scholarly journals Application of a General Computer Algorithm Based on the Group-Additivity Method for the Calculation of two Molecular Descriptors at both Ends of Dilution: Liquid Viscosity and Activity Coefficient in Water at infinite Dilution

2017 ◽  
Author(s):  
Rudolf Naef ◽  
William E. Acree
Keyword(s):  
Activity Coefficient ◽  
Infinite Dilution ◽  
Goodness Of Fit ◽  
Cross Validation ◽  
Viscosity Coefficient ◽  
Computer Algorithm ◽  
Group Additivity ◽  
Liquid Viscosity ◽  
Fitting Method ◽  
Complete Breakdown

The application of a commonly used computer algorithm based on the group-additivity method for the calculation of the liquid viscosity coefficient at 292.15K and the activity coefficient at infinite dilution in water at 298.15K of organic molecules is presented. The method is based on the complete breakdown of the molecules into their constituting atoms, further subdividing them by their immediate neighbourhood. A fast Gauss-Seidel fitting method using experimental data from literature is applied for the calculation of the atom groups’ contributions. Plausibility tests have been carried out on each of the calculations using a 10-fold cross-validation procedure which confirms the excellent predictive quality of the method. The goodness of fit (Q2) and the standard deviation (σ) of the cross-validation calculations for the viscosity coefficient, expressed as log(η), was 0.9728 and 0.11, respectively, for 413 test molecules, and for the activity coefficient log(γ)∞ the corresponding values were 0.9736 and 0.31, respectively, for 621 test compounds. The present approach has proven its versatility in that it enabled at once the evaluation of the liquid viscosity of normal organic compounds as well as of ionic liquids.

scholarly journals Calculation of Five Thermodynamic Molecular Descriptors by Means of a General Computer Algorithm Based on the Group-Additivity Method: Standard Enthalpies of Vaporization, Sublimation and Solvation, and Entropy of Fusion of ordinary Organic Molecules and Total Phase-Change Entropy of Liquid Crystals

2017 ◽  
Author(s):  
Rudolf Naef ◽  
William E. Acree Jr.
Keyword(s):  
Liquid Crystals ◽  
Phase Change ◽  
Goodness Of Fit ◽  
Cross Validation ◽  
Organic Molecules ◽  
Enthalpy Of Fusion ◽  
Computer Algorithm ◽  
Group Additivity ◽  
Entropy Of Fusion ◽  
Total Phase

The calculation of the standard enthalpies of vaporization, sublimation and solvation of organic molecules is presented using a common computer algorithm on the basis of a group-additivity method. The same algorithm is also shown to enable the calculation of their entropy of fusion as well as the total phase-change entropy of liquid crystals. The present method is based on the complete break-down of the molecules into their constituting atoms and their immediate neighbourhood; the respective calculations of the contribution of the atomic groups by means of the Gauss-Seidel fitting method is based on experimental data collected from literature. The feasibility of the calculations for each of the mentioned descriptors was verified by means of a 10-fold cross-validation procedure proving the good to high quality of the predicted values for the three mentioned enthalpies and for the entropy of fusion, whereas the predictive quality for the total phase-change entropy of liquid crystals was poor. The goodness of fit (Q2) and the standard deviation (σ) of the cross-validation calculations for the five descriptors was as follows: 0.9641 and 4.56 kJ/mol (N=3386 test molecules) for the enthalpy of vaporization, 0.8657 and 11.39 kJ/mol (N=1791) for the enthalpy of sublimation, 0.9546 and 4.34 kJ/mol (N=373) for the enthalpy of solvation, 0.8727 and 17.93 J/mol/K (N=2637) for the entropy of fusion and 0.5804 and 32.79 J/mol/K (N=2643) for the total phase-change entropy of liquid crystals. The large discrepancy between the results of the two closely related entropies is discussed in detail. Molecules, for which both the standard enthalpies of vaporization and sublimation were calculable, enabled the estimation of their standard enthalpy of fusion by simple subtraction of the former from the latter enthalpy. For 990 of them the experimental enthalpy-of-fusion values are also known, allowing their comparison with predictions, yielding a correlation coefficient R2 of 0.6066.

