Kinetic and Calorimetric Considerations in the Scale-Up of the Catalytic

水泥水化反应与混凝土自收缩的动力学模型①阎培渝,郑　峰(清华大学土木工程系,北京100084)摘　要:基于水泥的多组分和多尺度水化反应的原理,分别建立了水泥的水化反应和混凝土自收缩的动力学模型。

这2个模型均采用两阶段的经验公式,分别用于模拟水化反应和自收缩的快速发展阶段与平稳变化阶段。

实测数据检验结果表明,这2个模型可以用于模拟硅酸盐水泥的等温水化放热曲线,以及用硅酸盐水泥配制的混凝土的自收缩发展过程。

关键词:动力学模型;自收缩;水化反应;水泥;混凝土中图分类号:T U528 文献标识码:A 文章编号:1672-7029(2006)01-0056-04Dynamic models of hydration reaction of Portland cement andautogenous shrinkage of concreteY AN Pei2yu ZHE NG Feng(Department of Civil Engineering,Tsinghua University,Beijing100084,China)Abstract:The dynamic m odels of hydration reaction of cement and autogenous shrinkage of concrete were constructed respectively based on the multi-com position and multi-scale hydration reaction of cement1In both m odels tw o-step regressive equations are adopted to simulate the step of quick development and the step of even change of hydration re2 action and autogenous shrinkage1The experimental results show that these m odels can express precisely the is otherm hydration heat emission curve of P ortland cement and the autogenous shrinkage process of concrete prepared with P ort2 land cement1K ey w ords:dynamic m odel;autogenous shrinkage;hydration reaction;cement;concrete 高强高性能混凝土在现代土木工程中的应用越来越广泛。

