Thermodynamics Of Pharmaceutical Systems An Introduction To Theory And Applications Pdf


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Thermodynamics is a branch of physics that deals with heat , work , and temperature , and their relation to energy , radiation , and physical properties of matter. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities , but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering , especially physical chemistry , biochemistry , chemical engineering and mechanical engineering , but also in other complex fields such as meteorology. The initial application of thermodynamics to mechanical heat engines was quickly extended to the study of chemical compounds and chemical reactions.

THERMODYNAMICS OF PHARMACEUTICAL SYSTEMS

Experiments are always the go-to approach to reveal mysterious observations and verify new theories. However, scientific research has shifted to areas that are difficult to probe experimentally. Fortunately, computational approaches, such as molecular simulation, became available. With a rigorous theoretical foundation and microscopic insights, molecular simulation could explore unknown territories in physics and validate macroscopic theories.

Grand challenges in petroleum engineering require knowledge at the molecular scale more than ever, such as the behavior of confined fluids in shale nanopores. Although it is widely used in materials science, biophysics, and biochemistry, molecular simulation has been underutilized in subsurface modeling. However, the complexity of the subsurface systems and the heterogeneity of reservoir fluids, which currently challenge both our continuum modeling approaches and experimental techniques, could benefit from molecular insights.

In this Review, we briefly present the basics of molecular simulation and a few applications addressing current petroleum engineering challenges. These applications include 1 phase equilibria, where molecular simulation handles inaccessible experimental conditions such as high pressure, high temperature, or a toxic environment; 2 asphaltene aggregation, where molecular simulation enables the synthesis and evaluation of the solvent performance; 3 low-salinity water flooding, where molecular simulation reveals the key mechanisms; and 4 shale reservoirs, where molecular simulation derives the new physics controlling the transport phenomena in these reservoirs.

Our goal is to demonstrate that the molecular models can shed some light on numerous subsurface applications, moving toward more predictive physics-based models to optimize and control subsurface systems. Raman spectroscopy, as a rapid, high-precision, and nondestructive tool, can be used for analyzing the samples from gas to solid, from ex situ to in situ, from organic macromolecule to minerals.

It has been demonstrated as a powerful tool for characterizing carbonaceous solid fuels and their thermal conversion products. This review provides a systematic overview of the application of Raman spectroscopy for investigating the entire thermochemical processing of coal, biomass, and wastes. After introducing the fundamentals of Raman spectroscopy, its application for characterizing the feedstock raw coals, biomass, and wastes is reviewed.

Then, using the Raman spectroscopy for ex situ characterization of the products char and ash after reactions and in situ diagnostic during reactions are discussed. Besides, some potential advanced Raman spectroscopy techniques are further briefly introduced. Lastly, the challenges and prospects of using Raman spectroscopy to study thermochemical processes are discussed.

Enhancing oil recovery by injecting CO2 into the reservoirs is a widely employed technique in the oil industry. The density of solutions is a key property to affect the performance and design of CO2-enhanced oil projects.

A comprehensive review is presented on the available density data and correlations of the equation of state EOS for CO2—alkane binary and ternary solutions in this paper.

A sufficient set of data is available for CO2—alkane binary solutions, especially for CO2—decane solutions; however, for the rest of the CO2—alkane binary solutions, data of density are limited to a certain range of pressure and temperature at the phase-equilibrium and compressed-liquid states. Furthermore, data on CO2—alkane ternary solutions are limited. The temperatures and pressures in the seven available data sets reach From the validations of four selected EOS correlations, viz.

Research on gas hydrates is relevant to many industrial issues including flow assurance in oil and gas production and transportation, exploitation of new energy deposits in the form of natural gas hydrates, gas storage, separation, and more. The thermodynamic modeling of a gas hydrate formation is a fundamental work for all gas hydrate research. Since the establishment of the Chen—Guo model in the s, it has achieved wide applications in modeling of hydrate formation thermodynamics, kinetics, and hydrate-based technical processes.

The aim of this review is to summarize these applications, extensions, and modifications to the Chen—Guo model as well as the two-step mechanism in recent years. Almost references have been cited in this review.

We hope it will be helpful for the gas hydrate community. The wetting characteristics of shale rocks at representative subsurface conditions remain an area of active debate. A precise characterization of shale wettability is essential for enhanced oil and gas recovery, containment security during CO2 geo-storage, and flow back efficiency during hydraulic fracturing. While several methods were utilized in the literature to evaluate shale wettability e.

The objectives of this review are to a develop a repository of the recent shale wettability data sets using contact angle measurements at high pressure and temperature HPHT conditions, b explore the factors influencing shale wettability, c identify potential limitations associated with contact angle methods, and d provide a research outlook for this area.

