Ni-Co-LaNi5复合电极材料在碱性介质中的电催化析氢性能

电催化析氢反应是电能向化学能转化的一个有效途径,是电化学科学中一个非常值得深入研究的课题。阴极析氢超电势的降低,是提高析氢活性,降低电解能耗的关键。为了提高电极的电催化活性,一是可通过提高电极表面的真实表面积,来降低电解过程中电极表面的真实电流密度,达到降低析氢超电势的目的;另一发展方向是提高电极材料本身的电化学活性,即寻找高催化活性的新型析氢材料犤1犦。由于过渡金属具有特殊的d电于结构,是目前公认的电化学活性最好的电极材料,而在过渡金属中,Ni及Ni合金将是研究的主要方向,其中多元合金复合材料将成为该技术发展…     

Thermal studies and spectral characterization of the chelate of bis-(η5-cyclopentadienyl titanium(IV) with salicylidene-4-methylaniline

A new chelate (η⁵-C₅H₅)₂Ti(SB)₂, whereSB=O, N donor Schiff base salicylidene-4-methylaniline, was synthesized. The course of thermal degradation of the chelate was studied by thermogravimetric (TG) and differential thermal analysis (DTA) under dynamic conditions of temperature. The order of the thermal decomposition reaction and energy of activation was calculated from TG curve while from DTA curve the change in enthalpy was calculated. Evaluation of the kinetic parameters was performed by Coats-Redfern as well as Piloyan-Novikova methods which gaven=1, ΔH=1.114 kJ·mol^?1, ΔE=27.01 kJ·mol^?1, ΔS=?340.12 kJ·mol^?1·K^?1 andn=1, ΔH=1.114 kJ·mol^?1, ΔE=20.01 kJ·mol^?1, ΔS=?342.60 kJ·mol^?1·K^?1, respectively. The chelate was also characterized on the basis of different spectral studies viz. conductance, molecular weight, IR, UV-visible and¹H NMR, which enabled to propose an octahedral structure to the chelate.     

纳米掺铁二氧化钛的sol-gel法制备与表征 (Ⅱ)纳米掺铁二氧化钛的微晶特性与晶体生长

本文结合透电镜分析研究了sol-gel方法制备的纯二氧化钛和掺铁二氧化钛干凝胶的晶化过程,计算了在不同的煅烧温度下二氧化钛微晶的晶胸参数,晶粒度,畸变等参数的变化关系,应用非晶物质晶化晶核生长速率议程计算的昌粒生长活化能表明晶粒生长分为两个阶段,临界点大约为相变温度,纯的和掺铁的二氧化钛在两个阶段的晶粒生长活化能分别约为20．8kJ.mol^-1,70.9kJ.mol^-1和26．6kJ.mol^-1,78.8kJ.mol^-1.这个差别可能是由于相主过程首先发生在小晶粒上,导致小晶粒生长较为困难所致。     

纳米掺铁二氧化钛的sol-gel法制备与表征 (Ⅱ)纳米掺铁二氧化钛的微晶特性与晶体生长

本文结合透射电镜分析研究了 sol-gel方法制备的纯二氧化钛和掺铁二氧化钛干凝胶的晶化过程。计算了在不同的煅烧温度下二氧化钛微晶的晶胞参数,晶粒度,畸变等参数的变化关系。应用非晶物质晶化晶核生长速率方程计算的晶粒生长活化能表明晶粒生长分为两个阶段,临界点大约为相变温度。纯的和掺铁的二氧化钛在两个阶段的晶粒生长活化能分别约为 20.8kJ· mol-1,70.9kJ· mol-1和 26.6kJ· mol-1,78.8kJ· mol-1。这个差别可能是由于相变过程首先发生在小晶粒上,导致小晶粒生长较为困难所致。     

