Thermodynamic properties of nitro derivatives of diphenyl ether and biphenyl

The heat capacity of 4,4′-dinitrodiphenyl ether and 4-nitro-4′-biphenylcarboxylic acid were measured by adiabatic calorimetry (AC) in temperature ranges of 8–372 K and 10–372 K, respectively. The heat capacity of 4,4′-dinitrodiphenyl ether in the temperature range 323–500 K, the thermodynamic properties of fusion, and the purity of the ether were measured by differential scanning calorimetry (DSC). The main thermodynamic functions in the temperature range 5–370 K were calculated for both compounds using the heat capacities of adiabatic calorimetry. Related thermodynamic functions of 4,4′-dinitrodiphenyl ether in the temperature range 370–500 K were calculated on the basis of DSC data.     

Thermodynamics of semi-interpenetrating polymeric networks based on crosslinked poly(cyanurate) and linear poly(urethane) in the temperature region from T → 0 to 350 K

The temperature dependences of the heat capacity of linear poly(urethane) (PU) (M _n = 4·10⁴), which was synthesized from 4,4′-diphenylmethane diisocyanate, oligo(butylene glycol adipinate) (M _n = 1000), and chain-elongating agent butane-1,4-diol, and three samples of related semi-interpenetrating polymeric networks containing 25, 50, and 75 wt.% of crosslinked poly(bisphenol A) cyanurate were studied in a region of 6–350 K by adiabatic vacuum calorimetry. Their combustion energies were determined in a calorimeter with a static bomb and an isothermic shell. The thermodynamic functions of the compounds under study for the temperature region from T → 0 to 350 K, enthalpies of combustion, and thermodynamic characteristics of formation from simple substances at T = 298.15 K and p = 0.1 mPa were calculated. The thermodynamic parameters of formation of the semi-interpenetrating networks were calculated. The dependences of the isotherms of the thermodynamic properties and thermodynamic compatibility of the semi-interpenetrating networks on their composition were determined. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 648–654, April, 2006.     

Thermodynamic properties of an alternating copolymer of bicyclo[2.2.1]hepta-2,5-diene and carbon monoxide in a region from <Emphasis Type="Italic">T</Emphasis> → 0 to 550 K

The temperature dependence of the heat capacity of an alternating copolymer of bicyclo[2.2.1]hepta-2,5-diene and carbon monoxide in the temperature range 6–550 K (with an error of 0.2–0.5% at 6–350 K and 0.5–1.5% at 330–550 K) was studied by the adiabatic vacuum and dynamic calorimetry. Physical transformations of the copolymer in the studied temperature region were identified, and their thermodynamic characteristics were determined. The combustion energy of the copolymer at 298.15 K was measured in a calorimeter with a static bomb and isothermal jacket. The thermodynamic functions for a region of 0–550 K, enthalpy of combustion, and thermodynamic parameters of copolymer formation from simple substances at T = 298.15 K and p = 101.325 kPa were calculated from the obtained experimental data. The new results and earlier published data were used for the calculation of the thermodynamic characteristics of the alternate copolymerization of bicyclo[2.2.1]hepta-2,5-diene and CO under standard pressure for a region of 0–350 K for the bulk reaction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1483–1487, June, 2005.     

Thermodynamic properties of linear polyurethanes based on 1,6-hexamethylenediisocyanate with butane-1,4-diol and hexane-1,6-diol in the temperature range from T → 0 to 460 K

The temperature dependences of the heat capacity of partially crystalline linear polyurethanes based on 1,6-hexamethylenediisocyanate with butane-1,4-diol and hexane-1,6-diol were studied for the first time in a temperature range of 6–460 K by the methods of adiabatic vacuum and dynamic calorimetry. Physical changes in the state of polyurethanes were revealed and characterized; the standard thermodynamic functions, namely, C _p °(T), H°(T)-H°(0), S°(T), and G°(T)-H°(0), were calculated from the obtained experimental data in the temperature range from T → 0 to 460 K for the polymers in the crystalline, glassy, highly elastic, and liquid states. The energies of combustion of the polymers were measured by the bomb calorimetry method, and the standard thermodynamic characteristics of their formation at 298.15 K were calculated. The thermodynamic characteristics of bulk polycondensation of 1,6-hexamethylenediisocyanate with butane-1,4-diol and hexane-1,6-diol to form linear aliphatic polyurethanes-{4,6} and-{6,6} were determined in the range from T → 0 to 350 K at p° = 0.1 MPa. The thermodynamic properties of the polyurethanes under study and polymers of isomeric structure were compared. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 817–823, May, 2006.     

