their contents are: GAS-PVT (described above), KINETIC MOLECULAR THEORY (one-, two-, and three-dimensional speed and energy distributions), INTERMOLECULAR INTERACTIONS (relationships between Lennard-Jones and square-well potentials with virial coefficients and molecular trajectories during collisions), HEAT AND HEAT CAPACITY (harmonic and anharmonic oscillator and rigid rotor effects on heat capacity, Einstein-Debye heat capacities, heats of reaction as affected by temperature), EXPANSIONS AND COMPRESSIONS (PV plots for isothermal, adiabatic, reversible, irreversible expansions, and compressions), INTRODUCTION TO STATISTICAL THERMODYNAMICS (Boltzmann distributions, probabilities, partition functions, total energy, heat capacity, and entropy relations), ENTROPY (translational, rotational, vibrational, and total entropies), PHASE EQUILIBRIA (ideal and non-ideal vapor pressures of liquid solutions, bp diagrams, distillation and theoretical plates, eutectic mixtures), FREE ENERGY and EQUILIBRIA (relations between G, H, S, T, and K in tabular and graphical forms). Additional disks are INTRODUCTION TO QUANTUM MECHANICS (waves and uncertainty principle, particle on a line and particle in a box energies, wave functions, and probability distributions, H-atom probability functions, multi-electron atom probability distribution functions), INTRODUCTION TO SPECTROSCOPY (blackbody, rotational E's and spectra, vibrational E7sand spectra, rot-vib spectrum, spectral presentations), BOND ENERGY (harmonic and anharmonic oscillator potentials and energies compared, Morse potential), FIRST- AND SECOND-ORDER KINETICS (different plots of c, ln c, etc., versus time for selected half-lives, comparison of 1st- and 2nd-order behavior, 2nd-order plots, problem), COMPLEX KINETICS (A to B to C as 1st-order steps, steady-state versus exact behavior, equilibrium in first and both steps, flash photolysis experiment), ACID-BASE REACTIONS (titration curves for pH versus V, %HA and %A versus V for monoprotic and polyprotic species with any K's), DIFFUSION (conc. versus time and distance, random walks, extended source), and ULTRACENTRIFUGE (conc. profile for thin layer, for ultracentrifuge wedge, sedimentation velocity and sedimentation equilibrium examples and problems). Ease of use. Clearly a wide variety of topics are available to the student for exploration. With use we have found that students are hesitant at first to make decisions but that they quickly adapt to the program style and soon are looking for information on their own. Operation of the programs is straightforward and well annotated with prompts. If there are any bugs (such as a problem we had with programs locking when our first Grappler board was installed for the printer) the programs can be listed and modified as necessary for such details as printer commands. In general, programs are supplied by the author for the printer you specify. Other than A206
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this kind of simple problem we have found no significant errors in any of the programs except for some inconsistencies in the sedimentation equilibrium programs on the last disk. The user can easily drop out of a program at any point with CTRL C after which a RUN command will start the same program over again or RUN MENU will allow access to any of the other programs on the disk. After several uses of a program it may become tiring to have to go through the early parts of the program again but the discussion segments can be omitted. The time required for plotting some graphs also may become tedious after many uses, but at the same time the student has an opportunity to see what is developing in the process and make comparisons as the plot proceeds. All text is in uppercase and mathematical formulas (written in BASIC style) tend to be cumbersome in some of the discussion segments, but this is a trivial problem at the level of most physical chemistry courses. We advise students to have their texts and notes open when they are working with one of these programs so they can refer to appropriate formulas and tables of data. We also advise them to keep notes on what they are doing. In general, data entry is taken literally, so some care is necessary. If input is unacceptable semantically (entering letters instead of numbers for a physical parameter, for example) the programs usually alert the user. Many, but not all, quantities are expressed in SI units. In some cases choices can be made. All in all, the entire set is easy to use. While a typical physical chemist would sit down with this marvelous data base and simply start looking for specific comparisons, students are less likely to know what to look for without some guidance. Barrow has developed a set of study guides that provide some introductory discussion and contain specific assignments for the student to complete. These form a basis for using the programs without undue confusion on the student's part and help point out particular relationships that the student should not overlook. Once familiar with the content, many students continue to use the programs without further directions. The study guides are available separately so that they can be sold through the bookstore. Instructors undoubtedly will think of other kinds of problems they will wish to assign for specific courses. Summary. "Computer-Based Studies for Physical Chemistry" is a valuable source of relationships for students in physical chemistry and in other courses which touch on similar topics. The content ranges from elementary concepts to sophisticated models for treating real systems. There are no bells and whistles, no animated DNA molecules rotating in space or complicated molecular orbital wave functions plotted in 3D. Emphasis is on fundamentals. Data are presented in simple, clear graphical form and there is a great deal of flexibility in presentation. The user can work directly with the data on the monitor andlor can obtain a printed version to work with later. Imagine the expansion of textbook and classroom illustrations students can have in their notebooks. Manipulation of the programs is direct and uncomplicated. It is hard to imagine any teacher who could not find many ways in which these programs can
