The heat capacities of kaolinite (7 to 380 K) and of dimethyl sulfoxide (DMSO) intercalated kaolinite (20 to 310 K) were measured by adiabatically shielded calorimetry. The third law entropy of kaolinite, S298, is 200.9 ± 0.5 J·mol−1K−1.

The “melting point” of the DMSO in the intercalate, 288.0 ± 0.2 K, is 3.7 K lower than that of pure DMSO, 291.67 K. The heat capacity of DMSO in the intercalate above 290 K is approximately 5.2 J·mol−1·K−1 smaller than that of pure liquid DMSO at the same temperature.

Chlorites are petrogenetically important minerals, exercise controls on petroleum reservoir qualities, are common in alteration zones during hydrothermal ore mineralization, and may form during carbon sequestration in sedimentary formations. Chlorite thermochemistry and structure have been investigated, in the present study, to facilitate an improved understanding of chlorite equilibria.

Three natural IIb chlorites were studied by powder diffraction and calorimetric methods (low-temperature relaxation calorimetry using a Physical Properties Measurement System [PPMS] and differential scanning calorimetry [DSC]). The samples include a low-Fe clinochlore [Mg-Chl] and two Fe-rich chlorites from Windsor [Fe-Chl(W)] and Michigan [Fe-Chl(M)]. The structure of each chlorite was refined in the ideal C2/m symmetry using Rietveld techniques. Lattice parameters for the Windsor chlorite are a = 5.3786(6) Å, b = 9.3176(9) Å, c = 14.2187(6) Å, β = 96.98(10)°. The Michigan chlorite returned a = 5.3897(3) Å, b = 9.3300(3) Å, c = 14.2376(2) Å, β = 97.043(5)° whereas the low-Fe clinochlore yielded a = 5.3301(3) Å, b = 9.2231(8) Å, c = 14.2912(4) Å, β= 97.03(10)°.

Heat capacities (Cp) for the three natural chlorites were measured using both PPMS (2–303 K) and DSC (282–564 K). Employing a combination of Debye-Einstein-Schottky functions, the lattice dynamics component of the Cp at lower temperature was evaluated allowing a separation of the magnetic spin ordering component of Cp from the lattice vibrational part. For Mg-Chl, Fe-Chl(W), and Fe-Chl(M), the polynomials defining the temperature dependencies of the heat capacities between 280 and 570 K are:

Cp = 1185.44(±68.93) − 9753.21(±186.85)T−0.5 − 1.9094(±1.0288)·107T−2 + 3.3013(±1.5363)·109T−3

Cp = 1006.06(±48.46) − 4134.83 (±1515.16)T−0.5 − 40.0949(±6.9413)·106T−2 + 5.9386(±1.0287)·109T−3

and

Cp = 1268.60(±67.16) − 11983.09(±2107.07)T−0.5 − 7.6037(±9.6417)·106T−2 + 1.5398(±1.4187)·109T−3, respectively.

Standard state molar thermodynamic functions, CP, ST, (HT−H0)/T, and φ were evaluated for the samples. S298.15 for Fe-Chl(W), Mg-Chl, and Fe-Chl(M) were found to be 499.14 ± 3.40, 437.81 ± 3.00 and 515.06 ± 3.60 J mol-1K-1, respectively, whereas S° for Fe-Chl(W) and Mg-Chl were determined to be 578.24 ± 3.76 and 503.21 ± 3.60 J mol−1K−1, −1

The serpentine subgroup mineral berthierine was synthesized as a metastable precursor of the chlorite group mineral chamosite in cold seal pressure vessels at 575°C, 0.5 GPa and fO2-conditions of the NNO buffer from a glass of almandine bulk composition. The run products were investigated with X-ray powder diffraction (XRD), Mossbauer spectroscopy and electron microprobe analysis. One run product was also investigated by high-resolution transmission electron microscopy (HRTEM) and its heat capacity measured by heat pulse calorimetry and by differential scanning calorimetry in the temperature range 5–323 K. The XRD and HRTEM investigations clearly showed that the periodicity along the c axis of this sample is 7 Å demonstrating that the serpentine subgroup mineral berthierine of composition (Fe2+1.83Fe3+0.33Al0 67)[Si1.33Al0.67O5](OH)4 has formed in the synthesis experiments.

Integration of our heat capacity data, corrected to the composition (Fe2.5Al0.5)[Si1.5Al0.5O5](OH)4 for end-member berthierine, yields a standard entropy of 284.1±0.3 J mol−1 K−1. The Cp polynomial Cp = 610.72 − 5140.0 × T−0.5 − 5.8848 × 106T−2 + 9.5444 × 108T–3 is recommended for thermodynamic calculations above 298 K involving berthierine.

Considering the Panigrahi and Chatterjee model (2017) for variable generalised Chaplygin gas, in this paper we found for this kind of exotic matter an analytic expression for the adiabatic compressibility βs. It was analyzed the behaviour of the adiabatic compressibility in the limit of high and low pressure. The derived equation for βs was used to deduce the value of the heat capacity at constant pressure Cp for variable generalised Chaplygin gas.

