Chemical reactions

A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the nuclei (no change to the elements present), and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive elements where both electronic and nuclear changes can occur. The substance (or substances) initially involved in a chemical reaction are called reactants or reagents. Chemical reactions are usually characterized by a chemical change, and they yield one or more products, which usually have properties different from the reactants. Reactions often consist of a sequence of individual sub-steps, the so-called elementary reactions, and the information on the precise course of action is part of the reaction mechanism. Chemical reactions are described with chemical equations, which symbolically present the starting materials, end products, and sometimes intermediate products and reaction conditions. Chemical reactions happen at a characteristic reaction rate at a given temperature and chemical concentration. Typically, reaction rates increase with increasing temperature because there is more thermal energy available to reach the activation energy necessary for breaking bonds between atoms. A reaction may be classified as redox in which oxidation and reduction occur or non-redox in which there is no oxidation and reduction occurring. Most simple redox reactions may be classified as a combination, decomposition, or single displacement reaction. Different chemical reactions are used during chemical synthesis in order to obtain the desired product. In biochemistry, a consecutive series of chemical reactions (where the product of one reaction is the reactant of the next reaction) form metabolic pathways.

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MSE-101(a): Materials:from chemistry to properties

Ce cours permet l'acquisition des notions essentielles relatives à la structure de la matière, aux équilibres et à la réactivité chimique en liaison avec les propriétés mécaniques, thermiques, électri

MSE-431: Physical chemistry of polymeric materials

The student has a basic understanding of the physical and physicochemical principles which result from the chainlike structure of synthetic macromolecules. The student can predict major characteristic

ENV-200: Environmental chemistry

This course provides students with an overview over the basics of environmental chemistry. This includes the chemistry of natural systems, as well as the fate of anthropogenic chemicals in natural sys

In chemistry, the empirical formula of a chemical compound is the simplest whole number ratio of atoms present in a compound. A simple example of this concept is that the empirical formula of sulfur monoxide, or SO, would simply be SO, as is the empirical formula of disulfur dioxide, S2O2. Thus, sulfur monoxide and disulfur dioxide, both compounds of sulfur and oxygen, have the same empirical formula. However, their molecular formulas, which express the number of atoms in each molecule of a chemical compound, are not the same.

A nonmetal is a chemical element that, in the broadest sense of the term, has a relatively low density and high electronegativity; they range from colorless gases (like hydrogen) to shiny solids (like carbon, as graphite). They are usually poor conductors of heat and electricity, and brittle or crumbly when solid due to their electrons having low mobility. In contrast, metals are good conductors and most are easily flattened into sheets and drawn into wires since their electrons are generally free-moving.

HSAB concept is a jargon for "hard and soft (Lewis) acids and bases". HSAB is widely used in chemistry for explaining stability of compounds, reaction mechanisms and pathways. It assigns the terms 'hard' or 'soft', and 'acid' or 'base' to chemical species. 'Hard' applies to species which are small, have high charge states (the charge criterion applies mainly to acids, to a lesser extent to bases), and are weakly polarizable. 'Soft' applies to species which are big, have low charge states and are strongly polarizable.

Water quality and the biogeochemical engine

Learn about how the quality of water is a direct result of complex bio-geo-chemical interactions, and about how to use these processes to mitigate water quality issues.

Sorption and transport in cementitious materials

Learn how to study and improve the durability of cementitious materials.

Cement Chemistry and Sustainable Cementitious Materials

Learn the basics of cement chemistry and laboratory best practices for assessment of its key properties.

