CONCISE PHYSICAL CHEMISTRY
CONTENTS CONTENTS [CONTENTS] 1 BASIC TERMS THERMODYNAMIC SYSTEM ISOLATED SYSTEM CLOSED SYSTEM OPEN SYSTEM PHASE, HOMOGENEOUS AND HETEROGENEOUS SYSTEMS ENERGY HEAT WORK THERMODYNAMIC QUANTITIES INTENSIVE AND EXTENSIVE THERMODYNAMIC QUANTITIES THE STATE OF A SYSTEM AND ITS CHANGES THE STATE OF THERMODYNAMIC EQUILIBRIUM SYSTEM’S TRANSITION TO THE STATE OF EQUILIBRIUM THERMODYNAMIC PROCESS REVERSIBLE AND IRREVERSIBLE PROCESSES PROCESSES AT A CONSTANT QUANTITY CYCLIC PROCESS SOME BASIC AND DERIVED QUANTITIES MASS M AMOUNT OF SUBSTANCE N MOLAR MASS M CONTENTS [CONTENTS] ABSOLUTE TEMPERATURE T PRESSURE P VOLUME V PURE SUBSTANCE AND MIXTURE MOLE FRACTION OF THE ITH COMPONENT XI MASS FRACTION WI VOLUME FRACTION ?I AMOUNT-OF-SUBSTANCE CONCENTRATION CI MOLALITY MI 2 STATE BEHAVIOUR MAJOR TERMS, QUANTITIES AND SYMBOLS MOLAR VOLUME VM AND AMOUNT-OF-SUBSTANCE (OR AMOUNT) DENSITY C SPECI?C VOLUME V AND DENSITY ? COMPRESSIBILITY FACTOR Z CRITICAL POINT REDUCED QUANTITIES COE?CIENT OF THERMAL EXPANSION ?P COE?CIENT OF ISOTHERMAL COMPRESSIBILITY ?T PARTIAL PRESSURE PI EQUATIONS OF STATE CONCEPT OF THE EQUATION OF STATE EQUATION OF STATE OF AN IDEAL GAS VIRIAL EXPANSION BOYLE TEMPERATURE PRESSURE VIRIAL EXPANSION VAN DER WAALS EQUATION OF STATE REDLICH-KWONG EQUATION OF STATE BENEDICT, WEBB AND RUBIN EQUATION OF STATE THEOREM OF CORRESPONDING STATES 2 2 10 APPLICATION OF EQUATIONS OF STATE STATE BEHAVIOUR OF LIQUIDS AND SOLIDS DESCRIPTION OF STATE BEHAVIOUR USING THE COE?CIENTS OF THERMAL EXPANSION ?P AND ISOTHERMAL COMPRESSIBILITY ?T RACKETT EQUATION OF STATE SOLIDS STATE BEHAVIOUR OF MIXTURES DALTON’S LAW AMAGAT’S LAW IDEAL MIXTURE PSEUDOCRITICAL QUANTITIES EQUATIONS OF STATE FOR MIXTURES LIQUID AND SOLID MIXTURES 3 FUNDAMENTALS OF THERMODYNAMICS BASIC POSTULATES THE ZEROTH LAW OF THERMODYNAMICS THE ?RST LAW OF THERMODYNAMICS SECOND LAW OF THERMODYNAMICS THE THIRD LAW OF THERMODYNAMICS IMPOSSIBILITY TO ATTAIN A TEMPERATURE OF 0K DE?NITION OF FUNDAMENTAL THERMODYNAMIC QUANTITIES ENTHALPY HELMHOLTZ ENERGY GIBBS ENERGY HEAT CAPACITIES MOLAR THERMODYNAMIC FUNCTIONS FUGACITY FUGACITY COE?CIENT ABSOLUTE AND RELATIVE THERMODYNAMIC QUANTITIES SOME PROPERTIES OF THE TOTAL DI?ERENTIAL TOTAL DI?ERENTIAL TOTAL DI?ERENTIAL AND STATE FUNCTIONS TOTAL DI?ERENTIAL OF THE PRODUCT AND RATIO OF TWO FUNCTIONS INTEGRATION OF THE TOTAL DI?ERENTIAL COMBINED FORMULATIONS OF THE ?RST AND SECOND LAWS OF THERMODYNAMICS GIBBS EQUATIONS DERIVATIVES OF U, H, F, AND G WITH RESPECT TO NATURAL VARIABLES MAXWELL RELATIONS TOTAL DI?ERENTIAL OF ENTROPY AS A FUNCTION OF T, V AND T, P CONVERSION FROM NATURAL VARIABLES TO VARIABLES T, V OR T, P CONDITIONS OF THERMODYNAMIC EQUILIBRIUM CHANGES OF THERMODYNAMIC QUANTITIES TEMPERATURE DEPENDENCE CP DEPENDENCE ON PRESSURE CV DEPENDENCE ON VOLUME RELATIONS BETWEEN HEAT CAPACITIES IDEAL GAS INTERNAL ENERGY TEMPERATURE AND VOLUME DEPENDENCE FOR A HOMOGENEOUS SYSTEM CHANGES AT PHASE TRANSITIONS TEMPERATURE AND PRESSURE DEPENDENCE FOR A HOMOGENEOUS SYSTEM ENTROPY ABSOLUTE ENTROPY DEPENDENCE ON TEMPERATURE AND VOLUME TEMPERATURE AND PRESSURE DEPENDENCE CHANGES OF THERMODYNAMIC QUANTITIES DURING IRREVERSIBLE PROCESSES 4 APPLICATION OF THERMODYNAMICS REVERSIBLE VOLUME WORK IRREVERSIBLE VOLUME WORK OTHER KINDS OF WORK SHAFT WORK ADIABATIC PROCESS—POISSON’S EQUATIONS IRREVERSIBLE