Differential thermal analysis and thermogravimetry of ammonium perchlorate at pressures up to 51 ATM

The thermal decomposition of pure ammonium perchlorate (AP)was investigated in various gaseous atmospheres at pressures up to 51 atm, using a technique of thermal analysis. It is concluded that the first and second stage decompositions of AP in an atmosphere of oxygen or nitrogen are appreciably accelerated as the pressure is increased. Platinum has a catalytic effect in the high-temperature decomposition and suppresses the sublimation of AP at high temperature ranges in helium atmosphere even at 1 atm. The reaction heat for the high-temperature decomposition of AP in the platinum cell was calculated from the peak temperatures of DTA curves at various pressures to be 77.9 kcal mol^?1. The activation energies of the sublimation in helium at 1 atm and of the high-temperature decomposition in the platinum cell at various pressures of helium have also been obtained, giving similar values of 23–25 kcal mol^?1.     

The standard molar enthalpies of combustion and formation of 2-methylbenzothiazole, 2-methylbenzoxazole, and 2-methyl-2-thiazoline

A static-bomb combustion calorimeter and a rotating-bomb combustion calorimeter were used to determine the energies of combustion of 2-methylbenzothiazole, 2-methylbenzoxazole, and 2-methyl-2-thiazoline. The static- and rotating-bomb calorimeters were recently calibrated by the standard benzoic acid combustion runs and they were tested with adequate secondary combustion standards. The rotating-bomb calorimeter was tested using thianthrene and, in the present work, 1,2,4-triazole was used to test the static-bomb calorimeter. From the energies of combustion of the compounds under study, the liquid-phase standard molar enthalpies of formation were derived, at T = 298.15 K, as: (72.5 ± 1.5), (?50.7 ± 2.1), and (?88.5 ± 2.8) kJ mol^?1, respectively.     

High-resolution ac calorimetry and critical behavior at phase transitions

An AC calorimeter technique operating at very low frequencies has been developed for the study of second-order phase transitions. Only a small amount of sample is required (50 to 100 mg), and samples with low thermal conductivity, such as insulator crystals, fluids and liquid crystals, can be investigated at I atm and at pressures up to ～3000 bar. Two versions of this AC calorimeter will be described: a manually operated high-precision (±0.05%) calorimeter with a computerized data-acquisition system, and a fully computerized calorimeter with good precision (±0.2%) which can be operated in a scanning mode with linear drift rates in the range 0.01 K/hour to 1 K/hour. Experimental results and a discussion of their analysis will be presented for order-disorder transitions in ionic crystals (ammonium halides), consolute-point phase separation in binary liquids (3-methylpentane + nitroethane), orientational ordering in aqueous micelle solutions (cesium perfluoro-octanoate), and a variety of liquid crystal systems (with emphasis on transitions involving nematic and various smectic phases).     

一水合邻菲罗啉的热化学性质

用纯度为99.999%的量热基准苯甲酸标定了实验室建立的精密转动弹量热计,其能当量为18604.99±8.14J/K,测得一水合邻菲罗啉(phen·H2O)的燃烧能为-5757.45±2.53kJ/mol,换算成标准燃烧焓为-5759.93±2.53kJ/mol,进而计算出一水合邻菲罗啉的标准生成焓为-391.34±2.98kJ/mol。     

Thermal decomposition properties of double-base propellant and ammonium perchlorate

The thermal decomposition properties and the heat of combustion (ΔH) of samples with different ammonium perchlorate (AP)/double base propellant (DB) mass ratios under argon atmosphere were studied by the thermogravimetry–differential scanning calorimetry–mass spectrometry–Fourier transform infrared spectroscopy (TG–DSC–MS–FTIR) and automatic calorimeter method. The results show that decomposition process of AP/DB samples in negative and zero oxygen balance (OB) is different from that in positive OB. With the increasing of AP in the AP/DB samples, the decomposition of the samples becomes more and more severe. When the OB of the samples is positive, the phenomenon of deflagration or explosion could be observed in the decomposition process. The sample with OB = 0 has the greatest heat of combustion.     

Low‐Temperature Heat Capacities and Standard Molar Enthalpy of Formation of Gramine (C11H14N2)

Low‐temperature heat capacities of gramine (C₁₁H₁₄N₂) were measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 401 K. A polynomial equation of heat capacities as a function of temperature was fitted by least squares method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at 5 K intervals. The constant‐volume energy of combustion of the compound at T=298.15 K was measured by a precision oxygen‐bomb combustion calorimeter as Δ_cU=−(35336.7±13.9) J·g⁻¹. The standard molar enthalpy of combustion of the compound was determined to be Δ_cH_m⁰=−(6163.2±2.4) kJ·mol⁻¹, according to the definition of combustion enthalpy. Finally, the standard molar enthalpy of formation of the compound was calculated to be Δ;_cH_m⁰=−(166.2±2.8) kJ·mol⁻¹ in accordance with Hess law.     

