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The Modified Genetic Algorithm scheme, presented in Paper I to model crystal structures in organic compounds (MGAC), is applied here to test its performance in the determination of a polymorphic crystalline structure of benzene that has been observed at 25 Kbar. This polymorph, named here benzene II, is not a global minimum of the energy or even close to any of the local minimum determined using the energy evolution of benzene structures described in the previous paper. The benzene II structure corresponds to an enthalpy minimum. This paper shows that it is possible to use the MGAC procedure, modified to use the minimization of the enthalpy instead of the energy in the GA (Genetic Algorithm) selection process, to find this high pressure structure of benzene. [ABSTRACT FROM AUTHOR]

A common belief is that any closed, counterclockwise cycle on a pV diagram represents a refrigerator or heat pump. It has been established that this is not the case, but previous papers on this topic have made unnecessary assumptions about the temperatures of the energy reservoirs and about how the system exchanges energy with the reservoirs. Relaxing these assumptions leads to a wide array of unexpected behaviors. In some cases, the same pV cycle can be a heat pump, a cold pump, or a Joule pump simply by changing how the system is connected to the reservoirs. This paper explores the strange world of counterclockwise cycles. Editor's note: In this paper, author Randall Knight explores the rich behavior of counterclockwise thermodynamic cycles. A counterclockwise cycle can function as a heat pump or refrigerator, but this is not the only possibility. The choice of thermal reservoirs and the choice of which reservoir heat is absorbed from and exhausted to during the cycle affect the coefficient of performance and even the basic function of the device. The author illustrates these possibilities through an analysis of counterclockwise Carnot, Kelvin, Brayton, and Stirling cycles. The analysis includes interesting possibilities, such as a cycle that operates with a single reservoir, as well as practical applications like the role of heat exchangers. The surprising results of this analysis will likely be of interest to anyone who has studied thermodynamics, and the material can easily be incorporated into any course that includes thermodynamics, from introductory physics to graduate study. [ABSTRACT FROM AUTHOR]

Momentum work enables a complete shift from kinematics to dynamics. This involves changes in the very fundamentals of physics, not only in mechanics, statistical mechanics, and special relativity, as shown in Papers I–III [G. Kalies and D. D. Do, AIP Adv. 13(6), 065121 (2023); G. Kalies, D. D. Do, and S. Arnrich, AIP Adv. 13(5), 055317 (2023); and G. Kalies and D. D. Do, AIP Adv. (in press) (2023)] of this series, but also in thermodynamics. In this paper, we challenge the narrative that classical phenomenological thermodynamics is completed and show that it represents an efficient interim solution that hides essential information. The essence of heat transfer and entropy is revealed, and an answer is given to the question of why entropy had to remain abstract and elusive in the past. Furthermore, we uncover the specific forms of energy behind thermodynamic state variables, such as enthalpy, Helmholtz free energy, and Gibbs free energy, which play a central role in describing chemical reactions and phase transitions. We thereby lay the foundation for thermodynamics to evolve from a framework theory valid for macroscopic systems to vivid quantum-process thermodynamics. [ABSTRACT FROM AUTHOR]

Gibbs energies for reactions involving aqueous ions are challenging to predict due to the large solvation energies of such ions. A stringent test would be the ab initio reproduction of the aqueous-phase chelate effect, an entropic effect in reactions of very small enthalpy changes. This paper examines what is required to achieve such a reproduction for the paradigmatic reaction M(NH3)42+ + 2 en → M(en)22+ + 4 NH3 (en = 1,2-ethylenediamine), for which ΔrxnG* and ΔrxnH* are −2.3 and +1.6 kcal mol−1, respectively, if M = Zn. Explicit solvation via simulation was avoided in order to allow sufficiently accurate electronic structure models; this required the use of continuum solvation models (CSMs), and a great deal of effort was made in attempting to lower the relative errors of ΔsolvG*[M(NH3)42+] vs ΔsolvG*[M(en)22+] from the CSMs available in Gaussian software. CSMs in ADF and JDFTx software were also tested. A uniform 2.2 kcal mol−1 accuracy in ΔrxnG* for all three metal-atom choices M = {Zn, Cd, Hg} was eventually achieved, but not from any of the known CSMs tested, nor from cavity size reoptimization, nor from semicontinuum modeling: post facto solvation energy corrections [one per solute type, NH3, en, M(NH3)42+, M(en)22+] were needed. It is hoped that this study will aid (and encourage) further CSM development for coordination-complex ions. [ABSTRACT FROM AUTHOR]

