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This review is variously a presentation, reflection, synthesis and report with reference to more recent developments of an article – in a journal which has ceased publication – entitled "Some Electrode Theorems with Experimental Corroboration, Inclusive of the Ag/AgCl System"
The review and report here describes work which had a particular philosophical approach. There were several levels or hierarchies that went into this study, following a pattern that others have pioneered. The study was predicated on attempting to delineate in a broad manner phenomena concerning electrodes that could be quantified to arbitrary degree. Such types of research begins at the qualitative level [
Some of the key theories constructed to explain electrochemical phenomena seem to conform (understandably enough) to a linear superposition of independent physical concepts as a first approximation, without taking into consideration the possible special interference effects which might arise by juxtaposition of these concepts. An example of this approach is to be found in the general Stern modification of the basic Gouy-Chapman (GC) double layer theory. Here we observe a combination of the GC theory with the Helmholtz capacitance model, strictly without any interference. When interference effects are included, such as is suggested here (based on experimental and theoretical considerations) for the case of electrodes exchanging charge between the substrate electrode and the electrolyte across the Helmholtz inner layer, then the usual application of the Stern model to the electrode interface may not yield results compatible with experiment. The inadequacy here has nothing to do with the creation of "bad" theories or incomplete theories as opposed to better ones, nor the utilization of wrong concepts, but rather on not accounting for possible interference effects which would not be anticipated if the various key concepts were separately combined. Most of these cross-effects are of minor importance (such as those concerned with the electronic chemical potential), but others, such as those concerned with the double layer, can be quite dramatic, such as illustrated in
An example of minor interference is found in treatments of the solid state electronic chemical potential μ. In most electrochemical applications, it is inferred that since μ is an intensive quantity, it must be invariant with respect to system size, and since the electronic (or charge contribution) −Fψm accounts for the charge effects, it may be factored out of the pure, uncharged chemical potential contribution μ, which is in turn dependent on the free-electron (uncharged) number density ρ in the substrate lattice. On the other hand, there exists a charge transfer the instant the neutral electrode is inserted into the reactive electrolyte involved in the cell reaction, implying a change in the free-electron density ρ to ρ'. For fixed amount q of charge transferred, it is clear that ρ → ρ' as the volume V of the substrate becomes large (V → ∞) since
The fundamental premise in electrochemistry is that μ(e), the chemical potential of the electrons in the metallic phase substrate electrode is invariant during measurements [
In what follows, we use the conventional notion of electrochemical potentials with reference to an arbitrary spatial point for all components of interest [
Henceforth, F is the Faraday constant, the μ′s are chemical potentials, T the Kelvin temperature, R the gas constant and the a's represent activities. Eø is set constant for activity coefficient determination at a fixed temperature. The electrochemical potential of the electron is defined as
In order to test the regime of validity of Eø, the following lemmas (all of which have further applications to be elaborated) will be used. The results which the low resolution experiments obtained (despite the fact that these experiments could not determine unambiguously the predicted e.m.f. change of order of 0.1 mV with KCl concentration change of 0.1 m, compared to the actual cell e.m.f. values of ~ 1.5 mV over the entire concentration range) are in quantitative agreement to the theory developed from the lemmas. Each of the following lemmas will be applied to specific quantitative experiments. For what follows, the Greek letter symbols used follows the convention of the standard literature and this is sometimes unfortunate because of multiple usage of alphabets such as
In what follows, the different electrode types must be distinguished. The usual nomenclature [
If there exists a function Q = Q(ΔΨd,
However, there is no proof that the converse follows, i.e. that from one coupled equation, the two separate equations may be recovered as is sometimes supposed[
In particular, the hydrated ionic radius for the chloride ion is 3.5 Å [
For metals whose free electrons may be approximated by a highly degenerate electron gas, (and only a restricted set of metals may be so approximated) from (2c) we infer the introduction of electrons will only alter ψm and μF(e) if the other lattice parameters are constant (so that μl(e) is a constant).
We assume this to be the case since the volume change is theoretically never accounted for and is small compared to the bulk volume (V) of the electrode and from the statistical mechanics of the degenerate gas [
This expression, amongst others, will be used to compute μF which varies as charge is transferred to the electrode. The other definitions also used for computing μF will be given in the next section.
Clearly, not all metals conform to the above analysis, because of the Brilloun Zones formed by a periodic potential [
Other mechanical parameters cannot be directly correlated (such as the bulk modulus) since as noted μl(e), the lattice contribution to the free energy becomes an important factor when compressing a solid, and with strong binding by lower-level electrons, the effects from μl(e) will predominate over μe(e). However, we are only interested in the thermodynamical properties when there is no distortion of the lattice. The thermal properties such as the observed and calculated Hall coefficients and Lorentz numbers are in close agreement[
For the free electron gas jellium model, if the correlation and exchange energy is given (per particle) as εxc, then the Fermi-Dirac density distribution [
Consequently, the degeneracy g(ε) becomes:
Similarly, the Fermi-Dirac distribution transforms as:
Since [
These expressions are now in standard form [
The above expansion techniques lead to the standard series by elimination of μ′ as:
On the other hand [
For our computations, in addition to the form given by (5), which is in excellent agreement with the thermodynamical properties for Ag mentioned above, we will use two other expressions for the chemical potential for purposes of comparison, the often utilized [
The Seitz potential is [
It is possible to determine the approximate value of the cell standard potential relative to the solution by electrocapillary maximum (e.c.m.) measurements (illustrated by the Ag/AgCl electrode).
The equilibrium single electrode Nernst equation relative to the solution ions is:
The term capacitance has undergone development in meaning ever since the solution of Laplace's equation ∇2φ = 0 for a source free region with electrical potential φ. For a system of charges Qi (i = 1, 2,…. N) in a region of a fixed relative permittivity εo, Laplace's equation [
The important question is whether in a self-polarizing electrode (where it is assumed that it is mechanically similar to the GCS models, except that in the GCS models the potential is externally impressed and may be varied) it is meaningful to define or deduce properties such as its 'differential capacitance' at its equilibrium potential, since it must be conceded that these potentials are invariant at any particular concentration of electrolyte. In what follows, it is proved that there is a meaningful definition of differential capacitance that is compatible with experiment provided the self-polarizing electrode is mechanically equivalent to a specified ideally polarizable (GCS usually but not necessarily) type. By 'mechanical equivalence' is meant that the ionic interactions are the same, and that the metal substrate of the electrode is also the same in all respects for the two electrode systems. With these assumptions, we model the ions in solution as minute "conductors" of arbitrarily small spherical radius δr1 and δr2 (δr1, δr2 → 0) for cation and anion respectively having a fixed quantum (±e) of charge, which implies the normal surface field strength:
Then, subject to these boundary conditions, the Uniqueness Theorem [
We infer that:
With the above understanding, we can state a simplified capacitance theorem for self-polarizing electrodes that for electrodes reversible to the ion(s) in the solution, the differential capacitance is independent of the equilibrium potential but is dependent on the physical characteristic variables
For instance, let the model of the electrode be according to (3a); then differentiating (3a) with respect to Δφ yields the differential capacitance Cd written:
Consider the equilibrium electrode equation:
Let ℑo = (RT/F)ln α′ where α′ = exp(ℑo F/RT).
Since Δφ = – (RT/F)ln (a[Cl−]/α′), we get
The concentration of an ion in dielectric 1 may be determined in terms of its concentration in another dielectric 2 which is in thermodynamic equilibrium to phase 1 by the Gibbs equilibrium criterion.
The two different (approximate) methods developed here are based on the assumption (Method A) that the concentration of the ion at the boundary of the two dielectric phases is that of the bulk for the phase with the higher bulk concentration, and the other method (Method B) is derived using the Born equation; m represent the bulk concentrations in molality units, ρ the densities, μo the standard potentials, γ the activities, and c the concentration in moles per unit volume (liter if numbers are quoted), and subscripts refer to the phase concerned. The assumption in Method A is inspired by the fact that the concentration of the active species is much lower in the electrode dielectric than it is in the aqueous layer, and that rapid exchange of the active ion by diffusive processes in chemical equilibrium would make the concentration near the surface close to the one for the bulk aqueous layer. The equations below apply at 'low concentrations' (~ 0.05 m), of the same magnitude used in the experiments reported here.
The boundary conditions chosen are:
This method is highly dependent on (a) highly accurate values of the effective radii of the ion in the dielectric and vacuum phase (to 3 decimal places), both of which need not be the same, and even until now little is known of these ionic radii under different ionic environments and concentrations and (b) the assumption that the activity coefficients at the standard states in both dielectrics 1 and 2 are approximately equal, or are small enough to be neglected, and that they are known for other ionic concentrations in the solid state dielectrics; in the relatively recent field of solid state ionics, the activity coefficients are customarily neglected by being set to unity [
The work done to convert a charged ion in vacuum (I0) to a state of known molality concentration I4 may be done in a series of stages depicted as
Thus the concentration of the ions in equilibrium between dielectric phases 1 and 2 is governed by the equation:
Assuming no change in the compression energy q, the following equation obtains:
It does not immediately follow that if (3a) is true, that the converse always obtains, where the coupled equation may lead directly to ΔΨd i.e. Q(ΔΨd) ⇒ ΔΨd, as is sometimes supposed [
It appears that both the usual sinh expansion and/or Lemma 1 may be utilized to partially explain the many experimental phenomena connected with potentials of zero charge and the electrode interface. However, there is a way to distinguish the two rationalizations by carrying out measurements in a regime for which the sinh expansion is not valid.
If logarithmic behavior is still observed in these non-valid regimes, then it appears probable that the standard approximate relationship mentioned above may be open to question. The available data [
In the conventional analysis, the ϕ2 value as predicted by the conventional theories obtain when [
The value of the tenth-normal Ag|AgCl electrode potential is approximately 0.5125 V at this maximum [
At the constant Em regime, we note that a compensating (−RT/F)ln(a) factor to the strained value ℑstr leads to a constant, so that a solution to this regime is:
If the change of regime is reasonably abrupt, then at a[Cl−] = acrit, the critical activity, both (40e) and (40f) are jointly satisfied, and thus:
From the data [
Some writers have viewed the Hg electrode as a reversible cell [
(i) At sufficiently high concentrations of bulk solution electrolyte, the concentration of ions adsorbed within distance δl (where δl extends to a specified distance where negligible amounts of ions are present and which is expected from the Faraday demonstration of charges residing at the surface of the conductor) is approximately linear to first order in the bulk solution strength where the usual Gibbsian equilibrium conditions prevail written:
Applying the Gibbs criterion yields the electrode solution potential ΔφHg-S as:
Hence the total cell potential difference for the Hg and Ag|AgCl electrodes becomes:
However, at the e.c.m, the elementary Lippman theory in conjunction with the Gouy-Chapman description demands ΔφHg-S = 0, so that ℑstrHg (Em) = RT/Fln a[Cl−] and thus (44) becomes:
