Basic Physical Chemistry for the Atmospheric Sciences

by Peter V. Hobbs

• ISBN13: 9780521785679
• ISBN10: 0521785677
• Edition: 2nd
• Format: Paperback
• Copyright: 2000-09-04
• Publisher: Cambridge University Press

Summary

Newly revised and updated, Basic Physical Chemistry for the Atmospheric Sciences provides a clear, concise grounding in the basic chemical principles required for modern studies of atmospheres, oceans, and earth and planetary systems. Undergraduate and graduate students with little formal training in chemistry can work through the chapters and the numerous exercises within this book before accessing the standard texts in the atmospheric chemistry, geochemistry, and the environmental sciences. The book covers the fundamental concepts of chemical equilibria, chemical thermodynamics, chemical kinetics, solution chemistry, acid and base chemistry, oxidation-reduction reactions, and photochemistry. In a companion volume entitled Introduction to Atmospheric Chemistry (2000, Cambridge University Press) Peter Hobbs provides an introduction to atmospheric chemistry itself, including its applications to air pollution, acid rain, the ozone hole, and climate change. Together these two books provide an ideal introduction to atmospheric chemistry for a variety of disciplines.

Table of Contents

Preface to first edition	ix
Preface to second edition	xi
Chemical equilibrium	1	(16)
Some introductory concepts	1	(2)
Equilibrium constants	3	(5)
Reaction quotient	8	(2)
LeChatelier's principle	10	(7)
Exercises	12	(5)
Chemical thermodynamics	17	(26)
The first law of thermodynamics; enthalpy	17	(4)
Enthalpies of reaction and formation	21	(1)
Entropy and the second law of thermodynamics	22	(4)
The third law of thermodynamics; absolute entropies	26	(1)
Criteria for equilibrium and spontaneous transformation	27	(2)
Standard free energy changes	29	(2)
Free energy change and the equilibrium constant	31	(3)
Chemical potential; homogeneous nucleation of water-vapor condensation	34	(9)
Exercises	38	(5)
Chemical kinetics	43	(25)
Reaction rates	43	(3)
Reaction mechanisms	46	(4)
Reaction rates and equilibria	50	(2)
Collision theory of gaseous reactions	52	(3)
The effect of temperature on reaction rates: the Arrhenius' relation	55	(2)
Catalysis	57	(1)
Half-life, residence time, and renewal time	58	(10)
Exercises	61	(7)
Solution chemistry and aqueous equilibria	68	(15)
Definitions and types of solutions	68	(1)
Solution concentrations	68	(2)
Factors affecting solubility	70	(1)
Colligative properties	71	(1)
Aqueous solutions; electrolytes	72	(1)
Aqueous equilibria	73	(5)
Strong and weak electrolytes; ion-product constant for water	78	(5)
Exercises	80	(3)
Acids and bases	83	(21)
Some definitions and concepts	83	(3)
The nature of H-(aq)	86	(1)
The Bronsted-Lowry theory; conjugate acid-base pairs	86	(1)
Strengths of acids and bases; acid-dissociation (or ionization) constant	87	(1)
The Lewis theory	88	(1)
The pH scale	88	(2)
Polyprotic acids	90	(1)
Hydrolysis	90	(3)
Buffers	93	(3)
Complex ions	96	(1)
Mass balance and charge balance relations	97	(1)
The pH of rainwater	98	(6)
Exercises	101	(3)
Oxidation--reduction reactions	104	(33)
Some definitions	104	(1)
Oxidation numbers	105	(3)
Balancing oxidation-reduction reactions	108	(7)
Half-reactions in electrochemical cells	115	(1)
Strengths of oxidants and reductants; standard cell and half-cell potentials	116	(8)
Standard cell potentials and free-energy change	124	(2)
The Nernst equation	126	(2)
Redox potentials; Eh--pH diagrams	128	(2)
Gram-equivalent weight and normality	130	(7)
Exercises	132	(5)
Photochemistry	137	(22)
Some properties of electromagnetic waves	137	(2)
Some photochemical terminology and principles	139	(2)
Quantum yields	141	(2)
Rate coefficients for photolysis	143	(2)
Photostationary states	145	(1)
Stratospheric ozone and photochemistry; depletion of stratospheric ozone	146	(13)
Exercises	154	(5)
Appendix I International system of units (SI)	159	(1)
Appendix II Some useful numerical values	160	(1)
Appendix III Atomic weights	161	(3)
Appendix IV Equilibrium (or dissociation) constants for some chemical reactions	164	(5)
Appendix V Some molar standard Gibbs free energies of formation, molar standard enthalpies (or heats) of formation, and molar absolute entropies at 25°C and 1 atmosphere	169	(3)
Appendix VI Names, formulas, and charges of some common ions	172	(1)
Appendix VII Answers to exercises and hints and solutions to selected exercises	173	(14)
Index	187