ADIABATIC PROCESS HEAT ENGINES THE CARNOT HEAT ENGINE COOLING ENGINE HEAT ENGINE WITH STEADY ?OW OF SUBSTANCE THE JOULE-THOMSON E?ECT THE JOULE-THOMSON COE?CIENT INVERSION TEMPERATURE 5 THERMOCHEMISTRY HEAT OF REACTION AND THERMODYNAMIC QUANTITIES OF REACTION LINEAR COMBINATION OF CHEMICAL REACTIONS HESS’S LAW STANDARD REACTION ENTHALPY ?RH? STANDARD ENTHALPY OF FORMATION ?FH? STANDARD ENTHALPY OF COMBUSTION ?CH? KIRCHHO?’S LAW—DEPENDENCE OF THE REACTION ENTHALPY ON TEMPERATURE ENTHALPY BALANCES ADIABATIC TEMPERATURE OF REACTION 6 THERMODYNAMICS OF HOMOGENEOUS MIXTURES IDEAL MIXTURES GENERAL IDEAL MIXTURE IDEAL MIXTURE OF IDEAL GASES INTEGRAL QUANTITIES MIXING QUANTITIES EXCESS QUANTITIES HEAT OF SOLUTION (INTEGRAL) RELATIONS BETWEEN THE HEAT OF SOLUTION AND THE ENTHALPY OF MIX- ING FOR A BINARY MIXTURE DI?ERENTIAL QUANTITIES PARTIAL MOLAR QUANTITIES PROPERTIES OF PARTIAL MOLAR QUANTITIES RELATIONS BETWEEN SYSTEM AND PARTIAL MOLAR QUANTITIES RELATIONS BETWEEN PARTIAL MOLAR QUANTITIES PARTIAL MOLAR QUANTITIES OF AN IDEAL MIXTURE DETERMINATION OF PARTIAL MOLAR QUANTITIES EXCESS PARTIAL MOLAR QUANTITIES DI?ERENTIAL HEAT OF SOLUTION AND DILUTION THERMODYNAMICS OF AN OPEN SYSTEM AND THE CHEMICAL POTENTIAL THERMODYNAMIC QUANTITIES IN AN OPEN SYSTEM CHEMICAL POTENTIAL FUGACITY AND ACTIVITY STANDARD STATES ACTIVITY ACTIVITY COE?CIENT RELATION BETWEEN ? [X] I AND ?I RELATION BETWEEN THE ACTIVITY COE?CIENT AND THE OSMOTIC COEF- ?CIENT DEPENDENCE OF THE EXCESS GIBBS ENERGY AND OF THE ACTIVITY COE?CIENTS ON COMPOSITION WILSON EQUATION REGULAR SOLUTION 7 PHASE EQUILIBRIA BASIC TERMS PHASE EQUILIBRIUM COEXISTING PHASES PHASE TRANSITION BOILING POINT NORMAL BOILING POINT DEW POINT SATURATED VAPOUR PRESSURE MELTING POINT NORMAL MELTING POINT 7 1 10 FREEZING POINT 7 1 11 TRIPLE POINT THERMODYNAMIC CONDITIONS OF EQUILIBRIUM IN MULTIPHASE SYSTEMS EXTENSIVE AND INTENSIVE CRITERIA OF PHASE EQUILIBRIUM PHASE TRANSITIONS OF THE ?RST AND SECOND ORDER GIBBS PHASE RULE INDEPENDENT AND DEPENDENT VARIABLES INTENSIVE INDEPENDENT VARIABLES DEGREES OF FREEDOM PHASE DIAGRAMS GENERAL TERMS PHASE DIAGRAM OF A ONE-COMPONENT SYSTEM PHASE DIAGRAMS OF TWO-COMPONENT (BINARY) MIXTURES PHASE DIAGRAMS OF THREE-COMPONENT (TERNARY) MIXTURES MATERIAL BALANCE LEVER RULE PHASE EQUILIBRIA OF PURE SUBSTANCES CLAPEYRON EQUATION CLAUSIUS-CLAPEYRON EQUATION LIQUID-VAPOUR EQUILIBRIUM SOLID-VAPOUR EQUILIBRIUM SOLID-LIQUID EQUILIBRIUM SOLID-SOLID EQUILIBRIUM EQUILIBRIUM BETWEEN THREE PHASES LIQUID-VAPOUR EQUILIBRIUM IN MIXTURES THE CONCEPT OF LIQUID-VAPOUR EQUILIBRIUM RAOULT’S LAW LIQUID-VAPOUR EQUILIBRIUM WITH AN IDEAL VAPOUR AND A REAL LIQUID PHASE GENERAL SOLUTION OF LIQUID-VAPOUR EQUILIBRIUM PHASE DIAGRAMS OF TWO-COMPONENT SYSTEMS AZEOTROPIC POINT E?ECT OF THE NON-VOLATILE SUBSTANCE CONTENT ON THE BOILING PRESSURE AND TEMPERATURE HIGH-PRESSURE LIQUID-VAPOUR EQUILIBRIUM LIQUID-GAS EQUILIBRIUM IN MIXTURES BASIC CONCEPTS HENRY’S LAW FOR A BINARY SYSTEM ESTIMATES OF HENRY’S CONSTANT E?ECT OF TEMPERATURE AND PRESSURE ON GAS SOLUBILITY E?ECT OF PRESSURE OTHER WAYS TO EXPRESS GAS SOLUBILITY LIQUID-GAS EQUILIBRIUM IN MORE COMPLEX SYSTEMS LIQUID-LIQUID EQUILIBRIUM CONDITIONS OF EQUILIBRIUM AT CONSTANT TEMPERATURE AND PRESSURE TWO-COMPONENT SYSTEM CONTAINING TWO LIQUID PHASES THREE-COMPONENT SYSTEM CONTAINING TWO LIQUID PHASES LIQUID-SOLID EQUILIBRIUM