(ii) At very low concentrations, the reversible anion or cation mechanism breaks down and the electrode may be viewed as "inert" but as having the same potential as the solution within the limits of the Gouy-Chapman theory of electrodes since residual charges and the capacitance becomes arbitrarily small as the concentration drops. Hence:
(1) Another gross verification of the present capacitance theorem may be observed from the experimental data provided by Grahame [
If the mercury is envisaged as an electrode reversible to ions as outlined in (1) above and explained below, then, we might expect such a close fitting linearity (assuming similar values of activities) since Cd ~ constant for a fixed concentration of aqueous electrolyte, leading to the same gradients for the different curves. The parallel nature of the lines are due to changes in the physical conditions due to the different counter ions. For NaI, the curve is crudely of the form sinh(κφ) (constant κ, with potential φ), implying a net ideally polarizable inert electrode with non-reversibility of ions (no charge transfer).
(2) Concerning the constancy of the e.c.m. voltage, Grahame remarks [
In either case, the increase of potential Δφ′Hg-S relative to the solution due to the ionic interchange is such that Cd. Δφ′Hg-S = Qref, so that Δφ′Hg-S = Δφ′ref.
Hence at all moderate concentrations:
The similarity of value of potential in b′) for different electrolytes may be explained by postulating that the k values in (41 – 42) are approximately the same for each of the different types of anions (ka) and cations (kc), where ka is not necessarily equal to kc for strong electrolytes, and they might be treated as point charges independent of size within the surface of the mercury electrode. The above is clearly only an outline and other alternative net mechanisms may be adduced.
The setup of the system used for a low resolution experiment to determine e.m.f. contributions due to size effects is given in
Silver foil (Aldrich Chemicals, 99.98% purity) of square dimension 2 × 2 cm and thickness 0.025 mm and 1 mm were used for electrodes s2 and s1 respectively found in (1a). It was found that massive or heavy electrode holders or wiring [meaning ~2 gm (grams) excess weight for brass connectors] could alter the measured e.m.f. by ~ 0.5 mV if one of the electrodes were connected to such an arrangement. To avoid possible capacitive effects due to unequal metal mass contact, and also sheer mass of the connectors, the electrodes were directly spot soldered at one of the corners, (
The Ag foil electrodes were all electrolyzed under identical conditions, and the temperature was maintained at 25 ± 0.02 °C. This electrolysis to create the AgCl layer was carried out at 7.8830 mA for 1,200 seconds in HCl solution (1.5 M) using two platinum coated titanium gauzes as counterelectrodes for all electrodes s2 (under identical conditions) and the current corresponds to a total thickness of 2.5 μm (microns) of Ag which was converted to AgCl. The thickness mentioned refer to the Ag substrate and not to the AgCl deposit. The density of Ag was taken to be 10.501 gm cm–3 at 25 °C. The slight reduction in the average thickness of the Ag substrate was accounted for in the computations. The electrodes were dry weighed before and after electrolysis by a Mettler MT5 microbalance to determine the efficiency of conversion at ~ 92 ± 5%. The electrolysis utilized a commercially available potentiostat [EG & G Princeton Applied Research 363 Potentiostat (U.S.A)], and all e.m.f. measurements were made using a digital voltmeter [Keithley 197A Autoranging μV DMM (U.S.A.)]. Over 60 readings of cell e.m.f. Ec = ϕ10 – ϕ20 (where ϕj0 represents the potential of the Ag substrate j) were taken each lasting at least 1/2 hour; further details of the measurements follow below. One result (without exception) was that Ec was negative to the order exceeding 1 mV for all the 60 measurements used in the e.m.f. determination under controlled conditions. The KCl solution was prepared from Analar grade KCl and doubly distilled water by weighing (since molality units were used). For the ordered set of solution concentrations m (molality units) {0.01, 0.03, 0.05, 0.07, 0.1}, the corresponding ordered set of averaged - Ec values (units of mV [millivolt], with a maximum experimental fluctuation per reading of ± 0.2 mV) are {1.46, 1.51, 1.57, 1.56, 1.77}. Altogether, 24 separate s2 electrodes were fabricated and electrolyzed, and studied and used for the qualitative and quantitative studies.
Many of these electrodes were cleaned and re-electrolyzed to confirm the observations concerning the AgCl layer and the e.m.f. measurements. The measurements for different KCl concentrations were done slowly over a 10 month period (December 1997-September 1998), where two separate s1 electrodes were fabricated and used. The estimated cell e.m.f. observational errors is based on this relatively long time period of general experimental. It is deduced here that the inaccuracies are mainly attributable to the method of fabricating the electrodes and the inhomogeneity of the electrode materials, as discussed in the text. The cell e.m.f. results presented for any one KCl concentration is the average of measurements carried out at least twice at different times from different stock solutions. The input resistance of the Keithley instrument was > 1 GΩ for the range of e.m.f. measured, and so internal i-r drops and other associated effects causing extraneous e.m.f.s may be safely discounted. Further, the electrode e.m.f. was reset to zero volts by contact of the upper unelectrolyzed part of the electrode before immersing s2 into the solution, which would eliminate polarization e.m.f.s due to the circuitry other than the electrode system. That i-r drops are negligible for these measurements may also be inferred form the fact that no discernable change in e.m.f. (of 1 μV order) could be detected when distance between electrodes s1 and s2 were varied (to ~ 4 cm). Also, the observed e.m.f. polarity was the same for all of the measurements of the s1 – s2 couple, implying an intrinsic effect due to electrode size effects only. To confirm that the electrode e.m.f. differences were due to the Ag substrate size differences and not due to electrochemical differences caused by different coating thicknesses of the AgCl dielectric, five of the s2 electrodes were electrolyzed at half the current intensity for the same time (corresponding to total thickness of 1.25 μm of Ag converted to AgCl). It was experimentally found that the effects due to coating thickness was effectively negligible where the measured e.m.f. of cell (1a) is concerned, which accords with the common and fundamental electrochemical assumption (such as used in (2a)) where the solid dielectric or salt activity (in this case AgCl) is assigned value unity, with constant chemical potential for all electrodes regardless of amount. The surface area of s1 exposed to the solution was maintained constant, corresponding to a penetration depth (into the KCl solution measured from the tip of the electrode to the Ag-AgCl interface) of 1.920 cm measured by Vernier caliper, with an exposed solution area of approximately 6.90 cm2, but s2 varied by ~ 6 ± 0.5 cm2 because the electrolysis involved vigorous stirring, so that the Ag-AgCl line boundary could not be exactly fixed; so all readings were normalized to 8 cm2 surface area exposure for s2 by linear extrapolation with s1 fixed with the stated extent of surface area. That this is a reasonable extrapolation may be inferred from
This calculation was verified qualitatively by experiment, but because of the porosity of the AgCl dielectric, coupled with the effects of a solution film still present in areas not immersed in the solution, direct verification is difficult, but an e.m.f. change of ~ 0.5mV could be detected as a result of change in the degree of penetration of the s2 electrode into the KCl solution. The surface area are in units of square centimeter of electrode exposed to the reactive solution, and the potential that develops as a result of the charge transfer from the AgCl dielectric in contact with the solution.
Interestingly enough, a direct confirmation of this result is to be found in the award-winning work of K.L. Cheng [
For the bulky s1 electrode, calculations show that the cell e.m.f. varies by only ~ 0.02 mV for a 4 cm2 surface area change for a totally immersed s2 electrode, as expected. Hence it is sufficient to normalize just electrode s2. The normalization scale factor magnifies the raw experimental results by only an approximately further 0.3 mV. To conserve costs and to remove systematic errors, only one reference electrode s1 (0.1 cm thickness) was used for all the measurements involving s2. However, to check for consistency, another s1 electrode was made and immersed to the same extent into the solution, and after ½ hr (hour) equilibration, a maximum e.m.f. difference of 0.127 mV was observed between the two electrodes at 0.1 m KCl, in contrast to the value ~ 1.2 mV detected without fail when s2 is substituted. All the electrodes were stored in a solution comprising 0.05 M KCl and 0.05 M HCl. All e.m.f. cell measurements were conducted at the solution temperature of 25 ± 0.02 °C using a precision temperature controlled cooling unit with an inbuilt water circulation pump (Polyscience® Temperature Control Unit (U.S.A.)), where the cell was placed in a lagged glass cooling jacket. The depth of penetration of the electrodes was measured by means of a vernier caliper (±0.01 mm) by observing the change of vertical distance of the upper flat surface of the Aluminum holder to a point marked on the glass rod of the electrode when the pointed electrode corner tip just touches the solution to the position when the electrode is at rest with the solution level coinciding with the boundary line between the AgCl dielectric and that of the pure Ag surface (
The cell was constructed from a 250 mL glass beaker (of diameter 7.0 cm) cut to approximate height 7.8 cm, where the KCl test solution reached a height of ~ 3.5 cm. The length of the hollow soft glass (0.56 cm diameter) used in the electrodes was 14.5 cm. The electrodes s1 and s2 were placed at a fixed distance of 3.5 cm, and where aligned so that their major surfaces were parallel because it was observed through trial and error that for at least this configuration, there was no detectable e.m.f. change as the distance of the electrodes varied (due to the solution ir drop caused by the external measuring circuitry). Two large aluminum holders of approximate height 3.4 cm and diameter 3.8 cm with a hole in the center to accommodate the electrodes, which were held by the pressure of Allen screws tapped at the sides of the blocks, both of which were planed at one vertical side (see
The experimental outcome for the above series of experiments, derived over a 10-month period after repeated trials with many samples is reported in the figures of Section 5 together with the theoretical predictions. Some comments concerning the accuracy of these measurements are in order, together with the reasons why these measurements were made over a range of KCl solution concentrations. Firstly, this experiment was aimed at detecting second-order effects which are assumed to be non-existent in normal electrochemical practice, where the measured cell e.m.f.s are typically 50 – 100 times greater in magnitude to that presented here, with error margins of the same magnitude as the averaged results given here, because in normal practice, size is not a controlled variable, and the variation in size for the different electrodes is approximately of the same magnitude as that between electrode s1 and s2, leading to uncertainty in the region of some fraction of mV, to approximately 1.0 mV; here we have controlled the geometrical structure of the electrodes, and the polarity of the e.m.f. was the same and the magnitude of the e.m.f. was approximately the same for all 60 readings that were made, implying a size effect. If no size effect were present, then the polarity of the measured e.m.f. would vary randomly, and this was not observed at all. The measurements over different KCl solution concentrations were done to verify the curious 'non-Nernstian' effect predicted by the theory, where the minute change of the e.m.f. for the cell due to change in the KCl solution concentration (from 0.01 m to 0.10 m) was in the order of 0.13 – 0.06 mV (depending on the type of chemical potential used). A typically Nernstian result would be in the order of 2.303 RT/F Volts (~59.2 mV at 25 °C), larger by a factor of ~700. This theoretical prediction is borne out in the experiments, where there was no dramatic change in the e.m.f. over the stated range of KCl concentrations. It was never the intention of the experiment to attempt to map out the actual change of the e.m.f. with concentration; the errors in observation would preclude that, although there is a hint, based on average values, of a very slight general increase which may not be considered statistically significant at all. The main intention was to detect a size dependent, fairly stable and constant e.m.f. presence in a variety of conditions, such as varying electrolyte concentration, so as to rule out other factors which might cause these changes. Another advantage of measuring over a concentration range is to give an indication of the most appropriate electronic chemical potential of the substrate electrodes, since the predicted e.m.f. differences based on the different chemical potential models are greater than the errors of measurement; i.e. the band (or spread) of experimental e.m.f. values over the concentration range can give an indication of the most appropriate theoretical model of the chemical potential. The results obtained here seem to especially support the free-electron gas chemical potential, which is corroborated by the low-temperature experimental specific heat capacity results for Ag.