The purpose of the developed plasma jet generator is to study the effect of jet plasma on electromagnetic wave propagation, simulating the plasma sheath environment encountered during space vehicle reentry. Because the temperature and velocity of the plasma jet are high, it is difficult to measure temperature and electron density by the contact method. In addition to the normal flow of the entire apparatus, high-power magnetic field energy (generated by the power supply) is injected into the inductively coupled plasma (ICP) generation region. The energy of the magnetic field excites the gas and generates plasma. In this paper, the whole apparatus is calculated numerically, the energy term is added to the corresponding area of ICP, and the enthalpy distribution of the whole apparatus is calculated. The heat flux and total pressure are measured by slug calorimeter (heat flux probe) and total pressure probe, and then, the enthalpy is obtained. When the calculated enthalpy is consistent with the measured enthalpy, the value of the energy term in the numerical calculation process is the injected energy value. The ratio of the energy injected into the ICP region to the total energy provided by the power supply is the power injection proportion. The power injection proportion of the apparatus in this paper obtained by the above method is between 25% and 30%. [ABSTRACT FROM AUTHOR]

The temperature of the high-power inductively coupled plasma jet is very high, and its temperature is difficult to measure directly. The heat flux becomes a thermodynamic characteristic to measure the plasma jet. The existing heat flux calculation method is based on the temperature change rate after the response time. The slug is required to stay in the high enthalpy jet area for a longer time. With the slug temperature reaching the melting point as the upper limit, the shorter the residence time, the greater the upper limit of the measured heat flux. In this paper, the first-order transient solution is added to the steady-state solution of temperature (the calculation equation of the existing method), which can shorten the response time. The shortening of the response time can reduce the residence time of the slug in the jet region, and the reduction in the residence time can increase the upper limit of the calorimeter heat flux measurement. This paper uses numerical simulation and experimental methods to verify that the steady-state solution method and the first-order transient solution method can obtain consistent heat flux results. Using the first-order transient solution method can reduce the residence time of the slug calorimeter in the jet region. According to the shortening of the residence time, the method of using the first-order transient solution can increase the upper limit of the heat flux measurement by more than 25%. [ABSTRACT FROM AUTHOR]

We introduce probability thermodynamics and probability quantum fields. By probability we mean that there is an unknown operator, physical or nonphysical, whose eigenvalues obey a certain statistical distribution. Eigenvalue spectra define spectral functions. Various thermodynamic quantities in thermodynamics and effective actions in quantum field theory are all spectral functions. In the scheme, eigenvalues obey a probability distribution, so a probability distribution determines a family of spectral functions in thermodynamics and quantum field theory. This leads to probability thermodynamics and probability quantum fields determined by a probability distribution. In constructing spectral functions, we encounter a problem. The conventional definition of spectral functions applies only to lower bounded spectra. In our scheme, however, there are two types of spectra: lower bounded spectra, corresponding to the probability distribution with nonnegative random variables, and the lower unbounded spectra, corresponding to probability distributions with negative random variables. To take the lower unbounded spectra into account, we generalize the definition of spectral functions by analytical continuation. In some cases, we encounter divergences. We remove the divergence by a renormalization procedure. In virtue of spectral theory in physics, we generalize some concepts in probability theory. For example, the moment-generating function in probability theory does not always exist. We redefine the moment-generating function as the generalized heat kernel introduced in this paper, which makes the concept definable when the definition in probability theory fails. We construct examples corresponding to some probability distributions. Thermodynamic quantities, vacuum amplitudes, one-loop effective actions, and vacuum energies for various probability distributions are presented. [ABSTRACT FROM AUTHOR]

