AN ELECTRON SPIN RESONANCE STUDY OF S2O6F2-SO3F. EQUILIBRIUM . ENTHALPY OF CLEAVAGE

被引:27
作者
NUTKOWIT.PM
VINCOW, G
机构
[1] Department of Chemistry, University of Washington, Seattle
关键词
D O I
10.1021/ja01050a005
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The fluorosulfate free radical (SO3F·, II) is produced by the homolytic thermal cleavage of neat liquid peroxydisulfuryl difluoride (S2O6F2, I), and its esr spectrum is investigated over the temperature range 4°  t  180°. The spectrum consists of a single structureless component with g = 2.0108 ± 0.0001 and a width which is unusually large and is temperature dependent [ΔHms ≍ 25 G (17°); ΔHms ≍ 48 G (180°)]. An analysis of measurements of the esr intensity as a function of temperature (125°  t  150°) leads to a determination of the enthalpy of thermal dissociation of I. The value obtained is 22.4 ± 0.9 kcal/mole. This result is in good agreement with values of the enthalpy change for this reaction in the gas phase which have been previously obtained using PVT and spectrophotometric techniques. © 1969, American Chemical Society. All rights reserved.
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页码:5956 / +
页数:1
相关论文
共 16 条
[1]   OXIDES AND OXYIONS OF NON-METALS .2. CO2- AND NO2 [J].
ATKINS, PW ;
SYMONS, MCR ;
KEEN, N .
JOURNAL OF THE CHEMICAL SOCIETY, 1962, (AUG) :2873-&
[2]   DAS GLEICHGEWICHT F2S2O6 EQUALS 2FSO3 DAS ABSORPTIONSSPEKTRUM DES RADIKALS FSO3 UND DIE KINETIK DER THERMISCHEN REAKTION ZWISCHEN BIS-SULFURYLFLUORIDPEROXID UND SCHWEFELTETRAFLUORID [J].
CASTELLANO, E ;
SICRE, JE ;
GATTI, R ;
SCHUMACHER, HJ .
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-FRANKFURT, 1964, 42 (3-4) :174-&
[3]   ESR OF N2F4-NF2 EQUILIBRIUM [J].
DOORENBOS, HE ;
LOY, BR .
JOURNAL OF CHEMICAL PHYSICS, 1963, 39 (09) :2393-&
[4]   EQUILIBRIUM BETWEEN PEROXYDISULFURYL DIFLUORIDE AND FLUOROSULFATE FREE RADICALS [J].
DUDLEY, FB ;
CADY, GH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (21) :3375-&
[5]   PEROXYDISULFURYL DIFLUORIDE [J].
DUDLEY, FB ;
CADY, GH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1957, 79 (03) :513-514
[6]  
ETTINGER R, 1963, INORG CHEM, V2, P1311
[7]   PARAMAGNETIC RESONANCE OF LIQUID SULFUR - DETERMINATION OF MOLECULAR PROPERTIES [J].
GARDNER, DM ;
FRAENKEL, GK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1956, 78 (14) :3279-3288
[8]  
HOLM CH, 1956, B AM PHYS SOC, P397
[9]   RADICAL DECOMPOSITION OF PEROXYSULFURYL DIFLUORIDE FSO2OOF AND RELATED COMPOUNDS BY CHEMICAL AND ELECTRON PARAMAGNETIC RESONANCE METHODS [J].
NEUMAYR, F ;
VANDERKO.N .
INORGANIC CHEMISTRY, 1965, 4 (08) :1234-&
[10]  
NUTKOWITZ PM, 1967, THESIS U WASHINGTON