This mini review summarizes recent advances in experimental thermodynamics of metal–organic frameworks (MOFs). Taking advantage of the development in mechanochemistry, near-room temperature solution calorimetry, and low-temperature heat capacity measurements, the energetic landscape, entropy trends, and Gibbs free energy evolutions of MOFs with true polymorphism [Zn(MeIm)2, Zn(EtIm)2, and Zn(CF3Im)2] as framework topology varies were thoroughly explored by integrated calorimetric and computational methodologies. In addition, the formation enthalpies of MOFs with ultrahigh porosity (MOF-177 and UMCM-1) and the simplest structure (metal formates) have been determined. The studies summarized below highlight the complex interplays among interrelated compositional, chemical, and topological (structural) factors in the determination of the thermodynamic parameters of MOFs.

The heat capacity of synthetic lazulite, MgAl2(PO4)2(OH)2, has been measured between 35 and 298 K by means of low-temperature adiabatic calorimetry. A lazulite third-law entropy (S2980) value of 204(3) J K–1 mol–1 was retrieved after extrapolation of the lazulite heat capacity by a cubic temperature function, down to absolute temperature. Identical measurements on α-Al2O3 yielded S2980 = 51.2 J mol–1 K–1 instead of the recommended 50.94 J mol–1 K–1 value. This new lazulite third-law entropy along with other phosphate entropy data either derived from low-temperature adiabatic calorimetry or experimental phase equilibria under pressure and temperature, were computed to retrieve a (S–V)P2O5 value of 57.4(2.9) to predict phosphate entropies from oxide summation. The predicted third-law entropy for trolleite, Al4(PO4)3(OH)3, amounts to 285.4(8.5) J mol–1 K–1 ~13% higher than the previously published value. We propose a new formation enthalpy from the elements of –6504.2 kJ mol–1 and a new third-law entropy of 281.7 J mol–1 K–1 for trolleite, compatible with the predicted entropy from oxide summation as well as with the published brackets on the trolleite = berlinite + corundum + water reaction.

The low-temperature heat capacity of zinc chromite (ZnCr2O4) was measured between 6.5 K and 400 K using adiabatic calorimetry, and some thermochemical functions (CP(T), S(T), S°298, H(T)-H(0)) were derived from the results. The standard entropy (S°298 = 128.6±0.3 J mol-1 K-1) for zinc chromite was calculated from the results. Our calorimetric measurements indicate one extremely large anomaly in the heat capacity curve at ∼12.3 K which is related to the cubic-tetragonal transition in ZnCr2O4.

Earth has been habitable through most of its history, but the anthropogenically mediated greenhouse effect, if sufficiently strong, can threaten Earth's long-standing equability. This paper's main aim is to determine the strength of the anthropogenic greenhouse effect (the climate sensitivity) from observational data and basic physics alone, without recourse to the parameterisations of earth-system models and their inevitable uncertainties. A key finding is that the sensitivity can be constrained by harmonising historical records of land and ocean temperatures with observations of potential climate-change drivers in a non-steady state, energy-balance equation via a least-squares optimisation. The global temperature increase, for a CO2 doubling, is found to lie (95 % confidence limits) between 3.0oC and 6.3oC, with a best estimate of +4oC. Under a business-as-usual scenario, which assumes that there will be no significant change in people's attitudes and priorities, Earth's surface temperature is forecast to rise by 7.9oC over the land, and by 3.6oC over the oceans, by the year 2100. Global temperature rise has slowed in the last decade, leading some to question climate predictions of substantial 21st-Century warming. A formal runs test, however, shows that the recent slowdown is part of the normal behaviour of the climate system.

The premise of this paper is that the chemical potential of water strongly influences aging reactions in seeds, and that there will be an optimal chemical potential of water for seed longevity. If this is true, the optimum moisture content for storage and the optimal drying protocols should vary with the storage temperature, but should be predictable from water sorption isotherms. Isotherms for pea, soybean and peanut are given for temperatures between 65° and −150°C. Relative humidity/moisture content relationships were determined directly for temperatures between 5° and 50°C using saturated salt solutions. At extreme temperatures, isotherms were calculated from heat capacity measurements using differential scanning calorimetry or extrapolations of van't Hoff analyses. The family of isotherms was used to predict optimum moisture contents at storage temperatures between 65°C and −150°C. The optimal moisture contents for these three species are consistently shown to increase as the storage temperature is lowered.

