Pentamethylcyclopentadienyl Molybdenum(V) Complexes Derived from Iodoanilines: Synthesis, Structure, and ROP of ε-Caprolactone

The reaction of [Mo(η-C5Me5)Cl4] with the ortho-, meta-, or para-iodo-functionalized anilines 2-IC6H4NH2, 3-IC6H4NH2, 4-IC6H4NH2 yields imido or amine products of the type [Mo(η-C5Me5)Cl2(IC6H4N)] (2-I, 1, 3-I, 3, 4-I, 5) or [Mo(η-C5Me5)Cl4(IC6H4NH2)] (3-I, 2, 4-I, 4), respectively, depending on the reaction stoichiometry/conditions; we were unable to isolate an amine complex of the 2-I derivative. The reaction of [Mo(η-C5Me5)Cl4] with one equivalent of 2-I,4-FC6H3NH2 in the presence of Et3N afforded [Mo(η-C5Me5)Cl2(2-I,4-FC6H3N)]·MeCN (6·MeCN), which, upon exposure to air, afforded the Mo(VI) imido complex [Mo(η-C5Me5)Cl3(2-I,4-FC6H3N)] (7). For comparative studies, the structure of the aniline (C6H5NH2)-derived complex [Mo(η-C5Me5)Cl2(2-C6H3N)] (8) has also been prepared. The molecular structures of 1–8 have been determined and reveal packing in the form of zig-zag chains or ladders. The complexes catalyze, in the presence of benzyl alcohol under N2, the ring-opening polymerization (ROP) of ε-caprolactone affording relatively low molecular weight products. The MALDI-ToF spectra indicate that a number of polymer series bearing a variety of end groups are formed. Conducting the ROPs as melts or under air results in the isolation of higher molecular weight products, again bearing a variety of end groups. Kinetic studies reveal the aniline-derived imido complex 8 performs best, whilst a meta-iodo substituent and a Mo(V) centre are also found to be beneficial. The structures of the side products 2-IC6H4NH3Cl and 3-IC6H4NH3Cl are also reported.

Assessment of K-Struvite Precipitation as a Means of Nutrient Recovery From Source Separated Human Urine

The impact of nutrients on the environment, particularly on water bodies, has led to extensive studies for nutrient control. Within this context, studies have been focused on source separation of human urine from domestic wastewater to recover nutrients. Potassium is one of the most important components of human urine. However, data on potassium removal or recovery are quite limited except for some indirect information through use of zeolites for mostly ammonia removal. Potassium struvite or K-struvite (MgKPO4·6H2O) is a sparingly soluble salt belonging to struvite and has the potential of being used as a means of potassium and phosphate recovery from segregated human urine. This study aimed to assess the potential of K-struvite precipitation for control and recovery of nutrients. Within this context, K-struvite precipitation experiments were performed on both synthetically prepared samples and synthetic human urine solution to determine effect of operation parameters i.e. pH, stoichiometry, and temperature on potassium recovery performance. Results indicated that process performance as well as type of solid phases co-precipitated with K-struvite were closely related to initial potassium concentration, pH and reaction stoichiometry. At pH 10, the potassium recovery efficiency was maximized up to 87% by application of 100% excess dose of Mg and P for both synthetic samples and synthetic human urine solution. On the other hand, application of excess dose of K did not provide any improvement in K recovery efficiency. The effect of temperature on solubility of K-struvite was insignificant at the temperature of 24-90°C. Solid phase analyses confirmed that K-struvite was co-precipitated with either Mg3(PO4)2, MgNaPO4·7H2O, or MgHPO4·7H2O depending on pH and stoichiometry instead of a pure compound.

