A new regularity for internal pressure of dense fluids

In this paper, we derive a new regularity for dense fluids, both compressed liquids and dense supercritical fluids based on the Lennard-Jones (12-6) potential function and using speed of sound results. By considering the internal pressure by modeling the average configurational potential energy, and then taking its derivative with respect to volume, we predict that isotherm [(partial differential E/partial differential V)(T)/rhoRT]V(2) is a linear function of rho(2), where E is the internal energy, (partial differential E/partial differential V)(T)) is the internal pressure, and rho = 1/V is the molar density. The regularity is tested with experimental data for ten fluids including Ar, N(2), CO, CO(2), CH(4,) C(2)H(6), C(3)H(8), C(4)H(10), C(6)H(6), and C(6)H(5)CH(3). These problems have led us to try to establish a function for the accurate calculation of the internal pressure based on speed of sound theory for different fluids. The results of the fitting show limited success of the pure substances. The linear relationship appears to hold from the lower density limit at the Boyle density and from the triple temperature up to about double the Boyle temperature. The upper density limit appears to be reached at 1.4 times the Boyle density. The results are likely to be useful, although they are limited.     

Thermal conductivity of argon,krypton and their mixtures at low temperatures (90-270 k)

Experimental thermal conductivity values of argon, krypton and their mixtures have been measured at 1 atm (101.325 kN/m²) in a specially designed hot-wire cell in the temperature range 90-270 K. These values are compared with the recommended values based on available data for pure systems, and with the predictions of kinetic theory based on L-J (12-6), exp-six and (11-6-8) potentials. Combination rules for predicting the interaction parameters for unlike molecules from the knowledge of parameters for like molecules have been derived for (11-6-8) potential. Two variants of the procedures based on Sutherland-Wassiljewa expressions have also been examined for mixtures.     

Thermal conductivity of neon in the temperature range 400–2400K

Accurate measurements of the thermal conductivity of neon are given in the temperature range 400–2400K as obtained on an improved thermal conductivity column instrument. These data are found to be in good agreement with the earlier measurements of thermal conductivity from this laboratory and also with the available viscosity values. The present conductivity data are also compared with the predictions of kinetic theory in conjunction with several different forms for the intermolecular potential.     

Kinetic theory derivation of the transport coefficients of stochastic rotation dynamics

We use a kinetic theory approach to derive the continuum Navier-Stokes and heat conduction equations for stochastic rotation dynamics, a particle based algorithm for simulating a fluid. Hence we obtain expressions for the viscosity and thermal conductivity in two and three dimensions. The predictions are tested numerically and good agreement is found.     

Continua of interactions between pairs of atoms in molecular crystals

The electron density distributions in crystals of five previously studied DMAN complexes and five Schiff bases (two new ones) have been analysed in terms of various properties of bond critical points (BCPs) found in the pair-wise interactions in their lattices. We analysed the continua of interactions including covalent/ionic bonds as well as hydrogen bonds and all other types of weak interactions for all pairs of interacting atoms. The charge density at BCPs and local kinetic and potential energy densities vary exponentially with internuclear distance (or other measures of separation). The parameters of the dependences appear to be characteristics of particular pairs of atom types. The Laplacian and the total (sum of kinetic and potential) energy density at BCPs show similar behaviour with the dependence being of the Morse type. The components lambda1, lambda2, lambda3 of the Laplacian at BCPs vary systematically with internuclear distance according to the type of atom pair. For lambda1 and lambda2 the distribution is of the exponential type, whereas lambda3 does not seem to follow any simple functional form, consistent with previous theoretical findings. Analytical nonlinear dependences of Laplacian on charge density have been found. They agree reasonably well with those obtained by least square fit of the Laplacian to charge density data. There are four distinct regions of the [symbol: see text]2rho(BCP)/rho(BCP) space, generated by E(BCP) = 0 and G(BCP)/rho(BCP) = 1 conditions. Two regions clearly correspond to the shared-shell and closed-shell interactions and the other two to some intermediate situation.     

