Eugene S. Domalski

Estimation of the thermodynamic properties of C-H-N-O-S-halogen compounds at 298.15 K

An estimation method, which was developed by S. W. Benson and coworkers for calculating the thermodynamic properties of organic compounds in the gas phase, has been extended to the liquid and solid phases for organic compounds at 298.15 K and 101,325 Pa. As with a previous paper dealing with hydrocarbon compounds, comparisons of estimated enthalpies of formation, heat capacities, and entropies with literature values show that extension of the Benson’s group additivity approach to the condensed phase is easy to apply and gives satisfactory agreement. Corresponding values for the entropy of formation, Gibbs energy of formation and natural logarithm of the equilibrium constant for the formation reaction are also calculated provided necessary auxiliary data are available. This work covers 1512 compounds containing the elements: carbon, hydrogen, oxygen, nitrogen, sulfur, and halogens in the gas, liquid, and solid phases. About 1000 references are provided for the literature values which are cited. §

Selected Values of Heats of Combustion and Heats of Formation of Organic Compounds Containing the Elements C, H, N, O, P, and S.

Selected values of the heats of combustion and heats of formation of 719 organic compounds are reported here. The data tabulated pertain to compounds containing the elements carbon, hydrogen, nitrogen, oxygen, phosphorus, and sulfur (CHNOPS). The information is arranged according to classes of compounds and within each class, compounds are arranged by empirical formula. The general classes covered are: hydrocarbons, alcohols, phenols, polyols, ethers, aldehydes, ketones, acids,acid anhydrides, esters, steroids, lactones, carbohydrates, heterocyclic oxygen compounds, amines, amides, urea derivatives, guanidine derivatives, amino acids,peptides, alkaloids, heterocyclic nitrogen compounds,porphyrins, organic sulfur compounds, and organic phosphorus compounds. When a selection was made from among several investigators, commentary is provided to indicate the choice, and usually some relevant data. The number of references cited is 596. An alphabetical compound index is provided which gives the name, page number, empirical formula, and the Wiswesser Line Notation (WLN), for each compound.

Heat Capacities and Entropies of Organic Compounds in the Condensed Phase. Volume III

This compilation of data on the heat capacities and entropies of organic compounds in the condensed phase is a cumulative document and includes the following earlier published work on this subject: ‘‘Heat Capacities and Entropies of Organic Compounds in the Condensed Phase,’’ E. S. Domalski, W. H. Evans, and E. D. Hearing, J. Phys. Chem. Ref. Data 13, Suppl. 1 (1984) and ‘‘Heat Capacities and Entropies of Organic Compounds in the Condensed Phase, Volume II,’’ E.S. Domalski and E.D. Hearing, J. Phys. Chem. Ref. Data 19, 881–1047 (1990). In addition, the literature through 1993 has been searched and the pertinent data reported has been included in Volume III. The latter volume provides data on 5332 individual entries for 2503 discrete organic compounds for which over 2200 articles have been examined, evaluated, and referenced. In addition to values for the heat capacity and entropy at 298.15 K, phase transitions for solid/solid, solid/liquid, and in some instances, solid/gas and liquid/gas are tabulated as ...

Heat Capacity of Liquids: Critical Review and Recommended Values. Supplement II

A study was carried out in which new experimental data on heat capacities of pure liquid organic and some inorganic compounds were compiled, critically evaluated, and recommended values provided. Compounds included in the compilation have a melting point below 573 K. The bulk of the compiled data covers data published in the primary literature between 1993 and 1999 and some data of 2000. However, some data from older sources were also included. The data were taken from almost 1030 literature references. Parameters of correlating equations for temperature dependence of heat capacities of liquids were developed. This paper is an update of a two volume monograph entitled Heat Capacity of Liquids: Critical Review and Recommended Values (96ZAB/RUZ) that was published in 1996 in the Journal of Physical and Chemical Reference Data as Monograph No. 6 and was the product of the IUPAC Project No. 121/11/87.

Estimation of the Thermodynamic Properties of Hydrocarbons at 298.15 K

An estimation method developed by S. W. Benson and coworkers, for calculating the thermodynamic properties of organic compounds in the gas phase, has been extended to the liquid and solid phases for hydrocarbon compounds at 298.15 K. The second order approach which includes nearest neighbor interactions has been applied to the condensed phase. A total of 1311 comparisons are made between experimentally determined values and those calculated using additive group values. Of the 559 comparisons given for the enthalpy of formation (Δf H°) in the gas, liquid, and solid phases, the average difference (residual), without regard to sign, is 2.6 kJ/mol. The average differences for 390 comparisons for the heat capacity (C○p) and 352 comparisons for the entropy (S°) in the three phases are 1.9 and 2.3 J.mol⋅K, respectively. The good agreement between experimental and calculated values shows that the Benson group additivity approach to the estimation of thermodynamic properties of organic compounds is applicable to t...

