j271

Index

a Artifacts 245f AC (alternating current) calorimeter 194f, Artificial nose 225 217 Accelerating rate calorimeter (ARC) 198, 204 b Accuracy 133, 233ff Bacteria 2, 259ff Activation energy 39, 110, 264 Balances 19 – phase transition 39 Baseline 91ff, 98, 113, 121 Active measuring system 74 – DSC 98 Activity monitor 159f – drift 160, 231f Actual value (controller) 128 – stability 242 Adiabatic – step change 71, 98, 159 – calorimeter 68, 73, 75f, 77, 190 Battery calorimeter 160 ––measured curve 86f Berthelot bomb 45, 58, 148 – calorimetry 68 Binary system 54f – condition 75f Biological studies 2, 10, 13, 82, 160, 186, 212, – flow calorimeter 199 225, 256ff – reaction calorimeter 198, 204 – smearing of the measured curve 82 – scanning calorimeter 200 Boersma method 181 – scanning condition 77 Boiling curve 55 – whole body calorimeter 169, 199 Boiling point 55 Alternating current (AC) calorimeter 194f, Bomb calorimeter 132, 150 217 Books on calorimetry 4 Aluminum (heat capacity) 197 Boundary conditions 31f, 38, 40, 44f, 56, 59 Ammonia (gas-liquid transition) 138 Bronsted€ method 12 Amount of substance, measurement 19 Bunsen ice calorimeter 10, 135 Aneroid 13 – calorimeter 151 c Animal 10, 169, 256ff Calibration 14, 15, 19f, 140, 146f, 155, 158, Aperiodic limit (controller) 130 163, 175, 188, 200, 239ff Apparatus function 103, 105, 106, 169, 189, – enthalpy 241 232, 234, 243 – factor 14, 97, 98f, 119, 154f, 157, 164, 170, – Calvet calorimeter 166, 169 173, 180f – fluctuations 107 – flow calorimeter 170 – measurement 106 – heat 239ff Application of calorimetry 2f, 246ff – heat flow calorimeter 157f Approximation, reversible 41 – heat flow rate 224f, 239ff ARC (accelerating rate calorimeter) 198, – material 241f 204 – temperature 239, 241 Arrhenius equation 110f Caloric problems 246ff

Calorimetry: Fundamentals, Instrumentation and Applications, First Edition. Stefan M. Sarge, Gunther€ W. H. Hohne,€ and Wolfgang Hemminger. Ó 2014 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2014 by Wiley-VCH Verlag GmbH & Co. KGaA. 272j Index

Calorie (unit) 3 – liquid 13, 145, 151 Calorific value of gas 2f, 265ff – low temperature 192 Calorimeter 125 – manufacturers 211 – 3v 195 – microchip 177, 214ff – AC (alternating current) 194, 217 – mixing 145, 202 – accelerating rate (ARC) 204 – phase transition 9, 134 – adiabatic 75f, 86, 190, 199 – photo 206 –– reaction 198, 204 – power compensated 78, 99, 183ff –– scanning 200 – pressure 206 – aneroid 151 – quasi-adiabatic 201 – bomb 132, 150 – reaction 202ff – calibration 239ff – relaxation 224 – Calvet 161, 256 – requirements 237f – characteristics 132, 230ff, 239ff – scanning 76,93f, 145, 178 –– contactless energy supply 196 – selection 238, 247f, 256, 259f, 262f, 265f –– heat exchange sample-surroundings 144f – substance 13, 128, 134f, 151, 158, 202 –– linear temperature change of – system 125 surroundings 178f – testing 239ff –– liquid-gas phase transition 137f – titration 132, 143 –– non-linear temperature change 186 – twin 69, 71, 156, 164, 168, 179 –– phase transitions 134 – whole-body 169, 199 –– reacting calorimeter substance 202 Calorimetric bomb 135 –– reaction vessel 144ff, 202 Calorimetry –– thermally isolated sample 190f – adiabatic 68, 75, 190 –– thermoelectric compensation 