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Abstract  

The enthalpies of solution in water of L--methionine and its zinc complexes Zn(Met)Cl2, Zn(Met)2Cl2·2H2O, Zn(Met)(NO3)2·1/2H2O, Zn(Met)3(NO3)2·H2O and Zn(Met)SO4·H2O have been measured at 298.15 K. The standard enthalpy of formation of met(aq) has been calculated. The experimental results have been discussed.

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Abstract  

A fully automated adiabatic calorimeter controlled on line by a computer used for heat capacity measurements in the temperature range from 80 to 400 K was constructed. The hardware of the calorimetric system consisted of a Data Acquisition/Switch Unit, 34970A Agilent, a 7 1/2 Digit Nano Volt /Micro Ohm Meter, 34420A Agilent, and a P4 computer. The software was developed according to modern controlling theory. The adiabatic calorimeter consisted mainly of a sample cell equipped with a miniature platinum resistance thermometer and an electric heater, two (inner and outer) adiabatic shields, two sets of six junction differential thermocouple piles and a high vacuum can. A Lake Shore 340 Temperature Controller and the two sets of differential thermocouples were used to control the adiabatic conditions between the cell and its surroundings. The reliability of the calorimeter was verified by measuring the heat capacities of synthetic sapphire (α-Al2O3), Standard Reference Material 720. The deviation of the data obtained by this calorimeter from those published by NIST was within ±0.1% in the temperature range from 80 to 400 K.

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Abstract  

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 (Δfus H m 0), and the molar entropy (Δfus S m 0) 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 Δc H m 0 (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, Δr H m 0 (C6H8N2,cr)= −1.74±0.57 kJ mol−1.

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Abstract  

A solid complex Eu(C5H8NS2)3(C12H8N2) has been obtained from reaction of hydrous europium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen⋅H2O) in absolute ethanol. IR spectrum of the complex indicated that Eu3+ in the complex coordinated with sulfur atoms from the APDC and nitrogen atoms from the o-phen. TG-DTG investigation provided the evidence that the title complex was decomposed into EuS. The enthalpy change of the reaction of formation of the complex in ethanol, Δr H m θ(l), as –22.2140.081 kJ mol–1, and the molar heat capacity of the complex, c m, as 61.6760.651 J mol–1 K–1, at 298.15 K were determined by an RD-496 III type microcalorimeter. The enthalpy change of the reaction of formation of the complex in solid, Δr H m θ(s), was calculated as 54.5270.314 kJ mol–1 through a thermochemistry cycle. Based on the thermodynamics and kinetics on the reaction of formation of the complex in ethanol at different temperatures, fundamental parameters, including the activation enthalpy (ΔH θ), the activation entropy (ΔS θ), the activation free energy (ΔG θ), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained. The constant-volume combustion energy of the complex, Δc U, was determined as –16937.889.79 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16953.379.79 and –1708.2310.69 kJ mol–1, respectively.

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Abstract  

A complex of neodymium perchloric acid coordinated with L-glutamic acid and imidazole, [Nd(Glu)(H2O)5(Im)3](ClO4)6·2H2O was synthesized and characterized by IR and elements analysis for the first time. The thermodynamic properties of the complex were studied with an automatic adiabatic calorimeter and differential scanning calorimetry (DSC). Glass transition and phase transition were discovered at 221.83 and 245.45 K, respectively. The glass transition was interpreted as a freezing-in phenomenon of the reorientational motion of ClO4 ions and the phase transition was attributed to the orientational order/disorder process of ClO4 ions. The heat capacities of the complex were measured with the automatic adiabatic calorimeter and the thermodynamic functions [H T-H 298.15] and [S T-S 298.15] were derived in the temperature range from 80 to 390 K with temperature interval of 5 K. Thermal decomposition behavior of the complex in nitrogen atmosphere was studied by thermogravimetric (TG) analysis and differential scanning calorimetry (DSC).