The key contributing factors that underpin this high shale wettability variability include, but are not limited to, operating pressure and temperature conditions, total organic content TOC , mineral matter, and thermal maturity conditions. Thus, this review provides a succinct analysis of the shale wettability contact angle data sets and affords an overview of the current state of the art technology and possible future developments in this area to enhance the understanding of shale wettability.

Cerium oxides CeOx have been studied extensively as low-temperature SCR catalysts since they manifest prominent oxygen storage capacity in catalysis. This paper reviews the recent progress on the Ce-based catalysts for low-temperature SCR de-NOx with NH3, including three categories, single CeOx, Ce-based multimetal oxide, and Ce-based multimetal oxides with support. In the section on single CeOx, the reasons for the significant catalytic activity and the function of CeOx in the catalytic reactions are systematically reviewed.

For multimetal oxide catalysts, the various roles played by the components of catalysts are summarized from several aspects. In the introduction of supported metal oxide catalysts, according to the type of support, the function of each support in the reaction is analyzed methodically.

Finally, the development outlook and direction of the application of cerium oxide-based catalysts in the field of low-temperature SCR of NOx is prospected. The failure to match field data and laboratory-scale evidence of non-Darcy flow has led researchers to propose various gas-flow models for the shale reservoirs. There is extensive evidence that suggests the size of the pores in shale is microscopic in the range of a few to hundreds of nanometers also known as nanopores.

This work reviews the dominant gas-flow processes in a single nanopore on the basis of theoretical models and molecular dynamics simulations, and lattice Boltzmann modeling. We extend the review to pore network models used to study the gas permeability of shale. At a constant but low range of salinities, the longer alkyl chain IL exhibited a lower IFT value in the presence of diluted seawater dSW than the diluted formation water dFW.

The oil film after water flooding is a very important type of microscopic residual oil for an oil-wet reservoir. In this study, an artificial oil film model was designed to simulate the micro residual oil absorbed on the rock surface. Numerous experiments were carried out to explore the detachment mechanisms of two kinds of crude oil films and oil recovery performances in different fluid media with the flow rate. The results show that the increasing flow rate positively affects the oil film detachment but is still limited in the action area and displacement efficiency.

It is also found that surfactants with different interfacial tensions IFTs and emulsification behaviors all can promote the dislodging of the oil film. The results show that the most important factor contributing to the detachment of the oil film is the emulsification rather than IFT reduction. Strong emulsification is useful to lessen the thickness of the oil film and disperse the oil droplets into a smaller size without considering the flow rate.

This paper also provides evidence that, for the case of a higher proportion on heavy components of crude oil, strong emulsification capability is the chief driver for the oil enhancement mechanism for surfactant flooding. The well-developed tectonically deformed coals TDCs and the high heterogeneity of coalbed methane CBM occurrence severely restrict the sustainable development of the CBM industry in structurally complex areas.

To better understand micro- and mesopore structures 0—50 nm of TDCs and their influence on methane adsorption properties, we conducted methane adsorption tests and multifractal characterization based on N2 and CO2 gas adsorption tests on samples with different degrees of brittle deformation.

Multifractal analyses indicate that the pore volume PV and pore surface area PSA distributions of micro- and mesopores have multifractal characteristics. The multifractal dimensions can be used to quantitatively characterize the heterogeneity and continuity of PV and PSA distributions.

Correlation analyses demonstrated that the multifractal properties of the PV and PSA distributions of micro- and mesopores are significantly influenced by pore structure changes related to coal deformation. Interestingly, the multifractal dimensions of pore size distributions both the PV and PSA distributions, particularly 1—10 nm pores have significant negative correlations with the methane adsorption properties of coal, indicating that a uniform pore size distribution is favorable for a high maximum methane adsorption capacity.

The increase in 1—10 nm pore occurrence due to tectonic activity also enhanced the adsorption capacity of strongly deformed coals. The influences of coal deformation on the methane adsorption capacity of coal could be attributed to two aspects: increase in the PV and PSA of 1—10 nm pores and decrease in heterogeneity differences of pore size distributions. These two effects result in a higher gas content and pressure in the distribution areas of strongly deformed coals, which lead to higher risks of gas-related disasters.

Surfactant adsorption is a major problem encountered with the surfactant polymer flooding. A lot of additives have been used in this regard to tackle this problem. In the present study, a mixture of a nonionic and an anionic surfactant was used to investigate its effect on the various aspects of the surfactant polymer flooding.

The effect of temperature and the nonionic surfactant concentration on the critical micelle concentration of the anionic surfactant was explored. The adsorption behavior of the surfactant mixture on the sand particles was explored by comparing the initial and final concentrations of the surfactant mixture.

