Modern thermodynamics for chemists and biochemists:
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| Main Authors: | , |
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| Format: | Book |
| Language: | English |
| Published: |
Oxford
Oxford University Press
2018
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| Edition: | First edition |
| Subjects: | |
| Online Access: | Inhaltsverzeichnis Klappentext |
| Item Description: | Literaturangaben |
| Physical Description: | xxix, 870 Seiten Illustrationen, Diagramme |
| ISBN: | 9780198784708 9780198782957 |
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XXI
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Index of symbols
Index of units-of-measure xxvü
List of Tab!es xxviii
PARTI FUNDAMENTALS
1 Systems and states 3
SUMMARY 3
1.1 Some very familiar concepts. 3
1.2 The macroscopic viewpoint 4
1.3 The system, the surroundings, and the system boundary 5
1.4 State functions 5
1.5 Extensive and intensive state functions 6
1.6 The mole number n 7
1.7 The 'ideal' concept 8
1.8 Equilibrium 8
1.9 Changes in state 10
1.10 The surroundings have state functions too 13
1.11 Pressure 13
1.12 The ideal gas 16
1.13 Pressure - a molecular interpretation 17
EXERCISES 18
Work and energy 20
SUMMARY 20
2.1 Work - an initial definition 20
2.2 The work done by an expanding gas 21
2.3 Path functions 23
2.4 An important sign convention 26
2.5 Useful work. 27
2.6 . and wasted work 28
2.7 Quasistatic paths 28
2.8 Work and Boyle's Law 31
2.9 P, V diagrams 31
2.10 Changes at constant pressure 34
CONTENTS
2.11 Thermodynamic cycles 35
2.12 Energy 40
EXERCISES 40
3 Temperature and heat 43
SUMMARY 43
3.1 Temperature 43
3.2 The ideal gas law 46
3.3 A very important principle 48
3.4 Dalton's law of partial pressures 48
3.5 Some other equations-of-state 50
3.6 Heat 50
3.7 Some more definitions 56
3.8 How to get work from heat 58
3.9 Temperature - a deeper look 67
EXERCISES 74
4 Thermodynamics and mathematics 76
SUMMARY 76
4.1 What this chapter is about 76
4.2 Functions of more than one variable 77
4.3 Partial derivatives 78
4.4 Systems of constant mass 80
4.5 Partial derivatives and state functions 82
4.6 A look ahead . 84
EXERCISES 88
PART 2 THE THREE LAWS
5 The First Law of Thermodynamics 93
SUMMARY 93
5.1 The First Law 94
5.2 A molecular interpretation of internal energy 95
5.3 A reminder of some important sign conventions 96
5.4 Internal energy and temperature 96
5.5 The First Law, state functions, and path functions 99
5.6 The First Law and cycles 101
5.7 The mathematics of U 102
5.8 The First Law in open, closed and isolated systems 104
5.9 The First Law in an isolated system 105
5.10 The First Law in a closed system - the adiabatic change, dq = 0 106
5.11 The First Law in a closed system - the isochoric change, dV = 0 106
5.12 The heat capacity at constant volume, Cv 107
CONTENTS
5.13 The First Law in a closed system - the isothermal change, dT = 0,
for an ideal gas 114
5.14 The First Law in a closed system - the isobaric change, dP = 0 114
5.15 Reversible and irreversible paths 117
5.16 Mixing 126
5.17 Friction 128
5.18 Friction and irreversible paths 134
5.19 Real paths 140
exercises 144
6 Enthalpy and thermochemistry 146
SUMMARY 146
6.1 Man's most important technology 147
6.2 Enthalpy 148
6.3 The mathematics of H 151
6.4 Endothermic and exothermic reactions 153
6.5 Enthalpy, directionality and spontaneity 156
6.6 The difference AH- AU 158
6.7 Phase changes 161
6.8 Measuring enthalpy changes - calorimetry 163
6.9 Calculating enthalpy changes - Hess's law 165
6.10 Chemical standards 168
6.11 Standard enthalpies of formation 178
6.12 Ionic enthalpies 184
6.13 Bond energies 185
6.14 The variation of AH with temperature 190
