel Helwani gives the most up to date news regarding: Demetrious Johnson's next fight, what's next for Fabricio Werdum, a possible GSP return and an update on CM Punk's debut. watch video >>
UFC flyweight John Dodson. Follow: https://instagram.com/karatehottiemma/ watch video >>
SUBSCRIBE - https://twitter.com/SubmissionAus Full episode with Ryan Bader & Joanna Jedrzejczyk + UFC Fight Night Goiania discussion: http://youtu.be/B0aYbBR44oo (Photo Credit: Kyle Terada-USA TODAY watch video >>
http://www.MMAWeekly.com/ -- Joseph Benavidez talked to the press after his fight against John Moraga at the UFC 187 post fight press conference. (See Full Comments) watch video >>
UFC stars Chris Weidman, Daniel Cormier, Vitor Belfort, Anthony Johnson, John Dodson, as well as Ryan Bader and others discuss their UFC 187 fight card results. Subscribe: http://www.youtube.com/sub watch video >>
Dodson vs Makovsky
UFC 187 watch video >>
UFC flyweights Benavidez and Dodson on flyweight title picture after UFC 187 watch video >>
John "The Magician" Dodson vs Zach "Fun Size" Makovsky
UFC 187 - Johnson vs. Cormier
Full Fight Video
MGM Grand Garden Arena, Las Vegas, Nevada, United States
May 23 2015 watch video >>


text:
God's blessings supersede anyone else's curses. Here's scriptural proof. read more
Charisma Magazine
Page 5 of 24
How to Produce Divine Fruit
Jesus explicitly described what happens when His disciples fail to bear fruit. But in calling us to abide in Him—like branches to a vine—He also revealed the keys to yielding the fruit of the Holy Spirit. read more
The Most Incredible Miracle Sid Roth Has Ever Seen
The host of Sid Roth's It's Supernatural shares an incredible miracle that just transpired in Israel, something he believes will have an incredibly widespread impact on the kingdom. read more
The Miraculous Story of This Singer's Supernatural Voice
Facing a career-ending surgery, this Jewish singer surrendered her life to Jesus. What happened next will astound you! read more
Identifying—and Exercising—Your Spiritual Gifts
As a Christian, you've already been baptized by the Holy Spirit. Now identify your spiritual gifts and exercise them within the body of believers. Here's why it's important. read more
The Difference Between the 'Gift' and the 'Gifts' of the Holy Spirit
Do you know the difference between the "gift" of the Spirit and the "gifts" of the Spirit? Much confusion abounds in many churches because of this failure in understanding. Learn the difference. read more
An Incredible New Way to Pray Into Your Breakthroughs
Julie Meyer reveals this amazing method she uses to pray for breakthroughs ... with 100 percent success! Watch as she demonstrates this incredible gift on Sid Roth's It's Supernatural, and how you can use it too. read more
Bill Johnson: Claiming the Power to Heal As Jesus Did
God gave every believer the power to heal as Jesus did. But releasing such miracles through you is all about this often overlooked element. read more
10 Ways to Evangelize Supernaturally
It can seem daunting at times, but you, like all believers, are equipped to help fulfill the Great Commission. Here are 10 keys to sharing your faith with supernatural power. read more
4 Kingdom Laws for Understanding Angels
It is essential for us to know how to receive and activate God's supernatural (and often miraculous) influence of angels in our world. But do you understand how angels operate within God's laws? Find out. read more
Faith Comes by Hearing What Is Told
Get quality Christian content in a variety of programs including news, leadership, inspiring stories, women's topics, sports, and even more.
Start Your Mornings with the Holy Spirit
Begin each day inspired by a fresh encounter with the Holy Spirit.
Prophecy: Donald Trump Shall Become the Trumpet
"Trump shall become My trumpet to the American people, for he possesses qualities that are even ...
A Word for Those Fearing the Doom and Gloom
The Lord woke me up at 5:13 a.m. recently from a prophetic dream about believers sinking ...
James Goll: The Coming Collision Between Shaking and Glory
As end-time signs seem to be ramping up, what's next? James W. Goll dives into what we know ...
Prophecy: The Apostolic Mantle Is Coming on First Nations People
"There is a new breed of Native American warriors and Davidic minstrels coming forth."
WATCH: Sadie Robertson's Answer on 'Family Feud' Will Have You Giggling
But really, what would a "sexy perfume for a female dog" smell like?
5 Tests of a True Prophet
Respected prophet Kris Vallotton shares 5 tests to help you recognize whether a prophet may be true ...
3 Keys to Strengthen Yourself in the Lord
Bill Johnson reveals how you can strengthen yourself in the Lord and unlock God's power in your ...
Prophetic Voices We Did Not Heed
These prophets had their fingers on the pulse of America, recognized the fading heartbeat of the ...
How Can We Know That We Are Saved?
Check out Eddie Hyatt's dialogue with two Jehovah's Witnesses and the reaction he received.
Faith Comes by Hearing What Is Told
Get quality Christian content in a variety of programs including news, leadership, inspiring stories, women's topics, sports, and even more.
Start Your Mornings with the Holy Spirit
Begin each day inspired by a fresh encounter with the Holy Spirit.
10 Reasons Christ Followers Should Take Care of Themselves Physically
As a Christian, this is more of a spiritual issue than a physical one.
The Powerful Secret to Heal the Sick
I know that the thought of ministering healing in the name of Jesus can be rather intimidating for ...
Will Your Church Rehire the Holy Spirit?
Many congregations fired the Holy Spirit a long time ago. It's about time He became re-employed.
Don't Believe What the False Prophets Say About America
America is truly a divided nation, but the things that divide us may not be exactly what you think.
What's Next After You Have Been Slain in the Spirit?
If you've ever felt awkward in that moment, read this.
Guarding the Anointing That Breaks the Yoke
Religious activity and service void of the power of the Holy Spirit is of no concern to Satan.
WATCH: Rapper Trip Lee Has 3 Words for Christian Porn Addicts
And he's shocked when he finds this out.
Why is Speaking in Tongues So Controversial?
The baptism of the Holy Spirit with the evidence of praying in tongues and the interpretation of ...
God's Power at Work in the Church Today
Charisma's founder, Steve Strang writes about today's hottest topics affecting the Christian faith.
How to Pray for Your Future Husband
Are you still praying for a husband? Do you feel like giving up? Read this.
Prophecy: Front-line Leaders and Forerunners Are Shifting
I had a vision where I first heard the Lord say, "Front-line leaders and forerunners, batten ...