142 – application 246ff –– uncontrolled heat exchange 145 – books 4f –– zero temperature difference against – classification 131 surroundings 197 – conferences 5 – characterization 132, 230ff, 239ff – definition 1 – chip 177, 214ff – developments 213ff – choice 237ff – examples 2 – classification 131 – high pressure 221f – combustion 13, 148, 265ff – high temperature 222f – compensation 9, 12, 74, 78, 141, 183 – isoperibol 75, 154 – cooling methods 126 – isothermal 74, 134 – deformation 139 – journals 5 – description 131 – levitation 223 – drop 151, 223 – measuring principles 16 – electric compensation 12, 141 – methods 9 – evaluation 229ff – microchip 214ff – flash 220 – modes of operation 73 – flow 15, 170, 199 – nomenclature 131 – functional components 125 – scanning 93f, 178 – gas 266f – trends 213ff – gas combustion 2f, 150, 177, 266f – ultrafast 217ff – heat flow 15, 178 Calvet calorimeter 161, 256 – heating methods 126 – theory 162f – high pressure 221f Cement calorimeter 207 – high temperature 176, 201, 222f Certified reference material 241f – ice 9, 135 Characteristics of calorimeters 132 – isoperibol l75, 145, 154 Characterization of calorimeters 132, 230ff, – isothermal l74, 134 239ff – large volume 160 Charge (electric) 32 Index j273

Chemical composition 29 Coverage factor 133 Chemical energy 32, 34, 40, 43, 45 Creep case (controller) 130 Chemical potential 40 Crucible 243f Chemical reaction 38, 45, 81, 109f, 261ff Crystallization 219 – kinetic parameters 109f, 263f Crystallinity Chemistry, example 225, 261ff – polyethylene 219, 247ff Classification of calorimeters 131 – polyethylene terephthalate 247ff – construction principle 145 Curing reaction 262 – measuring principle 132 Curve-normalization (measured effect) 103, – operation condition 73, 78, 132 106 Clausius-Clapeyron equation 39, 53, 138 Coefficient of convection heat transfer 65 d Combined standard uncertainty 133 Damping (controller) 129 Combustion Decomposition 109f – calorimeter 58, 148 Deconvolution, see: Desmearing ––gas 2f, 177, 265ff Deformation 140 – calorimetry, example 265ff – calorimeter 139 – heat 10, 13, 58, 150 ––liquid-gas phase transition 139 Compensation – calorimetry 139f – calorimeter 9, 134 – heat 140 – electric effect 12f, 134, 141 – tensor 31, 34 – of the thermal effect 134 – work 139 – phase transition 9, 134f Degree of crystallinity 247ff Component of a thermodynamic system 47f, Degrees of freedom 32, 53f 52ff, 58 Density of water 11 – example 53ff Desmearing 92, 93, 98, 101ff, 109, 161, 163, Compression energy 34f 167, 217, 232 Concentration 52, 54, 143, 170, 198 – application limits 107 Condensation 50 – error 107 Condition – procedure 105f – adiabatic 75f, 190 – quality 107 – isoperibol 75, 78, 154 – resolution 107 – isothermal 74, 78, 134 Detection limit 133 – scanning 76, 78, 178 Dewar flask 192 Conduction of heat 61 Dickinson formula 146 Conductivity, thermal 16, 62 Differential (mathem.) Conferences (calorimetry) 5 – exact 33 Conservation of energy 43 – total 33, 35 Construction principle 125, 131 Differential measurement 69 Contactless energy transfer 196f Differential scanning calorimeter (DSC) 93ff, Control 178ff – behavior 130 – measured curve 93 ––example 130 Differential thermal analysis (DTA) 181f – electronic 76f Dirac function 102, 189, 165 – system 128ff Displacement energy 34, 35 Controller 128 Drift 136, 191f, 231f Convection 64 – of baseline 160 Convolution 102 – of ice calorimeter 136 – integral 102, 104, 106f Drop calorimeter 151f, 223 – solution 105 – examples 151, 152, 153 – theorem 105 DSC (differential scanning calorimetry) 93ff, Cooling, electric 12, 126 178ff Copper (heat capacity) 197 – heat flow 179 274j Index

