Relation between errors in enthalpy and entropy

In extracting enthalpy and entropy values from temperature‐dependent data, the error in the enthalpy is proportional to the error in the entropy, with a proportionality constant equal to an average temperature of measurement. This proportionality is verified experimentally in two recent studies. It is surprising how often published data do not obey this proportionality, and it is recommended that authors apply this simple procedure to verify their analyses of the temperature dependence of equilibria or rates. Copyright © 2012 John Wiley & Sons, Ltd.     

临界点附近H2气体的焓和熵的热力学计算

采用热力学方法和Benedict-Webb-Rubin(BWR)方程及相应的参数,计 算了临界温度附近H2气体的绝对焓和熵值,同时拟合了一组高准确度的定压比热容与温度 关联式参数.通过计算值与实验值的比较发现:在临界温度以上,计算值与实验值符合良好 ,对低于临界温度的未饱和H2气体也能计算出较好了结果.但对临界点和温度低于临界温 度、压强高于临界压强的过饱和H2气体的计算误差比较大,说明此时的H2气体的热力学性质特别,应当专门处理.     

The Fisher information measure and Shannon entropy for particulate matter measurements

We investigated the dynamics of particulate matter data, recorded in Tito, a small industrial area of southern Italy. The analysis of these signals was performed using the Fisher information measure (FIM), which is a powerful tool for investigating complex and nonstationary signals, and the Shannon entropy, which is a well-known tool for investigating the degree of disorder in dynamical systems. Our results point to an increase of disorder and complexity from fine to coarse particulates.     

Time-dependent paths,fictive temperatures and residual entropy of glass

After describing the Clausius limits of entropy, determined from the C _pd ln T integral, and its current use in determining the entropy of metastable (atomic) crystals, we determine two fictive temperature T _f values of four glasses – one from the integral of C _pdT and the other from C _pd ln T. The C _p data of the two metal–alloy glasses are from this calorimetric study; the C _p data of (i) quenched basalt composition glass fibers before and after partial annealing, and (ii) quenched NBS-710 composition glass fibers are taken from the literature. The C _pd ln T integral, which is not the entropy change, and the C _pdT integral yield the same T _f values. Therefore, the effect of the difference between the cooling and heating paths in the liquid–glass transformation range is too small to indicate whether the residual entropy, S _res, is a result of using the C _pd ln T integral. This questions the notion that S _res stems from use of the C _pd ln T integral. Extrapolation of the C _p values of the liquid and glass to high temperatures lead to erroneous T _f values, as do permanent (irreversible) loss of the strain and surface energies of glass on initial heating.     

New concept of organic homo‐rank compounds and its application in estimating enthalpy of formation of mono‐substituted alkanes

Based on the topological characteristics of distance matrices and adjacency matrices of molecular graphs, a new concept of organic homo‐rank compounds was proposed. Based on this concept, compounds can be classified into new groups other than the traditional homologues. Furthermore, novel structure–property relationship approach named as homo‐rank compounds method can be developed. The feasibility of homo‐rank compounds method was explored by estimating the enthalpy of formation of organic compounds. The group contribution index (GCI_X) and group polarizability potential index (GPI_X) of substituents X were defined and determined for mono‐substituted alkanes RX (X includes 20 substituents). The research results show that the enthalpies of formation of organic homo‐rank compounds and their isomers can be correlated very well with the parameters GCI_X and GPI_X. Combining the method of homologues with that of homo‐rank compounds, a general and simple quantitative correlation equation (8) was established to estimate the enthalpy of formation for RX, and the calculation precision is within the chemical accuracy ‘1 kcal/mol’. For 242 samples of RX, the average absolute deviation between the experimental and the calculated values is 2.42 kJ/mol. In addition, the enthalpies of formation of more than 2800 samples of RX were estimated. The approaches of organic homo‐rank compounds and organic homologues are independent of but complementary to each other. The combination of these two methods can help us to understand the organic molecular structure–property relationships more deeply, and to investigate these relationships more conveniently and accurately. Copyright © 2015 John Wiley & Sons, Ltd.     

Double‐trace deformations and entanglement entropy in AdS

We compute the bulk entanglement entropy of a massive scalar field in a Poincare AdS with the Dirichlet and Neumann boundary condition when we trace out a half space. Moreover, by taking into account the quantum back reaction to the minimal surface area, we calculate how much the entanglement entropy changes under a double‐trace deformation of a holographic CFT. In the AdS3/CFT2 setup, our result agrees with the known result in 2d CFTs. In higher dimensions, our results offer holographic predictions.     

