Apparent Enthalpy Research Articles

Electro-optical and thermal characterization of copper tartrate crystals grown in silica gel

Copper Tartrate crystals were grown by Gel Growth technique by single diffusion method. Silica gel of Optimum specific gravity was set with tartaric acid at optimum pH and aging period. Band gap of copper tartrate crystal is determined using to be 5.24 eV. In PL spectra broad peak is observed at nearly 367.44186 nm in the range 287 nm to 458 nm along with the sharp, intense transmission maxima peak at wavelength nearly 505.03876 nm which is characteristic of a material composition and electronic band structure. This shows the transparency of it in UV-Visible region and it as a filter in this range TGA analysis concludes that Copper tartrate has loss of one-half water molecule as crystalline water and is stable up to 85.02 ℃DSC analysis assigns the temperature value 314.5 ℃ as melting point and apparent enthalpy of fusion determined is 10.18 mW.

Electro-optical and thermal characterization of copper tartrate crystals grown in silica gel

Copper Tartrate crystals were grown by Gel Growth technique by single diffusion. Silica gel of Optimum specific gravity was set with tartaric acid at optimum pH and aging period. Band gap of copper tartrate crystal is determined using UV-Visible spectroscopy to be 5.24 eV. In PL spectra broad peak is observed at nearly 367.44186 nm in the range 287 nm to 458 nm along with the sharp, intense transmission maxima peak at wavelength nearly 505.03876 nm which is characteristic of a material composition and electronic band structure. This shows the transparency in UV-visible region and material is a filter in this range .TGA analysis concluded that Copper tartrate has one half water molecule as crystalline water and is stable up to 85.02 0 C.DSC analysis assigns the temperature value 314.5 0C as melting point and apparent enthalpy of fusion determined is 10.18 mW.

Upside-Down Adsorption: The Counterintuitive Influences of Surface Entropy and Surface Hydroxyl Density on Hydrogen Spillover.

Although hydrogen spillover is often invoked to explain anomalies in catalysis, spillover remains a poorly understood phenomenon. Hydrogen spillover (H*) is best described as highly mobile H atom equivalents that arise when H2 migrates from a metal nanoparticle to an oxide or carbon support. In the 60 years since its discovery, few methods have become available to quantify or characterize H*-support interactions. We recently showed in situ infrared spectroscopy and volumetric chemisorption can quantify reversible H2 adsorption on Au/TiO2 catalysts, where adsorbed hydrogen exists as H* and interacts with titania surface hydroxyl (TiOH) groups. Here, we report parallel thermogravimetric analysis and Fourier transform infrared spectroscopy methods for systematically manipulating the surface TiOH density. We examine the role of surface hydroxylation on spillover thermodynamics using van't Hoff studies to determine apparent adsorption enthalpies and entropies at constant H* coverage, which is necessary to maintain constant H* translational entropy. Although surface TiOH groups are the likely adsorption sites, the data show removing hydroxyl groups increases spillover. This surprising finding─that adsorption increases as the adsorption site density decreases─is associated with improved thermodynamics on dehydroxylated surfaces. A strong adsorption enthalpy-entropy correlation implicates the changing surface entropy of the titania support itself (i.e., an initial state effect) is deeply intertwined with the H* configurational entropy. These effects are surprising and should apply to all low-coverage adsorbates where entropy terms dominate more traditional enthalpic considerations. Moreover, this study points toward a kinetic test for invoking spillover in a reaction mechanism: namely, in situ dehydroxylation should enhance spillover processes.

Thermodynamically Traceable Calorimetric Results for Aqueous Sodium Chloride Solutions from T = (273.15 to 373.15) K up to the Saturated Solutions: Part 2 —The Quantities Associated with the Partial Molar Heat Capacity