6.15 The variation of ArH* with temperature 198
6.16 Flames and explosions 200
exercises 206
7 Ideal gas processes - and two ideal gas case studies too 208
SUMMARY 208
7.1 What this chapter is about 208
7.2 Ideal gases 209
7.3 Some important assumptions 210
7.4 Cv and CP for ideal gases 210
7.5 Three formulae that apply to all ideal gas changes 218
7.6 The isochoric path, dV = 0 218
7.7 The isobaric path, dP = 0 219
7.8 The isothermal path, dT = 0 220
7.9 The adiabatic path, dq = 0 221
7.10 The key ideal gas equations 229
7.11 Case Study: The Carnot cycle 230
7.12 Case Study: The thermodynamic pendulum 236
EXERCISES 254
CONTENTS
8 Spontaneous changes 258
SUMMARY 258
8.1 A familiar picture 258
8.2 Spontaneity, unidirectionality and irreversibility 260
8.3 Some more examples of spontaneous, unidirectional, and irreversible
changes 261
8.4 Spontaneity and causality 263
8.5 The significance of the isolated system 266
EXERCISE 266
9 The Second Law of Thermodynamics 267
SUMMARY 267
9.1 The Second Law 268
9.2 Entropy - a new state function 269
9.3 The Clausius inequality 272
9.4 Real changes 273
9.5 Two examples 275
9.6 The First and Second Laws combined 280
9.7 The mathematics of entropy 282
9.8 Entropy changes for an ideal gas 285
9.9 Entropy changes at constant pressure 290
9.10 Phase changes 291
9.11 The Third Law of Thermodynamics 296
9.12 T, S diagrams 297
EXERCISES 299
10 Clausius, Kelvin, Planck, Carathéodory and Carnot 303
SUMMARY 303
10.1 The Clausius statement of the Second Law 304
10.2 The Kelvin-Planck statement of the Second Law 309
10.3 Heat engines and heat pumps 313
10.4 Irreversibility 315
10.5 A graphical interpretation 317
10.6 The Carathéodory statement 321
10.7 Carnot engines and Carnot pumps 323
10.8 Real engines 328
exercise 331
11 Order, information and time 332
SUMMARY 332
11.1 What this chapter is about 332
11.2 Why do things get muddled? 333
11.3 Order and disorder 333
11.4 Macrostates and microstates 334
CONTENTS
11.5 Three important principles 337
11.6 Measuring disorder 337
11.7 What happens when a gas expands into a vacuum 340
11.8 The Boltzmann equation 341
11.9 Maxwell's demon 344
11.10 Entropy and time 347
11.11 Thermoeconomics 347
11.12 Organodynamics 348
EXERCISES 350
12 The Third Law of Thermodynamics 351
SUMMARY 351
12.1 The Third Law 351
12.2 Absolute entropies 352
12.3 Approaching absolute zero 357
EXERCISES 362
PART 3 FREE ENERGY, SPONTANEITY, AND EQUILIBRIUM
13 Free energy 365
SUMMARY 365
13.1 Changes in dosed systems 367
13.2 Spontaneous changes in closed systems 369
13.3 Gibbs free energy 374
13.4 The significance of the non-conservative function 375
13.5 Enthalpy- and entropy-driven reactions 377
13.6 The mathematics ofG 378
13.7 Helmholtz free energy 385
13.8 The mathematics of A 386
13.9 Maximum available work 386
13.10 How to make non-spontaneous changes happen 390
13.11 Coupled systems. 391
13.12 . an explanation of frictional heat, and tidying a room . 393
13.13 . and the maintenance of life 395
13.14 Climate change and global warming - the "big picture' 395
13.15 Standard Gibbs free energies 397
13.16 Gibbs free energies at non-standard pressures 399
13.17 The Gibbs free energy of mixtures 401
13.18 The 'Fourth Law' of Thermodynamics 408
EXERCISES 411
14 Chemical equilibrium and chemical kinetics
413
SUMMARY
14.1 Chemical reactions
14.2 How Gsys(r) varies over time
413
415
417
CONTENTS
14.3 Chemical equilibrium 423
14.4 The pressure thermodynamic equilibrium constantKp. 428
14.5 . and the meaning of ArGp* 430
14.6 Non-equilibrium systems 432
14.7 Another equilibrium constant, Kx. 436
14.8 . and a third equilibrium constant, Kc 437
14.9 Two worked examples - methane and ammonia 439
14.10 How the equilibrium constant varies with temperature 444