cable stayed bridge 斜拉桥 cad 计算机辅助设计 calculator 计算机 calculus of approximation 近似计算 calculus of finite differences 差分演算 calibration 校准 calibrator 校准器 calorific capacity 热容量 calorimetric measurement 量热测量 camber changing flap 改变机翼弯度的襟翼 canal 管道 canal vortex 沟渠涡旋 canal wave 沟渠波 canard 鸭翼 canonical coordinate 正则坐标 canonical distribution 正则分布 canonical equation of motion 正则运动⽅程 canonical equations 正则⽅程 canonical form 正则形式 canonical momentum 正则动量 canonical transformation 正则变换 canonical variable 正则变量 cantilever 悬臂梁 caoutchouc elasticity 橡胶弹性 capacitive transducer 电容传感器 capacity 功率 capacity measure 容积量度 capacity strain gage 电容应变计 capillarity ⽑细现象 capillary absorption ⽑细管吸收 capillary action ⽑细酌 capillary attraction ⽑细引⼒ capillary condensation ⽑细凝缩 capillary constant ⽑细常数 capillary energy 表⾯张⼒能 capillary fissure ⽑细裂纹 capillary flow ⽑管流 capillary force ⽑细⼒ capillary gravity wave ⽑细重⼒波 capillary level oscillation ⽑细⾯振动 capillary phenomenon ⽑细现象 capillary pressure ⽑细压⼒ capillary rise ⽑细升⾼ capillary tension ⽑细张⼒ capillary tube ⽑细管 capillary viscosimeter ⽑细管粘度计 capillary waves ⽑细波 capture 俘获 carbon fiber 碳纤维 cardan angle 卡登⾓ cardan rings 卡登环 cardiac dynamics ⼼脏动⼒学 cardiac work ⼼脏的⼯作 cargo 货物 carrier gas ⽓体载体 carrier inertial force 牵连惯性⼒ carrier liquid 载体液体 carrier oscillation 载波振荡 carrier rocket 运载⽕箭 carrier velocity 牵连速度 carrying capacity 负荷量 cartesian coordinates 笛卡⼉坐标 cartesian vector 笛卡⼉⽮量 cascade excitation 级联激发 cascade flow 翼栅怜 cascade of aerofoil 翼型叶栅 cascade tunnel 叶栅风洞 case depth 渗碳层深度 case hardening 表⾯硬化 casing 外壳 castigliano theorem 卡斯蒂利亚诺定理 casting stress 铸造应⼒ catapult 弹射器 catenary 悬链线 catenoid 悬链曲⾯ cauchy deformation tensor 柯挝变张量 cauchy equation of motion 柯嗡动⽅程 cauchy integral theorem 柯锡分定理 cauchy law of similarity 柯梧似性定律 cauchy residue theorem 柯涡数定理 cauchy riemann equations 柯卫杪 匠眺 cauchy stress tensor 柯桅⼒张量 caudad acceleration 尾向加速度 causality 因果律 caving 空泡形成 cavitating flow ⽓⽳流涡空流 cavitation ⽓蚀现象 cavitation bubble 空泡 cavitation damage 空化损坏 cavitation effect 空化效应 cavitation erosion 空蚀 cavitation nucleus 空化核 cavitation number 空化数 cavitation parameter 空化参数 cavitation phenomenon ⽓蚀现象 cavitation shock ⽓蚀冲击 cavitation tunnel 空泡试验筒 cavity 空腔 cavity collapse 空泡破裂 cavity drag 空泡阻⼒ cavity flow ⽓⽳流涡空流 cavity flow theory 空泡另论 cavity formation 空泡形成 cavity pressure 空腔压⼒ cavity resonator 空腔共振器 cavity vibration 共振腔振动 ceiling 上升限度 celestial mechanics 天体⼒学 cell model 笼⼦模型 cell reynolds number 格雷诺数 cellular grid 状栅格 cellular structure 栅格结构 center 中⼼ center line 中⼼线 center line average height 中线平均⾼度 center line of the bar 杆件轴线 center of area ⾯积中⼼ center of buoyancy 浮⼼ center of curvature 曲率中⼼ center of gravity 重⼼ center of inertia 惯性中⼼ center of inertia system 惯性中⼼坐标系 center of inversion 反演中⼼ center of mass 质⼼ center of mass coordinate 质⼼坐标系 center of mass law 质⼼定理 center of mass motion 质⼼运动 center of mass system 质⼼坐标系 center of mass theorem 质⼼定理 center of oscillation 震荡中⼼ center of percussion 撞恍⼼ center of rotation 转动中⼼ center of similarity 相似中⼼ center of twist 扭转中⼼ center of vorticity 涡⼼ center to center distance 中⼼距 center to center spacing 中⼼距 centered compressional wave 有⼼压缩波 centered rarefactional wave 有⼼稀疏波 centi 厘 centigrade temperature 摄⽒温度 centimetre 厘⽶ centimetre gramme second 厘⽶克秒 central 中⼼的 central angle 中⼼⾓；圆⼼⾓ central axis of inertia 惯性中⼼轴 central body 中枢体 central difference method 中⼼差分法 central force 有⼼⼒ central force field 有⼼⼒场 central gas stream 中⼼⽓流 central impact 对⼼碰撞 central limit theorem 中⼼极限定理 central line 中线 central moment 中⼼⼒矩 central point 中⼼点 central potential 有⼼⼒势 central principal axis of inertia 中⼼惯性轴 central principal moment of inertia 中⼼知动惯量 centre 中⼼ centre of buyoncy 浮⼼ centre of curvature 曲率中⼼ centre of force ⼒⼼ centre of gravity 重⼼ centre of gyration 旋转中⼼ centre of inertia 质⼼ centre of mass 质⼼ centre of mass motion 质⼼运动 centre of mass system 质⼼系 centre of percussion 撞恍⼼ centre of pressure 压⼒中⼼ centrifugal 离⼼的 centrifugal acceleration 离⼼加速度 centrifugal effect 离⼼效应 centrifugal field 离⼼⼒场 centrifugal force 离⼼⼒ centrifugal governor 离⼼式蒂器 centrifugal inertial force 惯性离⼼⼒ centrifugal load 离⼼荷载 centrifugal pendulum 离⼼摆 centrifugal potential 离⼼势 centrifugation 离⼼分离 centrifuge 离⼼机 centrifuge modelling 离⼼模拟 centripetal 向⼼的 centripetal acceleration 向⼼加速度 centripetal force 向⼼⼒ centrode 瞬⼼轨迹 centroid 质⼼ centroid axis 重⼼轴线 centroid of area ⾯⼼ centroidal principal axes of inertia 重⼼诌性轴 centrosymmetric 中⼼对称的 cgs system cgs 单位制 chain drive 链条传动 chain graph 链图 chain reaction 连锁反应 chain transmission 链条传动 chance event 随机事件 chance quantity 随机量 chance variable 随机变量 change 变化 change of coordinates 坐标变换 change of form 形态变化 change of state 物态变化 change of the variable 变数更换 change of the wind 风向改变 changing load 交变负载 channel 渠道 channel diffusion 通道扩散 channel flow 渠道怜 chaos 混沌 chaplygin correspondence principle 恰普雷⾦对应原理 chaplygin equation 恰普雷⾦⽅程 chaplygin fluid 恰普雷⾦铃 chaplygin function 恰普雷⾦函数 chapman enskog method 查普曼⾖科格⽅法 chapman enskog solution 查普曼⾖科格解 chapman jouguet condition 查普曼儒盖条件 chapman jouguet hypothesis 查普曼儒盖假设 chapman kolmogoroff equation 查普曼柯尔莫果洛夫⽅程 chapman layer 查普曼层 characteristic 特性 characteristic curve 特性曲线 characteristic datum 特盏 characteristic determinant 特招列式 characteristic diagram 特者图 characteristic einstein temperature 爱因斯坦特章度 characteristic energy 特哲量 characteristic equation 特性⽅程 characteristic frequency 特盏率 characteristic function 特寨数 characteristic hydraulic number 特蘸压数 characteristic length 特栅度 characteristic line 特性线 characteristic matrix 特肇阵 characteristic parameter 特性参数 characteristic plane 特战⾯ characteristic quantity 特性量 characteristic surface 特怔⾯ characteristic surge impedance 特性浪涌阻抗 characteristic temperature 特章度 characteristic value 特盏 characteristic vector 特崭量 characteristic velocity 特召度 characteristic wavelength 特炸长 characteristics 特性 charge 装药 charpy impact machine 却贝冲辉验机 charpy impact test 却贝冲辉验 chatter amplitude 颤动幅度 chatter mark 振颤痕 chatter vibration 颤动 chattering 颤动 check 校验 check analysis 检验分析 chilling 冷硬 choke 扼⼒ choke free ⽆阻塞的 choked nozzle 壅塞式喷管 choked wind tunnel 阻塞式风洞 choking 壅塞 choking coil 扼⼒ choking mach number 壅塞马赫数 choking region 壅柳 choking velocity 壅塞速度 chopped wave 斩波 choppy sea 三⾓浪 chord 翼弦 chord length 弦长 chronometry 测时 ciliary motion 纤⽑运动 circle errors of gyroscope 陀螺盘旋误差 circle of curvature 曲率圆 circle of inertia 惯性圆 circle of inflexions 挠曲圆 circular cone 圆锥 circular cylinder 圆柱 circular function 圆函数 circular motion 圆周运动 circular orbit 圆形轨道 circular pendulum 圆摆 circular shaft 圆轴 circular tube 圆管 circular velocity 圆速度 circular vibration 圆振动 circular vortex 圆涡 circular vorticity 圆涡 circular wave number vector 圆波⽮量 circular whirl 圆涡 circulating air 循环空⽓ circulating flow 环流 circulating water 循环⽔ circulation 循环 circulation branch 环林⽀ circulation coefficient 环恋数 circulation constant 环粒数 circulation free ⽆环聊 circulation index 环粮数 circulation layer 环零 circulation loop 循环管路 circulation of the vector field ⽮量场环路 circulation of water ⽔循环 circulation pattern 环良 circulation preserving motion 环量守恒运动 circulation process 循环过程 circulation theorem 环哩理 circulation water channel 循环⽔槽 circulator sector 扇形 circulatory flow 环流 circulatory integral 循环积分 circulatory motion 环了动 circulatory system 循环系统 circumference 圆周 circumferential component 周缘分量 circumferential direction 周向 circumferential force 切向⼒ circumferential speed 周向速率 circumglobal radiation 球⾯总辐射 circumgyration 回转 circumpolar vorticity 环极涡旋 circumsphere 外接球 cistern barometer 液槽⽓压计 civil engineering ⼟⽊⼯程 clamped beam 固⽀梁 clapeyron elastic body 克拉佩隆弹性体 clapotis 驻波 clapp oscillator 克拉普振荡器 classical mechanics 经典⼒学 classical physics 经典物理学 classical statistical mechanics 经典统计⼒学 classical theory of probability 经典概率论 classical thermodynamics 经典热⼒学 clausius clapeyron equation 克劳修斯克拉佩隆⽅程 clausius clapeyron relation 克劳修斯克拉佩隆⽅程 clausius duhem inequality 克劳修斯迪昂不等式 clausius planck inequality 克劳修斯普朗克不等式 clearance 间隙 cleavage 劈裂 cleavage crack 解理裂纹 cleavage fracture 解理断裂 cleavage fracture strength 解理断裂强度 cleavage plane 裂开⾯ cleavage strength 解理强度 cleft 裂纹 cleft family 裂⼝族 cleftiness 裂隙 climbing 攀移 climbing speed 上升速率 clinoaxis 斜轴 clipper 快速帆船 clockwise 顺时针⽅向的 clockwise rotation 顺时针旋转 closed loop 闭环 closed shell 闭壳 closed system 闭合系 closed wind tunnel 闭式回羚洞 closing pressure 关闭压⼒ co oscillating tides 共振潮 co oscillation 合振荡 co tidal line 等潮线 coagulation 凝聚 coalescence 聚并 coanda effect 柯安达效应 coasting motion 惯性运动 coating thickness 涂层厚度 cockpit 驾驶舱 coefficient of amplification 放⼤系数 coefficient of apparent expansion 表观膨胀系数 coefficient of compressibility 压缩系数 coefficient of condensation 凝结系数 coefficient of consolidation 固结系数 coefficient of contraction 收缩系数 coefficient of cubical expansion 体胀系数 coefficient of diffusion 扩散系数 coefficient of dispersion 弥散系数 coefficient of eddy viscosity 湍脸性系数 coefficient of elasticity 弹性系数 coefficient of elongation 伸长系数 coefficient of expansion 膨胀系数 coefficient of friction 摩擦系数 coefficient of heat conduction 热传导系数 coefficient of heat transmission 传热系数 coefficient of infiltration 浸渗系数 coefficient of internal friction 内摩擦系数 coefficient of kinetic friction 动摩擦系数 coefficient of linear extension 线伸长系数 coefficient of mutual diffusion 相互扩散系数 coefficient of pivoting friction 枢轴摩擦系数 coefficient of pressure diffusion 加压扩散系数 coefficient of regression 回归系数 coefficient of resistance 阻⼒系数 coefficient of restitution 恢复系数 coefficient of rolling friction 滚动摩擦系数 coefficient of sliding friction 滑动摩擦系数 coefficient of stability 稳定性系数 coefficient of static friction 静摩擦系数 coefficient of surface expansion 表⾯膨胀系数 coefficient of thermal conductivity 导热系数 coefficient of thermal expansion 热膨胀系数 coefficient of transmission 透射系数 coefficient of viscosity 粘性系数 coherence distance 相⼲距离 coherence function 相⼲函数 coherence length 相⼲距离 coherence scattering 相⼲散射 coherent structure of turbulence 湍拎⼲结构 coherent wave 相⼲波 cohesion 内聚 cohesion force 内聚⼒ cohesion pressure 内聚压⼒ cohesion strength 内聚强度 cohesionless soil ⽆粘聚性⼟ cohesive energy 内聚能 cohesive soil 粘聚性⼟ coiled spring 螺旋形弹簧 cold bending test 冷弯曲试验 cold brittleness 冷脆性 cold crack 冷裂纹 cold cutting 冷切 cold deformation 冷变形 cold drawing 冷拉 cold energy 冷能 cold flow 冷流 cold plasma 冷等离⼦体 cold pressure 冷压 cold rolling 冷轧 cold wave 冷波 cold working 冷加⼯ collapse 崩溃 collapse mechanism 破坏机构 collapsible tube 可折皱管 collapsing force 破坏⼒ collar vortex 涡环 collateral motion 次级运动 collective mode of motion 集体运动模式 collective motion 集体运动 collimation 视准 collision 碰撞 collision chain 碰撞链 collision cross section 碰撞截⾯ collision diameter 碰撞直径 collision diffusion 碰撞扩散 collision excitation 碰撞激发 collision frequency 碰撞频率 collision heating 碰撞加热 collision integral 碰撞积分 collision invariant 碰撞不变量。