IN MIXTURES GENERAL CONDITION OF EQUILIBRIUM TWO-COMPONENT SYSTEMS WITH TOTALLY IMMISCIBLE COMPONENTS IN THE SOLID PHASE TWO-COMPONENT SYSTEMS WITH COMPLETELY MISCIBLE COMPONENTS IN BOTH THE LIQUID AND SOLID PHASES TWO-COMPONENT SYSTEMS WITH PARTIALLY MISCIBLE COMPONENTS IN EITHER THE LIQUID OR THE SOLID PHASE FORMATION OF A COMPOUND IN THE SOLID PHASE THREE-COMPONENT SYSTEMS 7 10 GAS-SOLID EQUILIBRIUM IN MIXTURES 7 10 1 GENERAL CONDITION OF EQUILIBRIUM 7 10 2 ISOBARIC EQUILIBRIUM IN A TWO-COMPONENT SYSTEM 7 10 3 ISOTHERMAL EQUILIBRIUM IN A TWO-COMPONENT SYSTEM 7 11 OSMOTIC EQUILIBRIUM 8 CHEMICAL EQUILIBRIUM SYSTEMS WITH ONE CHEMICAL REACTION GENERAL RECORD OF A CHEMICAL REACTION GIBBS ENERGY OF A SYSTEM CONDITION OF CHEMICAL EQUILIBRIUM OVERVIEW OF STANDARD STATES EQUILIBRIUM CONSTANT REACTIONS IN THE GASEOUS AND LIQUID PHASES REACTIONS IN THE SOLID PHASE HETEROGENEOUS REACTIONS DEPENDENCE OF THE EQUILIBRIUM CONSTANT ON STATE VARIABLES DEPENDENCE ON TEMPERATURE INTEGRATED FORM DEPENDENCE ON PRESSURE CALCULATION OF THE EQUILIBRIUM CONSTANT CALCULATION FROM THE EQUILIBRIUM COMPOSITION CALCULATION FROM TABULATED DATA CALCULATION FROM THE EQUILIBRIUM CONSTANTS OF OTHER REACTIONS CONVERSIONS LE CHATELIER’S PRINCIPLE E?ECT OF INITIAL COMPOSITION ON THE EQUILIBRIUM EXTENT OF REACTION REACTIONS IN CONDENSED SYSTEMS E?ECT OF TEMPERATURE E?ECT OF INERT COMPONENT SIMULTANEOUS REACTIONS CHEMICAL EQUILIBRIUM OF A COMPLEX SYSTEM 9 CHEMICAL KINETICS BASIC TERMS AND RELATIONS RATE OF CHEMICAL REACTION KINETIC EQUATION SIMPLE REACTIONS, ORDER OF REACTION, RATE CONSTANT REACTION HALF-LIFE METHODS OF SOLVING KINETIC EQUATIONS SIMPLE REACTIONS SYSTEMATICS ZERO-ORDER REACTION TYPE OF REACTION INTEGRATED FORM OF THE KINETIC EQUATION FIRST-ORDER REACTIONS SECOND-ORDER REACTIONS TYPE INTEGRATED FORMS OF THE KINETIC EQUATION 9 2 3 10 KINETIC EQUATION 9 2 3 11 PSEUDO?RST-ORDER REACTIONS THIRD-ORDER REACTIONS 9 2 4 10 INTEGRATED FORMS OF THE KINETIC EQUATION 9 2 4 11 REACTION HALF-LIFE 9 2 4 12 TYPE 9 2 4 13 KINETIC EQUATION 9 2 4 14 INTEGRATED FORMS OF THE KINETIC EQUATION NTH-ORDER REACTIONS WITH ONE REACTANT NTH-ORDER REACTIONS WITH TWO AND MORE REACTANTS SUMMARY OF RELATIONS METHODS TO DETERMINE REACTION ORDERS AND RATE CONSTANTS PROBLEM FORMULATION INTEGRAL METHOD DI?ERENTIAL METHOD METHOD OF HALF-LIVES GENERALIZED INTEGRAL METHOD OSTWALD’S ISOLATION METHOD SIMULTANEOUS CHEMICAL REACTIONS TYPES OF SIMULTANEOUS REACTIONS RATE OF FORMATION OF A SUBSTANCE IN SIMULTANEOUS REACTIONS MATERIAL BALANCE IN SIMULTANEOUS REACTIONS FIRST-ORDER PARALLEL REACTIONS KINETIC EQUATIONS INTEGRATED FORMS OF THE KINETIC EQUATIONS WEGSCHEIDER’S PRINCIPLE SECOND-ORDER PARALLEL REACTIONS FIRST- AND SECOND-ORDER PARALLEL REACTIONS FIRST-ORDER REVERSIBLE REACTIONS REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIUM FIRST-ORDER CONSECUTIVE REACTIONS SPECIAL CASES MECHANISMS OF CHEMICAL REACTIONS ELEMENTARY REACTIONS, MOLECULARITY, REACTION MECHANISM KINETIC EQUATIONS FOR ELEMENTARY REACTIONS SOLUTION OF REACTION MECHANISMS RATE-DETERMINING PROCESS BODENSTEIN’S STEADY-STATE PRINCIPLE LINDEMANN MECHANISM OF ?RST-ORDER REACTIONS PRE-EQUILIBRIUM PRINCIPLE MECHANISM OF SOME THIRD-ORDER REACTIONS CHAIN REACTIONS 9 5 10 RADICAL POLYMERIZATION 9 5 11 PHOTOCHEMICAL REACTIONS 9 5 11 1 ENERGY OF A PHOTON ? 