Effect of pressure on the e{sup -} + pyrimidine pyrimidine{sup -} equilibrium in nonpolar solvents
- Brookhaven National LAb., Upton, NY (United States)
The thermodynamics of the equilibrium reaction e{sup -} + pyrimidine pyrimidine{sup -} was studied in tetramethylsilane (TMS) and 2,2,4-trimethylpentane (TMP) as solvents. In hexane, only the forward attachment reaction could be observed. The attachment rate constants (k{sub a}) increase with temperature in all solvents. The equilibrium shifts to the right with increasing pressure because of the large, negative reaction volumes (-200 to -330 cm{sup 3}/mol). The volume changes are consistent with electrostriction by the pyrimidine anion when a glass shell of solvent molecules is included. The free energy of reaction at 299 K is -0.43 eV in tetramethylsilane at 1 bar and -0.70 eV in 2,2,4-trimethylpentane at 150 bar. The solution free energies indicate the gas-phase (adiabatic) electron affinity of pyrimidine is -0.24 eV. 31 refs., 5 figs., 5 tabs.
- Research Organization:
- Brookhaven National Laboratory (BNL), Upton, NY
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 226770
- Journal Information:
- Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 11 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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