AbstractIn previous articles (Partanen and Partanen in J. Chem. Eng. Data 65: 5226 − 5239 (2020), J. Solution Chem. 52: 1352 − 1385 (2023)), we presented a traceable and transparent three-parameter model for thermodynamic activity and enthalpy quantities in aqueous NaCl solutions. The model is based on extended Hückel equations with parameters B, b1, and b2 and it applies from T = 273.15 to 373.15 K up to the saturated solutions. These studies demonstrate that the model explains the literature data of almost all thermodynamic quantities including apparent and partial molar enthalpies within experimental error. In the model, the ion-size parameter in the Debye–Hückel equation, B, is regarded as a constant while the parameters of the coefficients of the linear and quadratic molality terms, b1 and b2, respectively, possess quadratic temperature dependences. In this study, the results obtained for the heat capacity quantities of NaCl(aq) are considered. We show that the available heat capacity literature for these solutions can be predicted at least satisfactorily up to the saturated solutions with our new model. Following this success, we supplement the existing thermodynamic tables with the new values for the relative apparent and partial molar heat capacities for NaCl solutions. It is likely that the new tables contain the most reliable values determined so far even though no calorimetric data were used in the parameter estimation of our model. Graphical Abstract

The determination of the solubility, enthalpy, and entropy of solutions of methyl Furan-2,5-Dimethylenedicarbamate and its hydrides in different solvents

The solubilities of methyl furan-2,5-dimethylenedicarbamate (FDC) and methyl tetrahydrofuran-2,5-dimethylenedicarbamate (THFDC) in dimethyl carbonate (DMC), anhydrous ethanol (EtOH) and benzene were studied using the static equilibrium method combined with high-performance liquid chromatography under atmospheric pressure at temperatures ranging from 278.15 K to 318.15 K. The experimental results demonstrate that the solubility of FDC and THFDC exhibits an upward trend as temperature increases. Among the six correlation models used, all of them (modified Apelblat equation, Buchowski-ksiazczak (λh) model, simplified two-parameter equation, polynomial equation, NRTL model and Wilson model) can effectively correlate the solubility data. Notably, the Wilson model demonstrates superior correlation performance compared to others in FDC system and the NRTL model demonstrates superior correlation performance compared to others in THFDC system. Using the modified Van’t Hoff equation and Gibbs equation, we calculated the apparent standard dissolution enthalpy (ΔHsol), the standard dissolution entropy change (ΔSsol), and the standard dissolution Gibbs energy (ΔGsol) for FDC and THFDC in different solvents. The research resulted indicate that all these dissolution processes are non-spontaneous, entropy-increasing endothermic processes. This study provides valuable reference data for crystallization and purification in industrial production.

Consequences of Pore Polarity and Solvent Structure on Epoxide Ring-Opening in Lewis and Brønsted Acid Zeolites.

The structure of solvent molecules within zeolite pores influences the rates and selectivities of catalytic reactions by altering the free energies of reactive species. Here, we examine the consequences of these effects on the kinetics and thermodynamics of 1,2-epoxybutane (C4H8O) ring-opening with methanol (CH3OH) in acetonitrile (CH3CN) cosolvent over Lewis acidic (Zr-BEA) and Brønsted acidic (Al-BEA) zeolites of varying (SiOH) x density. Despite ostensibly identical reaction mechanisms across materials, turnover rates depend differently on (SiOH) x density between acid types. (SiOH) x -rich Zr-BEA (Zr-BEA-OH) provides ∼10 times greater rates than a (SiOH) x -poor material (Zr-BEA-F), while Al-BEA-OH and Al-BEA-F give turnover rates within a factor of 2. Zr-BEA-OH shows more positive activation enthalpies and entropies than Zr-BEA-F across the range of [CH3OH], which reflect the displacement of solvent molecules and lead to greater rates in Zr-BEA-OH due to the dominant role of entropic gains. Measurements of the density and composition of solvent within the pores show that the (SiOH) x nests within Zr-BEA-OH promote hydrogen-bonded solvent structures distinct from Zr-BEA-F, while the Brønsted acid sites confer interactions similar to (SiOH) x nests and give solvent structures within Al-BEA-F that resemble those within Al-BEA-OH. Correlations between apparent activation enthalpies and C4H8O adsorption enthalpies show that interactions with solvent molecules give proportional changes to both C4H8O adsorption and ring-opening transition state formation. The differences in intrapore environment carry consequences for both rates and regioselectivities of epoxide ring-opening, as demonstrated by product regioselectivities that increase by a factor of 3 in response to changes in solvent composition and the type of acid site in the *BEA structure (i.e., Lewis or Brønsted). These results demonstrate the ability to control rates, regioselectivities, and adsorption thermodynamics relevant for industrially relevant liquid-phase reactions through the design of noncovalent interactions among solvating molecules, reactive species, and (SiOH) x functions.