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Abstract  

A novel solid complex, formulated as Ho(PDC)3 (o-phen), has been obtained from the reaction of hydrate holmium chloride, ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phenH2O) in absolute ethanol, which was characterized by elemental analysis, TG-DTG and IR spectrum. The enthalpy change of the reaction of complex formation from a solution of the reagents, Δr H m θ (sol), and the molar heat capacity of the complex, c m, were determined as being –19.1610.051 kJ mol–1 and 79.2641.218 J mol–1 K–1 at 298.15 K by using an RD-496 III heat conduction microcalorimeter. The enthalpy change of complex formation from the reaction of the reagents in the solid phase, Δr H m θ(s), was calculated as being (23.9810.339) kJ mol–1 on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. The thermodynamics of reaction of formation of the complex was investigated by the reaction in solution at the temperature range of 292.15–301.15 K. The constant-volume combustion energy of the complex, Δc U, was determined as being –16788.467.74 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16803.957.74 and –1115.428.94 kJ mol–1, respectively.

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Thermodynamic investigation of several natural polyols (II)

Heat capacities and thermodynamic properties of sorbitol

Journal of Thermal Analysis and Calorimetry
Authors:
B. Tong
,
Z. Tan
,
Q. Shi
,
Y. Li
, and
S. Wang

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.

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Summary A ternary solid complex Gd(Et2dtc)3(phen) has been obtained from reactions of sodium diethyldithiocarbamate (NaEt2dtc), 1,10-phenanthroline (phen) and hydrated gadolinium chloride in absolute ethanol. The title complex was described by chemical and elemental analyses, TG-DTG and IR spectrum. The enthalpy change of liquid-phase reaction of formation of the complex, Δr H Θ m(l), was determined as (-11.628±0.0204) kJ mol-1 at 298.15 K by a RD-496 III heat conduction microcalorimeter. The enthalpy change of the solid-phase reaction of formation of the complex, Δr H Θ m(s), was calculated as (145.306±0.519) kJ mol-1 on the basis of a designed thermochemical cycle. The thermodynamics of reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A), the reaction order (n), the activation enthalpy (Δr H Θ ), the activation entropy (Δr S Θ ), the activation free energy (Δr G Θ ) and the enthalpy (Δr H Θ ), were obtained by combination of the thermodynamic and kinetic equations for the reaction with the data of thermokinetic experiments. The constant-volume combustion energy of the complex, Δc U, was determined as (-18673.71±8.15) kJ mol-1 by a RBC-II rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H Θ m, and standard enthalpy of formation, Δf H Θ m, were calculated to be (-18692.92±8.15) kJ mol-1 and (-51.28±9.17) kJ mol-1, respectively.

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Abstract  

Solid complexes of M(His)2Cl2 nH2O (M=Mn, Co, Ni, Cu) of MnCl26H2O, CoCl26H2O, NiCl26H2O, CuCl22H2O and L-α-histidine (His) have been prepared in 95% ethanol solution and characterized by elemental analyses, chemical analyses, IR and TG-DTG. The constant-volume combustion energies of the complexes have been determined by a rotating-bomb calorimeter. And the standard enthalpies of formation of the complexes have been calculated as well.

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Abstract  

The solid complexes of Cr(NO3)3 with L-α-amino acids (AA=Val, Leu, Thr, Arg, Phe and Try) have been prepared in 95% alcoholic, the compositions of which were identified as the general formula Cr(AA)2(NO3)32H2O by elemental and chemical analyses. The bonding characteristics of the title complexes were characterized by IR, indicating that nitrogen and oxygen atoms in the ligands coordinated to Cr3+ in a bidentate fashion. With the aid of TG-DTG and IR techniques, the complexes were subjected to thermal decomposition in an atmosphere of oxygen, presuming that the decompositions of the complexes consist of two steps and the complexes were decomposed into chromium hemitrioxide after undergoing dehydration and skeleton splitting of the complexes. The constant volume energies of combustion of the complexes were determined by a RBC-P type rotating-bomb calorimeter. According to Hess's law, the standard enthalpies of formation of the complexes were calculated as (-1831.404.40), (-2542.036.13), (-1723.813.99), (-2224.313.02), (-2911.616.53) and (-659.327.42) kJ mol-1, respectively.

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