– measured curve 93f Evaporation 140ff, 151, 159, 189 – power-compensated 78, 99, 183ff Event function 103 –– measured curve 93f Exact differential 33, 35 – stepscan 189 Example, illustrative calorimetric 213ff – temperature modulated 187 – biology 225, 256ff –– multifrequency 189 – chemistry 225, 261ff DTA (differential thermal analysis) 181f – combustion of gas 265ff – low temperature physics 224 e – material science 247ff Electric – medicine 225f, 259ff – compensation 134, 143 – plasma physics 224f – cooling 12, 126 Expanded uncertainty 133 – energy 34 Extension wires 27 – equivalent diagram (circuit) 162 Extensive variables 34f – field strength 34 External variables 32 Electromagnetic field 152 Extreme condition 40, 220ff Electromotive force 22 Emittance 66 f Energy 1, 33, 35, 57 Feedback control 130 – equivalent 14 Firms (manufacturers) 211 – forms 32, 34 First law of thermodynamics 42 – Gibbs free 37 Flow measurement 21 – stored 139 Flow calorimeter 15, 144, 170 – supply, contactless 196 – adiabatic 191 – transition 51, 57 – calibration factor 170 Enthalpy 33, 37, 45, 48, 58, 137, 154 – examples 175, 176, 177 – calibration material 241 – high pressure 176 – mixing 144, 175 – high temperature 176 – transition 48, 57, 181 – isoperibol 170 Entropy 40, 42f, 46, 48, 50, 53, 56, 67 – isothermal 144 – change 41, 43, 50 – problems 175 – increase of 40, 67 – quasi-adiabatic 170 – maximum 40 Flow tube 170, 173 Enzyme thermistor 225 Fluids 144, 170f Epoxy resin 262 – heat of reaction 144, 174, 202 Equation of heat conduction 61 Foodstuffs (combustion heat) 150 – solution 61f Forms of energy 32, 34 Equilibrium, thermodynamic 38 Fourier transform 105 – criterion 40 Free energy (Gibbs energy) 37 – condition 47 Freezing point 54 – heterogeneous 47 Frequency (temperature modulation) 186f, Equivalent diagram, electric 162, 167f 194 Error 232ff Frequency factor (kinetics) 109f – measurement 133 Fuels 150, 177 – random 116, 133 Functions of state 31 – sources 126, 142, 147, 196 Fundamental form 35, 37, 44, 56 – systematic 116, 133 – calorimetry 36, 38 – total 233f Furnace 73ff Evaluation 81ff, 109ff, 245 Further reading 4f – calorimeter 230ff – measured curves 81ff g – measurement (examples) 248ff, 258, 260, Gas combustion calorimeter 150, 177, 265ff 263f, 267 Gas-liquid phase transition calorimeter 137f Index j275

Gaseous substances 177, 199, 202 – model calculation 84ff, 162f – gross heating value 150, 177 Heat flow calorimeter 15, 155, 178 Gibbs function (Gibbs energy) 37, 39, 47f – baseline fluctuations 159 – one-component system 48 – Boersma type 181 Gibbs fundamental form 35 – Calvet type 181 Gibbs phase rule 52 – calibration 157 – examples 53f – disc-shaped 182 Gibbs-Thomson equation 216 – examples 159f Grashof number 65 – function principle 156 Green’s function 103, 232 – problems with 155, 159 Gross heating value 150, 177 – properties 155, 178 Guideline 229ff, 235ff – theory of 155f – time constant 157 h Heat flow DSC 93, 179 Heat 1, 3, 31f, 34 – application 256ff – calibration material 241 – measured curve 93f – combustion 10, 13, 58, 137, 148, 149f, 266ff Heat flow rate 15, 63 – deformation 140 – calibration material 242 – evaporation 138, 140 Heat leak 12, 14f, 61, 64, 66, 69f, 73, 87f, 96, – formation 150 126, 134, 162, 171, 173, 190, 192 – fusion 70, 135, 153 Heat pulse 88f, 106, 165ff, 189, 192 ––calibration material 241 Heat radiation 65f ––sample size dependence 216f Heat relaxation 102 – mixing 143, 144, 170 Heat shield 192 – organisms 2, 10, 137, 169 Heating rate 76, 99ff – reaction 2, 9, 15,31, 46, 144, 148, 158, 174, Heat transport 61ff, 66, 81f, 86, 154ff, 172, 201 202 – conduction 61 – solution 12, 141, 202 – convection 64 – transition 11, 38, 56, 58, 113f, 134, 178 – effect on baseline 98 Heat balance equation 219 – importance in calorimetry 68 Heat capacity 13f, 44, 45, 145f, 151, 162f, 180, – radiation 65f 187f, 190, 194, 196, 200 – transfer 67 – apparent 187f, 189 Helium, liquid 131, 192 – calibration material 242 Helmholtz function (Helmholtz energy) 37, – of a calorimeter 13, 146f, 151, 157, 171, 177 46 – complex 187f, 189, 194f Heterogeneous – fluids 172f, 175f, 199 – equilibrium 47 – gas 199 – system 47 – non-reversing 188 High pressure 176 – reversing 188 – calorimetry 221f – specific 1, 100, 109, 147, 170, 172, 191, 197 High temperature 176, 201 – total 188 – calorimetry 222f Heat-conduction 61 Homogeneous system 47 – equation 61 Honeybee 257ff ––solution 61f, 63 Hornet 258f – parasitic Hydrogen, catalytic oxidation 225 – path 89, 92ff Heat exchange i – sample-surrounding 144 Ice calorimeter 10, 135 – uncontrolled 145 – applications 137 Heat flux 61f, 63, 66 Ignition 148ff Heat flow rate 87ff, 101ff, 109, 113, 154ff, Illustrative example (calorimetry) 213ff, 246ff 161, 163ff, 179ff Independent variables 32ff 276j Index

Inert substance 98 Linearity 106, 133, 232f Infection diagnostics 225f, 259ff Liquid Integral, definite 35 – calorimeter 145 Intensive variables 34 – metals as calorimeter substance 153, 202 Internal variables 32 – substances 145ff, 148f, 185 Intrinsic noise (of sensor) 129 Liquid-in-glass thermometer 23 Iron (heat capacity) 197 Living organism 2, 10, 135, 169, 256ff Irreversible process 41, 46 Long-time noise, see: Noise Isolated system 40, 46 Low temperature calorimeter 192 Isoperibol 75, 154, 170 – calorimeter 75, 78, 89, 154, 170 m –– with controlled heat exchange 154 Magnetic field 224 –– measured curve 90ff Manufacturers (calorimeter) 211 – condition 75, 134, 145 Material science 2 – definition 75 – example 247ff – scanning condition 78 Measured curve 81ff, 86, 98, 100, 104 Isothermal – adiabatic calorimeter 86 – calorimeter 73f, 78, 134, 265ff – biological system 82 –– with electric compensation 141 – calorimeter types 86ff – condition 74 – chemical reaction 81, 109f – flow calorimeter 144 – dependence on parameters – titration calorimeter 143 – desmearing 101ff, 106 ITC (isothermal titration calorimeter) 143 – differential scanning calorimeter – applications 144 93f, 178ff IUPAC 240 – disturbances 108 – endothermic process 97 j – evaluation 81 Joule (unit) 3 – exothermic process 87, 97 Joule effect 17, 126ff, 