气体流动热量计和苯、苯-环己烷气体热容的测量

随着化学热力学理论研究的深入和石化工业的迅速发展,混合物热力学性质的实测数据日显短缺.气体热容的测量一直为人们所重视,先后出现了各种各样的测量方法,其中以流动量热法最突出,发展也较完善.对于混合气体热容的测量,国际上尽管有一些文献报导,但由于没有解决好稳定混合气流的产生问题,测量对象仅为一些沸点相近的二元物系,且测量温度不高,很难推广到多元物系乃至不定组成物系如石油馏分的测量.本文依据Powers等人热量计和Clarke 快速蒸发器的设计原理,从结构上进行了一些改进.并将两者有机地结合起来,建立了一套可在中、低压下测量各种气体热容的金属量热装置.     

金属态原子电负性的计算及应用(Ⅱ)

利用修正后的Pauling计算单键键能的公式对H2、O2、CO观原子分子在某些过渡金属上解离吸附参数（包括活化吸附热，金属-吸附物种表面键能）进行了计算，获得了丰富的表面键能量参数数值，弥补了实验数据的不足．从而，为在一定程度上帮助人们从分子微观动力学的角度认识催化反应的实质，报供了较为可靠的理论依据．     

Heat transfer to a particle under plasma conditions with vapor contamination from the particle

Heat transfer to a copper particle immersed into an argon plasma is considered in this paper, including the effects of contamination of the plasma (transport coefficients) by copper vapor from the particle. Except for cases of high plasma temperatures, the vapor content in the plasma is shown to have a considerable influence on heat transfer to a nonevaporating particle, and, to a lesser extent, on heat transfer to an evaporating particle. Evaporation itself reduces heat transfer to a particle substantially as shown in a previous paper [Xi Chen and E. Pfender, Plasma Chem. Plasma Process.,2, 185 (1982)]. Comparisons of the calculated results with those based on a method suggested in the above reference show that the simplified assumptions employed, i.e., that the surface temperature is equal to the boiling point and that plasma properties based on a fixed composition are applicable, can be employed to simplify calculations for many cases. This study reveals that a considerable portion of a particle must be vaporized before a steady concentration distribution is established around the particle.Nomenclature C _p specific heat at constant pressure - D diffusion coefficient of copper in the mixture - D _a diffusion coefficient of copper atoms in the mixture - D _i ambipolar diffusion coefficient of copper ions in the mixture - f mass fraction of copper in the mixture - f _a mass fraction of copper atoms in the mixture - f _i mass fraction of copper ions in the mixture - f mass fraction of copper in the plasma far away from the particle - f _s mass fraction of copper at the particle surface - G total mass flow rate due to evaporation - G _a mass flow rate of copper atoms - G _i mass flow rate of copper ions - H function defined in Eq. (19) - h specific enthalpy - h _s specify enthalpy at the particle surface - h specific enthalpy corresponding toT andf - k thermal conductivity - L latent heat of evaporation - M ₁ molecular weight of argon (M ₁=39.99) - M ₂ molecular weight of copper (M ₂=63.55) - p ₀ pressure of the gas mixture - p _s partial pressure of copper vapor at the particle surface - Q ₀ heat flux to a particle without evaporation - Q ₁ heat flux to a particle with evaporation - R gas constant - r radical coordinate - r _s particle radius - S heat conduction potential defined in Eq. (4) - S _s surface value ofS, corresponding toT _s andf _s - S free-stream value ofS, corresponding toT andf - T temperature - T _b boiling temperature of particle material - T _s particle surface temperature - T plasma temperature - density - T temperature step for numerical integration     

Heat capacity corrections to a standard state: a comparison of new and some literature methods for organic liquids and solids

The estimation methods commonly used to correct phase change enthalpies to the standard state are compared where possible to experimental measurements. Heat capacity corrections for liquid-gas equilibria are found to correlate with molecular structure, and we suggest an improved method for estimating these corrections using group methods. A similar improvement for estimating heat capacity corrections for solid-gas equilibria using group methods is also proposed. Heat capacity corrections for liquid-solid equilibria are examined. These corrections were found to be comparable in magnitude to the experimental error associated with heat capacity measurements, so it was not possible to obtain any meaningful correlations.     

Isothermal and non-isothermal melting of the binary solution inside an emulsion

The aim of the present paper is to study the melting process inside an emulsion using the non-equilibrium model of microscopic heat transfer between the emulsifying medium and the dispersed droplet of binary solution (DSC). DSC experiments are used to validate the numerical results. The effects of the heating rate, mass fraction of the dispersed saline binary solution, initial mass fraction of the solute and the sample mass on the kinetics of the melting process are examined.     

Thermoelectric power studies on MgO-stabilized β″-alumina

A study of the temperature dependence of thermopower is known to yield auxiliary information about the electronic conductivity of a mixed conductor. In light of the above, thermoelectric power (TEP) measurements were made on MgO-stabilized β″-alumina over the temperature range from 773 to 1223 K under conditions of different sodium activities in the ambient in order to substantiate the existing information on the electronic conductivity of sodium beta alumina (SBA). A mixture of Na _x Si _m O_{2 m + x /2} and SiO₂ in an environment of fixed served as electrodes reversible to Na⁺. The heat of transport obtained using the thermopower data at higher temperatures (973–1223 K) was in fair agreement with the activation energy of electrical conduction determined by other studies like impedance measurements and molecular dynamics simulation. It could be inferred from these results that there is negligible electronic conductivity in SBA under the conditions of measurement. The average TEP for SBA was determined to be 700–800 μV/K and the partial molar entropy of Na⁺ in SBA was found to be ~98 J mol^–1 K^–1. Electronic Publication     

