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A numerical method for the calculation of the composition of two phases in equilibrium is proposed for the case when the composition of one of the phases is known as function of the temperature. The thermodynamic properties of the phases are not needed to be known in the proposed procedure. The feature of this approach is the possibility to use fictitious thermodynamic functions in the intermediate stages of computation. The method has been applied for calculation of solidus in phase diagrams of potassium-rubidium, potassium-cesium and cesium-rubidium systems from experimental liquidus data.
Thermodynamic investigation of room temperature ionic liquid
Heat capacity and thermodynamic functions of BMIBF4
Abstract
The molar heat capacities of the room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C P,m (J K–1 mol–1)= 195.55+47.230 X–3.1533 X 2+4.0733 X 3+3.9126 X 4 [X=(T–125.5)/45.5] for the solid phase (80~171 K), and C P,m (J K–1 mol–1)= 378.62+43.929 X+16.456 X 2–4.6684 X 3–5.5876 X 4 [X=(T–285.5)/104.5] for the liquid phase (181~390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BMIBF4 relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass translation of BMIBF4 was observed at 176.24 K. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BMIBF4 was determined to be Δc H m o= – 5335±17 kJ mol–1. The standard molar enthalpy of formation of BMIBF4 was evaluated to be Δf H m o= –1221.8±4.0 kJ mol–1 at T=298.150±0.001 K.
Thermodynamic investigation of several natural polyols (II)
Heat capacities and thermodynamic properties of sorbitol
Abstract
The low-temperature heat capacity C p,m of sorbitol was precisely measured in the temperature range from 80 to 390 K by means of a small sample automated adiabatic calorimeter. A solid-liquid phase transition was found at T=369.157 K from the experimental C p-T curve. The dependence of heat capacity on the temperature was fitted to the following polynomial equations with least square method. In the temperature range of 80 to 355 K, C p,m/J K−1 mol−1=170.17+157.75x+128.03x 2-146.44x 3-335.66x 4+177.71x 5+306.15x 6, x= [(T/K)−217.5]/137.5. In the temperature range of 375 to 390 K, C p,m/J K−1 mol−1=518.13+3.2819x, x=[(T/K)-382.5]/7.5. The molar enthalpy and entropy of this transition were determined to be 30.35±0.15 kJ mol−1 and 82.22±0.41 J K−1 mol−1 respectively. The thermodynamic functions [H T-H 298.15] and [S T-S 298.15], were derived from the heat capacity data in the temperature range of 80 to 390 K with an interval of 5 K. DSC and TG measurements were performed to study the thermostability of the compound. The results were in agreement with those obtained from heat capacity measurements.
Polymorphism of paracetamol
Relative stability of the monoclinic and orthorhombic phase revisited by sublimation and solution calorimetry
Abstract
The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG sub 298=60.0 kJ mol−1; ΔH sub 298=117.9�0.7 kJ mol−1; ΔS sub 298=190�2 J mol−1 K−1. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition enthalpy at 298 K, ΔH tr 298(I→II)=2.0�0.4 kJ mol−1, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based on ΔH tr 298 (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification II were also estimated (ΔG sub 298=56.1 kJ mol−1; ΔH sub 298=115.9�0.9 kJ mol−1; ΔS sub 298=200�3 J mol−1 K−1). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported found by classical thermochemical methods.
The aromatic amino acid behaviour in aqueous amide solutions
The temperature dependence of the L -phenylalanine-urea interaction
Abstract
The enthalpies of solution of L-phenylalanine in the mixtures of water with the protein denaturant urea have been measured in the temperature range of 288.15–318.15 K. Using the results of the present research and literature data of free energies, the standard thermodynamic functions of the solute transfer from water to aqueous urea solutions have been estimated in a wide temperature range. The enthalpic, heat capacity, entropic and free energy parameters of the solute-urea pair and triplet interactions have been computed. The amino acid — amide pair interaction was found to be attractive in the temperature range studied due to the favourable enthalpic term. The triplet interaction being slightly repulsive reveals the enthalpic origin also. The examination of the Savage and Wood additivity-of-groups approach does indicate the inapplicability of this scheme to enthalpies and entropies of interaction. It has been found for the first time that the heat capacity of interaction changes its sign at 303 K, i.e. the temperature dependence of enthalpic and entropic parameters passes through the pronounced extrema near the temperature of the minimum of the heat capacity of pure water.