Lastly, can the accuracy of the experiments be further improved by suitable precautions? It may be improved, but the precautions taken would probably involve methods and facilities that go beyond the techniques routinely employed in college Electrochemical and Analytical laboratories and the experimental capabilities and facilities of our laboratories. For instance, it is known [
For cell (1a), the e.m.f. E is given by (2a-b) as:
The above sub-iterations are used to solve the following equation derived from
It will be noted that for each secant iteration in (37), the charge Q must be known, and this information is obtained by solving one of
The entire cell may be characterized as having the following potentials for the entire surface perpendicular to the line direction x (from the surface of the metal substrate of the electrode concerned) as depicted in
It was discovered that for concentrations from 0.01 – 0.1 M KCl, and ℑo ~ 0.39 – 0.5 V, the symmetrical neutral electrolyte M+Cl− electrode charge
In order to utilize M1, by the Uniqueness Theorem a boundary condition must be specified. Here we state that within the AgCl dielectric, when x → ∞, the concentration of the Cl− ions must correspond to that at the AgCl-Aqueous interface, implying analytical continuity of the chloride ion concentration; hence we set [Cl−] ≡ [Cl−]aq with the dielectric constant value of that for AgCl at this interfacial region, and we also set the potential gradient ∂φ/∂
It will be observed that the experimental results depicted in
It may be reasonably argued that the AgCl dielectric does not play a prominent role (despite its occluding the Ag substrate surface) in determining the cell e.m.f., apart from providing a reservoir for Ag and Cl− ions. This situation corresponds to solving for the cell e.m.f. with the H2O dielectric constant (ε = 78.54) at the vicinity of Cl− exchange at the electrode, the results of which are presented in
The types of electrode reactions that are applicable to the results presented in
It is clear that the computed values are far in excess of the experimental results and so it is safe to infer that AgCl does play a prominent role in distributing the Cl− ions within the dielectric to produce the observed e.m.f. apart from its role as a dielectric ionic reservoir.
It is well known that the Stern modification (GCS systems) with xd ≠ 0 is widely utilized as a refinement to the Gouy-Chapman theory [
The results of using the Stern model for the electrode processes in our equilibrium electrochemical system (1a) with ε = εAgCl, written:
It is clear from
In order to illustrate the feasibility of the method (even if it is not very applicable here) we solve
With the above (56) activity coefficient,
We may conclude from the above discussion that the so-called standard potentials Eiø for the various half-cells used to compute the overall cell e.m.f. E with standard Esø written:
Having observed the rough magnitude of the cell e.m.f. which is incompatible with the predictions made on the basis of the GCS interfacial model, we may perhaps attempt to understand why this is so from the point of view of charge accumulation on the electrodes. For the electrode reaction AgCl + e−(Met.) ↔ Ag + Cl− (aq) (where we assume that the AgCl dielectric is only a reservoir for ions with no other effect) the charged species in solution includes the cation, Cl− and electrons which are able to percolate through a pathway to the substrate Ag electrode, whereas the Gouy-Chapman (and Stern modification) assumes the ions being the only charge carriers (with finite size for the Stern modification of the Helmholtz double layer). This process pathway still obtains even if we should choose model M1 (but the charges on the electrode would be scaled down by a factor of approximately two, due to the lower value of the dielectric constant for AgCl). For purposes of calculation and comparison, if the (theoretical) substrate-solution potential were fixed at ℑo = 0.394031 V, then for model M1, the charge per unit area on the electrode may be computed for distances x2 = 3.5 Å (GCS model) and x2 = 10–9 Å (effective GC model). For the For the ordered set of KCl normalities {0.001; 0.005; 0.01; 0.05} with activity coefficients set to unity, the corresponding charge density (μCcm–2) for the electrode at x2 = 3.5 Å and x2 = 10–9 Å are the respective ordered sets with values {27.32, 33.46, 36.19, 42.70} and {398.37, 890.77, 1,259.74, 2,816.87}. If it is maintained that at very low concentrations, the Gouy-Chapman model may be accepted as fairly accurate [
From a strictly theoretical angle, there appears to be a (subtle) and probably minor peculiarity which is assumed in using the GCS model as an ideal polarized electrode. By definition, no charge transfer is envisaged with change of potential, yet there is a constant setting4 of σm = –σs in order to determine the charge on the electrode (σm) where –σs = –εεo(dϕ/dx)x = x2, where ϕ is the solution potential at x2 (x2 = 0 for the GC model). The reason is attributed to total charge neutrality; if this were the case then one must allow for charge transfer. On the other hand, if there were absolutely no charge transfer then a counter-electrode would have to be placed in the solution for electroneutrality, which would negate the model boundary conditions. As discussed below, this charge neutrality between electrode and solution is accounted for directly in the ideal self-polarizing electrode. These secondary considerations, in addition to those derived from experiment, make us choose the simplified Gouy-Chapman model of the interface because the electrode reaction mentioned above provides an electronic pathway across the interface for charging the electrode; the electronic factor is not considered in the Stern modification, which could lead to a much smaller x2 than predicted for an electrode system not reacting with the fluid ions.
For instance, consider the component electrode reactions for the AgCl|Cl electrode:
Most of the theorems presented here may be corroborated by well established experimental data. The preliminary experiment presented here indicate that electrode size effects which affect the cell e.m.f. does exist, and despite the 20% uncertainty in the measurement, due mainly to the unavoidable variation of physical properties of the substrate silver metal and the silver chloride constituents, are of a magnitude which does not contradict the standard theories, such as the postulated electronic chemical potential of Ag inferred from data such as its low temperature specific heat. Where change of e.m.f. with size electrode size is concerned, the problem then becomes one of determining the precise magnitude of these differences with the change of the thermodynamical variables (including size), so that a clear electrochemical standard may be prescribed. From a practical point of view, the standardization of electrodes following the recommendation of people like Bates and Macaskill [
The preceding theoretical results concerning the e.m.f. differences may conceivably be quantitatively improved further by using modified theories of the electrode-solution potential[
Recently, it has been shown [
One of the consequences of the electrode theorems above, corroborated by the experimental results is that
The other lemmas, such as those concerning the self-polarizing electrode are readily applied to a variety of problems such as those concerning capacitance; in particular, these electrodes also suggest, by way of operation another 3-dimensional treatment of the interfaces, where at present the 2-dimensional utilization of the Gibbs surface excess and surface tension equations are the main descriptions.
Concerning the electronic chemical potential, if accurate cell e.m.f. measurements are possible, then the (solid state) electronic correlation energy εxc(n) may be determined by using the expression such as μT [
The above work shows that with even very elementary methods, and relatively non-specialist skills, one can still pose and solve problems in a qualitative sense that suggests quantitative directions, and within a context that might appear attractive to those fragile political, social and scientific environments. But such solutions are not possible without in the first place the existence of a
I thank the management of MDPI for personally soliciting contributions to this Special Volume and to TWAS (Third World Academy of Science, Trieste, Italy) (1998) for financing this research and University of Malaya PJP grants for helping with preparation and publication of the work. Finally, I am grateful to Tan Hsiao Wei (postgraduate student, University of Malaya (2009)) for her help in typesetting.
The tables below represent the raw numerical values that were used in the quantitative Figures found in the main text. They are provided here merely to aid in quantitative analysis of the plots. The dimensions and scales of these numbers can be inferred from the corresponding Figures and plots in the main text and so column captions are superfluous.
Numbers used for plotting
−3.0 | 0.2018 | −3 | −0.2188 | −3.0 | −0.1469 | −3.0 | 0.1689 |
0.0 | 0.068 | 0.0 | −0.0719 | −0.0 | −0.0125 | 0.0 | 0.0347 |
Numbers used for plotting
−0.9536 | −24.0 | −1.0150 | −20.0 | −1.0731 | −20.0 | −1.1077 | −20.0 |
−0.5076 | −16.0 | −0.7385 | −16.0 | −0.8308 | −16.0 | −0.8539 | −16.0 |
−0.3115 | −12.0 | −0.5192 | −12.0 | −0.6000 | −12.0 | −0.6115 | −12.0 |
−0.1615 | −8.0 | −0.3000 | −8.0 | −0.3577 | −8.0 | −0.3692 | −8.0 |
0.0000 | 0.0 | 0.0000 | 0.0 | 0.0000 | 0.0 | 0.0000 | 0.0 |
0.1269 | 8.0 | 0.3000 | 8.0 | 0.2539 | 8.0 | 0.2539 | 8.0 |
0.2054 | 12.0 | 0.4385 | 12.0 | 0.3462 | 12.0 | 0.3000 | 12.0 |
0.2308 | 16.0 | 0.6000 | 16.0 | 0.4270 | 16.0 | 0.3577 | 16.0 |
Numbers used for plotting
0.05 | −0.2414 | −0.1438 | −0.1146 |
1.00 | 1.9329 | 1.1536 | 0.9194 |
2.00 | 4.2022 | 2.5123 | 2.0033 |
4.00 | 8.6818 | 5.2084 | 4.1575 |
6.00 | 13.0853 | 7.8765 | 6.2939 |
8.00 | 17.4150 | 10.5176 | 8.4127 |
9.00 | 19.5543 | 11.8281 | 9.4656 |
Numbers used for plotting
5.0000−3 | 1.6284 | 0.9826 | 0.7858 | xexp | yexp |
0.0100 | 1.6501 | 0.9959 | 0.7965 | 0.0100 | 1.4640 |
0.0200 | 1.6790 | 1.0135 | 0.8107 | 0.0300 | 1.5140 |
0.0300 | 1.6996 | 1.0263 | 0.8208 | 0.0500 | 1.5660 |
0.0400 | 1.7162 | 1.0364 | 0.8290 | 0.0700 | 1.5600 |
0.0500 | 1.7302 | 1.0450 | 0.8358 | 0.1000 | 1.7680 |
0.0600 | 1.7423 | 1.0524 | 0.8418 | ||
0.0700 | 1.7531 | 1.0589 | 0.8471 | ||
0.0800 | 1.7627 | 1.0649 | 0.8519 | ||
0.0900 | 1.7716 | 1.0703 | 0.8562 | ||
0.1000 | 1.7797 | 1.0752 | 0.8602 |
Numbers used for plotting
5.0000e-3 | 4.1163 | 2.5309 | 2.0358 | xexpt | yexpt |
0.0100 | 4.1686 | 2.5640 | 2.0628 | 0.0100 | 1.4640 |
0.0200 | 4.2380 | 2.6084 | 2.0985 | 0.0300 | 1.5140 |
0.0400 | 4.2877 | 2.6396 | 2.1242 | 0.0500 | 1.5660 |
0.0500 | 4.3275 | 2.6649 | 2.1447 | 0.0700 | 1.5600 |
0.0600 | 4.3610 | 2.6861 | 2.1620 | 0.1000 | 1.7680 |
0.0700 | 4.3899 | 2.7046 | 2.1771 | ||
0.0800 | 4.4156 | 2.7210 | 2.1904 | ||
0.0900 | 4.4387 | 2.7357 | 2.2023 | ||
0.1000 | 4.4598 | 2.7491 | 2.2133 | ||
0.0300 | 4.4791 | 2.7614 | 2.2238 |
Numbers used for plotting
−20.0223 | 173.1564 | 104.5700 | 83.6511 |
−15.4172 | 173.1228 | 104.558 | 83.6343 |
−13.1146 | 172.8186 | 104.3690 | 83.4821 |
−11.5052 | 171.4856 | 103.5420 | 82.8155 |
−10.8120 | 169.8613 | 102.5360 | 82.0041 |
−9.2026 | 158.3099 | 95.4024 | 76.2588 |
−8.5095 | 146.6338 | 88.2300 | 70.4922 |
−6.9000 | 98.6750 | 59.0810 | 47.1330 |
−6.2068 | 74.1631 | 44.3246 | 35.3413 |
−4.5974 | 30.2894 | 18.0615 | 14.3911 |
−3.9043 | 19.1034 | 11.3867 | 9.0717 |
−3.2112 | 11.6658 | 6.9520 | 5.5382 |
−2.8057 | 8.6350 | 5.1459 | 4.0993 |
−2.6515 | 7.6868 | 4.5803 | 3.6487 |
−2.2949 | 5.8486 | 3.4848 | 2.7760 |
Numbers used for plotting
5.0000e-3 | 0.9565 | 0.5742 | 0.4584 |
0.0100 | 0.9696 | 0.5821 | 0.4648 |
0.0200 | 0.9869 | 0.5926 | 0.4732 |
0.0300 | 0.9993 | 0.6001 | 0.4792 |
0.0400 | 1.0093 | 0.6062 | 0.4848 |
0.0500 | 1.0178 | 0.6113 | 0.4881 |
0.0600 | 1.0252 | 0.6158 | 0.4917 |
0.0700 | 1.0317 | 0.6197 | 0.4949 |
0.0800 | 1.0376 | 0.6233 | 0.4977 |
0.0900 | 1.0430 | 0.6266 | 0.5003 |
0.1000 | 1.0479 | 0.6296 | 0.5028 |
Numbers used for plotting
5.0000e-3 | 0.4239 | 0.2534 | 0.2015 |
0.0100 | 0.4297 | 0.2569 | 0.2048 |
0.0200 | 0.4375 | 0.2615 | 0.2086 |
0.0300 | 0.4430 | 0.2649 | 0.2112 |
0.0400 | 0.4475 | 0.2676 | 0.2134 |
0.0500 | 0.4513 | 0.2699 | 0.2152 |
0.0600 | 0.4546 | 0.2718 | 0.2168 |
0.0700 | 0.4575 | 0.2736 | 0.2182 |
0.0800 | 0.4602 | 0.2752 | 0.2194 |
0.0900 | 0.4626 | 0.2766 | 0.2206 |
0.1000 | 0.4648 | 0.2780 | 0.2217 |
Miscellaneous: For theoretical calculation, the exposed area of s1 corresponded to 6.8926 cm2 for the penetration depth of 1.920 cm. All computations were in double precision (32-bit machine).
Schematic of the regions considered at the electrode interface.
Concentration profile of ion between two dielectrics.
Variation of ϕ2 with bulk ionic concentration.
Charge on Hg in contact with 1M electrolytes at 25 °C.
(a) General setup of cell. (b) Plan view of square polyethylene top for electrode; (c) Electrode used in the experiments.
Variation of cell e.m.f. with area of electrode s2 exposed to 0.05 m aq. KCl.
Sketch of interfacial region with associated potentials.
Computed cell e.m.f.s for single Cl− ion electrode for various μ and experimental data.
Cell e.m.f. based on H2O dielectric constant μ.
Cell e.m.f. computed for various μ and Helmholtz Inner layer distances Xd.
Cell e.m.f. for various μ, based on solution of dielectric equation for KCl concentration in AgCl dielectric.
Cell e.m.f. for various μ, based on Born dielectric equation for KCl concentration in AgCl dielectric.


