Formation,growth and ageing of clathrate hydrate crystals in a porous medium

An experimental study was performed to visually observe the driving force dependence of hydrate growth in a porous medium filled with either liquid water and dissolved CO₂ or liquid water and gaseous CO₂. The given system subcooling, ΔT _sub, i.e. the deficiency of the system temperature from the triple CO₂?hydrate?water equilibrium temperature under a given pressure, ranged from 1.7?K to 7.3?K. The fine dendrites initially formed at ΔT _sub?=?7.3?K changed quickly into particulate crystals. For ΔT _sub?=?1.7?K, faceted hydrate crystals grew and the subsequent morphological change was hardly identified for an eight-day observation period. These results indicate that the physical bonding between hydrate crystals and skeletal materials becomes stronger with decreasing driving force, suggesting that the fluid dynamic and mechanical properties of hydrate-bearing sediments vary depending on the hydrate crystal growth process.     

Temperature‐dependent ferroelectric dynamic hysteresis properties of modified PMN–PZT relaxor ceramics

Temperature‐dependent ferroelectric dynamic hysteresis properties of modified Pb(Mg_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃ (PMN–PZT) ceramics have been investigated in a wide range from 298 to 433 K. Interestingly, it was found that back‐switching polarization P_bc increased while the hysteresis area 〈A 〉, coercive field E_c, saturation polarization P_s, and remnant polarization P_r all decreased linearly with temperature below 398 K (close to the macro–micro domain transition temperature T_nr). A set of simple linear temperature scaling relations was established, which is different from the power‐law scaling relations for soft and hard PZT ceramics. At further increased temperature, double‐loop features appeared and the ferroelectric properties varied nonlinearly due to the reversible macro–micro domain transition in the T > T_nr region. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Quadrupole interaction in In0.95 Ag0.045 Ga0.005 alloy

The temperature dependence of the quadrupole interaction of¹¹¹Cd in the In_0.95 Ag_0.045 Ga_0.005 alloy is determined by the time differential perturbed angular correlation method from 77 to 422 K. The electric field gradients produced by the lattice are derived. The temperature dependence of the electric field gradient is found to follow theT ^3/2 law observed in In between 77 K and room temperature and to deviate from it at higher temperatures. The widths of the electric field gradient distribution are 0.1147(259), 0.0924(340), 0.4954(601) and 1.344(175) at 77, 298, 373 and 422 K, respectively. This illustrates that the alloy is well ordered at 77 and 298 K and that it becomes less ordered at 373 and 422 K.     

Interaction between solute molecules in medium density solvents

Solvation properties of solutes in supercritical, medium density solvents have been analysed using hypernetted-chain theory with the emphasis on the solvent-mediated interaction between solute molecules. The solvent and solute molecules are Lennard-Jones particles, and the solute is present at infinite dilution. Also a pair of solute molecules separated by different distances has been considered using reference interaction site model theory. Mainly, solvents at two typical densities (1.09_pc and 2.91_pc; pc is the critical density) that are in medium and high density regions, respectively, are treated. The temperature is set at 1.04T_C (T_c is the critical temperature). When the solute size is larger than the solvent size and the strength of the solute-solvent attractive interaction is greater than that of the solvent-solvent in the medium density region, the solvent structure confined between a pair of solute molecules is largely different from that near a single solute molecule. The confined solvent becomes denser and more stabilized as the distance between the solute molecules decreases, and an attractive interaction is induced between them. The interaction becomes even more attractive as the strength of the solute-solvent attractive interaction increases. The observations are qualitatively different from those in the high density region. Another high density region, which is well below the critical temperature, has been considered, but the behaviour observed is similar to that in the high density region above the critical temperature.     

