Evaluation of the Vaporization Enthalpies and Liquid Vapor Pressures of (R)-Deprenyl, (S)-Benzphetamine, Alverine, and a Series of Aliphatic Tertiary Amines by Correlation Gas Chromatography at T/K = 298.15

Abstract

The vaporization enthalpies at T/K = 298.15 and vapor pressures from T/K = (283 to 313) of a series of tertiary aliphatic amines ranging in size from 12 to 24 carbons are evaluated using the literature values for triethylamine, tributylamine, N,N-dimethylbenzylamine, N,N-dimethyloctylamine, and N,N-dimethyldodecylamine by correlation gas chromatography. The vaporization enthalpies and vapor pressures evaluated are (Δl g H m(298.15 K/kJ·mol–1, p/Pa (298.15 K)): triisobutylamine (52.3 ± 2.2, 113), tri-n-butylamine (58.0 ± 1.9, 28), N,N-dimethyltetradecylamine (77.3 ± 1.9, 0.091), N,N-dimethylhexadecylamine (84.8 ± 1.0, 0.011), tribenzylamine (92.4 ± 1.4, 5.1·10–4), tri-n-octylamine (100.1 ± 1.4, 1.4·10–4). These amines were used to evaluate the following vaporization enthalpies and vapor pressures (Δl g H m(298.15 K kJ·mol–1, p/Pa (298.15 K)): (R)-deprenyl (64.3 ± 2.2, 2.5); (S)-benzphetamine (77.2 ± 0.7, 0.04); and alverine (89.3 ± 0.2, 1.4·10–3). The solid–solid and solid to liquid phase transitions of tribenzylamine were also measured; Δcr cr H m(342.5 K)/kJ·mol–1 = (1.1 ± 0.1); Δcr l H m(365.6 K)/kJ·mol–1 = (23.0 ± 0.1). Adjusted to T/K = 298.15 and combined with the vaporization enthalpy at this temperature, the sublimation enthalpy resulted as Δcr g H m(298.15 K)/kJ·mol–1 = (111.3 ± 2.1).

Aliphatic Amines: A Critical Analysis of the Experimental Enthalpies of Formation by Comparison with Theoretical Calculations

“…The enthalpy of vaporization of 31 was determined experimentally by several authors, and there is no reason to doubt its accuracy. Two experimental values , for 34 differ by 4.7 kJ·mol –1 , and a value that is in better agreement with the average of four estimated enthalpies of vaporization is accepted in this work. Thus, we do not expect a large error in the experimental Δ l g H m ° value for 34 .…”

“…The uncertainty corresponds to 2.5σ, 3.5σ, or 4.5σ, where σ is the standard deviation of the mean (see text for details). d References are given in chronological order; rec = recommended. e Reference . f Reference . g Obtained from the isodesmic reaction networks by combining the TPEPICO dissociation energies with ab initio calculations. h Calculated by HEAT-345­(Q) method. i Reference . j Reference . k Reference . l Estimated on the basis of Trouton’s rule. m Reference . n Reference . o Estimated in this work with the group-additivity values obtained in the cited paper. p Estimated using the relationship Δ f H m ° (l) = Δ f H m ° (g) – Δ l g H m ° . q Estimated by MEP model (Table S4). r Average of all estimates given in the table; uncertainty is equal to twice the standard deviation of the mean (2σ). s Reference . t Estimated using the Wadso equation, ref . u Reference . v Reference . w Reference . x Reference . y Reference . z Unpublished results. aa Reference . bb Reference . cc Reference . dd Error is noted for this value in ref . ee Reference . ff Calculated by G4 method using the atomization reaction. gg Reference . hh Reanalyzed data of ref . ii Reference . jj Reference . kk Average of the experimental values from...…”

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

“…Experimental data of vaporization enthalpies have essentially been extracted for this work from the large collection of Acree, Jr. and Chickos [ 8 ] and Chickos et al [ 10 , 11 , 12 , 13 , 14 ], supplemented by recent data from a number of further authors publishing experimental vaporization values of several acetophenones [ 23 ], aliphatic tertiary amines [ 24 ], azidomethyl- N -nitrooxazolidines [ 25 ], benzamides [ 26 ], benzocaine [ 27 ], bisabolol and menthol [ 28 ], crown ethers [ 29 ], N , N -dialkyl monoamides [ 30 ], fenpropidin and phencyclidine [ 31 ], flavors [ 32 ], long-chain fluorinated alcohols [ 33 ], whiskey- and metha-lactone [ 34 ], halogenated fluorenes [ 35 ], ibuprofen and naproxen [ 36 ], imidazo[1,2- a ]pyrazine and phthalazine [ 37 ], insect pheromones [ 38 ], morpholines [ 39 ], organo(thio)phosphates [ 40 ], dialkyl phthalates [ 41 ], nitrogen heteroaromatics [ 42 ], phenylimidazoles [ 43 ], 2-acetylthiophene [ 44 ], dicarboxylic n -pentyl esters [ 45 ], and cyclic amines, ethers and alcohols [ 46 ]. The result of the atom-group parameters, based on 3581 compounds, is summarized in Table 1 .…”

The Vaporization Enthalpy and Vapor Pressure of Fenpropidin and Phencyclidine (PCP) at T/K = 298.15 by Correlation Gas Chromatography

“…Vaporization enthalpies for N,N -dimethylbenzylamine, N,N -dimethyloctyl, and N,N -dimethyldodecylamine are literature values evaluated by various experimental techniques. The remaining standards in Table were evaluated by correlation gas chromatography using these and other tertiary amines as standards …”

“…In this work p refers to the vapor pressure and p ref refers to a reference pressure, either p o /Pa = 101325 or p o /Pa = 1 as noted in Table 3 by correlation gas chromatography using these and other tertiary amines as standards. 15 2.4. Vapor Pressure Standards.…”