Enthalpies of dilution of urea solutions in six polar solvents at several temperatures

Using the isothermal displacement calorimeter, enthalpies of dilution are obtained for solutions of urea in water, methanol, ethanol, formamide, N,N-dimethyl-formamide, and dimethyl sulfoxide. The results are discussed in terms of solute-solvent and solute-solute interactions.Now Diane Beaumont.     

Excess enthalpies of binary and ternary mixtures of acetonitrile with methanol,ethanol and benzene

Excess molar enthalpies are measured for the binary mixtures methanol—acetonitrile and ethanol—acetonitrile at 25 and 35°C and for the ternary mixtures methanol—acetonitrile—benzene and ethanol—acetonitrile—benzene at 25°C using an isothermal dilution calorimeter. The binary results are well reproduced with an association model which contains four equilibrium constants for the association of alcohol, two equilibrium constants for that of acetonitrile, and two solvation equilibrium constants between alcohol and acetonitrile molecules. The ternary results are compared with those calculated from the model with binary parameters.     

Thermodynamic properties of biofuels: Heat capacities of binary mixtures containing ethanol and hydrocarbons up to 20 MPa and the pure compounds using a new flow calorimeter

Heat capacities are of great significance in the design of new processes and the improvement of existing ones in R&D in production plants as well as the adaptation of new products, in this case, biofuels to their use in a variety of engines and technical devices. An automated flow calorimeter has been developed for the accurate measurement of isobaric heat capacities for pure compounds and mixtures over the range (250 to 400) K and (0 to 20) MPa. In this paper, isobaric heat capacities for heptane, ethanol and the binary mixtures of ethanol with heptane and toluene are reported.     

Activation energy of ignition for catalytic oxidation of ethanol in oscillatory regime

Activation energies of ignition for the thermokinetic oscillations obtained during the heterogeneous catalytic oxidation of ethanol on Pd/Al₂O₃ in a dynamic calorimeter were obtained using the minimum values of the temperature oscillations. These activation energies of ignition are greater than the activation energies of the corresponding oscillations. The obtained results are discussed by assuming a PdO_x redox cycle.     

模拟热谱曲线法(Ⅱ)──不可逆连串-级反应的热动力学研究

研究连串反应的动力学有十分重要的意义,文献［1,2]建立了两种连串一级反应的热动力学研究法．我们在前文[1]的基础上,建立了模拟热谱曲线法．该法可以直接从热导式量热计的热谱曲线上解析出连串一级反应中两步反应的速率常数．应用该法测定了邻苯二甲酸二乙酯和丁二酸...     

Enthalpic Interaction Coefficients of Formamide in Aqueous Methanol and Ethanol Solutions at 298.15 K

The dilution enthalpies of formamide in aqueous methanol and ethanol solutions have been determined using a CSC-4400 isothermal calorimeter at 298.15 K. The homogeneous solution enthalpic interaction coefficients have been calculated over a range of alcohol concentrations according to the excess enthalpy concept. The results show that the enthalpic pair interaction coefficients h ₂ of formamide are negative in aqueous alcohol solutions and pass through a minimum in mixed solvents, whereas the h ₂ coefficients of formamide in aqueous ethanol solutions are more negative than those in aqueous methanol solutions. The results are discussed in terms of solute-solute and solute-solvent interactions.     

脉冲激光光声量热装置的研制及用之对香豆素激光染料无辐射跃迁过程的研究

本文报道了一套适用于液相体系的高灵敏度脉冲激光光声量热装置的建立。用此仪器对香豆素激光染料C428, C47和C120的无辐射过程进行了研究, 测得它们在无水乙醇中的无辐射跃迁量子产额分别为0.50, 0.47和0.38。     

Excess isobaric heat capacities for water + alkanol mixtures at 298.15 K

Excess isobaric heat capacities for water + methanol, + ethanol, + 1-propanol and + 1-butanol mixtures were measured at 298.15 K. The apparatus used in this study was a flow microcalorimeter designed and constructed in our laboratory recently, which can determine excess heat capacities directly by a method different from that of a Picker type calorimeter.The results obtained are roughly in agreement with the literature values, except for the water + 1-propanol mixture. This discrepancy from the literature values may arise from the thermodynamic instability of the water + alkanol mixture with the long-chain alkyl group and the difference in the procedure for obtaining the excess heat capacity.     