This paper is a logical continuation of the 22 parameter, localized orbital correction (LOC) methodology that we developed in previous papers [R. A. Friesner et al., J. Chem. Phys. 125, 124107 (2006); E. H. Knoll and R. A. Friesner, J. Phys. Chem. B 110, 18787 (2006).] This methodology allows one to redress systematic density functional theory (DFT) errors, rooted in DFT’s inherent inability to accurately describe nondynamical correlation. Variants of the LOC scheme, in conjunction with B3LYP (denoted as B3LYP-LOC), were previously applied to enthalpies of formation, ionization potentials, and electron affinities and showed impressive reduction in the errors. In this paper, we demonstrate for the first time that the B3LYP-LOC scheme is robust across different basis sets [6-31G*, 6-311++G(3df,3pd), cc-pVTZ, and aug-cc-pVTZ] and reaction types (atomization reactions and molecular reactions). For example, for a test set of 70 molecular reactions, the LOC scheme reduces their mean unsigned error from 4.7 kcal/mol [obtained with B3LYP/6-311++G(3df,3pd)] to 0.8 kcal/mol. We also verified whether the LOC methodology would be equally successful if applied to the promising M05-2X functional. We conclude that although M05-2X produces better reaction enthalpies than B3LYP, the LOC scheme does not combine nearly as successfully with M05-2X than with B3LYP. A brief analysis of another functional, M06-2X, reveals that it is more accurate than M05-2X but its combination with LOC still cannot compete in accuracy with B3LYP-LOC. Indeed, B3LYP-LOC remains the best method of computing reaction enthalpies. [ABSTRACT FROM AUTHOR]

Heat transfer on a vapor bubble rising in superheated liquid is investigated by direct numerical simulation. The vapor–liquid system is described by the one-fluid formulation with the level set method capturing the interface. The proportional-integral-derivative controller is employed to keep the bubble's location fixed and evaluate interfacial forces. The heat transfer performance featured by the Nusselt number is evaluated based on the energy balance. Simulations are carried out for the bubble Reynolds number ranging from 20 to 500 and Morton number from 1.10 × 10−10 to 3.80 × 10−4. The aim of this paper is to shed some light on the effect of bubble deformation and oscillation on interfacial heat transfer. The results show that the front part of the bubble contributes to the majority of the interfacial heat transfer, while the rear part mainly affects the oscillation amplitude of the total heat transfer. The interface stretch during bubble oscillation is considered as a key mechanism in enhancing the instantaneous Nusselt number. The potential flow solution of the averaged Nusselt number is corrected by considering the influence of the aspect ratio. This research provides additional insights into the mechanism of interfacial heat transfer, and the results apply equally to interfacial mass transfer. [ABSTRACT FROM AUTHOR]

Charged hard-sphere mixtures consisting of two positively charged species and one negatively charged species (common anion mixtures) are used to represent binary mixtures of salts. Phase separation in the mixture is studied using the Gibbs free energy expression for common anion mixtures derived in paper I of this series. A detailed description of the dependence of the resulting phase diagrams on molecular size and charge of the species, and on the osmotic pressure of the mixture is presented. Binary mixtures of salts containing equal-sized ions exhibit type III phase behavior whereas binary mixtures of salts containing ions of unequal size exhibit either type II or type IV phase behavior. The type of phase behavior observed in binary mixtures of salts is characterized as a function of the critical pressures and critical volumes of the pure salts. Our results suggest that phase separation in mixtures of charged hard spheres is influenced by a competition between mixing effects (entropy), which encourage miscibility and ion-pairing effects (enthalpy), which encourage phase separation. Potential applications of the model to experimental systems are discussed. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Near-space hypersonic vehicles could encounter significant rarefied nonequilibrium effects during the flight through atmosphere, which largely influence the gas-surface momentum and heat transfer. In this paper, hypersonic boundary layer over a flat plate with velocity slip, temperature jump, and shear nonequilibrium effects is theoretically considered. The slip boundary conditions and nonlinear transport relations are embedded into the boundary-layer equations to describe the flow. Local similar solutions are derived, and key parameters for characterizing slip and shear nonequilibrium effects are determined. The velocity-slip and temperature-jump effects are determined by [ (2 − σ u) / σ u ] M a e / R e x and [ (2 − σ T) / σ T ] M a e / R e x respectively, and the shear nonequilibrium effect is characterized by M a e 2 / R e x . The obtained boundary-layer solutions are compared with the Navier–Stokes solutions for a Mach 4.5 slip flow, and the results of Direct Simulation Monte Carlo for a Mach 10 rarefied flow, good agreements are achieved. The separate and combined effects of velocity slip, temperature jump, and shear nonequilibrium on boundary-layer solutions and momentum/heat transfer are clarified. The results show that both the slip and shear nonequilibrium effects cause the boundary layer to become thinner and decrease the skin friction and Fourier heat conduction. However, with including sliding friction, the total heat flux might even increase as the slip degree increases. These results provide valuable insight into the boundary-layer characteristics of hypersonic near-continuum flows. [ABSTRACT FROM AUTHOR]

