RAMAN AND INFRARED SPECTRAL DATA, ASSIGNMENTS, AND CALCULATED WAVE NUMBERS AND THERMODYNAMIC PROPERTIES FOR $CD_{2}BrCl$ AND $CHDBrCl^{\ast}$
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Date
1962
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Volume Title
Publisher
Ohio State University
Abstract
Raman displacements $\Delta \sigma$ (in cycles/cm), semiquantitative relative intensities I, and quantitative depolarization ratios $\rho$ for the liquid; and infrared wave numbers $\sigma$ and estimated intensities $I_{e}$ for both the gas and the liquid have been obtained for $CD_{2}BrCl$ and for a mixture of $CH_{2}BrCl, CHDBrCl$, and $CD_{2}BrCl$. The vibrational data for CHDBrCl were obtained by eliminating the known bands of $CH_{2}BrCl^{1}$ and $CD_{2}BrCl$ from the data for the mixture. The assignments for $CD_{2}BrCl$ and CHDBrCl were checked by normal coordinate treatments, using the method of Wilson. The observed $\Delta \sigma(I) \rho$ values for the fundamentals of $CD_{2}BrCl$ are: $a^{\prime}--- 226(832)0.15, 574(1000)0.09, 702(98)0.61, 922(69)0,11, 1042(110)0.35$, and $2196(417)0.11; a^{\prime\prime}---667(9)0.82, 809(20)0.83$, and 2294(76)0.82. For CHDBrCl, the $\Delta \sigma$ values observed for the fundamentals (all of type a) are: 228, 586, 707, 743, 867, 1179, 1264, 2246, and 3024 c/cm. The $\sigma(I_{r})$ values are: $CD_{2}BrCl$, liquid---574(vs), 705(vs), 923(vs), 1041(s), 2195(s), 810(vw), 2302(s); gas---576(s), 709(vs), 926(vs), 2199(w), 811(vw), CHDBrCl, liquid---706(s), 743(w), 865(vs), 1183(vs), 1262(s), 2252(ms), 3031(s); gas---711(s), 743(w), 862(s), 1181(s) c/cm. The calculated wave numbers are: $CD_{2}BrCl, a^{\prime}---227, 564, 693, 926, 1055, 2161: a^{\prime\prime}---672, 810, 2250, CHDBrCl, a---227, 578, 704, 740, 878, 1155, 1283, 2205, 3020 c/cm$. The maximum and average deviations of these from the observed values are 2.0 and 1.0 per cent, respectively. The heat content, free energy, entropy, and heat capacity were calculated for both molecules for 12 temperatures from $100^{\circ}$ to $1000^{\circ}K$.
Description
$^{\ast}$ Aided by the National Science Foundation. $^{\dagger}$ Present address: Physics Department, Arizona State University, Tempe, Ariz. $^{\dagger}$ Present address: Chemistry Department, University of Michigan, Ann Arbor, Mich. $^{1}$ A. Weber, A. G. Meister, and F. F. Cleveland, J. Chem. Phys, 21, 930 (1953).
Author Institution: Physics Department, Illinois Institute of Technology
Author Institution: Physics Department, Illinois Institute of Technology