Part 2Kinetics and catalysis Mechanism of reaction:Can not be proven ‐‐‐there are “well‐accepted” or “established” mechanisms“t bli h d”h iDeciphering reactions mechanisms is still important!!!Chapter6Kinetic Analyses 6.1 coordinate diagram and related concepts61Reaction6.2 Transition state theory (TST) and related topics6.3 Postulates and principles related to kinetic analysis6.4 Kinetic experiments6.5 Experiments related to thermodynamics and kinetics616.1 Reaction coordinate diagramgFig.6.161Related concepts6.1•Rate‐determining steps / rate‐limiting steps R t d t i i t t li iti t•Activated complex Transition stateA ti t d l/T iti t t•Rates and rate constantsR t d t t t•Reaction order and rate laws/differential rate R ti d d t l/diff ti l t equations/integrated rate equations•Kinetic order and molecularity6.2 Transition state theory (TST) and relatedtopics•Activation parameters: ΔG≠,ΔH≠,ΔS≠A i i•between rate and activation Relationship constant parameters:•Macroscopic rate constants and microscopic rate constant•Enthalpy control and entropy controlE h l l d lstateTransitionFig.6.26.3 Postulates related to kinetic analysis The Hammond Postulate•Used for estimating the structures of activated complexes.•“If two states, as for example, a transition state and an unstable “f f l d blintermediate, occur consecutively during a reaction process and have nearly the same energy content, their inter‐conversion will involve only a small reorganization of the molecular structuresstructures”•In essence, the activated complex most resembles the adjacent reactant, intermediate, or product that it is in energy to.intermediate closest•The fundamental assumption of Hammond is that molecules do not rapid changes along a reaction undergo rapid, discontinuous structurecoordinate and structural changes are generally smooth and continuous along the reaction pathway.of Hammond Postulate ApplicationsFig.6.4Fig.6.3The vs.reactivity vs selectivity principle“The reactive a compound is, the less willmore is selective it be”•More reactive molecules can be viewed either as being higher in energy or having more exothermic reactions.reactions•The more reactive compound will produce a transition state resembling morethe reactant more.•The transition state is affected little by the structure of other components involved reaction and the products.in the products•The reaction is not selective.There are many exceptions! Applied with caution!!vs.ThermodynamicKinetic Control•Kinetic control: the ratio of two or more products is determined by the relative energies of the transition states these products.leading to products•Thermodynamic control: the ratio of two or more products is solely determined by the relative energies of products.the productsFig.6.56.4 Kinetic experiments64Ki ti i t •Typical kinetic experimentsKinetic for simple mechanisms •analyses6.5 Experiments related to thermodynamics and kinetics •Isotope effects•Substituent effects•Linear free energy relationships•Acid‐Base related effects。

农家慧，蒋倩，孔令艳，等. 基于凹凸棒稳定的姜精油纳米乳的性质表征和结肠靶向研究[J]. 食品工业科技，2023，44（11）：13−19.doi: 10.13386/j.issn1002-0306.2022100204NONG Jiahui, JIANG Qian, KONG Lingyan, et al. Study on Characterization and Colonic Targeting of Ginger Essential Oil Nanoemulsion Stabilized by Palygorskite[J]. Science and Technology of Food Industry, 2023, 44(11): 13−19. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2022100204· 青年编委专栏—食品营养素包埋与递送（客座主编：黄强、蔡杰、陈帅） ·基于凹凸棒稳定的姜精油纳米乳的性质表征和结肠靶向研究农家慧，蒋　倩，孔令艳，薛　梅，雷　红*（南京财经大学食品科学与工程学院，江苏省现代粮食流通与安全协同创新中心，江苏南京 210023）摘　要：为提高姜精油（Ginger essential oil, GEO ）的稳定性和利用度，本实验室以酸改性凹凸棒为稳定剂、亚麻籽胶作为乳化剂、壳聚糖盐酸盐做壁材制备了姜精油纳米乳。

本研究对姜精油纳米乳进行性质表征（包括形貌与形态、粒径分布、流变性、红外光谱、包埋率）并评价其结肠靶向和缓释性能。

研究结果表明姜精油纳米乳粒径呈正态分布，液滴平均粒径为329.6 nm ，PDI 为0.259，包埋率为91.26%±0.03%；通过荧光显微镜和扫描电镜观察，表明所制备姜精油纳米乳分散度良好，呈表面光滑的球形；红外光谱结果表明，姜精油被包封进纳米乳中且化学组成未被破坏，纳米乳中各组分的结合方式为物理结合；姜精油纳米乳在 4、25、40 ℃贮藏28 d 稳定性良好；通过体外模拟消化试验及动力学分析结果表明，姜精油纳米乳具有结肠靶向和缓释的性能。

反应动力学英语Reaction Kinetics: The Fundamental Principles of Chemical TransformationsChemical reactions are the heart of the natural world, driving the processes that sustain life and shape our environment. At the core of these transformations lies the field of reaction kinetics, a branch of chemistry that delves into the intricate details of how and why chemical reactions occur. Understanding the principles of reaction kinetics is crucial for a wide range of applications, from the development of new pharmaceuticals to the optimization of industrial processes.At its most fundamental level, reaction kinetics explores the rates at which chemical reactions take place. This involves the study of the factors that influence the speed of a reaction, such as temperature, pressure, and the concentrations of the reactants. By understanding these factors, scientists and engineers can manipulate the conditions of a reaction to achieve desired outcomes, whether it's maximizing the yield of a valuable product or minimizing the formation of unwanted byproducts.One of the key concepts in reaction kinetics is the rate law, which describes the relationship between the concentrations of the reactants and the rate of the reaction. The rate law is typically expressed as a mathematical equation, with the rate constant and the reaction order as the primary variables. The rate constant reflects the inherent reactivity of the substances involved, while the reaction order indicates how the rate of the reaction changes as the concentrations of the reactants are altered.Another important aspect of reaction kinetics is the concept of the activation energy, which is the minimum amount of energy required for a reaction to occur. Reactions with higher activation energies tend to be slower and less favorable, while those with lower activation energies are more likely to occur spontaneously. Understanding the factors that influence activation energy, such as the molecular structure of the reactants and the presence of catalysts, is crucial for designing efficient and cost-effective chemical processes.The study of reaction kinetics also encompasses the mechanisms by which chemical reactions take place. These mechanisms can be quite complex, involving a series of elementary steps that collectively result in the overall transformation. By elucidating the mechanism of a reaction, scientists can gain valuable insights into the fundamental nature of the chemical process, which can then be used to developmore effective strategies for controlling and optimizing the reaction.One of the key applications of reaction kinetics is in the field of chemical engineering, where it plays a crucial role in the design and optimization of chemical processes. By understanding the kinetics of a reaction, engineers can determine the optimal operating conditions, such as temperature, pressure, and residence time, to maximize the yield and efficiency of the process. This knowledge is particularly important in the production of fuels, pharmaceuticals, and other high-value chemicals, where even small improvements in reaction kinetics can have a significant impact on the bottom line.Another important application of reaction kinetics is in the field of environmental chemistry, where it is used to understand and predict the fate of pollutants in the environment. By studying the kinetics of reactions involving environmental contaminants, scientists can develop strategies for their removal or remediation, as well as predict the long-term impacts of these substances on ecosystems and human health.In the realm of biological chemistry, reaction kinetics plays a crucial role in understanding the complex biochemical processes that sustain life. From the enzymatic reactions that drive metabolic pathways to the signaling cascades that regulate cellular function, the principles of reaction kinetics are essential for unraveling theintricate mechanisms that underlie the living world.As the scientific community continues to push the boundaries of our understanding of the natural world, the field of reaction kinetics will undoubtedly play an increasingly important role. By unlocking the secrets of how and why chemical reactions occur, we can unlock the keys to a more sustainable, efficient, and innovative future, one that harnesses the power of chemistry to address the pressing challenges of our time.。

