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Chronocoulometry adsorption

According to experimental data,208,209 the SNIFTIR technique can be used to probe the electrical properties of the electrical double layer even in more concentrated solutions where cyclic voltammetry (cv), impedance, chronocoulometry, and other techniques are not applicable. Iwasita and Xia210 have used FTIR reflection-adsorption spectra to identify the potential at which the orientation of water molecules changes from hydrogen down to oxygen down. [Pg.41]

The third class of redox species are couples located near the conduction band of WSe2- The only outer-sphere example found, which is suitable for use in aqueous electrolytes, is Ru(NH3)e3+. Its reduction is characterized by an immediate onset upon accumulation in the semiconductor and a tafel slope of 130 mV/decade. The reduction mechanism appears to be direct reduction of the Ru(NH3)e3+ by electrons from the accumulation layer. The only member of the forth class of redox species is triiodide ion. It is characterized by adsorption onto the semiconductor surface as was demonstrated by the first application of chronocoulometry to a semiconductor electrode (another demonstration of the reproducibility and low background currents on... [Pg.444]

The adsorption of reactant in the system Cd(II) +1 M KBr/Cd(Hg) was investigated by using chronocoulometry [41]. The values of the reactant surface excess were calculated. The authors proposed the adsorption isotherm, which allows the adsorption of the reactant and ligand to... [Pg.771]

Hamelin [47] has shown that specific adsorption of OH ions increases in the following order Au(lll) < Au(lOO) < Au(311). Chen and Lipkowski [48] have applied chronocoulometry and subtractively normalized interfacial Fourier transform infrared spectroscopy to study adsorption of hydroxide ions on Au(lll) electrode. This process proceeded in three steps. Bonding of OH with gold atoms that is quite polar at negatively charged surface becomes less polar at positively... [Pg.847]

Subtractively normalized interfacial FTIR has been employed [242] to study the changes in the surface coordination of pyridine molecules on Au(lll). It has been deduced from the experiments that pyridine molecule is positioned upright at positive potentials and its plane rotates somewhat with respect to the electrode surface. In situ FTIR has also been used [243] to investigate adsorption of pyridine on Au(lll), Au(lOO), andAu(llO) electrodes. For the low-index electrodes, the behavior of band intensity located at 1309 cm and corresponding to the total adsorbed pyridine, agreed with the surface excess results obtained earlier from chronocoulometry. [Pg.868]

Sottomayor etal. [273] have investigated adsorption of n-hexanol on Au(lll) electrode from 0.2 M NaCl04 aqueous solution, applying chronocoulometry to measure dynamic capacitance and capacitive charge. They have found that in this case, adsorption may be described by the Frumkin isotherm and have determined the corresponding parameters. The obtained results were discussed and... [Pg.871]

Reconstruction of Au(lll) is observed in STM images as double rows separated from each other by 6.3 nm [335]. Some model calculations have been performed [362] to show that the energy difference of the reconstructed and unreconstructed Au(lll) is small. The effect of Triton X-100 on the reconstruction process of Au(lll) surface has been studied in chloride media [363] applying CV and double potential-step chronocoulometry. It has been found that adsorption of Triton X-100 stabilizes the reconstructed face of Au(lll). Hobara etal. [364] have used in situ STM to study reconstruction of Au(lll), following reductive desorption of 2-mercaptoethanesulfonic acid SAMs. [Pg.879]

Indicators and Dyes Abdel-Hamid [154] has studied adsorption of phe-nolphthalein at a HMDE in aqueous buffer solutions containing 10% v/v ethanol, applying cychc voltammetry and double potential-step chronocoulometry. At pH =... [Pg.980]

Duan etal. [187] have studied adsorptive and electrochemical behavior of estradiol valerate at a static mercury electrode using cyclic voltammetry and chronocoulometry. A sensitive and... [Pg.983]

