物理化学英文3The Second Law
Variation of G with Temperature
GT p S
G
Sgas Sliquid Ssolid
gas
liquid solid
T
Variation of G with Pressure
G p T
V
G
Vgas Vliquid Vsolid
gas
liquid solid
\ DA = wmax • dAT,V i.e. for constant T and V, A is a
minimum at equilibrium.
Gibbs Free Energy
• Definition: G U - TS + pV
• dGT,p = dU - TdS + pdV • dGT,p dU - dq - w • dGT,p dwe
Third Law Entropies
S 0 (T) S 0 (0) Tf CpdT DH fus
0T
Tf
Tb
Cp dT
DHvap
T
Cp dT
Tf T
Tb
Tb T
Third Law Entropy of Pb(s)
0.60 0.50 0.40 0.30 0.20 0.10 0.00
0
Third Law of Thermodynamics
• Nernst Heat Theorem: DS 0 as T 0. • Arbitrary convention: The entropy of an
element in its pure crystalline form is zero at T=0. • Third Law: Therefore the entropy of any perfect crystalline substance is zero at T=0.
DG(T1 ) T1
DH
1 T2
1 T1
Pressure dependence of DG
DG
p2
p2
p
T
DV
dDG
p1
DVdp
p1
p2
DG( p2 ) DG( p1) DVdp
p1
for gases: DG( p2 ) DG( p1) nRT ln( p2 / p1)
\ DG = wmax,e • If the only work is expansion/compression,
dGT,p i.e. for constant T and p, G is a minimum at equilibrium.
The Second Law
The Machinery
pure substance G
mixture G
n
ni
i is the slope of Gi vs. ni
• for a pure substance G = nGm and Gm=constant
• for a mixture, Gi vs. ni is not linear and is not constant
for solids and liquids, DG( p2 ) DG( p1)
Composition Dependence
dG
Gp
T ,n's
dp
GT
p,n's
dT
G n1
p,T
dn1
dG Vdp SdT 1dn1 2dn2
dG Vdp SdT i dni
i
Chemical Potential
2. This ratio may be written: q1/q2 = T1/T2 3. The entropy, S, defined by dS=(dq/T)rev is
a function of state.
4. In an isolated system, DS is zero for a reversible process, and positive for a spontaneous one.
The Fundamental Equations
• dU = TdS - pdV • dH = TdS + Vdp • dA = -SdT - pdV • dG = -SdT + Vdp
Maxwell Relations - Derivation
2U SV
2U V S
dU
U S
y(x)
y2 y1
x2 - x1
Debye Extrapolation
For low temperatures, Cp T3
Therefore,
T0
0
Cp dT T
1 3
Cp
(T0 )
Helmholtz Free Energy
• Definition: A U - TS
• dAT = dU - TdS • dAT dU - dq • dAT dw
50 100 150 200 250 300
T/K
Numerical Integration
• Trapeziodal Rule:
• divide total area into trapezoids
• trapezoid area =
½ (y2 + y1) (x2 - x1)
• integral equals sum of all trapezoid areas
Assume a reversible path at constant pressure. Then,
DS
Tf
dq
/
T
Tf
Cp dT
Ti
T Ti
DS
Cp
ln
Tf Ti
DS for an Ideal Gas Isotherm
dq dw pdV
dS pdV nR dV
T
V
DS nR ln Vf Vi
Physical Chemistry
The Second Law
The Second Law
The Concepts
The Laws of Thermodynamics
• First Law You can’t get something for nothing.
• Second Law You can’t even break even.
Heat Engines
• A heat engine converts heat into work.
• Th = temperature of heat source
• Tc = temperature of heat sink
• qh = heat supplied • qc = heat released • w = work produced
Ideal Gas Mixture Model
for a pure substance : G( p) = G( p0 ) nRT ln( p / p0 ) Gm ( p) Gm ( p0 ) RT ln( p / p0 )
( p) 0 RT ln( p / p0 )
for a substance in an ideal gas mixture :
• In an isolated system, any change for which dS>0 will occur spontaneously.
• In an isolated system at equilibrium, the entropy is at a maximum.