196 – heat pulse 90, 93 Journals (calorimetry) 5 – heat flow calorimeter 93 – isoperibol calorimeter 88, 89 k – normalization 103, 106 Kinetics 109f, 144, 174, 177, 198, 204 – phase transition 83 Kinetic – power compensated differential scanning – analysis 111 calorimeter 99, 183 – data 110 – smearing of 81ff – energy 32, 34 Measurement 229ff, 244f, 257, 260, – model 263f 263, 267 – parameters (measurement) 109f, 261ff – calorimetric problems 81 – electric quantities 21f l – error 116f Laplace, see: Lavoisier – evaluation 245, 248ff, 258, 260, 263f, 267 Laser beam 224f – interpretation 245f, 251f, 260f, 264, 268 Latent heat 9, 56, 138, 149, 151 – material quantities 20 Lavoisier ice calorimeter 10 – sample preparation 243f Laws of thermodynamics 42ff – temperatures 22f Leak, thermal, see: Heat leak – thermodynamic state functions 43 Legal metrology 2 – uncertainty estimation 115ff, 119, 246, Levitation calorimetry 223 252ff, 259, 261, 265, 268f Limit of detection 133 – variables of state 56 Linear Measuring – behaviour 105 – effect 9 – response 102, 123 – error 133 Index j277

– instruments in calorimetry 20 Normalization of curves 103, 106 – principle 16, 131 NTC-resistor 26 – problem (characterization) – system 73ff o ––active 130f 3v technique 195 ––passive 132 One-component system 48, 52, 53f, Medicine, example from 169, 259ff 56, 58 Melting 70 Operation condition 73, 78 Melting point 241 – adiabatic 75f, 78, 190ff – reference material 241 – adiabatic scanning 77, 200 – sample size dependence 216 – isoperibol 75, 78, 145,154ff Metal, liquid 151f – isoperibol scanning 78, 184 Metamorphosis, biological 256 – isothermal 74, 78, 134ff Metastable state 38f, 50 – modulated 145, 187 Methane 267ff – scanning 145, 178 Microcalorimeter 132, 151, 160, 161 Organism (living) 2, 10, 135, 169, 256ff – application 226 Oscillating case (controller) 130 Microchip Oxygen 148 – calorimetry 214ff – flow calorimeter 177 p Microorganisms 2, 259ff Passive measuring system 74 Mixing 160 Path 32f, 39, 41f, 58 – calorimeter 145f, 202 – reversible 41, 43 ––applications 145 Peltier ––classic 145 – coefficient 126 – calorimetry 13, 144, 147 – cooling 128 – enthalpy 144 – cooling power 128 Mode of operation, see: Operation – effect 17, 28f, 126 condition – power 126 Model calculation 84ff Phase 47 Monographs (calorimetry) 4 – diagram 55 Multiphase systems 47 – rule (Gibbs) 52f, 58 ––examples 53f n – transition 9, 47, 50, 56f, 83, 111, 134ff Naming of calorimeters 131 ––calorimeter 9f, 134 Nanocalorimeter 214ff ––liquid-gas 138 Natural gas 265ff ––one-component systems 48, 52f, 56 NBS-calorie 3 ––temperature 111 Nernst-calorimeter 153, 191 ––two-component systems 52, 54 Nernst’s method 192 ––variables of state (measurement) 56 – contactless energy transfer 196 Photo calorimeter 206 Newton’s law of cooling 65, 67 Picker calorimeter 175 Nickel (specific heat capacity) 197 Pfaundler, see: Regnault Nitrogen (gas-liquid transition) 131, 134, 139f, Plasma 224f 184, 192 Platinum 176, 183f, 192 Noise 129, 133, 160, 177, 179f, 183, 230ff, 242, – resistance thermometer 25, 183f 246 Polyethylene 217, 248ff – intrinsic 129 – crystallization 219 – long-time 231f Polyethylene terephthalate 219, 248 – short-time 231 Polypropylene 219 Nomenclature 131 Poorly adiabatic 88 Non-steady state 181 Potential function, thermodynamic 33, 34,56 Normal (Standard) 241f – minimum 39, 47 278j Index