text:
Brennan Daugherty Model
Hunter SheltonPhotographer Male Richmond, Virginia, US
Greensboro, North Carolina, US
My Website: Hunter Shelton PhotographyMy MM URL: http://www.modelmayhem.com/huntershelton
Mayhem # 27630
About Me
I'm a professional photographer specializing in fashion, commercial and editorial work. I am available for paid tests and assignments, but will occasionally consider testing on a trade basis with agency models who can benefit my book. If I initiate contact with you or send you a friend request, it means that I'm willing, at a minimum, to test with you at no charge. I never contact models to solicit paid test shoots.
Brennan Daugherty Model
Joelbonneau Model
MichaelSJ Model
Giulio Rizzo Model
Tyler_Nort... Model
ChanceDSch... Model
Loading Content


text:
Women of mythology; warriors, mothers & virgins: the art, Women of mythology; warriors, mothers & virgins: the art of howard david johnson. realistic paintings and pictures of legendary. Amazons: warrior women of history, mythology and fantasy, The warrior woman has emerged in recent times in our popular culture as ferocious and deadly as the mightiest male warriors of myth and history.. Read, i, pencil | library of economics and liberty, Complete text of read's 1958 essay. also includes an introduction by milton friedman and an afterword by donald boudreaux..
Zen pencils – cartoon quotes from inspirational folks, Get three pdf motivational posters, all the latest comics and store discounts when you join the zen pencils community. more info. Paper mate 12 count #2 mirado black warrior lead pencils, Paper mate 12 count #2 mirado black warrior lead pencils, medium soft (2254). Fantasy art warrior women | ebay, Find great deals on ebay for fantasy art warrior women . shop with confidence..
Crystal bridges museum collection | a sortable list of art, Disclaimer: this website is not affiliated with crystal bridges museum of american art nor does the museum endorse this site in any way. the thumbnails here may not. Arania's art gallery, News items happy update day! i am planning a major website revamp (this is from last month, but leaving it up since it's still relevant) i am currently in discussions. Turn image into a pencil drawing - gimp tutorial - youtube, If you find my tutorials helpful and you wish to donate, you can do it here - https://pledgie.com/campaigns/29638 inkscape tutorials - http://youtube.com.