Spontaneous Heat Transfer
DS for Phase Changes
• Melting
• Boiling
• T = Tm = constant • q = DHfus
• \ DS = DHfus / Tm
• T = Tb = constant • q = DHvap
• \ DS = DHvap / Tb
DS for a Temperature Change
The Entropy Function
• The entropy S is defined by
dS = dqrev/T
• dS dqirrev/T
reversible: dS = dq/T
state B
state A
irreversible:
dS dq/T
The Second Law (Clausius)
• |qc|>0 implies e < 1
You can’t even break even.
The Second Law (Kelvin)
• No process is possible in which the sole result is the absorption of heat from a reservoir and its complete conversion into work.
V
dS
U V
S
dV
TdS
pdV
\
T V
S
p S
V
Maxwell Relations - Summary
T V
S
p S
V
T p
S
V S
p
ቤተ መጻሕፍቲ ባይዱ
p T
V
S V
T
V T
p
S p
T
Thermodynamic Eq’n. of State
T
U V
物化词汇
一些物理化学专业英语词汇电泳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polyelectrolyteBET公式BET formula DLVO理论DLVO theoryHLB法hydrophile-lipophile balance methodpVT性质pVT property ζ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饱和蒸气压saturated vapor pressure饱和蒸气saturated vapor 饱和吸附量saturated extent of adsorption 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 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触变thixotropy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等焓过程isenthalpic process德拜－休克尔极限公式Debye-Huckel’s limiting equation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第三定律熵third-law entropy第二类永动机perpetual machine of the second kind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·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 控制步骤control step 库仑计coulometer扩散控制diffusion controlled雷利公式Rayleigh equation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雷利公式Rayleigh equation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non-localized particle systems离子的电迁移率mobility of ions 离子的标准摩尔生成焓standard molar formation of ion离子的迁移数transport number of ions离子氛ionic atmosphere离子独立运动定律law of the independent migration of ions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临界常数critical constant量子效率quantum yield 临界参数critical parameter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 product 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 reactionsLiveBandit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 无热溶液athermal solution维里系数virial coefficient 稳流过程steady flow process稳态近似法stationary state approximation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压缩因子compressibility factor循环过程cyclic process 压力商pressure quotient压缩因子图diagram of compressibility factor阳极anode亚稳状态metastable state 盐桥salt bridge盐析salting out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逸度fugacity依时计量学反应time dependent stoichiometric reactions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 workLiveBandit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optimal reaction temperature 最可几分布most probable distribution 最可几速率mostadikanghackneyed 陈腐的caustic 腐蚀性的erosion 腐蚀erode使腐蚀stale 陈腐的rot 腐烂rotten 腐烂的decay 腐败corrode 腐蚀decomposition 分解，腐烂rust 铁锈silica 硅土lime stone石灰石crystal 水晶gasoline 汽油methane 甲烷，沼气hydrocarbon 碳氢化合物petroleum 石油plastic 塑胶intermediary 媒介物catalysis 催化作用catalyst 催化剂adhesive 黏合剂scorch 使退色bleach 漂白，去色,漂白剂tint 染色，上色dye 染料chemistry 化学biochemistry 生物化学hydronic 液体循环加热的alchemy 炼金术，魔力artificial 人造的，假的，非原产地的ion 离子molecule 分子，些微solubility 溶度solution 解答溶液solvent 溶剂dissolve 溶解，解散element 元素impurity 杂质blend 混合compound 混合物substance 物质，实质particle 颗粒，微粒explosive 爆炸的，炸药blast 爆炸burning 燃烧的kindle 燃起sear 烧灼，烧焦ignite 使燃烧action 作用combination 化合，组合neutralize 中和polymerization 聚合functional 起作用的synthetic 综合的，合成的carbon 碳copper 铜lead 铅Mercury 水星nickel 镍platina 白金silver 银sodium 钠tin 锡，马口铁zinc 锌calcium 钙helium 氦silicon 