Conformational disorder in crystalline n-alkanes prior to melting

By means of infrared spectroscopy, the concentration of gauche bonds has been monitored as a function of increasing temperature for the crystalline n-alkanes, C{sub n}, n = 17, 25, 36, 50, and 60. For each n-alkane, the number of gauche bonds, and hence the degree of conformational disorder, is foun...

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Veröffentlicht in:Journal of physical chemistry (1952) 1989-10, Vol.93 (21), p.7520-7526
Hauptverfasser: Kim, Yesook, Strauss, H. L, Snyder, R. G
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container_title Journal of physical chemistry (1952)
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creator Kim, Yesook
Strauss, H. L
Snyder, R. G
description By means of infrared spectroscopy, the concentration of gauche bonds has been monitored as a function of increasing temperature for the crystalline n-alkanes, C{sub n}, n = 17, 25, 36, 50, and 60. For each n-alkane, the number of gauche bonds, and hence the degree of conformational disorder, is found to increase as the melting point is approached. The temperature at which the increase in disorder becomes measurable is 10-40 K below the melting point. For C{sub 17}, C{sub 25}, and C{sub 36}, the increase begins abruptly and occurs in association with a solid-solid phase transition. However, for the C{sub 50} and C{sub 60}, the onset of disorder is not associated with a solid-solid transition and occurs gradually. Therefore, C{sub 50} and C{sub 60} can be said to undergo true premelting. Although the onset of disordering for the shorter chains (C{sub 17}, C{sub 25}, C{sub 36}) occurs abruptly and that for the longer chains (C{sub 50}, C{sub 60}) gradually, there are, otherwise, close similarities. The similarities are in the width of the temperature range over which disordering occurs, in the total concentration of the disorder, and in its distribution. These similarities suggest a common disordering mechanism. Our earlier studies on conformational disorder for crystalline n-alkanes in the hexagonal phase suggest that the disordering mechanism involves longitudinal diffusion. In addition to premelting disorder, we have observed an inherent or background disorder for melt crystallized samples. The concentration of this disorder is temperature independent up to the temperature of premelting and, on a gauche bond per chain basis, has essentially the same value for all the n-alkanes studied here. The origin of this disorder is not clear, but it is probably associated with the lamellar surface.
doi_str_mv 10.1021/j100358a050
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L ; Snyder, R. G</creator><creatorcontrib>Kim, Yesook ; Strauss, H. L ; Snyder, R. G</creatorcontrib><description>By means of infrared spectroscopy, the concentration of gauche bonds has been monitored as a function of increasing temperature for the crystalline n-alkanes, C{sub n}, n = 17, 25, 36, 50, and 60. For each n-alkane, the number of gauche bonds, and hence the degree of conformational disorder, is found to increase as the melting point is approached. The temperature at which the increase in disorder becomes measurable is 10-40 K below the melting point. For C{sub 17}, C{sub 25}, and C{sub 36}, the increase begins abruptly and occurs in association with a solid-solid phase transition. However, for the C{sub 50} and C{sub 60}, the onset of disorder is not associated with a solid-solid transition and occurs gradually. Therefore, C{sub 50} and C{sub 60} can be said to undergo true premelting. Although the onset of disordering for the shorter chains (C{sub 17}, C{sub 25}, C{sub 36}) occurs abruptly and that for the longer chains (C{sub 50}, C{sub 60}) gradually, there are, otherwise, close similarities. The similarities are in the width of the temperature range over which disordering occurs, in the total concentration of the disorder, and in its distribution. These similarities suggest a common disordering mechanism. Our earlier studies on conformational disorder for crystalline n-alkanes in the hexagonal phase suggest that the disordering mechanism involves longitudinal diffusion. In addition to premelting disorder, we have observed an inherent or background disorder for melt crystallized samples. The concentration of this disorder is temperature independent up to the temperature of premelting and, on a gauche bond per chain basis, has essentially the same value for all the n-alkanes studied here. 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L</creatorcontrib><creatorcontrib>Snyder, R. G</creatorcontrib><title>Conformational disorder in crystalline n-alkanes prior to melting</title><title>Journal of physical chemistry (1952)</title><addtitle>J. Phys. Chem</addtitle><description>By means of infrared spectroscopy, the concentration of gauche bonds has been monitored as a function of increasing temperature for the crystalline n-alkanes, C{sub n}, n = 17, 25, 36, 50, and 60. For each n-alkane, the number of gauche bonds, and hence the degree of conformational disorder, is found to increase as the melting point is approached. The temperature at which the increase in disorder becomes measurable is 10-40 K below the melting point. For C{sub 17}, C{sub 25}, and C{sub 36}, the increase begins abruptly and occurs in association with a solid-solid phase transition. However, for the C{sub 50} and C{sub 60}, the onset of disorder is not associated with a solid-solid transition and occurs gradually. Therefore, C{sub 50} and C{sub 60} can be said to undergo true premelting. Although the onset of disordering