9 5 11 2 QUANTUM YIELD OF REACTION 9 5 11 3 RATE OF A PHOTOCHEMICAL REACTION TEMPERATURE DEPENDENCE OF THE RATE OF A CHEMICAL REACTION VAN’T HO?RULE ARRHENIUS EQUATION COLLISION THEORY THEORY OF ABSOLUTE REACTION RATES GENERAL RELATION FOR TEMPERATURE DEPENDENCE OF THE RATE CONSTANT CHEMICAL REACTORS TYPES OF REACTORS BATCH REACTOR FLOW REACTOR CATALYSIS HOMOGENEOUS CATALYSIS HETEROGENEOUS CATALYSIS TRANSPORT OF REACTANTS ADSORPTION AND DESORPTION CHEMICAL REACTION ENZYME CATALYSIS 10 TRANSPORT PROCESSES 10 1 BASIC TERMS 10 1 1 TRANSPORT PROCESS 10 1 2 FLUX AND DRIVING FORCE 10 1 3 BASIC EQUATIONS OF TRANSPORT PROCESSES 10 2 HEAT ?OW—THERMAL CONDUCTIVITY 10 2 1 WAYS OF HEAT TRANSFER 10 2 2 FOURIER’S LAW 10 2 3 THERMAL CONDUCTIVITY 10 2 3 1 DEPENDENCE ON STATE VARIABLES 10 2 4 FOURIER-KIRCHHO?LAW 10 3 FLOW OF MOMENTUM—VISCOSITY 10 3 1 NEWTON’S LAW 10 3 2 VISCOSITY 10 3 2 1 DEPENDENCE ON STATE VARIABLES 10 3 3 POISEUILLE’S EQUATION 10 4 FLOW OF MATTER—DI?USION 10 4 1 FICK’S ?RST LAW OF DI?USION 10 4 2 DI?USION COE?CIENT 10 4 2 1 DEPENDENCE ON STATE VARIABLES 10 4 3 FICK’S SECOND LAW OF DI?USION 10 4 4 SELF-DI?USION 10 4 5 THERMAL DI?USION 10 5 KINETIC THEORY OF TRANSPORT PROCESSES IN DILUTE GASES 10 5 1 MOLECULAR INTERPRETATION OF TRANSPORT PROCESSES 10 5 2 MOLECULAR MODELS 10 5 3 BASIC TERMS OF KINETIC THEORY 10 5 4 TRANSPORT QUANTITIES FOR THE HARD SPHERES MODEL 10 5 5 KNUDSEN REGION 11 ELECTROCHEMISTRY 11 1 BASIC TERMS 11 1 1 ELECTRIC CURRENT CONDUCTORS 11 1 2 ELECTROLYTES AND IONS 11 1 3 ION CHARGE NUMBER 11 1 4 CONDITION OF ELECTRONEUTRALITY 11 1 5 DEGREE OF DISSOCIATION 11 1 6 IN?NITELY DILUTED ELECTROLYTE SOLUTION 11 1 7 ELECTROCHEMICAL SYSTEM 11 2 ELECTROLYSIS 11 2 1 REACTIONS OCCURRING DURING ELECTROLYSIS 11 2 2 FARADAY’S LAW 11 2 3 COULOMETERS 11 2 4 TRANSPORT NUMBERS 11 2 5 CONCENTRATION CHANGES DURING ELECTROLYSIS 11 2 6 HITTORF METHOD OF DETERMINING TRANSPORT NUMBERS 11 3 ELECTRIC CONDUCTIVITY OF ELECTROLYTES 11 3 1 RESISTIVITY AND CONDUCTIVITY 11 3 2 CONDUCTIVITY CELL CONSTANT 11 3 3 MOLAR ELECTRIC CONDUCTIVITY 11 3 4 KOHLRAUSCH’S LAW OF INDEPENDENT MIGRATION OF IONS 11 3 5 MOLAR CONDUCTIVITY AND THE DEGREE OF DISSOCIATION 11 3 6 MOLAR CONDUCTIVITY AND TRANSPORT NUMBERS 11 3 7 CONCENTRATION DEPENDENCE OF MOLAR CONDUCTIVITY 11 4 CHEMICAL POTENTIAL, ACTIVITY AND ACTIVITY COE?CIENT IN ELECTROLYTE SOLUTIONS 11 4 1 STANDARD STATES 11 4 1 1 SOLVENT 11 4 1 2 UNDISSOCIATED ELECTROLYTE 11 4 1 3 IONS 11 4 2 MEAN MOLALITY, CONCENTRATION, ACTIVITY AND ACTIVITY COE?CIENT 11 4 3 IONIC STRENGTH OF A SOLUTION 11 4 4 DEBYE-H¨UCKEL LIMITING LAW 11 4 5 ACTIVITY COE?CIENTS AT HIGHER CONCENTRATIONS 11 5 DISSOCIATION IN SOLUTIONS OF WEAK ELECTROLYTES 11 5 1 SOME GENERAL NOTES 11 5 2 IONIC PRODUCT OF WATER 11 5 3 DISSOCIATION OF A WEEK MONOBASIC ACID 11 5 4 DISSOCIATION OF A WEAK MONOACIDIC BASE 11 5 5 DISSOCIATION OF WEAK POLYBASIC ACIDS AND POLYACIDIC BASES 11 5 6 DISSOCIATION OF STRONG POLYBASIC ACIDS AND POLYACIDIC BASES 11 5 7 HYDROLYSIS OF SALTS 11 5 8 HYDROLYSIS OF THE SALT OF A WEAK ACID AND A STRONG BASE 11 5 9 HYDROLYSIS OF THE SALT OF A WEAK BASE AND A STRONG ACID 11 5 10HYDROLYSIS OF THE SALT OF A WEAK ACID AND A WEAK BASE 11 6 CALCULATION OF PH 11 6 1 DE?NITION OF PH 11 6 2 PH OF WATER 11 6 3 PH OF A NEUTRAL SOLUTION 11 6 4 PH OF A STRONG MONOBASIC ACID 11 6 5 PH OF A STRONG MONOACIDIC BASE 11 6 6 PH OF A STRONG DIBASIC