Heavy oil reserves are recognized as being a significant yet challenging energy resource due to high viscosities. It is common knowledge that thermal recovery methods like in situ combustion rely on fuel deposition and oxidation to enhance oil mobility. This study explored micro and nanostructured manganese oxide catalysts to improve the efficiency of heavy oil oxidation. MnO composites were synthesized and characterized by X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-dispersive X-ray (EDX), Thermogravimetric analysis (TGA), and N-2 physisorption. It has been found that the smaller nanoparticles showed higher surface area (38 m(2)/g), oleic acid content, and mesoporosity compared to the larger microparticles which exhibited a surface area of 12.85 m(2)/g. Moreover, differential scanning calorimetry (DSC) analysis confirmed the catalytic activity of both particle types by intensifying oxidation peaks and lowering activation energies. However, the isoconversional calculations revealed minimal difference in oxidation times between MnO micro and nanoparticles at various conversion rates. To overcome aggregation issues, MnO nanoparticles were incorporated onto SiO2 nanospherical particles. As a result, MnO/SiO2 composites exhibited increased surface area and pore volume. Most importantly, they demonstrated significantly enhanced heavy oil oxidation rates, especially at a high temperature oxidation region which is considered the main key of a successful application of in situ combustion. This work highlights the promise of nanostructured MnO catalysts to improve the efficiency and economics of thermal heavy oil recovery. Further optimization of parameters like size, morphology, and dispersion extent within the reservoir could enable these materials to stabilize the combustion front and maximize heavy oil production.

This study presents a groundbreaking approach to heavy oil upgrading using water-soluble nickel acetate as a precatalyst, marking a shift from traditional oil-soluble catalysts. We demonstrate that nickel and copper acetates significantly enhance aquathermolysis, reducing the viscosity of heavy oil by almost 58% and the high-molecular-weight fractions from 38.3 to 23.5 wt % while increasing the lighter fractions from 61.7 to 76.5 wt %. The catalytic action of nickel and copper acetates facilitates the structural and compositional transformation of heavy oil, evidenced by the increased H/C atomic ratio and 30% reduction in the initial boiling point. Further, these catalysts yield an increase in light distillate production and promote the formation of stable free radicals, indicating a higher degree of hydrocarbon decomposition. Analytical techniques, including thermogravimetric analysis, kinetic analysis, X-ray diffraction, and scanning electron microscopy, confirm the effective decomposition of nickel and copper acetates into active nickel and copper species, predominantly nanoparticles smaller than 58 nm. The study underlines the potential of water-soluble catalysts such as nickel and copper acetates to enhance steam-based oil recovery and upgrading processes, offering a cost-effective and environmentally friendlier alternative to conventional methods. The ongoing research promises to solidify the role of catalysts in sustainable energy production.

In-situ combustion has received much attention in the last few decades for enhanced heavy oil recovery pro-cesses. Although a wide part of research efforts has only focused on the application of different oil soluble catalysts to improve the combustion flame stabilization, the effect of ligand structure and metal-ligand in-teractions on the performance of heavy oil oxidation in presence of oil soluble catalysts is poorly understood. In this study, sunflower oil as an eco-friendly and cheap source was used to synthesize a new ligand for the preparation of Fe, Ni, Co and Cu-based oil soluble catalysts. The interaction of metals with the ligand was investigated by computational study and the results revealed that Cu-based catalyst was the most effective catalytic system for enhancing heavy oil oxidation process because it possessed the strongest bond energy with the ligand at different temperatures. Subsequently, the impact of oil soluble catalysts on the oxidation of heavy oil was investigated via non-isothermal kinetics and thermodynamic studies using thermogravimetric (TG/DTG) and differential scanning calorimetric analyses (DSC) combined with the isoconversional (Friedman and Kissinger-Akahira-Sunose), and model-based approaches. As anticipated, the kinetic and thermodynamic data demonstrated the efficiency of the used catalysts on the process of heavy oil oxidation process and proved a maximum temperature shift of similar to 120 degrees C in high-temperature oxidation zone. To the best of our knowledge, this is the first superior catalyst among investigated oil-soluble catalysts for heavy oil oxidation. The evidence from the obtained results points toward the idea that the choice of the ligand and the associated metal is crucial to achieve the highly active and smart catalytic system for enhanced oil recovery methods.

