Thermogenesis: Determination of thermokinetic parameters

This work analyses the performance of the method of obtaining the time constant (rate reaction constant) defining a first-order process after the deconvolution of the experimental record given by a heat conduction calorimeter. The analysis is carried out for different signal/noise ratios and the results given in relative time and frequency scales.     

Phenomenological thermokinetic analysis of coffee husk pyrolysis: a study case

Journal of Thermal Analysis and Calorimetry - The thermokinetic analysis of the pyrolytic degradation of coffee husk reveals that the degradation path of its main pseudo-components at the maximum...     

Influence of neodymium content on the catalytic properties of zeolite NDHNaY

The influence of neodymium content on the catalytic properties of a HNaY zeolite was investigated using the cracking of n-heptane as model reaction. Neodymium zeolites were found to be more active for cracking and hydrogen transfer reactions than zeolites containing lanthanum, cerium or praseodymium.

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Study on the thermokinetic properties of bacterial growth

The power-time curves of bacterial growth at different temperatures were determined by using the 2277 Thermal Activity Monitor (Sweden). From these curves, the growth rate constant () and activation energy (E _a) were calculated. According to the transition state theory of reaction dynamics, the activation entropy (S), activation Gibbs free energy (G) and equilibrium constant (K ) of the activation state could be calculated. These results permitted thermodynamic analysis of the bacterial growth metabolism.Supported by the Natural Science Foundation of Shandong Province.     

镨配合物的热化学及其对酵母菌作用的热动力学研究

用六水合氯化镨、硫代脯氨酸(C4H7NO2S)和水杨酸(C7H6O3)合成了三元固体配合物[Pr(C7H5O3)2(C4H6NO2S)]-2H2O.根据盖斯定律设计一个热化学循环,用溶解-反应量热法研究得到合成反应的标准摩尔焓变为(133.70±1.02)kJ/mol,配合物298.15K时的标准摩尔生成焓为-(2909.3±3.2)kJ/mol.用TAMair微量热仪测定其在28.00℃时对粟酒裂殖酵母作用的产热曲线,进而算出在配合物作用下,酵母菌生长代谢的最大发热功率Pmax、速率常数κ、传代时间tG、抑制率I和半抑制浓度cI,50等热动力学参数.结果表明:稀土水杨酸硫代脯氨酸配合物在低浓度下对酵母菌有刺激作用,高浓度下为抑制作用,即稀土配合物对微生物的生长具有双向生物效应,也称为Hormesis效应.     

Influence of doping with indium and neodymium on energy characteristics of barium cerate

A new compound with the composition BaCe0.8Nd0.1In0.1O2.9 has been synthesized. The influence of doping with indium and neodymium on the energy characteristics of barium cerate, necessary to improve the range of devices, has been studied. It has been found that the lattice enthalpy of BaCe0.8Nd0.1In0.1O2.9 is greater than the lattice enthalpy of BaCe0.8Nd0.2O2.9 and BaCe0.7Nd0.2In0.1O2.85, which allows us to consider the investigated compound as a promising representative of solid-state compounds for various applications.     

Thermodynamic and thermokinetic study on pyrolysis process of heavy oils

Enthalpy of pyrolysis and its variation in the pyrolysis process of four heavy oils: Daqing vacuum residue (DQVR), Karamay vacuum residue (KRVR), Liaohe vacuum residue (LHVR), and Venezuela vacuum residue (VNVR), have been quantitatively studied by differential scanning calorimetry associated with thermogravimetry. The results indicate that overall enthalpies at different heating rates show a linear trend with respect to the final coke yields in the thermal analysis. Classical kinetic method (Friedman method) is used to further analyze pyrolysis enthalpy variation in the pyrolysis process and determine the thermokinetic parameters. The main stage of thermal reaction (conversion ranges from 0.1 to 0.9) could be described by 1.5 order reaction model for four heavy oils. The mean activation energies determined by Friedman method are 216.3, 194.9, 173.9, and 168.7 kJ mol^?1 for DQVR, KRVR, LHVR, and VNVR, respectively. It means that endothermic enthalpy of pyrolysis in the thermal process of VNVR is easier to change compared with other oil sample cases. For the sake of simplification of kinetic treatment, Sharp method is tentatively used to perform kinetic analysis. The comparison between results from two methods indicates that activation energies from Sharp method are valid to a certain degree under the condition that the mechanism of thermal process is properly chosen although isoconversional method (Friedman method) is recommended and thought to be the better way.     

