Thermodynamics of Pharmaceutical Systems (eBook)

Kenneth A. Connors is Professor Emeritus in the School of Pharmacy at the University of Wisconsin at Madison. His research interests include organic analytical reactions, their catalysis, mechanisms, and applications, kinetic methods for the analysis of mixtures and the chemistry of molecular complexes. Sandro Mecozzi received his PhD in 1996 from the California Institute of Technology, and joined the faculty of the Division of Pharmaceutical Sciences at the School of Pharmacy, University of Wisconsin-Madison, in 1999. He currently holds joint appointments in the departments of pharmacy and chemistry. His research interests include the areas of RNA recognition, fluorous self-assembly, and the development of novel drug delivery systems.

PREFACE.

PREFACE TO THE FIRST EDITION.

0. Review of Mathematics.

0.1. Introduction.

0.2. Dimensions and Units.

0.3. Logarithms and Exponents.

0.4. Algebraic and Graphical Analysis.

0.5. Dealing with Change.

0.6. Statistical Treatment of Data.

Problems.

I BASIC THERMODYNAMICS.

1. Energy and the First Law of Thermodynamics.

1.1. Fundamental Concepts.

1.2. The First Law of Thermodynamics.

1.3. The Enthalpy.

Problems.

2. The Entropy Concept.

2.1. The Entropy Defined.

2.2. The Second Law of Thermodynamics.

2.3. Applications of the Entropy Concept.

Problems.

3. The Free Energy.

3.1. Properties of the Free Energy.

3.2. The Chemical Potential.

Problems.

4. Equilibrium.

4.1. Conditions for Equilibrium.

4.2. Physical Processes.

4.3. Chemical Equilibrium.

Problems.

II THERMODYNAMICS OF PHYSICAL PROCESSES.

5. Introduction to Physical Processes.

5.1. Scope.

5.2. Concentration Scales.

5.3. Standard States.

Problems.

6. Phase Transformations.

6.1. Pure Substances.

6.2. Multicomponent Systems.

Problems.

7. Solutions of Nonelectrolytes.

7.1. Ideal Solutions.

7.2. Nonideal Solutions.

7.3. Partitioning Between Liquid Phases.

Problems.

8. Solutions of Electrolytes.

8.1. Coulombic Interaction and Ionic Dissociation.

8.2. Mean Ionic Activity and Activity Coefficient.

8.3. The Debye-Hückel Theory.

Problems.

9. Colligative Properties.

9.1. Boiling Point Elevation.

9.2. Freezing Point Depression.

9.3. Osmotic Pressure.

9.4. Isotonicity Calculations.

Problems.

10. Solubility.

10.1. Solubility as an Equilibrium Constant.

10.2. The Ideal Solubility.

10.3. Temperature Dependence of the Solubility.

10.4. Solubility of Slightly Soluble Salts.

10.5. Solubilities of Nonelectrolytes: Further Issues.

Problems.

11. Surfaces and Interfaces.

11.1. Thermodynamic Properties.

11.2. Adsorption.

Problems.

III THERMODYNAMICS OF CHEMICAL PROCESSES.

12. Acid-Base Equilibria.

12.1. Acid-Base Theory.

12.2. pH Dependence of Acid-Base Equilibria.

12.3. Calculation of Solution pH.

12.4. Acid-Base Titrations.

12.5. Aqueous Solubility of Weak Acids and Bases.

12.6. Nonaqueous Acid-Base Behavior.

12.7. Acid-Base Structure and Strength.

Problems.

13. Electrical Work.

13.1. Introduction.

13.2. Oxidation-Reduction Reactions.

13.3. Electrochemical Cells.

13.4. pH Measurement.

13.5. Ion-Selective Membrane Electrodes.

Problems.

14. Noncovalent Binding Equilibria.

14.1. Introduction.

14.2. The Noncovalent Interactions.

14.3. Binding Models.

14.4. Measurement of Binding Constants.

14.5. Applications.

Problems.

APPENDIXES.

Appendix A Physical Constants.

Appendix B Kinetic Theory of Gases.

Appendix C Extrathermodynamic Relationships.

ANSWERS TO PROBLEMS.

BIBLIOGRAPHY.

INDEX.

"In this 2nd edition, Professor Connors continues his career-long
commitment to ensuring that pharmacy students comprehend the
complexity of the chemistry that is so central to the practice of
pharmacy and the overall disciplines that comprise the
Pharmaceutical Sciences. While this book will continue to be
invaluable in those instances where required or elective courses
focused on mechanisms and pharmaceutical systems remain a part of
the Professional Pharmacy curriculum, it also could prove to be a
unique resource for first year pharmaceutics graduate students who
enter these programs with undergraduate majors in the biological,
rather than the chemical sciences.... Consistent with the treatment
of thermodynamics, kinetics and analytical chemistry in previous
textbooks, the authors lay out a logical systematic approach that
allow students to focus on basic definitions and principles, which
then build an understanding through increasingly complex
problems.... While this text was developed for pharmacy students,
its applicability to first year graduate students is noteworthy.
The pharmaceutical sciences have always struggled with the varied
backgrounds of a diverse student population and in most cases
background material in either the physical chemical or biological
sciences, is desirable depending upon their undergraduate
backgrounds. With the increasingly biological orientation of the
pharmaceutical sciences a large number of incoming students have
not had the basics of physical chemistry or thermodynamics which
are fundamental to drug discovery, design and understanding
mechanism of transport and action in the body. In addition, the
industry as well as the Food and Drug Administration through its
Critical Path initiative express an urgent need to move towards
much scientific orientation of formulation and manufacture to try
to reduce the extensive time needed to develop, test and eventually
market a drug often due to historic trial and error processes based
upon previously approved processes. This textbook could fill that
void nicely in many graduate programs and lay the foundation for
higher level courses."

--Dr. Jordan Cohen, Vice President for Research,
University of Iowa