Experimental determination of the enthalpies of formation of formyl cyanide and thioformyl cyanide in the gas phase

被引:22
作者
Born, M [1 ]
Ingemann, S [1 ]
Nibbering, NMM [1 ]
机构
[1] UNIV AMSTERDAM, INST MASS SPECTROMETRY, NL-1018 WS AMSTERDAM, NETHERLANDS
关键词
D O I
10.1021/jp9609141
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The enthalpies of formation of formyl cyanide (HC(O)CN) and thioformyl cyanide (HC(S)CN) in the gas phase have been determined with the use of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry, The enthalpy of formation, Delta H-f degrees(298 K), of formyl cyanide is determined to be 26 +/- 20 kJ mol(-1), whereas the value for thioformyl cyanide is 222 +/- 30 kJ mol(-1). These enthalpies of formation are derived from experimental values of (i) the gas-phase acidities of the methylene groups in the CH3OCH2CN and CH3SCH2CN species (Delta H(acid)degrees(CH3OCH2CN) = 1556 +/- 8 kJ mol(-1) and Delta H(acid)degrees(CH3SCH2CN) = 1494 +/- 8 kJ mol(-1)), (ii) the enthalpy change for the dissociation of the <CH3O(C)over bar HCN> and <CH3S(C)over bar HCN> carbanions into a methyl radical and the radical anion of formyl cyanide and thioformyl cyanide, respectively (BDE(<CH3O(C)over bar HCN>) = 116 +/- 10 kJ mol(-1) and BDE(<CH3S(C)over bar HCN>) = 133 +/- 10 kJ mol(-1)), and (iii) the electron affinities of the neutral formyl species (EA(HC(O)CN) = 65 +/- 3 kJ mol(-1) and EA(HC(S)CN) = 159 +/- 15 kJ mol(-1)), The structures of the two carbanions and the radical anions of the (thio)formyl species have been ascertained by high kinetic energy (8 keV) collision-induced charge-reversal (CR) experiments performed with the use of a double-focusing quadrupole hybrid mass spectrometer.
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页码:17662 / 17669
页数:8
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