dc.contributor.author |
Klimovitskiǐ A. |
|
dc.contributor.author |
Remizov A. |
|
dc.contributor.author |
Skvortsov A. |
|
dc.contributor.author |
Fishman A. |
|
dc.date.accessioned |
2018-09-17T21:46:54Z |
|
dc.date.available |
2018-09-17T21:46:54Z |
|
dc.date.issued |
2004 |
|
dc.identifier.issn |
0036-0244 |
|
dc.identifier.uri |
https://dspace.kpfu.ru/xmlui/handle/net/135427 |
|
dc.description.abstract |
The IR spectra and the exo ⇄ endo conformational equilibrium of 1,9,10,11,12,12-hexachloro-4,6-dioxatricyclo[9,2,1,02,8]dodeca-10- ene (HCA) in carbon disulfide were studied in the temperature range 230-300 K. The difference of the enthalpies was found to be 2.7(2) kJ/mol in favor of the exo conformer. The kinetics of the conformational transition of HCA in acetone-d6 and carbon disulphide was studied in the temperature range 213-220 K. The enthalpies ΔH≠exo and entropies ΔS≠exo of activation of the exo → endo conformational transition were found to be ΔH≠exo = 51(4) and 70(2) kJ/mol and ΔS≠exo = -76(20) and -11(7) J/(mol K) in acetone-d 6 and carbon disulphide, respectively. The ratios between the absorption coefficients of the endo and exo conformer bands (727 cm -1 and 786 cm-1, respectively) were found to be 0.63(9) in acetone-d6 and 0.65(5) in carbon disulfide. The differences of the entropies of the HCA conformers in these solvents [ΔS° = -5(2) J/(mol K)] were determined. The absorption bands were assigned based on the results of quantum-chemical ab initio calculations. |
|
dc.relation.ispartofseries |
Russian Journal of Physical Chemistry A |
|
dc.title |
An IR spectroscopic study of the kinetics of conformational transitions of 1,9,10,11,12,12-hexachloro-4,6-dioxatricyclo[9,2,1,02,8]dodeca-10- ene in solutions |
|
dc.type |
Article |
|
dc.relation.ispartofseries-issue |
2 |
|
dc.relation.ispartofseries-volume |
78 |
|
dc.collection |
Публикации сотрудников КФУ |
|
dc.relation.startpage |
249 |
|
dc.source.id |
SCOPUS00360244-2004-78-2-SID1642398951 |
|