Hydrolysis of COS on Titania Catalysts

Huisman, Henk; Berg, Patrik; Mos, R.; Dillen, A.J. van; Geus, J.W.

doi:10.1021/bk-1994-0552.ch032

Cited by 7 publications

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“…5 Therefore, the development of cost-effective and environmentally conscious technologies for the control of CS 2 is desirable and of an increased interest. [4][5][6] Some methods have been developed for the removal of carbon disulfide, including catalyzed-hydrogenation, 7 oxidation, 3,8,9 hydrolysis, [10][11][12] etc., in which the hydrolysis of CS 2 was recognized as the most promising process due to the mild reaction condition, cheapness, and higher conversion efficiency. The kinetics of CS 2 hydrolysis has been the subject of numerous research papers.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][10][11][12] There had been some experimental studies on the rate and mechanisms for the hydrolysis of carbon disulfide in natural water, 10 and the catalyzed CS 2 hydrolysis reaction by transition metals, for example, nanosized titania and zirconia, over a wide pH range in aqueous solution. 11,12 Even though the reaction has been studied experimentally in detail, few theoretical calculations have been performed on the hydrolysis of CS 2 . Luther studied the kinetics of the reaction of water with CO 2 , COS, and CS 2 using semiempirical PM3 calculation and frontier molecular orbital analysis, 13 indicating that the hydrolysis via water catalysis is retarded as the number of S atoms.…”

Section: Introductionmentioning

confidence: 99%

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Neutral hydrolyses of carbon disulfide: Anab initiostudy of water catalysis

Deng

Sun

et al. 2008

J Comput Chem

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The water-catalyzed hydrolysis reaction of carbon disulfide (CS(2)) has been investigated at the levels of HF and MP2 with the basis set of 6-311++G(d,p) using the combined supramolecular/continuum models, in which up to six water molecules are involved in the hydrolysis and the effect of water bulk solvent is taken into account according to the polarizable continuum model (PCM). The activation Gibbs free energies in water solution, DeltaG(sol) (not equal) (298 K), for the rate-determining steps of one up to six water hydrolyses are 247.9, 184.2, 152.3, 141.8, 134.4, and 118.9 kJ/mol, respectively. The most favorable hydrolysis path of CS(2) involves a sort of eight-membered ring transition structure formed by six water molecules, among which three water molecules are not involved in the proton transfer, two near to the nonreactive sulfur atom, and one below the parent carbon disulfide. This suggests that the hydrolysis of CS(2) can be mediated with the water molecule(s) and be significantly facilitated by the cooperative effects of the water molecule(s) in the nonreactive region. The catalytic effects of water molecule(s) due to the alleviation of ring strain in the proton transfer process may result from the synergistic effects of rehybridization and charge reorganization from the prereaction complex to the rate-determining transition state structure induced by water molecule(s). PCM solvation models could significantly lower the rate-determining activation Gibbs free energies by 20-38 kJ/mol when two up to six explicit water molecules involved in the neutral hydrolysis of CS(2).

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