分子极性对类胡萝卜素共振拉曼光谱的影响

测量了非极性分子β胡萝卜素和极性分子角黄素, 在非极性溶剂CS₂和极性溶 剂1,2二氯乙烷中243–293 K的温度范围内的共振拉曼光谱. 结果表明, 溶质和溶剂的极性对拉曼光谱影响很大. 非极性分子β胡萝卜素在非极性溶剂CS₂中的拉曼散射截面最大, 线宽最窄, 而极性分子角黄素在极性溶剂1,2二氯乙烷中的拉曼散射截面最小, 线宽最大. 用溶剂效应及线性多烯分子的“相干弱阻尼电子-晶格振动”, “有效共轭长度”模型给予了解释.     

Analysis of temperature and concentration dependence of flow stress in KCl–KBr single crystals with special reference to solute distribution

Available data on the temperature and concentration dependence of critical resolved shear stress (CRSS) of KCl–KBr solid-solution crystals containing 9, 17, 27 and 45?mol% KBr in the temperature range 77–230?K have been analyzed within the framework of the kink-pair nucleation model of plastic flow in solid- solution crystals. It is found that CRSS τ decreases with increasing temperature T in accordance with the model relation lnτ?=?A???BT, where A and B are positive constants. The CRSS τ at a given temperature depends on solute concentration c as τ?∝?c^p , where exponent p has a value between 0.33 and 0.57 as temperature T rises from 0 to 230?K. The model parameter W _o, i.e. binding energy between the edge-dislocation segment L _o involved in the unit activation process and the solute atoms close to it (T?→?0?K), which is inversely proportional to B, increases with solute concentration c monotonically as W _o?∝?c ^0.33 up to a critical value c _m?=?35?mol% KBr, which is in reasonable agreement with the model prediction W _o?∝?c ^0.25. However, W _o decreases with an increase in c beyond c _m, which indicates somewhat ordered distribution of solute in the host lattice of concentrated KCl–KBr solid solutions with c?>?c _m.     

Molecular dynamics study of reaction kinetics in viscous media

Predicted by stochastic models and observed experimentally in a number of isomerization reactions, viscosity-induced solvent effects manifest themselves in a significant departure of the reaction rates from the values expected on the basis of transition state theory. These effects are well understood within the framework of stochastic models; however, the predictive power of such models is limited by the fact that their parameters are not readily available. Experiment and molecular dynamics (MD) simulations can provide such information and can serve as the testing grounds for various stochastic models. In real solvents, a change in viscosity is inevitably associated with variation of at least one of the three factors – temperature, pressure, or solvent identity, resulting in different solvent–solvent and solvent–solute interactions. A model is proposed in which solvent viscosity is manipulated through mass scaling, which allows one to maintain other factors constant for a series of viscosities. This approach was tested on MD simulations of the kinetics of two model isomerization reactions in Lennard–Jones solvents, whose viscosity was varied over three orders of magnitude. The results reproduce the Kramers turnover and a strong negative viscosity dependence of the reaction rates in the high viscosity limit, somewhat weaker than η ^?1.     

Structure,thermodynamic and transport properties of imidazolium-based bis(trifluoromethylsulfonyl)imide ionic liquids from molecular dynamics simulations

Molecular dynamics (MD) simulations have been performed in order to investigate the properties of [C _n mim⁺][Tf₂N^?] (n?=?4,?8,?12) ionic liquids (ILs) in a wide temperature range (298.15?498.15?K) and at atmospheric pressure (1 bar). A previously developed methodology for the calculation of the charge distribution that incorporates ab initio quantum mechanical calculations based on density functional theory (DFT) was used to calculate the partial charges for the classical molecular simulations. The wide range of time scales that characterize the segmental dynamics of these ILs, especially at low temperatures, required very long MD simulations, on the order of several tens of nanoseconds, to calculate the thermodynamic (density, thermal expansion, isothermal compressibility), structural (radial distribution functions between the centers of mass of ions and between individual sites, radial-angular distribution functions) and dynamic (relaxation times of the reorientation of the bonds and the torsion angles, self-diffusion coefficients, shear viscosity) properties. The influence of the temperature and the cation's alkyl chain length on the above-mentioned properties was thoroughly investigated. The calculated thermodynamic (primary and derivative) and structural properties are in good agreement with the experimental data, while the extremely sluggish dynamics of the ILs under study renders the calculation of their transport properties a very complicated and challenging task, especially at low temperatures.     

