硅和四氯化硅耦合加氢反应体系的热力学分析

基于Gibbs自由能最小原理,对硅和四氯化硅（SiCl₄,STC）耦合加氢反应体系进行了热力学分析。通过化学平衡产物组成分布的分析,确定了反应体系主要产物为三氯硅烷（HSiCl₃,TCS）、二氯硅烷（H₂SiCl₂,DCS）、盐酸（HCl）,并构造了3个相应的独立反应,讨论了对应的反应热（ΔrHθm）、自由能（ΔrGθm）和平衡常数（Kθp）与温度的关系。计算所采用的温度为673~923 K,压力为101.325 ~2 026.5 kPa,原料H₂与SiCl₄物质的量比为1~5。结果表明,生成TCS和DCS的反应为体系随着温度升高,四氯化硅平衡转化率及三氯硅烷产率降低;高压和适中的原料配比（H₂与SiCl₄物质的量比）有利于四氯化硅转化率及三氯硅烷产率的提高。     

Equilibrium,Kinetic, and Thermodynamic Studies on the Biosorption of Selenium (IV) Ions onto Ganoderma Lucidum Biomass

The capacity of Ganoderma lucidum biomass for biosorption of selenium (IV) ions from aqueous solution was studied in a batch mode. In this study the effects of operating parameters such as solution pH, adsorbent dosage, initial metal concentration, contact time, and temperature were investigated. The adsorption capacity of G. lucidum was found to be 126.99 mg g^?1. The biosorption follows pseudo-first order kinetics and the isotherms fit well to both Langmuir and Freundlich isotherm models. Isotherms have been used to determine thermodynamic parameters of the process, that is, free energy, enthalpy, and entropy changes. Furthermore, the biosorbent was characterized by scanning electron microscopy and FT-IR analysis. FT-IR analysis of fungal biomass shows the presence of amino, carboxyl, hydroxyl, and carbonyl groups, which were responsible for the biosorption of selenium(IV) ions. The results indicated that the biomass of G. lucidum is an efficient biosorbent for the removal of selenium (IV) ions from aqueous solutions.     

Biosorptive Removal of Ni(II) from Aqueous Solution by Caesalpinia bonducella Seed Powder

The present work deals with the use of Caesalpinia bonducella seed powder (CBSP) as a biosorbent for Ni(II) removal from aqueous solution. The nature and morphology of the sorbent were determined using FTIR spectral, SEM, and EDX analysis. The biosorption characteristics of Ni(II) onto CBSP was investigated as a function of pH, biosorbent dosage, contact time, initial metal ion concentration, and temperature. Langmuir and Freundlich isotherms were used to fit the experimental data. The best interpretation for the equilibrium data was given by the Langmuir isotherm. The maximum biosorption capacity was found to be 188.7 mg/g for Ni(II) at pH 5.0 and at 323 K. The equilibrium biosorption data were well fitted with the pseudo-second-order kinetic equation. The values of thermodynamic parameters (ΔG^o, ΔH^o, and ΔS^o) indicated that the biosorption of Ni(II) onto CBSP was feasible, spontaneous and exothermic in nature. The FTIR results revealed that hydroxyl, amine, carboxyl, and carbonyl functional groups are responsible for Ni(II) biosorption onto CBSP.     

经典热力学发展概述

热力学三大基本定律是热现象宏观理论的基础,是研究热现象的必备条件,对化工生产乃至社会的发展起着不可磨灭的作用。为此,了解热力学三大基本定律的建立及其内容显得尤为必要。本文简要概述了经典热力学在化工生产中的应用及其发展历程和存在的局限性。     

2,4-二羟基苯甲酸在3种树脂上的吸附特性

通过静态和动态吸附实验, 研究了717(凝胶型,强碱)、D201(大孔型,强碱)和D301R(大孔型,弱碱)3种阴离子交换树脂对水溶液中2,4-二羟基苯甲酸的吸附特性. 结果表明,717和D201在pH 4~11时、D301R在pH 3~9时吸附能力最好. 在pH=5及温度293~313 K、初始浓度0.6488~6.488 mmol/L条件下,D301R, 717和D201对2,4-二羟基苯甲酸的等温吸附规律均符合Freundlich模型,最大平衡吸附量分别为2.98, 2.66和2.54 mmol/g(吸附未达饱和),均为物理性自发吸附的放热过程. 动力学实验数据用准一级模型方程拟合比准二级更接近实验值. 5%(w) NaCl+2%(w) NaOH脱附液100 mL均可有效洗脱3种树脂上吸附的2,4-二羟基苯甲酸,脱附率达99%. 相同条件下,D301R树脂对2,4-二羟基苯甲酸的吸附性能优于D201和717树脂.     