Estimation of the Heat Capacities of Organic Liquids as a Function of Temperature using Group Additivity. II. Compounds of Carbon, Hydrogen, Halogens, Nitrogen, Oxygen, and Sulfur

A second‐order group additivity method has been developed for the estimation of the heat capacity of liquid organic compounds containing carbon, hydrogen, halogens, nitrogen, oxygen, and sulfur. The method permits the estimation of the heat capacity as a function of temperature in the range from the melting temperature to the normal boiling temperature. Group contributions and structural corrections have been made temperature dependent by the use of a polynomial expression. The adjustable parameters in the polynomials have been calculated using a weighted least squares minimization procedure. This work has drawn information for both the development and testing of the method from a large compilation of critically evaluated heat capacity data for over 1300 organic liquids.

Estimation of the heat capacities of organic liquids as a function of temperature using group additivity. I: Hydrocarbon compounds

A second‐order group additivity method has been developed for the estimation of the heat capacity of liquid hydrocarbons as a function of temperature in the range from the melting temperature to the normal boiling temperature. The temperature dependence of group contributions and structural corrections has been represented by a polynomial expression. The adjustable parameters in the polynomials have been calculated using a weighted least squares minimization procedure. Recommended heat capacities from a large compilation of critically evaluated data that contains over 1300 organic liquids served as a database both for the development and testing of the method.

Enthalpies of combustion of triphenylphosphine and triphenylphosphine oxide

Abstract The energies of combustion of crystalline triphenylphosphine and triphenylphosphine oxide were determined in an aneroid adiabatic rotating bomb calorimeter. The standard molar enthalpies of combustion for the reactions at 298.15 K and p o = 1 × 10 5 Pa are: (C 6 H 5 ) 3 P(cr) + 23O 2 (g) = 18CO 2 (g) + (H 3 PO 4 + 6H 2 O)(aq), Δ c H m o = −(10295.35 ± 2.08) kJ · mol −1 ; (C 6 H 5 ) 3 PO(cr) + 22.5O 2 (g) = 18CO 2 (g) + (H 3 PO 4 + 6H 2 O)(aq), Δ c H m o = −(9971.92 ± 1.90) kJ · mol −1 . The derived enthalpies of formation for triphenylphosphine and triphenylphosphine oxide are: Δ f H m o = (207.02 ± 3.52) kJ · mol −1 and Δ f H m o = −(116.41 ± 3.42) kJ · mol −1 , respectively. The completeness of the combustion reactions was verified by determinations for carbon dioxide through absorption in Ascarite. Ion chromatography was used to analyze the bomb solution quantitatively for the nitrate, orthophosphate, pyrophosphate, and tripolyphosphate ions. The enthalpies and temperatures of melting were determined using d.s.c. The values obtained for the enthalpies of fusion at the melting temperatures for triphenylphosphine and triphenylphosphine oxide were (19.69 ± 0.18) kJ · mol −1 at 354.4 K and (24.22 ± 0.29) kJ · mol −1 at 431.9 K, respectively. Second-order group-contribution values were derived for calculating enthalpies of formation at 298.15 K from the experimental results on triphenylphosphine and triphenylphosphine oxide.

Enthalpy of combustion of 1,4-dimethylcubane dicarboxylate

Abstract The energy of combustion of crystalline 1,4-dimethylcubane dicarboxylate was measured in the NIST aneroid adiabatic rotating calorimeter. The standard molar enthalpy of combustion at 298.15 K and p rmo = 1 × 10 5 Pa for the reaction: C 12 H 12 O 4 (cr) + 13O 2 (g) = 12CO 2 (g) + 6H 2 O(l) is Δ c H m o = −(6518.09±1.42) kJ·mol −1 . The derived enthalpy of formation for crystalline 1,4-dimethylcubane dicarboxylate is −(218.99±2.12) kJ·mol −1 . An estimated enthalpy of formation of an unstrained crystalline 1,4-dimethylcubane dicarboxylate was calculated to be −809.7 kJ·mol −1 using group-contribution values. The corresponding strain energy is 590.7 kJ·mol −1 .

Enthalpy of combustion of adenine

Abstract The enthalpy of combustion for a commercial adenine sample of 99.9 moles per cent purity was measured in an aneroid adiabatic bomb calorimeter. The molar enthalpy of combustion at 298.15 K for the reaction: C 5 H 5 N 5 ( c )+6.25 O 2 ( g ) = 5 CO 2 (g)+2.5 H 2 O (1)+2.5 N 2 ( g ), was Δ c H m o = −(2779.02 ± 1.26) kJ · mol −1 . The corresponding molar enthalpy of formation for adenine, C 5 H 5 N 5 , was calculated to be Δ f H m o = (96.90 ± 1.29) kJ · mol −1 . The present results were found to be in good agreement with those of the earlier work of Stiehler and Huffman.