Principles of Chemical KineticsPrinciplesofChemicalKinetics Second EditionJames E.HouseIllinoisStateUniversityandIllinois WesleyanUniversityAMSTERDAM • BOSTON • HEIDELBERG • LONDONNEW YORK • OXFORD • PARIS • SAN DIEGOSAN FRANCISCO • SINGAPORE • SYDNEY • TOKYOAcademic Press is an imprint of ElsevierAcademic Press is an imprint of Elsevier30Corporate Drive,Suite400,Burlington,MA01803,USA525B Street,Suite1900,San Diego,CA92101-4495,USA84Theobald’s Road,London WC1X8RR,UKThis book is printed on acid-freeCopyrightß2007,Elsevier Inc.All rights reserved.No part of this publication may be reproduced or transmitted in any form or by any means,electronic or mechanical,including photocopy,recording,or any information storage and retrieval system,without permission in writing from the publisher. Permissions may be sought directly from Elsevier’s Science&Technology Rights Department in Oxford,UK:phone:(þ44)1865843830,fax:(þ44)1865853333,E-mail:************************.You may also complete your request on-linevia the Elsevier homepage(http:==),by selecting‘‘Support&Contact’’then‘‘Copyright and Permission’’and then‘‘Obtaining Permissions.’’Library of Congress Cataloging-in-Publication DataHouse,J.E.Principles of chemical kinetics/James E.House.–2nd ed.p.cm.Includes index.ISBN:978-0-12-356787-1(hard cover:alk.paper) 1.Chemical kinetics.I.Title. QD502.H6820075410.394–dc222007024528 British Library Cataloguing-in-Publication DataA catalogue record for this book is available from the British Library.ISBN:978-0-12-356787-1For information on all Academic Press publicationsvisit our web site at Printed in the United States of America07080910987654321Preface Chemical kinetics is an enormous W eld that has been the subject of many books,including a series that consists of numerous large volumes.To try to cover even a small part of the W eld in a single volume of portable size is a di Y cult task.As is the case with every writer,I have been forced to make decisions on what to include,and like other books,this volume re X ects the interests and teaching experience of the author.As with the W rst edition,the objective has been to provide an introduc-tion to most of the major areas of chemical kinetics.The extent to which this has been done successfully will depend on the viewpoint of the reader. Those who study only gas phase reactions will argue that not enough material has been presented on that topic.A biochemist who specializes in enzyme-catalyzed reactions may W nd that research in that area requires additional material on the topic.A chemist who specializes in assessing the in X uence of substituent groups or solvent on rates and mechanisms of organic reactions may need other tools in addition to those presented. In fact,it is fair to say that this book is not written for a specialist in any area of chemical kinetics.Rather,it is intended to provide readers an introduction to the major areas of kinetics and to provide a basis for further study.In keeping with the intended audience and purposes,derivations are shown in considerable detail to make the results readily available to students with limited background in mathematics.In addition to the signi W cant editing of the entire manuscript,new sections have been included in several chapters.Also,Chapter9‘‘Additional Applications of Kinetics,’’has been added to deal with some topics that do not W t conveniently in other chapters.Consequently,this edition contains substantially more material,including problems and references,than the W rst edition.Unlike the W rst edition,a solution manual is also available.As in the case of the W rst edition,the present volume allows for variations in the order of taking up the material.After the W rst three chapters,thevvi Prefaceremaining chapters can be studied in any order.In numerous places in the text,attention is drawn to the fact that similar kinetic equations result for di V erent types of processes.As a result,it is hoped that the reader will see that the assumptions made regarding interaction of an enzyme with a substrate are not that di V erent from those regarding the adsorption of a gas on the surface of a solid when rate laws are derived.The topics dealing with solid state processes and nonisothermal kinetics are covered in more detail than in some other texts in keeping with the growing importance of these topics in many areas of chemistry.These areas are especially important in industrial laboratories working on processes involving the drying, crystallizing,or characterizing of solid products.It is hoped that the present volume will provide a succinct and clear introduction to chemical kinetics that meets the needs of students at a variety of levels in several disciplines.It is also hoped that the principles set forth will prove useful to researchers in many areas of chemistry and provide insight into how to interpret and correlate their kinetic data.Contents1Fundamental Concepts of Kinetics11.1Rates of Reactions21.2Dependence of Rates on Concentration41.2.1First-Order51.2.2Second-Order81.2.3Zero-Order101.2.4N th-Order Reactions131.3Cautions on Treating Kinetic Data131.4E V ect of Temperature161.5Some Common Reaction Mechanisms201.5.1Direct Combination211.5.2Chain Mechanisms221.5.3Substitution Reactions231.6Catalysis27References for Further Reading30 Problems31 2Kinetics of More Complex Systems372.1Second-Order Reaction,First-Order in Two Components372.2Third-Order Reactions432.3Parallel Reactions452.4Series First-Order Reactions472.5Series Reactions with Two Intermediates532.6Reversible Reactions582.7Autocatalysis642.8E V ect of Temperature69References for Further Reading75 Problems75viiviii Contents3Techniques and Methods793.1Calculating Rate Constants793.2The Method of Half-Lives813.3Initial Rates833.4Using Large Excess of a Reactant(Flooding)863.5The Logarithmic Method873.6E V ects of Pressure893.7Flow Techniques943.8Relaxation Techniques953.9Tracer Methods983.10Kinetic Isotope E V ects102References for Further Reading107 Problems108 4Reactions in the Gas Phase1114.1Collision Theory1114.2The Potential Energy Surface1164.3Transition State Theory1194.4Unimolecular Decomposition of Gases1244.5Free Radical or Chain Mechanisms1314.6Adsorption of Gases on Solids1364.6.1Langmuir Adsorption Isotherm1384.6.2B–E–T Isotherm1424.6.3Poisons and Inhibitors1434.7Catalysis145References for Further Reading147 Problems148 5Reactions in Solutions1535.1The Nature of Liquids1535.1.1Intermolecular Forces1545.1.2The Solubility Parameter1595.1.3Solvation of Ions and Molecules1635.1.4The Hard-Soft Interaction Principle(HSIP)1655.2E V ects of Solvent Polarity on Rates1675.3Ideal Solutions1695.4Cohesion Energies of Ideal Solutions1725.5E V ects of Solvent Cohesion Energy on Rates1755.6Solvation and Its E V ects on Rates1775.7E V ects of Ionic Strength182Contents ix5.8Linear Free Energy Relationships1855.9The Compensation E V ect1895.10Some Correlations of Rates with Solubility Parameter191References for Further Reading198 Problems199 6Enzyme Catalysis2056.1Enzyme Action2056.2Kinetics of Reactions Catalyzed by Enzymes2086.2.1Michaelis–Menten Analysis2086.2.2Lineweaver–Burk and Eadie Analyses2136.3Inhibition of Enzyme Action2156.3.1Competitive Inhibition2166.3.2Noncompetitive Inhibition2186.3.3Uncompetitive Inhibition2196.4The E V ect of pH2206.5Enzyme Activation by Metal Ions2236.6Regulatory Enzymes224References for Further Reading226 Problems227 7Kinetics of Reactions in the Solid State2297.1Some General Considerations2297.2Factors A V ecting Reactions in Solids2347.3Rate Laws for Reactions in Solids2357.3.1The Parabolic Rate Law2367.3.2The First-Order Rate Law2377.3.3The Contracting Sphere Rate Law2387.3.4The Contracting Area Rate Law2407.4The Prout–Tompkins Equation2437.5Rate Laws Based on Nucleation2467.6Applying Rate Laws2497.7Results of Some Kinetic Studies2527.7.1The Deaquation-Anation of[Co(NH3)5H2O]Cl32527.7.2The Deaquation-Anation of[Cr(NH3)5H2O]Br32557.7.3The Dehydration of Trans-[Co(NH3)4Cl2]IO3 2H2O2567.7.4Two Reacting Solids259References for Further Reading261 Problems262x Contents8Nonisothermal Methods in Kinetics2678.1TGA and DSC Methods2688.2Kinetic Analysis by the Coats and Redfern Method2718.3The Reich and Stivala Method2758.4A Method Based on Three(a,T)Data Pairs2768.5A Method Based on Four(a,T)Data Pairs2798.6A Di V erential Method2808.7A Comprehensive Nonisothermal Kinetic Method2808.8The General Rate Law and a Comprehensive Method281References for Further Reading287 Problems288 9Additional Applications of Kinetics2899.1Radioactive Decay2899.1.1Independent Isotopes2909.1.2Parent-Daughter Cases2919.2Mechanistic Implications of Orbital Symmetry2979.3A Further Look at Solvent Properties and Rates303References for Further Reading313 Problems314 Index317。