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Not-So-Sweet Snickers and a Biting Maury Donna Kronenfeld's relationship with Snickers began when a friend found the 10-week-old Australian Shepherd wrapped in a blanket under a car. The two bonded instantly and had a very peaceful year together. Read more
A Separation-Anxiety Suffering Mongo, Big-Dog-Bully Gorby and a Biting Jake Danny Richards and his wife Andy own Mongo, a pit mix. Danny rescued Mongo about six years ago, but he has since developed a severe and potentially life threatening separation anxiety.When left alone the first time, Mongo managed to destroy his crate and the house. Read more
Actress Rhona Mitra's Dog-Aggressive Oscar and People-Fearing Luna Rhona Mitra is a London born actress who has appeared in such films as Sweet Home Alabama and Underworld: Rise of the Lycans. Rhona is also a knowledgeable dog owner who worked at a rescue when she was a teenager, but can't seem to curb her French Bulldog's dog aggressive tendencies. Read more
Expedition Wild's Casey Anderson's Uncontrollable Walkers JJ and Ellie, and Child-Aggressive Oscar Oscar was a stray that was rescued in Delaware. When the rescue group received an application from Sebastian and Renée, a professional couple living in Manhattan and Princeton, NJ, it was clear they had found the perfect home for Oscar. Read more
Dog-Aggressive Chloe and Gotti, and a Pouncing Madison Owner Jaime Crossman found Chloe on Craigslist and was warned of the Border Collie/Greyhound mix's nipping problems. Jaime quickly enrolled the dog in obedience training and nipped the problem in the bud. Read more
Bebe the Lampshade Stalker and Howie Mandel's Temperamental Chi Lola When Bob Haueter brought Bebe home for his daughter Kim, he thought they would have another perfect pet like their Golden Retriever/Lab mix Sadie. But the English Bulldog had her own agenda. Read more
An Unpredictable Aggressive Beagle and a Dog-Aggressive Pup Eight years ago, Janet Cantebury's kids brought home J, a female Beagle. Janet had no clue this adorable Beagle would have so much baggage! J, now 12-years old, continues her unpredictable, strange aggression. Read more
A Busy-Bodied Pit Bull and a Dog-Aggressive Rott/Shepherd Mix When it comes to pets, sometimes you can have too much of a good thing. Single mom, Athena Blakely and her daughters wouldn't mind if sometimes Maya, their affable Pit bull, would make herself a little less at home. Read more
An Aggressive Boxer and an Anti-Leash Shitzu The Alberts loved their Boxer, Moca, so much they decided to adopt another Boxer named Coach. Unfortunately, Coach was nothing like Moca. Read more
A Wheel-Obsessed Shepherd/Lab Mix and a Shadow-Aggressive Entlebucher Mountain Dog Circles and light. Sounds like the a bestseller in the new age section of your local bookstore. Alas, there is nothing calming about either of these items for the two dogs in this episode. Read more
Groomer-Fearing Maltese and a Water-Obsessed Chesapeake Bay Retriever Anxiety comes in many forms. In the first story we meet Josh, a lively Maltese who will not let anyone with a brush or pair of scissors near him. He would much rather chase the vacuum cleaner or run in circles around the house. Read more
Some Out of Control Grooming Clients and an Unstoppable Pit Bull Mix Lauren Warshaw is the proud and dedicated owner of Club Doggie Grooming Salon, a professional mobile grooming service that handles the desert cities near Palm Springs, California. As the only employee of her company, Lauren strives to provide her clients with the same service and care she would want for her own dogs. Read more
A Horse-Aggressive Greyhoung Mix, a Seperation Anxious German Shorthaired Pointer and a Broom-Attacking Yorkshire Terrier Life coach and Biggest Loser fitness trainer Jillian Michaels was in heaven after adopting Seven, a 14 month old greyhound mix. But when the avid horseback rider brought Seven to the equestrian center where she rides, Seven's good manners went to hell. Read more

