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.     

Heat conductivity of three periodic Hard Disks via nonequilibrium molecular dynamics

We use a driving field, of the type first suggested by Evans, to generate a steady heat current in the simplest possible system, a two-dimensional periodic fluid of three hard disks. Hard-disk motion equations can be conveniently derived from repulsive constant-force or linear-force potentials by considering the infinitely repulsive limit of these potentials. We show that the isoenergetic and isokinetic forms of the nonequilibrium equations of motion generate steady-state heat conductivities differing by terms of order 1/N, whereN is the number of particles. The resulting conductivities appear to vary as the logarithm of the driving field strength. Even at low fields, the three-body periodic-system results lie well below Enskog's infinite-system prediction.     

The thermodynamics of proton dissociation of adenine

The thermodynamic quantities associated with ionization of the N₁ and N₉ protons of adenine have been calorimetrically determined as a function of temperature. The H values for proton dissociation of these groups, with pK values of 4.19 and 9.92, were found to be 5.1 and 9.1 kcal/mole, respectively, at 25°C, =0.025. The C _p values for proton dissociation of these groups were estimated to be –11 and –17 cal/mole-deg. These results indicate that the large heat capacity changes observed during conformational transitions of polynucleotides are not the result of ionization of the bases.     

Non isothermal heat capacities and chemical reactions using a modulated DSC

An evaluation of measurements of heat capacities by modulated differential scanning calorimetry, MDSC is presented. Heat capacities were obtained from 130 to 550 K by a non isothermal technique in which a periodic modulation was added to the linear heating rate. Effects of amplitude and period of modulation, sample weight, sample type, pan type, and cell imbalance are described. Results are compared with those obtained using the isothermal technique. Heat capacity could be measured well into the decomposition region and separated from the non reversing signal due to chemical reaction (degradation), thus allowing a precise detection of onsets of the thermal degradation. This additional information will aid in the interpretation of the degradation chemistry, a field vital for the petroleum-industry.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayPart of this paper was presented at the 23rd Conference of the North American Thermal Analysis Society, Toronto, Canada, September 25–28, 1994.The author (MVN) acknowledges the experimental assistance provided by J. Balogh of Exxon Research and Engineering Company, Linden. Helpful discussions with A. Boller of the University of Tennessee at Knoxville, Dr. Y. Jin, General Electrical, and Dr. S. Sauerbrunn formerly of TA Instruments are also acknowledged.     

煤中有机硫形态结构和热解过程硫变迁特性的研究

利用热解 质谱并结合固定床热解反应装置，对煤中有机硫的形态主其对加氢热解过程 变迁特性的影响，进行了较系统的研究。结果表明，煤中有机硫的形态结构在褐煤中主要以脂肪族、芳香族硫化物为主，而在 煤中则主要以各种不同芳构化程度的噻吩结构为主，初步表明煤中有机硫形态结构随煤变质程度的变迁呈较强的连续递变性。煤热解过程中硫在呼产物中的变迁和分布与煤中有机硫的形态结构特点密切相关。较高芳构化噻吩结构不完全的氧     

Transfer activity coefficient of the proton in water-pyridine mixtures. A comparison of some extrathermodynamic assumptions

Various water-pyridine mixtures have been selected in order to compare several of the most popular extrathermodynamic assumptions involved in the determination of the transfer activity coefficient of the proton, _t(H⁺). Two techniques have been utilized for this purpose: voltammetry [study of the ferrocene, ferricyanide, or thallium(1) systems] and potentiometry at equilibrium (emf measurements of various galvanic cells, including liquid junctions and hydrogen electrode or silver electrode as a test electrode). The assumptions have been classified into various groups [e.g., _t(Z^p+)=_t(Z^q+) or _t(X^–)=_t(Y⁺)], and the values of _t(H⁺) have been experimentally determined in each case. The results vary depending upon the basic assumption (several pH units); less important differences (e.g., 0.5 pH unit) occur within a given group, and this may be assigned to the nature of the reference species chosen. A simple model of solvation has been also examined; the application of the law of mass action to the corresponding equilibrium provides results close to the _t(X^–) =_t(Y⁺)type of assumptions which ultimately leads to most self-consistent results.     

不同热管工质对热管冷却反应堆堆芯物理参数的影响与分析

热管冷却反应堆采用非能动传热技术,热响应速度快,可避免堆芯单点失效,具有功率密度大、寿命长、环境适应性强、工作性能稳定等特点,是目前空间核反应堆研究的热点。本文基于清华大学开发的反应堆蒙特卡洛中子输运程序RMC (Reactor Monte Carlo code),以美国爱荷华国家实验室(Idaho National Laboratory, INL)设计的热管冷却反应堆INL Design A为研究对象,选取3种热管工质开展热管冷却反应堆堆芯物理计算。计算结果表明：锂热管工质不仅拥有很好的热物性参数,并且使用锂热管工质的热管冷却反应堆缓发中子有效份额最大、中子能谱较硬、燃耗反应性损失最小、增殖性能最佳,有利于热管冷却反应堆堆芯小型化与长寿命。因此,推荐锂为热管冷却反应堆的热管工质。     

IRS辅助的MISO-SWIPT安全速率最大化算法

为增强系统的稳定性,基于智能反射面（intelligent reflection surface,IRS）辅助安全通信,为用户采用功率分配架构的无线携能传输（simultaneous wireless information and power transfer,SWIPT）技术以提高用户安全速率并降低用户的能量消耗,建立了系统安全速率最大化的目标函数模型;考虑IRS相移约束、基站最大发射功率、功率分配比率约束和用户最低能量采集约束,提出了一种基于交替优化的安全速率最大化算法。利用连续凸近似算法,将目标函数转化为凸的形式;采用交替优化,对耦合变量进行解耦处理;提出一种波束赋形算法以实现安全速率最大化。仿真表明,提出的算法能够有效提升IRS辅助的SWIPT系统的安全速率,至少比其他算法提高了2.63bps/Hz。     

专业“温度”与专业过热现象试析

本从数学角度探讨了专业“温度”及专业过热现象,并建立了一个防止专业过热的人才培养模型。     

Spectro-streak picosecond studies of intramolecular charge-transfer fluorescence

A spectro-streak photometer, an instrument for simultaneously measuring fluorescence intensity, time, and wavelength,I(t, ), with a single picosecond excitation pulse, has been constructed. Two typical and currently highly topical examples of mesurements are discussed. (1) the temporal development of the fluorescence form the intramolecular charge-transfer (ICT) state of the rigid aromatic compound 4,5-(1-methylindolino)3,4-naphthanthracene is studied in the protic solvent hexanol. (2) Propyl chain-linked pyrene/N,N-dimethylaniline is used as the model compound to study conformational changes associated with the transition from a contact ion pair to a sandwich exciplex.