物理化学英语词汇BET公式BET formulaDLVO理论DLVO theoryHLB法hydrophile-lipophile balance methodpVT性质pVT propertyζ电势zeta potential阿伏加德罗常数Avogadro’number阿伏加德罗定律Avogadro law阿累尼乌斯电离理论Arrhenius ionization theory阿累尼乌斯方程Arrhenius equation阿累尼乌斯活化能Arrhenius activation energy阿马格定律Amagat law艾林方程Erying equation爱因斯坦光化当量定律Einstein’s law of photochemical equivalence 爱因斯坦－斯托克斯方程Einstein-Stokes equation安托万常数Antoine constant安托万方程Antoine equation盎萨格电导理论Onsager’s theory of conductance半电池half cell半衰期half time period饱和液体saturated liquids饱和蒸气saturated vapor饱和吸附量saturated extent of adsorption饱和蒸气压saturated vapor pressure爆炸界限explosion limits比表面功specific surface work比表面吉布斯函数specific surface Gibbs function比浓粘度reduced viscosity标准电动势standard electromotive force标准电极电势standard electrode potential标准摩尔反应焓standard molar reaction enthalpy标准摩尔反应吉布斯函数standard Gibbs function of molar reaction 标准摩尔反应熵standard molar reaction entropy标准摩尔焓函数standard molar enthalpy function标准摩尔吉布斯自由能函数standard molar Gibbs free energy function 标准摩尔燃烧焓standard molar combustion enthalpy标准摩尔熵standard molar entropy标准摩尔生成焓standard molar formation enthalpy 标准摩尔生成吉布斯函数standard molar formation Gibbs function 标准平衡常数standard equilibrium constant标准氢电极standard hydrogen electrode标准态standard state标准熵standard entropy标准压力standard pressure标准状况standard condition表观活化能apparent activation energy表观摩尔质量apparent molecular weight表观迁移数apparent transference number表面surfaces表面过程控制surface process control表面活性剂surfactants表面吸附量surface excess表面张力surface tension表面质量作用定律surface mass action law波义尔定律Boyle law波义尔温度Boyle temperature波义尔点Boyle point玻尔兹曼常数Boltzmann constant玻尔兹曼分布Boltzmann distribution玻尔兹曼公式Boltzmann formula玻尔兹曼熵定理Boltzmann entropy theorem玻色－爱因斯坦统计Bose-Einstein statistics泊Poise不可逆过程irreversible process不可逆过程热力学thermodynamics of irreversible processes不可逆相变化irreversible phase change布朗运动brownian movement查理定律Charle’s law产率yield敞开系统open system超电势over potential沉降sedimentation沉降电势sedimentation potential沉降平衡sedimentation equilibrium触变thixotropy粗分散系统thick disperse system催化剂catalyst单分子层吸附理论mono molecule layer adsorption单分子反应unimolecular reaction单链反应straight chain reactions弹式量热计bomb calorimeter道尔顿定律Dalton law道尔顿分压定律Dalton partial pressure law德拜和法尔肯哈根效应Debye and Falkenhagen effect德拜立方公式Debye cubic formula德拜－休克尔极限公式Debye-Huckel’s limiting equation等焓过程isenthalpic process等焓线isenthalpic line等几率定理theorem of equal probability等温等容位Helmholtz free energy等温等压位Gibbs free energy等温方程equation at constant temperature低共熔点eutectic point低共熔混合物eutectic mixture低会溶点lower consolute point低熔冰盐合晶cryohydric第二类永动机perpetual machine of the second kind第三定律熵third-law entropy第一类永动机perpetual machine of the first kind缔合化学吸附association chemical adsorption电池常数cell constant电池电动势electromotive force of cells电池反应cell reaction电导conductance电导率conductivity电动势的温度系数temperature coefficient of electromotive force电动电势zeta potential电功electric work电化学electrochemistry电化学极化electrochemical polarization电极电势electrode potential电极反应reactions on the electrode电极种类type of electrodes电解池electrolytic cell电量计coulometer电流效率current efficiency电迁移electro migration电迁移率electromobility电渗electroosmosis电渗析electrodialysis电泳electrophoresis丁达尔效应Dyndall effect定容摩尔热容molar heat capacity under constant volume 定容温度计Constant voIume thermometer定压摩尔热容molar heat capacity under constant pressure 定压温度计constant pressure thermometer定域子系统localized particle system动力学方程kinetic equations动力学控制kinetics control独立子系统independent particle system对比摩尔体积reduced mole volume对比体积reduced volume对比温度reduced temperature对比压力reduced pressure对称数symmetry number对行反应reversible reactions对应状态原理principle of corresponding state多方过程polytropic process多分子层吸附理论adsorption theory of multi-molecular layers 二级反应second order reaction二级相变second order phase change法拉第常数faraday constant法拉第定律Faraday’s law反电动势back E.M.F.反渗透reverse osmosis反应分子数molecularity反应级数reaction orders反应进度extent of reaction反应热heat of reaction反应速率rate of reaction反应速率常数constant of reaction rate范德华常数van der Waals constant范德华方程van der Waals equation范德华力van der Waals force范德华气体van der Waals gases范特霍夫方程van’t Hoff equation范特霍夫规则van’t Hoff rule范特霍夫渗透压公式van’t Hoff equation of osmotic pressure非基元反应non-elementary reactions非体积功non-volume work非依时计量学反应time independent stoichiometric reactions 菲克扩散第一定律Fick’s first law of diffusion沸点boiling point沸点升高elevation of boiling point费米－狄拉克统计Fermi-Dirac statistics分布distribution分布数distribution numbers分解电压decomposition voltage分配定律distribution law分散系统disperse system分散相dispersion phase分体积partial volume分体积定律partial volume law分压partial pressure分压定律partial pressure law分子反应力学mechanics of molecular reactions分子间力intermolecular force分子蒸馏molecular distillation封闭系统closed system附加压力excess pressure弗罗因德利希吸附经验式Freundlich empirical formula of adsorption负极negative pole负吸附negative adsorption复合反应composite reaction盖·吕萨克定律Gay-Lussac law盖斯定律Hess law甘汞电极calomel electrode感胶离子序lyotropic series杠杆规则lever rule高分子溶液macromolecular solution高会溶点upper consolute point隔离法the isolation method格罗塞斯－德雷珀定律Grotthus-Draoer’s law隔离系统isolated system根均方速率root-mean-square speed功work功函work content共轭溶液conjugate solution共沸温度azeotropic temperature构型熵configurational entropy孤立系统isolated system固溶胶solid sol固态混合物solid solution固相线solid phase line光反应photoreaction光化学第二定律the second law of actinochemistry光化学第一定律the first law of actinochemistry光敏反应photosensitized reactions光谱熵spectrum entropy广度性质extensive property广延量extensive quantity广延性质extensive property规定熵stipulated entropy过饱和溶液oversaturated solution过饱和蒸气oversaturated vapor过程process过渡状态理论transition state theory过冷水super-cooled water过冷液体overcooled liquid过热液体overheated liquid亥姆霍兹函数Helmholtz function亥姆霍兹函数判据Helmholtz function criterion亥姆霍兹自由能Helmholtz free energy亥氏函数Helmholtz function焓enthalpy亨利常数Henry constant亨利定律Henry law恒沸混合物constant boiling mixture恒容摩尔热容molar heat capacity at constant volume恒容热heat at constant volume恒外压constant external pressure恒压摩尔热容molar heat capacity at constant pressure恒压热heat at constant pressure化学动力学chemical kinetics化学反应计量式stoichiometric equation of chemical reaction 化学反应计量系数stoichiometric coefficient of chemical reaction 化学反应进度extent of chemical reaction化学亲合势chemical affinity化学热力学chemical thermodynamics化学势chemical potential化学势判据chemical potential criterion化学吸附chemisorptions环境environment环境熵变entropy change in environment挥发度volatility混合熵entropy of mixing混合物mixture活度activity活化控制activation control活化络合物理论activated complex theory活化能activation energy霍根-华森图Hougen-Watson Chart 基态能级energy level at ground state基希霍夫公式Kirchhoff formula基元反应elementary reactions 积分溶解热integration heat of dissolution吉布斯－杜亥姆方程Gibbs-Duhem equation吉布斯－亥姆霍兹方程Gibbs-Helmhotz equation 吉布斯函数Gibbs function吉布斯函数判据Gibbs function criterion吉布斯吸附公式Gibbs adsorption formula 吉布斯自由能Gibbs free energy吉氏函数Gibbs function极化电极电势polarization potential of electrode 极化曲线polarization curves极化作用polarization极限摩尔电导率limiting molar conductivity几率因子steric factor计量式stoichiometric equation计量系数stoichiometric coefficient价数规则rule of valence简并度degeneracy键焓bond enthalpy胶冻broth jelly胶核colloidal nucleus胶凝作用demulsification胶束micelle胶体colloid胶体分散系统dispersion system of colloid胶体化学collochemistry胶体粒子colloidal particles胶团micelle焦耳Joule焦耳-汤姆生实验Joule-Thomson experiment 焦耳-汤姆生系数Joule-Thomson coefficient焦耳-汤姆生效应Joule-Thomson effect焦耳定律Joule`s law接触电势contact potential接触角contact angle节流过程throttling process节流膨胀throttling expansion节流膨胀系数coefficient of throttling expansion结线tie line结晶热heat of crystallization解离化学吸附dissociation chemical adsorption界面interfaces界面张力surface tension浸湿immersion wetting浸湿功immersion wetting work精馏rectify聚（合）电解质polyelectrolyte聚沉coagulation聚沉值coagulation value绝对反应速率理论absolute reaction rate theory绝对熵absolute entropy绝对温标absolute temperature scale绝热过程adiabatic process绝热量热计adiabatic calorimeter绝热指数adiabatic index卡诺定理Carnot theorem卡诺循环Carnot cycle开尔文公式Kelvin formula柯诺瓦洛夫－吉布斯定律Konovalov-Gibbs law科尔劳施离子独立运动定律Kohlrausch’s Law of Independent Migration of Ions可能的电解质potential electrolyte可逆电池reversible cell可逆过程reversible process可逆过程方程reversible process equation可逆体积功reversible volume work可逆相变reversible phase change克拉佩龙方程Clapeyron equation克劳修斯不等式Clausius inequality克劳修斯－克拉佩龙方程Clausius-Clapeyron equation控制步骤control step库仑计coulometer扩散控制diffusion controlled拉普拉斯方程Laplace’s equation拉乌尔定律Raoult law兰格缪尔－欣谢尔伍德机理Langmuir-Hinshelwood mechanism兰格缪尔吸附等温式Langmuir