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1.
《The Journal of chemical thermodynamics》2001,33(8):837-847
The Knudsen mass-loss effusion technique was used to measure the vapour pressures at different temperatures of the following compounds: 3-phenylpropionic acid, between T = 305.17 K and T = 315.17 K; 3-(2-methoxyphenyl)propionic acid, between T = 331.16 K and T = 347.16 K; 3-(4-methoxyphenyl)propionic acid, between T = 341.19 K and T = 357.15 K; 3-(3,4-dimethoxyphenyl)propionic acid, between T = 352.18 K and T = 366.16 K. From the temperature dependence of the vapour pressure, the standard molar enthalpies of sublimation ΔcrgHmowere derived by the Clausius–Clapeyron equation and the molar entropies of sublimation at equilibrium pressures were calculated. On the basis of estimated values for the heat capacity differences between the gas and the crystal phases of the studied compounds the standard, p ∘ = 105Pa, molar enthalpies, entropies and Gibbs energies of sublimation at T = 298.15 K, were derived: 相似文献
2.
Manuel A.V. Ribeiro da Silva Luís M. Spencer S. Lima Ana Rita G. Moreno Ana I.M.C.L. Ferreira José R.B. Gomes 《The Journal of chemical thermodynamics》2008,40(2):155-165
The standard (p° = 0.1 MPa) molar enthalpies of formation, at T = 298.15 K, of 4-chloro-3-nitroaniline and 5-chloro-2-nitroaniline, in the condensed phase, were derived from their standard molar energies of combustion, in oxygen, to yield CO2(g), N2(g), and HCl · 600H2O(l), measured by rotating bomb combustion calorimetry. From the temperature dependence of the vapour pressures of these compounds, measured by the Knudsen effusion technique, their standard molar enthalpies of sublimation, at T = 298.15 K, were derived by means of the Clausius–Clapeyron equation. The Calvet microcalorimetry was also used to measure the standard molar enthalpies of sublimation of these compounds, at T = 298.15 K. The combination of the standard molar enthalpies of formation in the condensed phases and the standard molar enthalpies of sublimation yielded the standard molar enthalpies of formation in the gaseous phase at T = 298.15 K for each isomer. Further, the standard (p° = 0.1 MPa) molar enthalpies, entropies and Gibbs free energies of sublimation, at T = 298.15 K, were also derived.The standard molar enthalpies of formation, in the gaseous phase of all the chloronitroaniline isomers were also estimated by the Cox scheme and by the use of computational thermochemistry and compared with the available experimental values. 相似文献
3.
《The Journal of chemical thermodynamics》2001,33(8):849-857
The Knudsen mass-loss effusion technique was used to measure the vapour pressures at different temperatures of the following crystalline compounds: 1,2-diphenylethane (bibenzyl), between T = 289.16 K and T = 303.20 K, and of 3-phenylpropiolic acid between T = 329.15 K and T = 343.15 K. From the temperature dependence of the vapour pressure, the standard molar enthalpies of sublimation at the mean temperature of the experimental range were derived by the Clausius–Clapeyron equation. From these results the standard, po = 105Pa, molar enthalpies, entropies, and Gibbs energies of sublimation at T = 298.15 K, were calculated: 相似文献
4.
《The Journal of chemical thermodynamics》2001,33(1):23-31
The Knudsen mass-loss effusion technique was used to measure the vapour pressures at different temperatures of the following crystalline dicarboxylic acids: succinic acid, between T = 360.11 K and T = 375.14 K; methylsuccinic acid, between T = 343.12 K and T = 360.11 K; 2,2-dimethylsuccinic acid, between T = 350.11 K, and T = 365.11 K; 2-methylglutaric acid, between T = 338.38 K and T = 347.63 K; and 2,2-dimethylglutaric acid between T = 342.18 K and T = 352.66 K. From the temperature dependence of the vapour pressure, the standard molar enthalpies of sublimation were derived by the Clausius–Clapeyron equation and the molar entropies of sublimation at equilibrium pressures were calculated. Using estimated values for the heat capacity differences between the gas and the crystal phases of the studied compounds, the standard, po = 105Pa, molar enthalpies, entropies and Gibbs energies of sublimation at T = 298.15 K, were derived: 相似文献
5.