The thermal wall function method offers an effective pathway for modeling heat transfer in engines. This paper reexamined the traditional construction method of the thermal wall function and improved it by correcting the integration scheme in the boundary layer; then, an enhanced heat transfer model was introduced. Since the heat release from the chemical reactions is of great significance to the near-wall flow, it is necessary to construct a law of the wall including the heat release effect. A new law of the wall including the impacts of the pressure work and the heat release from chemical reactions was obtained based on the analogy between the momentum transfer and the heat transfer predicted using the improved thermal wall function. In the analogy process, the formula of the eddy-viscosity ratio was reconstructed for the whole boundary layer, and then, the Prandtl number for turbulent flow was improved. The current research is beneficial for predicting the near-wall flow and heat transfer characteristics under conditions with strong interactions between the wall and the flame. [ABSTRACT FROM AUTHOR]

In this paper, an experimental study was performed to document the characteristics of underwater electrical explosions involving different wires made from 15 different metals/alloys. Experiments were undertaken with those wires (4 cm in length; 100–300 μm in diameter) driven by a pulsed current source with 500 J initial stored energy. The results indicated that the electrical and thermophysical properties of the metal were critical in the explosion process. Non-refractory metals, such as Al, Cu, Ag, and Au, absorbed about twice as much energy as their enthalpy of atomization before the voltage peak, while for refractory metals, such as Nb, Mo, Ta, and W, the deposited energy before the peak was close to their atomization enthalpy. Accordingly, the strongest measured shock wave for non-refractory metals was 12.4 MPa (peak pressure) while that for refractory metals was only 8.5 MPa (peak pressure). By contrast, the light intensities of non-refractory metals were at least an order of magnitude lower than those of refractory metals. From 100 to 300 μm, the estimated average temperature at the plasma-water interface decreased from ∼10 000 K to ∼4000 K. It was also found that, as evidenced from the time-integrated spectra, obvious chemical reactions occurred between water and relatively active metals such as Al, Ti, and Fe. In addition, Pt and Au, which have high first ionization energies, exhibited longer current pauses (>50 μs) or vaporization phases relative to the other metals. [ABSTRACT FROM AUTHOR]

The Surface Eroding Thermocouple (SETC) is a robust diagnostic utilized in DIII-D to provide fast, edge-localized modes (ELMs) resolved heat flux measurements, in particular in geometric regions that are too shadowed for traditional infrared thermography. In order to further investigate the power dissipation in the divertor region, a combination of flush-mounted and recessed SETCs was developed to assess the effect on surface heating from non-charged particles at the divertor target. Utilizing the Divertor Materials Evaluation System sample exposure platform, the first demonstration of the feasibility of using this new method to distinguish between the heat flux from charged particles and that from neutrals and radiative heating was achieved. This paper details the process of using the combination of flush SETCs and recessed SETCs to measure the multiple heat flux components at the divertor target and further discusses how to determine two important ratios, α (ratio of heat flux from charged particles deposit on recessed SETC to that deposit on flush SETC) and β (ratio of heat flux from non-charged particles deposit on recessed SETC to that deposit on flush SETC), in the estimation of the heat flux from non-charged particle sources. Using a time dependent ratio α, it was found that ∼50% of the total incident heat flux is attributable to the non-charged particles in the fully detached open divertor in DIII-D. Finally, the new application of similar SETC diagnostics in the Small Angle Slot divertor with a V-like configuration and partial tungsten coated surface (SAS-VW) is also introduced. [ABSTRACT FROM AUTHOR]