Isoniazid drug adsorption on the pristine and Al-doped zinc oxide nanosheets: a molecular modeling

Experimental works have exposed that Al-doping in the structure of ZnO nanostructures intensely increases their electronic sensitivity toward various chemicals. Herein, density functional theory calculations were employed to inspect the Al-doping effect on the sensitivity of a ZnO nanosheet (ZnOS) to the isoniazid (IS) drug. The pristine ZnOS physically adsorbs an IS molecule with adsorption energy (E _ad) of ?6.8?kcal/mol, and the sensing response value of 2.3 at 298?K. Replacing a Zn atom by an Al atom strengthens the interaction, increasing the E _ad to ?20.8?kcal/mol. Also, the Al-doping significantly increases the sensing response value to 150.3 by rising the electrical conductivity of the sheet. A short recovery time of 11.3 s is predicted for the Al-ZnOS-based sensor. The water solvent somewhat strengthens the interaction of IS drug with the Al-ZnOS, increasing the sensing response from 150.3 to 175.8. We concluded that the Al-doping makes the ZnOS a promising sensor for IS drug detection.     

Determination of the Solubility Parameter of Epoxidized Soybean Oil by Inverse Gas Chromatography

The thermodynamic parameters of epoxidized soybean oil (ESO) were determined by means of inverse gas chromatography (IGC) in the temperature range of 303.15 K-343.15 K. Two groups of probe solvents with different chemical natures and polarities were used to obtain information about ESO. The thermodynamic parameters—such as molar heat of sorption, weight fraction activity coefficient, Flory–Huggins interaction parameter, and partial molar heat of mixing—were obtained to judge the interactions between ESO and solvents at the studied temperatures. Also, the solubility parameters of ESO were found by plotting the graph of δ₁ ²/(RT) – χ^∞ ₁₂/V₁ vs. solubility parameters, δ₁, of the probes. The results showed that the selected solvent ethyl acetate was a moderate solvent for ESO; n-hexane was a moderate (but close to a better) solvent; while the probes n-heptane, n-octane, n-nonane, and chloroform were excellent solvents. From the extrapolation to 298 K, the solubility parameter value of ESO was 16.70 (J/cm³)^0.5.     

Thermal and magnetic properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The thermodynamic and magnetic properties of the La_{1 − x} Pb _x MnO₃ (0.24 ≤ x ≤ 0.40) solid solution system were investigated in the temperature range of 4.2–340 K. All objects were ferromagnetics with Curie temperature T _C ≈ 320–340 K, which slowly increased with x. The M(T) behavior in the magnetic ordering region indicated a nonuniform ground state, due possibly to the competition of ferromagnetic and antiferromagnetic interactions. The increase in the saturation magnetic moment with x can be described by a simple model of the binary bonds in La_{1 − x} Pb _x MnO₃.     

The Kirkwood correlation factor of dense methanol as a function of temperature and pressure under isochoric conditions and its statistical mechanical treatment

Experimental data of dielectric susceptibilities of methanol available in the literature over a wide range of temperature and pressure have been used for constructing a state function of the Kirkwood correlation factor g _K of methanol applicable in the homogeneous fluid region between 298 and 580?K and up to 350?MPa. Results of three isochores at 786.32, 820 and 850 kg m^?3 of this state function have been compared with predictions made by a statistical mechanical theory developed in previous work. The theory is based on an association model of alcohols accounting for the correlation of effective dipole moments of chains of all length as well as ringlike cluster formations. Most of the parameters such as association constants and association enthalpies have been obtained from quantum mechanical ab initio calculations of methanol clusters up to six members, reducing the numbers of adjustable parameters to three association constants and an averaged value of the angle between dipoles. The theory which has turned out to provide excellent results for alcohol + hydrocarbon and alcohol +?CCl₄ liquid mixtures at ambient pressure is also able to predict isochoric values of pure methanol up to a pressure of 350?MPa and temperatures of 570?K without adjusting further parameters in satisfying agreement with experimental data.     