In contrast to the chronocoulometric technique, the information obtained from the impedance technique concerns the derivatives with respect to potential of To, In /30 and d(ln (30)/dE. It is therefore needed to postulate an explicit isotherm in order to fit experimental data to the theoretical equations. However, the results, e.g. for (dT0/dE, can be integrated to give T0 as a function of potential within the faradaic region. As chronocoulometry is, by definition, applicable to potentials outside the faradaic region, the two methods may be considered as complementary tools to study adsorption phenomena that are hard to detect in the classical way, i.e. from double-layer data (e.g. the capacity Cd) that are influenced by the presence of electro-inactive absorbates. [Pg.316]

Adsorption phenomena have been studied by means of virtually every electrochemical technique, including recently developed spectroelectrochemical methods. Electrocapillary methods and measurements of double-layer capacitance have played a central role in the understanding of adsorption. AC studies have also been very useful and are very sensitive to adsorption effects. More recently, chronocoulometry (Chap. 3, Sec. II.C) has been applied effectively to the measurement of quantities of adsorbed electroactive species. The interested reader is referred to the sections that deal with these techniques for more detailed information. [Pg.49]

Figure 3.6 Effect of adsorption of electroactive species on chronocoulometry. (A) Charge-time curves for individual components contributing to total charge (Qtotai) as n Equation 3.8b. (B) Plots of charge versus t1/2 for Qtotal and Qdl. Figure 3.6 Effect of adsorption of electroactive species on chronocoulometry. (A) Charge-time curves for individual components contributing to total charge (Qtotai) as n Equation 3.8b. (B) Plots of charge versus t1/2 for Qtotal and Qdl.
To a large extent, the discovery and application of adsorption phenomena for the modification of electrode surfaces has been an empirical process with few highly systematic or fundamental studies being employed until recent years. For example, successful efforts to quantitate the adsorption phenomena at electrodes have recently been published [1-3]. These efforts utilized both double potential step chronocoulometry and thin-layer spectroelectrochemistry to characterize the deposition of the product of an electrochemical reaction. For redox systems in which there is product deposition, the mathematical treatment described permits the calculation of various thermodynamic and transport properties. Of more recent origin is the approach whereby modifiers are selected on the basis of known and desired properties and deliberately immobilized on an electrode surface to convert the properties of the surface from those of the electrode material to those of the immobilized substance. [Pg.246]

The chronocoulometry and chronoamperometry methods are most useful for the study of adsorption phenomena associated with electroactive species. Although less popular than cyclic voltammetry for the study of chemical reactions that are coupled with electrode reactions, these chrono- methods have merit for some situations. In all cases each step (diffusion, electron transfer, and chemical reactions) must be considered. For the simplification of the data analysis, conditions are chosen such that the electron-transfer process is controlled by the diffusion of an electroactive species. However, to obtain the kinetic parameters of chemical reactions, a reasonable mechanism must be available (often ascertained from cyclic voltammetry). A series of recent monographs provides details of useful applications for these methods.13,37,57... [Pg.86]

The double potential step is very powerful in identifying adsorption phenomena by chronocoulometry. From (10.34),... [Pg.207]

Double-step chronocoulometry is a powerful tool in identifying adsorption phenomena, in obtaining information on the kinetics of coupled homogeneous reactions and for the determination of the capacitive contribution. The double potential step is executed in such a way that after the first step from E to E2, a next step is applied, i.e., the reversal of the potential to its initial value Ei from 2 (see Fig. 3). [Pg.99]

Chronocoulometry — Figure 4. Chronocoulometric plots for double step experiments. Lines 1 and 2 correspond to the case when no adsorption of the reactant or product occurs. Lines 3 and 4 depict the linear responses when the reactant is adsorbed... [Pg.99]

