Studies of thermokinetics in an adiabatic calorimeter

Thermokinetic research methods for irreversible and reversible reactions in the adiabatic calorimeter are proposed. Four reaction systems, including an endothermic reaction, have been studied with an adiabatic calorimeter and the validity of these methods is verified.     

High-precision adiabatic calorimetry and the specific heat of cyclopentane at low temperature

We describe a fully automated adiabatic calorimeter designed for high-precision covering the temperature range 15 to 300 K. Initial measurements were performed on synthetic sapphire (20 g). The statistical error of the apparatus estimated from the scattering of theC _p data of sapphire is about 0.1% and the average absolute error of specific heat between 100 and 300 K was 0.7% compared to values given in the literature. The heat capacity and the three phase transitions of cyclopentane (C₅H₁₀) which is recommended as a standard for the temperature calibration of scanning calorimeters have also been measured. The transition temperatures were determined to be (literature values in parentheses): 122.23 K (122.39 K) 138.35 K (138.07 K) and 178.59 K (179.69 K), with an experimental error of ±40 mK.     

Application of an adiabatic precision calorimeter in the field of organic reactions

Adiabatic calorimetry is a suitable method for investigations of reactions because the generated heat remains completely in the reactor. For the investigation of organic reactions, the adiabatic precision calorimeter ACTRON 5 is used. The alcoholyses of phenyl isocyanate and 1,2-butyleneoxide were investigated. The temperature-time course was estimated by means of the nonlinear program TA-kin. Inclusion of the concentration-time course in the estimation procedure led to an increase in the reliability of the parameters. Probes were taken during isoperibolic measurements and were analysed by means of HPLC.     

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.     

Thermal risk evaluation of organic peroxide by automatic pressure tracking adiabatic calorimeter

An automatic pressure tracking adiabatic calorimeter (APTAC) has been developed to obtain the thermokinetic and vapor pressure data during runaway reactions. The heat onset temperature is important data for estimating the thermal hazardous materials. DTBP(di-tert-butyl peroxide)/toluene was chosen for evaluating the measurement values and the thermokinetic parameters. The relationships between the sample mass and the heat onset temperature in the addition to the maximum temperature were investigated to explain the heat of reaction measured by the APTAC. The apparatus properties and the reliability of the data obtained by the APTAC were examined on the basis of the experimental data.     

Overview of calorimeter chips for various applications

This paper gives an overview of some of the recent developments in the area of chip calorimetry. Using several chip calorimeters developed at Xensor Integration and tested by users, examples of chip calorimetry and its applications will be given. Examples of chip calorimeters developed at various universities are given to widen the overview. The examples will be used to give more insight in the design and fabrication of various chip calorimeters.     

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).     

The Specific Heat of Tetramethylammonium Salts

New measurements of the (N(CH₃ )₄ )₂ MnBr₄ specific heat by adiabatic calorimetry around the ferro- paraelastic phase transition shown by the crystal around 276 K are compared with previous calorimetric studies on similar tetramethylammonium bromide compounds. The thermodynamic behaviour of the tribromides and tetrabromides derivatives together with the influence on the phase transition parameters of the cation and halogen molecular substitutions are examined. The thermal relaxation experiments permit to study the behaviour of the crystals thermal conduction as a function of the temperature. Finally, the Landau theory for second order phase transitions is used to describe the thermodynamic behaviour of some of these crystals. This revised version was published online in July 2006 with corrections to the Cover Date.     

Equilibrium and non-equilibrium phase transitions studied by adiabatic calorimetry

An adiabatic calorimetry was used for some investigations of equilibrium and non-equilibrium phase transitions. For one of the substances studied (4,4′-di-n-heptyloxyazoxybenzene) it was possible to determine temperature dependence of an order parameter and number of clusters of high temperature phase in a region of a phase transition. For another substance (liquid 3,4 dimethylpiridine) an anomaly on the specific heat curves was interpreted as being responsible for a decay of molecules’ clusters. Non-equilibrium phase transitions were investigated for some liquid crystal substances. The process of transformation between metastable and stable phases was described quantitatively. The conclusions obtained concern the stability of metastable phases.     