The prediction of binding energies from the three-dimensional (3D) structure of a protein–ligand complex is an important goal of biophysics and structural biology. Here, we critically assess the use of empirical, solvent-accessible surface area-based calculations for the prediction of the binding of Src-SH2 domain with a series of tyrosyl phosphopeptides based on the high-affinity ligand from the hamster middle T antigen (hmT), where the residue in the pY+3 position has been changed. Two other peptides based on the C-terminal regulatory site of the Src protein and the platelet-derived growth factor receptor (PDGFR) are also investigated. Here, we take into account the effects of proton linkage on binding, and test five different surface area-based models that include different treatments for the contributions to conformational change and protein solvation. These differences relate to the treatment of conformational flexibility in the peptide ligand and the inclusion of proximal ordered solvent molecules in the surface area calculations. This allowed the calculation of a range of thermodynamic state functions (ΔCp, ΔS, ΔH, and ΔG) directly from structure. Comparison with the experimentally derived data shows little agreement for the interaction of SrcSH2 domain and the range of tyrosyl phosphopeptides. Furthermore, the adoption of the different models to treat conformational change and solvation has a dramatic effect on the calculated thermodynamic functions, making the predicted binding energies highly model dependent. While empirical, solvent-accessible surface area based calculations are becoming widely adopted to interpret thermodynamic data, this study highlights potential problems with application and interpretation of this type of approach. There is undoubtedly some agreement between predicted and experimentally determined thermodynamic parameters; however, the tolerance of this approach is not sufficient to make it ubiquitously applicable.

The contributions of backbone NH group dynamics to the conformational heat capacity of the B1 domain of Streptococcal protein G have been estimated from the temperature dependence of 15N NMR-derived order parameters. Longitudinal (R1) and transverse (R2) relaxation rates, transverse cross-relaxation rates (ηxy), and steady state {1H}–15N nuclear Overhauser effects were measured at temperatures of 0, 10, 20, 30, 40, and 50 °C for 89–100% of the backbone secondary amide nitrogen nuclei in the B1 domain. The ratio R2/ηxy was used to identify nuclei for which conformational exchange makes a significant contribution to R2. Relaxation data were fit to the extended model-free dynamics formalism, incorporating an axially symmetric molecular rotational diffusion tensor. The temperature dependence of the order parameter (S2) was used to calculate the contribution of each NH group to conformational heat capacity (Cp) and a characteristic temperature (T*), representing the density of conformational energy states accessible to each NH group. The heat capacities of the secondary structure regions of the B1 domain are significantly higher than those of comparable regions of other proteins, whereas the heat capacities of less structured regions are similar to those in other proteins. The higher local heat capacities are estimated to contribute up to ∼0.8 kJ/mol K to the total heat capacity of the B1 domain, without which the denaturation temperature would be ∼9 °C lower (78 °C rather than 87 °C). Thus, variation of backbone conformational heat capacity of native proteins may be a novel mechanism that contributes to high temperature stabilization of proteins.

A new computer program (CORE) is described that predicts core hydrophobic sequences of predetermined target protein structures. A novel scoring function is employed, which for the first time incorporates parameters directly correlated to free energies of unfolding (ΔGu), melting temperatures (Tm), and cooperativity. Metropolis-driven simulated annealing and low-temperature Monte Carlo sampling are used to optimize this score, generating sequences predicted to yield uniquely folded, stable proteins with cooperative unfolding transitions. The hydrophobic core residues of four natural proteins were predicted using CORE with the backbone structure and solvent exposed residues as input. In the two smaller proteins tested (Gβ1, 11 core amino acids; 434 cro, 10 core amino acids), the native sequence was regenerated as well as the sequence of known thermally stable variants that exhibit cooperative denaturation transitions. Previously designed sequences of variants with lower thermal stability and weaker cooperativity were not predicted. In the two larger proteins tested (myoglobin, 32 core amino acids; methionine aminopeptidase, 63 core amino acids), sequences with corresponding side-chain conformations remarkably similar to that of native were predicted.

Maltose binding protein (MBP) is a large, monomeric two domain protein containing 370 amino acids. In the absence of denaturant at neutral pH, the protein is in the native state, while at pH 3.0 it forms a molten globule. The molten globule lacks a tertiary circular dichroism signal but has secondary structure similar to that of the native state. The molten globule binds 8-anilino-1-naphthalene sulfonate (ANS). The unfolding thermodynamics of MBP at both pHs were measured by carrying out a series of isothermal urea melts at temperatures ranging from 274–329 K. At 298 K, values of ΔG°, ΔCp, and Cm were 3.1 ± 0.2 kcal mol−1, 5.9 ± 0.8 kcal mol−1 K−1 (15.9 cal (mol-residue)−1 K−1), and 0.8 M, respectively, at pH 3.0 and 14.5 ± 0.4 kcal mol−1, 8.3 ± 0.7 kcal mol−1 K−1 (22.4 kcal (mol-residue)−1 K−1), and 3.3 M, respectively, at pH 7.1. Guanidine hydrochloride denaturation at pH 7.1 gave values of ΔG° and ΔCp similar to those obtained with urea. The m values for denaturation are strongly temperature dependent, in contrast to what has been previously observed for small globular proteins. The value of ΔCp per mol-residue for the molten globule is comparable to corresponding values of ΔCp for the unfolding of typical globular proteins and suggests that it is a highly ordered structure, unlike molten globules of many small proteins. The value of ΔCp per mol-residue for the unfolding of the native state is among the highest currently known for any protein.