HEATS OF COMBUSTION AND STRAIN ENERGIES OF BICYCLO N.M.0!ALKANES
HEATS OF COMBUSTION AND STRAIN ENERGIES OF BICYCLO N.M.0!ALKANES
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DOI：
10.1021/ja00713a032
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发表时间：
1970-01-01
影响因子：
15
通讯作者：
HICKEY, MJ
中科院分区：
文献类型：
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作者：
CHANG, S;BOYD, RH;HICKEY, MJ
测定了一些双环烷烃的燃烧热、蒸气压和液体热容。导出的液体和气体在250下以千卡摩尔-1为单位的生成热如下：正己烷，1.3±0.7，9.3±0.8;顺式-双环[4.1. 0]庚烷，-8.7 ±0.8，0.4±1.0;顺式-双环[5.1. 01-辛烷，-4.2 ±0.5，-3.8 ±0.7;顺式二环[6.1. 0]壬烷，-19.4 ±0.8，-7.6 ±1.0;顺式-双环[4.2. 0]辛烷，-16.3 ±0.8，-6.1 ±1.1;顺式-双环[3.3.正辛烷，-32.6 ±0.3，-22.3 ±0.5;反式-双环[3.3. 0]辛烷，-26.1 ±0.4，-15.9 ±0.6; N-双环[5.3. 0]癸烷，-43.9 ±0.9，-31.1 ±1.2。实验应变能是由基团贡献导出的。应变能和几何形状也计算了能量最小化与一组可转移的价力势函数。应变能的计算值与实验值吻合较好。本文还计算了气相热力学函数（自由能函数、焓函数、热容和熵），鉴于近年来人们对张力环烃化学的极大兴趣，这类化合物的分子性质和结构的研究是十分必要的。特别重要的是希望获得的形成热，从经验应变能可以得出。本文的目的是研究一类重要的张力环化合物--[nm 0]双环烷烃。本文用氧燃烧量热法测定了一些这类化合物的生成热，得到了它们的应变能。该族烃的生成热为用可转移经验价力势进行能量最小化计算分子性质提供了重要的实验基础
Theheats of combustion, vapor pressures, and liquid heat capacities of a number of bicyclic alkanes have been determined. The derived liquid and gas heats of formation in kilocalories mole-1 at 250 are as follows: czs-bicyclo [3.1. Ojhexane, 1.3±0.7, 9.3±0.8; cw-bicyclo [4.1. 0] heptane,—8.7±0.8, 0.4±1.0; c/s-bicyclo [5.1. 01-octane,—4.2±0.5,—3.8±0.7; cz> bicyclo [6.1. 0] nonane,—19.4±0.8,—7.6±1.0; c/f-bicyclo [4.2. 0] octane,—16.3±0.8,—6.1±1.1; czs-bicyclo [3.3. Ojoctane,—32.6±0.3,—22.3±0.5; rra «í-bicyclo [3.3. 0] octane,—26.1±0.4,—15.9±0.6;«j-bicyclo [5.3. 0] decane,—43.9±0.9,—31.1±1.2. Experimental strain energies are de-rived from group contributions. Strain energies and geometries are also calculated by energy minimization with a set of transferable valence force potential functions. The agreement of calculated and experimental strain energies is satisfactory. The gas phase thermodynamic functions (freeenergy and enthalpy functions, heat capacity, and entropy) are also calculated.In view of the great interest in recent years in the chemistry of strained cyclic hydrocarbons, studies of molecularproperties and structure of such com-pounds are greatly in need. Of particular importance is the desirability of obtaining heats of formation from which empirical strain energies may be derived. It is the purpose of the present work to study an important family of strained ring compounds, the [nm 0] bicyclic alkanes. The heats of formation via oxygen combus-tion calorimetry of a number of such compounds have been measured in this work to arrive at strain energies. The heats of formation of this family of hydrocarbons provide an important testing ground for calcu-lation of molecular properties by energy minimization using transferable empirical valence force potential