ACID AND A STRONG DIACIDIC BASE 11 6 7 PH OF A WEAK MONOBASIC ACID 11 6 8 PH OF A WEAK MONOACIDIC BASE 11 6 9 PH OF WEAK POLYBASIC ACIDS AND POLYACIDIC BASES 11 6 10PH OF THE SALT OF A WEAK ACID AND A STRONG BASE 11 6 11PH OF THE SALT OF A STRONG ACID AND A WEAK BASE 11 6 12PH OF THE SALT OF A WEAK ACID AND A WEAK BASE 11 6 13BU?ER SOLUTIONS 11 7 SOLUBILITY OF SPARINGLY SOLUBLE SALTS 11 8 THERMODYNAMICS OF GALVANIC CELLS 11 8 1 BASIC TERMS 11 8 2 SYMBOLS USED FOR RECORDING GALVANIC CELLS 11 8 3 ELECTRICAL WORK 11 8 4 NERNST EQUATION 11 8 5 ELECTROMOTIVE FORCE AND THERMODYNAMIC QUANTITIES 11 8 6 STANDARD HYDROGEN ELECTRODE 11 8 7 NERNST EQUATION FOR A HALF-CELL 11 8 8 ELECTROMOTIVE FORCE AND ELECTRODE POTENTIALS 11 8 9 CLASSI?CATION OF HALF-CELLS 11 8 10EXAMPLES OF HALF-CELLS 11 8 10 1 AMALGAM HALF-CELL 11 8 10 2 HALF-CELL OF THE ?RST TYPE 11 8 10 3 HALF-CELL OF THE SECOND TYPE 11 8 10 4 GAS HALF-CELL 11 8 10 5 REDUCTION-OXIDATION HALF-CELL 11 8 10 6 ION-SELECTIVE HALF-CELL 11 8 11CLASSI?CATION OF GALVANIC CELLS 11 8 12ELECTROLYTE CONCENTRATION CELLS WITH TRANSFERENCE 11 8 13ELECTROLYTE CONCENTRATION CELLS WITHOUT TRANSFERENCE 11 8 14GAS ELECTRODE CONCENTRATION CELLS 11 8 15AMALGAM ELECTRODE CONCENTRATION CELLS 11 9 ELECTRODE POLARIZATION 12 BASIC TERMS OF CHEMICAL PHYSICS 12 1 INTERACTION OF SYSTEMS WITH ELECTRIC AND MAGNETIC ?ELDS 12 1 1 PERMITTIVITY 12 1 2 MOLAR POLARIZATION AND REFRACTION 12 1 3 DIPOLE MOMENT 12 1 4 POLARIZABILITY 12 1 5 CLAUSIUS-MOSSOTTI AND DEBYE EQUATIONS 12 1 6 PERMEABILITY AND SUSCEPTIBILITY 12 1 7 MOLAR MAGNETIC SUSCEPTIBILITY 12 1 8 MAGNETIZABILITY AND MAGNETIC MOMENT 12 1 9 SYSTEM INTERACTION WITH LIGHT 12 2 FUNDAMENTALS OF QUANTUM MECHANICS 12 2 1 SCHR¨ODINGER EQUATION 12 2 2 SOLUTIONS OF THE SCHR¨ODINGER EQUATION 12 2 3 TRANSLATION 12 2 4 ROTATION 12 2 5 VIBRATION 12 2 6 MOTION OF ELECTRONS AROUND THE NUCLEUS 12 3 INTERACTION OF MOLECULES WITH ELECTROMAGNETIC RADIATION 12 3 1 WAVE CHARACTERISTICS OF RADIATION 12 3 2 PARTICLE CHARACTERISTICS OF RADIATION 12 3 3 SPECTRUM 12 3 4 ELECTRONIC SPECTRA 12 3 5 VIBRATIONAL AND ROTATIONAL SPECTRA 12 3 6 RAMAN SPECTRA 12 3 7 MAGNETIC RESONANCE SPECTRA 13 PHYSICAL CHEMISTRY OF SURFACES 13 1 PHASE INTERFACE 13 1 1 INTERFACIAL TENSION 13 1 2 GENERALIZED GIBBS EQUATIONS 13 1 3 INTERFACIAL ENERGY 13 1 4 SURFACE TENSION AND SURFACE ENERGY 13 1 5 WORK OF COHESION, WORK OF ADHESION, AND SPREADING COE?CIENT 13 1 6 CONTACT ANGLE 13 1 7 LAPLACE-YOUNG EQUATION AND KELVIN EQUATION 13 1 7 1 KELVIN’S EQUATION 13 1 8 TEMPERATURE DEPENDENCE OF SURFACE TENSION 13 1 9 DEPENDENCE OF SURFACE TENSION ON SOLUTION COMPOSITION 13 1 10GIBBS ADSORPTION ISOTHERM 13 1 11SURFACE ?LMS 13 2 ADSORPTION EQUILIBRIA 13 2 1 QUALITATIVE DESCRIPTION OF ADSORPTION 13 2 2 ADSORPTION HEAT 13 2 3 PHYSICAL ADSORPTION AND CHEMISORPTION 13 2 4 QUANTITATIVE DESCRIPTION OF THE ADSORPTION ISOTHERM IN PURE GASES 13 2 5 LANGMUIR ISOTHERM FOR A MIXTURE OF GASES 13 2 6 CAPILLARY CONDENSATION 13 2 7 ADSORPTION FROM SOLUTIONS ON SOLIDS 14 DISPERSION SYSTEMS 14 1 BASIC CLASSI?CATION 14 2 PROPERTIES OF COLLOID SYSTEMS 14 2 1 LIGHT SCATTERING 14 2 2 SEDIMENTATION OF COLLOID PARTICLES 14 2 3 MEMBRANE EQUILIBRIA CHAP 1: BASIC TERMS [CONTENTS] CHAPTER ISOLATED SYSTEM A CHEMICAL SYSTEM EXCHANGING NEITHER MATTER NOR ENERGY WITH ITS SURROUNDINGS IS AN ISOLATED SYSTEM CHAP 1: BASIC