Dielectric behavior and low temperature phase transition in NH4IO3

The electrical properties namely ac conductivity σ(ω,?T) and the complex dielectric permittivity (ε*) are measured at selected frequencies (5–100?kHz) as function of temperature (95?K?T?4IO₃. The ferroelectric hysteresis loops and the X-ray diffraction pattern are also measured. The analysis of the data indicates that the compound undergoes a structural phase transition at ～103?K and the behavior of σ(ω,?T) obeys the power law. The trend of the temperature dependence of the angular frequency exponent s (0?s?4IO₃; (2) the data indicate that the compound undergoes a structural phase transition at 103?K; (3) the originality of this transition has been confirmed by X-ray diffraction; (4) no evidence for the existence of a ferroelectric transition at 103?K as mentioned earlier; and (5) the quantum mechanical tunneling is proposed as the main mechanism of the electric conduction.     

Influence of Fe doping on electrical properties of LCMO

The polycrystalline samples La_0.67Ca_0.33Mn_(1?x)Fe _x O₃ (x?=?0.00,?0.01,?0.03, and 0.1) have been grown in single phase by solid state route. The analysis of the reaction has been done by thermogravimetry and differential thermal analysis measurements. DC electrical resistivity measurements have been carried out down to 15?K. The samples with x?=?0.00, 0.01, and 0.03 exhibit metal–insulator (MI) transition at temperatures 221.5?K, 217?K, and 215?K respectively, whereas the sample with x?=?0.1 is insulating in nature for entire temperature range. Interestingly, the electric transport properties of these samples are not consistent with their magnetic phase transitions and the samples show MI transition at a temperature, T _MI, which is significantly lower than the paramagnetic to ferromagnetic transition temperature (T _c). The resistivity data below T _MI has been analyzed using the empirical relation ρ?=?ρ₀?+?ρ₁ T ⁿ and the data above this temperature has been analyzed using two existing models, Mott's variable range hopping model and spin polaronic conduction model.     

Elastic properties of monoclinic telluric acid ammonium phosphate,Te(OH)6·2NH4H2PO4·(NH4)2HPO4, near the paraelectric-ferroelectric transition

The elastic constants of Te(OH)₆·2NH₄H₂PO₄·(NH₄)₂HPO₄, TAAP, point symmetrym, have been measured by ultrasonic resonance methods passing through the paraelectric-ferroelectric transition at ca. 320 K. In the range between 273 and 340 K the elasticity tensor exhibits only a slight anisotropy. No discontinuity of the elastic constants is observed. However, some temperature derivatives of the elastic constants show slight anomalies within the range 310 to 325 K. The strongest effect occurs with the longitudinal elastic resistancec ₂₂. The thermal expansion which varies only slightly between 263 and 340 K, is highly anisotropic in contrast to the thermoelastic behaviour. A strong negative thermal expansion is observed in a direction within the mirror plane, ca. 45° apart from the direction of spontaneous polarization.This effect is not accompanied by a corresponding thermoelastic anomaly. The interactions connected with the transition are of the totally symmetric type. Like many other properties the elastic and thermoelastic behaviour of TAAP resembles that of triglycine sulphate (TGS). Larger differences between TAAP and TGS are found in the pressure dependence of various properties. For example the pressure dependence of the transition temperatureT is negative for TAAP (–3.8 K/kbar) and positive for TGS (3.9 K/kbar).Dedicated to Prof. Dr. H.E. Müser on the occasion of his 60th birthday     

