Macroscopic non-equilibrium thermodynamics in dynamic calorimetry

What is really measured in dynamic calorimetric experiments is still an open question. This paper is devoted to this question, which can be usefully envisaged by means of macroscopic non-equilibrium thermodynamics. From the pioneer work of De Donder on chemical reactions and with other authors along the 20th century, the question is tackled under an historical point of view. A special attention is paid about the notions of frequency dependent complex heat capacity and entropy production due to irreversible processes occurring during an experiment. This phenomenological approach based on thermodynamics, not widely spread in the literature of calorimetry, could open significant perspectives on the study of macro-systems undergoing physico-chemical transformations probed by dynamic calorimetry.     

变频压缩机空调系统的理论分析及实验研究

变频空调器是由变频压缩机驱动的空调系统,压缩机通过变频调节其转速使压缩机单位时间内的排气量变化,从而达到调节制冷量的目的。本文提出了变频空调器制冷系统的原理和设计方法,具体给出了制冷量和压缩机频率的关系方程,并从理论和实验两方面对变频空调器制冷系统进行了分析,得到了频率曲线图,为变频空调器制冷系统的设计提供了依据。     

Lemniscates and inequalities for the logarithmic capacities of continua

It is shown that if P(z) = z ⁿ + ? is a polynomial with connected lemniscate E(P) = {z: ¦P(z)¦ ≤ 1} and m critical points, then, for any n? m+1 points on the lemniscate E(P), there exists a continuum γ ? E(P) of logarithmic capacity cap γ ≤ 2^?1/n which contains these points and all zeros and critical points of the polynomial. As corollaries, estimates for continua of minimum capacity containing given points are obtained.     

Finite turns and the regular closure of linear context-free languages

Turn bounded pushdown automata with different conditions for beginning a new turn are investigated. Their relationships with closures of the linear context-free languages under regular operations are studied. For example, automata with an unbounded number of turns that have to empty their pushdown store up to the initial symbol in order to start a new turn are characterized by the regular closure of the linear languages. Automata that additionally have to re-enter the initial state are (almost) characterized by the Kleene star closure of the linear languages. For both a bounded and an unbounded number of turns, requiring to empty the pushdown store is a strictly stronger condition than requiring to re-enter the initial state. Several new language families are obtained which form a double-stranded hierarchy. Closure properties of these families under AFL operations are derived. The regular closure of the linear languages share the strong closure properties of the context-free languages, i.e., the family is a full AFL. Interestingly, three natural new language families are not closed under intersection with regular languages and inverse homomorphism. Finally, an algorithm is presented parsing languages from the new families in quadratic time.     

Relationships between characteristics in periodic Poisson queues

We study single server periodic queues in the day equilibrium conditions. The following characteristics of interest are considered at time of dayt: V^p(t)-the work load, L^p(t)-the number of customers and u^p(t)-the departure rate. We give relationships between E[V^p(t)], E[L^p(t)] and u^p(t). We also prove that E[V^p(t)] < and E[L^p(t)] < provided the second moment of the service time is finite.     

LiCoO2中锂离子固相扩散系数随循环次数的变化

The solid diffusion coefficient of lithium-ion in LiCoO₂ cathode material has been investigated by the capacity intermittent titration technique (CITT) at different voltages and at different charge/discharge cycles. By SEM, XRD and FTIR techniques, the structure of LiCoO₂ was studied before and after charge-discharge cycles, and the relationship between solid diffusion coefficient and crystal structure was further discussed. CITT results show that the value of Li⁺ solid diffusion coefficient of LiCoO₂ is about 10^-12 cm²·s^-1. During the whole charge-discharge cycles, the Li⁺ solid diffusion coefficient decreased within the voltage of 4.0～4.3 V, which is attributed to the change of the structure of LiCoO₂.     

划痕试验法对特殊薄膜系结合力的检测与评价

简要介绍了划痕试验法测量表面薄膜与基体结合力的测试原理和实验方法，讨论了影响临界载荷Lc测量值准确性的主要因素，通过对薄膜系的分类以及大量实际测量数据的总结和分析，认为被测薄膜以及基体的物理化学特性对临界载荷的测量具有重要的影响，单纯从声发射信号的变化来确定临界载荷的方法有可能存在较大误差，分析和讨论了某些特殊薄膜系的声发射信号与其实际临界载荷值之间存在较大偏差的现象和原因，并提出了针对不同膜系，合理利用声发射曲线，摩擦力斜率以及显微观测来正确判定临界载荷的必要性。     

Dimerization of some substituted benzoic acids in aqueous solution from conductance measurements

Precision molar conductances of benzoic, o-toluic, 2,6-dimethylbenzoic, 2,3,6-trimethylbenzoic, and, o-fluorobenzoic acids have been determined in aqueous solution as a function of temperature and of concentration up to near saturation (<0.035 M). At the higher concentrations molar conductances are found to be less than anticipated for the simple dissociation of a 1-1 electrolyte. Although the deviations are only 1% or less they have been interpreted to show that these acids are dimerized in solution. The interpretation includes an assumption that the dimer ionizes to produce a triple ion. Increasing numbers of methyl groups lead to increasing dimerization. For those acids with two ortho groups the dimerization increases with increasing temperature while the other three show decreasing dimerization with increasing temperature. Temperature functions have been determined for the dimerization constants and from these functions standard changes in enthalpy, entropy, and heat capacity have been determined. Comparisons are made with dimerization studies in non-aqueous solvents. From these as well as the behavior of benzene in water it is concluded that a major factor driving the dimerization is hydrophobic interaction. To provide a limiting conductance of the triple ion needed in the dimerization calculations a conductance study was also made for o-Phenylbenzoic acid on the assumption that its anion provides an approximate model of the triple ion.     

Microheterogeneity in aqueous-organic solutions: Heat capacities,volumes and expansibilities of some alcohols,aminoalcohol and tertiary amines in water

The heat capacities per unit volume and the densities of aqueous solutions of 2-propanol, neopentanol, tert-amylalcohol, 2-amino-2-methylpropanol, triethylamine and diethylmethylamine were measured, in many cases as a function of temperature, over the whole mole fraction or solubility range. Apparent and partial molal heat capacities, volumes and expansibilities were derived. The concentration dependence of these functions suggest the existence of transitions in some of these systems, in the water-rich region, qualitatively similar to micellization. The large relaxation contribution observed with some of the thermodynamic functions of hydrophobic alcohols and amines suggests a reinforcement of hydrophobic hydration due to strong hydrogen-bonding interactions of the polar groups with water.     

Thermodynamic properties of organic compounds in aqueous solution. II. Apparent molal heat capacities of piperidines,morpholines, and piperazines

Apparent molal heat capacities of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of ΔC _p for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined.