Thermodynamic consistency of the ternary functions

A ternary thermodynamic function has been developed based on statistico-thermodynamic considerations, with a particular emphasis on the higher-order terms indicating the effects of truncation at the various stages of the treatment. Although the truncation of a series involved in the equation introduces inconsistency, the latter may be removed by imposing various thermodynamic boundary conditions. These conditions are discussed in the paper. The present equation with higher-order terms shows that the α function of a component reduces to a quadratic function of composition at constant compositional paths involving the other two components in the system. The form of the function has been found to be representative of various experimental observations.

Low-temperature heat capacities and derived thermodynamic functions of cyclohexane

The low-temperature heat capacities of cyclohexane were measured in the temperature range from 78 to 350 K by means of an automatic adiabatic calorimeter equipped with a new sample container adapted to measure heat capacities of liquids. The sample container was described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on water. The deviations of experimental heat capacities from the corresponding smoothed values lie within +/-0.3%, while the inaccuracy is within +/-0.4%, compared with the reference data in the whole experimental temperature range. Two kinds of phase transitions were found at 186.065 and 279.684 K corresponding solid-solid and solid-liquid phase transitions, respectively. The entropy and enthalpy of the phase transition, as well as the thermodynamic functions {H-(T)- H-298.15 K} and {S-(T)-S-298.15 K}, were derived from the heat capacity data. The mass fraction purity of cyclohexane sample used in the present calorimetric study was determined to be 99.9965% by fraction melting approach.

Heat capacities and thermodynamic properties of chrysanthemic acid

The heat capacities of chrysanthemic acid in the temperature range from 80 to 400 K were measured with a precise automatic adiabatic calorimeter. The chrysanthemic acid sample was prepared with the purity of 0.9855 mole fraction. A solid-liquid fusion phase transition was observed in the experimental temperature range. The melting point, T-m, enthalpy and entropy of fusion, Delta(fus)H(m), Delta(fus)S(m), were determined to be 390.741 +/- 0.002 K, 14.51 +/- 0.13 kJ mol(-1), 37.13 +/- 0.34 J mol(-1) K-1, respectively. The thermodynamic functions of chrysanthemic acid, H-(T)-H-(298.15), S-(T)-S-(298.15) and G((T))-G((298.15)) were reported with a temperature interval of 5 K. The TG analysis under the heating rate of 10 K min(-1) confirmed that the thermal decomposition of the sample starts at ca. 410 K and terminates at ca. 471 K. The maximum decomposition rate was obtained at 466 K. The purity of the sample was determined by a fractional melting method.

Heat capacity and thermodynamic properties of crystalline ornidazole (C7H10ClN3O3)

The molar heat capacities of 1-(2-hydroxy-3-chloropropyl)-2-methyl-5-nitroimidazole (Ornidazole) (C7H10CIN3O3) with purity of 99.72mol% were measured with an adiabatic calorimeter in the temperature range between 79 and 380K. The melting-point temperature, molar enthalpy Delta(fus)H(m), and entropy, Delta(fus)S(m), of fusion of this compound were determined to be 358.59 +/- 0.04K, 21.38 +/- 0.02 kJ mol(-1) and 59.61 +/- 0.05 J K-1 mol(-1), respectively, from fractional melting experiments. The thermodynamic function data relative to the reference temperature (298.15 K) were calculated based on the heat capacities measurements in the temperature range from 80 to 380 K. The thermal stability of the compound was further investigated by DSC and TG. From the DSC curve an intensive exothermic peak assigned to the thermal decomposition of the compound was observed in the range of 445-590 K with the peak temperature of 505 K. Subsequently, a slow exothermic effect appears when the temperature is higher than 590 K, which is probably due to the further decomposition of the compound. The TG curve indicates the mass loss of the sample starts at about 440K, which corresponds to the decomposition of the sample. (C) 2003 Elsevier B.V. All rights reserved.