Influence of Uneven Secondary Air Supply and Burner Tilt on Flow Pattern, Heat Transfer, and NOx Emissions in a 500 MWe Tangential-Firing Coal Boiler

Tangential-firing boilers develop large swirling fireballs by using pulverized coal and air from the corners of the burner zone. During operation, however, the boiler may experience an uneven air supply between corners; this deforms the fireball, raising various issues concerning performance and structural safety. This study investigated the characteristic boiler performance and the role of burner tilting in a 500 MWe boiler with secondary air (SA) in two corners that are up to 1.9 times larger than those in the other corners. Computational fluid dynamics simulations with advanced coal combustion sub-models were employed with the following two sets of cases: (i) six cases of actual operation to validate the modeling and (ii) sixteen cases for the parametric study of SA flow ratio and burner tilt between −15° and +26°. The results showed that the uneven SA supply deteriorated the boiler performance in various aspects and the burner tilt can be used to alleviate its impact. With a larger SA supply from the left wind box, the mass flow, heat absorption, and O2 concentration were larger in the right half of the heat exchanger sections owing to the rotating flow. The corresponding imbalance in the reaction stoichiometry increased the peak temperature entering the tube bundles by up to 60 °C and NO emissions by 6.7% as compared with normal operations. The wall heat absorption was up to 19% larger on the right and front walls. The high burner tilt of +26° helped alleviate the impact of uneven SA supply on the heat distribution and uniformity of the flow pattern and temperature, whereas a +15° burner tilt was the least favorable.

Energetic scaling in microbial growth

Microbial growth is a clear example of organization and structure arising in nonequilibrium conditions. Due to the complexity of the microbial metabolic network, elucidating the fundamental principles governing microbial growth remains a challenge. Here, we present a systematic analysis of microbial growth thermodynamics, leveraging an extensive dataset on energy-limited monoculture growth. A consistent thermodynamic framework based on reaction stoichiometry allows us to quantify how much of the available energy microbes can efficiently convert into new biomass while dissipating the remaining energy into the environment and producing entropy. We show that dissipation mechanisms can be linked to the electron donor uptake rate, a fact leading to the central result that the thermodynamic efficiency is related to the electron donor uptake rate by the scaling law η∝μED−1/2 and to the growth yield by η∝Y4/5. These findings allow us to rederive the Pirt equation from a thermodynamic perspective, providing a means to compute its coefficients, as well as a deeper understanding of the relationship between growth rate and yield. Our results provide rather general insights into the relation between mass and energy conversion in microbial growth with potentially wide application, especially in ecology and biotechnology.

Gas Laws

Gas Laws summarizes the general laws that describe how the volume of a gas changes in response to changes in pressure (P), temperature (T in Kelvin) or the number of moles (n). The ideal gas law, which combines Boyle’s law, Charles’s law and Avogadro’s law, is presented, with explanations of using it to solve gas-law problems. Mathematical rearrangements of the ideal gas law to determine density and molar mass are described along with the use of Dalton’s law of partial pressures to find the pressure of each gas in a mixture. Finally the chapter presents ideal gas law and reaction stoichiometry, Graham’s law of effusion, and basic notions of real gases and their deviation from the ideal gas laws.

Volumetric Analysis

Volumetric Analysis describes the general process of quantifying acid-base reactions by titration in which the known concentration of one solution (often a standard solution) is used to determine the unknown concentration of another. Common terms are defined, and calculations involving acid-base titration based on the concept of reaction stoichiometry, number of moles, mole ratio and molarity are discussed. The treatment is then broadened to include calculations involving mass and percentage of substance titrated. Back (or indirect) titration, a method to determine the concentration of a volatile substance or an unknown solid that is insoluble or only partly soluble in water, is described. The Kjeldahl method of determining the nitrogen content in organic and inorganic samples is used to illustrate back titration.