scholarly journals Calculation of the Surface Tension of Ordinary Organic and Ionic Liquids by Means of a Generally Applicable Computer Algorithm Based on the Group—Additivity Method

2018 ◽  
Author(s):  
Rudolf Naef ◽  
William E. Acree
Keyword(s):  
Surface Tension ◽  
Ionic Liquids ◽  
Present Method ◽  
Goodness Of Fit ◽  
Direct Calculation ◽  
Computer Algorithm ◽  
Alkyl Chains ◽  
Fitting Method ◽  
Complete Breakdown ◽  
Fold Cross Validation

The calculation of the surface tension of ordinary organic and ionic liquids, based on a computer algorithm applying a refined group-additivity method, is presented. The refinement consists of a complete breakdown of the molecules into their constituting atoms, further distinguishing them by their immediate neighbour atoms and bond constitution. The evaluation of the atom-groups’ contributions was carried out by means of a fast Gauss-Seidel fitting method founded upon the experimental data of 1895 compounds from literature. The result has been tested for plausibility using a 10-fold cross-validation (cv) procedure. The direct calculation and the cv test proved the applicability of the present method by the close similarity and excellent goodness of fit R2 and Q2 of 0.9023 and 0.8821, respectively. The respective standard deviations are ±2.01 and ±2.16 dyn/cm. Some correlation peculiarities have been observed in a series of ordinary and ionic liquids with homologous alkyl chains which are illustrated and discussed in detail, exhibiting the limit of the present method.

scholarly journals Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at 298.15K by Means of a Generally Applicable Computer Algorithm Based on the Group-Additivity Method

2020 ◽  
Author(s):  
Rudolf Naef
Keyword(s):  
Experimental Data ◽  
Heat Capacity ◽  
Goodness Of Fit ◽  
Cross Validation ◽  
Solid Phase ◽  
Heat Capacities ◽  
Computer Algorithm ◽  
Molecular Volume ◽  
Complementary Method ◽  
Standard Deviations

The calculation of the isobaric heat capacities of the liquid and solid phase of molecules at 298.15 K is presented, applying a universal computer algorithm based on the atom-groups additivity method, using refined atom groups. The atom groups are defined as the molecules' constituting atoms and their immediate neighbourhood. In addition, the hydroxy group of alcohols are further subdivided to take account of the different intermolecular interactions of primary, secondary and tertiary alcohols. The evaluation of the groups' contributions has been carried out by means of a fast Gauss-Seidel fitting calculus using experimental data from literature. Plausibility has been tested immediately after each fitting calculation using a 10-fold cross-validation procedure. For the heat capacity of liquids, the respective goodness of fit of the direct (R2) and the cross-validation calculations (Q2) of 0.998 and 0.9975, and the respective standard deviations of 8.2 and 9.16 J/mol/K, together with a medium absolute percentage deviation (MAPD) of 2.69%, based on the experimental data of 1133 compounds, proves the excellent predictive applicability of the present method. The statistical values for the heat capacity of solids are only slightly inferior: for R2 and Q2, the respective values are 0.9915 and 0.9875, the respective standard deviations are 12.19 and 14.13 J/mol/K and the MAPD is 4.65%, based on 732 solids. The predicted heat capacities for a series of liquid and solid compounds has been directly compared to those received by a complementary method based on the "true" molecular volume [1] and their deviations elucidated.

