Investigation of the Potential Energy Surface for the First Step in the Alkaline Hydrolysis of Methyl Acetate

The potential energy surface for the first step of the alkaline hydrolysis of methyl acetate was explored by a variety of methods. The conformational search routine within SPARTAN was used to determine the lowest energy am1 and pm3 structures for the anionic tetrahedral intermediate. Ab initio single point and geometry optimization calculations were performed to determine the lowest energy conformer, and the linear synchronous transition (lst) method was used to provide an initial structure for transition state optimization. Transition states were obtained at the am1, pm3, 3-21G, and 3-21 + G levels of theory. These transition states were compared with the anionic tetrahedral intermediates to examine the assumption that the intermediate is a good model for the transition state. In addition, the Cramer/Truhlar sm3 solvation model was used at the semiempirical level to compare gas phase and aqueous alkaline hydrolysis of methyl acetate.

Pople's Gaussian-3 model chemistry applied to an investigation of (H2O)8 water clusters

The Gaussian-3 method developed by Pople and coworkers has been used to calculate the free energy of neutral octamer clusters of water, (H2O)8. The most energetically stable structures are in excellent agreement with those determined from experiment and those predicted from previous high-level calculations. Cubic structures are favored over noncubic structures over all temperature ranges studied. The D2d cubic structure is the lowest free energy structure and dominates the potential energy and free energy hypersurfaces from 0 K to 298 K.

Hydraulic Conductivity of Model Soil-Bentonite Backfills Subjected to Wet-Dry Cycling

The potential for changes in hydraulic conductivity, k, of two model soil-bentonite (SB) backfills subjected to wet-dry cycling was investigated. The backfills were prepared with the same base soil (clean, fine sand) but different bentonite contents (2.7 and 5.6 dry wt %). Saturation (S), volume change, and k of consolidated backfill specimens (effective stress = 24 kPa) were evaluated over three to seven cycles in which the matric suction, Ym, in the drying stage ranged from 50 to 700 kPa. Both backfills exhibited susceptibility to degradation in k caused by wet-dry cycling. Mean values of k for specimens dried at Ym = 50 kPa (S = 30-60 % after drying) remained low after two cycles, but increased by 5- to 300-fold after three or more cycles. Specimens dried at Ym ≥ 150 kPa (S < 30 % after drying) were less resilient and exhibited 500- to 10 000-fold increases in k after three or more cycles. The greater increases in k for these specimens correlated with greater vertical shrinkage upon drying. The findings suggest that increases in hydraulic conductivity due to wet-dry cycling may be a concern for SB vertical barriers located within the zone of a fluctuating groundwater table.