Integration of complete elemental mass-balanced stoichiometry and aqueous-phase chemistry for bioprocess modelling of liquid and solid waste treatment systems – Part 1: The physico-chemical framework

Bioprocesses interact with the aqueous environment in which they take place. Currently integrated bioprocess and three-phase (aqueous–gas–solid) multiple strong and weak acid/base system models are being developed for a range of wastewater treatment applications, including anaerobic digestion, biological sulphate reduction, autotrophic denitrification, biological desulphurization and plant-wide wastewater treatment systems. In order to model, measure and control such integrated systems, a thorough understanding of the interaction between the bioprocesses and aqueous-phase multiple strong and weak acid/bases is required. This first in a series of five papers sets out a conceptual framework and methodology for deriving bioprocess stoichiometric equations. It also introduces the relationship between alkalinity changes in bioprocesses and the underlying reaction stoichiometry, which is a key theme of the series. The second paper develops the stoichiometric equations for the main biological transformations that are important in wastewater treatment. The link between the modelling and measurement frameworks, which uses summary measures such as chemical oxygen demand (COD) and alkalinity, is described in the third and fourth papers. The fifth paper describes an equilibrium aquatic speciation algorithm which can be combined with bioprocess stoichiometry to provide integrated models of wastewater treatment processes.

New insights into pathways and kinetic of magnesiothermic reduction of titanium tetrachloride in titanium metallurgy

There is still no consensus on the reaction pathways and kinetic modeling of magnesiothermic reduction of titanium tetrachloride, and the theoretical innovations are required for further research of titanium metallurgy. We determined efficient reaction pathways via chemical reaction stoichiometry methodology, and proposed an innovative kinetic modeling approach of magnesiothermic reduction of titanium tetrachloride. We explained the reaction pathways by the steps of the phase change near the gas-liquid interfaces, the homogeneous reaction in the gas phase, the heterogeneous reduction near the gas-liquid interfaces, and the like dissolves like in the liquid phase. Net chemical reaction rate of titanium sponge decreased with decreasing of titanium tetrachloride feeding rata and with increasing of gauge pressure. The excellent fitness of the reaction rate constants, f(Δp) and k(Tin), show that the proposed kinetic equation accuately describes the reaction mechanism, and is reasonable and acceptable for magnesiothermic reduction of titanium tetrachloride in titanium metallurgy.

Non-Equilibrium Thermodynamics View on Kinetics of Autocatalytic Reactions—Two Illustrative Examples

Autocatalytic reactions are in certain contrast with the linear algebra of reaction stoichiometry, on which rate equations respecting the permanence of atoms are constructed. These mathematical models of chemical reactions are called conservative. Using a non-equilibrium thermodynamics-based theory of chemical kinetics, it is shown how to introduce autocatalytic step into such (conservative) rate equation properly. Further, rate equations based on chemical potentials or affinities are derived, and conditions for the consistency of rate equations with the entropic inequality (the second law of thermodynamics) are illustrated. The theory illustrated here can be viewed as a tool for verifying and generalizing traditional mass-action kinetics by means of modern non-equilibrium thermodynamics, which is able to deal also with such rather problematic cases.

Na, K-ATPase as a biological target for gold(III) complexes: a theoretical and experimental approach

Background: Gold-based complexes represent a new class of potential metallodrugs. Although their action mechanism is not entirely understood, it was shown that gold complexes inhibit some enzymes’ activities. One among them, Na,K-ATPase is emerging as an essential target for various anticancer drugs. The functionalization of nanoparticles by gold(III) complexes could facilitate their delivery into the cells and enable the following of their distribution in the target tissues. Objective: The paper presents an overview of Na, K-ATPase interaction with representative and structurally related cytotoxic gold(III) complexes. The results obtained by the employment of theoretical methods (DFT and docking studies) combined with the experimental approach involving a variety of nanotechnology-base techniques (UV/Vis, Raman and fluorescence spectroscopy, CD, AFM, DLS) are discussed. Detailed information was gained on the enzyme’s conformational and structural changes upon binding the gold(III) complexes. The experimentally determined reaction parameters (constants of dissociation and the reaction stoichiometry) were predicted theoretically. Conclusion: The presented results offer further support to the view that Na,K-ATPase may be a relevant biomolecular target for cytotoxic gold(III) compounds of medicinal interest.