无水硫酸铀酰和三水合硝酸铀酰的真空绝热量热学研究

建立了一套真空绝热量热计。在60-300K间测定了氯化钾的摩尔热容,所得结果同文献值相比能较好地符合,说明所建量热计是可靠的。用该量热计在60-300K间测定了无水硫酸铀酰和三水合硝酸铀酰的摩尔热容,在所研究的温度范围内未发现热容反常。无水硫酸铀酰和三水合硝酸铀酰在298.15K下的C_P^o、S_T^o-S_{O^o、HT^o-HO^o和-(GT^o-GO^o)/T值,前者分别为33.46卡/度·摩尔、39.7±0.4卡/度·摩尔、5925±20卡/摩尔和19.7±0.2卡/度·摩尔;后者分別为76.50卡/度·摩尔、88.3±0.9卡/度·摩尔、13282±50卡/摩尔和43.7±0.4卡/度·摩尔。}     

A small sample-size automated adiabatic calorimeter from 70 to 580 K

An automatic adiabatic calorimeter for measuring heat capacities in the temperature range 70-580 K, equipped with a small sample cell of 7.4 cm³ 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 automatically with a personal computer using a predetermined program. To verify the accuracy of the calorimeter, the heat capacities of α-Al₂O₃ of the calorimetric standard reference material is measured. The standard deviations of experimental heat capacity values from the smoothed values are within ± 0.28%, while the inaccuracy is within ±0.4% compared with those of the National Bureau of Standards over the entire working temperature range. Project supported by the National Natural Science Foundation of China (Grant No. 29573133).     

三甲醇丙烷—季戊四醇固体溶液的热容和相变焓

前曾报道季戊四醇在461.60K有一个固-固相变,其相交含为41.37kJmol~(-1)。但是,作为低温储能材料,该物质的相变温度偏高。从有关固-固相变储能材料的热力学研究中,我们发现三甲醇丙烷-季戊四醇固体溶液具有较低的固-固相变温度。本文测定了三甲醇丙烷-季戊四醇(摩尔比60:40)固体溶液的相变热参数和热容。     

A simple adiabatic low-temperature calorimeter based on a helium refrigerator system

The construction of an adiabatic calorimeter for the 15-300 K range is described. It is fully automated and set up in a helium refrigerator system. The operation of the calorimeter was tested by measuring the specific heat capacity of a pure copper sample. The results show good agreement with the standard literature values. The specific heat capacity of a magnesium hydride sample was also determined. For MgH₂, the standard molar entropy of S⁰(298.15)=30.64 J mol⁻¹ K⁻¹ was calculated from the obtained data.     

Conformational contribution to the heat capacity of the starch and water system

The heat capacities of starch and starch—water have been measured with adiabatic calorimetry and standard differential scanning calorimetry and are reported from 8 to 490 K. The amorphous starch containing 11–26 wt % (53–76 mol %) water shows a partial glass transition decreasing from 372 to 270 K, respectively. Even the dry amorphous starch gradually increases in heat capacity above 270 K beyond that set by the vibrational density of states. This gradual increase in the heat capacity is identified as part of the glass transition of dry starch that is, however, not completed at the decomposition temperature. The heat capacities of the glassy, dry starch are linked to an approximate group vibrational spectrum with 44 degrees of freedom. The Tarasov equation is used to estimate the heat capacity contribution due to skeletal vibrations with the parameters Θ₁ = 795.5 K, Θ₂ = 159 K, and Θ₃ = 58 K for 19 degrees of freedom. The calculated and experimental heat capacities agree better than ±3% between 8 and 250 K. Similarly, the vibrational heat capacity has been estimated for glassy water by being linked to an approximate group vibrational spectrum and the Tarasov equation (Θ₁ = 1105.5 K and Θ₃ = 72.4 K, with 6 degrees of freedom). Below the glass transition, the heat capacity of the solid starch—water system has been estimated from the appropriate sum of its components and also from a direct fitting to skeletal vibrations. Above the glass transition, the differences are interpreted as contributions of different conformational heat capacities from chains of the carbohydrates interacting with water. The conformational parts are estimated from the experimental heat capacities of dry starch and starch—water, decreased by the vibrational and external contributions to the heat capacity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3038–3054, 2001     

Application of a novel type of adiabatic scanning calorimeter for high-resolution thermal data near the melting point of gallium

A novel type of adiabatic scanning calorimeter (ASC) based on Peltier elements (PEs) is used to obtain high-resolution enthalpy and heat capacity data on the melting transition of gallium. The accuracy of the specific heat capacity and specific enthalpy is about 2 %, for a sub-mK temperature resolution. The simultaneously determined equilibrium specific heat capacity and specific enthalpy are used to determine the heat of fusion and the purity. In addition, the use of the PE-based ASC as a classical heat step calorimeter and as a constant rate (DSC-type) calorimeter is discussed. A comparison of the ASC results with literature data and DSC data shows the advantages of ASC for the study of phase transitions.     