Tribochemistry and kinetics of Al2(SO4)3·xH2O decomposition

The thermal decomposition of tribochemically activated Al₂(SO₄)₃·xH₂O was studied by TG, DTA and EMF methods. For some of the intermediate solids, X-ray diffraction and IR-spectroscopy were applied to learn more about the reaction mechanism. Thermal and EMF studies confirmed that, even after mechanical activation of Al₂(SO₄)₃·xH₂O, Al₂O(SO₄)₂ is formed as an intermediate. Isothermal kinetic experiments demonstrated that the thermochemical sulphurization of inactivated Al₂(SO₄)₃·xH₂O has an activation energy of 102.2 kJ·mol^?1 in the temperature range 850–890 K. The activation energy for activated Al₂(SO₄)₃·xH₂O in the range 850–890 K is 55.0 kJ·mol^?1. The time of thermal decomposition is almost halved when Al₂(SO₄)₃·xH₂O is activated mechanically. The results permit conclusions concerning the efficiency of the tribochemical activation of Al₂(SO₄)₃·xH₂O and the chemical and kinetic mechanisms of the desulphurization process.     

Thermodynamic analysis of the structure of aqueous solutions of C<Subscript>12</Subscript>–C<Subscript>18</Subscript> hydrocarbons

Thermodynamic cycles including the increments \(\Delta G_{CH_2 }^0 , \Delta H_{CH_2 }^0 \), and \(T\Delta S_{CH_2 }^0 \) were constructed for dissolution, evaporation, hydrophobic hydration of C₅–C₉ hydrocarbons, and transfer from vapor (\(\Delta G_{CH_2 }^0 \) = ?0.7 kJ·mol^?1, \(\Delta H_{CH_2 }^0 \) = 2.9 kJ·mol^?1, \(T\Delta S_{CH_2 }^0 \) = 3.6 kJ·mol^?1) and water (\(\Delta G_{CH_2 }^0 \) = ?1.4 kJ·mol^?1, \(\Delta H_{CH_2 }^0 \) = 5.8 kJ·mol^?1, \(T\Delta S_{CH_2 }^0 \) = 7.2 kJ·mol^?1) to micelles of C₁₂–C₁₈ hydrocarbons. The formation of bistable hydrated micelles of C₁₂–C₁₈ is explained by a transition between the order-disorder states in an assembly of small (nano) systems of water. The extensive parameters of small systems and critical phenomena predicted by fluctuation theory are discussed.     

Effect of alkali additives on the kinetics of WO3+CCl4 reaction

The chlorination kinetics of alkali-added (K and Li) tungsten trioxide were studied by thermogravimetry, using gaseous CCl₄ as chlorinating agent. The reactivity of the modified samples was compared to the results on the chlorination of pure WO₃. Similar apparent activation energies were found for the pure and alkali-added samples. However, potassium additive resulted in a strong decrease of the initial reaction rate, while surface lithium has no influence on it.During the chlorination a continuous decrease of the linear reaction rate was observed for both samples, which was explained by retarding effects of surface by-products and alkali additives. For describing the isothermal TG curves an appropriate kinetic model, based on the monotonously increasing inhibition of these species was assumed. The curve calculated with this model fits well to the experimental results.

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Zusammenfassung Mittels Thermogravimetrie wurde die Chlorierungskinetik von alkaliversetztem (K und Li) Wolframtrioxid untersucht, wobei CCl₄ als Chlorierungsreagens fungierte. Die Reaktivität der modifizierten Proben wurden mit der von reinem WO₃ verglichen. Für die reinen und für die alkaliversetzten Proben wurden ähnliche scheinbare Aktivierungsenergien gefunden. Der Zusatz von Kalium verursacht jedoch eine starke Abnahme der ursprünglichen Reaktionsgeschwindigkeit, während oberflächiges Lithium keinen Effekt zeigt.Während der Chlorierung wurde eine ständige Senkung der linearen Reaktionsgeschwindigkeit für beide Proben festgestellt, was mit Rückhalteeffekten von oberflächigen Nebenprodukten und Alkalizusätzen erklärt wird. Zur Beschreibung der isothermen TG-Kurven wurde ein entsprechendes kinetisches Modell angenommen, welches auf einer monoton steigenden Inhibition dieser Proben basiert. Die auf der Grundlage dieses Modelles berechnete Kurve stimmt recht gut mit den experimentellen Ergebnissen überein.