Order and chaos in soft condensed matter

Soft matter, like colloidal suspensions and surfactant gels, exhibit strong response to modest external perturbations. This paper reviews our recent experiments on the nonlinear flow behaviour of surfactant worm-like micellar gels. A rich dynamic behaviour exhibiting regular, quasi-periodic, intermittency and chaos is observed. In particular, we have shown experimentally that the route to chaos is via Type-II intermittency in shear thinning worm-like micellar solution of cetyltrimethylammonium tosylate where the strength of flow-concentration coupling is tuned by the addition of sodium chloride. A Poincaré first return map of the time series and the probability distribution of laminar length between burst events show that our data are consistent with Type-II intermittency. The existence of a ‘Butterfly’ intensity pattern in small angle light scattering (SALS) measurements performed simultaneously with the rheological measurements confirms the coupling of flow to concentration fluctuations in the system under study. The scattered depolarised intensity in SALS, sensitive to orientational order fluctuations, shows the same time-dependence (like intermittency) as that of shear stress.     

Jensen-Shannon divergence in conjugate spaces: The entropy excess of atomic systems and sets with respect to their constituents

The disorder of a composite system or of a set of different systems is always higher than the mere sum of the internal disorder of its constituents. One of the most widely used functionals employed for measuring the randomness of a single distribution is the Shannon entropy, from which the increase of disorder within the composite system with respect to those of the constituents is quantified by means of the Jensen-Shannon Divergence (JSD). In this work two different applications of the JSD in the study of the information content of atomic electron densities are carried out: (i) finding the contribution for a given atom of its composing subshells to the total atomic information; (ii) and similarly for selected sets of atoms, such as periods and groups throughout the Periodic Table as well as isoelectronic series. In both cases, the analysis is performed in the two conjugate position and momentum spaces, and the results are interpreted according to physically relevant quantities such as the ionization potential.     

An entropy group and its representation in thermodynamics of nonextensive systems

The Abel entropy group and its matrix representation with the general law of nonextensive entropy composition and quadratic nonlinearity are defined. Four types of matrices for the corresponding parametrical entropies are given and geometries for their measures are determined. New two-parameter entropy is introduced, and a distribution is found for equilibrium thermodynamics of nonextensive systems. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 79–86, February, 2009.     

热场动力学理论中的Husimi分布函数及Wehrl熵的研究

利用量子相空间技术和信息熵理论,研究了热场动力学理论中量子纯态与相应混合态的Husimi分布函数及Wehrl熵的一致性问题.结果表明,热相干态与相应混合态的Husimi分布函数及Wehrl熵完全相同,支持了热场动力学理论.且热相干态的Wehrl熵与平移因子无关,故在热相干态中,量子系统的可观测量的量子涨落及不确定关系也与平移因子无关.     

Single-atom entropy squeezing and quantum entanglement in Tavis--Cummings model with atomic motion

We examine the single-atom entropy squeezing and the atom-field entanglement in a system of two moving twolevel atoms interacting with a single-mode coherent field in a lossless resonant cavity.Our numerical calculations indicate that the squeezing period,the squeezing time and the maximal squeezing can be controlled by appropriately choosing the atomic motion and the field-mode structure.The atomic motion leads to a periodical time evolution of entanglement between the two-atom and the field.Moreover,there exists corresponding relation between the time evolution properties of the atomic entropy squeezing and that of the entanglement between the two atoms and the field.     

Hydrogen adsorption on the faujasite-type zeolite Mg-X: An IR spectroscopic and thermodynamic study

Hydrogen adsorption (physisorption) on the faujasite-type zeolite Mg-X was studied by means of variable-temperature (80-140 K) FT-IR spectroscopy. Perturbation of the adsorbed H₂ molecules by the cationic adsorbing centres of the zeolite renders the H-H stretching mode IR active, at 4065 cm⁻¹. Simultaneous measurement of IR absorbance and hydrogen equilibrium pressure, for a series of spectra recorded at the increasing temperature, allowed standard adsorption enthalpy and entropy to be determined. They resulted to be ΔH⁰ = −13 kJ mol⁻¹ and ΔS⁰ = −114 J mol⁻¹ K⁻¹, respectively. Both, spectroscopic and thermodynamic results are discussed in the broader context of corresponding data for hydrogen adsorption on other alkali and alkaline-earth cation exchanged zeolites, showing that, while an approximate correlation exists between ΔH⁰ and H-H stretching frequency, deviations can be expected for the case of zeolites containing small metal cations.     