《The Journal of chemical thermodynamics》2001,33(1):103-112
The Knudsen mass-loss effusion technique was used to measure the vapour pressures at different temperatures of the following six compounds: 2-methyl-3-nitrobenzoic acid, between T = 357.16 K and T = 371.16 K; 2-methyl-6-nitrobenzoic acid, between T = 355.16 K and T = 369.16 K; 3-methyl-2-nitrobenzoic acid, between T = 371.16 K and T = 385.14 K; 3-methyl-4-nitrobenzoic acid, between T = 363.21 K and T = 379.16 K; 4-methyl-3-nitrobenzoic acid, between T = 363.10 K and T = 377.18 K; 5-methyl-2-nitrobenzoic acid, between T = 355.18 K and T = 371.08 K. From the temperature dependence of the vapour pressure, the standard molar enthalpies of sublimation were derived by the Clausius–Clapeyron equation and the molar entropies of sublimation at equilibrium pressures were calculated. Using estimated values for the heat capacity differences between the gas and the crystal phases of the studied compounds the standard, po = 105Pa, molar enthalpies ΔcrgHmo, entropies ΔcrgSmoand Gibbs energies ΔcrgGmoof sublimation at T = 298.15 K, were derived: 相似文献
6.
Ana Filipa L.O.M. Santos Manuel A.V. Ribeiro da Silva 《The Journal of chemical thermodynamics》2010,42(6):734-741
The standard (p° = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, of 1-phenylpyrrole and 1-(4-methylphenyl)pyrrole, at T = 298.15 K, were derived from the standard molar energies of combustion in oxygen, measured by static-bomb combustion calorimetry. For these compounds, the standard molar enthalpies of sublimation, at T = 298.15 K, were determined from the temperature–vapour pressure dependence, obtained by the Knudsen mass-loss effusion method. Using estimated values for the heat capacity differences between the gas and the crystal phases of the studied compounds, the standard (p° = 0.1 MPa) molar enthalpies, entropies, and Gibbs energies of sublimation, at T = 298.15 K, were derived. From the experimental values, the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, were calculated.Additionally, the enthalpies of formation of both compounds were estimated using the composite G3(MP2)//B3LYP approach together with adequate gas-phase working reactions. There is a very good agreement between computational and experimental results. 相似文献
7.
《The Journal of chemical thermodynamics》2001,33(10):1277-1284
The enthalpies of dilution of aqueous solutions of {Co(en)3}Cl3and {Co(tn)3}Cl3(where en = 1,2-diaminoethane andtn = 1,3-diaminopropane) have been measured up to m = 1 mol · kg − 1at T = 278.15 K and atmospheric pressure with an isoperibol calorimeter by the long-jump method. Relative apparent molar enthalpies Lφ,mhave been extracted from an empirical polynomial of the molality square root. Previously reported data at T = 298.15 K are compared with the new experimental dilution results. A noticeable decrease in Lφ,mwas observed at every experimental concentration when temperature diminished from 298.15 K to 278.15 K. An inversion in the relative layout for the Lφ,mcurves of aqueous {Co(en)3}Cl3and {Co(tn)3}Cl3was also found. 相似文献
8.
《The Journal of chemical thermodynamics》2001,33(7):745-754
The Knudsen mass-loss effusion technique was used to measure the vapour pressures at different temperatures of the following substituted benzoic acids: 2-amino-3-methylbenzoic acid at T between 343.16 K and 357.17 K; 2-amino-5-methylbenzoic acid at T between 345.15 K and 361.16 K; 2-amino-6-methylbenzoic acid at T between 339.17 K and 355.15 K; 3-amino-2-methylbenzoic acid at T between 367.16 K and 381.22 K; 3-amino-4-methylbenzoic acid at T between 363.18 K and 377.16 K; and 4-amino-3-methylbenzoic acid at T between 367.17 K and 383.14 K. The standard, p0 = 105Pa, molar enthalpies, entropies, and Gibbs energies of sublimation at T = 298.15 K were derived from the temperature dependence of the vapour pressure using estimated values for the heat capacity differences between the gas and the crystal phases of the studied compounds. 相似文献
9.