Dielectric response of modified Hubbard models with neutral-ionic and Peierls transitions

The dipole P(F) of systems with periodic boundary conditions in a static electric field F is applied to one-dimensional Peierls-Hubbard models for organic charge-transfer (CT) salts. Exact results for P(F) are obtained for finite systems of N=14 and 16 sites that are almost converged to infinite chains in deformable lattices subject to a Peierls transition. The electronic polarizability per site, alpha(el)=(partial differential P/partial differential F)0, of rigid stacks with alternating transfer integrals t(1+/-delta) diverges at the neutral-ionic transition for delta=0 but remains finite for delta>0 in dimerized chains. The Peierls or dimerization mode couples to charge fluctuations along the stack and results in large vibrational contributions alpha(vib) that are related to partial differential P/ partial differential delta and that peak sharply at the Peierls transition. The extension of P(F) to correlated electronic states yields the dielectric response kappa of models with neutral-ionic or Peierls transitions, where kappa peaks >100 are found with parameters used previously for variable ionicity rho and vibrational spectra of CT salts. The calculated kappa accounts for the dielectric response of CT salts based on substituted TTF's (tetrathiafulvalene) and substituted CA's (chloranil). The role of lattice stiffness appears clearly in models: soft systems have a Peierls instability at small rho and continuous crossover to large rho, while stiff stacks such as TTF-CA have a first-order transition with discontinuous rho that is both a neutral-ionic and Peierls transition. The transitions are associated with tuning the electronic ground state of insulators via temperature or pressure in experiments, or via model parameters in calculations.     

Static and dynamic thermal quantities near the consolute point of the binary liquid mixture aniline-cyclohexane studied with a photopyroelectric technique and adiabatic scanning calorimetry

We studied the thermal conductivity, thermal effusivity, and specific heat capacity at constant pressure of the critical binary liquid mixture aniline-cyclohexane near the consolute point, using a photopyroelectric (PPE) technique and adiabatic scanning calorimetry (ASC). According to recent theoretical predictions based on renormalization group theory calculations, a substantial (but not diverging) enhancement in the thermal conductivity in the homogeneous phase near the critical temperature was expected for this binary system near the consolute point. However, within an experimental precision of 0.05%, we found no deviation from linear behavior in the range of 5 K above Tc down to Tc. The specific heat capacity calculated from the results for the thermal conductivity and effusivity is in good agreement with that measured by ASC. For the ASC results, the theoretical power law expression with the Ising critical exponent was fitted to the specific heat capacity both above and below the transition temperature. Good agreement with theory was found both for the amplitude ratio and the two-scale universality.     

Viscosity and thermal conductivity of some refrigerants at moderate and high densities on the basis of Rainwater–Friend theory and the corresponding states principle

The initial density dependence of viscosity and thermal conductivity was formulated on the basis of Rainwater–Friend (RF) theory. In this work, we have first focused on the calculation of viscosity and thermal conductivity of moderately dense argon by using RF theory and an accurate ab initio potential function. This theory which was originally presented for spherical potentials have been adapted for calculation of viscosity and translational contribution of thermal conductivity of some refrigerants by introducing the corresponding states correlations for the second transport virial coefficients. Then the internal states contribution for the thermal conductivity has been determined based on the Mason–Monchick and modified Enskog theories. So, we have calculated the viscosity and thermal conductivity of some refrigerants, R32, R14, R12, R13, R22, R134a, R143a, R125, R123, R142b, at moderate densities up to about 2 mol dm⁻³. At high densities, beyond the validity range of RF theory, we have applied correlation expressions for the viscosity and thermal conductivity residual functions to calculate the viscosity and thermal conductivity of supercritical refrigerants and then compared with the available experimental data. In conclusion, we have shown that the RF theory in conjunction with the corresponding states residual functions present the reliable model for calculation of viscosity and thermal conductivity of refrigerants over a comparatively wide temperature and pressure range up to 65 MPa within the experimental errors.     

Transport properties of high temperature air components: A review

The methods for the calculation of the transport properties of high temperature gases are reviewed from the points of view of both kinetic theory and transport cross sections. Particular emphasis is given to the poor convergence of the Chapman-Enskog method for calculating the thermal conductivity of free electrons and of the possible sources of errors when applying well known simplified formulae for calculating the translational thermal conductivity of heavy components and the viscosity of partially ionized gases. The transport cross sections (collision integrals) of high temperature air components are then discussed by comparing old and new calculations particularly emphasizing atom-atom, atom-molecule and atom-ion interactions. Special consideration is dedicated to the knowledge of transport cross sections of electronically excited states. The role of inelastic processes in affecting the transport cross sections is also briefly discussed. Finally the possibility to extend the results to non equilibrium situations is analysed.     