Quantum tunneling and information entropy in a double square well potential: The ammonia molecule

We study the implications of quantum tunneling on information entropy measures (Shannon and Fisher), disequilibrium and LMC complexity in a Double Square Well Potential (DSWP), using the ammonia molecule as a test bed. We also apply a similar analysis to the Infinite Square Well Potential (ISWP) in order to compare the corresponding results with a system where tunneling is absent. In particular, we show that contrary to the Heisenberg uncertainty product, information-theoretic tools provide a more sensitive analysis and manage to differentiate DSWP from ISWP case, formulating an empirical criterion whether the tunneling effect is present or not.     

Investigation of surface properties of liquid transition metals: Surface tension and surface entropy

In the present study, surface properties namely surface tension and surface entropy of liquid transition metals have been reported. The surface entropy of liquid Fe, Co and Ni metals has been investigated using the expression derived by Gosh et al. [R.C. Gosh, A.Z. Ziauddin Ahmed, G.M. Bhuiyan, Eur. Phys. J. B 56 (2007) 177]. To describe interionic interaction the pseudopotential approach has been used and radial distribution functions have been determined from the solution of Ornstein-Zernike integral equation. The calculated values of surface tension and surface entropy agree well with experiment. The present study shows that the expression derived by Gosh et al. leads to a good estimation for the surface entropy.     

Black hole entropy and the modified uncertainty principle: A heuristic analysis

Recently Ali et al. (2009) proposed a Generalized Uncertainty Principle (or GUP) with a linear term in momentum (accompanied by Plank length). Inspired by this idea here we calculate the quantum corrected value of a Schwarzschild black hole entropy and a Reissner-Nordström black hole with double horizon by utilizing the proposed generalized uncertainty principle. We find that the leading order correction goes with the square root of the horizon area contributing positively. We also find that the prefactor of the logarithmic contribution is negative and the value exactly matches with some earlier existing calculations. With the Reissner-Nordström black hole we see that this model-independent procedure is not only valid for single horizon spacetime but also valid for spacetimes with inner and outer horizons.     

Double magnetic entropy change peaks and high refrigerant capacity in Gd1-xHoxNi compounds in the melt-spun form

Gd_1-xHo_xNi melt-spun ribbons were fabricated by a single-roller melt spinning method. All the compounds crystallize in an orthorhombic CrB-type structure. The Curie temperature (T_C) was tuned between 46 and 99 K by varying the concentration of Gd and Ho. A spin reorientation (SRO) transition is observed around 13 K. Different from T_C, the SRO transition temperature is almost invariable for all compounds. Two peaks of magnetic entropy change (ΔS_M) were found. One at the higher temperature range was originated from the paramagnet-ferromagnet phase transition and the other at the lower temperature range was caused by the SRO transition. The maximum of ΔS_M around T_C is almost same. The other maximum of ΔS_M around SRO transition, however, had significantly positive relationship with x. It reached a maximum about 8.2 J kg⁻¹ K⁻¹ for x = 0.8. Thus double large ΔS_M peaks were obtained in Gd_1-xHo_xNi melt-spun ribbons with the high Ho concentration. And the refrigerant capacity power reached a maximum of 622 J kg⁻¹ for x = 0.6. Gd_1-xHo_xNi ribbons could be good candidate for magnetic refrigerant working in the low temperature especially near the liquid nitrogen temperature range.     

The Kirkendall effect in single-phase multicomponent systems: dependence on drift and entropy distribution

This paper concerns interdiffusion in a diffusion couple and determination of the Kirkendall plane. The “entropy density” model is proposed in which the entropy is used to predict the position of the Kirkendall plane in a multicomponent system. It is shown that the marker position depends on the drift velocity and pressure field only. Application of the model is presented for ternary CoFeNi diffusion couples of three various initial compositions. The concentration profiles and entropy densities are calculated for each diffusion couple. The positions of the Kirkenadl planes are determined and compared with those obtained by velocity-curve and trajectory methods.     

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH,and radicals

Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔH_f^o, S^o and C_p(T)) of 3 corresponding hydroperoxides CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ?H_f^o values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CH_2, CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, and CH₃SCH₂CH₂OOH are ?14.0, ?33.0, ?37.2, and ?32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.     

Measure of irreversibility and entropy production in open quantum systems

A new concept of a measure of irreversibility for quantum dynamics in open systems is introduced as a suitably regularized substitute for the common notion of entropy production, which, unfortunately, yields infinite values for so many irreversible processes of physical relevance.