     

Studies of dehydration kinetics of Li2SO4·H2O by the master plots method

The kinetics of Li₂SO₄·H₂O dehydration in static air atmosphere was studied on the basis of nonisothermal measurements by differential scanning calorimetry. Dehydration data were subjected to an integral composite procedure, which includes an isoconversional method, a master plots method and a model-fitting method. Avrami-Erofeev equation was found to describe all the experimental data in the range of conversion degrees from 0.1 to 0.9. The determined activation energy equals 65.45 kJ·mol⁻¹ with standard deviation ±0.47 kJ·mol⁻¹. The estimated value of parameter m in Avrami-Erofeev equation is 2.15 with standard deviation ±0.11. Also, the obtained pre-exponential factor is 7.79×10⁵ s⁻¹ with standard deviation ±0.55×10⁵ s⁻¹. The results show that the present integral composite procedure gives self-consistent kinetic parameters.     

The thermal decomposition of N,N-dimethyl-3-oxaglutaramic acid and the kinetics of its second-stage thermal decomposition reaction

N,N-dimethyl-3-oxa-glutaramic acid was purified and characterized by ¹H-NMR, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis. The thermal decomposition of the title compound was studied by means of thermogravimetry differential thermogravimetry (TG-DTG) and FT-IR. The kinetic parameters of its second-stage decomposition reaction were calculated and the decomposition mechanism was discussed. The kinetic model function in a differential form, apparent activation energy and pre-exponential constant of the reaction are 3/2 [(1?α)^1/3?1]^?1, 203.75 kJ·mol^?1 and 10^17.95s^?1, respectively. The values of ΔS ^≠, ΔH ^≠ and ΔG ^≠ of the reaction are 94.28 J·mol^?1·K^?1, 203.75 kJ·mol^?1 and 155.75 kJ·mol^?1, respectively.     

Zur Thermochemie der Zinnhalogenide

The enthalpy change of the reaction at 298 K between Br₂ (l) and Sn(c) in CS₂ as solvent giving SnBr₄ (s) has been determined by calorimetry to be (?374, 2±1.4) kJ·mol^?1, [(?89.45±0.33) kcal·mol^?1]. By the same method the heat of solution of SnBr₄ (c) in CS₂ has been found to be (11.9±0.3) kJ·mol^?1, [(2.84±0.08) kcal·mol^?1]. Combining these results, a value of (?386.1±1.5) kJ·mol^?1, [(?92.3±0.4) kcal·mol^?1] is derived for the standard heat of formation of SnBr₄ (c). Substituting this figure in the thermochemical cycle hitherto used for calculating the heat of formation of SnBr₄ (c) gives ?124.3 kcal·mol^?1 for the standard heat of formation of SnCl₄ (l), which is in reasonable agreement with a recent determination of this quantity⁸.     

TG study of the chlorination of WO3 by COCl2 and CCl4

The chlorination kinetics of tungsten trioxide was studied by thermogravimetry, using COCl₂ and gaseous CCl₄ as chlorinating agents. Thermochemical calculations were made on the main chlorination reactions and also on some assumed side reactions. On the basis of the kinetic results CCl₄ proved to be more reactive than COCl₂. For both gases apparent activation energies of about 100 kJ.mol^–1 and reaction orders of 0.5 were obtained in the temperature ranges where the reaction was controlled by chemical processes.During the chlorination by COCl₂ the conversionvs. time data could be described by the contracting sphere model. When chlorinating by CCl₄ a continuous decrease of the linear reaction rate was observed. Thus, for describing the isothermal TG curves a kinetic model, based on the retarding effect of non-removable surface side products, was assumed. With this model a fairly good correspondence of the measured and calculated kinetic curves was obtained.