硅ammonia 氨sulfur 硫磺iodine 碘nitrogen 氮oxygen 氧1.reagent 反应力反应物 4. molecule 分子摩尔5. electron 电子6. isotope 同位素核素7. polymer 聚合体 8. alloy 合金10. metalloid 非金属 11. derivative 衍生物12. alkali 碱金属 13. hydrate 水合物14. action 作用Catalysis are sometimes used to accelerate chemical action.15. adhesive 粘合剂胶粘的18. bleach 去色漂白Please soak shirts in bleach to remove the stains.19. blast 爆破 [例] The village was blast by enemy bombs.23. caustic 腐蚀性的 [例] Some chemicals are caustic by nature.24. combination 化合组合 [例] The safe combination of the two chemicals required a complicated chemical process./ This is a combination of two powerful ingredients.25. corrode 腐蚀 [例] The metal has corroded because of rust.26. crystal 结晶状的27. decay 腐败 [例] Sugar decays our teeth.29. erode 腐蚀 [例] The sea has eroded the cliff face over the years.30. explode 使爆炸 [例] The red balloon exploded when I popped it with a pin.31. explosive 爆炸的炸药 [例] Dynamite is highly explosive. / Politics can be explosive issue.33. ignite 使燃着 [例] A smoldering cigarette ignited the newspapers.37. neutralize 中和 [例] Alkalis neutralize acids. 38. nickel 镍41. polymerization 聚合42. scorch 使褪色 [例] Do not leave the iron on the delicate fabric or the heat will scorch it.52. rotten 腐烂的 [例] The rotten fruit smelled horrible.Bunsen burner 本生灯 product 反应产物flask 烧瓶 apparatus 设备 matrass 卵形瓶 litmus 石蕊PH indicator PH值指示剂，氢离子（浓度的）负指数指示剂litmus paper 石蕊试纸 graduate, graduated flask 量筒，量杯reagent 试剂 test tube 试管 burette 滴定管 retort 曲颈甑still 蒸馏釜 cupel 烤钵 crucible pot, melting pot 坩埚pipette 吸液管 filter滤管 stirring rod 搅拌棒。
物理化学英语词汇
物理化学英语词汇分布 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。
关于物理三定律的英语作文
关于物理三定律的英语作文English:The three laws of physics, also known as Newton's Laws of Motion, are fundamental principles that govern the behavior of objects in motion. The first law, also known as the law of inertia, states that an object at rest will remain at rest, and an object in motion will remain in motion at a constant velocity unless acted upon by an external force. The second law defines the relationship between an object's mass, its acceleration, and the applied force. It states that the force acting on an object is equal to the mass of the object multiplied by its acceleration. Finally, the third law states that for every action, there is an equal and opposite reaction. This means that when one object exerts a force on a second object, the second object exerts an equal and opposite force back on the first object. These laws provide a framework for understanding and predicting the behavior of objects in motion, and they have wide-ranging applications in fields such as engineering, astronomy, and everyday life.中文翻译:物理学的三大定律，也被称为牛顿的运动定律，是控制物体运动行为的基本原则。
物理化学3.第二定律
热力学第二、第三定律 特定条件下△G的物理 意义 规定熵、标准反应熵、 熵增原理
自发过程
热力学第一定律
研究各种形式能量相 互转化以及它们之间 的定量关系 本质是能量守恒 热和功可以相互转化
热 和 功 是 否 可 以 任 意 转 化 ？
程不 是违 否背 都热 能力 进学 行第 ？一 定 律 的 过
关于熵……
熵的特点：
–
–
– –
基准：0K时完美晶体的熵为0——热力学第三定律 同种物质，气态＞ 液态＞ 固态 同一物质，同聚集态，温度上升，熵增大 同一温度，同种聚集态，物质结构复杂者熵较大
热力学第二定律的另一种说法
在隔离系统中发生的自发过程总是导致熵增大 这也称为：熵判据 或 熵增原理
由热力学第一定律，单纯pVT 变化过程中
Q r＝ dU W r dU pdV
dS ＝
Q
T
r
dU pdV T
S＝
2
基本公式：
Q
T
r
1
2
dU pdV T
1
适用条件：封闭系统，可逆过程，W’=0
1、恒温变化过程
T S＝
2
Q T
r
1
2
dU pdV T pdV T ( dT 0 , dU 0 )
dS
Qr
T
pVT 变化
相变化
化学反应
封闭系统绝热可逆过程 dS = 0
熵变的计算
基本公式：
dS
Qr
T
或
2 1S
1 (
2
Qr
物理化学-专业词汇中英文对照表
非自发过程 non-spontaneous
平衡 equilibrium 热机 heat engine
不可逆 irreversible 可逆 reversible
3.2 卡诺循环和卡诺定理 Carnot cycles and Carnot’Law
热机效率 efficiency of the heat engine
8.4 可逆电池和可逆电极 Reversible cell and electrode
国际理论和应用化学联合会 IUPAC(International Union of Pure and Applied Chemistry)
化学电源 electrochemical cell
8.5 可逆电池热力学 reversible cell thermodynamics