Gibbs Free Energy and Enthalpy–Entropy Compensation in Protein–Ligand Interactions

The thermodynamics of protein–ligand interactions seems to be associated with a narrow range of Gibbs free energy. As a consequence, a linear enthalpy–entropy relationship showing an apparent enthalpy–entropy compensation (EEC) is frequently associated with protein–ligand interactions. When looking for the most negative values of ∆H to gain affinity, the entropy compensation gives rise to a barely noticeable increase in affinity, therefore negatively affecting the design and discovery of new and more efficient drugs capable of binding protein targets with a higher affinity. Originally attributed to experimental errors, compensation between ∆H and T∆S values is an observable fact, although its molecular origin has remained obscure and controversial. The thermodynamic parameters of a protein–ligand interaction can be interpreted in terms of the changes in molecular weak interactions as well as in vibrational, rotational, and translational energy levels. However, a molecular explanation to an EEC rendering a linear enthalpy–entropy relationship is still lacking. Herein, we show the results of a data search of ∆G values of 3025 protein–ligand interactions and 2558 “in vivo” ligand concentrations from the Protein Data Bank database and the Metabolome Database (2020). These results suggest that the EEC may be plausibly explained as a consequence of the narrow range of ∆G associated with protein–ligand interactions. The Gaussian distribution of the ∆G values matches very well with that of ligands. These results suggest the hypothesis that the set of ∆G values for the protein–ligand interactions is the result of the evolution of proteins. The conformation versatility of present proteins and the exchange of thousands (even millions) of minute amounts of energy with the environment may have functioned as a homeostatic mechanism to make the ∆G of proteins adaptive to changes in the availability of ligands and therefore achieve the maximum regulatory capacity of the protein function. Finally, plausible strategies to avoid the EEC consequences are suggested.

Volatility Basis Set Distributions and Viscosity of Organic Aerosol Mixtures: Insights from Chemical Characterization Using Temperature-Programmed Desorption-Direct Analysis in Real-Time High-Resolution Mass Spectrometry.

Quantitative assessment of gas-particle partitioning of individual components within complex atmospheric organic aerosol (OA) mixtures is critical for predicting and comprehending the formation and evolution of OA particles in the atmosphere. This investigation leverages previously documented data obtained through a temperature-programmed desorption-direct analysis in real-time, high-resolution mass spectrometry (TPD-DART-HRMS) platform. This methodology facilitates the bottom-up construction of volatility basis set (VBS) distributions for constituents found in three biogenic secondary organic aerosol (SOA) mixtures produced through the ozonolysis of α-pinene, limonene, and ocimene. The apparent enthalpies (ΔH*, kJ mol-1) and saturation mass concentrations (CT*, μg·m-3) of individual SOA components, determined as a function of temperature (T, K), facilitated an assessment of changes in VBS distributions and gas-particle partitioning with respect to T and atmospheric total organic mass loadings (tOM, μg·m-3). The VBS distributions reveal distinct differences in volatilities among monomers, dimers, and trimers, categorized into separate volatility bins. At the ambient temperature of T = 298 K, only monomers efficiently partition between gas and particle phases across a broad range of atmospherically relevant tOM values of 1-100 μg·m-3. Partitioning of dimers and trimers becomes notable only at T > 360 K and T > 420 K, respectively. The viscosity of SOA mixtures is assessed using a bottom-up calculation approach, incorporating the input of elemental formulas, ΔH*, CT*, and particle-phase mass fractions of the SOA components. Through this approach, we are able to accurately estimate the variations in SOA viscosity that result from the evaporation of its components. These variations are, in turn, influenced by atmospherically relevant changes in tOM and T. Comparison of the calculated SOA viscosity and diffusivity values with literature reported experimental results shows close agreement, thereby validating the employed calculation approach. These findings underscore the significant potential for TPD-DART-HRMS measurements in enabling the untargeted analysis of organic molecules within OA mixtures. This approach facilitates quantitative assessment of their gas-particle partitioning and allows for the estimation of their viscosity and condensed-phase diffusion, thereby contributing valuable insights to atmospheric models.