The effects of fast neutron,gamma-ray and combined radiations on the thermal decomposition of ammonium perchlorate powder-aluminum particle mixtures

The thermal decomposition kinetics of irradiated and unirradiated ammonium perchlorate and ammonium perchlorate powder-aluminum particle mixtures has been studied by determining decomposition gas pressurevs. heating time with samples at a controlled temperature Qualitatively the radiation induced changes are similar to those obtained in previous studies on ‘pure’ ammonium perchlorate. The induction period is shortened and the acceleratory and decay period rate constants are increased. The data have been analyzed using Avrami-Erofeev kinetics. The results for pure unirradiated material are in accord with published results. The activation energies for the induction, acceleratory and decay periods for pure pellets were found to be 133.5±6.7, 131.8±6.7 and 127.2±6.7 kJ·mol, respectively. Samples were exposed to either a single gamma-ray irradiation, fission neutron irradiation followed by a gamma-ray irradiation, or to a proton irradiation. When compared on an equal energy deposited basis, the fast neutron induced changes are appreciably larger than the gamma-ray changes. However, the proton induced changes are comparable or slightly more than the gamma-ray effects. Some, or all, of the fast neutron effects can be attributable to the concentrated radiation damage ‘spikes’ along the path of lattice atom recoils. It is likely that these become thermal decomposition sites when the crystals are heated. Protons create fewer spikes than fast neutrons. Overall, the results indicate that any ammonium perchlorate-aluminum propellant mixtures that may be exposed to radiation environments, such as used in this study, should be subjected to a thorough radiation effects analysis if reliable performance is required. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

An isoperibol micro-bomb calorimeter for measurement of the enthalpy of combustion of organic compounds. Application to the study of succinic acid and acetanilide

A micro static-bomb combustion calorimeter, developed from a 1107 Parr semi-micro bomb, has been provided with a new micro-bomb and calorimetric bucket. In the best conditions of operation, the energy equivalent of this calorimetric arrangement is just ε(calor)=(731.82 ± 0.22) J · K⁻¹, which means an uncertainty of 0.03 per cent for the calibration with benzoic acid NIST 39j. This combustion calorimeter has been used in the measurement of the enthalpy of combustion of the succinic acid and acetanilide, giving −(1489.3 ± 1.6) kJ · mol⁻¹ and −(4222.5 ± 1.1) kJ · mol⁻¹, respectively, for these substances.     

烟酸的低温热容和标准摩尔生成焓

利用精密自动绝热热量计测量了分析纯烟酸在78～400 K温区的低温热容. 用最小二乘法将实验摩尔热容对温度进行拟合, 得到了热容随温度变化的多项式方程. 用此方程进行数值积分, 得到在此温区每隔5 K的舒平热容值和相对于298.15 K时的热力学函数值. 利用精密静止氧弹燃烧热量计测定了烟酸在298.15 K时的恒体积燃烧能为 Δ_cU＝ －(24528.3±16.1) J•g^－1. 依据物质燃烧焓定义计算出烟酸的标准摩尔燃烧焓为: Δ_cH_m^o＝－(3019.05±1.98) kJ•mol^－1. 最后, 依据Hess定律计算出烟酸的标准摩尔生成焓为: Δ_fH_m^o＝－(56.76±2.13) kJ•mol^－1.     

Construction,calibration and testing of a micro-combustion calorimeter

An isoperibolic micro-combustion calorimeter was designed, built and set up in our laboratory, taking as base a 1107 Parr combustion bomb of 22 cm³ of volume. Taken into account the geometrical form of the bomb, it was designed and constructed a vessel and a submarine chamber in brass. All of the pieces of the calorimeter were chromium-plated to reduce heat loss by radiation. The calorimeter was calibrated by using pellets of standard benzoic acid (mass approximate of 40 mg) leading to the energy equivalent of ε(calor) = (1283.8 ± 0.6) J · K⁻¹. In order to test the calorimeter, combustion experiments of salicylic acid were performed leading to a value of combustion energy of Δ_cu^∘ = −(21,888.8 ± 10.9) J · g⁻¹, which agrees with the reported literature values. The combustion of piperonylic acid was carried out as a further test leading to a value of combustion energy of Δ_cu^∘ = −(20,215.9 ± 10.4) J · g⁻¹ in accordance with the reported literature value. The uncertainty of the calibration and the combustion of salicylic acid and piperonylic acid was 0.05%.     