Thermodynamic study of ibuprofen by adiabatic calorimetry and thermal analysis

Molar heat capacities of ibuprofen were precisely measured with a small sample precision automated adiabatic calorimeter over the temperature range from 80 to 400 K. The polynomial functions of C-p,C-m (J K-1 mol(-1)) versus T were established on the heat capacity measurements by means of the least fitting square method. The functions are as follows: for solid ibuprofen, at the temperature range of 79.105 K less than or equal to T less than or equal to 333.297 K, C-p,C-m = 144.27 + 77.046X + 3.5171X(2) + 10.925X(3) + 11.224X(4), where X = (T - 206.201)/127.096; for liquid ibuprofen, at the temperature range of 353.406 K less than or equal to T less than or equal to 378.785 K, C-p,C-m = 325.79 + 8.9696X - 1.6073X(2) - 1.5145 X-3, where X = (T - 366.095)/12.690. A fusion transition at T = 348.02 K was found from the C-p-T curve. The molar enthalpy and entropy of the fusion transition were determined to be 26.65 kJ mol(-1) and 76.58 J mol(-1) K-1, respectively. The thermodynamic functions on the base of the reference temperature of 298.15 K, (H-T - H-298.15) and (S-T - S-298.15), were derived. Thermal characteristic of ibuprofen was studied by thermo-gravimetric analysis (TG-DTG) and differential scanning calorimeter (DSC). The temperature of fusion, the molar enthalpy and entropy of fusion obtained by DSC were well consistent with those obtained by adiabatic calorimeter. The evaporation process of ibuprofen was investigated further by TG and DTG, and the activation energy of the evaporation process was determined to be 80.3 +/- 1.4 kJ mol(-1). (C) 2003 Elsevier B.V. All rights reserved.

Investigation of thermodynamic properties of Co2O3 powder

The isobaric molar heat capacities of powder of Co2O3 were determined by an adiabatic calorimeter in the temperature range from 78 to 350 K. No phase transition takes place in this temperature range. The relationship of C-p,C-m with thermodynamic temperature T was established as C-p,C-m = -5 x 10(-6)T(3) + 0.0026T(2) + 0.0325T + 4.2592 (J K-1 mol(-1)), fitting coefficient R-2 = 0.9996. According to this relationship and the relationships between thermodynamic functions, the thermodynamic functions of powder of C2O3 were derived with 298.15 K as reference temperature. Thermal decomposition of Co2O3 powder was studied through thermogravimetry (TG). The possible mechanism of the thermal decomposition reaction was suggested according to the TG result. (C) 2003 Elsevier Science B.V. All rights reserved.

Heat capacities and thermodynamic functions of p-chlorobenzoic acid

The heat capacities of p-chlorobenzoic acid were measured in the temperature range from 80 to 580 K by means of an automatic adiabatic calorimeter equipped with a small sample cell of internal volume of 7.4cm(3). The construction and procedures of the calorimetric system were described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on alpha-Al2O3. The deviations of experimental heat capacities from the corresponding smoothed values lie within +/-0.28 per cent, while the inaccuracy is within +/-0.40 per cent, compared with the recommended reference data in the whole experimental temperature range. A fusion transition at T = 512.280 K was found from the C-p-T curve of p-chlorobenzoic acid. The enthalpy and entropy of the phase transition, as well as the thermodynamic functions {G((T)) - G((298.15))}, {H-(T) - H-(298.15)} and {S-(T) - S-298.15}, were derived from the heat capacity data. The mass fraction purity of p-chlorobenzoic acid sample used in the present calorimetric study was determined to be 0.99935 by fraction melting approach. (C) 2002 Elsevier Science Ltd. All rights reserved.