Overview of Activity Coefficient of Thiophene at Infinite Dilution in Ionic Liquids and their Modeling Using COSMO-RS

2016 ◽  
Vol 55 (3) ◽  
pp. 788-797 ◽  
Author(s):  
Pranesh Matheswaran ◽  
Cecilia Devi Wilfred ◽  
Kiki A. Kurnia ◽  
Anita Ramli
Keyword(s):  
Ionic Liquids ◽  
Activity Coefficient ◽  
Infinite Dilution

Rapid Method to Determine Activity Coefficient at Infinite Dilution

1967 ◽  
Vol 31 (2) ◽  
pp. 123-126,a1
Author(s):  
Yasuo Hirose ◽  
Masashi Iino ◽  
Hitoshi Hiraiwa ◽  
Masamichi Hirata
Keyword(s):  
Activity Coefficient ◽  
Rapid Method ◽  
Infinite Dilution

Solvation effects on the conductivity of concentrated electrolyte solutions

1976 ◽  
Vol 54 (18) ◽  
pp. 2953-2966 ◽  
Author(s):  
Douglas E. Goldsack ◽  
Raymond Franchetto ◽  
Arlene (Anttila) Franchetto
Keyword(s):  
Activity Coefficient ◽  
Alkali Halide ◽  
Infinite Dilution ◽  
Electrolyte Solutions ◽  
Molar Conductance ◽  
The Other ◽  
Solvation Number ◽  
Parameter Equation ◽  
Conductance Data ◽  
Halide Salts

The Falkenhagen–Leist–Kelbg equation for the conductivity of electrolyte solutions has been extended to include the effect of solvation on the concentration of the salt. Two equations have been derived, both of which have only two freely adjustable parameters at any temperature: Λ0 the molar conductance of the salt at infinite dilution and H0, a solvation number parameter for the salt. In one of these equations H0 is assumed to be independent of concentration. In the other, H0 is assumed to be dependent on concentration and an explicit concentration dependent formula is derived for H0. Conductance data for the alkali halide salts in the 0.5 to 10 m concentration range and 0 to 60 °C temperature range were found to be adequately reproduced by both these equations, but with the variable hydration parameter equation yielding better fits to the data. The H0 parameters from the fixed hydration parameter equation are found to be similar to those obtained from the analysis of activity coefficient and other data whereas the variable hydration parameter equation yields H0 parameters which are much larger.

Evaluation of Safety Performance Functions Based on Experimental Design Using a Cross-Validation Method

2017 ◽  
Vol 2636 (1) ◽  
pp. 62-72 ◽  
Author(s):  
Jung-Han Wang ◽  
Mohamed A. Abdel-Aty ◽  
Jaeyoung Lee
Keyword(s):  
Goodness Of Fit ◽  
Cross Validation ◽  
Safety Performance ◽  
Major Road ◽  
Highway Safety Manual ◽  
Annual Average Daily Traffic ◽  
Minor Road ◽  
Safety Performance Functions ◽  
The One ◽  
Leave One Out

The Highway Safety Manual (HSM) Part C provides a series of safety performance functions (SPFs) for different roadway conditions. The SPFs suggested in the HSM are formulated on the basis of exposure variables: the logarithms of the annual average daily traffic (AADT) on the major road and on the minor road under the base condition. In this research, data from 7,802 intersections in Florida were collected and processed. These intersections were categorized into seven types based on area type (rural or urban), number of legs (three or four), and number of approaches controlled by stop signs. Twenty-two SPF formulations, including the one suggested by the HSM, were developed for each intersection type for examination of the goodness-of-fit measures of the SPFs. In addition, the goodness of fit of each model of the 22 SPFs in each category was examined with 10-fold leave-one-out cross-validation (LOOCV). With a comparison of the delta values generated with the LOOCV method, it is suggested that the SPF with the logarithm of the total entering vehicle volume and the ratio of the AADT on the minor road and the AADT on the major road are important. In addition, the SPFs with the AADT on the major road and the AADT on the minor road and their logarithmic transformations are also important. Therefore, it is suggested that the future HSM compare these two SPF formulations—as suggested in the current research, along with the original SPF formulation in the manual—and select the one with the best model fit on the basis of the delta value using LOOCV.

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