A small sample-size automated adiabatic calorimeter from 70 to 580 K——Molar heat capacities of α-Al_2O_3

An automatic adiabatic calorimeter for measuring heat capacities in the temperature range 70—580 K, equipped with a small sample cell of 7.4 cm~3 in the internal volume has been developed. In order to obtain a good adiabatic condition of the calorimeter at high temperature, the calorimeter was surrounded in sequence by two adiabatic shields, three radiation shields and an auxiliary temperature-controlled sheath. The main body of the cell made of copper and the lid made of brass are silver-soldered and the cell is sealed with a copper screw cap. A sealing gasket made of Pb-Sn alloy is put between the cap and the lid to ensure a high vacuum sealing of the cell in the whole experimental temperature range. All the leads are insulated and fixed with W30-11 varnish, thus a good electric insulation is obtained at high temperature. All the experimental data, including those for energy and temperature are collected and processed automatically with a personal computer using a predetermined program. To verify the     

Low-temperature Heat Capacities and Thermodynamic Properties of Hydrated Sodium Cupric Arsenate [NaCuAsO4·1.5H2O（s）]

Low-temperature heat capacities of the solid compound NaCuAsO4·1.5H2O(s)were measured using a precision automated adiabatic calorimeter over a temperature range of T=78 K to T=390 K.A dehydration process occurred in the temperature range of T=368-374 K.The peak temperature of the dehydration was observed to be TD=(371.828±0.146)K by means of the heat-capacity measurement.The molar enthalpy and entropy of the dehydration were ΔDHm=(18.571±0.142)kJ/mol and ΔDSm=(49.946±0.415)J/(K·mol),respectively.The experimental values of heat capacities for the solid(Ⅰ)and the solid-liquid mixture(Ⅱ)were respectively fitted to two polynomial equations by the least square method.The smoothed values of the molar heat capacities and the fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated at an interval of 5 K.     

NATIONAL STANDARD OF HEAT CAPACITY MEASUREMENT OF SOLIDS IN THE RANGE OF 4.2—90K——AN AUTOMATED ADIABATIC CALORIMETER FROM 25 TO 90K AND MOLAR HEAT CAPACITIES OF α-ALUMINA

The construction of an automated adiabatic calorimeter for heat capacity measurement ofsolids in the temperature range of 25- 90K is described in detail. The sample vessel of thecalorimeter has thin radial vanes which make no contact with its inner wall and are distrib-uted evenly, thus greatly improving the internal thermal equilibration of the vessel. Theprecision of temperature control for the adiabatic shields and electrical leads of the calori-metric system are heightened to a great extent by using the high precision ACD- 79 modeladiabatic controller specially developed by us for this purpose. Measurements of the heatcapacities of high purity α-Al_2O_3, one of the internationally-accepted standard referencematerials, agree with those of the National Bureau of Standards (NBS), USA within ±0.3%,demonstrating the reliability of this apparatus.     

Crystal Structure and Thermodynamic Study of Ephedrine Hydrochloride C10H16NOCI（s）

The crystal structure of ephedrine hydrochloride was determined by means of X-ray crystallography.The crystal system of the compound is monoclinic,and the space group is P21.Unit cell parameters are a=0.7308(6) nm,b=0.6124(5) nm,and c=1.2618(11) nm;α=90°,β=102°,and γ=90°;Z=2.Low-temperature heat capacities of the title compound were measured with an improved precision automated adiabatic calorimeter over a temperature range from 77 K to 396 K.A polynomial equation of the heat capacities as a function of temperature in the temperature region was fitted by the least-squares.Based on the fitted polynomial equation,the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at the intervals of 5 K.     

水与正丁醇二元体系最低共沸混合物的热容

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 estabhshed for the azeotropic mixture. A glass transition was observed at （111.9±1.2） K. The phase transitions took place at （179.26±0.77） and （269.69±0.14） K corresponding to the solid-hquid 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 estabhshed, 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.     

AN AUTOMATED ADIABATIC CALORIMETER FOR USE FROM 80 TO 600 K——HEAT CAPACITIES OF α-ALUMINA

The construction of an automated adiabatic calorimeter for use from 80 to 600 K is reported. The main feature of the calorimoter is to mount three radiation shields in the cryostat for advancing the working tomperature. The molar heat capacity of α-Al_2O_3 has been measured in order to assess the reliability of the calorimeter. Deviations of the experimental heat capacities of α-Al_2O_3 from the smoothed curve are within ±0.3% except for a few experimental points. Our smoothed results agree with those of tho National Bureau of Standards. USA, within ±0.3% over the entire working temperature range.     