Fast relaxation in metallic glasses studied by measurements of the internal friction at high frequencies

We performed high-frequency (0.4–1.7 MHz) measurements of the internal friction (IF) on 14 bulk metallic glasses (MGs). It is found that 12 of these MGs display relaxation IF peaks at temperatures ≈ 400–500 K, which are weakly affected by heat treatment within the amorphous state. The corresponding relaxation time is about 0.3 μs. This fast relaxation is reported for the first time in the literature. The apparent activation enthalpy for 4 MGs is determined. It is shown that if measured at a low frequency of 1 Hz, these IF peaks would appear near room temperature or by 30–50 K below it. Thus, the IF peaks found in the present investigation are direct analogues of low-temperature/low-frequency β′- and/or γ-relaxations described in the literature. It is argued that the origin of these IF peaks is related to the relaxation of structural defects similar to dumbbell interstitials, which are frozen in solid glass from the liquid state upon melt quenching. These defects can be considered as elastic dipoles and their re-orientation in the applied stress provides anelastic deformation and corresponding IF peak. After correction for temperature dependence of the shear modulus, the true activation enthalpy (0.62–1.08 eV) and activation entropy (4 ≤ΔS∕kB≤15) for defect re-orientation are determined.

The Dominance of Pretransitional Effects in Liquid Crystal-Based Nanocolloids: Nematogenic 4-methoxybenzylidene-4'-butylaniline with Transverse Permanent Dipole Moment and BaTiO3 Nanoparticles.

The report presents static, low-frequency, and dynamic dielectric properties in the isotropic liquid, nematic, and solid phases of MBBA and related nanocolloids with paraelectric BaTiO3 nanoparticles (spherical, d = 50 nm). MBBA (4-methoxybenzylidene-4'-butylaniline) is a liquid crystalline compound with a permanent dipole moment transverse to the long molecular axis. The distortions-sensitive analysis of the dielectric constant revealed its hidden pretransitional anomaly, strongly influenced by the addition of nanoparticles. The evolution of the dielectric constant in the nematic phase shows the split into two regions, with the crossover coinciding with the standard melting temperature. The 'universal' exponential-type behavior of the low-frequency contribution to the real part of the dielectric permittivity is found. The critical-like pretransitional behavior in the solid phase is also evidenced. This is explained by linking the Lipovsky model to the Mossotti catastrophe concept under quasi-negative pressure conditions. The explicit preference for the 'critical-like' evolution of the apparent activation enthalpy is worth stressing for dynamics. Finally, the long-range, 'critical-like' behavior of the dissipation factor (D = tgδ), covering the isotropic liquid and nematic phases, is shown.

Intact Transition Epitope Mapping-Force Interferences by Variable Extensions (ITEM-FIVE).

Investigations on binding strength differences of non-covalent protein complex components were performed by mass spectrometry. T4 fibritin foldon (T4Ff) is a well-studied miniprotein, which together with its biotinylated version served as model system to represent a compactly folded protein to which an Intrinsically Disordered Region (IDR) was attached. The apparent enthalpies of the gas phase dissociation reactions of the homo-trimeric foldon F-F-F and of the homo-trimeric triply biotinylated foldon bF-bF-bF have been determined to be rather similar (3.32 kJ/mol and 3.85 kJ/mol) but quite distinct from those of the singly and doubly biotinylated hetero-trimers F-F-bF and F-bF-bF (1.86 kJ/mol and 1.08 kJ/mol). Molecular dynamics simulations suggest that the ground states of the (biotinylated) T4Ff trimers are highly symmetric and well comparable to each other, indicating that the energy levels of all four (biotinylated) T4Ff trimer ground states are nearly indistinguishable. The experimentally determined differences and/or similarities in enthalpies of the complex dissociation reactions are explained by entropic spring effects, which are noticeable in the T4Ff hetero-trimers but not in the T4Ff homo-trimers. A lowering of the transition state energy levels of the T4Ff hetero-trimers seems likely because the biotin moieties, mimicking intrinsically disordered regions (IDRs), induced asymmetries in the transition states of the biotinylated T4Ff hetero-trimers. This transition state energy level lowering effect is absent in the T4Ff homo-trimer, as well as in the triply biotinylated T4Ff homo-trimer. In the latter, the IDR-associated entropic spring effects on complex stability cancel each other out. ITEM-FIVE enabled semi-quantitative determination of energy differences of complex dissociation reactions, whose differences were modulated by IDRs attached to compactly folded proteins.