水-乙醇二元体系共沸混合物的热力学研究

用全自动低温绝热量热计测定了水、乙醇以及水和乙醇组成的共沸混合物在不同温区的摩尔热容Cp,m. 建立了共沸混合物Cp,m与温度T的函数关系.结果表明,水和乙醇组成的共沸混合物在98.496 K发生玻璃态转化,在158.939 K 和270.95 K发生固-液相变.获得了其相应的相变焓和相变熵.计算了以298.15 K为基准的该共沸混合物的热力学函数和超额热力学函数.     

Excess enthalpies of alcohol + amine mixtures. Experimental results and theoretical description using the ERAS-model

New experimental data of the molar excess enthalpy H^E of mixtures containing eight liquids - propylamine + methanol, ethanol, propan-1-ol, butan-1-ol, butylamine + methanol, ethanol, propan-1-ol, butan-1-ol - are presented using a quasi-isothermal flow calorimeter. The results are used for testing the ERAS-model which provides a theoretical concept accounting for the self-association and cross-association of alcohol and amine molecules, as well as for non-associative intermolecular interactions. Excess molar volumes V^E are also successfully described by the model. It turns out that the strong cross-association occurring between alcohol and amine molecules is the predominant reason for the remarkably low exothermic values of H^E observed for the mixtures studied.     

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.     

Characteristic parameter method for studying chemical kinetics in calorimeter

A novel thermokinetic research method for determination of rate constants of simple-order reaction in batch conduction calorimeter under isothermal condition, the characteristic parameter method, is proposed in this paper. Only needing the characteristic time parameter tm obtained from the measured thermoanalytical curve, the kinetic parameters of reactions studied can be calculated conveniently with this method. The saponifications of ethyl propionate and ethyl acetate in aqueous ethanol solvent, the polymerization of acrylamide in aqueous solution, the ring opening reaction of epichlorohydrin with hydrobromic acid have been studied. The experimental results indicate that the characteristic parameter method for simple-order reaction is correct. This revised version was published online in August 2006 with corrections to the Cover Date.     

Temperature Oscillations Characterized by An Overall Activation Energy

Temperature oscillations obtained during the heterogeneous catalytic oxidation of ethanol on Pd-Al₂ O₃ in a dynamic calorimeter were characterized by an overall activation energy. This parameter was determined by a non-isothermal kinetic method using the minimum and maximum values of the oscillations temperature. Using the bifurcation diagram with the oxygen as a bifurcation parameter an E value between 27.6 and 28.2 kJ mol^-1 was obtained. With ethanol as bifurcation parameter the E values lies between 28.1 and 31.1 kJ mol^-1 for 3.5 to 4.0 vol% ethanol and between 25.8 and 27.6 kJ mol^-1 for 4.0 to 4.7 vol% ethanol. These results have been discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

The rapid mass calorimeter: Understanding reduced-scale fire test results

The effects of reducing specimen size on the fire behavior of polymeric materials were investigated by means of the rapid mass calorimeter, a high-throughput screening instrument. Results from the rapid mass calorimeter were compared with those from the cone calorimeter. Correlation coefficients between the different measures of each method and between the two methods are discussed to elucidate the differences and similarities in the two methods. Materials with characteristic heat release rate (HRR) curves in the cone calorimeter were evaluated in detail. The rapid mass calorimeter produces valuable and interpretable results with HRR curve characteristics similar to cone calorimeter results. Compared to cone calorimeter measurements, material savings of 96% are achieved, while maintaining the advantages of a macroscopic fire test.     