Low Temperature Heat Capacities and Thermodynamic Properties of Zinc L-Threonate Zn（C4H7O5）2（s） by Adiabatic Calorimetry

Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295？322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be （316.269±1.039） K, （11.194±0.335） kJ？mol-1, and （35.391±0.654） J？K-1？mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions of 78？295 K and 322？374 K were fitted to two polynomial equations of heat capacities（Cp,m） with reduced temperatures（X） and [X = f（T）], with the help of the least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound, relative to that of the standard reference temperature 293.15 K, were calculated on the basis of the fitted polynomials and tabulated with an interval of 5 K. In addition, the possible mechanism of thermal decomposition of the compound was inferred by the result of TG-DTG analysis.     

Low Temperature Heat Capacities and Thermodynamic Properties of Zinc L-Threonate Zn(C_4H_7O_5)_2(s) by Adiabatic Calorimetry

Low-temperature heat capacities of the solid compound Zn(C4H7O5)2(s) were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295?322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be (316.269±1.039) K, (11.194±0.335) kJ?mol-1, and (35.391±0.654) J?K-1?mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions o...     

Low-temperature Heat Capacities and Thermodynamic Properties of Solid State Coordination Compound Zn(nicotinate)_2·H_2O(s)

A novel compound—monohydrated zinc nicotinate was prepared via room temperature solid phase synthesis and ball grinding.FTIR,chemical and elemental analyses and X-ray powder diffraction technique were applied to characterizing the structure and composition of the complex.Low-temperature heat capacities of the solid coordination compound were measured by a precision automated adiabatic calorimeter over a temperature range from 77 to 400 K.A solid-solid phase transition process occurred in a temperature range...     

丙酮+环己烷+甲醇组成的最低共沸混合物热力学性质的研究

Molar heat capacities of the pure samples of acetone,methanol and the azeotropic mixture composed of acetone,cyclohexane and methanol were measured by an adiabatic calorimeter from 78 to 320 K.The solid-solid andsolid-liquid phase transitions of the pure samples and the mixture were determined based on the curve of the heatcapacity with respect to temperature.The phase transitions took place at(126.16±0.68)and(178.96±1.47)K forthe sample of acetone,(157.79±0.95)and(175.93±0.95)K for methanol,which were corresponding to thesolid-solid and the solid-liquid phase transitions of the acetone and the methanol,respectively.And the phase tran-sitions occurred in the temperature ranges of 120 to 190 K and 278 to 280 K corresponding to the solid-solid andthe solid-liquid phase transitions of mixture of acetone,cyclohexane and methanol,respectively.The thermody-namic functions and the excess thermodynamic functions of the mixture relative to standard temperature of 298.15K were derived based on the relationships of the thermodynamic functions and the function of the measured heatcapacity with respect to temperature.     

Thermochemistry on the Complex of Erbium Perchlorate with L-α-Glutamic Acid [Er2（L-Glu）2（H2O）6]（ClO4）4·6H2O（s）

A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）, was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with relevant literatures, its chemical composition and structure were established. The mechanism of thermal decomposition of the complex was deduced on the basis of the TG/DTG analysis. Low-temperature heat capacities were measured by a precision automated adiabatic calorimeter from 78 to 318 K. An endothermic peak in the heat capacity curve was observed over the temperature region of 290-318 K, which was ascribed to a solid-to-solid phase transition. The temperature Ttrans, the enthalpy △transHm and the entropy △transSm of the phase transition for the compound were determined to be： （308.73±0.45） K, （10.49±0.05） kJ·mol^-1 and （33.9±0.2） J·K^-1·mol^-1. Polynomial equation of heat capacities as a function of the temperature in the region of 78-290 K was fitted by the least square method. Standard molar enthalpies of dissolution of the mixture [2ErCl3·6H2O（s）＋2L-Glu（s）＋6NaClO4·H2O（s）] and the mixture {[Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）＋6NaCl（s）} in 100 mL of 2 mol·dm^-3 HClO4 as calorimetric solvent, and {2HClO4（1）} in the solution A＇ at T=298.15 K were measured to be, △dHm,1=（31.552±0.026） kJ·mol^-1, △dHm,2 = （41.302±0.034） kJ·mol^-1, and △dHm,3 = （ 14.986 ± 0.064） kJ·mol^-1, respectively. In accordance with Hess law, the standard molar enthalpy of formation of the complex was determined as △fHm-=-（7551.0±2.4） kJ·mol^-1 by using an isoperibol solution-reaction calorimeter and designing a thermochemical cycle.     