Background: Overexpression of the transsulfuration enzyme cystathionine-beta-synthase (CBS), and overproduction of its product, hydrogen sulfide (H2S) are recognized as potential pathogenetic factors in Down syndrome (DS). The purpose of the study was to determine how the mitochondrial function and core metabolic pathways are affected by DS and how pharmacological inhibition of CBS affects these parameters. Methods: 8 human control and 8 human DS fibroblast cell lines have been subjected to bioenergetic and fluxomic and proteomic analysis with and without treatment with a pharmacological inhibitor of CBS. Results: DS cells exhibited a significantly higher CBS expression than control cells, and produced more H2S. They also exhibited suppressed mitochondrial electron transport and oxygen consumption and suppressed Complex IV activity, impaired cell proliferation and increased ROS generation. Inhibition of H2S biosynthesis with aminooxyacetic acid reduced cellular H2S, improved cellular bioenergetics, attenuated ROS and improved proliferation. C-13 glucose fluxomic analysis revealed that DS cells exhibit a suppression of the Krebs cycle activity with a compensatory increase in glycolysis. CBS inhibition restored the flux from glycolysis to the Krebs cycle and reactivated oxidative phosphorylation. Proteomic analysis revealed no CBS-dependent alterations in the expression level of the enzymes involved in glycolysis, oxidative phosphorylation and the pentose phosphate pathway. DS was associated with the dysregulation of several components of the autophagy network; CBS inhibition normalized several of these parameters. Conclusions: Increased H2S generation in DS promotes pseudohypoxia and contributes to cellular metabolic dysfunction by causing a shift from oxidative phosphorylation to glycolysis.

ELSEVIER2022

Delayed Hydride Cracking in Irradiated and Unirradiated Zircaloy-2 Cladding

Aaron William Colldeweih

Zirconium alloys used in the nuclear industry are exposed to extreme conditions undergoing high levels of irradiation damage and corrosion. Zircaloy-2 is used as nuclear fuel cladding in boiling water reactors and for the encapsulation of the spallation target in the neutron source SINQ at the Paul Scherrer Institute. As a result of oxidation, hydrogen is produced and partially taken up into the zirconium matrix. As the hydrogen reaches the solubility limit, it precipitates in the form of a zirconium hydride. A number of deleterious effects of hydrides have been extensively studied, including the embrittlement of the material and a unique cracking phenomenon, namely delayed hydride cracking (DHC). DHC occurs as hydrogen in solid solution diffuses towards locations of higher tensile stress, where it subsequently precipitates as the local solvus limit is reached. Once the hydride grows to a critical size, it fractures, which can continue to propagate in repeated steps by the same mechanism.Several studies have been performed in order to understand properties of DHC based on parameters like, alloy type, cracking temperature, hydrogen content, and cracking direction. The most important mechanical properties include the fracture toughness and cracking velocity, which governs the material failure conditions. Crystallographic properties have been investigated in order to understand how complex hydride precipitation develops within the context of DHC conditions. In this project, radial DHC is explored in irradiated and unirradiated thin-walled Zircaloy-2 nuclear fuel cladding with and without an inner liner, in addition to spallation target rod material. A unique three-point bending test, applicable also for irradiated samples in the hotlab, was developed to induce a consistent radially propagating outside-in crack. Results have provided insight into the effects of the inner liner on cracking velocity, showing correlations with the hydrogen depletion. The combined DHC and creep mechanisms, which cannot be decoupled, is coined as âcreep-delayed hydride crackingâ. As the initiating conditions for DHC are of great technical importance, the threshold stress intensity factor has been investigated, under ideal DHC conditions, where a minimum value occurs around 6 MPaâm. Quantitative analysis of the hydrogen distribution around the tip of an arrested DHC crack tip has been performed with neutron radiography at the SINQ. Trends show that the hydrogen concentration around the crack tip increases with temperature resulting likely from the larger hydrogen diffusion, and that the liner reduces the hydrogen available for DHC. Crystallographic analysis has provided insight on the hydride phases responsible for DHC with synchrotron micro X-ray diffraction, performed at the Swiss Light Source at PSI. The results directly suggest that the Î³-hydride is a stable phase precipitated at low temperatures. Testing of irradiated material provided insight into the crack initiation of DHC as a result of the strongly irregular outer surface generated from the oxidation. The propagation pattern is highly irregular compared to the unirradiated material due to the embrittled nature of the cladding from irradiation damage.