14.11 Le Chatelier's principle 448
14.12 Thermodynamics meets kinetics 449
14.13 The Arrhenius equation 455
14.14 The overall effect of temperature on chemical reactions 459
14.15 A final thought 460
EXERCISES 461
PART4 CHEMICAL APPLICATIONS
15 Phase equilibria 467
SUMMARY 467
15.1 Vapour pressure 467
15.2 Vapour pressure and external pressure 470
15.3 The Gibbs free energy of phase changes 471
15.4 Melting and boiling 472
15.5 Changing the external pressure Pex 478
15.6 The Ciapeyron and Clausius-Clapeyron equations 481
15.7 Phase changes, ideal gases and real gases 485
15.8 The mathematics of Gs G| and Gg 497
EXERCISES 500
16 Reactions in solution 502
SUMMARY 502
16.1 The ideal solution 503
16.2 The Gibbs free energy of an ideal solution 511
16.3 Equilibria of reactions in solution 517
16.4 Dilute solutions, molalities and molar concentrations 520
16.5 Multi-state equilibria and chemical activity 522
16.6 Coupled reactions in solution 526
EXERCISES 530 17 * *
17 Acids, bases and buffer solutions 534
SUMMARY - 534
17.1 Dissociation 535
17.2 The ionisation of pure water, pH and pOH 536
17.3 Acids 538
17.4 Bases 545
17.5 The Henderson-Hasselbalch approximation 548
17.6 Buffer solutions 549
17.7 Why buffer solutions maintain constant pH 552
17.8 How approximate is the Henderson-Hasselbalch approximation? 553
17.9 Buffer capacity 554
17.10 Other reactions involving hydrogen ions 561
17.11 The mass action effect 566
17.12 Water as a reagent 567
EXERCISES 569
18 Boiling points and melting points 571
SUMMARY 571
18.1 Non-volatile solutes 571
18.2 Elevation of the boiling point 572
18.3 Depression of the freezing point 575
EXERCISE 579
19 Mixing and osmosis 580
SUMMARY 580
19.1 Mixing 580
19.2 Osmosis 582
19.3 Osmotic pressure 583
19.4 Reverse osmosis 588
19.5 A note on hydrostatic pressure 588
EXERCISES 590 20
20 Electrochemistry 591
SUMMARY 591
20.1 Work and electricity 592
20.2 Electrical work and Gibbs free energy 594
20.3 Half-cells 596
20.4 The electrochemical cell 599
20.5 Anodes and cathodes. 600
20.6 . and the flow of ions and electrons 601
20.7 The chemistry of the Daniell Cell 602
20.8 Currents, voltages and electrode potentials 603
20.9 A different type of Daniell cell 604
20.10 Different types of electrode 605
20.11 Different types of electrochemical cell 607
20.12 The electromotive force 612
20.13 Oxidising agents and reducing agents 619
20.14 The thermodynamics of electrochemical cells 621
CONTENTS
20.15 The Nernst equation 624
20.16 Redox reactions 628
EXERCISES 631
21 Mathematical round up 633
SUMMARY 633
21.1 The fundamental functions 634
21.2 Pure substances 635
21.3 Heat capacities 636
21.4 The Maxwell relations 637
21.5 The chain rule 640
21.6 The thermodynamic equations-of-state 641
21.7 The difference CP - Cv 645
21.8 Thejoule-Thomson coefficient 648
21.9 The compressibility factor 652
EXERCISES 654
22 From ideal to real 655
SUMMARY 655
22.1 Real gases and fugacity 656
22.2 Real solutions and activity 659
22.3 A final thought 668
EXERCISES 668
PARTS BIOCHEMICAL APPLICATIONS
23 The biochemical standard state 673
SUMMARY 673
23.1 Thermodynamics and biochemistry 674
23.2 A note on standards 675
23.3 The biochemical standard state 676
23.4 Why this is important 678
23.5 The implications of the biochemical standard state 679
23.6 Transformed equations 681
23.7 G(H+) and G'(H+), and AfG*(H+) and AfG*'(H+) 683
23.8 E*(H+, H2) and ET(H\ H2) 686
23.9 AfG*'(H2) 689
23.10 Transformed standard molar Gibbs free energies of formation AfG*' 691
23.11 ArG* and ArG*/ 694
23.12 Kr and Kr' 696
23.13 Gsys and Gsys' for an unbuffered reaction 697
23.14 Gsys and Gsys' fora buffered reaction 704
CONTENTS
23.15 Water as a biochemical reagent 707