Sintering kinetics and microstructure development of synthetic lunar highlands and mare regolith

Kinetics and microstructure development during pressureless sintering of two Lunar regolith simulants are reported and discussed. Dry-pressed cylindrical specimens of either a Highlands simulant or a Mare simulant were heated at 80 K min−1 to a prescribed sintering temperature and held for ten hours while dimensional changes were tracked in situ by optical dilatometry. The axial and volumetric strains and densification rates were calculated as a function of time and temperature. Possible phase transformations were evaluated by quantitative X-ray powder diffraction. The relative density increased with the logarithm of time at any temperature, and densification rates decreased continuously and sharply with increasing density. Sintered microstructures and compositional characteristics were observed by scanning electron microscopy and X-ray microprobe analysis of polished surfaces. The microstructures of both materials show evidence of heterogeneous densification, with large but isolated high-density domains surrounded by lower-density regions with interconnected porosity. No significant compositional differences were detected between the higher- and lower-density regions, meaning that the heterogeneous local densities are caused by gradients in particle size or packing that induce locally varying thermodynamic driving forces for densification. The apparent activation enthalpy for densification was measured as 445 kJ mol−1 and 440 kJ mol−1 for the Highlands and Mare simulants, respectively, values that were observed to be independent of temperature and sintered density to within the measurement uncertainty.

Molecular dynamics simulation, thermodynamic parameters and solute–solvent molecular interactions of cilostazol (form A) dissolution in (ethylene glycol / ethanol + water) mixtures

This research work reports the cilostazol (form A) dissolution in (ethylene glycol / ethanol + water) mixtures. The co-solvency phenomenon only occurs in mixture of ethanol + water, the maximum solubility in mole fraction is 3.034 × 10-3 at the composition of 0.85. It was found that the solvation performance of cilostazol in two mixtures mainly depend on the ability of forming hydrogen bond (H-bond) of the solutions and van der Waals interaction. According to the preferential solvation results, it is conjecturable that cilostazol molecules are preferentially solvated by water in water-rich regions. With the increase of alcohol concentration, the destruction of water molecular ordered structure by alcohol through hydrogen bond, and solute molecules are preferentially solvated by ethanol and EG. Nonetheless, when 0.86 < x1 < 1 in mixture of ethanol + water, solute molecules are preferentially solvated by water again. The calculation of radial distribution function (RDF) between the atoms of H and O for ethanol and the atoms of N and H for solute is to achieve the interaction of the solute and solvents. The correlation fitting was performed for the solubility data through Jouyban Acree model and its derivative models, and the statistical analysis showed that the Apelblat-Jouyban Acree model is more suitable to present the solubility correlation. Meanwhile, the values of apparent molar standard dissolution enthalpy (ΔHsolo) and apparent molar standard dissolution entropy (ΔSsolo) are positive in each solvents, which reveals that the dissolution process of cilostazol form A is endothermic and entropy favorable within the given temperature range.

Mass Spectrometric ITEM-ONE and ITEM-TWO Analyses Confirm and Refine an Assembled Epitope of an Anti-Pertuzumab Affimer.

Intact Transition Epitope Mapping-One-step Non-covalent force Exploitation (ITEM-ONE) analysis reveals an assembled epitope on the surface of Pertuzumab, which is recognized by the anti-Pertuzumab affimer 00557_709097. It encompasses amino acid residues NSGGSIYNQRFKGR, which are part of CDR2, as well as residues FTLSVDR, which are located on the variable region of Pertuzumab's heavy chain and together form a surface area of 1381.46 Å2. Despite not being part of Pertuzumab's CDR2, the partial sequence FTLSVDR marks a unique proteotypic Pertuzumab peptide. Binding between intact Pertuzumab and the anti-Pertuzumab affimer was further investigated using the Intact Transition Epitope Mapping-Thermodynamic Weak-force Order (ITEM-TWO) approach. Quantitative analysis of the complex dissociation reaction in the gas phase afforded a quasi-equilibrium constant (KD m0g#) of 3.07 × 10-12. The experimentally determined apparent enthalpy (ΔHm0g#) and apparent free energy (ΔGm0g#) of the complex dissociation reaction indicate that the opposite reaction-complex formation-is spontaneous at room temperature. Due to strong binding to Pertuzumab and because of recognizing Pertuzumab's unique partial amino acid sequences, the anti-Pertuzumab affimer 00557_709097 is considered excellently suitable for implementation in Pertuzumab quantitation assays as well as for the accurate therapeutic drug monitoring of Pertuzumab in biological fluids.