I. The structure and properties of closed circular duplex DNA. II. Chemically interacting systems at equilibrium in a buoyant density gradient

I. The binding of the intercalating dye ethidium bromide to closed circular SV 40 DNA causes an unwinding of the duplex structure and a simultaneous and quantitatively equivalent unwinding of the superhelices. The buoyant densities and sedimentation velocities of both intact (I) and singly nicked (II) SV 40 DNAs were measured as a function of free dye concentration. The buoyant density data were used to determine the binding isotherms over a dye concentration range extending from 0 to 600 µg/m1 in 5.8 M CsCl. At high dye concentrations all of the binding sites in II, but not in I, are saturated. At free dye concentrations less than 5.4 µg/ml, I has a greater affinity for dye than II. At a critical amount of dye bound I and II have equal affinities, and at higher dye concentration I has a lower affinity than II. The number of superhelical turns, τ, present in I is calculated at each dye concentration using Fuller and Waring's (1964) estimate of the angle of duplex unwinding per intercalation. The results reveal that SV 40 DNA I contains about -13 superhelical turns in concentrated salt solutions.

The free energy of superhelix formation is calculated as a function of τ from a consideration of the effect of the superhelical turns upon the binding isotherm of ethidium bromide to SV 40 DNA I. The value of the free energy is about 100 kcal/mole DNA in the native molecule. The free energy estimates are used to calculate the pitch and radius of the superhelix as a function of the number of superhelical turns. The pitch and radius of the native I superhelix are 430 Å and 135 Å, respectively.

A buoyant density method for the isolation and detection of closed circular DNA is described. The method is based upon the reduced binding of the intercalating dye, ethidium bromide, by closed circular DNA. In an application of this method it is found that HeLa cells contain in addition to closed circular mitochondrial DNA of mean length 4.81 microns, a heterogeneous group of smaller DNA molecules which vary in size from 0.2 to 3.5 microns and a paucidisperse group of multiples of the mitochondrial length.

II. The general theory is presented for the sedimentation equilibrium of a macromolecule in a concentrated binary solvent in the presence of an additional reacting small molecule. Equations are derived for the calculation of the buoyant density of the complex and for the determination of the binding isotherm of the reagent to the macrospecies. The standard buoyant density, a thermodynamic function, is defined and the density gradients which characterize the four component system are derived. The theory is applied to the specific cases of the binding of ethidium bromide to SV 40 DNA and of the binding of mercury and silver to DNA.

Thermochemical and thermal analysis on N-(p-methylphenyl)-N '-(2-pyridyl)urea

Low temperature heat capacities of N-(p-methylphenyl)-N'-(2-pyridyl)urea were determined by adiabatic calorimetry method in the temperature range from 80 to 370 K. It was found that there was not any heat anomaly in this temperature region. Based on the experimental data, some thermodynamic function results were obtained. Thermal stability and decomposition characteristics analysis of N-(p-methylphenyl)-N'-(2-pyridyl)urea were carried out by DSC and TG. The results indicated that N-(p-methylphenyl)-N'-(2-pyridyl)urea started to melt at ca. 426 K (153degreesC) and the melting peak located at 447.01 K (173.86degreesC). The melting enthalpy was 204.445 kJ mol(-1) (899.6 J g(-1)). The decomposition peak of N-(p-methylphenyl)-N'-(2-pyridyl)urea was found at 499.26 K (226.11degreesC) from DSC curve. This result was similar with that from TG and DTG experiment, in which the mass loss peak was determined as 500.4 K (227.2degreesC).

Studies on synergistic extraction of rare earths(III) with HBTMPTP and primary amine N1923

The synergistic extraction of rare earths(III) with binary systems containing HBTMPTP and primary amine N1923 from sulfuric acid medium was observed, The syner gistic extraction factor(R) decreased with increasing atomic number of lanthanides. Through the methods of slope analysis, constant mole and saturation titration, the synergistic extraction stoichiometry was obtained, The thermodynamic function was calculated, The IR spectra of the saturated synergistic extraction completely confirmed the mechanism.