for the shorter chains (C{sub 17}, C{sub 25}, C{sub 36}) occurs abruptly and that for the longer chains (C{sub 50}, C{sub 60}) gradually, there are, otherwise, close similarities. The similarities are in the width of the temperature range over which disordering occurs, in the total concentration of the disorder, and in its distribution. These similarities suggest a common disordering mechanism. Our earlier studies on conformational disorder for crystalline n-alkanes in the hexagonal phase suggest that the disordering mechanism involves longitudinal diffusion. In addition to premelting disorder, we have observed an inherent or background disorder for melt crystallized samples. The concentration of this disorder is temperature independent up to the temperature of premelting and, on a gauche bond per chain basis, has essentially the same value for all the n-alkanes studied here. 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G</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a424t-729dd337b8a9376dfc3cfd09c6909359b88463066b3b811acc5e4655816bff1c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1989</creationdate><topic>ALKANES</topic><topic>Condensed matter: structure, mechanical and thermal properties</topic><topic>CONFORMATIONAL CHANGES</topic><topic>CRYSTAL-PHASE TRANSFORMATIONS</topic><topic>Crystalline state (including molecular motions in solids)</topic><topic>Crystallographic aspects of phase transformations; pressure effects</topic><topic>DATA</topic><topic>DATA ANALYSIS</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>HYDROCARBONS</topic><topic>INFORMATION</topic><topic>INFRARED SPECTRA</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>MEASURING INSTRUMENTS</topic><topic>MEASURING METHODS</topic><topic>MELTING</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>PHASE TRANSFORMATIONS</topic><topic>Physics</topic><topic>SPECTRA 400201 -- Chemical &amp; Physicochemical Properties</topic><topic>Structure of solids and liquids; crystallography</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kim, Yesook</creatorcontrib><creatorcontrib>Strauss, H. L</creatorcontrib><creatorcontrib>Snyder, R. G</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of physical chemistry (1952)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kim, Yesook</au><au>Strauss, H. L</au><au>Snyder, R. G</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Conformational disorder in crystalline n-alkanes prior to melting</atitle><jtitle>Journal of physical chemistry (1952)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1989-10</date><risdate>1989</risdate><volume>93</volume><issue>21</issue><spage>7520</spage><epage>7526</epage><pages>7520-7526</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><coden>JPCHAX</coden><abstract>By means of infrared spectroscopy, the concentration of gauche bonds has been monitored as a function of increasing temperature for the crystalline n-alkanes, C{sub n}, n = 17, 25, 36, 50, and 60. For each n-alkane, the number of gauche bonds, and hence the degree of conformational disorder, is found to increase as the melting point is approached. The temperature at which the increase in disorder becomes measurable is 10-40 K below the melting point. For C{sub 17}, C{sub 25}, and C{sub 36}, the increase begins abruptly and occurs in association with a solid-solid phase transition. However, for the C{sub 50} and C{sub 60}, the onset of disorder is not associated with a solid-solid transition and occurs gradually. Therefore, C{sub 50} and C{sub 60} can be said to undergo true premelting. Although the onset of disordering for the shorter chains (C{sub 17}, C{sub 25}, C{sub 36}) occurs abruptly and that for the longer chains (C{sub 50}, C{sub 60}) gradually, there are, otherwise, close similarities. The similarities are in the width of the temperature range over which disordering occurs, in the total concentration of the disorder, and in its distribution. These similarities suggest a common disordering mechanism. Our earlier studies on conformational disorder for crystalline n-alkanes in the hexagonal phase suggest that the disordering mechanism involves longitudinal diffusion. In addition to premelting disorder, we have observed an inherent or background disorder for melt crystallized samples. The concentration of this disorder is temperature independent up to the temperature of premelting and, on a gauche bond per chain basis, has essentially the same value for all the n-alkanes studied here. The origin of this disorder is not clear, but it is probably associated with the lamellar surface.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/j100358a050</doi><tpages>7</tpages></addata></record>
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ispartof Journal of physical chemistry (1952), 1989-10, Vol.93 (21), p.7520-7526
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source American Chemical Society Journals
subjects ALKANES
Condensed matter: structure, mechanical and thermal properties
CONFORMATIONAL CHANGES
CRYSTAL-PHASE TRANSFORMATIONS
Crystalline state (including molecular motions in solids)
Crystallographic aspects of phase transformations
pressure effects
DATA
DATA ANALYSIS
Exact sciences and technology
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MEASURING INSTRUMENTS
MEASURING METHODS
MELTING
NUMERICAL DATA
ORGANIC COMPOUNDS
PHASE TRANSFORMATIONS
Physics
SPECTRA 400201 -- Chemical & Physicochemical Properties
Structure of solids and liquids
crystallography
title Conformational disorder in crystalline n-alkanes prior to melting
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