绝热式热动力学的研究III:二级反应的热谱解析

本文建立了二级发应在绝热系统中的热动力学研究, 并用自制的绝热式自动量热计, 研究了几个放热反应体系的热动力学, 而且对吸热反应体系的热动力学研究进行了探索。     

单细胞视角下铅的体内代谢与检测

在全球工业需求和储能需求持续增加的背景下,铅污染仍然是当前主要的环境问题之一。持续的铅暴露导致了复杂的体内毒理效应,其临床治疗效果受限于铅检测技术的缺乏与铅动力学研究的不足。单细胞水平上铅的检测技术,可以揭示动力学相关的细胞机制,从微观角度考量细胞异质性对人体内铅运输和铅分布的影响。分析了铅污染现状并归纳了铅暴露源特征,总结了单细胞水平上铅代谢与检测方面的研究进展。细胞机制与细胞异质性对完善铅的动力学模型和理解有关机制的作用不容忽视。单细胞检测技术作为有效的研究工具,包括流式细胞技术、质谱流式细胞技术以及基于电感耦合等离子体质谱的单细胞电感耦合等离子体质谱技术、电感耦合等离子体飞行时间质谱技术和激光烧蚀-电感耦合等离子体质谱技术等,需要更加标准化与体系化的检测方案。基于生物数学模型与单细胞检测技术的发展,单细胞视角下铅的动力学研究有望进一步细化与完善。     

绝热式热动力学的研究4: 可逆反应的热谱解析

本文建立了可逆反应在绝热系统中的热动力学研究法, 并用自制的绝热式自动热量计, 研究了三个可逆反应体系的热动力学, 验证了本文方法的正确性。     

Glycine adsorption on a mercury electrode modified by neodymium

Ranges of neodymium reduction potentials in aqueous solutions of potassium chloride at pH = 2 and in solutions containing glycine were determined by differential pulse polarography. The glycine complex with neodymium is not formed in the range of the amino acid concentration 0.001–0.12 M. Glycine adsorption on a mercury electrode and on an electrode modified with neodymium was studied by the cyclic voltammetry method.     

Polymerization of isoprene on a modified “neodymium” catalytic system

Polymerization of isoprene using the catalytic system NdCl₃·3i-C₃H₇OH-Al(i-C₄H₉)₃ modified with methylalumoxane was studied. The kinetic parameters of the process and the molecular characteristics of the polyisoprene obtained were determined.     

Quality and limits of a thermokinetic method to study gas—solid interactions

In order to test the qualities and limits of a thermokinetic method for the determination of adsorption rates, the adsorption of separate doses of oxygen on an initially nearly stoichiometric nickel oxide was studied at 473 K by two independent methods: calorimetry and pressure measurements.The calorimetric curves were corrected for instrumental distortion and compared with the results based on pressure curves. The following aspects of the correction procedure are discussed: determination of the instrument response function, smoothing procedure, influence of the ratio of the velocities of the instrument response and of the reaction under study.     

Development and use of a constant flow stirred thermokinetic reactor (steady-state TKR)

In addition to studies of reaction kinetics by a transient method in a batch reactor (nonsteady-state), such studies should also be carried out by continuous operation in a stirred-flow reactor (steady-state). Only in this way, for instance, can the extent be recognized to which the simplifying assumptions often made in the evaluation of industrial kinetics from transient investigation are reasonable and whether the kinetics obtained are applicable to complex reactor design. The thermokinetic reactor (TKR), with which it has only been possible to measure the rate of heat evolution in experiments under transient conditions (batch TKR), has now been modified so that investigations can also be carried out in the stirred-flow manner (steady-state TKR).

