Surface inactivity

Tucceri R I and Posadas D 1990 The effect of surface charge on the surface conductance of silver in surface inactive electrolytes J. Electroanal. Chem. 283 159-66... 

If M and R are in the same solvent S containing only an inert, surface-inactive supporting electrolyte, AE equals the difference in the potentials of zero charge between the two metals ... 

The contact potential difference between Hg and water (actually a dilute aqueous solution of a surface-inactive electrolyte) has been measured42,43 to be -0.25 V. The negative sign means that the work function of Hg decreases upon contact with water. Since 4.50( 0.02) cV is the currently accepted5 value for 0 of Hg, the value of 0 for the uncharged metal (at the potential of zero charge) is 4.25 eV. 

For an electrochemical cell consisting of a metal at the potential of zero charge in a solution of surface-inactive electrolyte and a reference electrode (let us assume that any liquid junction potential can be neglected), the electrode potential is given by (cf. Eq. (20)]... 

Japaridze et al.m 323 have studied the interface between Hg and a number of vicinal and nonvicinal diols such as 1,2-, 1,3-, 2,3- and 1,4-butanediol (BD), ethanediol (ED), and 1,3-propanediol. KF and LiC104 were used as surface-inactive electrolytes. The potential of zero charge was measured by the capacitance method against an SCE in water without correction for the liquid junction potential at the solvent/H20 contact (such a potential drop is estimated to be in the range of 20 to 30 mV). The potential of the capacitance minimum was found to be independent of the electrolyte concentration while capacitance decreased with dilution. Therefore, Emin was taken to measure E . These values are reported in Table 4. 

The electrical double-layer structure at Ga/DMF, In(Ga)/DMF, and Tl(Ga)/DMF interfaces upon the addition of various amounts of NaC104 as a surface-inactive electrolyte has been investigated by differential capacitance, as well as by the streaming electrode method.358 The capacitance of all the systems was found to be independent of the ac frequency, v. The potential of the diffuse layer minimum was independent of... 

Cu crystallizes in the fee and its melting point is 1356 K. The experimental data for single-crystal Cu/H20 interfaces are also controversial. 567 570,572 57X The first studies with Cu(l 11), Cu(100), and Cu(l 10) in surface-inactive electrolyte solutions (NaF, Na2S04) show a capacitance minimum at E less negative than the positive limit of ideal polarizability of Cu electrodes (Table 11). depends on the method of surface... 

The impedance characteristics of pc-Pb have been obtained in aque-ous 220-221,599-607 an(j n0naqueous (glacial acetic acid, MeOH, EtOH, dimethyl formamide)10,74,608-612 surface-inactive electrolyte solutions. The first attempt to obtain the potential of zero charge of pc-Pb with a mechanically polished and remelted surface was made by Borissova et al.220,221 in 1948 and 1950. Pc-Pb anodically polished in H20 + NaF (0.001 < cNlF < 0.1 M) was studied by Rybalka and Leikis.599 The value of = -0.810 0.02 V(SCE) was found to be independent of c the... 

The electrical double layer at pc-Zn/fyO interfaces has been studied in many works,154 190 613-629 but the situation is somewhat ambiguous and complex. The polycrystalline Zn electrode was found to be ideally polarizable for sufficiently wide negative polarizations.622"627 With pc-Zn/H20, the value of Eg was found at -1.15 V (SCE)615 628 (Table 14). The values of nun are in reasonable agreement with the data of Caswell et al.623,624 Practically the same value of Eff was obtained by the scrape method in NaC104 + HjO solution (pH = 7.0).190 Later it was shown154,259,625,628 that the determination of Eo=0 by direct observation of Emin on C,E curves in dilute surface-inactive electrolyte solutions is not possible in the case of Zn because Zn belongs to the group of metals for which E -o is close to the reversible standard potential in aqueous solution. 

Therefore some indirect methods have been worked out to determine the value of ff=0.154,259 In particular (1) salting out of organic compounds from a surface-inactive electrolyte solution, (2) F"" for 1-pentanol or other organic compounds with a high attractive interaction constant a, and (3) dependence of the capacitance minimum on thiourea concentration. It should be noted that indirect estimates based on TU adsorption give... 

Zinc crystallizes in the hexagonal close-packed system its electronic structure is 4s2 and the melting point is 693 K. Since the zinc dissolution takes place at potentials very close to ffa0 the differential capacitance curves in the region of Ea=c in pure surface-inactive electrolyte solutions (KC1, pH = 3.7) can be determined directly for the Zn(llJO) face only... 

Studies in surface-inactive electrolyte solutions with various organic compounds (cyclohexanol, 1-pentanol, 2-butanol, camphor, tetra-buthyl ammonium ion, TBN+) show that the adsorption-desorption peak shifts to more negative potentials in the order (0001) < (1010) < (1120) this was explained by the increasing negative value of Eff=0 in the same direction.259 629-635... 

Vitanov and Popov et al.156 660-662 have studied Cd(0001) electrolyti-cally grown in a Teflon capillary in an aqueous surface-inactive electrolyte solution. The E is independent of ce) and v. The capacity dispersion is less than 5%, and the electrode resistance dispersion is less than 3%. The adsorption of halides increases in the order Cl" < Br" < I".661 A comparison with other electrodes shows an increase in adsorption in the sequence Cd(0001) < pc-Cd < Ag( 100) < Ag(l 11). A linear Parsons-Zobel plot with /pz = 1.09 has been found at a = 0. A slight dependence has been found for the Cit a curves on ce, ( 5%) in the entire region of a. Theoretical C, E curves have been calculated according to the GCSG model. 