subset: commoncrawl


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NEWS ROOM ITD News USDOT News Associated Press News Link
TRANSPORTATION ORGANIZATIONS State of Idaho ITD Home Page AAMVA AASHTO USDOT Federal Highways TRIP TRB NTSB NHTSA
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Combo re-elected vice chairman
Idaho Transportation Board members re-elected Jack Combo vice-chairman at its Feb. 26 meeting in Boise.
Combo, from Idaho Falls, was first appointed to the board in 1990. He served as chairman from 1991 until 1995.
By statute, the board members elect a vice-chairman annually during its February meeting and have chosen Combo for the position every year since 1999. He is an attorney in private practice and is former chief counsel and deputy manager of the Department of Energys Idaho Operations Office.
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Councilman, clerk object to Philippi mayor casting voteFebruary 5, 2014PHILIPPI — Philippi Mayor Jerry Mouser attempted to cast a vote at Tuesday's Philippi City Council meeting, but was not able to after one council member objected and the city clerk refused to help...... corruption1aMansfield upset that Smokey Ray isn't paying his city bills? or happy he is Gambling away his money at the local mob's hot dog shop? 0 Agrees | 0 Disagrees | Report Abuse » Mansfieldmama57The City Clerk should be just that. Keep quiet and take the minutes of the meeting. That's what you get paid to do. 1 Agrees | 1 Disagrees | Report Abuse » Mansfieldmama57Then Mouser said he was going to cast a vote as well, citing zstate code that he said gave him the right to vote on any issue before Council. 1 Agrees | 1 Disagrees | Report Abuse » bluemamaHow can you be mayor and not know City Code? The mayor should know all of the city ordinances by heart. The previous mayor did. 1 Agrees | 1 Disagrees | Report Abuse » TruthSeekerAnd for Nellie: When the government's boot is on your throat, whether it is a left boot or a right boot is of no consequence. – Gary Lloyd 0 Agrees | 0 Disagrees | Report Abuse » TruthSeekerGiving money and power to government is like giving whiskey and car keys to teenage boys. – P.J. O'Rourke I think this sums it up alright! 1 Agrees | 0 Disagrees | Report Abuse » Mansfieldmama57And here we go again. Our public city officials have nothing better to do than to argue like a bunch of high schoolers. Step down Mouser and Larry. You two are nothing but self- serving morons. 2 Agrees | 1 Disagrees | Report Abuse » Showing 7 of 7 comments
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Dendrobate action
This is a discussion on Dendrobate action within the Dendrobatids: Poison Arrow/Dart Frogs forums, part of the Anura: Frogs & Toads category; Like the silverstoni threads - let's keep the Dendrobate action going! Prize for the first person who can identify my ...
Dendrobatids: Poison Arrow/Dart Frogs The place to discuss Dendrobatids. |
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22nd August 2004 | #6 (permalink) |
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D. imator isnt as red, and always has the black Spots D. i. intermedius is more red, and may lack the red spots. Those look like D. i. intermedius Very nice whatever they are. did you breed them yourself? AJfr0ggy (Message edited by ajfr0ggy on August 22, 2004) |
23rd August 2004 | #7 (permalink) |
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After spending a week researching the taxonomy of this group, I'm convinced they are D. imitator (see http://www.ncbi.nlm.nih.gov/entrez/q..._uids=14555763). No, I didn't breed them myself, but I hope to in future! |
7th October 2005 | #15 (permalink) |
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D. imitator intermedius will probably not have the name last long. There is such diversity in the species, very few of it covered by subspeciating D. i. intermedius. They are actually pretty much a mid elevation D. imitator. I'll have more details in a few months after a few trips to Peru. j |
8th October 2005 | #17 (permalink) |
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Back when I kept a lot of that group I would often just soak down the tank. My D. imitator colonies would produce best when the tank's bottom was wet mud, they even hid almost a dozen tadpoles in the mud that I didn't catch the eggs in time. I also had regularly found clutches of 4 with them. Try lots of overlapping new leaves from things like Japanese evergreen (more Philodendron looking of a plant) and the like. They really seem to like super smooth places. I also used fish flake containers flipped over with a hole in them (like a small coconut hut) placed at different elevations. They like to lay in darker humid spots, so make them if you don't have enough already. j |
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I just had room temps with a shop light on top. The tank was a 50 gallon lizard lounge that I did most breeding in, and I had almost all vents covered. Some excess babies I put in a 90 gallon and had them grow and breed as well-- I just didn't take care of their tadpoles, they had to do all the work. I can help you further later if you need more advice, but that should be enough to get them going. I also had a higher sex ration of males to females, but this was accidental. I started with 4 and after a few years I tore the tank down for cleaning and pulled out 25 despite collecting eggs several times a week for most of the time. If you have any more questions, just ask. I may have to trade you for Caudate knowledge. j |
9th October 2005 | #20 (permalink) |
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lol, cool man. i think my frogs are still a little young for them to know what the heck theyre doin. theyre at most a year old. well, everything u said there, i am going already. the temps temd to climb to the 80's during the day. i suspect with the oncomming of winter, ill be able to balance the high around 72 or so. i feel that is when im going to get breeding action. anytime u want to swap knowledge, lemme know. im mostly into ensatina and eurasian newts. do u have any instant messanger programs? it would be much easier to chat there. well, take care justin -josh |
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Jolie Euro shams
A few decorative pillows can be an instant room enhancer if you're looking for a quick way to inject colour into your otherwise boring bedroom. Arrange a few of these brightly coloured shams with some bold solids to complement the orange, teal and green in the quilted pattern. $49, Pottery Barn.
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How to Slackline: Jump Line To Line
Jumping line-to-line is an advanced slackline skill requiring great balance. This skill has several forms, one of which involves jumping forward on the line and landing a few feet from where you started. If you've progressed in your slacklining ability and need a challenge to take you to the next level, try catching some air off the line and landing on it again. Get ready to feel exhilarated, the first time you hit this trick.
1Adjust your slackline so that it is tight enough to absorb the landing without touching the ground.Ad
2Start near one end of the slackline with both feet on the line, with your shoulders perpendicular to the line.
3Prepare for the jump by shifting your awareness to the precise location of your center of gravity.
4As you balance on the line, wait for your center of gravity to be directly over the line.
5This is your launch moment.
6Bend your knees and weight load the line--similar to jumping on a trampoline.
7As your weight rises, push forward off the line and catch some air.
8If your launch was centered over the line, your center should be coming down on the line.
9At this (sometimes scary) moment you have to decide whether to commit to landing on the line or not. If you don't decide quickly, you'll probably land somewhere in between and get thrown from the line or worse.
10Turn your feet sideways to line to make landing easier.
11Catch your balance and smile at the spectators.AdAd
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Yeah seems like analyzing the bettors is just as big a part of analyzing the teams sometimes. Which is (one of several reasons) why people saying stuff like "OSU would be underdogs against 7 SEC teams" was so stupid.
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I could see how someone could hear just the first sentence and feel insulted by it though.
This is totally hilarious, because Michigan.
Not sure Neal realizes how hard it is to get into Michigan is though. On average, this coach was right. Average UM football player had an SAT score of 997 (1600 scale). http://www.usnews.com/education/blogs/paper-trail/2008/12/30/athletes-show-huge-gaps-in-sat-scores - That article is kinda old I guess but it can't be that far off. In UM's most recent freshman class, per CollegeBoard, only 2% of students got below 500 in reading, and only 1% in math. Plus the median 50% had scores of 620-720 in reading, and 660-760 in math, so the median student got 1280-1480.
Even if it's true though, you'd think an important part of recruiting would be knowing the kid and the family well enough to realize that saying something like that would set them off.
It's probably more trouble than it's worth, but I'd be interested to see similar numbers for other top 10 offenses and defenses.
Amazing. I don't even care that that's not the side of the sign you see going that way. I kinda want to make a coffee mug out of this. Or a mousepad, or whatever else they do that kind of stuff to. Bravo.
According to the Cincinnati.com link:
Cincinnati police also determined McClain and Payne had outstanding capiases for failing to either appear in court or pay $130 fines after UC police cited them Feb. 8 with misdemeanor drug (marijuana) possession.
Their court date was probably a few weeks after the citation, but that's still over 6 months without going to court or paying the fine. You'd think someone from UC should have followed up on that.
The revenue directly from going to bowl games is an obvious effect. But all I could find about revenue from the 2011 season is here. It says there was a 5% loss, but I'm not sure what all that includes. 5% is noticeable, but that's still probably in the upper echelon of college football programs.
If Michael Jordan makes a Seattle - exclusive shoe I don't think anyone says no.
the Queen City often forgets they're part of THE BUCKEYE STATE
This is so true. It's even worse when people in Cincinnati root for Kentucky because "it's right there." Umm, Ohio is right here...
That article is terrific. Thanks for sharing.
To me, trash talk is on the field/court/whatever playing surface. It gets inside your opponent's head, rattles them, makes you feel confident, whatever. That's fine. It's usually funny. I don't see how yelling at a reporter and camera is trash talking. An expression of emotion, sure. But I don't think he was emotional about the game. He didn't seem happy, he seemed pissed off. He admitted it in his SI article that he was upset about something, but people are still trying to say stuff like "Oh, he's so smart he uses trash talk to manipulate the opponent, he's just creating a character."
Call it what it is, an emotional outburst about something other than the game. Applaud that, treat it with disdain, whatever.
That might be what the hype was from, but its not what it should have been. Dude is a freak. He had 8 sacks and 12 tfl as a freshman, followed it up with 13 and 23.5. Reportedly runs a 4.5 40. He's for real.
Won't happen.
The Big House has turf, and the Grass Eater needs his mid-game snacks.
The bigger point is: how does any of this make the jump safer?