adsorption isotherm formula雷利公式Rayleigh equation冷冻系数coefficient of refrigeration冷却曲线cooling curve离解热heat of dissociation离解压力dissociation pressure离域子系统non-localized particle systems离子的标准摩尔生成焓standard molar formation of ion离子的电迁移率mobility of ions 离子的迁移数transport number of ions 离子独立运动定律law of the independent migration of ions离子氛ionic atmosphere离子强度ionic strength理想混合物perfect mixture理想气体ideal gas接触电势contact potential接触角contact angle节流过程throttling process节流膨胀throttling expansion节流膨胀系数coefficient of throttling expansion结线tie line结晶热heat of crystallization解离化学吸附dissociation chemical adsorption界面interfaces界面张力surface tension浸湿immersion wetting浸湿功immersion wetting work精馏rectify聚（合）电解质polyelectrolyte聚沉coagulation聚沉值coagulation value绝对反应速率理论absolute reaction rate theory绝对熵absolute entropy绝对温标absolute temperature scale绝热过程adiabatic process绝热量热计adiabatic calorimeter绝热指数adiabatic index卡诺定理Carnot theorem卡诺循环Carnot cycle开尔文公式Kelvin formula柯诺瓦洛夫－吉布斯定律Konovalov-Gibbs law科尔劳施离子独立运动定律Kohlrausch’s Law of Independent Migration of Ions可能的电解质potential electroly可逆电池reversible cell可逆过程reversible process可逆过程方程reversible process equation可逆体积功reversible volume work可逆相变reversible phase change克拉佩龙方程Clapeyron equation克劳修斯不等式Clausius inequality克劳修斯－克拉佩龙方程Clausius-Clapeyron equation控制步骤control step库仑计coulometer扩散控制diffusion controlled拉普拉斯方程Laplace’s equation拉乌尔定律Raoult law兰格缪尔－欣谢尔伍德机理Langmuir-Hinshelwood mechanism兰格缪尔吸附等温式Langmuir adsorption isotherm formula雷利公式Rayleigh equation冷冻系数coefficient of refrigeration冷却曲线cooling curve离解热heat of dissociation离解压力dissociation pressure离域子系统non-localized particle systems离子的标准摩尔生成焓standard molar formation of ion离子的电迁移率mobility of ions离子的迁移数transport number of ions离子独立运动定律law of the independent migration of ions离子氛ionic atmosphere离子强度ionic strength理想混合物perfect mixture理想气体ideal gas理想气体的绝热指数adiabatic index of ideal gases理想气体的微观模型micro-model of ideal gas 理想气体反应的等温方程isothermal equation of ideal gaseous reactions理想气体绝热可逆过程方程adiabatic reversible process equation of ideal gases理想气体状态方程state equation of ideal gas理想稀溶液ideal dilute solution理想液态混合物perfect liquid mixture粒子particles粒子的配分函数partition function of particles连串反应consecutive reactions链的传递物chain carrier链反应chain reactions量热熵calorimetric entropy量子统计quantum statistics量子效率quantum yield临界参数critical parameter临界常数critical constant临界点critical point临界胶束浓度critical micelle concentration临界摩尔体积critical molar volume临界温度critical temperature临界压力critical pressure临界状态critical state零级反应zero order reaction流动电势streaming potential流动功flow work笼罩效应cage effect路易斯－兰德尔逸度规则Lewis-Randall rule of fugacity露点dew point露点线dew point line麦克斯韦关系式Maxwell relations 麦克斯韦速率分布Maxwell distribution of speeds麦克斯韦能量分布MaxwelIdistribution of energy 毛细管凝结condensation in capillary毛细现象capillary phenomena米凯利斯常数Michaelis constant摩尔电导率molar conductivity摩尔反应焓molar reaction enthalpy摩尔混合熵mole entropy of mixing摩尔气体常数molar gas constant摩尔热容molar heat capacity摩尔溶解焓mole dissolution enthalpy摩尔稀释焓mole dilution enthalpy内扩散控制internal diffusions control内能internal energy内压力internal pressure能级energy levels能级分布energy level distribution能量均分原理principle of the equipartition of energy能斯特方程Nernst equation能斯特热定理Nernst heat theorem凝固点freezing point凝固点降低lowering of freezing point凝固点曲线freezing point curve凝胶gelatin凝聚态condensed state凝聚相condensed phase浓差超电势concentration over-potential浓差极化concentration polarization浓差电池concentration cells帕斯卡pascal泡点bubble point泡点线bubble point line配分函数partition function配分函数的析因子性质property that partition function to be expressed as a p roduct of the separate partition functions for each kind of state碰撞截面collision cross section碰撞数the number of collisions偏摩尔量partial mole quantities平衡常数（理想气体反应）equilibrium constants for reactions of ideal gases 平动配分函数partition function of translation平衡分布equilibrium distribution平衡态equilibrium state平衡态近似法equilibrium state approximation平衡状态图equilibrium state diagram平均活度mean activity平均活度系统mean activity coefficient平均摩尔热容mean molar heat capacity平均质量摩尔浓度mean mass molarity平均自由程mean free path平行反应parallel reactions破乳demulsification铺展spreading普遍化范德华方程universal van der Waals equation其它功the other work气化热heat of vaporization气溶胶aerosol气体常数gas constant气体分子运动论kinetic theory of gases气体分子运动论的基本方程foundamental equation of kinetic theory of gases气溶胶aerosol气相线vapor line迁移数transport number潜热latent heat强度量intensive quantity强度性质intensive property亲液溶胶hydrophilic sol氢电极hydrogen electrodes区域熔化zone melting热heat热爆炸heat explosion热泵heat pump热功当量mechanical equivalent of heat热函heat content热化学thermochemistry热化学方程thermochemical equation热机heat engine热机效率efficiency of heat engine热力学thermodynamics热力学第二定律the second law of thermodynamics热力学第三定律the third law of thermodynamics热力学第一定律the first law of thermodynamics热力学基本方程fundamental equation of thermodynamics 热力学几率thermodynamic probability热力学能thermodynamic energy 热力学特性函数characteristic thermodynamic function 热力学温标thermodynamic scale of temperature 热力学温度thermodynamic temperature热熵thermal entropy热效应heat effect熔点曲线melting point curve熔化热heat of fusion溶胶colloidal sol溶解焓dissolution enthalpy溶液solution溶胀swelling乳化剂emulsifier乳状液emulsion润湿wetting润湿角wetting angle萨克尔－泰特洛德方程Sackur-Tetrode equation三相点triple point三相平衡线triple-phase line熵entropy熵判据entropy criterion熵增原理principle of entropy increase渗透压osmotic pressure渗析法dialytic process生成反应formation reaction升华热heat of sublimation实际气体real gas舒尔采－哈迪规则Schulze-Hardy rule松驰力relaxation force松驰时间time of relaxation速度常数reaction rate constant速率方程rate equations速率控制步骤rate determining step塔费尔公式Tafel equation态－态反应state-state reactions唐南平衡Donnan equilibrium淌度mobility特鲁顿规则Trouton rule特性粘度intrinsic viscosity体积功volume work统计权重statistical weight统计热力学statistic thermodynamics统计熵statistic entropy途径path途径函数path function外扩散控制external diffusion control完美晶体perfect crystalline完全气体perfect gas微观状态microstate微态microstate韦斯顿标准电池Weston standard battery维恩效应Wien effect维里方程virial equation维里系数virial coefficient稳流过程steady flow process稳态近似法stationary state approximation无热溶液athermal solution无限稀溶液solutions in the limit of extreme dilution物理化学Physical Chemistry物理吸附physisorptions吸附adsorption吸附等量线adsorption isostere吸附等温线adsorption isotherm吸附等压线adsorption isobar吸附剂adsorbent吸附量extent of adsorption吸附热heat of adsorption吸附质adsorbate析出电势evolution or deposition potential析因子性质property that partition function to be expressed as a product of the separate partition functions for each kind of state稀溶液的依数性colligative properties of dilute solutions稀释焓dilution enthalpy系统system系统点system point系统的环境environment of system相phase相变phase change相变焓enthalpy of phase change相变化phase change相变热heat of phase change相点phase point相对挥发度relative volatility相对粘度relative viscosity相律phase rule相平衡热容heat capacity in phase equilibrium相图phase diagram相倚子系统system of dependent particles悬浮液suspension循环过程cyclic process压力商pressure quotient压缩因子compressibility factor压缩因子图diagram of compressibility factor亚稳状态metastable state盐桥salt bridge盐析salting out阳极anode杨氏方程Young’s equation液体接界电势liquid junction potential液相线liquid phase lines一级反应first order reaction一级相变first order phase change依时计量学反应time dependent stoichiometric reactions逸度fugacity逸度系数coefficient of fugacity阴极cathode荧光fluorescence永动机perpetual motion machine永久气体Permanent gas有效能available energy原电池primary cell原盐效应salt effect增比粘度specific viscosity憎液溶胶lyophobic sol沾湿adhesional wetting沾湿功the work of adhesional wetting真溶液true solution真实电解质real electrolyte真实气体real gas真实迁移数true transference number振动配分函数partition function of vibration振动特征温度characteristic temperature of vibration 蒸气压下降depression of vapor pressure正常沸点normal point正吸附positive adsorption支链反应branched chain reactions直链反应straight chain reactions指前因子pre-exponential factor质量作用定律mass action law制冷系数coefficient of refrigeration中和热heat of neutralization轴功shaft work转动配分函数partition function of rotation转动特征温度characteristic temperature of vibration转化率convert ratio转化温度conversion temperature状态state状态方程state equation状态分布state distribution状态函数state function准静态过程quasi-static process准一级反应pseudo first order reaction自动催化作用auto-catalysis自由度degree of freedom自由度数number of degree of freedom自由焓free enthalpy自由能free energy自由膨胀free expansion组分数component number最低恒沸点lower azeotropic point最高恒沸点upper azeotropic point最佳反应温度optimal reaction temperature 最可几分布most probable distribution最可几速率most。