expand upon current instructional resources. Barrow has collected a number of the more introductory of these programs into another set suitable for use in general chemistry courses. Jeff C. Davis, Jr. University of South Florida Tampa, FL 33620
Review I1
"Computer-Based Studies for Physical Chemistry" by Gordon Barrow (Milne press) is a collection of programs to accompany a junior-level physical chemistry course. They run on arl Apple I1 with 48K memory and a graphics capable printer such as the EPSON MX80. There are 17 disks averaging 6 programs per disk and grouped into 6 topic areas. These topics are usually included in a junior level physical chemistry course and every standard physical chemistry textbook. Details of subject matter coverage have been given by reviewer I and will not be repeated here. These programs can be used in several ways: (a) for homework exercises, (b) for lecture demonstrations, and (c) as interactive tutorials to augment and enrich the lectures and textbook. Each program features an optional introduction which briefly reviews principles, units, notation, and operating procedures. All the programs are organized around unique interactive graphics routines for planning, editing, and printing a graph pertaining to the concept or principle of interest. These routines operate by printing a hi-res graphics page that is typically produced in a sequence of steps: the program prompts for the scales on each axis of a planar Cartesian coordinate system and the parameters in the function to be graphed. The graph is then drawn on the graphics page and the user is given the option to edit the scales. When editing is complete, the option to print the graph may be exercised. Features and Intent. Elementary-level programs tend to be highly specialized to single topics within a discipline, use motivational gimmicks such as games, sounds, and reward statements ("Very good, Johnny!"), and rigid pedagogic methods such as drill and practice, or problem solving. Advanced-level programs tend to be highly generalized subroutines for various functions (such as matrix inversion, numerical quadrature, or leastsquares fits) that are to be linked by the user to solve his particular problem. Barrow's programs are intermediate; they are devoted to a single broad topic but are often openended. They never contain gimmicks or rewards (which would surely insult college juniors). A few programs adopt specific strategies such as simulation or problem generation. K-M SIMULATION simulates the motion of a gas molecule and its collisions with the container walls while accumulating a timeaveraged pressure on each wall. Several programs on the Introduction to Spectroscopy disk simulate rotational and vibrational spectra. FIRST-SECOND PROBLEM randomly generates and prints a graph of concentration versus time data for a reaction whose order may be determined by the student, and SEDIMENTATION VELOCITY PROBLEM generates concentration versus distance data from which to determine par-
ticle mass of a solute molecule. Many of these programs would serve well in other courses that cover some of the same material. For example, a course in thermodynamics or one in elementary quantum mechanics or spectroscopy. Other programs are open-ended and can be used in many ways. For example,the program RADIATION VERSUS WAVELENGTH draws graphs of intensity versus wavelength of radiation from black bodies whose temperatures are chosen by the user. This program can be used as a tutorial to exhibit the qualitative properties of BB radiation. Alternatively, it can be used, in conjunction with a study guide, to lead the student to discover Wien's and Stefan's laws. Being open-ended these programs can contribute to different degrees toward the objectivesof a course. Their graphics features allow homework exercises that would otherwise be impossible; students can painlessly produce near-perfect graphs as part of their homework solutions. The graphics are also valuable for lecture demonstrations; the teacher can rapidly produce accurate graphs and vividly show the effect of changing physical parameters. Documentation. Three kinds of documentation are used. The programs, in BASIC, are reasonably well documented by internal remarks to enable them to be modified if necessary. Each program also contains an optional brief introduction. For the teacher, and for students who have read their textbooks, this suffices to describe its purpose and how to use it. (Almost any physical chemistry textbook could accompany Barrow's programs.) Finally, a thorough study guide is provided. About 20% of the programs (as I received them) contained a fatal programming error that caused them to "hang" during the print option. Thanks to the internal remarks, this error was relatively easy to discover and correct with a minimal knowledge of Apple BASIC. Many program introductions, comments, and prompts contained spelling and grammatical errors. These are easy though tedious to correct. For each program the Study Guide provides: suggested uses, a brief description, directions for use, tables of data, questions, and exercises. I used the study guide as a source of problem ideas for homework problems I wrote myself. (I intend to make greater use of it next year by duplicating appropriate sections for the students. This is permitted and encouraged by the publisher.) Ease of Use. The programs ran on our departmental computers as received, but they were not compatible with the "smart card" printer interface in our library computers. A slight modification corrected the problem. Programs on a disk are selected from a convenient menu; it is easy to stop, restart, or return to the menu at the end of each program. All programs rely exclusively on keyboard input. A few programs perform slow computations (e.g., evaluating the Debye heat capacity for a crystal) but warn the user to be patient. The programs are immune to the most common operator errors. When alphabetic input is erroneously substituted for numeric input, the program prints a message and repeats the prompt. I gave a single keyboard demonstration to introduce Barrow's