Amorphous polymers currently have a wide range of applications, including the production of amorphous solid dispersions in the pharmaceutical industry. This application requires knowledge of the kinetic parameters of the glass transition process, which are the key to the formation of the end product. In the present work, we have thoroughly investigated the glass transition in the biocompatible polymer polyvinylpyrrolidone as a function of the polymer molecular mass, using differential scanning calorimetry, fast scanning calorimetry, and broadband dielectric spectroscopy. We have determined the dependence of the difference between the isobaric specific heat capacities of the liquid and the glass on the dynamic glass transition temperature, volume, and number of particles included in the cooperatively rearranging regions. A linear dependence between the shift factor from the Frenkel-Kobeko-Reiner equation and the molecular mass of polyvinylpyrrolidone was established. The results of the present work help in choosing the optimal excipient for the development of solid dispersions based on amorphous polymers.

The application of drugs in the amorphous state is one way to improve their bioavailability. As such, the determination of the optimal conditions for production and the assessment of the stability of the amorphous system are actively researched topics of present-day pharmaceutical science. In the present work, we have studied the kinetic stability and glass-forming ability of the thermally labile quinolone antibiotics using fast scanning calorimetry. The critical cooling rates for avoiding crystallization of the melts of oxolinic and pipemidic acids and sparfloxacin were determined to be 10 000, 40, and 80 K·s-1, respectively. The studied antibiotics were found to be "strong" glass formers. Based on a combination of nonisothermal and isothermal kinetic approaches, the Nakamura model was suitable for describing the crystallization process of the amorphous forms of the quinolone antibiotics.

The reaction of cyclopentaphosphine cyclo-(P5 Ph5 ) (1) with ketones (acetone and cyclooctanone) in the presence of [Mo(CO)4 (cod)] (cod=cycloocta-1,5-diene) led to air-stable trinuclear complexes in which the bis-phosphanido ligands (PPh-PPh-PPh-PPh-CMe2 O-PPh)2- (complex 2) and (PPh-PPh-PPh-PPh-C(CH2 )7 O-PPh)2- (complex 3) bridge a Mo(CO)3 -Mo(CO)3 unit. This extends the reaction of 1 with transition metal carbonyl complexes to further substrates and represents the first examples of insertion of carbonyl compounds into the P-P bond of cyclic oligophosphorus compounds. Complexes 2 and 3 have been characterized by 31 P NMR spectroscopy and single crystal X-ray diffraction. Furthermore, the thermal properties of the obtained complexes have been studied by differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC).

Reducing the amount of CO2 in the atmosphere is a very important task. Therefore, the development and search for new approaches to the synthesis of catalytic systems, allowing for the catalytic conversion of CO2 into valuable products, is an urgent task. In this work, the catalyst was obtained by the thermolysis of a double complex compound. In this regard, kinetic studies of the parameters of the thermolysis process of double complex salts-[Co(NH)3]6][Fe(CN)6] were additionally determined using isoconversion and model approaches of non-isothermal kinetics. The catalyst was studied using various physicochemical methods—X-ray diffraction (XRD), infrared (IR)-spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). It was shown that, at the stage of catalyst preparation, the formation of a CoFe alloy occurred, while the surface mainly consisted of carbon in sp2-hybridization, and the metals existed in the form of spinel CoFe2O4. It was shown that catalysts based on bimetallic salts were active in the process of hydrogenation of carbon dioxide without a pre-activation stage (CO2 conversion reached 28%, with a specific activity of 4.0 µmolCO2/gMe·s). It was established that it was possible to change the selectivity of the carbon dioxide hydrogenation process by pre-treating the catalyst with hydrogen (selectivity for methane formation in the presence of an unreduced catalyst is 46.4–68.0%, whereas in the presence of a reduced catalyst it is 5.1–16.5%).