This paper reports vapour pressures measured at several different temperatures using the Knudsen effusion method of ortho-acetoxybenzoic acid (aspirin) (341.1 to 361.1) K, meta-acetoxybenzoic acid (344.2 to 362.2) K, ortho-acetamidobenzoic acid (367.2 to 389.2) K, and meta-acetamidobenzoic acid (423.2 to 441.1) K. The experimental results enabled the determination of the standard molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, of the four compounds studied. DSC experiments yield results of the temperature and enthalpy of fusion. The experimental results were compared with literature ones for the para isomers of the acids acetoxybenzoic and acetamidobenzoic. Correlations involving temperature of fusion, and standard molar enthalpy and Gibbs energy of sublimation of several substituted benzoic acids were proposed. Those correlation equations allow a good estimative of volatility of benzoic acid derivatives from their enthalpies of sublimation and temperatures of fusion. 相似文献
10.
《The Journal of chemical thermodynamics》2001,33(8):899-903
The standard (po = 0.1 MPa) molar enthalpies of formation for 2,3-, 2,4-, 2,5-, 3,4- and 3,5- trans -dimethoxycinnamic acids, in the gaseous phase, were derived from the standard molar enthalpies of combustion in oxygen, of the crystalline compounds, determined by static bomb combustion calorimetry at T = 298.15 K and from the literature values for the respective enthalpies of sublimation. 相似文献
11.
This report presents a comprehensive experimental and computational study of the thermodynamic properties of two fluorene derivatives: 2-aminofluorene and 2-nitrofluorene. The standard (p° = 0.1 MPa) molar enthalpies of formation in the crystalline phase of these compounds were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. A Knudsen effusion method was used to perform the vapour pressure study of the referred compounds, yielding an accurate determination of the standard molar enthalpies and entropies of sublimation. The enthalpies of sublimation were also determined using Calvet microcalorimetry and the enthalpy and temperature of fusion were derived from DSC experiments. Derived results of standard enthalpy and Gibbs energy of formation in both gaseous and crystalline phases were compared with the ones reported in literature for fluorene. A theoretical study at the G3 and G4 levels has been carried out, and the calculated enthalpies of formation have been compared to the experimental values. 相似文献
12.
The Knudsen mass-loss effusion technique was used to measure the vapour pressures of the three crystalline isomers of methylbenzamide. From the temperature dependence of the vapour pressures, the standard molar enthalpies of sublimation and the enthalpies of the intermolecular hydrogen bonds N−H⋯O were calculated. The temperature and molar enthalpy of fusion of the studied isomers were measured using differential scanning calorimetry. The values of the standard (p° = 0.1 MPa) molar enthalpy of formation in the crystalline phase, at T = 298.15 K, of the compounds studied were derived from their standard massic energies of combustion measured by static-bomb combustion calorimetry. From the experimental values, the standard molar enthalpies of formation in the gaseous phase, at T = 298.15 K, were calculated and compared with the values estimated by employing computational calculations that were conducted using different quantum chemical methods: G3(MP2), G3, and CBS-QB3. Good agreement between experimental and theoretical results is verified. The aromaticity of the compounds has been evaluated through nucleus independent chemical shifts (NICS) calculations. 相似文献
13.