The specific heat of the ferroelectric phase transition in N(CH3)4CdBr3

The specific heat of N(CH₃)₄CdBr₃ from 50 to 300 K has been measured by adiabatic calorimetry, using both static and dynamic methods. The obtained results have permitted a careful study of the ferro-paraelectric phase transition the crystal shows at 160 K. The available spectroscopic data have been used to generate a reliable baseline which accounts for the normal lattice contribution to the specific heat. These results allow for an accurate estimation of the phase transition thermodynamic functions: ΔH=2620 J·mol^?1 and ΔS=18.04 J·(mol°C)^?1. These high values are in agreement with the predictions of the 6 well potential Frenkel model.     

Studies on thermokinetics of consecutive first-order reactions

The transformation equation for the thermokinetics of consecutive first-order reactions has been deduced, and a thermokinetic research method of irreversible consecutive first-order reactions, which can be used to determine the rate constants of two steps simultaneously, is proposed. The method was validated and its theoretical basis was verified by the experimental results.     

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.     

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.     

Fuzzy control for the precision water bath of the heat exchange calorimeter

Fuzzy inference approach was applied to select the control input for the precision water bath of the heat exchange calorimeter used at a non-air-conditioned laboratory. The thermal fluctuation of the bath water was necessary to be kept within a narrow range. The cooling water or coolant kept at a temperature lower than the set temperature was circulated in the bath. The deviation corresponding to the difference between the set temperature and the observed temperature was observed as the input signal. The output or control input to be given to the heather element in the water bath was calculated by the fuzzy modus. The output function was simplified by means of circulating the cooling water. The contribution of each membership function was changed according to the thermal progress of the observed temperature of the water. The whole system including the control programs was examined by a practical water bath, and fairly good results were obtained. Reasonable recoveries were also shown for external thermal disturbances given to the controlled system.

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Zusammenfassung Zur Wahl des Regel-Inputs des Präzisionswasserbades für ein Wärmeaustauschkalorimeter in einem nicht klimatisierten Laboratorium wurde eine Unschärfeschlußnäherung angewendet. Die thermischen Schwankungen des Wassers im Wasserbad müssen in engen Grenzen gehalten werden. Das Kühlwasser oder Kühlmittel mit einer niedrigeren Temperatur als die eingestellte Temperatur wird im Bad zirkuliert. Die Abweichung durch die Differenz zwischen der eingestellten Temperatur und der gemessenen Temperatur wird als Input-Signal beobachtet. Der an das Heizelement im Wasserbad weiterzuleitende Output oder Regel-Input wird mittels des Unschärfe-Modus berechnet. Die Output-Funktion wird durch das Zirkulieren des Kühlwassers vereinfacht. Der Beitrag jeder Teilfunktion wird in Abhängigkeit vom thermischen Verlauf der gemessenen Wassertemperatur geändert. Einschließlich der Regelprogramme wurde das gesamte System an einem praktischen Wasserbad erprobt und man erhielt recht gute Ergebnisse. Akzeptable Diagnosen konnten auch für externe thermische Störeinflüsse gezeigt werden, denen das geregelte System ausgesetzt wurde.

     

Characterisation of an exothermic reaction using adiabatic and isothermal calorimetry

A simple esterification reaction is used to demonstrate standard procedures for determining the thermokinetic parameters of an exothermic reaction from adiabatic calorimetric data. The influence of variations in the heat capacity of the sample due to changes in temperature and concentration is explored. Shortcomings in the simple interpretation of adiabatic data are identified and isothermal heatflow calorimetry is used to reveal autocatalytic effects which were not apparent from the adiabatic experiments. A more rigourous interpretation of the adiabatic and isothermal data is outlined and used to predict the conditions which can lead to exothermic runaway in a batch reactor. Mathematical simulation of the conditions in a jacketed reactor is used to demonstrate the importance of developing reliable kinetic expressions before assessing the safety of a batch process.