Measurements of the heat capacity of an azeotropic mixture of water and n-butanol from 78 to 320 K

Molar heat capacities of n-butanol and the azeotropic mixture in the binary system [water (x=0.716) plus n-butanol (x=0.284)] were measured with an adiabatic calorimeter in a temperature range from 78 to 320 K. The functions of the heat capacity with respect to thermodynamic temperature were established for the azeotropic mixture. A glass transition was observed at (111.9 +/- 1.1) K. The phase transitions took place at (179.26 +/- 0.77) and (269.69 +/- 0.14) K corresponding to the solid-liquid phase transitions of. n-butanol and water, respectively. The phase-transition enthalpy and entropy of water were calculated. A thermodynamic function of excess molar heat capacity with respect to temperature was established, which took account of physical mixing, destructions of self-association and cross-association for n-butanol and water, respectively. The thermodynamic functions and the excess thermodynamic ones of the binary systems relative to 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity and the calculated excess heat capacity with respect to temperature.

X-ray diffraction and theoretical investigation of the Gedunin crystal structure

The Gedunin compound (C28H34O6) is a natural product extracted from Trichilia pallida that has shown a wide activity. The crystallographic structure shows two conformers in the asymmetric unit, which differ in a rotation of the furan group. To understand this molecular arrangement, the density functional calculations. Molecular Electrostatic Potential (MEP) and thermodynamic function calculation have been performed at the B3LYP/6-311++g(d,p) level. Both conformers were optimized and the agreement with the experimental structure was very good, making possible further theoretical analysis of the structure. The inter-conversion between two conformers depends on the energy barrier. This process is studied in the vacuum and shows two transition states with a low energetic barrier for a potential energy curve scanning rigid around furan group: 4.37 kcal/mol and 16.52 kcal/mol. As the first transition state has a notably lower energetic barrier, the preferred inter-conversion pathway between the conformers involves the first rather than the second transition state. Understanding this transition state in detail led us to perform its optimization, showing an energetic barrier around 3.66 kcal/mol. The negative free energy and low enthalpy confirm that the process is spontaneous and exothermic. The results show that this requirement makes the existence of the two conformers in the asymmetric unit possible. The structure of molecules in the asymmetric unit is better understood when the MEP is used on the interaction between molecules. For Gedunin, both molecules have shown MEP with well-defined regions, and this behavior contributes to the observed link between molecules and for the negative regions complementing positive regions of another molecule. (C) 2011 Elsevier B.V. All rights reserved.

Multidimensional modelling to investigate interspecies hydrogen transfer in anaerobic biofilms

Anaerobic digestion is a multistep process, mediated by a functionally and phylogenetically diverse microbial population. One of the crucial steps is oxidation of organic acids, with electron transfer via hydrogen or formate from acetogenic bacteria to methanogens. This syntrophic microbiological process is strongly restricted by a thermodynamic limitation on the allowable hydrogen or formate concentration. In order to study this process in more detail, we developed an individual-based biofilm model which enables to describe the processes at a microbial resolution. The biochemical model is the ADM1, implemented in a multidimensional domain. With this model, we evaluated three important issues for the syntrophic relationship: (i) is there a fundamental difference in using hydrogen or formate as electron carrier? (ii) Does a thermodynamic-based inhibition function produced substantially different results from an empirical function? and; (iii) Does the physical colocation of acetogens and methanogens follow directly from a general model. Hydrogen or formate as electron carrier had no substantial impact on model results. Standard inhibition functions or thermodynamic inhibition function gave similar results at larger substrate field grid sizes (> 10 mu m), but at smaller grid sizes, the thermodynamic-based function reduced the number of cells with long interspecies distances (> 2.5 mu m). Therefore, a very fine grid resolution is needed to reflect differences between the thermodynamic function, and a more generic inhibition form. The co-location of syntrophic bacteria was well predicted without a need to assume a microbiological based mechanism (e.g., through chemotaxis) of biofilm formation.

Thermodynamic properties of water sorption of jackfruit (Artocarpus heterophyllus Lam.) as a function of moisture content

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