Chemical Dynamics by J Gray, H Hammond, G Dence

By J Gray, H Hammond, G Dence

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For this step i t is also easier to measure the enthalpy rather than the free energy change. The logical way to do this might be to establish equilibrium between the three species involved, and to directly measure the equilibrium constant at some temperature. However, this is difficult to do because K for a step such as this one is likely to be extremely small. Actually, even though there are several very sensitive tools which we could use to measure the equilibrium concentration of, say, hydrogen atoms, the real reason K is not measured directly is in fact because it is difficult to bring the system to a state of equilibrium.

L - - - - A good example showing this is the variation of the vapor pressure of water with temperature; see H. B. Gray and G. P. , Basic Principles of Chemistry, p. 73, W. A. , New York, 1967. I [ 2 2 1 CHEMICAL DYNAMICS The second step of the Born-Haber cycle consists of the symmetrical scission of the acid to give two species, a hydrogen atom and a free radical. For this step i t is also easier to measure the enthalpy rather than the free energy change. The logical way to do this might be to establish equilibrium between the three species involved, and to directly measure the equilibrium constant at some temperature.

Correlation of these simple dissociation reactions with each other highlights the irregularities noted. A major challenge is posed for theoretical structural chemists by the anomalous strength of the H-F bond and weakness of the F-F bond. Reasonably satisfactory rationalizations of the remarkable effects have been supplied, but require rather sophisticated analyses of the details of electronic interactions in the molecules. CHEMICAL DYNAMICS EXERCISES 1. Using appropriate gas phase data determine whether bromine or chlorine should be the stronger oxidant.

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