text:
Real news. Real funny.
Real news. Real funny.
If you can read this, either the style sheet didn't load or you have an older browser that doesn't support style sheets. Try clearing your browser cache and refreshing the page.
You might try our Headline Search for easier navigation here.
These links may be stale and generate errors. Can't do much about it. Tastes like chicken.
NEW To Fark? Find Out HOW TO FARKX
Sun June 25, 2000
Sat June 24, 2000
Fri June 23, 2000
Thu June 22, 2000
Wed June 21, 2000
Tue June 20, 2000
Mon June 19, 2000
Displayed 136 of about 768 links -- join TotalFark to see them all
Submit a Link »
In Other Media
Stories from our partner sites:
Fake Cop Pulls Over Real Cop, Gets Re...
Drive-Thru Robot Freaks Out Innocent...
Inflatable Minion Causes 'Despicable'...
Rare Albino Wallaby Seen Hopping Arou...
More news at HuffPostWeirdNews »
Healthy 75-Year-Old Ends Her Life So...
Bizarre Border Dispute Ends After 70...
US Huntress Poses With Her Kills
How a CEO's Move to Pay All at Least...
More news at Newser »


text:
Heritage Hills Apartments
1250 Village Green Dr,Jefferson Hills, PA 15025 Map Jefferson Hills, PA Jefferson Hills, PA2 bd1 ba
apartment836 sqftLeave the city behind and come home to our Apartment Excellence Award winning community. The... More
3 bd3.5 ba
rentalNewer townhouse that was model home. 1st floor master bedroom additional den or bedroom next to... More
You know what you want.
Unfortunately nothing matches this search criteria. Try removing a filter or two
Or check out these popular homes
Summary for Jefferson Hills
There are currently 90 resale and new homes in Jefferson Hills on Trulia, including 1 home in the pre-foreclosure, auction, or bank-owned stages of the foreclosure process. The average listing price for homes for sale in Jefferson Hills PA was $329,000 for the week ending Jul 29, which represents a decrease of 0%, or $0, compared to...


text:
Movie Info
Based on the book by Terry Pratchett, the adventure begins for thirteen-year-old Johnny Maxwell and his four friends when they come to the aid of eccentric homeless woman, Mrs Tachyon, and are left minding her trolley full of black bags while she is hospitalised. When the children later visit her in hospital, Mrs Tachyon lets them into the secret that her black bags-- or 'Bags of Time-- are special and can be used to create a gateway to the past. The five youngsters end up during the Blitz where fun and games turn serious when they quickly realise the prejudices of the era. But when they return to their own time, the gang discover they have somehow changed history as a result Johnny's grandmother died in a bombing as a teenage girl meaning Johnny's mother and, in turn, himself were never born. The children are now in a race to fix the path in order to save the future but can they succeed before the bombs start falling...? … More
|Drama, Action & Adventure, Kids & Family, Science Fiction & Fantasy, Comedy
|Directed By:
|Dermot Boyd
|In Theaters:
|Jan 15, 2006 Wide