23.16 The rules for converting into the biochemical standard 708
EXERCISES 708
24 The bioenergetics of living cells 711
SUMMARY 711
24.1 Creating order without breaking the Second Law: open systems 711
24.2 Metabolic pathways, mass action and pseudo-equilibria 712
24.3 Life's primary 'energy currency' - ATP 712
24.4 NADH is an energy currency too 715
24.5 Glycolysis - substrate-level phosphorylation of ADP 716
24.6 The metabolism of pyruvate 719
24.7 The TCA cycle 720
24.8 Oxidative phosphorylation, and the chemi-osmotic potential 723
24.9 The efficiency of glucose metabolism 735
24.10 Photosynthesis 737
EXERCISES 745
25 Macromolecular conformations and interactions 747
SUMMARY 747
25.1 Protein structure 747
25.2 The thermodynamics of protein folding 748
25.3 Protein-ligand interactions 763
25.4 Protein folding kinetics 769
EXERCISES 779 26
26 Thermodynamics today - and tomorrow 780
SUMMARY 780
26.1 Self-assembly of large complexes 780
26.2 Non-ideal gases and the formation of liquids 781
26.3 Kinetics of nucleated molecular polymerisation 782
26.4 Molecular mechanisms in protein aggregation 786
26.5 The end-point of protein aggregation 787
26.6 The thermodynamics of self-assembly for systems with defined final
structures 781
26.7 Towards the design of self-assembling systems 791
EXERCISES 793
Glossary
Bibliography
Index
795
844
847
Thermodynamics is fundamental to university and college curricula in chemistry, physics, engineering, and many
life sciences around the world. It is also notoriously difficult for students to understand, learn, and apply. What
makes this book different, and special, is the clarity of the text. The writing style is fluid, natural, and lucid, and
everything is explained in a logical and transparent manner. Thermodynamics is a deep, and important, branch
of science, and this book does not make it 'easy'. But it does make it intelligible.
This book introduces a new, 'Fourth Law' of Thermodynamics based on the notion of Gibbs free energy, which
underpins almost every application of thermodynamics and which the authors claim is worthy of recognition as
a 'law'. The last four chapters bring thermodynamics into the twenty-first century, dealing with bioenergetics (how
living systems capture and use free energy), macromolecule assembly (how proteins fold), and macromolecular
aggregation (how, for example, virus capsids assemble). This is of great current relevance to students of
biochemistry, biochemical engineering, and pharmacy, and is covered in few other texts on thermodynamics.
The book also contains many novel and effective examples, such as the explanations of why friction is
irreversible, what happens when liquids boil, and the significance of the biochemical standard state.
Dennis Sherwood is Managing Director of The Silver Bullet Machine Manufacturing Company Limited.
Paul Dalby is Professor of Biochemical Engineering and Biotechnology at University College London.
Remembering my own time as an undergraduate, thermodynamics was always a struggle, concepts seeming
to get lost in a sea of equations. Yet at its heart, all of thermodynamics follows from a few beautiful ideas,
from which the whole field emerges. This book clearly articulates these concepts to the benefit of us students
at all career stages!
Professor Miles Padgett, Kelvin Chair of Natural Philosophy, University of Glasgow
This is an excellent book, covering many of the essential elements of a topic which is of central importance
to scientists and engineers. The book is highly readable and accessible, making it suitable for undergraduate
students, and yet it contains sufficient advanced material to make it of interest to postgraduates and
experienced researchers.