An adiabatic low-temperature calorimeter for heat capacity measurement of small samples

A small sample adiabatic calorimeter for measuring heat capacities in the temperature range 60–350 K using the Nernst method has been constructed. The sample cell of the calorimeter is 6 cm³ in the internal volume, equipped with a miniature platinum thermometer and surrounded by two adiabatic shields. Two sets of 6-junction chromel-copel thermocouples were mounted between the cell and the shields to indicate the temperature differences between them. The adiabatic conditions of the cell were automatically controlled by two sets of temperature controller. A mechanical pump was used to pump out the vapour of liquid nitrogen in the cryostat to solidify N₂ (1), and 60 K or even lower temperature was obtained. The performance of this apparatus was evaluated by heat capacity measurements on α-alumina. The deviations of experimental results from a smoothed curve lie within ±0.2%, while the inaccuracy is within ±0.5% compared with the recommended reference data in the wole temperature range.     

Differential AC-chip calorimeter for glass transition measurements in ultrathin films

A differential AC-chip calorimeter capable of measuring the step in heat capacity at the glass transition in nanometer-thin films is described. Because of the differential setup, pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below 1 ng in broad temperature range as needed for the study of the glass transition in nanometer-thin polymeric films. Relative accuracy is sufficient to investigate the changes in heat capacity as the step at the glass transition of polystyrene. The step is about 25% of the total heat capacity of polystyrene. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin polystyrene films (50–4 nm) was determined at well-defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K)—neither at constant frequency (40 Hz) nor for the trace in the activation diagram (1 Hz–1 kHz). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2996–3005, 2006     

A Low-temperature Automated Adiabatic Calorimeter Heat Capacities of High-purity Graphite and Polystyrene

A computerized adiabatic calorimeter for heat capacity measurements in the temperature range 80–400 K has been constructed. The sample cell of the calorimeter, which is about 50 cm³ in internal volume, is equipped with a platinum resistance thermometer and surrounded by an adiabatic shield and a guard shield. Two sets of 6-junction chromel-copel thermocouples are mounted between the cell and the shields to indicate the temperature differences between them. The adiabatic conditions of the cell are automatically controlled by two sets of temperature controller. The reliability of the calorimeter was verified through heat capacity measurements on the standard reference material α-Al₂O₃. The results agreed well with those of the National Bureau of Standards (NBS): within ±0.2% throughout the whole temperature region. The heat capacities of high-purity graphite and polystyrene were precisely measured in the interval 260–370 K by using the above-mentioned calorimeter. The results were tabulated and plotted and the thermal behavior of the two materials was discussed in detail. Polynomial expressions for calculation of the heat capacities of the two substances are presented. This revised version was published online in August 2006 with corrections to the Cover Date.     

A fully automated adiabatic calorimeter for heat capacity measurement between 80 and 400 K

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.     

Definition of parameters phase equilibria and identification of phases of system hydrocarbon Water on the basis of calorimetric measurements

A new calorimetric method and the results of determination of binary systems phase equilibria having a region of phase stratification on the basis of calorimetric measurements are described in this paper. Isochoric heat capacity temperature dependence of binary system of hydrocarbon-water has been studied by the method of high-temperature adiabatic calorimeter. Parameters of the phase stratification region have been determined on the basis of revealed peculiarities of this dependence at phase transitions liquid-liquid and liquid-vapour and phase diagram have been made.     

Estimating the reversing and non‐reversing heat flow from standard DSC curves in the glass transition region

A mathematical model for the total heat flow obtained in differential scanning calorimetry (DSC) experiments from polymers with enthalpic relaxation is proposed. It is limited to the glass transition and enthalpic relaxation range of temperature and to the cases where the enthalpic relaxation is the only non‐reversing process taking place. The model consists of a mixture of functions representing the heat capacity heat flow of the glassy and non‐glassy fractions, the glass transition progress and the enthalpic relaxation heat flow. Optimal fittings of the model were performed on the experimental total heat flow data, obtained from two thermoplastics with different aging times. Considering which functions of the mixture represent reversing and non‐reversing processes, the reversing and non‐reversing heat flows were also estimated. The estimated reversing and non‐reversing signals were compared with the ones obtained by modulation. On the whole a good match was found, which was even better considering that the estimates are not affected by the frequency effect of the modulated temperature DSC (MTDSC) measurements. The model assumes linear trends for the heat capacity heat flow of the glassy and non‐glassy structures. The glass transition progress is represented by a generalized logistic function and the enthalpic relaxation heat flow by the first derivative of another generalized logistic. It brings about a new approach to these phenomena, where the parameters of these functions represent the temperature at which each event is centered, the change of heat capacity (C_p) at the glass transition and the energy involved in the enthalpic recovery. Copyright © 2011 John Wiley & Sons, Ltd.     