programs during the first lecture of the semester. This was sufficient for most students to begin using them on their own. Student Reaction. I have used this version of Barrow's programs in a two-semester junior-level physical chemistry course at WSU during the academic year 1982-83. Chem 331, taught in the fall semester and covering chemical thermodynamics and chemical kinetics, had an initial enrollment of 55 of which 7 were undergraduate chemistry majors, 4 were beginning chemistry graduate students (judged to be deficient on the basis of advisory exams), 26 were chemical engineers, 5 were undergraduates in preengineering, and the remaining 12 were undergrads and graduate students from environmental science, general biology, zoology, geology, material science, and physical education. Chem 332, given in the spring semester, covered quantum theory, bonding, solids, and macromolecules and had an enrollment of 20 of which 10 were undergraduate chemistry majors, 3 were chemistry graduate students, 4 were in general biology, 1was a biochemistry undergrad, 1 was a computer science major, 2 were graduate students in wood technology, and 1was a special student. The students were required to use the programs as part of their weekly homework assignments. On average, ten textbook problems and one Apple exercise were assigned each week. For Chem 331, the Apple exercise required about 30 minutes to work. For Chem 332, I assigned more open-ended Apple exercises which required about 60 minutes to work. The exercises generated printed output that was turned in with homework. About once each week I used a program for a lecture demonstration. Student evaluations were obtained in Chem 331 using a questionnaire at the end of the semester. The questions are listed here and the numbers of true (T) and false (F) responses indicated: These exercises helped me learn the subject (38T,9F). They stimulated my interest (30T, 15F). Some programs contain serious errors (2T,43F). The internal introductions should be read the first time through these programs (34T,12F). The programs often "die" or "hang" in the middle when the user makes a mistake (13T,32F). These programs are easy to use (44T,3F). They should be used more in the future (36T,lOF).I used only the assigned programs on a disk and never looked at others (22T,24F). Lecture demonstrations using these programs were helpful (45T,3F). A written text or manual for the programs should have helped me (28T,19F). I wish more courses would incorporate computeraided instruction (35T,12F). I recommend that these programs play a bigger role in future offerings (26T,19F).I often needed help to use these programs (3T,43F). Barrow's programs are self-explanatory and need no supplement to be useful (32T,15F). These programs sometimes confused me rather than helped me understand (6T,41F). These programs require more time than is justified by what they teach (18T,28F). I enjoyed using these computer programs (38T78F).(Forty eight responses were received; some students chose not to respond to some of the statements.) For Chem 332 a shorter questionnaire was used: The Apple computer exercises stimu-
lated my interest (7T,7F). The Apple computer exercises helped me to learn P. Chem (9T,5F). The Apple computer problems were too difficult (7T,6F). I would have preferred more Apple exercises and fewer textbook problems (lT,l3F). Usually I learned more by working one text problem than from one Apple exercise (9T,4F). Recommendations for Improvement. The serious errors need to be eliminated: in particular, the print option causes some programs to die. Spelling and grammar should be corrected also. I would prefer consistent use of SI units instead of the mixture in these programs. Although it is important to be able to convert among various units (calories, Angstroms, liters, etc.), SI is now nearly universal among textbooks and the conversions required in these programs obscure the objectives. Additional subject matter should be added: electrochemistry, chemical bonding, molecular symmetry, crystallography (the study guide contains a description of programs for X-ray powder patterns of cubic crystals, but the programs are omitted from the disks), liquids. Some subjects already included would be improved greatly if augmented. For example, parallel reaction mechanisms could be compared with sequential. Calculator functions would be very helpful in some programs. Summary. These programs cover a wide range of topics and show a good perception of those that are difficult. They rely on graphics to teach concepts, in most cases one or more line graphs in planar rectangular Cartesian coordinates. This pedagogical approach is very effective among students who are experienced at reading and understanding graphs. My Chem 331 class responded favorably to Barrow's programs and the assigned problems based on them. They thought the programs were easy to use, stimulating, and helped them to learn. Although