Low-Temperature Heat Capacities and Thermodynamic Properties of Hydrated Nickel L-Threonate Ni（C4H7O5）2·2H2O（S）

Low-temperature heat capacities of the compound Ni（C4H7O5）2·2H2O（S） have been measured with an auto- mated adiabatic calorimeter. A thermal decomposition or dehydration occurred in 350--369 K. The temperature, the enthalpy and entropy of the dehydration were determined to be （368.141 ±0.095） K, （18.809±0.088） kJ·mol ^-1 and （51.093±0.239） J·K^-1·mol^-1 respertively. The experimental values of the molar heat capacities in the temperature regions of 78-350 and 368-390 K were fitted to two polynomial equations of heat capacities （Cp,m） with the reduced temperatures （X）, [X=f（T）], by a least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated on the basis of the fitted polynomials. The smoothed values of the molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated with an interval of 5 K.     

乙醇和甲苯组成的最低共沸混合物热力学性质的研究

The molar heat capacity of the azeotropic mixture composed of ethanol and toluene was measured by a high precision adiabatic calorimeter from 80 to 320 K. The glass transition and phase transitions of the azeotropic mixture were determined based on the heat capacity measurements. A glass transition at 103.350 K was found. A solid-solid phase transition at 127.282 K, two solid-liquid phase transitions at 153.612 and 160.584 K were observed, which correspond to the transition of metastable crystal to stable crystal of ethanol and the melting of ethanol and toluene, respectively. The thermodynamic functions and the excess ones of the mixture relative to the standard temperature 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature.     

Low-Temperature Heat Capacities and Thermodynamic Properties of Octahydrated Barium Dihydroxide,Ba（OH）2·8H2O（s）

Low-temperature heat capacities of octahydrated barium dihydroxide, Ba（OH）2·8H2O（s）, were measured by a precision automated adiabatic calorimeter in the temperature range from T=78 to 370 K. An obvious endothermic process took place in the temperature range of 345-356 K. The peak in the heat capacity curve was correspondent to the sum of both the fusion and the first thermal decomposition or dehydration. The experimental molar heat capacifies in the temperature ranges of 78-345 K and 356-369 K were fitted to two polynomials. The peak temperature, molar enthalpy and entropy of the phase change have been determined to be （355.007±0.076） K, （73.506±0.011） kJ·ol^-1 and （207.140±0.074） J·K^-1·mol^-1, respectively, by three series of repeated heat capacity measurements in the temperature region of 298-370 K. The thermodynamic functions, （Hr-H298.15 k ）and （Sr-S298.15k）, of the compound have been calculated by the numerical integral of the two heat-eapacity polynomials. In addition, DSC and TG-DTG techniques were used for the further study of thermal behavior of the compound. The latent heat of the phase change became into a value larger than that of the normal compound because the melfing process of the compound must be accompanied by the thermal decomposition or dehydration of 71-120.     

微量热法测定RE(Et2dtc)3(phen)配合物的比热容

A calculation formula for determining the specific heat capacity of solid compound with an improved RD496-Ⅲ microcalorimeter was derived. The calorimetric constant and precision determined by the Joule effect were （63.901±0.030）μV/mW and 0.3% at 298.15 K, respectively, and the total disequilibrium heat has been measured by the Peltier effect. The specific heat capacities of two standard substances （benchmark benzoic acid and α-Al2O3） were obtained with this microcalorimeter, and the differences between their calculated values and literature values were less than 0.4%. Similarly, the specific heat capacities of thirteen solid complexes, RE（Et2dtc）3（phen） （RE=La, Pr, Nd, Sm-Lu, Et2dtc： diethyldithiocarbamate ion, phen： 1,10-phenanthroline） were gained, and their total deviations were within 1.0%. These values were plotted against the atomic numbers of rare-earth, which presents tripartite effect, suggesting a certain amount of covalent character in the bond of RE^3＋and ligands, according to Nephelauxetic effect of 4f electrons of rare earth ions.     