Carnot 定理 Carnot law
可逆热机 revisable engine
不可逆热机 irreversible engine
冷冻系数 freezing coefficient
3.3 熵的概念 the concept of entropy
熵 entropy
克劳修斯不等式 Clausius inequality
Ideal dilute solution
4.7 相对活度的概念 relative activity
4.8 稀溶液的依数性 colligative properties of the dilute solution
依数性 colligative properties
渗透压 osmotic pressure
第 7 章 化学反应动力学 Chemical Reaction kinetics
7.1 动力学的基本概念 basic concepts of kinetics
关于物理三定律的英语作文
关于物理三定律的英语作文The Three Laws of Physics: A Profound Understanding of the Universe.Physics, the natural science that studies matter andits motion through space and time, has been a fundamental discipline in understanding the laws that govern the universe. Among the principles that have shaped our understanding of physics, the three laws of motion, proposed by Sir Isaac Newton, stand out as the foundation upon which much of classical mechanics is built. These laws, simple yet profound, provide a mathematical framework to describe and predict the behavior of objects in motion.The First Law of Motion, also known as the Law of Inertia, states that an object at rest remains at rest, and an object in motion continues in motion with the same speed and direction unless acted upon by an external force. This law underscores the fundamental principle that objects tend to maintain their state of motion or rest unless compelledto change by an external agent. The inertia exhibited by objects is a direct consequence of this law, and it is the inertia that we experience when trying to move a stationary object or change the speed of a moving one.The Second Law of Motion, known as the Law of Force and Acceleration, states that the force acting on an object is equal to the mass of the object multiplied by its acceleration. This law establishes a direct relationship between force, mass, and acceleration, and it is the basis for understanding how objects respond to external forces. The acceleration produced by a force depends on the mass of the object; heavier objects require greater forces to achieve the same acceleration as lighter ones. This law also explains why it is easier to push a lighter box than a heavier one.The Third Law of Motion, known as the Law of Action and Reaction, states that for every action, there is an equal and opposite reaction. This law underscores the fact that forces always occur in pairs, with one force acting on an object and another force acting on the object exerting theforce. The action and reaction forces are equal in magnitude but opposite in direction, and they act on different objects. This law explains why a person pushing against a wall feels a force pushing back against them; the wall exerts an equal and opposite reaction force on the person.The three laws of motion provide a unified frameworkfor understanding the mechanics of objects in motion. They explain why objects behave in certain ways when acted upon by forces and how those forces are related to the object's mass, acceleration, and the reaction forces they produce. These laws have found applications in various fields, including engineering, aerospace, and robotics, among others, where the prediction and control of motion are crucial.Moreover, the three laws of motion have served as a foundation for the development of more complex theories and principles in physics. They have been refined and extended by subsequent scientists, leading to the development of theories such as relativity and quantum mechanics, whichhave further deepened our understanding of the universe.In conclusion, the three laws of motion, proposed bySir Isaac Newton, have played a pivotal role in shaping our understanding of the universe. They provide a fundamental framework for describing and predicting the behavior of objects in motion and have served as a launchpad forfurther research and the development of more advanced theories in physics. The simplicity and elegance of these laws have made them timeless and continue to inspire scientists and researchers worldwide.。
