Temperature dependence of the rate and activation parameters for tert-butyl chloride solvolysis: Monte Carlo simulation of confidence intervals

A new treatment of the solvent effect on the solvolysis of tert-butyl chloride is proposed. This treatment is based on activation free energy measurements and on transfer free energy measurements of the reactant (R) on the one hand and of a model (M) of the activated complex (AC) on the other hand. Solute–solvent interaction free energies for the reactant, the activated complex and the model compound are estimated. This estimation involves the calculation of the free energy of cavity formation of these various solutes (R, AC, and M) in all the solvents. These cavity terms, which are a function of the cohesive properties of the solvent and of the surface of the cavity do not reflect the electronic structure of the solute whereas the interaction free energy term does. The method we propose can be described as a new 'experimental' approach for the study of the charge separation in an activated complex.

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ChemInform Abstract: EVALUATION OF THE FORCE CONSTANT FOR THE CARBON-CHLORIDE STRETCHING VIBRATION FOR TERT-BUTYL CHLORIDE USING MINDO 3

Chemischer Informationsdienst ◽

10.1002/chin.197609044 ◽

1976 ◽

Vol 7 (9) ◽

pp. no-no

Author(s):

DONALD G. GRACZYK ◽

ROBERT L. JULIAN ◽

JAMES W. TAYLOR ◽

S. D. WORLEY

Keyword(s):

Force Constant ◽

Butyl Chloride ◽

Tert Butyl ◽

Stretching Vibration ◽

Tert Butyl Chloride

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Monte Carlo simulation and analysis of free-form surface registration

Proceedings of the Institution of Mechanical Engineers Part B Journal of Engineering Manufacture ◽

10.1243/0954405981516544 ◽

1997 ◽

Vol 211 (8) ◽

pp. 605-617 ◽

Cited By ~ 11

Author(s):

D Brujic ◽

M Ristic

Keyword(s):

Monte Carlo Simulation ◽

Monte Carlo ◽

Confidence Intervals ◽

Computer Aided Design ◽

Maximum Error ◽

Surface Registration ◽

Performance Criteria ◽

Free Form ◽

Registration Method ◽

Free Form Surfaces

Accurate dimensional inspection and error analysis of free-form surfaces requires accurate registration of the component in hand. Registration of surfaces defined as non-uniform rational B-splines (NURBS) has been realized through an implementation of the iterative closest point method (ICP). The paper presents performance analysis of the ICP registration method using Monte Carlo simulation. A large number of simulations were performed on an example of a precision engineering component, an aero-engine turbine blade, which was judged to possess a useful combination of geometric characteristics such that the results of the analysis had generic significance. Data sets were obtained through CAD (computer aided design)-based inspection. Confidence intervals for estimated transformation parameters, maximum error between a measured point and the nominal surface (which is extremely important for inspection) mean error and several other performance criteria are presented. The influence of shape, number of measured points, measurement noise and some less obvious, but not less important, factors affecting confidence intervals are identified through statistical analysis.

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