Structural Transitions in Complementary G-Rich and C-Rich Strands and Their Mixture at Various pH Conditions.

We used circular dichroism spectroscopy, UV spectrophotometry, and differential scanning calorimetry to investigate pH-dependent structural transitions in an equimolar mixture of complementary G-rich d[5'-A(GGGTTA)3GGG-3'] (TelG) and C-rich d[3'-T(CCCAAT)3CCC-5'] (TelC) human telomeric DNA strands. Our studies were conducted at neutral (pH 7.0) and slightly acidic (pH 5.5 and 6.5) pH. We analyzed the melting thermodynamics of TelG and TelC and their equimolar mixture. Our analysis revealed that the preferred conformation of an equimolar mixture of TelG and TelC is the duplex. At pH 5.5, however, in addition to the duplex state, we observed a significant population of the i-motif state formed by TelC. Our results are consistent with the picture in which an increase in pH from 5.5 to 7.0 has little effect on the melting enthalpy of an isolated G-quadruplex while causing a strong reduction in the melting enthalpy of an isolated i-motif (the latter diminishes to 0 at pH 7.0). These effects summarily lead to a decrease in the contribution of the i-motif to the melting enthalpy of the mixture and, hence, an increase in the apparent melting enthalpy and overall stability of the duplex state.

Rapid stress relaxation of high‐Tg conjugated polymeric thin films

AbstractConjugated polymers consist of complex backbone structures and side‐chain moieties to meet various optoelectronic and processing requirements. Recent work on conjugated polymers has been devoted to studying the mechanical properties and developing new conjugated polymers with low modulus and high‐crack onset strain, while the thin film mechanical stability under long‐term external tensile strain is less investigated. Here we performed direct mechanical stress relaxation tests for both free‐standing and thin film floated on water surface on both high‐Tg and low‐Tg conjugated polymers, as well as a reference nonconjugated sample, polystyrene. We measured thin films with a range of film thickness from 38 to 179 nm to study the temperature and thickness effect on thin film relaxation, where an apparent enthalpy–entropy compensation effect for glassy polymer PS and PM6 thin films was observed. We also compared relaxation times across three different conjugated polymers and showed that both crystalline morphology and higher modulus reduce the relaxation rate besides higher glass transition temperature. Our work provides insights into the mechanical creep behavior of conjugated polymers, which will have an impact on the future design of stable functional organic electronics.

Dissolution and thermodynamic study of lamotrigine in propylene glycol + 1-propanol mixtures

ABSTRACT The solubility of lamotrigine (LTG) was investigated in non-aqueous mixed solvents of propylene glycol (PG) and 1-propanol by a shake-flask technique in the temperatures of 293.2–313.2 K. The obtained experimental data were correlated by five cosolvency mathematical models include the van’t Hoff, the Jouyban–Acree, the Jouyban–Acree–van’t Hoff, the mixture response surface and the modified Wilson models, and reliability of the models was checked. Furthermore, the apparent standard Gibbs energy, enthalpy and entropy of dissolution of LTG in the studied mixtures were computed using van’t Hoff and Gibbs equations at mean harmonic temperature. The solubility of LTG increases with increasing the amount of PG, and maximum solubility was reached in PG mass fraction of 0.7 at 313.2 K. The experimental results were correlated by the above mentioned models, and mean relative deviations (%) for the computed data were reported to be less than 5.0.

