Analytical Electochemistry, Second Edition by Joseph Wang(auth.)

By Joseph Wang(auth.)

Content material:
Chapter 1 primary recommendations (pages 1–27):
Chapter 2 examine of Electrode Reactions (pages 28–59):
Chapter three Controlled?Potential recommendations (pages 60–99):
Chapter four sensible concerns (pages 100–139):
Chapter five Potentiometry (pages 140–170):
Chapter 6 Electrochemical Sensors (pages 171–202):

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For reduction, the energy of the electrons in the electrode must be higher than their energy in the receptor orbital of R. Since the net reaction rate is Vnet ˆ Vf À Vb ˆ kf CO …0; t† À kb CR …0; t† …1-20† and as the forward and backward currents are proportional to Vf and Vb, respectively, if ˆ nFAVf …1-21† ib ˆ nFAVb …1-22† 1-2 FARADAIC PROCESSES 13 the overall current is given by the difference between the currents due to the forward and backward reactions: inet ˆ if À ib ˆ nFA‰kf CO …0; t† À kb CR …0; t†Š …1-23† By substituting the expressions for kf and kb (equations 1-17 and 1-18), one obtains i ˆ nFAk  fCO …0; t† exp‰ÀanF…E À E  †=RT Š À CR …0; t† exp‰…1 À a†nF…E À E  †=RT Šg …1-24† which describes the current±potential relationship for reactions controlled by the rate of electron transfer.

The shape of the p  voltammogram is a function of k  = paD (where a ˆ nFv=RT ). As k  = paD increases, p the process approaches the reversible case. , at very fast v) the system exhibits an irreversible behavior. Overall, the voltammograms of a quasi-reversible system are more drawn-out and exhibit a larger separation in peak potentials compared to those of a reversible system (Figure 2-5, curve B). 2 Study of Reaction Mechanisms One of the most important applications of cyclic voltammetry is for qualitative diagnosis of chemical reactions that precede or succeed the redox process (1).

The various scanning probe microscopies have similar subcomponents but different sensing probes. These high-resolution microscopies rely on sensing the interactions between a probe tip and the target surface while scanning the tip across the surface. Different types of interactions can be sensed by the tip to yield different imaging signals. Such signals are displayed as gray-scale portraits, re¯ecting the extent of the tip±surface interaction. With microcomputers, the image processing becomes possible in very short times.

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