化学溶石方法由来已久，是针对泌尿系结石的一种不容忽视的治疗方式，有其独特优势。

溶解液通过与结石成分化学反应，使结石成分重新溶解在液相中，随着液体被带出体外。

由于液体的流动性和溶液成分的可扩散性，较各种手术手段更容易到达肾脏的各个角落，不容易有治疗死角，因而处理结石更加彻底、干净。

随着现代泌尿外科微创技术的发展，各种内镜技术的成熟，包括肾造瘘管、输尿管导管、双J 管、导尿管在内的各种常规导管形成的通路成为术后溶石治疗的理想平台，使溶石治疗能够方便地与外科治疗相结合。

因而，化学溶石治疗的应用前景更加明朗。

笔者［1］前期已针对溶石溶液的成分进行了一定的基础研究，改进了磷酸盐结石溶解液的成分，仿照经典的Suby 氏液配制了以乳酸、α酮戊二酸为主要成分的两种溶解溶液，并证实新溶解液较经典溶液的溶解效率明显提高。

然而，新溶液的临床应用任重道远，尚面临许多未解决的现实问题。

首先是灌注溶石的过程采用何种速度的问题。

按照反应的一般规律，如果灌注速度过高，溶液从结石表面快速流过，还没来及充分反应就脱离了反应界面，浪费溶液。

此外灌注速度过高可能会导致肾盂压力升高而导致患者不适或溶液吸收，发生危险。

如果灌注过慢，虽然反应深度较好，溶液利用率较高，但产物带走慢，阻碍反应进行，溶解效率将较低。

此外人体尿液产生的速度相对恒定，灌注速度慢的情况下，相对而言尿液对溶解液的稀释作用将更为严重，溶解效率会进一步降低。

如果溶解效率太低将丧失临床治疗的现实可能性。

灌流过快或过慢均有明显弊端，因而采用合适的灌流速度是结石溶解治疗的需要解决的一个重要问题。

查阅既往文献，各学者采用的灌流速度并不相同，临床常用流量为100~120mL/h ，但之前的文献中并未说明原因，也查阅不到关于确定灌流速度的相关文献。

为了解决上述问题，阐明结石溶解doi ：10.3969/j.issn.1006⁃5725.2017.16.022基金项目：中山市科技计划项目基金资助（编号：2014A1FC120）作者单位：528415广东省中山市，南方医科大学附属小榄医院泌尿外科体外试验模拟肾结石溶解治疗的反应动力学张劲勍杨增士叶宁卓红兵沈勇虎林豪胜李刚【摘要】目的探索结石溶解溶液在模拟人体环境下溶解结石过程中的反应动力学规律，为临床应用提供参考。

本征动力学的英语Intrinsic KineticsThe study of intrinsic kinetics is a fundamental aspect of chemical engineering and chemistry, providing insights into the underlying mechanisms and rate-controlling steps of chemical reactions. Intrinsic kinetics refers to the inherent rate of a reaction, unaffected by external factors such as mass transfer limitations or heat transfer effects. Understanding intrinsic kinetics is crucial for the design, optimization, and scale-up of chemical processes, as well as for the development of new materials and catalysts.One of the key concepts in intrinsic kinetics is the rate equation, which describes the relationship between the reaction rate and the concentrations of the reactants and products. The rate equation is typically expressed as a function of the reactant concentrations raised to various powers, known as the reaction order. Determining the reaction order is a crucial step in understanding the underlying mechanism of a reaction, as it provides information about the molecularity of the rate-determining step.Another important aspect of intrinsic kinetics is the activation energy,which represents the energy barrier that must be overcome for the reaction to occur. The activation energy is related to the temperature dependence of the reaction rate, as described by the Arrhenius equation. By studying the temperature dependence of the reaction rate, researchers can determine the activation energy and gain insights into the energy requirements of the reaction.The study of intrinsic kinetics also involves the investigation of reaction mechanisms, which describe the sequence of elementary steps that occur during a chemical reaction. Understanding the reaction mechanism is essential for the rational design of catalysts and the optimization of reaction conditions. Various experimental and computational techniques, such as kinetic studies, spectroscopic methods, and quantum chemical calculations, are used to elucidate reaction mechanisms.One of the key applications of intrinsic kinetics is in the field of heterogeneous catalysis, where the rate-determining step often involves the adsorption, surface reaction, and desorption of reactants and products on the catalyst surface. By studying the intrinsic kinetics of these surface processes, researchers can develop more efficient catalysts and optimize reaction conditions to improve the overall performance of the catalytic system.Another important application of intrinsic kinetics is in the designand optimization of chemical reactors. The intrinsic kinetics of a reaction, combined with information about the reactor geometry and operating conditions, can be used to predict the performance of the reactor and optimize its design. This knowledge is crucial for the scale-up of chemical processes from the laboratory to industrial scale.In recent years, the study of intrinsic kinetics has also become increasingly important in the field of renewable energy and sustainable chemistry. As the world transitions towards more environmentally friendly energy sources and chemical processes, understanding the intrinsic kinetics of reactions involved in these technologies, such as biofuel production, CO2 conversion, and water splitting, is essential for improving their efficiency and viability.In conclusion, the study of intrinsic kinetics is a fundamental and multifaceted field of chemical engineering and chemistry, providing valuable insights into the underlying mechanisms and rate-controlling steps of chemical reactions. By understanding intrinsic kinetics, researchers and engineers can develop more efficient and sustainable chemical processes, design better catalysts, and optimize the performance of chemical reactors. As the world continues to face complex challenges in areas such as energy, materials, and the environment, the importance of intrinsic kinetics will only continue to grow.。