Thermodynamics of alternating copolymer of ethylene and carbon monoxide in the 0–600 K region

The temperature dependence of the heat capacity of the alternating copolymer (ACP) of carbon monoxide with ethylene was studied, and temperatures and enthalpies of its phase transformations were measured by adiabatic vacuum, dynamic, and isothermal calorimetry in the temperature range from 8 to 600 K. The energy of burning of ACP was measured at 298.15 K in a calorimeter with the static bomb and isothermal shell. The thermodynamic parameters of transformation of the α-form of ACP crystals into the β-form and fusion of the β-form were determined. The thermodynamic functions for the 0–507 K range and thermodynamic characteristics atT=298.15 K andp=101.325 kPa were calculated. The thermodynamic parameters of the alternating copolymerization of ethylene and CO at 0–507 K and standard pressure were calculated for the bulk reaction. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 284–288, February, 1998.     

Thermodynamics of alternating copolymer of propylene and CO in the 0–550 K region

The temperature dependences of the heat capacity and the temperatures and enthalpies of physical transitions of the alternating copolymer of propylene and CO were studied in the 5–550 K region by adiabatic vacuum and dynamic calorimetry techniques. The heat of combustion of the copolymer was measured at 298.15 K in a calorimeter with a static bomb and an isothermal shield. The thermodynamic parameters of glass transition and fusing were estimated. The thermodynamic functions in the 0–450 K region and the thermodynamic characteristics of the formation of the copolymer from simple substances atT=298.15 K andp=101.325 kPa were calculated. The thermodynamic parameters of the alternating copolymerization of bulk propylene and CO were calculated in the 0–450 K region at standard pressure.     

Combined study of thermochemical properties of nitroform and its salts

A combined method for determination of the standard enthalpies of formation of nitroform and its salts was proposed. The enthalpies of dissolution of nitroform and its ammonium, hydrazinium, guanidinium, and potassium salts in water were measured. The enthalpy of combustion of hydrazinium salt of nitroform was determined by a combustion calorimetry, and its standard enthalpy of formation was calculated. The enthalpy of formation of trinitromethyl anion in indefinitely diluted aqueous solution −24.94±0.79 kJ mol⁻¹, was calculated on the basic of the data obtained for enthalpies of formation and dissolution of ammonium and hydrazinium salts of nitroform. Standard enthalpies of formation of nitroform and its salts were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2451–2454, December, 1998.     

Thermodynamics of vaporization of gallium trichloride

The unsaturated and saturated pressures of gallium trichloride vapor were measured by the static method with membrane-gauge manometers in wide pressure (0.2–760 Torr) and temperature (313–1071 K) intervals. Scanning calorimetry was used to determine the thermodynamic characteristics of GaCl₃ fusion. The thermodynamic characteristics were obtained for sublimation, fusion, vaporization, and association in the vapor of GaCl₃ molecules. The enthalpies of formation and the absolute entropies of GaCl₃ in the liquid and gaseous phases and Ga₂Cl₆ in the gaseous phase were calculated using literature data. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1266–1269, July, 2007.     

Thermochemical study of three dimethylpyrazine derivatives

The standard (p ⁰=0.1 MPa) molar enthalpies of formation, in the gaseous phase, at T-298.15 K, for 2,5-dimethylpyrazine (2,5-DMePz) and for the two dimethylpyrazine-N,N′-dioxide derivatives, 2,3-dimethylpyrazine-1,4-dioxide (2,3-DMePzDO) and 2,5-dimethylpyrazine-1,4-dioxide (2,5-DMePzDO), were derived from the measurements of standard massic energies of combustion, using a static bomb calorimeter, and from the standard molar enthalpies of vaporization or sublimation, measured by Calvet microcalorimetry. The mean values for the molar dissociation enthalpy of the nitrogen-oxygen bonds, 〈DH _m⁰〉(N-O), were derived for both N,N′-dioxide compounds. These values are discussed in terms of the molecular structure of the two N,N′-dioxide derivatives and compared with 〈DH _m⁰〉(N-O) values previously obtained for other N-oxide derivatives.     

Thermochemistry of heteroatomic compounds 22. Enthalpies of combustion and formation of alkyl(aryl)arsines and arsenites in the condensed and gaseous phases

The enthalpies of combustion (ΔH _comb) of five primary, secondary, and tertiary alkyl(aryl)arsines in the condensed state were calculated using the equation ΔH _comb = −385.8–110.3N, where N is the number of bond-forming electrons. The dependence presented is used for the calculation of the enthalpies of combustion of full esters and amidoesters of arsinous acid of noncyclic and cyclic structures. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1042–1043, May, 2007.     