First attempts to study the electrical double layer at A1 electrodes in aqueous and nonaqueous solutions were made in 1962-1965,182,747,748 but the results were not successful.190 The electrical double-layer structure at a renewed Al/nonaqueous solution of surface-inactive electrolytes such as (CH3)4NBF4) (CH3)4NC104, (CH3>4NPF6, and (C4H9)4NBF4, has been investigated by impedance.749-751 y-butyrolactone (y-BL), DMSO, and DMF have been used as solvents. In a wide region of E [-2.5 [Pg.128]

The first studies of the electrical double-layer structure at Sn + Pb and Sn + Cd solid drop electrodes in aqueous surface-inactive electrolyte solutions were carried out by Kukk and Piittsepp.808 Alloys with various contents of Pb (from 0.2 to 98%) were investigated by impedance.615,643,667,816 Small amounts of Pb caused dramatic shifts of toward more negative values. For alloys with Pb bulk content 0.2%, was the same as for pc-Pb. The was independent of Crf and frequency. C xt Cjl plots were linear, with/pz very close to unity. Thus the surface of Sn + Pb alloys behaves as if it were geometrically smooth, and Pb appears to be the surface-active component. 

In Table 25 the values of E Lo - in molten salt (eutectic LiCl + KC1 melt) are compared with AE in aqueous solutions (relative to the value of Eo=0 for a pc-Pb electrode in a surface-inactive aqueous electrolyte). According to these data, the difference of AEaf in aqueous electrolytes and molten salts is not very high to a first approximation, it can be assumed that the quantity in square brackets in Eq. (61) has the greatest... 

At high alkali coverages (near monolayer coverage), when the adsorbed alkali overlayer shows a metal-like character, alkali-methoxy species are formed. As shown by TPD experiments in the system K/Ru(001) these alkali-methoxy species are more stable than the methoxy species on clean Ru(001) and adsorbed methanol on 0.1K/Ru(001). On metal surfaces inactive for methanol decomposition, e.g. Cu(lll), these alkali-methoxy species are formed even at low alkali coverages, due to the weaker interaction of the alkali atoms with the metal surface. The formation of these species stabilizes the methoxy species on the metal surface and enhances the activity of the metal surface for methanol decomposition. 

The surface actlve/surface inactive difference between p-polarlsed/ s-polarised radiation has enabled an alternative modulation technique, polarisation modulation, to be developed (15,16). In electrochemical applications, it allows surface specificity to be achieved whilst working at fixed potential and without electrochemical modulation of the interface. It can be implemented either on EMIRS or on SNIFTIRS spectrometers and can be very valuable in dealing with electrochemically irreversible systems however, the achievable sensitivity falls well short of that obtained with electrochemical modulation. It should also be noted that its "surface specificity" is not truly surface but extends out into the electrolyte with decreasing specificity to about half a wavelength. 

Specific adsorption of ions changes the value of E, hence, one distinguishes the notion of a point of zero charge, in solutions of surface-inactive electrolytes, which depends on the metal, from that of a point of zero charge, in solutions of surface-active ions, which in addition depends on the nature and concentration of these ions. The difference between these quantities. 

The charge density on the electrode a(m) is mostly found from Eq. (4.2.24) or (4.2.26) or measured directly (see Section 4.4). The differential capacity of the compact layer Cc can be calculated from Eq. (4.3.1) for known values of C and Cd. It follows from experiments that the quantity Cc for surface inactive electrolytes is a function of the potential applied to the electrode, but is not a function of the concentration of the electrolyte. Thus, if the value of Cc is known for a single concentration, it can be used to calculate the total differential capacity C at an arbitrary concentration of the surface-inactive electrolyte and the calculated values can be compared with experiment. This comparison is a test of the validity of the diffuse layer theory. Figure 4.5 provides examples of theoretical and experimental capacity curves for the non-adsorbing electrolyte NaF. Even at a concentration of 0.916 mol dm-3, the Cd value is not sufficient to permit us to set C Cc. 

Fig. 4.4 The dependence of the potential difference in the diffuse layer on the difference E — Epzc (the rational potential) for various concentrations of the surface inactive electrolyte KF. (According to R. Parsons)... 

Fig. 4.7 Schematic dependence of the quantities y, y°, o °o, Ce — C and T on the electrode potential. The quantities with the superscript 0 refer to a surface-inactive electrolyte while those without a superscript refer...

The results of experiments with crude oil fractions in this study also suggest that several species were present in reaction interface. There are mainly long chain carboxylic acids. The difference in size and structure is expected to give them different pka values. As a result, different surface activity (i.e., IFT value) is obtained with different levels of alkali concentration. Crude oil fractions with lower surface activity only yield surface inactive salts that may appear as precipitates at the interface. 

Ferric hydroxide coprecipitation techniques are lengthy, two days being needed for a complete precipitation. To speed up this analysis, Tzeng and Zeitlin [595] studied the applicability of an intrinsically rapid technique, namely adsorption colloid flotation. This separation procedure uses a surfactant-collector-inert gas system, in which a charged surface-inactive species is adsorbed on a hydrophobic colloid collector of opposite charge. The colloid with the adsorbed species is floated to the surface with a suitable surfactant and inert gas, and the foam layer is removed manually for analysis by a methylene blue spectrometric procedure. The advantages of the method include a rapid separation, simple equipment, and excellent recoveries. Tzeng and Zeitlin [595] used the floation unit that was devised by Kim and Zeitlin [517]. 

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