ДИМЕРИЗАЦИЯ ИЗОМЕРОВ ФТОРСПИРТОВ CnF2n+1CKH2k+1OH С ПРОТИВОПОЛОЖНЫМ НАПРАВЛЕНИЕМ ЗАКРУЧИВАНИЯ ФТОРУГЛЕРОДНЫХ РАДИКАЛОВ НА ПОВЕРХНОСТИ РАЗДЕЛА ФАЗ ВОДА/ВОЗДУХ
Електронний архів E-archive DonNTU – (Electronic archive Donetsk National Technical University)
Переглянути архів Інформація| Поле | Співвідношення | |
| Title |
ДИМЕРИЗАЦИЯ ИЗОМЕРОВ ФТОРСПИРТОВ CnF2n+1CKH2k+1OH С ПРОТИВОПОЛОЖНЫМ НАПРАВЛЕНИЕМ ЗАКРУЧИВАНИЯ ФТОРУГЛЕРОДНЫХ РАДИКАЛОВ НА ПОВЕРХНОСТИ РАЗДЕЛА ФАЗ ВОДА/ВОЗДУХ
DIMERIZATION OF FLUOROALCOHOL ISOMERS CnF2n+1CkH2k+1OH WITH THE OPPOSITE DIRECTION OF TWISTING OF THE FLUOROCARBON RADICALS AT THE AIR/WATER INTERFACE |
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| Creator |
Болдырева, Фаина Леонидовна
Беляева, Елена Александровна Высоцкий, Юрий Борисович |
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| Subject |
димеры
поверхность раздела вода/воздух фторспирты термодинамические параметры dimers water/air interface fluoroalcohols thermodynamic parameters |
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| Description |
В данной работе были изучены особенности димеризации изомеров фторспиртов с противоположным направлением закручивания фторуглеродных радикалов с общей формулой CnF2n+1CkH2k+1OH на поверхности раздела фаз вода/воздух. В рамках полуэмперического метода PM3 были рассчитаны термодинамические параметры образования и димеризации димеров фторспиртов, в которых спираль одного из мономеров закручена вправо, второго – влево. Показано, что самопроизвольная димеризация таких структур начинается длине фторуглеродного радикала 9-10 атомов углерода.
In this paper dimerization of the fluoroalcohols isomers with the opposite direction of twisting of the fluorocarbon radicals with the common formula CnF2n+1CkH2k+1OH at the air/water interface. It is known that fluorocarbon radicals are spiral-like and this influences strongly on its properties in particular their thermodynamic parameters of dimerization. Earlier thermodynamic parameters (enthalpy, entropy and Gibbs’ energy) for the structures with the same direction of twisting of fluorocarbon radicals were calculated. Spontaneous dimerization for such structures starts for the structures possess 4-5 carbon atoms. Now our aim was to investigate if the change of direction of the twisting of one monomer in dimer influence on its dimerization parameters. So in the frameworks of the semiempirical PM3 method thermodynamic parameters of the dimers of fluoroalcohols which possess one monomer twisted clockwise and another twisted counter-clockwise. Due to spiral-like structure of the fluorocarbon radical thermodynamic properties of such dimers have periodic character. There two regions in molecule of fluoroalcohols: with the intermolecular distance between Fluor atoms of the two monomers in dimer less than 2.7 nm and with intermolecular distance more than 2.7 nm. Dependencies of thermodynamic parameters of dimerization on the number of the intermolecular H-H and F-F interactions were gotten. Spontaneous dimerization for such structures starts when the length of the fluorocarbon radical is equal to 9-10 Carbon atoms. So formation dimers of fluoroalcohols with the same direction of twisting of fluorocarbon radicals is more thermodynamically preferable then formation dimers with the opposite twisting of fluorocarbon radicals. In this paper dimerization of the fluoroalcohols isomers with the opposite direction of twisting of the fluorocarbon radicals with the common formula CnF2n+1CkH2k+1OH at the air/water interface. It is known that fluorocarbon radicals are spiral-like and this influences strongly on its properties in particular their thermodynamic parameters of dimerization. Earlier thermodynamic parameters (enthalpy, entropy and Gibbs’ energy) for the structures with the same direction of twisting of fluorocarbon radicals were calculated. Spontaneous dimerization for such structures starts for the structures possess 4-5 carbon atoms. Now our aim was to investigate if the change of direction of the twisting of one monomer in dimer influence on its dimerization parameters. So in the frameworks of the semiempirical PM3 method thermodynamic parameters of the dimers of fluoroalcohols which possess one monomer twisted clockwise and another twisted counter-clockwise. Due to spiral-like structure of the fluorocarbon radical thermodynamic properties of such dimers have periodic character. There two regions in molecule of fluoroalcohols: with the intermolecular distance between Fluor atoms of the two monomers in dimer less than 2.7 nm and with intermolecular distance more than 2.7 nm. Dependencies of thermodynamic parameters of dimerization on the number of the intermolecular H-H and F-F interactions were gotten. Spontaneous dimerization for such structures starts when the length of the fluorocarbon radical is equal to 9-10 Carbon atoms. So formation dimers of fluoroalcohols with the same direction of twisting of fluorocarbon radicals is more thermodynamically preferable then formation dimers with the opposite twisting of fluorocarbon radicals. |
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| Date |
2013-04-12T15:39:49Z
2013-04-12T15:39:49Z 2013 |
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| Type |
Article
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| Identifier |
2074-6652
УДК 539.192 http://ea.donntu.edu.ua/handle/123456789/18451 |
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| Relation |
Наукові праці ДонНТУ;Серія: Хімія і хімічна технологія, 2013. - Вип.2(21). - С.22-28
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| Publisher |
Донецк, ДонНТУ
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