Research on synthesis and thermodynamic properties of 2-methoxycyclohexanol

2-Methoxycyclohexanol is synthesized through an alcoholysis reaction of cyclohexene oxide and methanol with Ag₂CsPW₁₂O₄₀ as catalyst. The elemental analyzer, FT-IR, GC, and NMR are used to analyze and confirm elements, functional groups, purity, and molecular structure of 2-methoxycyclohexanol. The equation between the specific heat capacity (C _p) and the temperature from 280 to 340 K is fitted by the results of differential scanning calorimeter to examine 2-methoxycyclohexanol. Bomb calorimeter is introduced to determine the standard enthalpy change of combustion of 2-methoxycyclohexanol (? 3938.6 ± 2.0 kJ mol^?1). The standard enthalpy of formation has been calculated as ? 816.88 ± 2.21 kJ mol^?1, based on Hess’s law. These basic thermodynamic parameters are deemed to facilitate the exploitation of new production route of 2-methoxycyclohexanol.     

1,2,4-Triazole as a reference material for combustion calorimetry of N-containing compounds

A micro-bomb combustion calorimeter recently designed for samples of mass  ≈ 80 mg has been improved and tested with m -methoxybenzoic acid in order to verify the chemistry of the combustion process and the accuracy of the energy corrections involved in the analysis of results. From measurements in this calorimeter, the standard massic energy of combustion of 1,2,4-triazole was determined to beΔ_cu^o =  − (19200.3  ±  3.4)J · g ^− 1. Some new measurements with our macro combustion calorimeter confirm an earlier result from this laboratory of  − (19203.1  ±  1.2)J · g ^− 1. Determination of the purity by d.s.c. of 1,2,4-triazole purified some 10 years ago reveals that samples of this compound remained unchanged and suggest that 1,2,4-triazole be used as a possible reference material for organic compounds with a high content of nitrogen. From the experimental results with the micro-bomb combustion calorimeter, the actual and earlier results from macro-bomb combustion calorimetry, and those obtained in other laboratories, the standard massic energy of combustion of 1,2,4-triazole was deduced to beΔ_cu^o =  − (19202.5  ±  1.7)J · g ^− 1.     

Thermochemistry of copper complex of 6-benzylaminopurine

The copper(II) complex of 6-benzylaminopurine (6-BAP) has been prepared with dihydrated cupric chloride and 6-benzylaminopurine. Infrared spectrum and thermal stabilities of the solid complex have been discussed. The constant-volume combustion energy, Δ_c U, has been determined as −12566.92±6.44 kJ mol⁻¹ by a precise rotating-bomb calorimeter at 298.15 K. From the results and other auxiliary quantities, the standard molar enthalpy of combustion, Δ_c H _m ^θ, and the standard molar of formation of the complex, Δ_f H _m ^θ, were calculated as −12558.24±6.44 and −842.50±6.47 kJ mol⁻¹, respectively.     

Determination of constant‐volume combustion energy for the complexes of zinc nitrate with three amino acids

Five solid complexes of zinc with L‐α‐methionine, L‐α‐phenylalanine and L‐α‐histidine were prepared. The constant‐volume combustion energies of the complexes, ΔE_c (coordination), were determined by a precise rotating bomb calorimeter at 298.15 K. They were ‐ 2969.03 ± 0.34, ‐2929.46 ± 1.59, ‐9597.13 ± 6.12, ‐4378.98 ± 3.27 and ‐14047 ± 6.75 kJ/mol, respectively. Their standard enthalpies of combustion, ΔH^θ_m,c(coordination, s, 298.15 K), and standard enthalpies of formation, ΔH^θ_m,f (coordination, s, 298.15 K), were calculated. They were ‐2959.73 ± 0.34, ‐2923.88 ± 1.59, ‐9649.18 ± 6.12, ‐4373.40 ± 3.27, ‐14048.53 ± 6.75 kj/mol and ‐1180.94 ± 0.92, ‐1401.26 ± 1.77, ‐2501.69 ± 6.50, ‐1381.47 ± 3.49, ‐1950.19 ± 7.65 kJ/mol, respectively.     

On the principles and mechanism of the combustion of ammonium perchlorate

Conclusions The dependence of the rate of combustion of ammonium perchlorate on the pressure, temperature, particle size, density, and addition of ammonium chloride was studied, and a mechanism of the combustion of ammonium perchlorate was formulated on the basis of the principles obtained.     

