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Any increase in precision results from the greater ease, in some cases, of increasing the number of experimental observations. Furthermore, a knowledge of R,, is not required. The latter is mainly a matter of convenience, since it can usually be obtained ex- 44 JACOB BIGELEISEN A N D MAX M’OLFSBERG perimentally either by extrapolation or by successive approximation in the cumulative product method. If R,, is known in the successive fraction method, the intercept gives (k/k’- 1). This is the equivalent of an additional experiment in the cumulative product met hod.
TABLE V. Frequency Assignment for Triangular H,C1 Complex. 16' I< 200 cm-1 approximated 720i cm-l calculated by WTE for a linear model IObT Fig. 5 . Relative rates of reaction of t h e isotopic hydrogen molecules with chlorine atoms as a funckion of temperature. Solid lines calculated for an isosceles triangular H,C1 comples, v,+ = 1002 cm-1.
8, are each less than, but probably close to unity. 9 for the change of the isotope effect with pressure does not appear at all unreasonable. This theory predicts that the low-pressure isotope effect should change from unity with temperature. We may utilize the experimental ratio (KH/KT)P=m/(KH/KT)P=m to evaluate some of the factors in the high-pressure isotope effect. - -17 In addition we assume [ ( E , + i ~ h v T , * ) / ( E , + ~ ~ h v H i * ) ] 3 nN and uTi/uHi is evaluated from molecular data and the product rule.