Molal Volume Relationships among Aliphatic Hydrocarbons at their Boiling Points.

Egloff, Gustav; Kuder, Robert C.

doi:10.1021/j150410a013

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“…The use of these temperatures derives from the fact that for the members of a series either temperature is approximately a constant fraction of the respective critical temperatures, the desirability of comparison at equal reduced temperatures being recognized from the theory of corresponding states. The best data show, however, that in the case of aliphatic hydrocarbons at their boiling points (7) the molecular volume of homologs is not a strictly additive function, and that in the case of aliphatic hydrocarbons at their melting points (8) the situation is complicated by the effects of molecular symmetry and alternating melting points.…”

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confidence: 99%

Molecular Volume of Liquid Alkanes at Corresponding Temperatures

Egloff¹,

Kuder²

1942

Ind. Eng. Chem.

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Section: Literature Citedmentioning

confidence: 99%

Molecular Volume of Liquid Alkanes at Corresponding Temperatures

Egloff¹,

Kuder²

1942

Ind. Eng. Chem.

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“…In n-nonane 53 C1 to Cn = 36, 53 C* to C" = n=2 n-3 9 28, 53 Cs to C" = 21, etc. PF(normal) = 36 + n = 4 28 + 21 + 15 + 10 + 6 + 3 + 1 = 120] Note: a short method for calculating W(isomer), which greatly reduces the computational labors, has been suggested by Wiener.39b W may be computed by multiplying the number of C atoms on one side of a bond by the number on the other side and summing the products for all bonds. Thus for 2,2,3,4-tetramethylpentane, the product for bond CMD2 is 18 = 8; for C2-C6, 8-1 = 8; for C2-C7, 8-1 = 8; for C2-C3, 4-5 = 20; for C3-C8, 81 = 8; for C3-C4, 6-3 = 18; for C^C9, 81 =8; for C4-C6, 81 = 8.…”

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Molecular Structure and Properties of Hydrocarbons and Related Compounds

Greenshields¹,

Rossini²

1958

J. Phys. Chem.

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March, 1958 MOLECULAR STRUCTURE AND PROPERTIES OF HYDROCARBONS 27 1ably results in a rather high concentration of N204 right near the burning surface. I n this way gemdinitropropane can concentrate Nz04 in the region in which it is most effective in suppressing reaction 5. Previous studies showed that gem-dinitropropane is formed in the reaction between 2-nitropropane and nitric acid a t about 160O.I Consequently, in the 2-nitropropane-nitric acid system gem-dinitropropane can be formed deep in the preheat zone and then decompose again right near the top of the preheat zone where the temperature is above 180". This means that the system 2-nitropropanenitric acid is somewhat unique in that one of the products of reaction 5 is a material which tends t o inhibit reaction 5. Thus the inhibiting effect of gemdinitropropane would be acting in the same direction as the shortening dwell-time for reactants in the preheat zone as consumption rate increases. This may be the reason why the change in slope in the upper part of the step is very sharp in the 2-nitropropane-nitric acid system as compared t o the other nitroparaffin systems. Table IV gives burning rate data for the system gem-dinitropropane-nitric acid and it can be seen that the consumption rate curve is linear and there is nothing unusual about the absolute value of the rates. If the above interpretation of the effect of N204 on the combustion of other nitroparaffin systems is correct, then addition of Nz04 to the gemdinitropropanenitric acid system should have no appreciable effect on the shape or absolute value of its consumption rate curve. The data in Table IV show this to be true. Both of these systems have a property of burning with and without flame. A comparison of rates in corresponding regions shows that the Nz04 does not alter the rate in either region. There is a discontinuity in the consumption rate curve a t the point of transition from flameless to flame combustion. However, this is a true discontinuity and has no relation to the low pressure step which has been shown to be a continuous phenomenon.2.3 I n view of the above and previous results, it appears that the proposed mechanism has been able to predict correctly several observable effects of chemical composition on the low pressure step, and has served as a good basis for correlating many phenomena observed in the combustion of nitric acid systems. Consequently, it continues to be an acceptable working hypothesis.Acknowledgment.-The author wishes to express his thanks to Mr. C. Stanifer and Mr. E. Dimitroff for their assistance in obtaining some of the consumption rate data.Empirical equations, involving only structural parameters, are presented for calculating the isomeric variation in the values of certain physical and thermodynamic properties of the paraffin hydrocarbons. Those properties are the molal volume, the molal refraction, the standard heat of formation, the standard heat of vaporization (all a t 25"), the normal boiling point and the boiling point a t 10 mm. As an example of the...

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Die Brechzahlen und Dichten innerhalb homologer Kohlenwasserstoffreihen Theoretische Deutung der empirischen Beziehungen von J. Smittenberg und D. Mulder

Hubert

Schultze

1957

Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft

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Ausgehend von einfachen Vorstellungen über die Polarisierbarkeit und die Raumerfüllung der Molekeln und unter Benutzung eines Molekelmodelles von K. Wisseroth werden die empirisch gefundenen Smittenberg‐Mulderschen Beziehungen, die den Verlauf der Brechzahlen und Dichten innerhalb homologer Kohlenwasserstoffreihen wiedergeben, physikalisch begründet. Die Zahlenwerte der theoretischen Parameter stimmen innerhalb der Fehlergrenze mit den empirisch gefundenen Werten überein.Für die n‐Alkine‐1, die 2‐Methylalkane, die 3‐Methylalkane und die 2,3‐Dimethylalkane werden die empirischen Parameterwerte angegeben, mit deren Hilfe die Berechnung der Brechzahlen und Dichten von flüssigen Homologen dieser Reihen mit mindestens 5 C‐Atomen in der Molekel möglich ist.Es wird gezeigt, daß sich die Wiedergabegüte der Meßwerte einer Reihe durch die Smittenberg‐Mulderschen Gleichungen aus der Konstitution des Grundkohlenwasserstoffes voraussagen läßt.

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Molal Volume Relationships among Aliphatic Hydrocarbons at their Boiling Points.

Cited by 4 publications

References 4 publications

Molecular Volume of Liquid Alkanes at Corresponding Temperatures

Molecular Volume of Liquid Alkanes at Corresponding Temperatures

Molecular Structure and Properties of Hydrocarbons and Related Compounds

Die Brechzahlen und Dichten innerhalb homologer Kohlenwasserstoffreihen Theoretische Deutung der empirischen Beziehungen von J. Smittenberg und D. Mulder

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