Thermochemistry of iron manganese oxide spinels

Oxide melt solution calorimetry has been performed on iron manganese oxide spinels prepared at high temperature. The enthalpy of formation of (Mn_xFe_1−x)₃O₄ at 298 K from the oxides, tetragonal Mn₃O₄ (hausmannite) and cubic Fe₃O₄ (magnetite), is negative from x=0 to x=0.67 and becomes slightly positive for 0.67<x<1.0. Relative to cubic Mn₃O₄ (stable at high temperature) and cubic Fe₃O₄ (magnetite), the enthalpy of formation is negative for all compositions. The enthalpy of formation is most negative near x=0.2. There is no significant difference in the trend of enthalpy of formation versus composition for cubic (x<0.6) and tetragonal (x>0.6) spinels of intermediate compositions. The enthalpies of formation are discussed in terms of three factors: oxidation-reduction relative to the end-members, cation distribution, and tetragonality. A combination of measured enthalpies and Gibbs free energies of formation in the literature provides entropies of mixing. ΔS_mix, consistent with a cation distribution in which all trivalent manganese is octahedral and all other ions are randomly distributed for x>0.5, but the entropy of mixing appears to be smaller than these predicted values for x<0.4.     

Thermobiochemical evidence for the rapid metabolic rate in hybridoma cells genetically engineered to overexpress the anti-apoptotic protein bcl-2 in batch culture

A serious problem in the culture of animal cells to produce therapeutic proteins is apoptosis (programmed cell death) because it restricts the ability of the cell culture to yield the heterologous material. One means to delay apoptosis is genetically to engineer the anti-apoptotic gene bcl-2 into the genome. This had been adopted elsewhere to give TB/C3 hybridoma cells that overexpressed bcl-2 (pEF bcl-2-MC1neopA plasmid) and a control, pEF, which contained a nonsense sequence (pEF-MC1neopA). In the spinner cultures used in the present investigation, bcl-2 cells grew for 60 h to give greater cell density at a faster specific rate and with prolonged better viability than the controls in which, after 36 h, the membrane integrity and the apoptotic index of the cells declined rapidly leading to death. Prior to 36 h, production of the monoclonal antibody was only slightly higher in the pEF control giving little evidence for the metabolic burden of its production on antibody synthesis. Bcl-2 synthesis, however, was associated with 125% increase in heat flow rate (HFR) measured in the chemically (triacetin) calibrated batch microcalorimeter. HFR is a function of the metabolic rate and it is suggested that its greater level in the bcl-2 cells than the control was caused by the increased protein production due to the bcl-2 gene expression. The bcl-2 cells had an increased lactate flux compared with the control. The calorimetric-respirometric (CR) ratio confirmed the likelihood that glycolysis rather than glutaminolysis was the primary reason for this increase. It may be due to the limitation in mitochondrial capacity and/or the paucity of biosynthetic precursors leading to production of them from glucose.The stationary liquid phase balance (SLPB) was shown to be the appropriate on-line method to measure the oxygen uptake rate (OUR) in the dilute cell suspensions grown in the tank bioreactor. The metabolic rate expressed as HFR was measured in a customised flow microcalorimeter, which had been calibrated using the enthalpy of hydrolysis produced by the new test reaction using methyl paraben. Both HFR and OUR declined before the decrease in cell density in batch culture, indicating that they were sensitive indicators of deteriorating environmental conditions. However, neither proved to be an early detector of the onset of apoptosis.     

Evaluating microbial activity in composts using microcalorimetry

Microcalorimetric isothermal monitoring was carried out for compost and compost-containing growing medium, to provide fingerprints of compost microbial activity at different conditions. Microbial activity is a key property of composts used in agricultural practice. Two aspects are addressed in this study: (1) microcalorimetric evaluation of compost response to glucose as a model stimulating agent; (2) examination of the impact of compost pre-drying and re-wetting on its biological activity.

Addition of glucose solution to the compost involved a strong increase in microbial activity, which was associated with a significant heat evolution without a lag period. In certain cases, this heat evolution was of complicated shape thus manifesting the heterogeneity of microbial populations in composts. Relation between cumulative energy evolved and the amount of added glucose was found to be helpful in distinguishing between aerobic and anaerobic regime of compost microbial activity. As distinct from non-dried compost or growing mixture, glucose addition to samples pre-dried at 65 °C resulted in delayed heat response with initial exponential-like heat evolution. This delay in heat evolution suggests that biological activity was significantly suppressed upon compost drying. Such a temperature-induced inactivation process might also result in dominance of a relatively homogeneous microbial population which survived the heating, thus involving a smooth, exponential-like initial step of the heat evolution. Noteworthy, addition of water (without glucose) to pre-dried compost results in an outburst of activity as compared with non-dried compost. This heat evolution outburst was also characterized by a lag period and an initial exponential-like phase. The heat evolution obtained with pre-dried compost upon water addition was not related to the compost wetting energy but rather reflected the formation of new carbon source due to the changes in compost organic matter upon heating or to the dead biomass of those microbial populations that did not resist the compost heating/drying.     

History repeats itself: Progress in a.c. calorimetry

Periodic heating has been applied more than a century ago to study thermophysical properties of materials. The measurement of heat capacity using a.c. calorimetry was first performed by Corbino in 1910. In connection with the technological development and the progress in science and technology, new and sophisticated apparatus have been constructed in an a.c. calorimetric heat capacity measurements. In this measurement, the noise level of a.c. temperature can be reduced markedly as opposed to the other nonperiodic methods and, therefore, high precision determination can be attained. Furthermore, not only the amplitude but also the phase in a.c. temperature is a useful parameter in constructing much advanced apparatus.