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We cannot get the stink of "Honey Boo Boo" off of our shoes, like dog shit that is pure tar. Awful stuff. More fodder for the ladies of The Talk as the Custody Battle of the century begins: Which felonious parent will claim little Boo Boo?
Plus, 'The McCarthys' Cast Visits & Host Sheryl Underwood's Birthday Surprise – THE TALK (10/28)
Honey Boo Boo Custody Battle Brewing?
Honey Boo Boo's father Sugar Bear reportedly took her to a police station to keep her from Mama June and her alleged boyfriend who is a convicted child molester. The ladies and guest co-host Kevin Frazier of "Entertainment Tonight" weigh in.
'The McCarthys' Cast Discuss Series Premiere
The stars of the new CBS comedy, "The McCarthys" including Tyler Ritter, Laurie Metcalf, Joey McIntyre, Jack McGee, Kelen Coleman and Jimmy Dunn discuss this Thursday's series premiere.
'The McCarthys' Star Joey McIntyre Demos Pre-Show Dance
Singer turned actor Joey McIntyre of CBS's "The McCarthys" shows off his pre-show dance moves made famous while performing with "New Kids on the Block."
Sheryl Underwood's Special Birthday Surprise
The ladies celebrate host Sheryl Underwood's birthday and special guest, El DeBarge surprises her with a serenade.


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What is status of D Brown
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Re: What is status of D Brown
Originally Posted by
House of Pain
I heard D. Brown on the radio this morning talking about how much pain he was in during the game. He indicated that his ANKLE was in a great deal of pain and but for the tape job the trainers did, he probably wouldn't have been able to out there.
Is anyone else starting to get worried about this? We can lose a lot of players and still potentially make a deep playoff, but Brown is irreplaceable.
It actually makes sense. I laid out how he may have come back into the game after an ankle. If Kubiak got it right, and he did have a turf toe...........he suffered both a turf toe and an ankle injury aggravation, unfortunately most probably high ankle, during the game.
Originally Posted by
Ankle injuries can at times not immediately demonstrate significant performance deficiency, especially if immediately wrapped. However, within 48 hours when swelling has been given a time to develop, the physical effects can change and present dramatically. Let me remind you that Brown was already listed with an "ankle" on the injury report, making it somewhat more concerning. At this point, an MRI will probably be performed tomorrow to make a definitive decision on the presence or absence of additional damage. We should know more after that......maybe.
Originally Posted by
The play that the injury occurred on didn't seem awful. He was rolled up by the LG but it didn't seem to really catch his leg caught in the turf.
Originally Posted by
It doesn't take much to turn a simple ankle sprain to high ankle sprain...........just a little twist while your cleats catch in the turf. Let's hope that is not the case.
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Realtek AC'97 drivers 32/64 bit A4.06
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Lomond at the Stationery exhibition in Istanbul!
Lomond company attend Stationery exhibition in Istanbul with Turkish partner Aksel. Enjoy the photos from exhibition!
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Copyright (c) 2011 Lomond Trading Ltd. All rights reserved
contact us | set as homepage | add to favorites HTML4.01 CSS en.sk main |


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The storm had winds as high as 73 mph when it came ashore in mainland China about 4 p.m. local time, with waves more than 30 feet high, China's official Xinhua news agency reported.
Soulik was moving northwest at 12-15 mph and was expected to enter Jiangzu Province after midnight, meteorologists at the Fujian weather station said.
More than 300,000 people had fled Fujian Province ahead of Soulik, the seventh typhoon to hit the Chinese mainland this year.
In Taiwan, more than 8,500 people were evacuated from mountainous regions and other dangerous areas as the storm hit.
Schools and offices in Taipei were closed Friday afternoon and more than 50,000 soldiers had been put on standby.


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Quick View Sweet Thoughts Locked Diary by Mudpuppy In stock online $9.95 With a purple background, silver foil stamped highlights, and colorful words and images, this Sweet Thoughts locked diary from Mudpuppy is a real eyecatcher! - Color-coordinated yellow padlock with 2 keys - Phthalate free and printed with nontoxic inks - 192 lined pages with decorative icons on… See Details $9.95 was $9.95
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Jun 10, 2013 6:56 AM
12U Team looking for Mid-week games
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Central KY Kaos 12U is looking for some mid-week games. We will come to you or you can come to us. Willing to split the cost of umpires. If interested please call Brian at 502 803 6143.
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Shahs of Sunset Star Lilly Ghalichi Flaunts Massive Engagement Ring and New Rolls Royce (PHOTOS)
Lilly Ghalichi Flaunts Massive Engagement Ring and New Rolls Royce
It's been quite the last few months for Shahs of Sunset star Lilly Ghalichi. Not only did the 31-year-old beauty get engaged to Dhar Mann back in early April (after only two months of dating, no less!), but the Persian Princess got the birthday surprise of her life just a few weeks later.
After earning millions from his medical marijuana company WeGrow, Dhar wasn't content to gift his lady with anything as simple as flowers and cake. Instead, Dhar surprised Lilly with a $500,000 white Rolls Royce while leaving her birthday dinner at Mastro's Steakhouse. (Um, does he have a single brother?)
Of course, Lilly couldn't wait to show off her new wheels, which she definitely did the following week. On Tuesday, May 6, the brunette beauty was photographed posing with her Rolls and flaunting her ring while heading to a nail salon in Beverly Hills.
Lilly's engagement ring certainly can't be missed — in fact, we're willing to bet it can almost be seen from space! The stunning sparkler boasts a 15-carat diamond and put Dhar back a whopping $1.2 million!
Click through to see photos of Lilly flaunting her ring and ride in Beverly Hills!