Power compensated calorimeter 78, 99f, – material 70, 99, 102f, 241f 183ff – sample 70 – application 247ff, 261ff Regnault and Pfaundler correction method 88, Precision 133 146, 150 Preexponential factor 110, 264 Relaxation, thermal 81, 154 Preset value (controller) 128 Relaxation calorimeter 224 Pressure 31, 32, 34, 54f, 58, 144, 149f, 169, Regression, linear method 176 Repeatability 133, 235, 245f – calorimeter 176, 206 – measurement 133 – measurement 21 Reproducibility 133, 235 – perturbation calorimeter 206 Resistance Principles of measurement 9, 131 – NTC 26 Privalov calorimeter 185 – thermal 64, 74ff, 92, 95, 144, 154–171, 181, Process 31ff, 41,56 190–195 – cyclic 33 – thermometer 25 – irreversible 41 Resolution 133 – path 33, 35, 58 Resolution – reversible 41 – measurement – steady state 40 Response Proceedings, conference 5 – calorimeter 103, 105 p-T diagram 53f –– example 107 Pt-100-sensor (thermometer) 25f – function 232, 234 Pulse heating calorimeter 189, 201 – linear (theory) 102 Pulse-like event (heat pulse) 88f, 106, 192 Reversible 41 Purity 29 – approximation 41 – determination 114f – limit 41 Pyrometer 23, 26, 153, 197, 201 – path 41 – process 41 q Reversing heat capacity 188 Quasi-adiabatic 73, 170, 201 Rotational energy 34 Quasi-isothermal 73, 134, 142, 169 s r Sample Radiation 65 – container 243f – heat transfer 65f – crucible 243f – shield 66, 68, 146, 151, 155, 176, 191ff, 199 – deformation, see: deformation calorimeter Random error 133 – heat transfer 180 Raoult’s law 55 – preparation 243f Reaction – size dependence 216f – analysis 109f – temperature relaxation 81f – calorimeter 198, 202ff Scanning – chemical 45, 109f, 171, 174, 189f, 198, 202 – calorimeter 76, 93f, 145, 178 – kinetics 109f, 144, 177, 198, 204, 261ff –– adiabatic 200 –– parameters 110, 264 –– Boersma type 181 – order 110, 264 –– Calvet type 161, 181 – rate 109f, 261ff –– power compensated 183ff – vessel 134, 144–155, 173, 202ff – condition 76, 178 Recursion method (desmearing) 105f –– adiabatic 77 Reconstruction –– isoperibol 78 – temperature field 101f –– surroundings 77, 178 – true thermal event 101ff Second law of thermodynamics 42f Reference 70 Selection of a calorimeter 238, 247f, 256, 259f, – junction (thermocouples) 27 262f, 265f Index j279

Semiconductor thermometer 23, 26 – heat generation 12 Sensitivity 11, 13f, 129,133–198, 230 Stored energy 139 – controller 129 Stress tensor 31, 33 – ice calorimeter 135f Subsystems 40f – measurement Supercooling 50, 51, 223 Separation (into subsystems) 51 Superheating 50, 51 Set value (controller) 130 Superposition principle 104f, 107 Short-time noise, see: Noise Surface Silicon – coefficient of heat transfer 67 – chip 214ff – energy 34f, 50 – membrane 214ff Surroundings 73ff Single-component system 47 System Smearing – binary 55 – biological thermal effects 82 – description 36f, 41 – measured curve 63, 71, 102 – heterogeneous 47 – thermal event 71 – homogeneous 47 Solution calorimeter 202 – isolated 40, 46 Space of states 33, 39, 41, 48 – multiphase 47 Space craft 224f – one component 48, 52, 53f Specific heat capacity 1, 13f, 147, 170, 172, 191, – ternary 55 197 – thermodynamic 