Modifying reaction rates and stimulus-responsive behavior of polymer-coated catalysts using aprotic solvents

The impact of solvent composition on the reaction rates and apparent activation barriers for the reduction of nitrobenzene on Pd has been investigated by changing the solvent from pure water to mixtures with increasing concentrations of 1-methyl-2-pyrrolidone (NMP). When using pure NMP as the solvent, the activity was negligible and a high activation energy barrier was observed. Surprisingly, switching to water led to faster reaction rates and lower apparent barriers. Considering that previous research has demonstrated that water molecules near the catalyst surface facilitate the hydrogen insertion on R-NO* and R-HNO* surface species via proton-electron transfer, it is possible to link the herein observed trends in activity for the nitrobenzene hydrogenation to the ability of the reaction media to shuttle protons during the reaction. Furthermore, the polymer-induced solvation effects were investigated using thermo-responsive Pd/SiO2-p-NIPAM catalyst. Here, we observed that the utilization of NMP inhibits the thermo-responsive behaviour of poly N-isopropylacrylamide (p-NIPAM). This explains the constant particle size of Pd/SiO2-p-NIPAM catalyst observed at different temperatures during dynamic light scatting characterization (DLS). We speculate that this non-responsive behaviour of the p-NIPAM in the presence of NMP is the cause of the constant activation energy barrier at temperatures above and below the lower critical solution temperature (LCST) of the polymer (32 °C). When the reaction was conducted in pure water, the polymer-coated catalyst showed significant changes in both the apparent enthalpy and entropy of activation for temperatures below and above the LCST. This suggests that the microenvironment induced by the polymer can significantly influence the reaction rate.

Thermodynamically Traceable Calorimetric Results for Aqueous Sodium Chloride Solutions from T = (273.15 to 373.15) K up to the Saturated Solutions: Part 1—The Quantities Associated with the Partial Molar Enthalpy

The three-parameter extended Hückel equations with parameters B, b1, and b2 have recently been successfully tested against existing vapor pressure, electrochemical, and solubility data for aqueous NaCl solutions at temperatures from (273 to 373) K (Partanen and Partanen in J. Chem. Eng. Data 65:5226–5239, 2020). In the present study, we extend this model to the apparent and partial molar enthalpy data of these solutions. The enthalpy equations were determined using a new calculation method that gives practically the same results as that used in another previous study (Partanen et al. in J. Chem. Eng. Data 62:2617–2632, 2017), but the new method is much simpler. In the previous enthalpy study, dilute NaCl solutions up to m = 0.2 mol⋅kg−1 were considered in the range from T = 273 to 353 K. Following the success of the three-parameter extended Hückel model within the whole concentration range at various temperatures, we tabulate new values for relative apparent and partial molar enthalpies for NaCl solutions at rounded molalities. The resulting values are extensively tested against the literature ones. The best agreement is obtained for temperatures below 288 K and between 313 and 353 K. Elsewhere, at least a reasonable agreement is obtained. As no enthalpy or heat capacity data were used in the estimation of our model’s parameters and as the model has excelled in explaining other high-precision thermodynamic data, we argue that the recommended enthalpy values should be preferred even for the temperatures where the agreement is only reasonable due to potential problems associated with the literature values. These problems are also considered in the study.Graphical

Solubility measurement and data correlation of 3-ethoxysalicylaldehyde in twelve pure solvents at temperatures from 278.15 to 313.15 K

The solubility of 3-ethoxysalicylaldehyde in twelve pure solvents (water, methanol, ethanol, n-propanol, n-butanol, iso-propyl alcohol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetonitrile, and acetone) was determined by an isothermal saturation method over the temperatures ranging from 278.15 to 313.15 K at 101.6 ± 1.2 kPa. The solubility of 3-ethoxysalicylaldehyde in all studied solvents increases with the increase in temperature. The mole fraction solubility of 3-ethoxysalicylaldehyde is observed highest in acetone (0.6053 at 313.15 K), followed by methyl acetate, ethyl acetate (acetonitrile), propyl acetate, butyl acetate, methanol, ethanol, n-propanol, n-butanol, iso-propyl alcohol, and water. Three solubility fitting models were used to correlate the experimental mole solubility data, including the van’t Hoff model, modified Apelblat model, and λh model. The three models showed good fitting results, with the average RAD less than 5%. The thermodynamic properties of 3-ethoxysalicylaldehyde, including apparent standard dissolution enthalpy (ΔHsol), standard dissolution Gibbs energy (ΔGsol), and standard dissolution entropy change (ΔSsol), were calculated via the van’t Hoff equation. The positive values of ΔHsol and ΔGsol indicate that the dissolution process of 3-ethoxysalicylaldehyde is endothermic. The studied solubility data and the relevant thermodynamic analysis have an important guiding significance for the design and optimization of the crystallization process of 3-ethoxysalicylaldehyde.