Molar heat capacities and standard molar enthalpy of formation of 2-amino-5-methylpyridine

The heat capacities (C _p,m) of 2-amino-5-methylpyridine (AMP) were measured by a precision automated adiabatic calorimeter over the temperature range from 80 to 398 K. A solid-liquid phase transition was found in the range from 336 to 351 K with the peak heat capacity at 350.426 K. The melting temperature (T _m), the molar enthalpy (Δ_fus H _m⁰), and the molar entropy (Δ_fus S _m⁰) of fusion were determined to be 350.431±0.018 K, 18.108 kJ mol⁻¹ and 51.676 J K⁻¹ mol⁻¹, respectively. The mole fraction purity of the sample used was determined to be 0.99734 through the Van’t Hoff equation. The thermodynamic functions (H _T-H _298.15 and S _T-S _298.15) were calculated. The molar energy of combustion and the standard molar enthalpy of combustion were determined, ΔU _c(C₆H₈N₂,cr)= −3500.15±1.51 kJ mol⁻¹ and Δ_c H _m⁰ (C₆H₈N₂,cr)= −3502.64±1.51 kJ mol⁻¹, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. The standard molar enthalpy of formation of the crystalline compound was derived, Δ_r H _m⁰ (C₆H₈N₂,cr)= −1.74±0.57 kJ mol⁻¹.     

Thermodynamics of alternating copolymer of styrene and CO in the 0—600 K region

The temperature dependence of heat capacity and the temperatures and enthalpies of physical transitions of the alternating copolymer of styrene and CO were studied in the 5—600 K region by the adiabatic vacuum and dynamic calorimetric techniques. The heat of combustion of the copolymer was measured at 298.15 K in a calorimeter with a static bomb and an isothermal shield. The thermodynamic parameters of glass transition and fusion were determined. The thermodynamic functions in the 0—550 K region and thermodynamic characteristics of the formation of the copolymer from simple substances at T = 298.15 K and p = 101.325 kPa were calculated. The thermodynamic parameters of alternating copolymerization in the bulk of styrene and CO were calculated in the 0—350 K region at a standard pressure.     

Study on the thermodynamic properties of cholesterol

The standard molar enthalpy of combustion of cholesterol was measured at constant volume. According to value of Δ_r U _m^θ(−14358.4±20.65 kJ mol⁻¹), Δ_r H _m^θ(−14385.7 kJ mol⁻¹) of combustion reaction and Δ_f H _m^θ(2812.9 kJ mol⁻¹) of cholesterol were obtained from the reaction equation. The enthalpy of combustion reaction of cholesterol was also estimated by the average bond enthalpies. By design of a thermo-chemical recycle, the enthalpy of combustion of cholesterol were calculated between 283.15∼373.15 K. Besides, molar enthalpy and entropy of fusion of cholesterol was obtained by DSC technique.     

Thermodynamic characteristics of protolytic equilibria of L-serine in aqueous solutions

The heat effects of the reaction of aqueous solution of L-serine with aqueous solutions of HNO₃ and KOH were determined by calorimetry at temperatures of 288.15, 298.15, and 308.15 K, and ionic strength values of 0.2, 0.5, and 1.0 (background electrolyte, KNO₃). Standard thermodynamic characteristics (Δ_r H ^o, Δ_r G ^o, Δ_r S ^o, ΔC _p ^o) of the acid-base reactions in aqueous solutions of L-serine were calculated. The effect of the concentration of background electrolyte and temperature on the heats of dissociation of amino acid was considered. The combustion energy of L-serine by bomb calorimetry in the medium of oxygen was determined. The standard combustion and formation enthalpies of crystalline L-serine were calculated. The heats of dissolution of crystalline L-serine in water and solutions of potassium hydroxide at 298.15 K were measured by direct calorimetry. The standard enthalpies of formation of L-serine and products of its dissociation in aqueous solution were calculated.     

Reaction of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with naphthalen-1-amine,quinolin-8-amine,and 1,3-diketones

Condensation of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with naphthalen-1-amine and cyclohexane-1,3-dione, methyl 2,2-dimethyl-4,6-dioxocyclohexane-1-carboxylate, or dimedone gave the corresponding 7-(2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-yl)-7,8,9,10,11,12-hexahydro-12H-benzo[c]acridin-8-ones. The reaction of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with naphthalen-1-amine and indan-1,3-dione produced 7-(2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-yl)-8H-benzo[h]indeno[1,2-b]quinolin-8-one. 7-(2′-Hydroxy-1,1′: 3′,1″-terphenyl-5′-yl)-7,8,9,10,11,12-hexahydrobenzo[b][1,10]phenanthrolin-8-ones were obtained by three-component condensation of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with quinolin-8-amine and cyclohexane-1,3-dione, methyl 2,2-dimethyl-4,6-dioxocyclohexane-1-carboxylate, or dimedone.     