EPFL2022

Model-based scale-up of a continuously operated consolidated bioprocess based on a microbial consortium for the production of ethanol

David Beat Dempfle

This work demonstrated that consolidated bioprocessing is a promising concept for conversion of lignocellulose to ethanol at industrial scale. CBP offers great cost saving potential, is feasible to be operated continuously and may be scaled up due to extensive knowledge of the process from a chemical engineering point of view.Cost savings of up to 27.5% of the total costs compared to conventional bioethanol production from lignocellulose, as stated by a techno-economic assessment, make continuous CBP the strongest lever to reduce processing costs of lignocellulosic ethanol. A cost sensitivity analysis identified scale and yield as the main cost-pushers from a process point of view, whereas the price level of the plant location has the highest impact on the investment conditions.To prove the feasibility of continuous CBP, and therefore the mentioned cost savings, experiments with a maximum titer of 3.258±0.007 g/L, a productivity of 0.025 g/(Lh) and constant enzyme production over 750h were conducted. Furthermore, the continuous experiments showed that experiments with identical volumetric oxygen transfer rate k_L a, but different oxygen fluxes per membrane area, showed titer differences of ca. 80% (1.83 g/L vs 3.26 g/L) in favor of setups with the large membrane surface. A rigorous process model was developed for continuously operated CBP. 9 species were considered (oxygen, glucose, total concentration Trichoderma reesei, secondary mycelia concentration of T. reesei, enzymes, cellulose, cellobiose, yeast density and ethanol). 8 of these 9 species needed to be modelled spatially resolved to account properly for mass transfer limitations. The fungal biofilm thickness d_f was found to be a critical parameter with an optimum for every membrane configuration. Smaller d_f reduced the fungal biofilm volume and thus, the enzyme production and larger d_f increased the diffusion path length causing shortage in nutrient supply as well as lower enzyme concentrations in the bulk. The enzyme synthesis rate of the secondary mycelia was fitted by reducing it by ca. 40% (0.67 FPU/(mLd) vs 1.152 (FPU/(mL*d) compared to batch models.With the process model as centerpiece, a scale-up framework consisting of the model and a set of non-dimensional parameters was developed to scale CBP from 2.7L laboratory scale to 130L pilot scale. The majority of the non-dimensional parameters could be kept constant during scale-up as requested by the similarity paradigm. Necessary changes were simulated with the model. Again, the fungal biofilm thickness d_f proved to be a relevant parameter for scale-up considerations. In general, the relative loss of biofilm volume is compensated by longer residence times since the residence time has by far the least impact on the process economics.Finally, popular rate-controlled separation techniques were investigated regarding their potential with CBP, since they offer the potential to reduce yeast inhibition, to avoid separation limitations by the azeotrope and they are not bound to the vapor-liquid-equilibrium of highly diluted ethanol-water mixtures. However, most of the mechanisms fail to handle the solids of the fermentation broth. Pervaporation, being the most promising concept for in-situ product removal, would be a cost-saving alternative to distillation for batch operation, but is limited by an unfavorable vapor-liquid equilibrium due to low bulk concentrations during continuous operation.

EPFL2022

Covers coordination numbers, common ligands, and preferred geometries in coordination chemistry, emphasizing the spatial distribution between ligands and the role of d⁸ electron configurations.

Explores the sulfur and nitrogen cycles, discussing bacterial diversity, key compounds, biogeochemistry, and environmental impacts.

Explores microbial processes in the sulfur cycle and energy conservation mechanisms.

Chemical substances

A chemical substance is a form of matter having constant chemical composition and characteristic properties. Chemical substances can be simple substances (substances consisting of a single chemical element), chemical compounds, or alloys. Chemical substances that cannot be separated into their simpler constituent elements by physical means are said to be 'pure'; this notion intended to set them apart from mixtures.

Organometallic chemistry

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide (metal carbonyls), cyanide, or carbide, are generally considered to be organometallic as well.

Organic compound

In chemistry, many authors consider an organic compound to be any chemical compound that contains carbon-hydrogen or carbon-carbon bonds, however, some authors consider an organic compound to be any chemical compound that contains carbon. The definition of "organic" versus "inorganic" varies from author to author, and is a topic of debate. For example, methane () is considered organic, but whether some other carbon-containing compounds are organic or inorganic varies from author to author, for example halides of carbon without carbon-hydrogen and carbon-carbon bonds (e.