TERMS [CONTENTS] PHASE, HOMOGENEOUS AND HETEROGENEOUS SYSTEMS THE TERM PHASE IS USED FOR THAT PORTION OF THE INVESTIGATED SYSTEM VOLUME IN WHICH ITS PROPER- TIES ARE CONSTANT OR CONTINUOUSLY CHANGING IN SPACE IF A SYSTEM BEHAVES IN THIS WAY THROUGHOUT ALL ITS VOLUME, WE CALL IT A HOMOGENEOUS SYSTEM IF A SYSTEM CONTAINS MORE PHASES, WE CALL IT A HETEROGENEOUS SYSTEM EXAMPLE LET US IMAGINE A BOTTLE OF WHISKY HOW MANY PHASES DOES THIS SYSTEM CONSIST OF? CHAP 1: BASIC TERMS [CONTENTS] SOLUTION IF WE ARE, FROM THE THERMODYNAMIC POINT OF VIEW, INTERESTED SOLELY IN THE LIQUID CONTENT OF THE BOTTLE, THE SYSTEM IS HOMOGENEOUS IT CONTAINS ONE LIQUID PHASE (A MIXTURE OF WATER, ETHANOL AND SOME ADDITIVES) IF, ON THE OTHER HAND, WE ARE INTERESTED IN THE ENTIRE CONTENT OF THE BOTTLE BUT NOT THE BOTTLE ITSELF, THE SYSTEM IS HETEROGENEOUS IN THIS CASE IT CONSISTS OF TWO PHASES, LIQUID AND GASEOUS, WITH THE LATTER CONTAINING AIR AND WHISKY VAPOUR IF, HOWEVER, WE FOCUS OUR ATTENTION ON BOTH THE BOTTLE CONTENT AND THE BOTTLE ITSELF, WE HAVE A HETEROGENEOUS SYSTEM AGAIN, BUT THIS TIME IT ALSO CONTAINS OTHER PHASES IN ADDITION TO THE GASEOUS AND LIQUID ONES, I E THE GLASS OF THE BOTTLE, ITS CAP, LABEL, ETC CHAP 1: BASIC TERMS [CONTENTS] WORK OTHER FORMS OF ENERGY EXCHANGE, WHICH ARE USUALLY DRIVEN BY SOME FORCES ACTING BETWEEN THE SYSTEM AND ITS SURROUNDINGS, ARE CALLED WORK BASED ON THE TYPE OF INTERACTION BETWEEN THE SYSTEM AND ITS SURROUNDINGS, WE DISTINGUISH VOLUME WORK [SEE 3 1 2], ELECTRICAL WORK, SURFACE WORK, ETC U MAIN UNIT: J CHAP 1: BASIC TERMS [CONTENTS] INTENSIVE AND EXTENSIVE THERMODYNAMIC QUANTITIES LET US CONSIDER A HOMOGENEOUS SYSTEM WITHOUT ANY EXTERNAL FORCE ?ELDS PRESENT WE DISTINGUISH BETWEEN EXTENSIVE AND INTENSIVE THERMODYNAMIC QUANTITIES OF A SYSTEM INTENSIVE QUANTITIES ARE THOSE WHOSE VALUES DO NOT CHANGE WHEN THE SYSTEM IS DIVIDED INTO SMALLER SUB-SYSTEMS EXTENSIVE QUANTITIES ARE THOSE WHOSE VALUES ARE PROPORTIONAL TO THE AMOUNT OF SUBSTANCE OF THE SYSTEM AT A ?XED TEMPERATURE AND PRESSURE (SEE FIGURE 1 1) TEMPERATURE, PRESSURE, AND COMPOSITION EXPRESSED BY MOLE FRACTIONS ARE TYPICAL INTENSIVE QUANTITIES VOLUME, MASS AND THE NUMBER OF PARTICLES ARE TYPICAL EXTENSIVE QUANTITIES NOTE: SOME QUANTITIES, E G THE SYSTEM SURFACE, ARE NEITHER EXTENSIVE NOR INTENSIVE EVERY EXTENSIVE QUANTITY MAY BE CONVERTED INTO AN INTENSIVE ONE IF WE RELATE IT TO A CERTAIN CONSTANT MASS OF THE SYSTEM WE THEN OBTAIN SPECI?C OR MOLAR QUANTITIES (SEE 3 2 5) FOR EVERY EXTENSIVE QUANTITY X AND THE RESPECTIVE MOLAR AND SPECI?C QUANTITIES XM AND X WE MAY WRITE X = NXM , (1 1) X = MX, (1 2) WHERE N IS THE AMOUNT OF SUBSTANCE AND M IS THE MASS OF THE SYSTEM S SYMBOLS: WE WILL USE THE SUBSCRIPT M TO DENOTE MOLAR QUANTITIES AND SMALL LETTERS TO DENOTE SPECI?C QUANTITIES CHAP 1: BASIC TERMS [CONTENTS] THE STATE OF THERMODYNAMIC EQUILIBRIUM THE STATE OF THERMODYNAMIC EQUILIBRIUM (EQUILIBRIUM STATE, EQUILIBRIUM) IS A STATE IN WHICH NO MACROSCOPIC CHANGES OCCUR IN THE SYSTEM AND ALL QUANTITIES HAVE CONSTANT VALUES IN TIME NOTE: IN THE STATE OF THERMODYNAMIC EQUILIBRIUM, CHANGES TAKE PLACE AT THE MICROSCOPIC LEVEL FOR INSTANCE, WHEN THE LIQUID AND VAPOUR PHASES ARE IN EQUILIBRIUM, SOME MOLECULES CONTINUOUSLY MOVE FROM THE LIQUID TO THE VAPOUR PHASE AND OTHERS FROM THE VAPOUR TO THE LIQUID PHASE HOWEVER, THE TEMPERATURE