Bockris and Habib

According to Bockris and Habib, the potential difference at the metal/solution interface at pzc is a result of the contribution of two components the surface potential (electron overlap) of the metal go and solvent dipoles oriented at the electrode surface, go- The value of go cannot be experimentally measured because the absolute value of the electrode potential is not known. However, the value of go can be estimated from the relation... 

Direct experimental observation of the restructuring of water as a function of an applied field has been reported by several groups. For example, Bockris and Habib used Fourier Transform Infra-Red (FTIR) spectroscopy to show that water molecules stand up as the field in-... 

As mentioned in Section 6.3.10, the surface potential cannot be measured. However, its value can be calculated (Bockris and Habib, 1976). Thus, from Eq. (6.60),... 

Source J. O M. Bockris and M. A. Habib, J. Electroanal. Chem. 68 367, copyright 1976, Table 1, with permission from Elsevier Science. 

M. A. Habib, Solvent dipoles at the electrode-solution interface, in Modern Aspects of Electrochemistry. Vol. 12, J. O M. Bockris, and B. E. Conway, editors. Plenum Press, New York, 1977, pp. 131-182. 

S. Trasatti. The Electrode Potential, in Comprehensive Treatise of Electrochemistry, Vol. 1, J. O M. Bockris, B.E. Conway and E. Veager. Eds. Plenum (1980), chapter 2 B.E. Conway, The State of Water and Hydrated Ions at Interfaces, Adv. Colloid Interface Sci. 8 (1977) 91 W.R. Fawcett, Molecular Models for Solvent Structure at Polarizable Interfaces. Isr. J. Chem. 18 (1979) 3 M.A. Habib, Solvent Dipoles at the Electrode-Solution Interface. in Modem Aspects of Electrochemistry, Vol. 12, J. O M. Bockris and B.E. Conway. Eds. Plenum (1977) 131 S. Trasatti, Solvent Adsorption and Double Layer Potential Drop at Electrodes, in Modem Aspects of Electrochemistry, B.E. Conway and J. O M. Bockris, Eds. Vol. 13 Plenum (1979) chapter 2 J. O M. Bockris. K-T. Jeng, Water Structure at Interfaces The Present Situation. Adv. Colloid Interface Set 33 (1990) 1. 

It is beyond the scope of this chapter to describe Fourier transform infrared spectroscopy in detail. Recent papers by Pons et Pons, and Habib and Bockris have reported the use of FTIRS for in situ spectroelectro-chemical studies. 

A significant advance was the application of the Fourier transform technique to enhance the signal. The optical arrangement of a Fourier transform infrared (FUR) spectrometer is shown in Fig. 27.37 (Habib and Bockris, 1984). A beam of light from an IR source is directed to a beamsplitter, where part of the beam is transmitted to a... 

FIGURE 27.37 Optical arrangement of an FTIR spectrophotometer. (From Habib and Bockris, 1984, with permission from Elsevier.)... 

Habib, and surface potential determination, 893 Habib llockris model of water, 899 I Iabib Bockris isotherm, 943,949 Half-crystal position, electrodeposition,... 

Irreversible reaction, 1251, 1419 Isoconic, definition, 933, 978, 982 Isotherm, 932, 964, 1197 applicability, 941 and charge transfer, 954, 955 Conway and Angersein-Kozlowska, 943 definition, 933 in electrode kinetics, 1197 Flory—Huggins type, 941,942, 944, 965 Frumkin, 938, 942, 965 Frumkin-Temkin, 1197, 1198 Habib-Bockris, 943... 

Guidelli model of, 899 Habib and Bockris, 899 at the interface, importance of, 918 -ion interaction energy, 924 -metal interactions, 896 chemical forces, 897, 972 lateral forces, 897 monomers of, definition, 899 orientation of, 898 Parsons model of, 899 and potential of the electrode. 900. 924 preferential orientation of, 912 and solvent excess entropy, 912 the "three-state water model 898, 899 Wave nature of electrons, 788 Wavenumber, 799 Waves... 

To summarize, three possible species may populate the electrode surface two types of monomers—the flip-up and flop-down water molecules—and one associated species—the dimers. This model is called, for obvious reasons, the three-state water model (Habib and Bockris, 1977). 

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