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Zusammenfassung Mittels Thermogravimetrie wurde die Kinetik der Chlorierung von Wolframtrioxid mit COCl₂ bzw. gasförmigem CCl₄ untersucht. Für die Hauptchlorierungsreaktionen und einige angenommene Nebenreaktionen wurden thermochemische Berechnungen getÄtigt. Ausgehend von den kinetischen Ergebnissen erwies sich CCl₄ als reaktionsfreudiger als COCl₂. In dem Temperaturbereich, in dem die Reaktion durch chemische Prozesse kontrolliert wird, erhielt man eine scheinbare Aktivierungsenergie von etwa 100 kJmol^–1 und eine Reaktionsordnung von 0.5.Bei der Chlorierung mit COCl₂ können die Konversion/Zeit Daten mit dem Contractingsphere Modell beschrieben werden. Bei der Chlorierung mit CCl₄ kann eine stÄndige Abnahme der linearen Reaktionsgeschwindigkeit beobachtet werden. Somit wurde für die Beschreibung der isothermen TG-Kurven ein kinetisches Modell angenommen, welches auf dem Rückhalteeffekt von unabspaltbaren Nebenprodukten an der OberflÄche beruht. Mit diesem Modell konnte eine gute übereinstimmung zwischen experimentellen und rechnerischen kinetischen Kurven erzielt werden.

     

Etude thermique et thermodynamique du cyclohexaphosphate de lithium Li6P6O18·5H2O

We report in this paper the results of our thermal and thermodynamic investigation on lithium cyclohexaphosphate, Li₆P₆O₁₈·5H₂O between 298 and 1007 K. The different transitions with respect to temperature (successive dehydrations, solid-solid transition and melting) were studied with the help of differential thermal analysis and thermogravimetry. The different phases were characterized by X-ray diffraction and by infrared absorption. Finally, the enthalpy of these phasesvs. temperature was measured by isothermal drop calorimetry. Their heat capacities as well as the enthalpies of dehydration, of solid-solid transition and of melting were deduced. We pointed out that the lithium cyclohexaphosphate loses a molecule of water at 333 K (54.3 kJ·mol^?1), three molecules of water at 413 K (151 kJ·mol^?1) and the last one at 488 K (50.6 kJ·mol^?1). The anhydrous lithium cyclohexaphosphate, Li₆P₆O₁₈, give the polyphosphate, LiPO₃, at 708 K (second order transition) and melt at 933 K (24.6 kJ·mol^?1).     

脉冲光声量热法测量n-C4H9Co(Salen)H2O的Co-C键离解能

By using photoacoustic calorimetry, a photoacoustic measurement system is applied to determine the Co-C bond dissociation energy of n C₄H₉Co(Salen)H₂O, which is 116±8kJ·mol^-1. This value is in agreement with the activation enthalpy of the Co-C bond homolytic cleavage reaction that obtained by the kinetic method.     

Solid-state studies on crystalline and glassy flutamide

Flutamide usually crystallizes in the orthorhombic non-centrosymmetric space group Pna2₁ (from I) and melts atT _fus =384 K with Δ_fus H=30 kJ·mol^?1. It may be obtained in the glassy state (T _g =272 K) by quenching the melt. Although evidence of polymorphism could not be obtained by means of crystallography, DSC studies of the recrystallization process indicate that a metastable form (form II) occurs first and is transformed into the stable form at room temperature. ΔH for the transition I→II (2.52 kJ·mol^?1) is close to the difference in energy (about 2 kJ·mol^?1) calculated for the two possible conformers of flutamide.     

Ti基化学镀Ni-P和Ni-P-Cg镀层晶化动力学

利用化学镀技术在Ti基体材料表面制备了Ni-P合金镀层和Ni-P-Cg复合镀层。利用SEM、XRD和EDS等分析了镀层的晶化过程,用差热分析仪研究了Ni-P合金镀层和复合镀层的晶化动力学,运用Ozawa、Freeman-Carroll、Achar和Coats-Redfern方法对非等温动力学数据进行了分析和比较。结果发现,复合镀层的特征温度T_m和晶化激活能E均高于Ni-P合金镀层,而热焓值｜ΔH｜却低于Ni-P镀层;计算出Ni-P合金镀层和Ni-P-Cg复合镀层晶化激活能分别为308.9 kJ·mol^-1和412.99 kJ·mol^-1、指前因子A分别为58.03 s^-1和77.84 s^-1,确定了Ni-P合金镀层和复合镀层晶化动力学方程。     