AND PRESSURE OF THE SYSTEM DO NOT CHANGE THE STATE OF THERMODYNAMIC EQUILIBRIUM EMBRACES THE FOLLOWING PARTIAL EQUILIBRIA: MECHANICAL (PRESSURE) EQUILIBRIUM—THE PRESSURE IN ALL PARTS OF THE SYSTEM IS THE SAME 1, THERMAL (TEMPERATURE) EQUILIBRIUM—THE TEMPERATURE IN ALL PARTS OF THE SYSTEM IS EQUAL- IZED, CONCENTRATION EQUILIBRIUM—THE CONCENTRATION OF THE SYSTEM COMPONENTS IS THE SAME IN ALL PARTS OF EACH PHASE OF THE SYSTEM, BUT THE COMPOSITION OF INDIVIDUAL PHASES IS USUALLY DI?ERENT, CHEMICAL EQUILIBRIUM—NO CHANGES IN COMPOSITION OCCUR AS A RESULT OF CHEMICAL REACTIONS, PHASE EQUILIBRIUM—IF A SYSTEM IS HETEROGENEOUS (SEE 1 1 4), THE COMPONENTS OF ITS PHASES ARE IN EQUILIBRIUM 1THE OSMOTIC EQUILIBRIUM IS AN EXCEPTION CHAP 1: BASIC TERMS [CONTENTS] THERMODYNAMIC PROCESS IF THE PROPERTIES OF A SYSTEM CHANGE IN TIME, I E IF AT LEAST ONE THERMODYNAMIC QUANTITY CHANGES, WE SAY THAT A CERTAIN THERMODYNAMIC PROCESS TAKES PLACE IN THE SYSTEM THE TERM PROCESS RELATES TO A VERY BROAD RANGE OF MOST VARIED PROCESSES, FROM SIMPLE PHYSICAL CHANGES SUCH AS, E G , HEATING, VARIOUS CHEMICAL REACTIONS, UP TO COMPLEX MULTISTAGE PROCESSES INDIVIDUAL KINDS OF PROCESSES MAY BE CLASSI?ED ACCORDING TO SEVERAL CRITERIA CHAP 1: BASIC TERMS [CONTENTS] PROCESSES AT A CONSTANT QUANTITY IN MOST INVESTIGATED PROCESSES, ONE OR MORE THERMODYNAMIC QUANTITIES ARE MAINTAINED CONSTANT DURING THE WHOLE PROCESS THESE PROCESSES ARE MOSTLY TERMED USING THE PRE?X ISO- (IS-), AND DENOTED USING THE SYMBOL [X], WITH X INDICATING THE GIVEN CONSTANT QUANTITY THE FOLLOWING PROCESSES ARE ENCOUNTERED MOST OFTEN: CHAP 1: BASIC TERMS [CONTENTS] CYCLIC PROCESS A CYCLIC PROCESS IS SUCH AT WHICH THE ?NAL STATE OF THE SYSTEM IS IDENTICAL WITH ITS INITIAL STATE IN A CYCLIC PROCESS, CHANGES OF THERMODYNAMIC QUANTITIES ARE ZERO NOTE: HEAT AND WORK ARE NOT THERMODYNAMIC QUANTITIES AND THEREFORE THEY ARE NOT ZERO DURING A CYCLIC PROCESS CHAP 1: BASIC TERMS [CONTENTS] EXAMPLE LET OUR SYSTEM BE A CUBE OF ICE WITH A MASS OF 1G, AND THE INITIAL STATE BE A TEMPERATURE OF ?10 ?C AND A PRESSURE OF 100KPA THE SEQUENCE OF PROCESSES TAKING PLACE IN THE SYSTEM WAS AS FOLLOWS: THE CUBE WAS HEATED TO 0 ?C AT WHICH IT MELTED THE LIQUID WATER WAS ELECTROLYZED AT THIS TEMPERATURE THE RESULTING MIXTURE OF HYDROGEN AND OXYGEN WAS EXPANDED TO 200PA AND IGNITED THE WATER VAPOUR RESULTING FROM THE REACTION HAD A TEMPERATURE OF 500 ?C AT THE END OF THE REACTION IT WAS THEN COOLED TO ?10 ?C AND COMPRESSED TO 100KPA IN THE COURSE OF COMPRESSION DESUBLIMATION (SNOWING) OCCURRED, AND THE SYSTEM RETURNED TO ITS INITIAL THERMODYNAMIC STATE A CYCLIC PROCESS TOOK PLACE CHAP 1: BASIC TERMS [CONTENTS] PRESSURE P U MAIN UNIT: PA OLDER UNITS: BAR (1BAR = 105 PA), ATM (1ATM = 101 325PA), TORR (760TORR = 101 325PA) CHAP 1: BASIC TERMS [CONTENTS] VOLUME V U MAIN UNIT: M3 OLDER UNITS: LITRE (1L = 1DM3) CHAP 1: BASIC TERMS [CONTENTS] XI = 1 (1 7) NOTE: INSTEAD OF MOLE FRACTIONS, THE EXPRESSION MOLE PERCENT IS OFTEN USED, MEANING 100- TIMES THE MOLE FRACTIONS CHAP 1: BASIC TERMS [CONTENTS] EXAMPLE A BINARY MIXTURE CONTAINS 4MOLES OF SUBSTANCE A AND 6MOLES OF SUBSTANCE B EXPRESS THE COMPOSITION OF THE MIXTURE USING MOLE FRACTION AND MOLE PERCENT SOLUTION ACCORDING TO (1 6), THE AMOUNT OF SUBSTANCE IN THE MIXTURE IS N = 4+6 = 10 MOL FROM (1 5) WE GET XA = 4/10 = 0 4, XB = 6/10 = 0 6 THE