Love is a profound and enduring emotion that has been celebrated in literature,art, and music throughout history.The concept of a couple being together for an eternity, often referred to as forever and ever,is a romantic ideal that many people aspire to achieve.Here are some key points to consider when writing an essay on the topic of couples and everlasting love:1.Definition of Eternal Love:Begin by defining what eternal love means.It could be described as a love that transcends time and space,a bond that remains unbroken regardless of the challenges faced.2.Historical and Cultural Perspectives:Discuss how different cultures and societies have viewed eternal love.For example,the concept of till death do us part in Western wedding vows,or the idea of soulmates in various mythologies.3.The Role of Commitment:Emphasize the importance of commitment in a relationship. Eternal love is not just a feeling but also a promise to stand by each other through all circumstances.4.Overcoming Obstacles:Talk about the various obstacles that couples may face,such as distance,personal growth,or external pressures,and how overcoming these can strengthen a relationship.munication and Understanding:Highlight the significance of open communication and mutual understanding in maintaining a lasting relationship.These are the foundations upon which trust and respect are built.6.Personal Growth:Discuss how individuals in a relationship must grow together and support each others personal development.This growth can help ensure that the relationship remains dynamic and fulfilling.7.Shared Values and Goals:Explain how couples with shared values and life goals are more likely to have a lasting relationship.These commonalities provide a solid foundation for the partnership.8.The Importance of Love and Respect:Stress the importance of love and respect in a relationship.Without these fundamental elements,a relationship cannot truly be described as eternal.9.Coping with Change:Address the inevitability of change and how couples need to adapt and evolve together to maintain their bond.10.RealLife Examples:Provide examples of couples who have demonstrated eternal love, either from history,literature,or personal anecdotes.11.Conclusion:Conclude by summarizing the key points and reiterating the importance of eternal love in a couples relationship.You might also reflect on the challenges and joys of pursuing such a profound connection.Remember to use a narrative style that is engaging and reflective,allowing readers to connect with the emotional depth of the e descriptive language to evoke the beauty and complexity of eternal love,and consider including a personal touch to make the essay more relatable.。

Archaeological discoveries have long fascinated scholars and the general public alike,offering a window into the past and providing invaluable insights into the lives and cultures of ancient civilizations.Here are some key aspects to consider when writing an essay on archaeological finds:1.Introduction to Archaeology:Begin by explaining what archaeology is and its importance in understanding human history.Mention how it helps us uncover the remains of past societies,from artifacts to architectural structures.2.Significance of Recent Discoveries:Discuss recent archaeological findings that have captured the worlds attention.For example,you could talk about the discovery of the tomb of Tutankhamun,which shed light on ancient Egyptian culture,or the unearthing of the Terracotta Army in China,which provided a glimpse into the military and artistic achievements of the Qin dynasty.3.Technological Advancements:Describe how technology has improved the field of archaeology.Techniques such as remote sensing,LIDAR,and DNA analysis have allowed archaeologists to make discoveries that were previously impossible.4.Cultural and Historical Insights:Elaborate on the cultural and historical information that these discoveries have provided.Discuss how they have contributed to our understanding of ancient languages,religious practices,social structures,and daily life.5.Ethical Considerations:Address the ethical dilemmas that sometimes arise in archaeology,such as the repatriation of artifacts,the disturbance of sacred sites,and the potential for looting and vandalism.6.Impact on Modern Society:Reflect on how archaeological discoveries influence modern society.This could include the impact on tourism,the inspiration for art and literature,and the role of archaeology in national identity and pride.7.Challenges and Future Directions:Discuss the challenges faced by archaeologists,such as funding constraints,political instability in certain regions,and the need for international cooperation.Also,look towards the future and speculate on how archaeology might evolve,including the potential for underwater archaeology and space archaeology.8.Conclusion:Summarize the main points of your essay,emphasizing the importance of archaeological discoveries in enriching our understanding of the past and their relevance to contemporary society.Remember to use specific examples and evidence from archaeological findings to support your points.Additionally,ensure that your essay is wellstructured,with a clear introduction,body,and conclusion.。

Chemistry—Ch. 13Use your textbook and/or the power point to complete the statements.13.1The Nature of Gases1.The energy an object has because of its motion is called ___________________.2.According to the kinetic theory, all matter consists of tiny particles that are in constantmotion. The fundamental assumptions about gases are (key concepts p. 385):a)b)c)3.Gas pressure is ____________________________________________________;atmospheric pressure results from _____________________________________.4.The SI unit of pressure is the _____________. At STP, standard pressure is __________,______________, or ___________.5. At absolute zero (0 K or –273 C), particles ___________________________________________________________________________________________________. 13.2The Nature of Liquids6.Based on the kinetic theory, a key difference between gases and liquids is:7.The conversion of a liquid to a gas or vapor is ____________________; when it occurs atthe surface of a liquid it is called ______________________.8.Copy key concept on p. 391: During evaporation,9.Copy key concept on p. 392: In a system at constant vapor pressure,10.The temperature at which the vapor pressure of the liquid is just equal to the externalpressure on the liquid is the _______________________.11.Normal boiling point is ______________________________________________.12. Copy the information from figure 13.8 on p. 39413.3 The Nature of Solids13.Write the information in the first paragraph under ―A Model for Solids‖ on p. 396.13. 4 Changes of State14.A phase diagram gives __________________________________________________________________________________________________________________.15.The triple point ____________________________________________________.16.Draw the phase diagram of water on p. 403 and explain.17.from power point: copy the kinetic theory information (Hein-Arena version)18. from power point: draw the chart for physical phasesChemistry—Ch. 13 textbook problemsp. 406 (26-30, 38-39, 49, 54-56, 65, 70)26. What is meant by an elastic collision?27. Which of these statements are characteristic of matter in the gaseous state?a)gases fill their containers completelyb)gases exert pressurec)gases have massd)the pressure of a gas is independent of its temperaturee)gases are compressiblef)the distances between particles in a gas are relatively large28. List the various units used to measure pressure and identify the SI unit (show equivalence).29. Change 1656 kPa to atm.30. Convert 190 mm Hg to the following.a.kilopascalsb.atmospheres of pressure38. Describe what is happening at the molecular level when a dynamic equilibrium occurs.39. Explain why increasing the temperature of a liquid increases its rate of evaporation.49. Explain why a liquid stays at a constant temperature while it is boiling?54. The table gives the vapor pressure of isopropyl alcohol at various temperatures. Graph the data. Use aa.What is the estimated normal boiling point of isopropyl alcohol?—show on graphb.What is the boiling point of isopropyl alcohol when the external pressure is increased to twicestandard pressure?—show on graph55.In a series of liquids, as the intermolecular forces of attraction strengthen, would you expect thevapor pressure to increase or decrease? Explain.56.Predict the physical state of each of these substances at the indicated temperature. Use the meltingpoint and boiling point data from the table below.a.phenol at 99o Cb.ammonia at –25o Cc.methanol in an ice-water bathd.methanol in a boiling-water bathe.ammonia at –100o Cf.phenol at 25o C65. How does perspiration help cool your body on a hot day?70. Why are pressure cookers recommended for cooking at high-altitude?Reading Phase Diagrams1. What variables are plotted on a phase diagram?2. How many phases of water are represented in its phase diagram? What are they?e the phase diagram for water to complete the following table.4.What phases of water coexist at each point along the curve AC?5.What two-phase changes occur at each point along curve AB in the phase diagram forwater?6.Look at the phase diagram for carbon dioxide. Above which pressure and temperature iscarbon dioxide unable to exist as a liquid?7.At which pressure and temperature do the solid, liquid, and gaseous phases of carbondioxide coexist?。

Translation of Marxism and LeninismMarxism and Leninism are two fundamental ideologies that have significantly influenced political, social, and economic systems around the world. As such, accurate and precise translations of the concepts and principles are crucial for effective dissemination and understanding of these ideas globally. In this document, we will discuss the key considerations and challenges in translating Marxism and Leninism into English.Cultural ContextOne of the primary challenges in translating Marxism and Leninism is capturing and conveying the cultural context in which these ideologies originated. Marxism and Leninism have deep roots in the socio-political history of Russia and China, and their translation into English requires a careful balance of linguistic accuracy while retaining the essence of the original context.Translators must strive to find English equivalents that resonate with the target audience’s cultural background. This involves understanding the historical, social, and political nuances specific to the source language and transferring them effectively to the target language.Translating Key TermsTranslating key terms in Marxism and Leninism poses another significant challenge. Many of these terms have specific meanings within the context of these ideologies and may not have direct English equivalents. Translators must carefully analyze the connotations and implications of each term to ensure accurate translation.For instance, the term。