In this paper, we examine the transition from a molecular to monatomic solid in hydrogen over a wide pressure range. This is achieved by setting up two models in which a single parameter δ allows the evolution from a molecular structure to a monatomic one of high coordination. Both models are based on a cubic Bravais lattice with eight atoms in the unit cell; one belongs to space group [formula], the other to space group [formula]. In [formula] one moves from effective 1-coordination, a molecule, to a simple cubic 6-coordinated structure but through a very special point (the golden mean is involved) of 7-coordination. In [formula], the evolution is from 1 to 4 and then to 3 to 6-coordinate. If one studies the enthalpy as a function of pressure as these two structures evolve (δ increases), one sees the expected stabilization of minima with increased coordination (moving from 1 to 6 to 7 in the [formula] structure, for instance). Interestingly, at some specific pressures, there are in both structures relatively large regions of phase space where the enthalpy remains roughly the same. Although the structures studied are always higher in enthalpy than the computationally best structures for solid hydrogen - those emerging from the Pickard and Needs or McMahon and Ceperley numerical laboratories - this result is suggestive of the possibility of a microscopically non-crystalline or 'soft' phase of hydrogen at elevated pressures, one in which there is a substantial range of roughly equi-enthalpic geometries available to the system. A scaling argument for potential dynamic stabilization of such a phase is presented. [ABSTRACT FROM AUTHOR]

This paper applies the multiscale coarse-graining method [S. Izvekov and G. A. Voth, J. Phys. Chem. B 109, 2469 (2005); J. Chem. Phys. 123, 134105 (2005)] to analyze many-body effects in concentrated methane solutions. Pairwise decompositions of N-particle solute-solute potentials of mean force (PMFs), and the respective solvent cavity potentials, enthalpic, entropic, and heat capacity of hydrophobic association, are calculated directly from unconstrained molecular-dynamics simulations of methane solutions at different molar fractions, with the highest being 0.055. The many-body effects in hydrophobic hydration are further studied using N-methane PMFs, which are explicitly dependent on solvent coordinates [ABSTRACT FROM AUTHOR]

Completely renormalized (CR) coupled-cluster (CC) approaches, such as CR-CCSD(T), in which one corrects the standard CC singles and doubles (CCSD) energy for the effects of triply (T) and other higher-than-doubly excited clusters [K. Kowalski and P. Piecuch, J. Chem. Phys. 113, 18 (2000)], are reformulated in terms of the left eigenstates ≤[uppercase_phi_synonym]|L of the similarity-transformed Hamiltonian of CC theory. The resulting CR-CCSD(T)L or CR-CC(2,3) and other CR-CCL methods are derived from the new biorthogonal form of the method of moments of CC equations (MMCC) in which, in analogy to the original MMCC theory, one focuses on the noniterative corrections to standard CC energies that recover the exact, full configuration-interaction energies. One of the advantages of the biorthogonal MMCC theory, which will be further analyzed and extended to excited states in a separate paper, is a rigorous size extensivity of the basic ground-state CR-CCL approximations that result from it, which was slightly violated by the original CR-CCSD(T) and CR-CCSD(TQ) approaches. This includes the CR-CCSD(T)L or CR-CC(2,3) method discussed in this paper, in which one corrects the CCSD energy by the relatively inexpensive noniterative correction due to triples. Test calculations for bond breaking in HF, F2, and H2O indicate that the noniterative CR-CCSD(T)L or CR-CC(2,3) approximation is very competitive with the standard CCSD(T) theory for nondegenerate closed-shell states, while being practically as accurate as the full CC approach with singles, doubles, and triples in the bond-breaking region. Calculations of the activation enthalpy for the thermal isomerizations of cyclopropane involving the trimethylene biradical as a transition state show that the noniterative CR-CCSD(T)L approximation is capable of providing activation enthalpies which perfectly agree with experiment. [ABSTRACT FROM AUTHOR]

Specific heat is usually analyzed only for common thermodynamic processes, leaving us with the impression that it can always be expressed as a single-valued function of temperature. In this paper, we show that specific heat functions may be multivalued even for processes that are mathematically simple, such as an ideal gas following a linear path with a negative slope in the pressure–volume diagram. Although this example has been studied previously, we show that the multivalued approach provides additional physical insights, and we establish the conditions that any path must satisfy in order to have a single-valued specific heat. As a final application of our approach, we demonstrate a geometric theorem. [ABSTRACT FROM AUTHOR]