Atkins’PhysChem 08(物理化学课件英文版)
machinery
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1
Chapter 5 The Second Law: The machinery
Combining the First and Second Laws
5.1 The fundamental equations 5.2 Properties of the internal energy Properties of the Gibbs energy 5.3 General considerations 5.4 The variation of the Gibbs energy with temp. 5.5 The variation of the Gibbs energy with pressure
G f (T , p) compare with
dG
G T
p
dT
G p
T
dp
dG SdT Vdp
G T
p
S
;
G p
T
V
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Chapter 5 The Second Law: The machinery
5.2 Properties of the internal energy
P T V
nR V nb
T
nRT
nRT
an2
V nb V nb V 2
an2 V2
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(c) The variation of U、H and S with T
U T
V
CV
nCV ,m
H T
p
Cp
nC p,m
物理化学 热力学第二定律
上式为
B
A
δ
Q T
ir
A B
δ Qr T
0
B
A
δ
Q T
ir
ABS
0
BAS
B A
δ
Q T
ir
S δTQ
> ir =r
Clausius Inequality
(1) 意义：在不可逆过程中系统的熵变大于过程 的热温商，在可逆过程中系统的熵变等于过 程的热温商。即系统中不可能发生熵变小于 热温商的过程。 是一切非敞开系统的普遍规律。
= r cycle （可逆循环）
意义：的极限 提高的根本途径
Carnot定理的理论意义：
§2－4 熵 (Entropy)
一、熵函数的发现 (Discovery of entropy)
1 T2
T1
即
1 Q2 1 T2
Q1
T1
< ir cycle = r cycle
Q1 Q2 0 T1 T2
1mol He(g) 200K
1m3o0l0HK2(g)
101.3kPa 101.3kPa
解：求末态 过程特点：孤立系统， U = 0
U U (He) U (H 2 )
n
3 2
RT2
200 K
n
5 2
RT2
300 K
0
T2 = 262.5K
1mol He(g) 200K
101.3kPa
1mol H2(g) 300K
对两个热源间的可逆循环：热温商
之和等于0
Q1 Q2 0 T1 T2
对任意可逆循环(许许多多个热源)：
pቤተ መጻሕፍቲ ባይዱ
chapter03 The Second Law of Thermodynamics
A reversible heat engine is an idealization of real heat engines.
12
Physical Chemistry ENTROPY
Chapter 3
dq qC qH 0 (3.16) T TC TH For any closed system that undergoes a Carnot cycle, Eq. dqrev (3.16) shows that integral of around the cycle is zero. T
(3.9) (3.10)
(Sec. 1.8)
Physical Chemistry
T1 C (T ) T1 C (T ) dT T3 CV (T ) V dT dT V dT 0 CV (T ) T T T T T T T
1 3 1
9
P
Physical Chemistry
(a)
V Fig. 3.5
c s r d
(b)
V
14
Physical Chemistry
Chapter 3
Since these areas give the negative of the reversible work w done on the system in each process, wamnb = wab,
P
V
13
Chapter 3 Physical Chemistry (a) An arbitrary cyclic process. (b) Draw dashed adiabats (dashed lines) that divided the cycle into adjacent strips. Consider one such a strip, bounded by curve ab and cd at the top and bottom. Draw the reversible isotherm mn so that the area under the zigzag curve amnb equals the area under the smooth curve ab. P P m b a n
Chapter 3-1(A) The second Law of thermodynamics(part 1)
Chapter 3 The Second Law of Thermodynamics
3.1 Spontaneous process and its characteristic
That First law of thermodynamics, however, can’t tell us the direction of those permissible changes. The processes which happen in the nature are all obedient to the First law, but all processes in which energy is conserved can’t occur. For example: ① ② ③ ④ ⑤ work heat 100% potential energy heat Q high temperature object diffusion process Zn+CuSO4→Cu+ZnSO4
Chapter 3 The Second Law of Thermodynamics
3.2 The Second Law of Thermodynamics
⑤热力学第二定律原则上可用来判断任何一过程进行的方 向问题，但实际上对每一过程根据“第二类永动机不可能 造成”这一结论来判断过程的方向，这就太抽象，太繁了。 再说，这一判断方法并不能指出过程进行到什么程度为止。 因此，最好能像第一定律，找出像内能Ｕ 和焓Ｈ 那样的热 力学函数，只需计算ΔＵ和ΔＨ 就可知道－过程的能量变化 那样，在第二定律中，是否就可以找到这样的热力学函数， 只要计算此函数的变化值，就可判断过程的方向和限度呢？ 由于一切自发过程的方向性最后都可归结为热功转化 问题，故所要寻找的热力学函数亦得从热功转化的关系中 去找。这就是下面要讲的内容。