Experiments in Physical Chemistry 8th Edition
This book is designed for use in a junior-level laboratory course in physical chemistry. It is assumed that the student will be taking concurrently (or has taken previously) a lecture course in physical chemistry. The book contains 48 selected experiments, which have been tested by extensive use.
Three of the experiments are new, and all of these involve optical measurements. One concerns a study of the birefringence of a liquid crystal to determine the evolution of nematic order near the nematic-isotropic phase transition (Exp. 15). The second is a study of the dynamic light scattering from an aqueous dispersion of polystyrene spheres in order to determine their particle size (Exp. 33). The third is a study of the absorption and fluorescence spectra of CdSe nanocrystals with an analysis based on predictions from a quantum model (Exp. 45). To conserve space, three experiments that appeared in the seventh edition have been deleted. These are the binary solid-liquid phase diagram, osmotic pressure, and single-crystal x-ray diffraction. All the other experiments from the seventh edition have been reviewed, and in some cases small changes have been made to either the theory or the experimental procedures. The most extensive of such changes occur in Experiments 1 (gas thermometry) and 4 (viscosity of gases), where the apparatus and procedure have been changed to eliminate the use of mercury. In numerous other experiments, mercury manometers and mercury-in-glass thermometers have been replaced by direct reading pressure gauges and temperature sensors.
Experiments. The 48 experiments provide a balance between traditional and modern topics in physical chemistry, with most of the classical topics in Chapters IV–X (Exps. 1–24) and most of the modern topics in Chapters XI–XV (Exps. 25–48). These experiments are not concerned primarily with “techniques” per se or with the analytical applications of physical chemistry. We believe that an experimental physical chemistry course should serve a dual purpose: (1) to illustrate and test theoretical principles, and (2) to develop a research orientation by providing basic experience with physical measurements that yield quantitative results of important chemical interest.
Each experiment is accompanied by a theoretical development in sufficient detail to provide a clear understanding of the method to be used, the calculations required, and the significance of the final results. The depth of coverage is frequently greater than that which is available in introductory physical chemistry textbooks. Experimental procedures are described in considerable detail as an aid to the efficient use of laboratory time and teaching staff. Emphasis is given to the reasons behind the design and procedure for each experiment, so that the student can learn the general principles of a variety of experimental techniques. Stimulation of individual resourcefulness through the use of special projects or variations on existing experiments is also desirable. We strongly urge that on some occasions the experiments presented here should be used as points of departure for work of a more independent nature.
Introductory and background material. In addition to the experiments themselves, nine chapters contain material of a general nature. These chapters should be useful not only in an undergraduate laboratory course but also in special-project work, thesis research, and a broad range of general research in chemistry. The first three chapters provide material that is valuable for all experimental work in physical chemistry, and it is recommended that these be read before beginning any laboratory work. Chapter I contains a wide range of introductory material, including advice on the preparation of laboratory reports, and Chapter II covers techniques for data analysis and the assessment of error limits. Chapter III, on the use of computer software and selected aspects of computer interfacing, has been revised and updated. The software aspect emphasizes the application of spreadsheets for the recording, plotting, and leastsquares fitting of experimental data. Also discussed, and illustrated with examples, are more sophisticated programs such as Mathcad and Mathematica, along with the program Gaussian, which can be used to obtain molecular structures and properties from ab-initio quantum mechanics. Relevant theoretical calculations using such programs are suggested at the end of a number of experiments.
Chapters XVI–XX deal with basic experimental methods of broad value in many types of experimental work—electronic measurements, temperature measurement and control, vacuum techniques, diverse instruments that are widely used, and miscellaneous laboratory procedures. These chapters have been revised and updated in various ways. In the case of Chapters XVI and XVIII, the text has also been shortened from that which appeared in the seventh edition. Finally, Chapter XXI presents a thorough discussion of least-squares fitting procedures.
References cited at the end of each experiment and each of the general chapters have been updated. In cases where no new literature source could be found that covers a given topic as well as the source cited in the seventh edition, the original citation has been retained, since most libraries have available copies of older books and monographs. In the development of the new experiments in this edition, we acknowledge expert advice from Prof. M. Bawendi (MIT), Prof. J. Thoen (Katholieke Universiteit Leuven), and Dr. B. Weiner (Brookhaven Instruments) as well as the assistance of faculty, teaching assistants, and undergraduate students (especially Nicole Baker, Matthew Martin, Colin Shear, Brain Theobald, and Robert Zaworski) at Oregon State University. Helpful comments also have come from a number of reviewers and from those who have used this book at other universities, and for these we are very appreciative. We encourage and welcome feedback from all who use this book, either as students or instructors. Finally, we wish to acknowledge the suberb proofreading effort of Janelle Pregler, who has made the production of this edition go very smoothly.
Carl W. Garland
Joseph W. Nibler
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