TPEPICO spectroscopy of vinyl chloride and vinyl iodide: neutral and ionic heats of formation and bond energies.
The 0 K dissociative ionization onsets of C2H3X --> C2H3(+) + X (X = Cl, I) are measured by threshold photoelectron-photoion coincidence spectroscopy. The heats of formation of C2H3Cl (Delta H(f,0K)(0) = 30.2 +/- 3.2 kJ mol(-1) and Delta(H f,298K)(0) = 22.6 +/- 3.2 kJ mol(-1)) and C2H3I (Delta(H f,0K)(0) = 140.2 +/- 3.2 kJ mol(-1) and Delta(H f,298K)(0) = 131.2 +/- 3.2 kJ mol(-1)) and C- X bond dissociation enthalpies as well as those of their ions are determined. The data help resolve a longstanding discrepancy among experimental values of the vinyl chloride heat of formation, which now agrees with the latest theoretical determination. The reported vinyl iodide heat of formation is the first reliable experimental determination. Additionally, the adiabatic ionization energy of C2H3I (9.32 +/- 0.01 eV) is measured by threshold photoelectron spectroscopy.
Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA.
Nicholas S
NS
Shuman
Melony A
MA
Ochieng
Bálint
B
Sztáray
Tomas
T
Baer
D002273:Carcinogens / Q000737:chemistry*; D007455:Iodine; D013057:Spectrum Analysis; D013816:Thermodynamics; D014752:Vinyl Chloride / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry
D002273:Carcinogens; D014753:Vinyl Compounds; D007455:Iodine; D014752:Vinyl Chloride