二水草酸锌脱水的热分解动力学研究

提出一种多升温速率-等温法确定机理函数g(α)的新方法;并用迭代的等转化率法求出较为可靠的活化能Ea;在Ea和g(α)的基础上计算出指前因子A.用该法对二水草酸锌（ZnC2O4•2H2O）脱水反应的热分解动力学三因子进行了求算,得出Ea为87.22 kJ•mol－1, A为4.2120×108～7.2328×108 s－1;以及随机成核和随后生长型机理函数Am（Avrami-Erofeer）,其积分形式g(α)=[－ln(1－α)] 1/m和微分形式f(α)=m(1－α)•[－ln(1－α)](1－1/m),调节因子m=1.85～2.00.     

Zr（OH）4的热分解及ZrO2的相变过程

利用TG-TDG-DTA热分析技术研究了由Zr（OH）4热分解制备ZrO2的脱水过程,并结合X射线粉末衍射技术研究了ZrO2的相变过程．发现在82℃的吸热峰对应Zr（OH）4的脱水,而435℃附近出现的放热峰则为四方ZrO2向单斜ZrO2的晶相转变．采用外推法确定了Zr（OH）4脱水过程遵循三维扩散机理,其函数方程为g（α）=[{1／（1-α）}^1/3-1]^2．以实验获得的动力学参数ln A和E为基础,用最小二乘法对ln A和E进行线性拟合,得到动力学补偿效应表达式为ln A=0．437E-20．69．     

Binless estimation of the potential of mean force

For a system in thermal equilibrium, described by classical statistical mechanics, we derive an unbiased estimator for the marginal probability distribution of a coordinate of interest, rho( x). This result provides a "binless" method for estimating the potential of mean force, Phi = -beta (-1) ln rho, eliminating the need to construct histograms or perform numerical thermodynamic integration. In our method, the distribution that we seek to compute is expressed as the sum of a reference distribution, rho 0(x)essentially an initial guess or estimate of rho( x)and a correction term. While the method is valid for arbitrary rho 0, we speculate that an accurate choice of the reference distribution improves the convergence of the method. Using a model molecule, simulated both in vacuum and in solvent, we validate our proposed approach and compare its performance with the histogram and thermodynamic integration methods. We also discuss and validate an extension in which our approach is used in combination with a biasing force, meant to improve uniform sampling of the coordinate of interest.     

Accelerating the convergence of the total energy evaluation in density functional theory calculations

A special feature of the Strutinsky shell correction method (SCM) [D. Ullmo et al., Phys. Rev. B 63, 125339 (2001)] and the recently proposed orbital-corrected orbital-free density functional theory (OO-DFT) [B. Zhou and Y. A. Wang, J. Chem. Phys. 124, 081107 (2006)] is that the second-order corrections are incorporated in the total energy evaluation. In the SCM, the series expansion of the total electronic energy is essentially the Harris functional with its second-order correction. Unfortunately, a serious technical problem for the SCM is the lack of the exact Kohn-Sham (KS) density rho KS(r) required for the evaluation of the second-order correction. To overcome this obstacle, we design a scheme that utilizes the optimal density from a high-quality density mixing scheme to approximate rho KS(r). Recently, we proposed two total energy density functionals, i.e., the Zhou-Wang-lambda (ZW lambda) and the Wang-Zhou-alpha (WZ alpha) functionals, for use in the OO-DFT method. If the two interpolation parameters, lambda and alpha, are chosen to allow the second-order errors of the ZW lambda and the WZ alpha functionals to vanish, these two functionals reduce to the Hohenberg-Kohn-Sham functional with its second-order correction. Again, the optimal density from a high-quality density mixing scheme is used to approximate rho KS(r) in the evaluation of lambda and alpha. This approach is tested in iterative KS-DFT calculations on systems with different chemical environments and can also be generalized for use in other iterative first-principles quantum chemistry methods.     

