Structure of the n-alkane binary solid n-C19H40/n-C21H44 by infrared spectroscopy and calorimetry

Mark Maroncelli, H. L. Strauss, R. G. Snyder

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Abstract

The n-alkane binary solid n-C19/n-C21 has been studied by differential scanning calorimetry (DSC) and infrared spectroscopy. Measurements on the low-temperature ordered solid (phase I) and the high-temperature disordered solid (phase II) have been made as a function of temperature and composition. From the DSC measurements, the phase diagram has been determined as well as the transition enthalpies for the phase I to phase II transition and the phase II to liquid transition. A plot of the excess enthalpy of mixing vs. composition is symmetric for both solid phases. For the 1:1 mixture, the excess enthalpies are 2.4 ± 0.2 and 1.5 ± 0.1 kcal/mol for phase I (275 K) and II (306 K), respectively. The infrared spectra of C19/C21 mixtures incorporating one n-alkane that is selectively deuterated, n-C19H38D2 (2,2) or n-C21H42D2 (2,2), have been measured, and, from these spectra, the concentrations of gauche bonds at the chain ends of both components have been determined. Phase I of the C19/C21 mixtures consists primarily of all-trans chains with some end-gauche C21. In general, the concentration of gauche bonds, which are mostly at the chain ends, is higher for the mixture than for the neat components. The concentration of end-gauche C21 is highly dependent on concentration, going to 100% at infinite C21 dilution. The concentration dependence of end-gauche C21 can be accounted for in terms of a model based on nearest-neighbor chain interaction. The conformational disorder in phase II mixtures appears to be separable into two types: (i) One type of conformational disorder is associated with the lamellar surface; this end-chain disorder arises from the chain-length mismatch between the two n-alkane components, and therefore its concentration is highly dependent on the composition of the mixture. (ii) The second type of conformational disorder is that inherent to phase II; therefore, the concentration of this type of disorder is nearly independent of composition.

Original languageEnglish (US)
Pages (from-to)5260-5267
Number of pages8
JournalJournal of Physical Chemistry
Volume89
Issue number24
DOIs
StatePublished - Jan 1 1985

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

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