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By J J Lagowski (Auth.)

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Extra resources for The Chemistry of Nonaqueous Solvents. Volume IV: Solution Phenomena and Aprotic Solvents

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An open-chain dimer should have stretching -1 and deformation modes of comparable intensity. T w o strong bands at 222 and 116 c m were reported, supporting the linear 24 dimer model. Similar work by these authors on e t h a n o l in an argon matrix gave evidence for an open-chain dimer, but extra bands suggested that a second type of dimer, perhaps with a nonlinear hydrogen bond, was present also. T h e complete infrared spectrum of both these alcohols in matrices was measured and evidence found for a variety of higher polymers both linear 15 and cyclic.

They found this value of D to be constant for aliphatic amines and alcohols. These thermo­ dynamic studies helped confirm the theory which treats the hydrogen bond 63 as an electrostatic entity. G r a m s t a d found similar trends in nitrogen compounds with phenol. There was a correlation between log ^ a sc of s othe nitrogen base complex with phenol and the heat of mixing of these bases with chloroform. In addition there was a linear relationship between logKassocof pyridines and quinolines 4 with phenol and the pKa values of the bases.

Is localized to some extent, there are other factors, such as the potential 16 function, which are influenced by steric effects and polymer formation. Jakobsen and B r a s c h who studied the hydrogen bond in phenols found it useful to calculate the force constant by an independent method and then use it to make further calculations. T h e force constant can be calculated if the 1 178of the hydrogen bonding complex is known. 0; they related this force constant to R, the O • • O distance in the complex.

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