Additivity Rule of the Partial Molal Volume. 3. Anomaly of Cycloalkane Molecules and Volume Change for the Ring Formation Reaction

Yoshimura, Y.; Nakahara, Masaru

doi:10.1002/bbpc.19850890915

Cited by 8 publications

(2 citation statements)

References 13 publications

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“…The reason is as follows: for normal alkanes, VoConf in eq. [5] can be written as (10) where V '(-CH2-) and V 0(CH3-) denote the contributions of the methylene and methyl groups to VoConf, respectively; a and a 2 denote the ratios V O (-CH,-)/ v,(-CH,-) and…”

Section: Discussionmentioning

confidence: 99%

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Additivity of the partial molar volumes of organic compounds

Nishimura¹,

Tanaka²,

Motoyama³

1987

Can. J. Chem.

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N o~i o NISH~MURA, TOHRU TANAKA, and TAKUSH~ MOTOYAMA. Can. J. Chem. 65, 2248Chem. 65, (1987. A critical test of additivity for partial molar volume has been made at 25' C in CCI4 with polyethylene glycol dimethyl ethers, crown ethers, cycloalkanes, n-alkanes, and others. Plots of partial molar volume at infinite dilution (v O ) against the properly chosen number of repeating unit ( n ) are linear except for small cyclic molecules, and the slopes of homologous straight chain and ring compounds are the same. The values of v O extrapolated to 11 = 0 for cycloalkanes and crown ethers support the validity of the contribution due to the translational kinetic energy that has been predicted recently on a theoretical basis. The importance of packing efficiencies around the solute molecules has been examined by means of simple models.NORIO NISHIMURA, TOHRU TANAKA et TAKUSH~ MOTOYAMA. Can. J. Chem. 65,2248Chem. 65, (1987. OpCrant i 25"C, dans des solutions de CC14, on a effectuC une Cvaluation critique de I'additivitC des volumes molaires partiels pour des Cthers dimtthyliques du polyCthylkne glycol, des Cthers couronnes, des cycloalcanes, des n-alcanes et d'autres composCs. A l'exception des molCcules contenant des petits cycles, on a trouvC qu'il existe une relation linCaire entre les volumes molaires partiels i dilution infinie (a O) et le nombre choisi appropriC d'unitts periodiques (n); de plus, les pentes des courbes pour les composCs homologues aliphatiques sont les mkmes que celles pour les composts cycliques. Pour les cycloalcanes et pour les Cthers couronnes, les valeurs de (v O ) extrapolCes i n = 0 sont en accord avec la prCdiction qui a rCcemment CtC faite sur une base thCorique et selon laquelle on pr6voit une contribution de la part de 1'Cnergie cinCtique de translation. Utilisant des moddes simples, on a CtudiC I'importance des efficacitCs d'empilement autour des moltcules de solutCs.[Traduit par la revue]

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Section: Discussionmentioning

confidence: 99%

“…Their ideas are of great significance for high pressure kineticists since they have not been taken into account for the activation volume (AV*) and reaction volume (AV). They further developed the additivity rule of the partial molar volume (9,10). Based on the virial theorem, they have derived the following equation:…”

Section: Introductionmentioning

confidence: 99%

Additivity of the partial molar volumes of organic compounds

Nishimura¹,

Tanaka²,

Motoyama³

1987

Can. J. Chem.

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Additivity Rule of the Partial Molal Volume. 4. Its Proof Based on the Postulate of Independent Volume Changes for Unit Reactions

Yoshimura

Nakahara

1986

Ber Bunsenges Phys Chem

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The additivity rule of the partial molal volume is proved to be equivalent to the postulate of independent volume changes for unit reactions which states that the (configurational) volume changes are determined by the reaction sites and not affected by the other sites in the composite molecule. The postulate of independent volume change leads to the reduction of the multiple body distribution function to the product of the pair distribution functions between the nearest‐neighbor sites in the composite molecule. The postulate is applied to the model system of n‐alkane solution composed of hard spheres. The calculated result based on a proper pair cavity distribution function well reproduces the characteristics of the additivity rule of the partial molal volume of n‐alkanes, and predicts molecular dimensions of n‐alkane in a reasonable manner.

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Calculation of the partial volume of organic compounds and polymers

Durchschlag

Zipper

Ultracentrifugation

117

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Additivity Rule of the Partial Molal Volume. 3. Anomaly of Cycloalkane Molecules and Volume Change for the Ring Formation Reaction

Cited by 8 publications

References 13 publications

Additivity of the partial molar volumes of organic compounds

Additivity of the partial molar volumes of organic compounds

Additivity Rule of the Partial Molal Volume. 4. Its Proof Based on the Postulate of Independent Volume Changes for Unit Reactions

Calculation of the partial volume of organic compounds and polymers

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