A linear comprehensive adsorption model of hydrogen on super activated carbon under supercritical conditions

The adsorption isotherms of hydrogen on super activated carbon were measured systematically, covering a temperature range of 93-293 K at 20 K intervals and pressures up to 7 MPa. All the experimental data were linearized by adopting the coordinates ln ln(n) vs 1/(ln P). The results indicate that the adsorption limit (P(lim), n(lim)) exists virtually at high pressure and has a certain physical meaning. Based on the adsorption limit, further analyses were carried out by modeling the adsorption isotherms in the coordinates ln(n(lim)/n) vs ln(RT(ln(P(lim)/P) and a linear comprehensive adsorption model was proposed in the form n (lim)=n.exp(psi T+lambda/T-c/) (beta).[RT ln( P (lim)P )] (b) which can predict the adsorption isotherm of hydrogen on activated carbon in supercritical conditions.     

Quantitative thermal analysis,VI. Initial conditions of the mathematical description of thermal curves (gradient theory)

The fundamental concept of the theory of thermal analysis developed in this paper involves the movement of the transformation front in the mass of the sample. Equations are developed for the motion of the transformation front (in the case of invariant processes) for the simplest model of the thermoanalytical cell. For a cylindrical sample, the equation is $$t = \sqrt {\frac{{Hd}}{{\lambda B}}\left( {\frac{{R^2 - r^2 }}{2} - r^2 \ln \frac{R}{r}} \right)} $$ whereR is the external radius of the sample,H the thermal effect of the transformation,B the heating rate,D the density,λ the thermal conductivity,r the position of the transformation front, andt time. The equation is experimentally confirmed by the finding that, as concluded from the equation, the height of the peak is directly proportional to the square root of the rate of sample heating.     

Thermal conductivity and heat capacity of liquid and glassy poly(vinyl acetate) under pressure

The dependence of thermal conductivity λ and heat capacity per unit volume pc_p on temperature and pressure for poly(vinyl acetate) has been measured by a transient hot-wire probe technique. The measurements were made under pressures up to 0.5 GPa over a temperature range of 270–470 K. The temperature coefficient of thermal conductivity (? lnλ/?T)_p was found to increase with pressure for both the liquid and the glassy state. The change in heat capacity per unit volume in the region of the glass-transition temperature was found to decrease with increasing pressure. The Ehrenfest relation does not explain the variation of the pressure coefficient of the glass-transition temperature.     

A new semi-analytical model for effective thermal conductivity of nanofluids

A new theoretical model for thermal conductivity of nanofluids is developed incorporating effective medium theory, interfacial layer, particle aggregation and Brownian motion-induced convection from multiple nanoparticles/aggregates. The predicated result using aggregate size, which represents the particle size in the actual condition of nanofluids, fits well with the experimental data for water-, R113- and ethylene glycol (EG)-based nanofluids. The present model also gives much better predictions compared to the existing models. A parametric analysis, particularly particle aggregation, is conducted to investigate the dependence of effective thermal conductivity of nanofluids on the properties of nanoparticles and fluid. Aggregation is the main factor responsible for thermal conductivity enhancement. The dynamic contribution of Brownian motion on thermal conductivity enhancement is surpassed by that of static mechanisms, particularly at high volume fraction. Predication also indicated that the viscosity increases faster than the thermal conductivity, causing the highly aggregated nanofluids to become unfavourable, especially for d_f = 1.8.     

Kinetics and mechanism of the addition of benzylamines to benzylidenediethylmalonates in acetonitrile

Kinetic studies of the benzylamine additions to benzylidenediethylmalonates (BDM: YC(6)H(4)CH[double bond]C(COOEt)(2)) in acetonitrile at 20.0 degrees C are reported. The rates in acetonitrile are consistent with that expected from the through-conjugative electron-accepting power of the activating groups, (COOEt)(2). The sign and magnitude of the cross-interaction constant, rho(XY) = -0.45, are in general agreement with those for the single-step amine additions to activated olefins. The kinetic isotope effects (k(H)/k(D) > 1.0) measured with deuterated benzylamines (XC(6)H(4)CH(2)ND(2)) increase with a stronger electron-acceptor substituent in benzylamines (partial differential sigma(X) > 0) and a stronger electron donor in the substrate (partial differential sigma(Y) < 0). These trends are the same as those found for benzylidene-1,3-indandiones but are exactly opposite to those for other activated olefin series, e.g., beta-nitrostyrene. It has been shown that the former series are thermodynamically controlled, whereas the latter are intrinsically controlled with a relatively strong transition state imbalance. The activation parameters, Delta H(++) and Delta S(++), also support our proposed transition state involving concurrent C(alpha)-N and C(beta)-H bond formation with a four-membered cyclic structure.