The adsorption data were fitted in the different adsorption isotherms Langmuir, Freundlich, and Temkin. The interfacial property and the rock wetting characteristics of the surfactant mixture were investigated by measuring the surface tension and contact angle, respectively.

Next, the viscosity of the chemical slug surfactant and polymer was analyzed at different temperatures. The viscosity results were fitted in the power law model to understand the fluid flow behavior.

Finally, the sand pack flooding experiments were performed using the chemical slug composed of a surfactant mixture and an industrial-grade polymer. Also, the binary surfactant mixture achieved an ultralow interfacial tension value of 0.

The pore structure characteristics of shale reservoirs are an intense research topic in unconventional oil and gas exploration and development. With an increase in temperature, abundant liquid hydrocarbons will undergo secondary cracking to generate wet gas. The thermal simulation samples mainly develop wedge-shaped or slit-shaped pores. The pore size distribution mainly exists within the bimodal distributions 0. The residue of liquid hydrocarbons can block some mesopores and macropores, which is shown by comparing the pore volume before and after Soxhlet extraction.

Moreover, the pore structure of the samples is more complex than the pore surface during the hydrocarbon evolutionary process. The pore evolution of shale can be divided into three stages: the complex development stage of pores in the low-maturity stage, the massive development stage of pores in the middle maturity to high-maturity stage, and the uniform development stage of pores in the overmature stage.

Additionally, during the entire thermal evolution of shale, residual oil and diagenesis are the main factors affecting the differential development of pores and the variation in the fractal dimension.

Fourier transform infrared spectroscopy, nuclear magnetic resonance hydrogen spectra, and thermogravimetric analysis were utilized to explore their structure and thermal stability.

It indicated that the two hyperbranched demulsifiers had good thermal stability. To evaluate their demulsification performance, some important factors such as concentration of the demulsifier, types of emulsion, temperature, and settling time were systematically investigated. The corresponding oil removal rate reached as high as The possible demulsification mechanism was discussed by the interfacial tension, zeta potential, and micrograph analysis.

The current work provided new hyperbranched demulsifiers, and the discussion on the mechanism also provided some references for the research of a demulsifier. Knowing of gas shale permeability reduction is vital for gas production from shale gas reservoirs stimulated by multistage hydraulic fracturing. However, the role of shale matrix permeability reduction is not well addressed for evaluating the contribution on gas well production.

In this study, the experiments of slickwater treatment at different injection pressures, injection volumes, and slickwater compositions were conducted by using an experimental apparatus based on the steady-state method. The results show that slickwater flow in the core is seriously affected by microfracture. The cumulative gas volume through the core with microfracture increases nearly linearly with time.

Then, we analyzed the effect of injection pressure gradients, injection volume, and slickwater compositions on the permeability reduction and flowback efficiency.

The permeability reduction and flowback efficiency both increase slightly at beginning and then nearly linearly in the middle and gradually at last with the increase of injection pressure gradient.

Permeability reduction and flowback efficiency both decrease quickly at first and then slightly with the increase of injection volume, indicating only a small proportion of slickwater, which occupied much more small pores, can be displaced and flow back to the entrance piece of core sample.

The permeability reduction and flowback efficiency after different chemical solution treatments are in the order from highest to lowest of cleanup additive, slickwater, clay stabilizer, defoamer, and friction reducer, indicating the synergy effect of slickwater compositions on the permeability reduction and flowback efficiency.

These results can be helpful for optimizing the slickwater formulation and understanding the damage mechanism of shale formation during hydraulic fracturing.

Thermodynamics

Experiments are always the go-to approach to reveal mysterious observations and verify new theories. However, scientific research has shifted to areas that are difficult to probe experimentally. Fortunately, computational approaches, such as molecular simulation, became available. With a rigorous theoretical foundation and microscopic insights, molecular simulation could explore unknown territories in physics and validate macroscopic theories. Grand challenges in petroleum engineering require knowledge at the molecular scale more than ever, such as the behavior of confined fluids in shale nanopores. Although it is widely used in materials science, biophysics, and biochemistry, molecular simulation has been underutilized in subsurface modeling. However, the complexity of the subsurface systems and the heterogeneity of reservoir fluids, which currently challenge both our continuum modeling approaches and experimental techniques, could benefit from molecular insights.

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Thermodynamics

An introductory text that covers the fundementals of thermodynamics as it applies to pharmaceutical science, the new edition explores topics such as drug discovery and drug delivery, supramolecular chemistry, molecular recognition, and nanotecnologies in greater depth. This book introduces students of pharmacy to the profound thermodynamic applications in the laboratory while also serving as a handy resource for practicing researchers. Preis inkl. MwSt, zzgl.

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