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Zusammenfassung Neben reaktionskinetischen Untersuchungen in diskontinuierlicher Arbeitsweise sollten tunlichst solche in kontinuierlicher Arbeitsweise (steady-state) durchgeführt werden. Nur dadurch ist beispielsweise zu erkennen, inwieweit die bei der Eruierung einer Formalkinetik aus diskontinuierlich durchgeführten Versuchen oft gemachten, vereinfachenden Annahmen vertretbar sind und die erarbeitete Formalkinetik für komplexe Reaktionsplanung verwendbar ist. Der Thermokinetische Reaktor TKR, mit dem es bisher nur möglich war, in diskontinuierlich durchgeführten Versuchen den zeitlichen Verlauf der Wärmeproduktionsrate zu messen (Batch TKR) wurde dahingehend weiterentwickelt, daß nunmehr auch Versuche in kontinuierlicher Arbeitsweise durchgeführt werden können (steady-state TKR).

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Separation of samarium and neodymium: a prerequisite for getting signals from nuclear synthesis

(146)Sm (T(1/2) = 10(8) y) is a long-lived radionuclide which has been produced in significant amounts during burning in a supernova (SN). Detection of this SN produced long-lived radionuclide on Earth may be helpful for getting information on nuclear synthesis at the time of our solar system's formation. Only accelerator mass spectrometry (AMS) can determine such minute traces of (146)Sm still expected in the Earth's crust. However, the villain of (146)Sm measurement through AMS is its naturally occurring stable isobar (146)Nd which is a million times more abundant than the trace amount of (146)Sm. Therefore an efficient method for the separation of samarium and neodymium is required to measure (146)Sm through AMS. A simple liquid-liquid extraction (LLX) based method for separation of samarium and neodymium has been developed using radiometric simulation. Di-(2-ethylhexyl)phosphoric acid (HDEHP) has been used as the organic reagent. A very high separation factor ( approximately 10(6)) can be achieved when a solution containing samarium and neodymium is reduced by hydroxylamine hydrochloride followed by extraction with 0.1% HDEHP diluted in cyclohexane from 0.025 M HCl solution.     

Copolymerization of 1,3-butadiene and styrene with a neodymium catalyst

Homo- and copolymerization of butadiene and styrene in the presence of the catalyst system Nd(octanoate)₃/CCl₄/Al(iBu)₃ (iBu: isobutyl) were investigated at 60°C in heptane as solvent. The initiating catalyst system is very effective in the polymerization of butadiene. However, the presented copolymerization of butadiene and styrene is only practicable when using a special addition order of the catalyst components and a prescribed ageing phase. Copolymers obtained from various monomer feed ratios were characterized by ¹H and ¹³C NMR spectroscopy and gel-permeation chromatography (GPC). The copolymer characteristics especially microstructure, molar mass and molar-mass distribution (MMD) are strongly dependent on the composition of the monomer mixture.     

Thermodynamic study on complex of neodymium with glycine

Neodymium complex with glycine, Nd(Gly)₂Cl₃·3H₂O, was synthesized and characterized by IR spectra. The thermal stability of the complex was tested through TG and DTG and a possible mechanism of thermal decomposition was proposed. The heat capacities of the complex were measured by using an automated adiabatic calorimeter over the temperature range from T = (80 to 380) K, the thermodynamic functions, [H_T − H_298.15] and [S_T − S_298.15], were calculated based on the heat capacity measurements. Two (solid + solid) phase transitions in the ranges of T = (170 to 247) K were observed with the peak temperatures of 184.896 K and 231.217, respectively. The standard molar enthalpy of formation of [Nd(Gly)₂Cl₃·3H₂O] was determined to be (−3081.3 ± 1.1) kJ · mol⁻¹ in terms of an isoperibol solution-reaction calorimeter.     

Magnetic properties of a polyfluorene derivative containing complexed neodymium ions

Poly[9,9′‐dihexylfluorene‐2,7‐diyl)‐6,6″‐(2,2′:6′,2″‐terpyridine)] (LaPPS75) and its complexes with neodymium were synthesized and characterized. Magnetic measurements showed that the noncomplexed polymer presented a ferromagnetic contribution due to the formation of π stacking, and that in absence of those, the ferromagnetic behavior is suppressed. The pristine polymer, the complexed one and a low‐molecular‐weight model compound with the same structure of the complexed site in the parent polymer were studied. The observed behavior found is presented and discussed, the most important finding was that when a conjugated chain is used as a host for the metallic ion, an amplification of four times for the magnetization is achieved, using the same metallic content for complexed polymer and model compound for comparison. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 304–311