GeI2 monolayer: a model thermoelectric material from 300 to 600 K

ABSTRACT

In this work, the electronic structure, optical properties and thermoelectric properties of the GeI₂ monolayer are calculated by the first principles with the Boltzmann transport equation. The monolayer is calculated as an indirect band gap semiconductor with an indirect band gap of a value 2.19?eV. This GeI₂ monolayer is good for absorbing low-energy photons, and it is insensitive to high-energy photons. The material is stable at temperatures up to 600?K, so we calculated the thermal conductivity (K_L), Seebeck coefficient (S), power factor (PF) and thermoelectric figure of merit (ZT) of the GeI₂ monolayer at various carrier concentrations from 300 to 600?K. Due to the lower group velocity, the GeI₂ monolayer has a lower thermal conductivity of 0.48?W/m?K at 300K. In P-type doping, the power factor can up to 0.11?mW/m?K², and its ZT value is 4.04 at 600?K of the GeI₂ monolayer, indicating that the GeI₂ monolayer is a potential thermoelectric material.     

A scaling equation of state near the critical point and the stability boundary of a liquid

A new scaling equation of state is proposed to describe the equilibrium thermodynamic properties of liquids near the critical point. In distinction from the existing scaling equations, which are parametric, the new equation is nonparametric and is expressed directly in terms of the physical quantities (pressure, temperature, and so on). It creates a number of advantages for the traditional representation and data processing. The equation gives rise to a binodal, spinodal, and a curve of thermal capacity divergence (pseudospinodal). The equation is expressed in terms of reduced variables (the ratio of the deviation of a thermodynamic variable from its critical value to the critical value) and contains 3 system-dependent adjustable constants. With the help of this equation, we conducted an approximation of the experimental PVT data in the critical region of ⁴He, C₂H₄, and H₂O with a pressure error of 0.4% and carried out a calculation of the C _v ⁴He thermal capacity with no more than 4% error using a three-system constant determined from the PVT data.     

Effect of laser irradiation on the electrical properties of dysprosium doped LiCo-Ferrite

The effect of laser irradiation on the electrical properties of Li_0.5+z Co _z Dy _x Fe_2.5?2z?x O₄ ferrite (0.0 ≤ x ≤ 0.2, z = 0.1) has been studied in the temperature range 300 K ≤ T ≤ 750 K at frequencies of 10 kHz?5 MHz, using a LIMO-IR laser diode, at a wavelength of 808 nm. It was found that laser irradiation increases the polarization, the resistivity and the paramagnetic region. As the result of electronic rearrangement and lattice defects, small polorons and clusters were created. The doping of LiCo-Ferrite by Dy³⁺ increases both the AC and DC resistance of the investigated material. The variation of the AC and DC resistance with the Dy-content (x) obeys the following correlations R _ac/100 = 50x ²+4x+0.005 and R _dc/1000 = 31x ²+0.099x+0.09, respectively. A peculiar behaviour was obtained for the sample with Dy-content x = 0.075, as the resistance notably decreases. The applicable result is that laser irradiation increases the resistance of LiCo-ferrite by about 17% while its doping by dysprosium at x = 0.15 increases the resistance by about 23%. Its value is nearly stable for the temperature range from 340 to 480 K.     

The NMR indirect nuclear spin–spin coupling constant of the HD molecule

We present new calculated and experimental values of the NMR indirect nuclear spin–spin coupling constant in HD. In the quantum-chemical ab initio calculations, the full configuration-interaction (FCI) method is used, yielding an equilibrium value of 41.22?Hz in the basis-set limit. Adding a calculated zero-point vibrational correction of 1.89?Hz and a temperature correction of 0.20?Hz at 300?K, we obtain a total calculated spin–spin coupling constant of J _FCI(HD)?=?43.31(5)?Hz at 300?K. This result is within the error bars of the experimental gas-phase NMR value, J _exp(HD)?=?43.26(6)?Hz, obtained by extrapolating values measured in HD–He mixtures to zero density.