text:
All Android applications categories
All Android games categories
RC Bluetooth Remote Control
RC Bluetooth Remote Control Application can control RC Car Toy with IO...
Similar app: IOIO Bluetooth Device Control
Free | 311
Bluetooth remote control
This app allows you to remote control bluetooth devices. Connect to a...
Similar app: Echo: Time Travelling Recorder
Free | 254
Bdoo-Bluetooth remote control
Bdoo !! Bluetooth Remote Controller - Easy control between Android de...
Similar app: Blue Car Tethering on Demand
Free | 209
NXT Bluetooth Remote Control
Control your Lego NXT robot over Bluetooth! Make settings and save the...
Similar app: NXT Easy Button Remote Control
Free | 131
Bluetooth Remote Controller
This is a remote control application for CNSBG OTT Boxes only. You can...
Similar app: NextGen Bluetooth Extender
Free | 8
MXRC1 Bluetooth Remote Control
A very easy to use application which works with our MXRC1 8-Channel Bl...
Similar app: MXRC1E BT Remote Control
Free | 9
This app acts as a remote controller for controlling the remote applia...
Similar app: Bluetooth Terminal
Free | 5
HOVIS BT Remote Controller
HOVIS Bluetooth Remote Controller for HOVIS LITE/ECO
Similar app: Vibrator for BT Remote Shutter
Free | 4
MintyRemote offers free bluetooth remote control for the tripod, Selfi...
Similar app: Selfie Sticks Available
Free | 95
Blueberry is an application that uses the phone's Bluetooth featur...
Similar app: DoBots Arduino
Free | 7
Cherry Camera!
This application will allow you to make cute pictures. ♡ Simple and Ea...
Similar app: HQ Camera (silent)
Free | 3K
Remote Link (PC Remote)
【Remote control for your PC】 ASUS Remote Link turns your Android mobil...
Similar app: ZenWatch Manager
Free | 12.6K
bluetooth remote control, remote control bluetooth, bluetooth remote, remote bluetooth, mypeople, unroot pro, macro photo, smart pad download music, rfcomm, terminal serial port bluetooth, garage remote


