Thermodynamic Properties of Organic Compounds: Estimation Methods, Principles and Practice, Revised Edition focuses on the progression of practical methods in computing the thermodynamic characteristics of organic compounds. Divided into two parts with eight chapters, the book concentrates first on the methods of estimation. Topics presented are statistical and combined thermodynamic functions; free energy change and equilibrium conversions; and estimation of thermodynamic properties. The next discussions focus on the thermodynamic properties of simple polyatomic systems by statistical thermodynamic methods. Discussed are molecular energy of an ideal gas; partition function and thermodynamic properties; and calculation of statistical thermodynamic functions. The book also notes the dynamic properties of long chain hydrocarbons and the method of structural similarity. Tabulations and numerical representations are presented as well. Discussions also focus on methods of group contributions and group equations. Included are paraffins, unsaturated carbons, cyclic hydrocarbons, and nonhydrocarbon groups. The last part of the text focuses on heat formation and heat capacity; the applications of thermodynamic method; and numerical data. Included in the discussions are bond energies and binding energies; gaseous free radicals and ions; and hydrogenation of benzene. The book is an important source of data for readers interested in studying the thermodynamic characteristics of organic compounds.

For more than 100 years the Beilstein Handbook has been publishing checked and evaluated data on organic compounds. It has become the major reference book for the chemical and physical properties of organic com pounds. The prediction of these physical properties was the subject of the Beilstein workshop. The ability to predict physical properties is for several reasons of great interest to the Beilstein Institute. It is of primary importance to be able to check the abstracted data for accuracy and to eliminate simple mistakes like typing errors. Presently all the work whether manuscript writing or evaluation of data is carried out manually. This is very time consuming, with the entry of Beilstein into electronic data gathering and publication, the opportunity for computerized consistency checking has become available. Contrary to belief, when one examines the Beilstein Handbook or Chemical Abstracts there is a dearth of chemical information. There are a great many compounds but few are well defined resulting in large gaps in the information available to the chemist. These information gaps could be filled by using algorithmic methods to estimate the properties of interest. An important question to answer is "What is the chemist's reaction to estimated data?" Will he accept it for use, within limits defined by the method, or will it be unacceptable and therefore detrimental for the data base. However if one could partly fill gaps in the data base the increase in the power of the search techniques would be marked.

This research suggests two new group contribution methods to facilitate phase behavior calculation when reliable experimental data are lacking. The first method pertains to the implementation of an updated version of the Elliott and Natarajan method to the Statistical Associating Fluid Theory (SAFT) and Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) equations of state. Shape factor parameters have been correlated for 878 compounds including different variety of families and the parameters from Elliott and Natarajan have been updated to improve accuracy for alcohols. Thereafter, thermodynamic properties such as boiling temperatures and vapor pressures have been predicted. We obtain 36%, 65%, and 32% AAD% in pressures for the ESD, SAFT, and PC-SAFT equations of state. Additionally, we have compared our GC-PC-SAFT to the one by Tihic et al., applying their suggested First-Order and Second-Order groups for 650 non-associating compounds. We observed higher accuracy for our method relative to the Tihic et al. The resulting P AAD% were 53% for Tihic FOG and 42% for Tihic SOG. The second method suggests a new group contribution model for Tb at 760mmHg and Tb at 10 mmHg. These correlations recognize a finite limit in boiling temperature as infinite molecular weight is approached. The availability of two vapor pressures enables straightforward application of the Clausius-Clapeyron equation to estimate boiling temperatures at other points. In the presented approach, there are 3 parameters and 72 functional groups for each temperature which are regressed through a database consisting of 336 hydrocarbons and 642 non-hydrocarbons. The average absolute percent deviations (AAD%) between the correlated and experimental temperatures are calculated in comparison with Joback-Reid and Gani approaches. We obtain 3.5, 4.7, and 4.1 AAD% in temperature for the present work, Joback, and Gani methods, respectively. Additionally, the accuracy of the present work is evaluated by calculating the vapor pressures from the DIPPR correlation at the predicted temperatures of each model. We obtained 33.2, 104.3 and 48.1 AAD% in pressure for the present work, Joback, and Gani methods. Finally, the accuracy of the presented correlations are tested against Asher and Pankow model, UNIFAC-PL°, for 66 volatile compounds in the temperature range of 290-320 K. For the vapor pressure at the 10mmHg boiling temperature, we obtain 36.9 AAD% for the present work and 94.5 AAD% for the Asher method. Overall, these group contribution methods establish a standard for comparison of more fundamental methods like molecular simulations with transferable potentials. Transferable potentials generally provide accuracy of 10-30AAD% in pressure, but have only been developed for relatively small databases over narrow temperature ranges.