Robust determination of the parameters governing the stability of the amorphous drugs is one of the key tasks of modern pharmaceutics. The kinetic stability of such systems is of crucial importance, as it affects their practical applications. In the present work we have determined the critical cooling rates, and the kinetic parameters of the cold crystallization of four slowly crystallizing sulfonamides, i.e. sulfaguanidine, sulfapyridine, sulfalene, and sulfadimidine. The Nakamura crystallization model was shown to have a good prognostic ability, as it allows determination of the stability time profile of the drug systems prone to crystallization from the non-isothermal thermokinetic data.

In the present work, the vapour pressures over solid samples of sulfamethoxazole, sulfapyridine and sulfamethazine were measured by fast scanning calorimetry (FSC). Due to the thermal decomposition of the samples, it was not possible to measure the vapour pressure of these compounds by transpiration method. The IR spectrum of the condensed sample in the sulfamethoxazole transpiration experiment showed that the transferred substance was 5-methyl-3-isoxazolamine. The temperature dependencies of the vapour pressure determined using FSC were used to determine the enthalpy of sublimation at the mean temperature of the experiment. Fusion enthalpies and heat capacities of solid and supercooled liquid samples of sulfamethoxazole, sulfapyridine and sulfamethazine were measured by differential and fast scanning calorimetries. The dependencies of the heat capacity over wide temperature ranges were approximated by linear equations. The fusion enthalpies were compared with literature data and used to calculate weighted averages. The weighted mean values of the fusion enthalpies at the melting temperature were adjusted to 298.15 K using Kirchhoff's law. In addition, the values of the heat capacity difference between the solid and gaseous phases were estimated using the experimental values of the heat capacities and the empirical approach. These values were used to adjust the enthalpy of sublimation from experimental temperature to 298.15 K. Using the sublimation and fusion enthalpies, the vaporization enthalpies of three sulfonamides at 298.15 K were determined.

The stability of glassy materials, including polymer-based ones, is one of the important subjects of material science and technology. This interest is due to the dependence of the properties of the end products, based on glassy materials, on the processing and storage conditions. In particular, the application of amorphous solid dispersions based on polymer excipients requires an understanding of the kinetics of the formation and the physical aging of the glassy state. The kinetic parameters of the glass transition of polyvinylpyrrolidone, a widely used polymer in the pharmaceutical industry, were determined in the present work using fast scanning calorimetry. The dependencies of the Vogel temperature and the kinetic fragility on the molecular mass of the polymer were determined, as well as the apparent activation energy of the physical aging process, which changes from 256 kJ.mol(-1) in the case of polyvinylpyrrolidone with a molecular mass of 3500 g.mol(-1) to 565 kJ.mol(-1) in the case of polyvinylpyrrolidone with a molecular mass of 1,300,000 g.mol(-1). The results of the current work can be used to optimize the processing of polymer-based glassy materials to obtain the desired properties for application in different fields of technology, including pharmaceuticals.

Peat has attracted considerable interest as a potential source of alternative fuel in terms of improving hydrocarbons production and satisfying market demand. The next decade is likely to witness a raise in its exploitation. Nevertheless, the characteristics of peat pyrolysis process, via which many experts expect a considerable generation of hydrocarbons, have not been dealt with in depth. In the present study we have applied thermal analysis combined with isoconversional and model methods for clarifying the kinetic and thermodynamic aspects of the process of generating hydrocarbons from peat via pyrolysis in the absence and presence of iron tallates as a catalytic agent. The obtained results showed a positive effect of the opted catalyst on the process of peat pyrolysis. It has been shown that the catalyst is able to reduce the energy of activation of peat pyrolysis process. Moreover, the Gibbs energy, enthalpy and entropy of complex formation values have been found lower in the presence of iron tallates for all the applied isoconversional methods (Friedman and KAS). The evidence from the present study points toward the beneficial effect generated from the utilization of iron tallates in the processes of hydrocarbons generation from peat for improving energy production in the future.