Large scale quantum calculations for molar enthalpy of formation (Δf H0), standard entropy (S0), and heat capacity (CV) are presented. A large data set may help to evaluate quantum thermochemistry tools in order to uncover possible hidden shortcomings and also to find experimental data that might need to be reinvestigated, indeed we list and annotate approximately 200 problematic thermochemistry measurements. Quantum methods systematically underestimate S0 for flexible molecules in the gas phase if only a single (minimum energy) conformation is taken into account. This problem can be tackled in principle by performing thermochemistry calculations for all stable conformations [Zheng et al., Phys. Chem. Chem. Phys. 13, 10885-10907 (2011)], but this is not practical for large molecules. We observe that the deviation of composite quantum thermochemistry recipes from experimental S0 corresponds roughly to the Boltzmann equation (S = R lnΩ), where R is the gas constant and Ω the number of possible conformations. This allows an empirical correction of the calculated entropy for molecules with multiple conformations. With the correction we find an RMSD from experiment of ≋13 J/mol K for 1273 compounds. This paper also provides predictions of Δf H0, S0, and CV for well over 700 compounds for which no experimental data could be found in the literature. Finally, in order to facilitate the analysis of thermodynamics properties by others we have implemented a new tool obthermo in the OpenBabel program suite [O'Boyle et al., J. Cheminf. 3, 33 (2011)] including a table of reference atomization energy values for popular thermochemistry methods. [ABSTRACT FROM AUTHOR]

Normal shocks are generally treated by defining a stationary adiabatic shock discontinuity with a supersonic upstream velocity. A fundamental feature of this approach is that the problem is steady, and the stagnation enthalpy is constant across the shock, greatly simplifying the analysis. However, shocks are generally not stationary, but rather are unsteady flow features often translating into a quiescent medium. Moreover, the stagnation enthalpy of a fluid will rise in a moving shock, an often unexpected result for students studying compressible flow. In this paper, stationary normal shocks are analyzed using the classic Rankine–Hugoniot equations. The analysis is then transformed to consider a moving shock propagating into a quiescent medium. This analysis produces a simple expression relating the stagnation enthalpy rise across a moving normal shock as a function of the shock strength as measured by either the shock pressure ratio or differential pressure across the shock. An unsteady integral control volume analysis is then used to show that the cause for the stagnation enthalpy rise is the work done by the fluid downstream of the shock to compress the upstream fluid upstream. [ABSTRACT FROM AUTHOR]

In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition. [ABSTRACT FROM AUTHOR]

Improving the fireproof performance of polymers is crucial for ensuring human safety and enabling future space colonization. However, the complexity of the mechanisms for flame retardant and the need for customized material design pose significant challenges. To address these issues, we propose a machine learning (ML) framework based on substructure fingerprinting and self-enforcing deep neural networks (SDNN) to predict the fireproof performance of flame-retardant epoxy resins. Our model is based on a comprehensive understanding of the physical mechanisms of materials and can predict fireproof performance and eliminate the needs for properties descriptors, making it more convenient than previous ML models. With a dataset of only 163 samples, our SDNN models show an average prediction error of 3% for the limited oxygen index (LOI). They also provide satisfactory predictions for the peak of heat release rate PHR and total heat release (THR), with coefficient of determination (R2) values of 0.87 and 0.85, respectively, and average prediction errors less than 17%. Our model outperforms the support vector model SVM for all three indices, making it a state-of-the-art study in the field of flame retardancy. We believe that our framework will be a valuable tool for the design and virtual screening of flame retardants and will contribute to the development of safer and more efficient polymer materials. [ABSTRACT FROM AUTHOR]

The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state. [ABSTRACT FROM AUTHOR]

This paper deals with the experimental investigation on the MHD (magneto-hydro-dynamic or magneto-fluid-dynamic) interaction around a test body immersed into a hypersonic unseeded air flow. The experiments have been carried out in the CIRA plasma wind tunnel SCIROCCO. Two test conditions have been utilized for the experiments with a total pressure of 2.5 and 2.3 bar respectively, a total specific enthalpy of 16 and 12.1 MJ/kg respectively. The air flow was accelerated in the nozzle up to Mach 10. The magnetic induction field is generated by an electromagnet enclosed in the test body and reaches a 0.8 T maximum value in the interaction region. [ABSTRACT FROM AUTHOR]