Majda and co-workers provided an elegant demonstration of through-bond and chain-chain hopping processes as parallel mechanisms for electron transfer across SAMs [46, 133]. In n-alkanethiol monolayers formed on hanging drop mercury electrodes, the adsorbate coverage T is measured by chronocoulometry of the mercuric thiolate formed upon adsorption. For the as-adsorbed films, geometric con-... [Pg.2943]

Inner-sphere reaction pathways may be diagnosed when the precursor state is sufficiently stable to allow the adsorbed reactant to be detected by analytical means. Convenient techniques for this purpose include chronocoulometry - and thin-layer voltammetry". Aside from detecting the presence of precursor (or successor) intermediates, these methods can enable the adsorption thermodynamics (and hence the work terms Wp and w ) in Eq. (n) in 12.3.7.2 to be determined. The extent of adsorption is obtained within potential regions where the reactant (or product) is stable with respect to reduction or oxidation. The required values of w and w in the potential region of kinetic interest can then be determined by extrapolation, or sometimes directly by means of a thermodynamic analysis of potential-pulse data . [Pg.238]

The bromide-induced adsorption of thallium complex on pc-Ag electrode has been studied using CV and chronocoulometry [125]. [Pg.927]

Lobacz et al. [52] have described partial adsorption of Tl -cryptand (2,2,2) complex on mercury electrode. From voltocoulom-etry, cyclic voltammetry, and chronocoulometry, it has been deduced that electroreduction of this complex proceeds via two parallel pathways from the solution and from the adsorbed states, which are energetically close. Also, Damaskin and coworkers [53] have studied adsorption of the complexes of alkali metal cations with cryptand (2,2,2) using differential capacity measurements and a stationary drop electrode. It has been found that these complexes exhibit strong adsorption properties. Novotny etal. [54] have studied interfacial activity and adsorptive accumulation of U 2 -cupferron and UO2 + -chloranilic acid complexes on mercury electrodes at various potentials in 0.1 M acetate buffer of pH 4.6 and 0.1 M NaClO4, respectively. [Pg.969]

At solid polarizable electrodes, the charge density on the electrode can be measured directly using chronocoulometry [11]. This has been applied successfully to the study of molecular adsorption at single crystal gold electrodes. As discussed above, a reference potential E is chosen at which molecular adsorption is absent. The potential of the polarizable electrode is then stepped to a new value f ,- and the current transient which results is recorded. By integrating this transient, one obtains the change in charge density between the two potentials ... [Pg.523]

The intercept of Q vs. is therefore Q + hFAYq. A common application of chronocoulometry is to evaluate surface excesses of electroactive species hence it is of interest to separate these two interfacial components. However, doing so reliably usually requires other experiments, such as those described in the next section. An approximate value of nFATo can be had by comparing the intercept of the plot obtained for a solution containing O, with the instantaneous charge passed in the same experiment performed with supporting electrolyte only. The latter quantity is Qdi the background solution, and it may approximate Q for the complete system. Note, however, that these two capacitive components will not be identical if O is adsorbed, because adsorption influences the interfacial capacitance (see Chapter 13). [Pg.212]

Chronocoulometry can also be applied to the cases discussed in Section 14.3.2 where only adsorbed species are electroactive (57). In this situation the potential step causes only double-layer charging and the electrolysis of the adsorbed species. One can estimate Qdi by steps between a potential at the foot of the adsorption wave, and potentials, Ef, beyond the adsorption wave. If Q is not a function of E in the region of the wave, the following equation results (57) ... [Pg.605]


See other pages where Chronocoulometry adsorption is mentioned: [Pg.230]    [Pg.241]    [Pg.586]    [Pg.587]    [Pg.270]    [Pg.867]    [Pg.265]    [Pg.63]    [Pg.84]    [Pg.97]    [Pg.555]    [Pg.213]    [Pg.867]    [Pg.870]    [Pg.981]    [Pg.213]    [Pg.212]    [Pg.103]    [Pg.2757]   
See also in sourсe #XX -- [ Pg.57 ]




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Chronocoulometry

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