Abstract
In an adiabatic vacuum calorimeter the temperature dependence of the heat capacity C p 0 of 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrocyclotetrasiloxane and polymethylhydrosiloxane on its basis was measured between 6 and 350 K mainly with accuracy of about 0.2%. Two-phase transitions corresponding, probably, to the fusion of cis-and trans-conformations of the monomer as well as the glass transition of the polymer were detected. The results obtained were used to calculate the thermodynamic functions C p 0, H 0(T)-H 0(0), S 0(T), G 0(T)-H 0(0) of the monomer and polymer in the range from T→0 to T=340 K, and to estimate the zero entropy S 0(0) of amorphous polymer. Standard entropies of formation ΔS f 0 of the tested monomer and polymer at T=298.15 K as well as the entropy of synthesis of polymethylhydrosiloxane from 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrocyclotetrasiloxane over the range from T→0 to 340 K were estimated. The value of fractal dimension D in the heat capacity function of the multifractal variant of the Debye’s theory of heat capacity was found to be 1.5 for polymer in the 18–35 K range, that testifies to its layer-chain structure.
Abstract
The 'hydrophobic effect' of the dissolution process of non-polar substances in water has been analysed under the light of a statistical thermodynamic molecular model. The model, based on the distinction between non-reacting and reacting systems explains the changes of the thermodynamic functions with temperature in aqueous systems. In the dissolution of non-polar substances in water, it follows from the model that the enthalpy change can be expressed as a linear function of the temperature (ΔH app =ΔH ø +n w C p,w T ). Experimental solubility and calorimetric data of a large number of non-polar substances nicely agree with the expected function. The specific contribution of n w solvent molecules depends on the size of solute and is related to destructuring (n w >0) of water molecules around the solute. Then the study of 'hydrophobic effect' has been extended to the protein denaturation and micelle formation. Denaturation enthalpy either obtained by van't Hoff equation or by calorimetric determinations again depends linearly upon denaturation temperature, with denaturation enthalpy, ΔH den , increasing with T . A portion of reaction enthalpy is absorbed by a number n w of water molecules (n w >0) relaxed in space around the denatured moieties. In micellization, an opposite process takes place with negative number of restructured water molecules (n w <0) because the hydrophobic moieties of the molecules joined by hydrophobic affinity occupy a smaller cavity.
Abstract
The heat capacities of fenpropathrin in the temperature range from 80 to 400 K were measured with a precise automatic adiabatic calorimeter. The fenpropathrin sample was prepared with the purity of 0.9916 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, 
fus
H
m,
fus
S
m, were determined to be 322.48±0.01 K, 18.57±0.29 kJ mol–1 and 57.59±1.01 J mol–1 K–1, respectively. The thermodynamic functions of fenpropathrin, 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. 450 K and terminates at ca. 575 K. The maximum decomposition rate was obtained at 558 K. The purity of the sample was determined by a fractional melting method.
Abstract
The heat capacities of trans-(R)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid in the temperature range from 78 to 389 K were measured with a precise automatic adiabatic calorimeter. The sample was prepared with the purity of 0.9874 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, Δfus H m, Δfus S m, were determined to be 344.75±0.02 K, 13.75±0.07 kJ mol−1, 39.88±0.21 J K−1 mol−1, respectively. The thermodynamic functions of the sample, 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 thermal decomposition of the sample was studied by TG analysis, the thermal decomposition starts at ca. 421 K and terminates at ca. 535 K, the maximum decomposition rate was obtained at 525 K. The order of reaction, pre-exponential factor and activation energy, are n=0.14, A=1.15·108 min−1, E=66.27 kJ mol−1, respectively.
Abstract
By kinetics of decomposition of solids in both isothermal and non-isothermal conditions, the compensation effect (CE) is rather
a rule.
The topic of this work is to suggest an activation mechanism which leads to the dependences similar with CE.
The solid is assimilated to a system of the harmonic oscillator with a Bose-Einstein energy distribution.
Considering an activation process due to a vibrational energy transfer from a homogeneous and isotropic field of thermic oscillators
to the solid-state oscillator, the thermodynamic functions are in the relationship