Effect of ammonia on the thermal decomposition of orthorhombic and cubic ammonium perchlorate

The inhibiting effect of ammonia vapours on the kinetics of the thermal decomposition of ammonium perchlorate(AP) in the temperature range 215–270°C has been investigated. An initial ammonia pressure of about 200 Torr is necessary for the practically full suppression of the decomposition of the orthorhombic crystals at temperatures close to the point of AP polymorphic transformation (240°C). With the cubic crystals, 0.5 Torr is the corresponding pressure required. In the case of complete inhibition of the decomposition in the presence of ammonia, AP crystals become yellowish. The activation energy of decomposition of the orthorhombic modification is 29 ± 0.6 kcal mole^?1 in the absence of ammonia, and 38 ± 1.1 kcal mole^?1 under ammonia vapour pressure of 6.5 Torr. A kinetic analysis of the traditional proton model of AP decomposition has been made showing that the increase of the activation energy in the presence of ammonia may be derived from this model.     

4-硝基苯甲醇的低温热容和标准摩尔生成焓

用精密自动绝热量热计测定了4-硝基苯甲醇（4-NBA）在78 ~ 396 K温区的摩尔热容。其熔化温度、摩尔熔化焓及摩尔熔化熵分别为:(336.426 ± 0.088) K, (20.97 ± 0.13) kJ×mol-1 和 (57.24 ± 0.36) J×K-1×mol-1.根据热力学函数关系式,从热容值计算出了该物质在80 ~ 400 K温区的热力学函数值 [HT - H298.15 K] 和[ST - S298.15 K]. 用精密氧弹燃烧量热计测定了该物质在T＝298.15 K的恒容燃烧能和标准摩尔燃烧焓分别为 (C7H7NO3, s)＝- ( 3549.11 ± 1.47 ) kJ×mol-1 和 (C7H7NO3, s)＝- ( 3548.49 ± 1.47 ) kJ×mol-1. 利用标准摩尔燃烧焓和其他辅助热力学数据通过盖斯热化学循环, 计算出了该物质标准摩尔生成焓 (C7H7NO3, s)＝- (206.49 ± 2.52) kJ×mol-1 .     

High-precision micro-combustion calorimetry of anthracene

A high-precision micro-combustion calorimeter was developed. Details of the calorimeter are described. The energy equivalent of the calorimeter and the standard deviation of the mean were determined to be (67.8330  ±  0.0024)J · K ^− 1after calibration with thermochemical standard benzoic acid (five experiments). The standard enthalpy of combustion of anthracene was determined to be  − (7065.0  ±  1.1)kJmol ^− 1.     

Combustion and thermal decomposition characteristics of composite solid propellan

The role of thermal decomposition of the binder and the oxidiser in the thermal decomposition, ageing and combustion of composite solid-propellants has been investigated. The present study shows that the burning rate and ageing of polystyrene and ammonium perchlorate propellant are related to the thermal decomposition of the propellant itself and ammonium perchlorate.     

RE(C5H8NS2)3(C12H8N2)的标准摩尔生成焓

在无水乙醇中, 使低水合氯化稀土 (RE = Ho, Er, Tm, Yb, Lu) 与吡咯烷二硫代氨基甲酸铵 (APDC)和1,10-菲咯啉 (o–phen•H₂O) 反应, 制得其三元固态配合物. 用化学分析和元素分析确定它的组成为RE(C₅H₈NS₂)₃(C₁₂H₈N₂) (RE = Ho, Er, Tm, Yb, Lu). IR光谱说明RE³⁺ 分别与3个PDC^–的6个硫原子双齿配位, 同时与o–phen的2个氮原子双齿配位, 配位数为8. 用精密转动弹热量计测定了它们的恒容燃烧热△_cU分别为(-16788.46 ± 7.74), (-15434.53 ± 8.28), (-15287.80 ± 7.31), (-15200.50 ± 7.22)和(-15254.34 ± 6.61) kJ•mol^-1; 并计算了它们的标准摩尔燃烧焓△_cH_m^θ和标准摩尔生成焓△_fH_m^θ分别为( -16803.95 ± 7.74), (-15450.02 ± 8.28), (-15303.29 ± 9.28), (-15215.99 ± 7.22), (-15269.83 ± 6.61) kJ • mol^-1和 (-1115.42 ± 8.94), (-2477.80 ± 9.15), (-2619.95 ± 10.44), (-2670.17 ± 8.22), (-2650.06 ± 8.49) kJ•mol^-1.