text:
OSI-Approved Open Source (81)
- GNU General Public License version 2.0 (20)
- GNU Library or Lesser General Public License version 2.0 (16)
- Apache Software License (1)
- Artistic License (1)
- BSD License (1)
- Common Development and Distribution License (1)
- Common Public License 1.0 (1)
- IBM Public License (1)
- MIT License (1)
- Mozilla Public License 1.0 (1)
- Mozilla Public License 2.0 (1)
- PHP License (1)
- Sun Public License (1)
- Zope Public License (1)
- wxWindows Library Licence (1)
- Other License (3)
- Windows (73)
- Grouping and Descriptive Categories (69)
- Linux (63)
- Modern (39)
- Mac (29)
Top Apps
- Audio & Video
- Business & Enterprise
- Communications
- Development
- Home & Education
- Games
- Graphics
- Science & Engineering
- Security & Utilities
- System Administration
PortableApps.com: Portable Software/USB
Portable software for USB, portable, and cloud drives827,902 weekly downloads
A powerful, cross platform, SQL database system19,997 weekly downloads
Hunspell is a spell checker and morphological analyzer library and program designed for languages with rich morphology and complex compounding or character encoding. Hunspell interfaces: Curses, Ispell compatible pipe interface, OpenOffice.org UNO module1,156 weekly downloads
JEDI VCL for Delphi
JEDI VCL for Delphi1,034 weekly downloads
Dirac is a general-purpose video codec aimed at resolutions from QCIF (176x144) to HDTV (1920x1080) progressive or interlaced. It uses wavelets, motion compensation and arithmetic coding and aims to be competitive with other state of the art codecs.740 weekly downloads
Open Workbench
Open Workbench is a desktop application for project management and scheduling in which you can define a work breakdown structure, set dependencies and resource constraints, assign resources to tasks, auto schedule and then monitor progress.437 weekly downloads
GLScene is an OpenGL based 3D library for Delphi, C++Builder and Lazarus. It provides visual components and objects allowing description and rendering of 3D scenes in an easy, no-hassle, yet powerful manner.328 weekly downloads
Hcon Security Testing Framework
Open Source Penetration Testing / Ethical Hacking Framework396 weekly downloads
A community supported fork of the Songbird media player and library.764 weekly downloads
Colorer Library
Colorer provides source text syntax highlighting services. It colorizes source codes in editor systems (more than 200 syntaxes). Uses powerful HRC format(XML, RE, context free grammas), allowing to support any language. Available as Eclipse plugin.121 weekly downloads
Deadly Rooms of Death (Caravel DROD)
Deadly Rooms of Death is a puzzle game for Windows. You control a sword-swinging character that explores dungeons and fights monsters. The game was previously released as a commercial product, and future improvements should make it even more fun.569 weekly downloads
Activa for Asterisk
Activa brings the Asterisk IP PBX to the call center. Built on top of Asterisk, Activa components enable successful call center implementations adding value in areas such as computer telephony, screenpop&click2dial, agent control, automatic dialing...81 weekly downloads
GNU Gettext for Delphi, C++ and Kylix
GNU GetText translation tools for Borland Delphi and Borland C++ Builder39 weekly downloads
Python Computer Graphics Kit
The Python Computer Graphics Kit is a collection of Python modules that contain the basic types and functions to be able to create 3D computer graphics images (focusing on Pixar's RenderMan interface).41 weekly downloads
Jitterbit - Open Source Integration
Jitterbit is an open source integration tool that delivers a quick and simple way to design, configure, test, and deploy integration solutions. It supports many document types and protocols: XML, web services, database, LDAP, text, FTP, HTTP(S), file15 weekly downloads
Java Mozilla Html Parser
MozillaParser is a Java Html parser based on mozilla's html parser. it acts as a bridge from java classes to Mozilla's classes and outputs a java Document object from a raw ( and dirty) HTML input17 weekly downloads
A Library for Interactive Modelling and Visualisation15 weekly downloads
VISL Constraint Grammar Compiler
The VISL Constraint Grammar Compiler is a natural language parser generator. It is an implementation of Pasi Tapanainen's CG-2 constraint grammar formalism.2 weekly downloads
Game Boy Xport
Game Boy Advance Xport Software Distribution. This site contains examples and libraries for the Xport 2.0 and Xport Robot Controller for the Game Boy Advance. eCos and RedBoot ports for the Game Boy Advance are also found here.12 weekly downloads
Zeka FP support library
A library encapsulating the work with Zeka Fiscal Printer device. The library is a thin wrapper around Zeka FP serial communication protocol. It provides C++ library, COM object and java library (.jar). API documentation and several samples included.12 weekly downloads
psimpl - generic n-dimensional polyline simplification. psimpl is a lightweight C++ library that is generic, easy to use, and supports multiple simplification algorithms, including Douglas-Peucker.11 weekly downloads
Fusion Operating System
Fusion OS is a Open Source Operating System, mainly licensed under the MPL 1.1. Parts of it are licensed upder the GNU GPL or other open source licenses. Fusion OS is based on the ReactOS project, and we contribute any bugs found in ReactOS back to them6 weekly downloads
NokSync - Thunderbird / NOKIA Sync'ing
NokSync is a Thunderbird extension, which synchronizes contacts between Mozilla Thunderbird and most NOKIA phones. NokSync will compare Thunderbird address books with contacts in a NOKIA phone, and synchronize them under user control.10 weekly downloads
The OpenSIPStack Library is an implementation of the Session Initiation Protocol as described in RFC 3261. Applications: * OpenSBC (B2BUA) * OSSPhone (Softphone) Source code is available at http://www.opensipstack.org.2 weekly downloads
caspin is a thin wrapper library around Mozilla's Tamarin Project, which enables you to seamlessly integrate the AVM2 (Adobe Virtual Machine 2) into your C/C++ Projects.5 weekly downloads


text:
Log Out
Our Terms of Use and Privacy Policy have changed. We think you'll like them better this way.
Call in to speak with the host
(347) 327-9906
Callers: A man hates his controlling mother. A first-time caller thinks people don't take him seriously. A caller expresses concerns on the medical matrix. One caller is curious how to choose the right person to marry. A man feels guilty and can't move out of the big city.
Sorry we couldn't complete your registration. Please try again.
Please enter your email to finish creating your account.
old-style code for hosted blogs
Player Size
300 x 295
400 x 370
640 x 550
Receive a personalized list of podcasts based on your preferences.