Uncertainty analysis of theoretical methods for adiabatic temperature rise determination in calorimetry

The main methods for the determination of the temperature rise in calorimetric experiments corrected of heat losses to surroundings (called adiabatic temperature rise) are described thereafter. This corrected temperature rise is obtained analytically from experimental temperature–time curves. The general scheme reported by Henri Régnault and Leopold Pfaundler for the first time in the 19th century is considered as the basis for all methods elaborated afterwards. A bibliographical study raised five methods including Régnault–Pfaundler’s. These methods have been applied on five experimental temperature–time curves obtained with an isoperibolic reference gas calorimeter at the French national metrology and testing institute (LNE) on combustion of pure methane. This paper deeply details a new analytical method elaborated at LNE exposing best heat transfer phenomena representation occurring in the water bath calorimeter. A comparative study of the five methods of the temperature rise determination and of their associated uncertainties is here presented.     

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. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic properties of ferrocene dicarboxylic acid

The temperature dependence of the heat capacity of crystal ferrocene dicarboxylic acid is studied in a precision adiabatic vacuum calorimeter in the range of 8 to 350 K. Its standard thermodynamic functions are calculated in the range of T → 0 to 350 K. The thermal and physical heat properties of ferrocene dicarboxylic acid are studied on a differential scanning calorimeter in the range of 260 to 573 K. The enthalpy of combustion for the investigated compound is measured in an isoperibol calorimeter. The standard thermodynamic functions of the formation of ferrocene dicarboxylic acid in the crystal state at 298.15 K are calculated.     

Thermodynamic properties of LiZr2(PO4)3 crystal phosphate

The temperature dependence of the heat capacity of LiZr₂(PO₄)₃ crystal phosphate is studied in an adiabatic vacuum calorimeter in the temperature range of 6 to 358 K. A phase transition caused by the transition of a low-temperature (triclinic) modification to a high-temperature (rhombohedral) modification is observed in the temperature range of 290–338 K and its standard thermodynamic characteristics are estimated and analyzed. Standard thermodynamic functions are calculated from experimental data: heat capacity, enthalpy, entropy, and Gibbs function in the range of T → 0 to 358 K. Fractal dimensionality D is calculated from the data on low-temperature (20 K ≤ T ≤ 50 K) heat capacity and the topology of the phosphate’s structure is estimated.     

Low-temperature heat capacities and thermodynamic properties of rare-earth triisothiocyanate hydrates (Ⅲ)——Sm(NCS)_3·6H_2O,Gd(NCS)_3·6H_2O,Yb(NCS)_3·6H_2O and Y(NCS)_3·6H_2O

The heat capacities of four RE isothiocyanate hydrates,Sm( NCS)3 6H2O,Gd( NCS)3 6H2O,Yb(NCS)3 6H2O and Y( NCS)3 6H2O,have been measured from 13 to 300 K with a fully-automated adiabatic calorimeter No obvious thermal anomaly was observed for the above-mentioned compounds in the experimental tem-peiatnre ranges.The polynomial equations for calculating the heat capacities of the four compounds in the range of 13-300K were obtained by the least-squares fitting based on the experimental Cp data.The Cp values below 13 K were estimated by using the Debye-Einstem heat capacity functions.The standard molar thermodynamic functions were calculated from 0 to 300 K.Gibbs energies of formation were also calculated.     

Determination of the specific heat capacity of hemoglobin- and methemoglobin-water mixtures using an adiabatic calorimeter

The specific heat capacity of bovine hemoglobin-, methemoglobin-, and thermally denatured hemoglobin-water mixtures were measured in the temperature range from 10 to 80°C. The partial specific heat capacities for mass fractions of the protein between 0 and 1 were computed. Significant differences of the partial quantities were obtained for the native, respectively denatured state of protein and for the protein in the native state in fluid mixtures, respectively in rather dry mixtures. For mixtures with protein mass fractions up to 0.45, exceeding the value in living human red cells, partial specific heat capacities of either components are found to be constant. The accuracy of the used adiabatic calorimeter will be described briefly.     

硝酸肼的量热研究

用精密自动绝热量热计测定了在220 K—370 K温度范围内硝酸肼的热容、熔化热、熔化温度和熔化熵。所得热容数据的精密度以百分偏差的均方根值表示为±0.2％。三次熔化热测定的相对偏差为±0.1％。为验证结果的可靠性, 用该装置测定了冰的熔化热和熔化温度, 其结果与文献值一致; 又用法国SETARAM公司的高温量热计测定了硝酸肼的熔化热和熔化温度, 其结果与我们用量热法测定的结果一致; 从量热结果计算出了该试样的纯度, 该结果亦与化学分析的结果一致。这些均可说明我们所测得的数据是可靠的。