The inverted phase, in which the swollen minority block plus solvent forms the continuous microdomain, has been frequently observed in block copolymer (BCP)/preferential good solvent solutions in our previous experimental works. In this paper, self-consistent field theory is employed to study the formation of inverted phase in A-B BCP solutions. The parameters of both the BCP and solvent are studied. The results show that the characteristics of both the BCP and the solvent are responsible for the inverted phase formation. With the value of χABN (χAB is the Flory interaction parameter between A and B blocks and N is the degree of the polymerization), the preferential affinity of the solvent for the minority block, or the solvent monomer size increasing, the existence window of the inverted phases enlarges. Meanwhile, we analyze and discuss the formation of the inverted phase in terms of the enthalpy interaction and entropy contribution of the solvent and the results suggest that both of them play important roles in the formation of inverted phase and the comparative importance of the two items depends on the solvent molecular size. [ABSTRACT FROM AUTHOR]

Accurate predictability of high-pressure turbine nozzle guide vane aero-thermal performance is highly desired in the development campaign due to the exposure of the component to a frequent and high heat load. In this paper, the representative vane profile in modern aero-engines is numerically studied. Aerodynamics and aero-thermal validations of the blade profile have been performed in comparison with the available experimental data. It has been shown that a satisfactory agreement could be achieved with the use of the transitional turbulence model shear stress transport γ–θ due to its superiority in capturing the laminar–turbulent transition. Sensitivity studies on the increase in the inlet turbulence intensity, inlet endwall boundary layer thickness, and inlet total temperature profile have been performed to understand the impact of inflow conditions' uncertainty on the aero-thermal predictability. Increasing the inlet turbulence intensity increases the pressure surface heat transfer coefficient and induces an earlier transition onset on the suction surface. Due to the rapid decay of turbulence intensity in the numerical model, the use of an artificially high inlet turbulence intensity has been shown to be effective in the prediction improvement. On the other hand, the change in the inlet boundary layer thickness influences the formation and strength of the secondary flow, namely, horseshoe vortex and passage vortex. These secondary flow phenomena affect the local blade surface heat transfer coefficient in the near-endwall region although the most significant rise in heat transfer is found on the endwall. The temperature distortion amplitude of a hot streak and its relative clocking position with the vane significantly affect the heat flux distribution. In contrast, the heat transfer coefficient is less sensitive to the change in hot streak conditions. However, it has been shown that increasing the temperature distortion amplitude could induce a larger difference among different clocking configurations. In addition, decreasing the difference between the fluid and wall temperature would delay the transition onset and stabilize the boundary layer. Further analysis of the unsteady effects has been carried out by comparing the steady and time-averaged flow solutions. It has been observed that the discrepancy between these solutions is attributed to the flow field nonlinearity. Thus, a significant discrepancy can be found in the laminar–turbulent transition as well as in the trailing edge region. However, since the contribution of these regions on the total area-averaged heat transfer is small, their influence on the total vane heat transfer is limited. [ABSTRACT FROM AUTHOR]

The lattice cluster theory for solutions of telechelic polymer chains, developed in paper I, is applied to determine the enthalpy Δhp and entropy Δsp of self-assembly of linear telechelics and to evaluate the Flory-Huggins (FH) interaction parameter χ governing the phase behavior of these systems. Particular focus is placed on examining how these interaction variables depend on the composition of the solution, temperature, van der Waals and local 'sticky' interaction energies, and the length of the individual telechelic chains. The FH interaction parameter χ is found to exhibit an entropy-enthalpy compensation effect between the 'entropic' and 'enthalpic' portions as either the composition or mass of the telechelic species is varied, providing unique theoretical insights into this commonly reported, yet, enigmatic phenomenon. [ABSTRACT FROM AUTHOR]