Solvent induced quadrupole polarization of the molecules of diazo and diazocarbonyl compounds: Quantum-chemical investigation

Equilibrium structural parameters, atomic charges, and quadrupole moments of the molecules of 2,4,6-tris(diazo)cyclohexane-1,3,5-trione, 3,6-bis(diazo)cyclohexane-1,2,4,5-tetraone and its anion, isomeric 3,6-bis(diazonium)cyclohexanediondioles and 4,4′-bis(diazonium)-1,1′-biphenyl in a vacuum and in dichloromethane were calculated by the quantum chemical method PBE0/cc-pVTZ using the polarizable continuum model (PCM).The p-quinoid dication is more favorable than o-quinoid dication by 20 kcal mol-1 in a vacuum and by 13 kcal mol⁻¹ in dichloromethane.The norm of the quadrupole moment of the centrosymmetric molecules in a polarizable medium increases while that of the dications decreases. The quadrupole polarization of molecules and molecular ions by the solvent does not change their symmetry point group.     

Thermodynamics of the effects of substituent,degree of substitution,and pH on complex formation of hydroxypropyl-α- and hydroxypropyl-β-cyclodextrins with ascorbic acid

The interaction of ascorbic acid with hydroxypropyl-α- and hydroxypropyl-β-cyclodextrins of different degree of substitution was studied at 298.15 K and different pH using solution calorimetry. In an aqueous solution, only hydroxypropyl-β-cyclodextrins form weak molecular complexes with the nonionized form of ascorbic acid. The thermodynamic functions of complex formation and stability constants of the complexes were calculated. The systems with weak intermolecular interaction without complex formation were characterized by enthalpic virial coefficients. On the basis of the obtained thermodynamic characteristics it was shown that the selectivity of complex formation of hydroxypropyl-α- and hydroxypropyl-β-cyclodextrins with ascorbic acid is determined by the size of the macrocyclic cavity, the presence of the hydroxypropyl substituent, and the medium acidity. The degree of substitution of hydroxypropyl-β-cyclodextrins exerts no substantial effect on the thermodynamic parameters of interaction with ascorbic acid. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1828–1831, August, 2005.     

The thermodynamic properties of delta-lactones

The enthalpies of formation of δ-hexanolactone and δ-nonanolactone were determined by combustion calorimetry. Conformational analysis and quantum-chemical calculations of equilibrium structures, fundamental vibrations, moments of inertia, and total energies were performed for δ-pentanolactone (I), δ-hexanolactone (II), and δ-nonanolactone (III) by the B3LYP/6-311G(d,p), B3LYP/6-311++G(d,p), and G3MP2 methods. The experimental IR spectra and calculated vibrational frequencies were used to suggest the assignment of vibrational frequencies of stable conformations. The thermodynamic properties of I–III in the ideal gas state were determined over the temperature range 0–1500 K. A thermodynamic analysis of mutual isomerization in the gas and liquid phases over the temperature range 298.15–900 K and liquid-phase polymerization of γ- and δ-pentanolactones and 4-pentenoic acid over the temperature range 298.15–500 K was performed.     

Standard molar enthalpies of formation and sublimation of <Emphasis Type="Italic">N</Emphasis>-phenylphthalimide

The standard (p ⁰=0.1 MPa) molar enthalpy of formation, Δ_f H ⁰ _m, for crystalline N-phenylphthalimide was derived from its standard molar enthalpy of combustion, in oxygen, at the temperature 298.15 K, measured by static bomb-combustion calorimetry, as –206.0±3.4 kJ mol^–1. The standard molar enthalpy of sublimation, Δ^g _cr H ⁰ _m , at T=298.15 K, was derived, from high temperature Calvet microcalorimetry, as 121.3±1.0 kJ mol^–1. The derived standard molar enthalpy of formation, in the gaseous state, is analysed in terms of enthalpic increments and interpreted in terms of molecular structure.     

Heat capacity of α-glycylglycine in a temperature range of 6 to 440 K

Heat capacity of α-glycylglycine was measured using adiabatic calorimetry (6 to 304 K) and DSC (264 to 443 K), and then thermodynamic functions were calculated. Heat capacity has no anomalies. The molecular crystal melts at 493 K (enthalpy of melting is about 62 kJ mol^–1). The melting is accompanied by decomposition. C _P(T) function for glycylglycine is very similar to those of three glycine polymorphs. The ‘universal’ curve consists of two parts: low-temperature Debye-like function (from 0 to about 120 K) and a straight line (up to the melting point). At very low temperatures rigid molecules oscillate as a whole, and the Debye temperature is proportional to the molecular mass to the power of 3/2.