31, 42 – fluids 170, 175 – two component 52, 54f – gases 199 Systematic error 133 – low temperatures 191 – measurement 10, 14, 100, 109 t – Nernst method 192 Temperature 22, 31, 33 Stability, chemical 109f – absolute 23, 28, 43 Stable state 49, 60 – calculation 63, 85 Standard – calibration material 241 – enthalpy of formation 148 – differences (measurement-method) 13ff – material 241f – field 61ff, 85, 94, 101 – reference substances – local 15 – uncertainty 133 – measurement 22, 23 ––combined 133 – relaxation 81, 88 – variables 33, 36 – scale 23 State 31 – time-dependent 13, 178 – aggregation 47 Temperature modulated DSC 187 – equation 32 Terminology 230ff – equilibrium 38,41 Ternary system 55f – final 33 Testing of calorimeters 239ff – function (thermodynamic) 32,42 Theory ––measurement 43 – Calvet calorimeter 163ff – initial 33 – heat flow calorimeter 178ff – metastable 38f Thermal – space of 33, 39, 41, 48 – conductance 66 – stable 49, 60 – conductivity 16, 62, 178ff – unstable 51 – effect 9 – variables 32, 38 – leakage, see: Heat leak Steady state 40, 129f, 140, 154ff, 179 – resistance 64, 74ff, 92, 95, 142, 155–171, 181, Steam table calorie 3 190–195 Stepscan DSC 189 Thermistor 26, 175 Stirrer Thermocouple 27f, 126f – correction – electromotive force 22, 28, 127 280j Index

– extension wires 27 – energy 57 – reference junction 28 – enthalpy 57 – reference thermostat 28 Trends in calorimetry 213ff – series connection 27f Twin Thermodynamic – calorimeter 69, 71, 156, 162, 168, 179 – boundary conditions 38, 40f, 44f, 47f, 59 – design 94, 96, 98, 111, 143, 154ff, 160, – equilibrium 38 175ff, 183 – fundamentals 35 Two-component system 52, 54f – laws 42 Two-phase system 48f, 50f – potential functions 35, 47f, 50, 56 –– measurement 56 u – potentials 33, 35 Ultrafast calorimetry 218f – process 32 Uncertainty 133 – state functions 43, 56 – desmearing 107 – state 32 – estimation 115ff, 246, 252ff, 259, 261, – system 31, 42 265, 268f – thin films 216f –– example 119 – variables 31 – random 235 Thermoelectric Unexpected phases 56 – compensation (calorimeter) 142 Units XV, 3 – effect, see: Peltier effect – conversion 3 Thermometer 23 – gas 24 v – liquid in glass 23 Vapor – platinum resistance 25 – calorimeter 137ff – resistance 25 – pressure 25, 145 – semiconductor 26 – thermometer 23,24 – vapor pressure 24 Variables 31 Thermopile 27f, 142f, 156, 161f, 177, 181, 185f – extensive 34f Thermostat 126, 128, 131, 142–205 – external 32 – thermocouple reference junction 28 – independent 32 Thermovoltage 28 – intensive 34f Third law of thermodynamics 43 – internal 32 Three-component system 55 – standard 33 Tian – state 31, 32, 38 – calorimeter 142 –– measurement 43,56 – equation 163 – thermodynamic 31 Time Volume 20, 34 – constant 88, 93, 102, 109, 129, 142, 155–188, – measurement 20 218, 238 –– adiabatic calorimeter 86f, 190ff w –– Calvet calorimeter 166ff Water –– DSC 178ff – density 11 –– flow calorimeter 170ff – gas-liquid transition 138 –– isoperibol calorimeter 93, 154 – value 14, 82, 147 – lag 81, 86, 88, 171 Weighing 20 Titration calorimeter 132, 143f Whole-body calorimeter 169, 199 – isothermal 143 Work, mechanical 32, 34, 53, 58, 139 Total differential 33 Total error 116 z Transition (phase) 9, 47, 50, 56f Zeroth law of thermodynamics 42