Some Free-energy Data for Typical Hydrocarbons Containing Six or More Carbon Atoms.

It is to be expected that for the higher members of a homologous series the heat of formation at a given temperature and state of aggregation is a linear function of the number of C atoms in the normal alkyl group; the increment of the heat of formation per C atom is independent of the nature of the series.Assuming that this law remains true for infinitely diluted solutions, corollaries are derived for various thermodynamic equilibria in which a member of a homologous series occurs.It is found that the relations derived for the distribution equilibrium for two liquid phases at infinite dilution, the equilibrium constant for chemical reactions at infinite dilution, the vapour pressure of a homologous series at a given temperature, etc. contain either a ) quantities independent of n (i.e. the number of C atoms in the normal alkyl group), b) quantities linearly related to n, or c) quantities whose logarithms are linearly related to n.

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Hydrocarbon Conversion with Special Reference to the Thermodynamical Calculations for the Isomerization Reactions. I

HamaiSenzo¹

1943

Bulletin of the Chemical Society of Japan

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Synopsis.(1) In order to grasp the general trend of isomerization reactions of saturated hydrocarbons, the free energy equations, as a function of temperature convenient for practical calculations, are derived based on one of the more recent data available.The free energy equations of some of the useful reactions such as the formation of neohexane by alkylation, and the formation of isooctane by the coupling (4) Discussions in connection with these thermodynamical calculations for isomerization reactions are presented.(5) Discussions of the isomerization in connection with so-called "Bond Free Energy Equation" of Bruins and Czarnecki are presented.(6) In general, isomerization reactions of hydrocarbons, with few exceptions, are favoured thermodynamically at a lower temperature.(7) Isomerization reactions from simpler structures to more complicated and branched compounds are favoured thermodynamically, more or less, at a lower temperature.(8) In the isomerization reactions of di-or tri-methylated compounds involving merely an exchange of the position of the carbon to which methyl or ethyl groups are attached, a structure which is more non-symmetrical favours the isomerization thermodynamically at a higher temperature.(9) Free energy changes involved in the isomerization reactions are of small magnitude as compared with those of ordinary chemical reactions.(10) The errors involved in the data of the free energy changes of isomerizaticn often amount to a magnitude as big as the free energy change itself. Hence in the selection of data for such calculations, much caution should be taken into consideration.

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Some Free-energy Data for Typical Hydrocarbons Containing Six or More Carbon Atoms.

Cited by 3 publications

References 10 publications

Das Physikalisch‐chemische Problem der Motorischen Zündung von Gasgemischen

Das Physikalisch‐chemische Problem der Motorischen Zündung von Gasgemischen

Thermodynamic study on the influence of the carbon chain length of homologous compounds on physical and chemical equilibria in systems consisting of one or more phases

Hydrocarbon Conversion with Special Reference to the Thermodynamical Calculations for the Isomerization Reactions. I

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