The kinetic fragility of a liquid is correlated to the magnitude of enthalpy hysteresis in various glass-forming materials during thermal cycling across the glass transition. While the lower bound of liquid fragility is well known, there has been little research into the possibility of an inherent upper limit to fragility. In this paper, we present a theoretical argument for the existence of a maximum fragility and show that the correlation between fragility and enthalpy hysteresis allows for an empirical evaluation of the upper limit of fragility. This upper limit occurs as the enthalpy hysteresis involved in thermal cycling about the glass transition approaches zero, leading to mmax≈175. This result agrees remarkably well with our previous estimate. The dynamics of maximum fragility liquids are discussed, and a critical temperature of ∼1.5 Tg (where Tg is the glass transition temperature) is revealed where a transition from nonexponential to exponential structural relaxation occurs. [ABSTRACT FROM AUTHOR]

For decades the Vogel-Fulcher-Tammann equation has dominated the description of dynamics of the non-Arrhenius behavior in glass forming systems. Recently, this dominance has been questioned. Hecksher et al. [Nat. Phys. 4, 737 (2008)], Elmatad et al. [J. Phys. Chem. B 113, 5563 (2009)], and Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)] indicated superiority of several equations showing no divergence at a finite (nonzero) temperature. This paper shows distortion-sensitive and derivative based empirical analysis of the validity of leading equations for portraying the previtreous evolution of primary relaxation time. [ABSTRACT FROM AUTHOR]

Functionalizing nanoparticles with organic ligands, such as oligomers, polymers, DNA, and proteins, is an attractive way to manipulate the interfacial interactions between the nanoparticles and the medium the particles are placed in, and thus control the nanoparticle assembly. In this paper we have conducted a Monte Carlo simulation study on copolymer grafted spherical nanoparticles to show the tremendous potential of using monomer sequence on the copolymers to tune the grafted chain conformation, and thus the effective interactions between copolymer grafted nanoparticles. We have studied AB copolymers with alternating, multiblock, or diblock sequences, where either A monomers or B monomers have monomer-monomer attractive interactions. Our focus has been to show the nontrivial effect of monomer sequence on the conformations of the grafted copolymers at various particle diameters, grafting densities, copolymer chain lengths, and monomer-monomer interactions in an implicit small molecule solvent. We observe that the monomer sequence, particle diameter, and grafting density dictate whether (a) the grafted chains aggregate to bring attractive monomers from multiple grafted chains together (interchain and intrachain monomer aggregation) if the enthalpy gained by doing so offsets the entropic loss caused by stretching of chains, or (b) each grafted chain folds onto itself to bring its attractive monomers together (only intrachain monomer aggregation) if the entropic loss from interchain aggregation cannot be overcome by the enthalpic gain. For six copolymers of chain length N=24 grafted on a spherical particle of diameter D=4, interchain and intrachain monomer aggregation occurs, and the radius of gyration varies nonmonotonically with increasing blockiness of the monomer sequence. At larger particle diameters the grafted chains transition to purely intrachain monomer aggregation. The radius of gyration varies monotonically with monomer sequence for intrachain monomer aggregation because as the sequence becomes blockier (like monomers are grouped together), the copolymer chain has to fold less compactly to maximize the enthalpically favorable contacts while maintaining high conformational entropy. The radius of gyration of alternating and diblock copolymers scales with chain length N through a power law g2>1/2=αNν with the prefactor α and scaling exponent ν, varying with monomer sequence and monomer-monomer attraction strength. [ABSTRACT FROM AUTHOR]

In this paper, an extra error source for high-quality ab initio calculation of conformation equilibrium in normal alkanes—intramolecular basis set superposition error (BSSE)—is discussed. Normal butane (n-butane) and normal hexane (n-hexane) are used as representative examples. Single-point energy difference and BSSE values of trans and gauche conformations for n-butane (and trans-trans-trans and gauche-gauche-gauche conformations for n-hexane) were calculated using popular electron correlation methods: The second-order Moller–Plesset (MP2), the fourth-order Moller–Plesset (MP4), and coupled cluster with single and double substitutions with noniterative triple excitation [CCSD(T)] levels of theory. Extrapolation to the complete basis set is applied. The difference between BSSE-corrected and uncorrected relative energy values ranges from ∼100 cal/mol (in case of n-butane) to more than 1000 cal/mol (in case of n-hexane). The influence of basis set type (Pople or Dunning) and size [up to 6-311G(3df,3pd) and aug-cc-pVQZ] is discussed. [ABSTRACT FROM AUTHOR]