连续一级反应的热动力学研究法: 自函数回归法

根据热动力学基本理论,推导出了热导式量热计测量的连续一级反应的热谱曲线的动力学解析方程,并推出了连续一级反应热动力学的自函数递推方程,由此建立了一种研究连续一级反应的热动力学新方法-自函数回归法。通过对丁二酸二乙酯和邻苯二甲酸二乙酯的皂化反应的热谱曲线分析,验证了自函数回归法的正确性。     

汽化热量热计的建立及物质汽化潜热的测定

在J.H.Mathews仪器的基础上进行适当改进,本文建立了一种等温绝热型汽化热量热计,经对甲醇、乙醇、苯、甲苯和水等物质的测定,精度可达0.1-0.2%,与文献值对比,准确度在0.3%以内,在纯物质测定的基础上,对水+乙醇、苯+甲醇两个二元物系进行了等压积分汽化潜热的测定,文中对采用“差分-积分图”方法反映汽化过程中体系的焓变作了一些探讨,另外,本文还就我国石油轻馏分汽化热的测定进行了初步的探索和研究。     

Investigation on the fire hazard characteristics of ethanol–water mixture and Chinese liquor by a cone calorimeter

In this study, a series of ethanol–water mixture and Chinese liquor combustion experiments were conducted using an ISO5660-1 cone calorimeter and an automatic flash point tester. The main purpose was to obtain key fire parameter data, including the burning duration, mass loss rate, mass loss rate per unit area, heat release rate per unit area, CO and CO₂ volume fraction, CO₂/CO ratio and closed-cup flash point. At the same time, the experimental differences between Chinese liquor and ethanol–water mixture were analyzed. Also, the fire risk classification was discussed based on the code of GB 50016-2014. When the ethanol volume fraction of Chinese liquor is greater than 34.8 vol%, the fire risk is the most dangerous level, Class I. While the critical ethanol volume fraction of ethanol–water mixture is 38.9 vol%, it needs to pay more attention to the fire safety of Chinese liquor storage and usage when the ethanol volume fraction is generally from 30 to 65 vol%.

     

Excess Thermodynamic Properties of Binary Liquid Mixtures Containing N,N -Dimethylacetamide with Some Alkan-1-Ols (C 1 -C 6 ) At 298.15 K

Excess molar enthalpies, $ H_m^E $ of N , N -dimethylacetamide + methanol, + ethanol, + propan-1-ol, + butan-1-ol, + pentan-1-ol, and + hexane-1-ol have been determined at 298.15 K and atmospheric pressure using a Parr 1455 solution calorimeter. While the excess molar enthalpies are negative for methanol and ethanol mixtures, those for propan-1-ol, butan-1-o1, pentane-1-ol, and hexan-1-ol mixtures are positive over the entire range of composition of N , N -dimethylacetamide. The $ H_m^E $ at around x , 0.5 follow the order: methanol<ethanol<propan-1-ol<butan-1-ol<pentan-1-ol<hexan-1-ol. The results are explained in terms of the self-association exhibited by the alkan-1-ols and the formation of aggregates between unlike molecules through OHO hydrogen bonding. The experimental results for mixtures are well represented by the Redlich - Kister equation.     

A simple calorimeter for the heats of mixing study of associated liquids: Enthalpy of hydrogen bonded ethanol-butylamine complex

A simple dewar type calorimeter has been constructed to determine the enthalpy of mixing in dilute concentration range and its performance checked by determining the heats of mixing of cyclohexane (l)-n-hexane (2) and ethanol (1)n-hexane (2) systems. The heats of mixing ofn-butylamine withn-hexane and ethanol have been determined at 30° C. The enthalpy of ethanol-butylamine complex calculated by a thermochemical cycle was found to be-40.3 kJ/mol. NCL Communication No. 2492     

Flow microcalorimeter for heat capacities of solutions

A new type of flow microcalorimeter for measuring heat capacities at constant pressure of liquids and solutions was constructed. This calorimeter is the similar in design to Picker's except for the flow system, which consists of two syringe type of pumps and two flowing paths in each flow cell. It was found that the magnitude of heat loss from cells depended on liquids themselves used and the flow rates of sample liquids. The molar heat capacities, C_p of benzene and ethanol were determined relative to those of cyclohexane and water, respectively. The excess molar heat capacities, C_p(E) for the systems of benzene + cyclohexane and water + ethanol were also determined at 298.15K by the direct mixing method. An inaccuracy for C_p(E) was estimated to be within ± 1%.