Thermal Behavior of N,N＇Bis[N-（2,2,2-trinitroethyl）-N-nitro]ethylenediamine

The thermal behavior and kinetic parameters of the exothermic decomposition reaction of N‐N‐bis[N‐(2,2,2‐tri‐nitroethyl)‐N‐nitro]ethylenediamine in a temperature‐programmed mode have been investigated by means of differential scanning calorimetry (DSC). The results show that kinetic model function in differential form, apparent activation energy E_a and pre‐exponential factor A of this reaction are 3(1 ‐α)^2/3, 203.67 kJ·mol^?1 and 10^20.61s^?1, respectively. The critical temperature of thermal explosion of the compound is 182.2 °C. The values of ΔS^≠ ΔH^≠ and ΔG^≠ of this reaction are 143.3 J·mol^?1·K^?1, 199.5 kJ·mol^?1 and 135.5 kJ·mol^?1, respectively.     

Removal of thorium from aqueous solution by ordered mesoporous carbon CMK-3

The ability of ordered mesoporous carbon CMK-3 has been explored for the removal and recovery of thorium from aqueous solutions. The textural properties of CMK-3 were characterized using small-angle X-ray diffraction and N₂ adsorption–desorption, and the BET specific surface area, pore volume and the pore size were 1143.7 m²/g, 1.10 cm³/g and 3.4 nm. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The CMK-3 showed the highest thorium sorption capacity at initial pH of 3.0 and contact time of 175 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, △G°(298 K), △H° and △S° were determined to be -0.74 kJ·mol^?1, 9.17 kJ·mol^?1 and 33.24 J·mol^?1·K^?1, respectively, which demonstrated the sorption process of CMK-3 towards Th(IV) was feasible, spontaneous and endothermic in nature. The adsorbed CMK-3 could be effectively regenerated by 0.02 mol/L HCl solution for the removal and recovery of Th(IV).     

Kinetic Study on the Exothermic First-stage Decomposition Reaction of 2,4,8,10-Tetranitro-2,4,8,10-tetraaza- spiro[5,5]undecane-3,9-dione

Introduction 2,4,8,10-Tetranitro-2,4,8,10-tetraazaspiro[5,5]udecane- 3,9-dione is a typical cyclourea nitramine (Figure 1). Its crystal density is 1.91 gcm-3. The detonation velocity according to =1.90 gcm-3 is about 8670 ms-1. Its sensitivity to impact is better than that of cyclotrimethy- lenetrinitramine. So it is the potential high explosive. Its preparation,1-3 properties,1-3 hydrolytic behavior4 and electronic structure3 have been reported. In the present work, we report its kinetic pa…     

Kinetic and thermodynamic parameters of volatilization of biodiesel from babassu, palm oil and mineral diesel by thermogravimetric analysis (TG)

The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol^?1), followed by babassu biodiesel (E = 76.37 kJ mol^?1), and palm biodiesel (E = 87.00 kJ mol^?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol^?1 K^?1, ΔH = +80.38 kJ mol^?1 and ΔG = +142.74 kJ mol^?1. For palm biodiesel ΔS = ?119.26 J mol^?1 K^?1, ΔH = + 90.53 kJ mol^?1 and ΔG = +141.21 kJ mol^?1, and for diesel ΔS = ?131.3 J mol^?1 K^?1, ΔH = +53.29 kJ mol^?1 and ΔG = +115.13 kJ mol^?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.     

Preparation and Thermal Chemical Property of Complexes of Zinc Nitrate with Trytophan

IntroductionZincisanessentialtraceelementtothelife .Manydiseasesarousedfromadeficiencyofzincelementhavere ceivedconsiderableattention .L α Aminoacidsarebasicunitsofproteins .L α Trytophanisoneoftheeightspeciesofaminoacidsindispensableforlife ,whichhastobeab sorbedfromfoodbecauseitcannotbesynthesizedinthehumanbody .InviewofthecomplexesofL α trytophanandessentialelementsasaddictiveswidelyusedinsuchfieldsasfoodstuff,medicineandcosmetic ,1 3theyhaveabroadenprospectforapplications .Briefly ,ab…