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Client Profile: Summary, 2008
A special interest's lobbying activity may go up or down over time, depending on how much attention the federal government is giving their issues. Particularly active clients often retain multiple lobbying firms, each with a team of lobbyists, to press their case for them.
Total Lobbying Expenditures: $110,000
Subtotal for Parent Oregon Water Resources Congress: $110,000
Industry | Total |
Misc Energy | $110,000 |
Firms Hired | Total Reported by Filer | Reported Contract Expenses (included in Total Reported by Filer) |
Will & Carlson | - | $110,000 |
$110,000 |
Feel free to distribute or cite this material, but please credit the Center for Responsive Politics. For permission to reprint for commercial uses, such as textbooks, contact the Center: firstname.lastname@example.com


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Issue 50 Money Summer 2013Artist Project / Gold DustPeter SimenskyCabinet's new issue comes sprinkled with gold dust, courtesy of artist Peter Simensky. Visiting Cabinet HQ the day the issue arrived, Simensky scattered 7.9 grams of 24-karat gold over the magazines, an amount equal in value to the cost of printing the two pages allotted to his project. Peter Simensky is a New York–based artist. Simensky's work has been featured in solo exhibitions at the Museum of Contemporary Art San Diego; Project Row Houses, Houston; and Museum 52 and the Swiss Institute, New York. He was recently an artist-in-residence at the MacDowell Colony in Peterborough, New Hampshire. Cabinet is published by Immaterial Incorporated, a non-profit organization supported by the Lambent Foundation, the Orphiflamme Foundation, the New York City Department of Cultural Affairs, the National Endowment for the Arts, the New York State Council on the Arts, the Danielson Foundation, the Katchadourian Family Foundation, the Edward C. Wilson and Hesu Coue Wilson Family Fund, and many individuals. All our events are free, the entire content of our many sold-out issues are on our site for free, and we offer our magazine and books at prices that are considerably below cost. Please consider supporting our work by making a tax-deductible donation by visiting here.
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Texans Talk Football talk only please. Keep it to the game, the players, the coaches and management. |
Thread Tools | Display Modes |
09-24-2006 | #1 |
All Pro
Texans - Redskins impressions
- We got absolutely blown out for the 3rd straight game...... by an 0-2 team..
- David Carr came back to earth, he had time to throw and he looked slightly above average. He's never going to be Carson Palmer or Peyton Manning, but I still think he's a good QB and we can win with him. Yea he fumbled, so what. Ben Roethlisberger and the conservative Steelers turned the ball over 5 times today, it's not unheard of for a QB to lose a fumble. We simply have bigger fish to fry at this point, IMO. - AJ had a good game, despite a drop or two. Moulds is solid when we get the ball out to him. - Dayne should be a 3rd stringer, but atleast he fights for extra yards. - Our OL pass protected fairly well, too bad they can't run block. DHog looked like he was listening to a different snap count than everyone else. - Our DL sucks. They can't rush the passer, they can't stop the run. Mario looks like a marginal starter. TJ and Payne got into the backfield but couldn't do much from there. Babin and Kalu aren't providing much of a spark. - Dunta could be a really good #2 in the right situation. He's a gamer, but he's not that great when you put him on an island. Our safeties are not NFL starting quality. When they make it past our linebackers, it's gonna be a 25+ yard gain and/or TD, our safeties aren't functioning well as safety valves. Lewis Sanders isn't playing well, but for a street FA as a starting CB I guess he's ok. - We've established now that teams can beat us by: 1. Running the ball. (Washington) 2. Passing the ball. (Indy) 3. A combination of the two. (Philly). In the past I got frustrated because we'd stay close and then our offense would blow it at the end of the game. Now our defense blows it in the first half, so I don't even get to watch a close game. The suspense dissipates at the end of the 1st quarter. - We're gonna have a top 5 pick this next draft, but don't get your hopes up drooling over the studs coming out of college this year, aside of AJ we don't seem to have a great track record in the top 5. |
09-24-2006 | #2 |
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Nice summery. Here is mine:
We suck ~Proteus |
09-24-2006 | #3 |
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I think you are exaggerating this loss a bit.
We were a penalty and TD away from OT. Granted, we would have had to convert 2 2 pointers as well, but that doesn't change the fact that we were there. We got beat but it wasn't a blow out by any stretch of the imagination. Regarding Dunta, I read a comment on here about moving Dunta to safety that I am inclined to agree with. If we could pick up a big name CB in FA this off season and draft one with a high pick we could move Dunta to safety where he could utilize his strengths. |
09-24-2006 | #4 |
All Pro
09-24-2006 | #5 |
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- We're gonna have a top 5 pick this next draft, but don't get your hopes up drooling over the studs coming out of college this year, aside of AJ we don't seem to have a great track record in the top 5.
Reply With Quote Maybe our laundry list of needs on defense will convince our FO that we need to trade down, and we will get a couple picks in the 12-20 range |
09-24-2006 | #6 |
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Well put by all of you :brickwall
09-24-2006 | #7 | |
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09-24-2006 | #8 | |
All Pro
Grid, I could totally go for us trading down next draft to fill some of our many, many holes. And I'm obviously being a little rough on the current staff, as Rick Smith has not had a chance to try his hand at a Texans draft yet. Maybe we'll turn it around with some new people calling the shots. Last edited by blockhead83; 09-24-2006 at 06:14 PM. |
09-24-2006 | #9 | |
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09-24-2006 | #10 |
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My opinion is that we build around one side of the ball. Considering we have moulds and andre johnson on offense, I would start building on that side of the ball.
Adrian Peterson would help this offense tremendously as well. And he might be the best player on our defense by keeping them off the field with longer sustained drives. You can look through the rest of the draft to pick up more defensive players ala early 2nd round you can still find playmakers. This team is missing a playmaker. While andre johnson is a great player, he wont take over games. I think having a player of peterson's level for many years will help raise the opinions of other team's/free agents to come play in our organization. Like the effect vick has had with the falcons. I think building an exciting offense to hang with the colts, and a consistent improvement on defense would be the best route. Last edited by ComstockLode; 09-24-2006 at 06:37 PM. |
09-24-2006 | #11 |
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i say lets see if we can get any momentum from the miami game and then see what happens after the bye. this thing may yet come together yet. there has to be a low point to every season, i think this game may have been it.
09-24-2006 | #12 |
The Right Track
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We're really bad right now and there's really no denying it. I still believe that the Texans will pull it together in the second half of the season and that will be the "springboard" for whatever progress we make this season.
Our defense just mystifies me. I expected us to have offensive growing pains over the first half of the season and I expected our defense to not be dominant. What I didn't expect was for our defense to not even be visible. On paper this isn't that bad a group. We're lower half without a doubt but we don't look this bad on paper. In reality though we're monumentally bad. That to me was surprising. Now I'm wondering what wer'e going to do about it. To me the line looks slow and weak. They're getting defeated easily out there. The linebackers look hesitant to me and the defensive backs look like they're just trying to keep people from getting behind them. It's like they know if they don't play way off their man then they'll get beat and give up the big play. Dunta Robinson in particular looks very frustrated to me.
Fitz makes bad decisions. That's not going to change. |
09-24-2006 | #13 |
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Location: HOUSTON
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Is it just me, but my wife and daughters were all at the game, watching in sadness again today .....But does it just seem the Texans give up, and stop playing.....it's like someone let the air out of them, they just seem to give up............
Antwan Peek is my daughter's favorite player ! WE WILL MISS YOU ANTWAN GOOD LUCK IN CLEVELAND ! |
09-24-2006 | #14 | |
Hall of Fame
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Your local CruiseOne Vacation specialist. www.firstclasscruising.biz Visit me on Facebook. |
09-24-2006 | #15 |
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Another thing, Mario would have had his first sack (or possibly half a sack) on that play when both tackles were called for holding.
09-24-2006 | #16 | |
All Pro
Along what Herv said, based on my assumptions heading into the season and what I saw in pre-season, I'm really surprised in alot of ways by what I've seen on the field. I thought our D would get burned for the big play, but I thought they'd get after the quarterback and send more blitzes than they are. I also thought our passing game was going to take a while to come along while the run game would be picking up the slack. It's the other way around. Our run game is sputtering while our passing game looks light years ahead of what it did in the past. All the people who complained in the Capers era about not atleast putting up some big plays in our losses should be happy now. Carr is hitting some big plays now, but our D is playing so poorly that it doesn't matter. How exciting. |
09-24-2006 | #17 | |
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I held the same sentiments about the defense. I was touting our "top 5 DL" all preseason. |
09-24-2006 | #18 |
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Actually thinking the Texans were in this game is an absolute joke. The Redskins owned them in every aspect of this game. They got to 31-15 because the Skins lightened up a bit on their intensity. If they wanted to, they could have won this game by 30 points.
And, thinking now, "Hey, we need a playmaker and a running back would really help us" and "let's build up one side of the team" means we really should have drafted Reggie Bush. Mario looked terrible again today. He looked lost, played without intensity, and hasn't shown anything at all that would show him deserving of being a first round pick, much less a No. 1 overall pick. But hey - at least the Saints got Bush (they needed that shot in the arm there), and maybe the Texans get Adrian Peterson. Kind of funny, going with an OU guy a year after passing on UT's legend (Vince Young). |
09-24-2006 | #19 |
Utopian Dreamer
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Here's my thoughts in the Fanblog, with stat badness: Link
The short version: Both Texans lines look overmatched. The offense is ungood, but it is remarkable that Carr has been able to throw at all when the run blocking is non-good. (Usually that is death). He seemed to have more time in the pocket today. This offense needs the run to work, but it is hard to run much when your defense can't make a stop. Still too many stupid mistakes. The Texans defense might be irretrievably bad this year. Personnel-wise, there are few guys on the defense that you would really want on your team as a starter. We are having to depend on rookies for key positions without too many good experienced guys helping them. We have young guys, and old guys, but few really good peak of their career middle guys. All that being said, there is no excuse for giving up that many yards per game for three games in a row. That is a coaching/scheme issue. And Richard Smith does not have the sort of long standing track record as a defensive mind that makes you feel confident that he is going to turn this puppy around. (Though I am sure we will start to hear the 2005 Dolphins song and dance soon enough--not really comparable, I don't think).
More? Please check out Ultimate Texans Chronicle Blog & Steph Stradley Blog & Twitter @StephStradley |
09-24-2006 | #20 | |
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Age: 44
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Great points. We are three games into the season, and I am already tired of Richard Smith's act. The aggressive, blitzing defense is just not there, and according to reports, he ducked out again after the game and chose not to face the music. Just like his defense, pretty pathetic! |
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Pop-up animation tells story of a water droplet
Revolution is an animated short that showcases the life-cycle of a single drop of water. Watch this incredible pop-up inspired work.
This brilliantly creative short animation from Chris Turner, Helen Friel and Jess Deacon brings the pop-up book to animated life. The video depicts the revolutionary nature of the life cycle of a droplet of water and its cyclical journey.
From the original idea, through the creative development and process, Chris, Jess and Helen's individual skill sets enabled the project to spring to life. Chris took care of the photography, whilst Helen worked as the paper engineer and Jess on the animation.
The short was nearly a year in the making and was shot in one continuous take. The post production was done by Neil Cunningham, with Joe Shetcliffe taking care of the cute sound and music. Pop-ups and animation? We couldn't love it more!
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80's Table Cover
Eighties Table Cover
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Cover your tables with some good old fashion 8-bit fun!
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Great job! Love getting out there
- Miles:
- 277 total / 0 in 2015
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Run 10k without walking. Want to run a 10K in March
Ange ran: Have never run with f...
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- 3 miles
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Evening run with my girlfriend
11:30 pace
Have never run with friends before. Most of the ladies were walking but my BF and I ran. It was different talking while running and then I ate too late so was feeling... well - ya know! Overall it was a good time!


