Reaction Kinetics in Solution

Rudolph (Rudy) Marcus was born in 1923 at Montreal, Quebec, Canada, where he also grew up and went to school. He entered McGill 

1943 and a Ph.D. in 1946. His doctoral research under Professor Carl Winkler was in the area of chemical kinetics. He then spent two years as a post-doctoral fellow at the National Research 

Council in Ottawa, Canada where he worked in the photochemistry laboratory of E.W.R. 

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Kuznetsov, A. M., Stochastic and Dynamic Views of Chemical Reaction Kinetics in Solutions, Presses Polytechniques et Universitaires Romandes, Lausanne, Switzerland, 1999. Kuznetsov, A. M., and J. Ulstrup, Electron Transfer in Chemistry and Biology, Wiley, Chichester, West Sussex, England, 1999. 

Before turning our attention to reaction kinetics in solution, a few general comments are appropriate. 

Because of the gaseous nature of many of the important primary and secondary pollutants, the emphasis in kinetic studies of atmospheric reactions historically has been on gas-phase systems. However, it is now clear that reactions that occur in the liquid phase and on the surfaces of solids and liquids play important roles in such problems as stratospheric ozone depletion (Chapters 12 and 13), acid rain, and fogs (Chapters 7 and 8) and in the growth and properties of aerosol particles (Chapter 9). We therefore briefly discuss reaction kinetics in solution in this section and heterogeneous kinetics in Section E. 

By contrast, few such calculations have as yet been made for diffusional problems. Much more significantly, the experimental observables of rate coefficient or survival (recombination) probability can be measured very much less accurately than can energy levels. A detailed comparison of experimental observations and theoretical predictions must be restricted by the experimental accuracy attainable. This very limitation probably explains why no unambiguous experimental assignment of a many-body effect has yet been made in the field of reaction kinetics in solution, even over picosecond timescale. Necessarily, there are good reasons to anticipate their occurrence. At this stage, all that can be done is to estimate the importance of such effects and include them in an analysis of experimental results. Perhaps a comparison of theoretical calculations and Monte Carlo or molecular dynamics simulations would be the best that could be hoped for at this moment (rather like, though less satisfactory than, the current position in the development of statistical mechanical theories of liquids). Nevertheless, there remains a clear need for careful experiments, which may reveal such effects as discussed in the remainder of much of this volume. 

Refs. [i] Landau LD, Lifshitz EM (1970) Statistical physics, 2nd edn. Pergamon, Oxford [ii] Kuznetsov AM (1997) Stochastic and dynamic views of chemical reaction kinetics in solutions. Presses polytechniques et universitaire romandes, Lausanne [iii] Kornyshev AA, Leikin S, Sut-mann G (1997) Electrochim Acta 42 849... 

The Hammett relation, og(hyjko)= pa, has been applied for many years to substituent eifects on reaction kinetics in solution, and has been particularly successful for reactions of benzene compounds. Attempts have also been made to apply Hammett correlations to other phenomena such as infrared (T. L. Brown, 1960), ultraviolet (Jaffe and Orchin, 1962a) and nuclear magnetic resonance absorption frequencies (Bothner-By and Glick, 1956). 

Chemistry. There are many parts of mainline chemistry that originated in electrochemistry. The third law of thermodynamics grew out of observations on the temperature variations of the potential of electrochemical reactions occurring in cells. The concepts of pH and dissociation constant were formerly studied as part of the electrochemistry of solutions. Ionic reaction kinetics in solution is expressed in terms of the electrochemical theory developed to explain the activity of ions in solution. Electrolysis, metal deposition, syntheses at electrodes, plus half of the modem methods of analysis in solution depend on electrochemical phenomena. Many biomolecules in living systems exist in the colloidal state, and the stability of colloids is dependent on the electrochemistry at their contact with the surrounding solution. 

This chemical kinetics book blends physical theory, phenomenology and empiricism to provide a guide to the experimental practice and interpretation of reaction kinetics in solution. It is suitable for courses in chemical kinetics at the graduate and advanced undergraduate levels. This book A/ill appeal to students in physical organic chemistry, physical inorganic chemistry, biophysical chemistry, biochemistry, pharmaceutical chemistry and vi/ater chemistry—all fields concerned with the rates of chemical reactions in the solution phase. 

Kuznetsov, A.M., Stochastic and Dynamic Views of Chemical reaction Kinetics in Solutions, Press Polytechniques et Universitaires Romandes Lausanne, 1999. 

The study of reaction kinetics in solution has seen tremendous advances since the 1960s. This progress has been recognized by four Nobel Prizes. In 1967, Manfred Eigen, Ronald Norrish, and Sir George Porter received the Nobel Prize for their studies of extremely fast reactions affected by disturbing a solution equilibrium by... 

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