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Zusammenfassung Anhand einer einfachen Veresterungsreaktion wurden Standardverfahren zur Ermittlung thermokinetischer Parameter exothermen Reaktionen aus adiabatischen kalorimetrischen Daten demonstriert. Dabei wurde der Einfluß von Temperatur und Konzentration auf Änderungen der Wärmekapazität untersucht. Fehler bei der einfachen Interpretation adiabatischer Daten wurden identifiziert und isotherme Wärmeflußkalorimetrie wurde angewendet, um autokatalytische Effekte aufzuzeigen, die sich anhand der adiabatischen Experimente nicht ersehen lassen. Es wurde eine gründlichere Interpretation adiabatischer und isothermer Daten umrissen und verwendet, um die Bedingungen vorherzusagen, die in einem Kesselreaktor zu einem exothermen Davonlaufen der Reaktion führen. Mathematische Simulation der Bedingungen in einem Mantelkessel wurde angewendet, um zu zeigen, von welch großer Bedeutung die Entwicklung zuverlässiger kinetischer Ausdrücke ist, bevor man die Sicherheit einer Reaktion in einem Kesselreaktor beurteilt.

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过氧化苯甲酰的热分解研究

The thermal decomposition process of benzoyl peroxide was investigated by Accelerating Rate Calorimeter. The curves of thermal decomposition temperature and pressure versus time for the systems were obtained. The curves of temperature rising-rate versus thermal decomposition temperature were also obtained. After the data revision disposal and analysis processing, thermal decomposition parameters and kinetic data of benzoyl peroxide were calculated, respectively.     

Application of a new type of safety calorimeter

Safety production in chemical plants is a high-priority task, especially as concerns reactions which can change mechanism suddenly under defined conditions, e.g. from a simple well-defined to an undesired autocatalytic reaction. An example of this kind, the reaction of chloronitrobenzene with alkaline alcohol, was investigated with the new adiabatic precision calorimeter ACTRON 5, designed with a safety concept. It is shown that the reaction can be interrupted safely under predicted conditions.     

DSC and adiabatic calorimetry study of the polymorphs of paracetamol

Monoclinic (I) and orthorhombic (II) polymorphs of paracetamol were studied by DSC and adiabatic calorimetry in the temperature range 5 - 450 K. At all the stages of the study, the samples (single crystals and powders) were characterized using X-ray diffraction. A single crystal → polycrystal II→ I transformation was observed on heating polymorph II, after which polymorph I melted at 442 K. The previously reported fact that the two polymorphs melt at different temperatures could not be confirmed. The temperature of the II→I transformation varied from crystal to crystal. On cooling the crystals of paracetamol II from ambient temperature to 5 K, a II→ I transformation was also observed, if the 'cooling-heating' cycles were repeated several times. Inclusions of solvent (water) into the starting crystals were shown to be important for this transformation. The values of the low-temperature heat-capacity of the I and II polymorphs of paracetamol were compared, and the thermodynamic functions calculated for the two polymorphs. This revised version was published online in July 2006 with corrections to the Cover Date.     

绝热式热动力学的研究4: 可逆反应的热谱解析

本文建立了可逆反应在绝热系统中的热动力学研究法, 并用自制的绝热式自动热量计, 研究了三个可逆反应体系的热动力学, 验证了本文方法的正确性。     

绝热式热动力学的研究II: 一级反应的热谱解析

本文采用自制的绝热式自动量热计,对两个反应体系进行了一级反应的绝热式热动力学研究.速率常数的计算结果在误差范围内,与文献值符合均好.本文还在实验数据处理中提出了局外过程热效应的线性校正法.