HEAT SHRINKING BEHAVIOUR OF γ-RADIATION CROSSLINKED POLYETHYLENE

Heat shrinking material of γ-radiation erosslinked polyethylene is widely used for various application in industry. In this study, DSC, TMA, WAXD and density measurement techniques were used to investigate the influence of MI and thermal history of LDPE on the effectiveness of network formation. Based on the results of heat stretching and heat shrinkage tests, it is found that the formation of a network as perfect as possible is indispensable to the irradiated material if good heat shrinkage property is desired. To this end, quenching technique and polyethylene with appropriate MI must be used so that an effective radiation effect will be obtained with a minimum amount of radiation dose. In spite of that the mechanical property of the irradiated polyethylene in the rubbery state is basically in agreement with the classical expression of the theory of high elasticity, only about 90% shrinkage can be reached. Besides, the heat shrinkage temperature T_s and the % shrinkage Sare both related to the radiation dose.     

LOW-TEMPERATURE HEAT CAPACITIES AND THERMODYNAMIC PROPERTIES OF LANTHANUM AND CERIUM TRIISOTHIOCYANATE HYDRATESI (Ⅰ)——La(NCS)_3, 7H_2O AND Ce(NCS)_3. 7H_2O

The heat capacities of La(NCS)_3. 7H_2O and Ce(NCS)_3. 7H_2O have been measured from 13 to 300K with a fully-automated adiabatic calorimeter. The construction and procedures of the calorimetric system are described in detail. No obvious thermal anomaly was observed for both compounds in the experimental temperature range. The polynomial equations for calculating the heat capacity values of the two compounds in the range 13—300K were obtained by the least-squares fitting based on the experimental C_p data. The C_p values below 13K were estimated by using the Debye and Einstein heat Capacity functions. The standard molar thermodynamic functions were calculated from 0 to 300K. Gibbs energies of formation were also calculated.     

2-氯-N,N-二甲基尼古丁酰胺的热容和热力学性质研究

Low-temperature heat capacities of 2-chloro-N,N-dimethylnicotinamide were precisely measured with a high-precision automated adiabatic calorimeter over the temperature range from 82 K to 380 K. The compound was observed to melt at （342.15±0.04） K. The molar enthalpy AfusionHm, and entropy of fusion, △fusionSm, as well as the chemical purity of the compound were determined to be （21387±7） J·mol^-1, （62.51±0.01） J·mol^-1·K^-1, （0.9946±0.0005） mass fraction, respectively. The extrapolated melting temperature for the pure compound obtained from fractional melting experiments was （342.25±0.024） K. The thermodynamic function data relative to the reference temperature 298.15 K were calculated based on the heat capacity measurements in the temperature range from 82 to 325 K. The thermal behavior of the compound was also investigated by different scanning calorimetry.     

Heat Capacities and Thermodynamic Properties of 3-（2,2-Dichloroethenyl）-2,2-dimethylcyclopropanecarboxylic Acid

The heat capacities of 3 - (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid ( a racemic mixture,molar ratio of cis-/trans-structure is 35/65) in a temperature range from 78 to 389 K were measured with a precise automatic adiabatic calorimeter. The sample was prepared with a purity of 98.75% ( molar fraction). A solid-liquid fusion phase transition was observed in the experimental temperature range. The melting point, Tm, enthalpy and entropy of fusion, △fusHm, △fusSm, of the acid were determined to be ( 331.48 ± 0.03 ) K, ( 16. 321 ± 0.031 ) kJ/mol,and (49.24 ± 0.19) J/( K·mol), respectively. The thermodynamic functions of the sample, HT - H298.15, ST -S298.15 and GT - G298.15, were reported at a temperature intervals of 5 K. The thermal decomposition of the sample was studied using thermogravimetric (TG) analytic technique, the thermal decomposition starts at ca. 418 K and ends at ca. 544 K, the maximum decomposition rate was obtained at 510 K. The order of reaction, preexponential factor and activation energy are n =0.23, A =7. 3 × 107 min -1, E =70.64 KJ/mol, respectively.     

Temperature waves in chemical reaction-diffusion-heat conduction systems with two ends respectively subject to Dirichlet and no-flux conditions

Taking the Lindemann model as a sample system in which there exist chemical reactions,diffusion and heat conduction,we found the theoretical framework of linear stability analysis for a unidimensional nonhomogeneous two-variable system with one end subject to Dirichlet conditions,while the other end no-flux conditions.Furthermore,the conditions for the emergence of temperature waves are found out by the linear stabilily analysis and verified by a diagram for successive steps of evolution of spatial profile of temperature during a period that is plotted by numerical simulations on a computer.Without doubt,these results are in favor of the heat balance in chemical reactor designs.