Effect of Pressure on the Frequency of the O–H Band in Butanol Solutions
Effect of Pressure on the Frequency of the O–H Band in Butanol Solutions
复制标题
压力对丁醇溶液中 O-H 谱带频率的影响
DOI：
10.1063/1.1742544
复制
发表时间：
1956
影响因子：
4.4
通讯作者：
H. G. Drickamer
中科院分区：
文献类型：
--
作者：
E. Fishman;H. G. Drickamer
在10 ~ 12000大气压的压力下，在3微米范围内观察到了正丁醇稀溶液的红外光谱。随着压力的增加，尖锐的“单体”O-H波段向较低的频率移动。如果我们将Δv定义为其在每种溶剂中在一个大气压和25°C时的值的频率变化，则在最大压力下Δv从2,3二甲基丁烷中的11 cm‐1变化到碘化正丙基中的41 cm‐1。发现频移是密度平方和溶剂键极化率的线性函数，尽管后者的关系不是定量的。这种转变被合理地解释为由于O-H键和溶剂之间的范德华力。压力使醇的聚合大大增加，由此估计聚合时的体积变化在1 ~ 5820大气压范围内为-4.64 cm3/mol，在5820 ~ 11330大气压范围内为-2.47 cm3/mol。
The infrared spectra of dilute solutions of normal butanol have been observed in the 3‐micron region at pressures from 10 to 12 000 atmospheres. The sharp ``monomeric'' O–H band shifts toward lower frequencies as the pressure increases. If we define Δv as the shift in frequency from its value at one atmosphere and 25°C in each solvent, Δv at the maximum pressure varies from 11 cm‐1 in 2, 3 dimethyl butane to 41 cm‐1 in n‐propyl iodide. The frequency shift is found to be a linear function of the square of the density and the polarizability of solvent bonds, though this latter relationship is not quantitative. The shifts are plausibly explained as due to van der Waals' forces between the O–H bond and the solvent. The pressure causes a large increase in the polymerization of the alcohol, from which the change of volume on polymerization is estimated to be —4.64 cm3/mole in the 1 to 5820 atmosphere range, and —2.47 cm3/mole in the 5820 to 11 330 atmosphere range.