MIXTURE CONTAINS 40MOLE PERCENT OF SUBSTANCE A, AND 60MOLE PERCENT OF SUBSTANCE B A MIXTURE IN WHICH MOLE FRACTIONS OF ALL COMPONENTS HAVE THE SAME VALUE IS CALLED AN EQUIMOLAR MIXTURE EXAMPLE CALCULATE THE MOLE FRACTIONS OF AN EQUIMOLAR MIXTURE OF HYDROGEN AND OXYGEN, AND THE MOLE FRACTIONS OF AN EQUIMOLAR MIXTURE OF NITROGEN, OXYGEN AND ARGON SOLUTION IT FOLLOWS FROM THE DE?NITION OF AN EQUIMOLAR MIXTURE THAT XH2 = XO2 = AND XN2 = XO2 = XAR = MASS FRACTION WI DE?NITION WI = MI M , (1 8) WHERE MI IS THE MASS OF COMPONENT I, AND M = PK I=1 MI IS THE MASS OF THE MIXTURE U MAIN UNIT: DIMENSIONLESS QUANTITY CHAP 1: BASIC TERMS [CONTENTS] XJMJ (1 10) EXAMPLE A MIXTURE CONTAINS 5G OF SUBSTANCE A WITH A MOLAR MASS MA = 25 GMOL?1, AND 15G OF SUBSTANCE B WITH A MOLAR MASS MB = 75 GMOL?1 CALCULATE THE MASS FRACTIONS AND THE MOLE FRACTIONS SOLUTION SUBSTITUTING INTO (1 8) GIVES WA = 5 + 15 = 0 25, WB = XJV M,J , (1 11) CHAP 1: BASIC TERMS [CONTENTS] OF WATER IS IT POSSIBLE TO CALCULATE THE VOLUME OF THE SOLUTION BASED ON THIS DATA? SOLUTION FROM (1 11) WE OBTAIN ?WATER = 160 + 40 = 0 8, ?ETHANOL = 160 + 40 = 0 2 THE VOLUME OF A SOLUTION CANNOT BE CALCULATED USING THE VOLUMES OF PURE SUBSTANCES, BUT IT HAS TO BE MEASURED IN THE CONSIDERED MIXTURE OF ETHANOL AND WATER IT WILL BE SMALLER THAN 160 + = 200 CM3 CHAP 1: BASIC TERMS [CONTENTS] AMOUNT-OF-SUBSTANCE CONCENTRATION CI DE?NITION CI = NI/V , (1 13) WHERE V IS THE TOTAL VOLUME OF THE MIXTURE U MAIN UNIT: MOLM?3 IN A PURE COMPONENT THIS QUANTITY IS IDENTICAL WITH THE AMOUNT-OF- SUBSTANCE DENSITY NOTE: THE EXPRESSION AMOUNT-OF-SUBSTANCE CONCENTRATION IS USUALLY ABBREVIATED TO AMOUNT CONCENTRATION OR SUBSTANCE CONCENTRATION THE SAME APPLIES TO THE EXPRESSION AMOUNT- OF-SUBSTANCE DENSITY WHEN THERE IS NO RISK OF AMBIGUITY, THE WORD CONCENTRATION MAY BE USED ALONE IN OLDER LITERATURE, THE TERM MOLARITY MAY BE FOUND INDICATING THE SAME QUANTITY (USING THE UNIT MOLDM?3) EXAMPLE A MIXTURE OF SUBSTANCES WITH A VOLUME OF 5DM3 CONTAINS 56G OF NITROGEN CALCULATE ITS CONCEN- TRATION SOLUTION THE AMOUNT OF SUBSTANCE OF NITROGEN IS NN2 = 28 = 2MOL FROM EQUATION (1 13) WE OBTAIN CN2 = MOLALITY MI DE?NITION MI = NI/MSOLVENT (1 14) CHAP 1: BASIC TERMS [CONTENTS] = 2MOLKG?1 THE MOLALITY OF THE OBTAINED SOLUTION IS 2MOLKG?1 CHAP 2: STATE BEHAVIOUR [CONTENTS] STATE BEHAVIOUR THE TEMPERATURE, PRESSURE, VOLUME AND AMOUNT OF A PURE SUBSTANCE ARE NOT INDEPENDENT IN A HOMOGENEOUS SYSTEM, ANY THREE OF THESE QUANTITIES MAY BE CHOSEN, WITH THE FOURTH BEING IMPLICITLY GIVEN FOR INSTANCE, WE MAY CHOOSE THE AMOUNT OF A GIVEN SUBSTANCE, THE VOLUME IN WHICH IT IS ENCLOSED, AND ITS TEMPERATURE THE PRESSURE AS THE FOURTH QUANTITY IS THEN IMPLICITLY GIVEN THE STATE BEHAVIOUR OF A SUBSTANCE (OR, MORE ACCURATELY, THE DESCRIPTION OF ITS STATE BEHAVIOUR) IS EXPRESSED BY THE RELATION BETWEEN ITS TEMPERATURE, PRESSURE, VOLUME AND AMOUNT OF SUBSTANCE WE OBTAIN THIS RELATION EITHER EXPERIMENTALLY (I E WE MEASURE THE STATE BEHAVIOUR) OR THEORETICALLY (I E WE CALCULATE THE STATE BEHAVIOUR) THE STATE BEHAVIOUR OF A HOMOGENEOUS MIXTURE IS EXPRESSED BY THE RELATION BETWEEN THE TEM- PERATURE, PRESSURE, VOLUME AND THE AMOUNT OF SUBSTANCE OF ITS COMPONENTS IN A K-COMPONENT MIXTURE, WE MAY CHOOSE ANY (K + 2) OF THE (K + 3) QUANTITIES, WITH THE (K + 3)RD QUANTITY BEING IMPLICITLY GIVEN WE MAY, E G , CHOOS