Crystal structures of n-alkanes with branches of different size in the middle

Keisuke Ikedou, Hiroko Yamamoto, Hideo Nagashima, Norio Nemoto, Kohji Tashiro

Research output: Contribution to journalArticle

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Abstract

We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P212121) and the triclinic (P1̄) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches.

Original languageEnglish
Pages (from-to)10668-10675
Number of pages8
JournalJournal of Physical Chemistry B
Volume109
Issue number21
DOIs
Publication statusPublished - Jun 2 2005

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Alkanes
Paraffins
alkanes
Crystal structure
crystal structure
Raman Spectrum Analysis
Phase Transition
Interfacial energy
X-Ray Diffraction
Computer Simulation
spectroscopy
Freezing
surface energy
Melting point
Raman spectroscopy
solid phases
Infrared spectroscopy
Carbon
computerized simulation
Phase transitions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Crystal structures of n-alkanes with branches of different size in the middle. / Ikedou, Keisuke; Yamamoto, Hiroko; Nagashima, Hideo; Nemoto, Norio; Tashiro, Kohji.

In: Journal of Physical Chemistry B, Vol. 109, No. 21, 02.06.2005, p. 10668-10675.

Research output: Contribution to journalArticle

Ikedou, Keisuke ; Yamamoto, Hiroko ; Nagashima, Hideo ; Nemoto, Norio ; Tashiro, Kohji. / Crystal structures of n-alkanes with branches of different size in the middle. In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 21. pp. 10668-10675.
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