There is still considerable controversy surrounding the mechanisms, thermodynamics, and kinetics of heavy oil aquathermolysis and pyrolysis processes. The present paper aims to widen our knowledge about the effect of iron tallates on pyrolysis and aquathermolysis of Cuban heavy oil. The obtained SARA (S: saturates, A: aromatics, R: resins, A: asphaltenes) analysis has shown a significant increase in light hydrocarbon content during aquathermolysis. Moreover, the elemental analysis has indicated an increase in C and H content by almost 4% and 6%, respectively, with a significant decrease in S and O content by up to 23% in the presence of iron tallates. These results have been further confirmed by infrared spectrometry. The obtained IR data indicated that asphaltene and resin compounds transform into light hydrocarbons after aquathermolysis. On another hand, the activation energy of heavy oil pyrolysis decreased in the presence of the utilized catalyst; meanwhile, the reaction rate increased, especially in the temperature range of 200–480 °C, which may validate a significant effect of the used catalyst in real conditions. Moreover, the obtained thermodynamic data showed a decrease in the enthalpy and entropy of activation of oil pyrolysis in the presence of iron tallates. Our results are encouraging in terms of energy consumption, optimization, and process control and should be validated by a larger sample size.

Peat is a resource used for heat and energy, particularly in countries where peat is abundant and conventional fuels are not available. Some countries have made extensive use of peat resources to produce electricity and heat in addition to light hydrocarbons. By doing so, they were able to reduce the cost of importing fossil fuels. To the best of our knowledge, there is a lack of a detailed description of the peat oxidation process in the presence of other substances. Herein, the process of peat oxidation was studied in-depth by means of thermal analysis in the presence of iron tallate acting as a catalytic agent. Differential scanning calorimetry and thermogravimetric analysis demonstrated an oil-like oxidation behavior during the combustion of the used peat. The process of peat oxidation includes two main regions: low-temperature oxidation (LTO), which occurs during the oxidation of light hydrocarbons, followed by the so-called high-temperature oxidation (HTO), which includes the oxidation of the obtained coke-like product. Moreover, the application of non-isothermal kinetics experiments based on the isoconversional and model approach principle have confirmed the role of 2% iron tallate in peat mass by improving the oxidation rate at low- and high-temperature oxidation (HTO) regions. The results obtained from this study have proven that the added catalyst improves efficiency with regards to the energy activation in the process by leading to its significant decrease from 110.8 ± 7.8 kJ/mol to 81.8 ± 7.5 kJ/mol for LTO and from 157.8 ± 19.1 kJ/mol to 137.6 ± 9.3 kJ/mol for HTO. These findings clearly confirm the improvement in the rate of the process by shifting the LTO and HTO peaks to lower regions in the presence of the catalyst. These results further emphasize the possible impact which could be generated by the application of thermally enhanced oil recovery methods on peat development and exploitation.

Dantrolene represents yet another interesting example of abundant molecular crystal polymorphism existing in at least six different neat polymorphs, three of which can be obtained via crystallization (I-III) and an additional three (IV-VI) via solid-state dehydration from three different monohydrates (MH-I-MH-III). The reasons for polymorph formation were rationalized by analyzing the crystal structures of the polymorphs and hydrates used in their preparation. The thermodynamic relations among the polymorphs were established from calorimetric data, solubility measurements, and lattice energy calculations.

In recent years, protection of the environment from activities associated with enhanced oil recovery has been considered a crucial priority for decision-makers in the international community. The in situ combustion process as a promising thermal enhanced oil recovery method has been attracting considerable interest in terms of improving oil production and environmental protection. However, this technique is not yet well studied. This paper outlines a new approach to improve the process of heavy oil oxidation by designing new biobased oil-soluble catalysts that are able to maintain and stabilize the combustion flame front of the in situ combustion process. A comprehensive theoretical and experimental study including thermal analysis (thermogravimetry/differential scanning calorimetry, TG/DSC) and quantum calculations was used to shed light on the effect of the ligand structure in the oil-soluble catalytic system on the heavy oil oxidation process. The obtained accurate results proved that metal interaction with the designed ligands increased, which led to a decrease in the energy of activation and an increase in the heavy oil oxidation reaction rate. Besides, the obtained DSC curves showed one peak in the presence of Cu and biobased ligands, contrary to the curves obtained for heavy oil oxidation reported with other ligands and metals. In other words, the obtained catalysts merged low-temperature- and high-temperature oxidation regions into one region. These findings reveal that the structure of ligands can significantly affect their interaction with metals in oil-soluble catalysts, and therefore the efficiency of catalysts is dramatically improved. We believe that our work could be usefully employed for further studies to clarify the mechanism of the in situ combustion behavior of heavy oil for a better impact on the environment.