text:
Press release from PR Newswire
The Home Depot Names Mark Vadon to Its Board of Directors
Friday, September 21, 2012
The Home Depot Names Mark Vadon to Its Board of Directors08:33 EDT Friday, September 21, 2012ATLANTA, Sept. 21, 2012 /PRNewswire/ -- The Home Depot®, the world's largest home improvement retailer, today announced the appointment of Mark Vadon, 42, to the Company's board of directors. Vadon will be a member of the Audit and Finance Committees. His appointment gives the Company 11 directors, 10 of whom are independent.(Logo: http://photos.prnewswire.com/prnh/20030502/HOMEDEPOTLOGO)In 1999, Vadon co-founded Blue Nile, Inc., the leading online retailer of diamonds and fine jewelry, and has served as the chairman of its board of directors since its inception. During Blue Nile's history, Vadon has also served as its executive chairman (from 2008 to 2011), chief executive officer (from 1999 to 2008) and president (from 1999 to 2007). Prior to co-founding Blue Nile, Vadon was a consultant for Bain & Company, a management consulting firm, which he joined in 1992. In 2009, Vadon co-founded zulily, Inc., a daily deals site for moms, babies and kids. He serves as the chairman of its board of directors. "Mark's expertise in developing and implementing successful online strategies will be a benefit to our company and an asset to our board," said Frank Blake, chairman & CEO. "I am pleased to welcome him to the board and look forward to his contributions." The Home Depot is the world's largest home improvement specialty retailer, with 2,250 retail stores in all 50 states, the District of Columbia, Puerto Rico, U.S. Virgin Islands, Guam, 10 Canadian provinces and Mexico. In fiscal 2011, The Home Depot had sales of $70.4 billion and earnings of $3.9 billion. The Company employs more than 300,000 associates. The Home Depot's stock is traded on the New York Stock Exchange (NYSE: HD) and is included in the Dow Jones industrial average and Standard & Poor's 500 index. SOURCE The Home DepotFor further information: Financial Community: Diane Dayhoff, Vice President, Investor Relations, +1-770-384-2666, firstname.lastname@example.com; News Media: Paula Drake, Director, Corporate Communications, +1-770-384-3439, firstname.lastname@example.com


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Montana Canvas Kenai 10' x 20' Tent with Sewn-In Floor, 2 Windows and Screen Door 10 oz Canvas
Product #: 190793
Montana Canvas #:
This product ships from Montana Canvas, with no shipping charge, and usually arrives within 3 to 4 weeks.
- Information
Similar to tents used in the 19th century, this classically styled tent is as functional today as it was in the past. It features four windows, a stove jack with flap and 3' walls. There are two doors and a floor is sewn into the tent which adds additional protection from the elements. Frame is not included.
Technical Information
Windows are 18" x 24" each
Stove jack with flap
Walls are 3' in height
Total weight approximately 51 lbs
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text:
Mr. Sibby's, Inc. filed as a Domestic for Profit Corporation in the State of Florida and is no longer active. This corporate entity was filed approximately nineteen years ago on Friday, March 15, 1996 as recorded in documents filed with Florida Department of State.
Thomas Hill served as the Director and has interests in other corporate entities including Thomas W. Hill & Company, LLC, Sgt Corporation and four more corporations. Thomas's past corporate affiliations include Real One Investments, Inc., Paradise Point Development Corporation of Lee Co and twenty-six others.
Thomas W. Hill is also the registered agent for the company. Also known as a statutory or resident agent, the registered agent is responsible for receiving legal notifications regarding court summons, lawsuits, and other legal actions involving the corporate entity.
Key roles for Mr. Sibby's, Inc. |
Thomas W. Hill
Inactive |
Rainer Siebrecht
Inactive |
Christine Siebrecht
Inactive |
Filing Type: | Domestic for Profit Corporation |
Status: | Inactive |
State: | Florida |
State ID: | P96000024625 |
Date Filed: | Friday, March 15, 1996 |
Registered Agent | Thomas W. Hill |
Comprehensive Insight Plus Report |
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The D&B Comprehensive Insight Plus Report for Mr. Sibby's, Inc. combines D&B's proprietary statistical scoring with business, payment and financial information all in one report. | |
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The D&B U.S. Company Profile contains basic information such as address and telephone number, executive names and titles, line of business and SIC codes, D-U-N-S Numbers, organization status, and year and location of incorporation for Mr. Sibby's, Inc.. |


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Recently purchased a 2011 dbl cab (sport) l/b, the JBL system was working great at first. All the door speakers still in good working order...it's the sub that is creating the problem...VIBRATION! I have tried pullin the entire system out, and re-installing but still have the same problem. Have used gaskets to get rid of it but no results.
Anyone have any solutions to this problem?


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Accoring to the US Census Bureau, Kornhaus ranked #148,244 in frequency out of 151,671 surnames for which statistics were released from the 2000 Census. 102 people, or approximately 1 in every 2,644,726 individuals in the US had this surname in 2000.
Source: "Genealogy Data: Frequently Occurring Surnames from Census 2000", US Census Bureau.
Histopolis currently has 0 grave(s) with the surname Kornhaus.
The surname Kornhaus has a Soundex code of K652. The following 348 surname(s) may sound similar to Kornhaus since they share the same Soundex code.


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Researchers have developed a more powerful method of electron beam melting to build metal blades for jet engines.
Read More »Tag Archives: GE Aviation
GE Aviation to Build High Volume Additive Manufacturing Factory
GE Aviation has announced it will be building a $50 million high volume additive manufacturing factory in Auburn, AL.
Read More »NAMII Announces Second Project Call Winners
Certainly not everything has gone the way President Obama might have wished during his presidency, but one move that seems to be working just fine is the foundation of the National Additive Manufacturing Innovation Institute (NAMII), which was recently branded ...
Read More »A Look Back at Additive Manufacturing in 2013
This year was an interesting one for additive manufacturing (AM), with plenty of big moves inside the industry and hints of upcoming changes to the landscape from without. Medical uses for 3D printing really started to gather steam, with prosthetics ...
Read More »GE Launches CAD Challenge
Most of the hype around "democratization" as applied to additive manufacturing (AM) is based on the idea that people can design and manufacture unique products that wouldn't otherwise exist. Of course, designing your own unique product requires you understand the ...
Read More »


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Portland Yiddish Hour on 12/25/11
Portland Jewish Hour
Air date:
Sun, 12/25/2011 - 10:00am - 11:00am
Short Description:
Portland Yiddish Hour About the only place on the radio dial where you won't hear any Christmas Music. At least for an hour.
Join host Ed Kraus for a mix of Klezmer, Chanukah music, and a story by Reb Aryeh.


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5:45 am
Tue April 17, 2012
Housing Starts Drop, But Building Permits Are Up
By Mark Memmott
There was a 5.8 percent drop in housing starts from February to March, the Census Bureau and Department of Housing and Urban Development just reported.
Bloomberg News says the decline was unexpected and left starts at a five-month low.
Still, the number of starts was up 10.3 percent from March 2011.
Looking ahead, the data are more positive. The number of building permits issued rose 4.5 percent from February to March and was up 30.1 percent from March 2011. Permits are at their highest level in the past 3 1/2 years, Reuters says.
Copyright 2012 National Public Radio. To see more, visit http://www.npr.org/.