This report presents a comprehensive experimental and computational study of the thermodynamic properties of two bromine fluorene derivatives: 2-bromofluorene and 2,7-dibromofluorene. The standard (p° = 0.1 MPa) molar enthalpies of formation in the crystalline phase of these compounds were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The vapour pressures of the crystalline phase of the two compounds were measured using the Knudsen effusion method and a static method that has also been used to measure the liquid vapour pressures of 2-bromofluorene. From these results the standard molar enthalpies, entropies and Gibbs energies of sublimation of the two compounds studied and of vapourisation of 2-bromofluorene were derived. The enthalpies and temperatures of fusion were determined from DSC experiments. Derived results of standard enthalpies and Gibbs energies of formation, in both gaseous and crystalline phases, were compared with the ones reported in the literature for fluorene.The experimental values of the gas-phase enthalpies of formation of each compound were compared with estimates based on density functional theory calculations using the B3LYP hybrid exchange–correlation energy functional with the 6-311++G(d,p) basis set. 相似文献
14.
《The Journal of chemical thermodynamics》2001,33(10):1263-1275
The standard (p ∘ = 0.1MPa) molar enthalpies of combustion in oxygen, at T = 298.15 K, for crystalline picolinamide (2-NH2COPy), nicotinamide (3-NH2COPy), isonicotinamide (4-NH2COPy), nicotinamide N -oxide (3- NH2COPyNO), and isonicotinamide N - oxide (4-NH2COPyNO) were measured by static-bomb calorimetry. These values were used to derive the standard molar enthalpies of formation of the crystalline compounds. The standard molar enthalpies of sublimation, at T = 298.15 K, for the three pyridinecarboxamide isomers were measured by microcalorimetry and the standard molar enthalpies of sublimation for the two pyridinecarboxamide N -oxide compounds were measured by a mass-loss effusion technique. From the enthalpies of formation of the gaseous compounds, the molar dissociation enthalpies Dmoof the (N + – O − ) covalent bonds were derived. Comparison has been made with Dmo(N–O) values in pyridine N -oxide derivatives. 相似文献
15.
The vapor pressures of crystalline and liquid phases of methyl p-hydroxybenzoate and of methyl p-methoxybenzoate were measured over the temperature ranges (338.9 to 423.7) K and (292.0 to 355.7) K respectively, using a static method based on diaphragm capacitance gauges. The vapor pressures of the crystalline phase of the former compound were also measured in the temperature range (323.1 to 345.2) K using a Knudsen mass-loss effusion technique. The results enabled the determination of the standard molar enthalpies, entropies and Gibbs free energies of sublimation and of vaporization, at T = 298.15 K, as well as phase diagram representations of the (p, T) experimental data, including the triple point. The temperatures and molar enthalpies of fusion of both compounds were determined using differential scanning calorimetry and were compared with the results indirectly derived from the vapor pressure measurements. The standard (p° = 105 Pa) molar enthalpies of formation, in the crystalline phase, at T = 298.15 K, of the compounds studied were derived from their standard massic energies of combustion measured by static-bomb combustion calorimetry. From the experimental results, the standard molar enthalpies of formation, in the gaseous phase at T = 298.15 K, were calculated and compared with the values estimated by employing quantum chemical computational calculations. A good agreement between experimental and theoretical results is observed. To analyze the thermodynamic stability of the two compounds studied, the standard Gibbs free energies of formation in crystalline and gaseous phases were undertaken. The standard molar enthalpies of formation of the title compounds were also estimated from two different computational approaches using density functional theory-based B3LYP and the multilevel G3 methodologies. 相似文献
16.
Manuel A.V. Ribeiro da Silva Joana I.T.A. Cabral 《The Journal of chemical thermodynamics》2008,40(5):829-835
The standard (p° = 0.1 MPa) molar enthalpies of combustion of 1-(2H)-phthalazinone and phthalhydrazide, both in the solid phase, were measured at T = 298.15 K by static bomb calorimetry. Further, the standard molar enthalpies of sublimation, at T = 298.15 K, of these two phthalazine derivatives were derived from the Knudsen effusion technique. The combustion calorimetry results together with those obtained from the Knudsen effusion technique, were used to derive the standard molar enthalpies of formation, at T = 298.15 K, in the gaseous phase for 1-(2H)-phthalazinone and phthalhydrazide, respectively as, (79.1 ± 1.8) kJ · mol?1 and ?(107.4 ± 2.4) kJ · mol?1. 相似文献
17.