Significant deviations were found between the solution enthalpy in benzene at 298.15 K and the fusion enthalpy at the melting temperature of 1,2,3,4-tetraphenylnaphthalene (3.9 +/- 0.5 kJ mol(-1) and 23.6 +/- 0.6 kJ mol(-1) (470.8 K), respectively) and 1,3,5-triphenylbenzene (20.1 +/- 0.2 kJ mol(-1) and 32.4 +/- 1.2 kJ mol(-1) (447.3 K)). These aromatic compounds are structurally related to benzene and their solution enthalpies in hypothetical liquid state at 298.15 K in benzene should be close to zero, so the differences between the solution enthalpy of crystal and the fusion enthalpy at the melting temperature should be attributed to the temperature dependence of the fusion enthalpy. Direct adjustment of the fusion enthalpy to 298.15 K requires knowledge of the supercooled liquid state heat capacity, which is hardly attainable by conventional methods due to fast crystallization. The heat capacities of 1,2,3,4-tetraphenylnaphthalene and 1,3,5-triphenylbenzene in liquid, deeply supercooled liquid, glassy and crystalline states were obtained for the first time by using fast scanning calorimetry in wide temperature ranges. Crystalline 1,2,3,4-tetraphenylnaphthalene heat capacity was measured over the temperature range from 323 to 410 K by conventional DSC. The temperature dependences of the heat capacities of the studied compounds in supercooled liquid state were fitted with the linear equations. The experimental results obtained by fast scanning calorimetry are in excellent agreement with the data obtained by solution calorimetry and conventional DSC. (C) 2019 Elsevier B.V. All rights reserved.

The solution calorimetry approach for determination of the fusion enthalpy at 298.15 K of aromatic compounds not capable of self-association was extended to those forming intermolecular hydrogen bonds. Two groups of such compounds, namely phenol and aniline derivatives, were investigated. From the solution enthalpies at 298.15 K of phenols in anisole and aromatic amines in aniline the fusion enthalpies at 298.15 K can be derived. Validity of the solution calorimetry approach was checked using differential scanning calorimetry and fast scanning calorimetry. The solution enthalpies of 12 compounds in anisole and aniline at 298.15 K and the fusion enthalpies at the melting temperature of 9 compounds were measured. Resorcinol, 1,6-dihydroxynaphthalene, and 1,3-diaminobenzene were additionally studied using fast scanning calorimetry. The molar heat capacities of crystalline 1,6-dihydroxynaphthalene and liquid 1,3-diaminobenzene were measured by conventional DSC in the wide temperature range. (C) 2019 Elsevier Ltd.

Fusion enthalpy temperature dependence is related to the difference in heat capacity of the liquid and solid. Below the melting temperature, it is hard to measure the liquid heat capacity using conventional methods due to fast crystallization. Based on an indirect solution calorimetry approach, we previously concluded that the temperature dependence of heat capacities below the melting temperature is the extrapolation of the linear function above it. In this study, we employed a fast scanning calorimetry technique to test the validity of this conclusion. Three compounds were studied: two organic glass formers, benzophenone and o-terphenyl, for which the liquid and supercooled liquid heat capacities were known to be accurately described by a linear function of temperature, and m-terphenyl, which had never been studied in the supercooled liquid state. The results were in good agreement with the literature for liquid benzophenone and o-terphenyl heat capacities above and below the melting temperature. The heat capacity of the supercooled liquid and glassy m-terphenyl was obtained for the first time. The measured molar heat capacity of supercooled liquid m-terphenyl was the linear extrapolation of the temperature dependence of the heat capacity of the melt found in the literature. The molar heat capacity of the solid, the enthalpy and fusion temperature of m-terphenyl were determined by conventional DSC. Kirchhoffs integral, calculated from the measured molar heat capacities of solid and liquid m-terphenyl, was in accordance with the fusion and solution thermochemistry data.