Professor Omar Matar, Department of Chemical Engineering, Imperial College London
Proper understanding of classical thermodynamics is a daunting challenge for teacher and student alike. This
book nicely navigates the transition from elegant concepts to modern applications, particularly in the context
of biochemical systems.
Professor Alan Cooper, School of Chemistry, University of Glasgow
This book's structure of unambiguous explanation of the fundamentals, followed by the application of those
principles to chemical and biochemical settings, allows the reader to see thermodynamics as a tool to
understand and design biological systems, rather than as an end in itself.
Professor Daniel Bracewell, Department of Biochemical Engineering, University College London
Cover image: The cover image is a structural homology model of an antigen-binding fragment (Fab)
of a human antibody, with the light and heavy protein chains coloured differently.
OXfORD
UNIVERSITY PRESS
ISBN 978-0-19-878295-7
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9 |
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| edition | First edition |
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| genre | (DE-588)4123623-3 Lehrbuch gnd-content |
| genre_facet | Lehrbuch |
| id | DE-604.BV044877093 |
| illustrated | Illustrated |
| indexdate | 2024-09-29T04:00:10Z |
| institution | BVB |
| isbn | 9780198784708 9780198782957 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-030271408 |
| oclc_num | 1042892730 |
| open_access_boolean | |
| owner | DE-29T DE-703 DE-19 DE-BY-UBM DE-20 DE-11 DE-634 |
| owner_facet | DE-29T DE-703 DE-19 DE-BY-UBM DE-20 DE-11 DE-634 |
| physical | xxix, 870 Seiten Illustrationen, Diagramme |
| publishDate | 2018 |
| publishDateSearch | 2018 |
| publishDateSort | 2018 |
| publisher | Oxford University Press |
| record_format | marc |
| spelling | Sherwood, Dennis 1949- Verfasser (DE-588)128479302 aut Modern thermodynamics for chemists and biochemists Dennis Sherwood and Paul Dalby First edition Oxford Oxford University Press 2018 xxix, 870 Seiten Illustrationen, Diagramme txt rdacontent n rdamedia nc rdacarrier Literaturangaben Thermodynamik (DE-588)4059827-5 gnd rswk-swf Biochemie (DE-588)4006777-4 gnd rswk-swf Thermodynamics Thermodynamics / Textbooks SCIENCE / Mechanics / Thermodynamics (DE-588)4123623-3 Lehrbuch gnd-content Thermodynamik (DE-588)4059827-5 s Biochemie (DE-588)4006777-4 s DE-604 Dalby, Paul Verfasser (DE-588)1164258796 aut Erscheint auch als Online-Ausgabe 978-0-19-108582-6 Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=030271408&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=030271408&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA Klappentext |
| spellingShingle | Sherwood, Dennis 1949- Dalby, Paul Modern thermodynamics for chemists and biochemists Thermodynamik (DE-588)4059827-5 gnd Biochemie (DE-588)4006777-4 gnd |
| subject_GND | (DE-588)4059827-5 (DE-588)4006777-4 (DE-588)4123623-3 |
| title | Modern thermodynamics for chemists and biochemists |
| title_auth | Modern thermodynamics for chemists and biochemists |
| title_exact_search | Modern thermodynamics for chemists and biochemists |
| title_full | Modern thermodynamics for chemists and biochemists Dennis Sherwood and Paul Dalby |
| title_fullStr | Modern thermodynamics for chemists and biochemists Dennis Sherwood and Paul Dalby |
| title_full_unstemmed | Modern thermodynamics for chemists and biochemists Dennis Sherwood and Paul Dalby |
| title_short | Modern thermodynamics for chemists and biochemists |
| title_sort | modern thermodynamics for chemists and biochemists |
| topic | Thermodynamik (DE-588)4059827-5 gnd Biochemie (DE-588)4006777-4 gnd |
| topic_facet | Thermodynamik Biochemie Lehrbuch |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=030271408&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=030271408&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA |
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