柠檬酸热力学性质研究及晶型含量测定

运用新型平行反应器Poly Block快速测量了柠檬酸在水中的溶解度,并用传统的静态法验证了其准确性。建立了一种简单且行之有效的测定溶解度的方法,测量周期短,结果可靠,可以用于实验室和工业生产中。改进静态法试验装置研究柠檬酸在水中的晶型转化过程,利用DSC测量平衡固相含量,确定无水及一水柠檬酸比例,判断晶型转化终点,最终得到准确的柠檬酸相转变点温度。用改进Apelblat简化经验方程对试验数据进行了关联,其回归及计算结果与试验值符合良好。     

甲基橙在桉木基磁性活性炭上的吸附行为

以桉木屑为原料,KOH为活化剂,FeCl_3·6H_2O为赋磁剂一步法制备了桉木基磁性活性炭。用全自动比表面积及孔径分析仪、FTIR、XRD、VSM等手段对其结构与性能进行了表征与测试。以其为吸附剂,考察了吸附剂用量、甲基橙初始浓度、pH值、吸附时间等对甲基橙吸附效果的影响,并分析了吸附热力学和动力学。结果表明,桉木基磁性活性炭MAC-0.42的比表面积为1430.32 m~2/g,总孔体积为0.893 cm~3/g,平均孔径为2.49nm。在吸附剂用量为0.045 g、甲基橙初始质量浓度为0.25 g/L、溶液在自然pH(约为6.82)、吸附时间为10 h的条件下,进行了吸附动力学和吸附等温线实验。桉木基磁性活性炭的碘吸附值和亚甲基蓝吸附值分别为1571.4和315.52 mg/g。桉木基磁性活性炭表面含有—OH、—C==O、—COO等官能团,其中有磁性物质Fe和Fe3O4,MAC-0.42的饱和磁化强度为48.65emu/g,在外加磁场时能快速将其从溶液中分离出来。其对甲基橙的吸附符合Langmuir模型,最大吸附量为333.33 mg/g;吸附过程是自发吸热过程,吸附动力学符合准二级动力学模型。     

Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

Coal-based ethanol production by hydration of ethylene is limited by the low equilibrium ethylene conversion at elevated temperature. To improve ethylene conversion, coupling hydration of ethylene with a potential ethanol consumption reaction was analyzed thermodynamically. Five reactions have been attempted and compared: (1) dehydration of ethanol to ethyl ether ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff{\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (2) dehydrogenation of ethanol to acetaldehyde ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{CHO+H}}_{\mathrm{2}}), (3) esterification of acetic acid with ethanol ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+CH}}_{\mathrm{3}}\mathrm{COOH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (4) dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}), and (5) oxidative dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+O}}_{\mathrm{2}}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}\mathrm{O}). The equilibrium constants and equilibrium distributions of the coupled reactions were calculated and the effects of feed composition, temperature and pressure upon the ethylene equilibrium conversion were examined. The results show that dehydrogenation of ethanol to acetaldehyde has little effect on ethylene conversion, whereas for dehydrogenation of ethanol to acetaldehyde and ethyl acetate, ethylene conversion can be improved from 8% to 12.8% and 18.5%, respectively, under conditions of H₂O/C₂H₄ = 2, 10 atm and 300°C. The esterification of acetic acid with ethanol can greatly enhance the ethylene conversion to 22.5%; in particular, ethylene can be actually completely converted to ethyl acetate by coupling oxidative dehydrogenation of ethanol.     

Estimation of the critical properties of compounds using volume-based thermodynamics

The importance, yet scarcity of the critical constants of thermally unstable fluids warrants the development of reliable methods for the estimation of these essential thermodynamic properties. A thorough investigation undertaken in this study on 1,589 compounds belonging to 83 chemical classes, indicated that the ratio of critical temperature to critical pressure of both low and high molecular weight compounds could be well expressed in terms of their volumetric properties. In addition, two new methodologies are presented for estimating V_c, as well as an indirect approach for prediction of T_c from surface tension data, altogether allowing the calculation of Z_c. Moreover, comparative studies are made with five group contribution methods. It is also demonstrated that by employing the Peng-Robinson EOS, and without prior knowledge of the critical properties, it is possible to calculate various thermophysical properties including P^sat., T_b, , ∆H^vap. , C_p, and even the T_c and P_c themselves.