Reactions of Schiff bases (H2apahR) derived from acetophenone and acid hydrazides, triethylamine and [Ru(PPh3)3Cl2] (1:2:1 mole ratio) in methanol provide cyclometallated ruthenium(III) complexes of formula trans-[Ru(apahR)(PPh3)2Cl] in 74–81% yields. The complexes have been characterized by elemental analysis, magnetic susceptibility, spectroscopic (infrared, electronic and EPR) and electrochemical measurements. X-ray crystal structures of two representative complexes have been determined. In each complex, the metal centre is in distorted octahedral CNOClP2 coordination sphere assembled by the C,N,O-donor meridionally spanning apahR2?, the chloride and the two mutually trans-oriented PPh3 molecules. All the complexes are one-electron paramagnetic (μeff. = 1.85–1.98 μB) and display rhombic EPR spectra in frozen (120 K) dichloromethane-toluene (1:1) solution. Electronic spectra of the complexes display several absorptions within 470–270 nm due to ligand-to-metal charge transfer and ligand centred transitions. The complexes are redox active and display a Ru(III) → Ru(II) reduction and a Ru(III) → Ru(IV) oxidation in the potential ranges ?0.66 to ?0.70 V and 0.75 to 0.80 V (vs. Ag/AgCl), respectively. 相似文献
18.
《The Journal of chemical thermodynamics》2007,39(9):1286-1291
Density data for dilute aqueous solutions of two aliphatic ketones (3-pentanone, 2,4-pentanedione) are presented together with partial molar volumes at infinite dilution calculated from the experimental data. The measurements were performed at temperatures from T = 298 K up to either T = 573 K (3-pentanone) or T = 498 K (2,4-pentanedione) and at pressure close to the saturated vapour pressure of water, at pressures between 15 MPa and 20 MPa and at p = 30 MPa. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter. 相似文献
19.
Kamel Khimeche Abdallah Dahmani Jacques Jose 《The Journal of chemical thermodynamics》2008,40(5):777-781
The vapour pressures of liquid (3-diethylaminopropylamine (3-DEPA) + n-heptane) mixtures were measured by a static method between T = (303.15 and 343.15) K at 10 K intervals. The molar excess enthalpies HE at T = 303.15 K were measured for the systems {3-DEPA + CnH2n+2 (n = 6, 7, 12)}. The molar excess Gibbs free energies GE were obtained with Barker’s method and fitted to the Redlich–Kister equation. The Wilson equation was also used. Deviations between experimental and predicted GE and HE, by using group contribution UNIFAC (Gmehling version) model, were evaluated. 相似文献
20.
Maria das Dores M.C. Ribeiro da Silva Manuel A.V. Ribeiro da Silva Vera L.S. Freitas Maria Victoria Roux Pilar Jiménez Manuel Temprado Juan Z. Dávalos Pilar Cabildo Rosa M. Claramunt José Elguero 《The Journal of chemical thermodynamics》2008,40(3):386-393
A thermophysical and thermochemical study has been carried out for crystalline imidazolidin-2-one and N,N′-trimethyleneurea [tetrahydropyrimidin-2(1H)-one]. The thermophysical study was made by differential scanning calorimetry, d.s.c., in the temperature intervals between T = 268 K and their respective melting temperatures. Several solid–solid transitions have been detected in imidazolidin-2-one. The standard (p° = 0.1 MPa) molar enthalpies of formation, at T = 298.15 K, for crystalline imidazolidin-2-one and N,N′-trimethyleneurea [tetrahydropyrimidin-2(1H)-one], were determined using static-bomb combustion calorimetry. The standard molar enthalpies of sublimation, at T = 298.15 K, for the two compounds were derived from the variation of their vapour pressures, measured by the Knudsen effusion method, with the temperature. These two thermochemical parameters yielded the standard molar enthalpies of formation of the two cyclic urea compounds studied in the gaseous phase at T = 298.15 K. These values are discussed in terms of molecular structural contributions and interpreted on the bases of the “benzo-condensed effect” and of the ring strain of imidazolidin-2-one. 相似文献