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Calculation of the Heat Capacity Curves of Crystalline Benzene and Benzene‐d6
dc.contributor.authorLord, R. C.en_US
dc.contributor.authorAhlberg, J. E.en_US
dc.contributor.authorAndrews, D. H.en_US
dc.date.accessioned2010-05-06T20:46:56Z
dc.date.available2010-05-06T20:46:56Z
dc.date.issued1937-08en_US
dc.identifier.citationLord, R. C.; Ahlberg, J. E.; Andrews, D. H. (1937). "Calculation of the Heat Capacity Curves of Crystalline Benzene and Benzene‐d6." The Journal of Chemical Physics 5(8): 649-654. <http://hdl.handle.net/2027.42/69555>en_US
dc.identifier.urihttps://hdl.handle.net/2027.42/69555
dc.description.abstractThe heat capacity curve for solid benzene has been computed with the help of the set of internal frequencies previously proposed by Lord and Andrews. The agreement with experiment is satisfactory over the entire temperature range in which the internal frequencies contribute, indicating that the frequency values are essentially correct. A prediction of the heat capacity of benzene‐d6 has also been made.en_US
dc.format.extent3102 bytes
dc.format.extent387898 bytes
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dc.publisherThe American Institute of Physicsen_US
dc.rights© The American Institute of Physicsen_US
dc.titleCalculation of the Heat Capacity Curves of Crystalline Benzene and Benzene‐d6en_US
dc.typeArticleen_US
dc.subject.hlbsecondlevelPhysicsen_US
dc.subject.hlbtoplevelScienceen_US
dc.description.peerreviewedPeer Revieweden_US
dc.contributor.affiliationumDepartment of Chemistry, University of Michigan, Ann Arbor, Michiganen_US
dc.contributor.affiliationotherDepartment of Chemistry, Johns Hopkins University, Baltimore, Marylanden_US
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/69555/2/JCPSA6-5-8-649-1.pdf
dc.identifier.doi10.1063/1.1750092en_US
dc.identifier.sourceThe Journal of Chemical Physicsen_US
dc.identifier.citedreferenceLord and Andrews, J. Phys. Chem. 41, 149 (1937).en_US
dc.identifier.citedreferenceD. H. Andrews, Proc. Roy. Soc. Amst. 29, 744 (1926); Chem. Rev. 5, 533 (1928); E. O. Salant, Proc. Nat. Acad. Sci. 12, 334, 370 (1926).en_US
dc.identifier.citedreferenceJ. E. Ahlberg, E. R. Blanchard, and W. O. Lundberg, J. Chem. Phys. 5, 539 (1937).en_US
dc.identifier.citedreferenceBlackman, Proc. Roy. Soc. A148, 365, 384 (1935).en_US
dc.identifier.citedreferenceV. Deitz, J. Frank. Inst. 219, 459, 565, 703 (1935).en_US
dc.identifier.citedreferenceMie, Ann. d. Physik 11, 657 (1903).en_US
dc.identifier.citedreferenceGrüneisen, Handbuch der Physik, Vol. X, p. 22 ff. See also Eucken, Handbuch der Experimentalphysik, Vol. VIII, part 1, p. 281.en_US
dc.identifier.citedreferenceCf. Eucken, reference 7, p. 282; cf. Grüneisen, Ann. d. Physik 26, 211 (1908).en_US
dc.identifier.citedreferenceThe numerical determination of the two constants is made most reliably by utilizing the Cp−CυCp−Cυ difference at two rather widely different temperatures, e.g. at 150° and 250°. The constants found at these two temperatures may be used in turn to calculate the expansion term for all other temperatures. The constants may also be evaluated separately. In the region 60°–100°, CυCυ (internal) makes no appreciable contribution to the Cp−CυCp−Cυ difference. Hence the constant a may be determined independently of b at any temperature in this region. The evaluation of b is then possible at a single temperature above 100°, preferably at a temperature high enough so that the CυCυ (internal) term is relatively large. The a and b values found in this way agree well with those found by simultaneous solution of two numerical equations obtained from Eq. (12). It is of interest to note that the value of the constant a, 8.3×10−38.3×10−3 reciprocal calories, agrees reasonably well with the value one would compute from the formula proposed by Nernst and Lindemann (Zeits. f. Elektrochem. 17, 817 (1911)) for this constant, namely a2  =  0.0214/Tm,a2=0.0214∕Tm, where TmTm is the fusion temperature of the crystal. The value of a calculated from this expression is 8.77×10−3.8.77×10−3.en_US
dc.identifier.citedreferenceW. Nernst, Ann. d. Physik 36, 395 (1911).en_US
dc.identifier.citedreferenceHuffman, Parks, and Daniels, J. Am. Chem. Soc. 52, 1547 (1930).en_US
dc.identifier.citedreferenceWilson, Phys. Rev. 45, 706 (1934).en_US
dc.identifier.citedreferenceAngus, Bailey, Hale, Ingold, Leckie, Raisin, Thompson and Wilson, J. Chem. Soc. (London) 984 (1936).en_US
dc.identifier.citedreferenceOne might object, with considerable reason, that it is hardly legitimate to use here a constant found empirically under the assumption of different values for certain of the internal frequencies. This objection may be answered in part by remarking that the value of the constant used is close to that given by the independent formula of Nernst and Lindemann (reference 9). In addition it should be remembered that we are attaching no particular theoretical significance to the hypothetical CpCp curve other than its utility in demonstrating the improbability of the presence of the very low frequencies in benzene. Even if the expansion term is disregarded entirely, the low frequencies still cause some contradiction with experiment, for in the region 80°–140 °K the calculated CυCυ is larger than observed CpCp by 1–2 percent.en_US
dc.owningcollnamePhysics, Department of


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