the print errors described above were corrected in all assigned programs, some students (29%)said that the programs would die or hang. Evidently these occurred while they were exploring unassigned programs. A majority (78%to 58%) felt that greater use should be made of CAI in the future. Half said that they examined programs that were not assigned; I interpret this to mean they felt the programs were a useful learning resource. Only 7% said they often needed help to use the programs; they were inconsistent about the need for a written manual: 60% wanted one, but 68% said the programs were self explanatory. Chem 332 responses were less favorable. I think this is because I made the secondsemester problems open-ended while the first-semester problems were not. I wanted the Chem 332 students to exercise a degree of independence, originality, and creativity in solving these problems. They were divided on whether the exercises stimulated their interest, helped them to learn, or were too difficult. They overwhelmingly preferred the closed-ended textbook exercises (hardly surprising) but 4 out of 13 admitted to
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learning more from the open-ended Apple exercises than from the textbook problems. I enjoyed using Barrow's programs for lecture demonstrations, which 94% of the students thought were helpful. The graphics are well written and appropriate for the concepts being taught. The format of our lecture hall is very convenient for computer demonstrations: the Apple drives monitors located throughout the hall for good visibility. In view of the favorable student response, and their recommendation to make greater use of Barrow's programs, I will increase the proportion of Apple exercises from 1:lO to 2:6 in Chem 331 next year. I will also distribute appropriate sections of Barrow's Study Guide with the homework assignments. Despite the divided and negative responses by Chem 332 students, I still believe the open-ended problems based on Barrow's programs can be more instructive than the closed-ended style I assigned in Chem 331. Ronald D. Poshusta Washington State University Pullman, WA 99164
Thermodynamics and Its Applications, Second Edition Michael Mode11and Robert C. Reid, Prentice-Hall, lnc., Engelwood Cliffs, NJ, 1983. xi 450 pp. Figs. and tables. 15.5 X 23.5 cm. $34.95.
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Students rarely master classical thermodynamics as undergraduates, due probably to the subject's abstract nature and its application to an unlimited variety of real-world problems. Yet in many disciplines for people to understand and work effectively, they must master both thermodynamic theory and problem solving. This truth plagues graduate students and graduate departments, especially in chemical engineering, and to some extent in chemistry, earth sciences, biology, and other engineering disciplines. One just cannot offer or require enough courses to give everyone this level of understanding. Some consider thermodynamics, in fact, to be the most difficult subject in all of academia for students to master. Mode11 and Reid have addressed the need for students to do more work in thermodynamics, either through formal courses or on their own, by putting together discussions and problems at an advanced and challenging level from which interested people can choose what they consider most important to meet their needs. The authors know the subject, write clearly and tersely, and the practice problems offered help to develop skills of particular value to chemical engineers. By and large, the topics covered are the usual ones of an undergraduate course, augmented
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by chapters on the effects on thermodynamics of electric, magnetic, or gravitational fields, mechanical stress, and surfaces. Faculty members could profitably teach from the book, stressing the sections they feel their students need most. Faculty could also profitably utilize problems and explanations from the book for exams, assignments, and illustrations. Students could profitably study from it on their own to develop the thermodynamics knowledge and skills they will most certainly want to have. Thus, everyone can benefit from having available this useful collection of theoretical amplifications and practical problems. Frank C. Andrews
"Basic Physical Chemistry" is well designed and well produced. I t is remarkably free of misprints and errors. Instructors who want a somewhat briefer text to use in a course designed for chemistry majors may find it more useful than those teaching a physical chemistry course for nonchemistry majors. James E. Finholt Carleton College Northfield, MN 55057
University of California Santa Cruz, CA 95064
Basic Physical Chemistry
Calculations in Analytical Chemistry
Walter J. Moore, Prentice-Hall, lnc., En711 pp. glewood Cliffs, NJ, 1983. xx Figs. and tables. 18 X 24 cm.
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No author has had a more profound influence on the teaching of physical chemistry than Moore. Since the appearance of the first edition of "Physical Chemistry" in 1950, his texts have been the touchstones by which all other physical chemistry texts have been judged. Those who have used and admired the many editions of "Physical Chemistry'' will find few surprises in "Basic Physical Chemistry." The breadth of coverage, arrangement of topics, and writing style of this text are very similar to its predecessors. The writing is a bit more terse, and less space is devoted to the derivations. SI units are used throughout the book. This text was written for "science and engineering students who need to understand the basic foundations of physical chemistry.'' One might expect to find many examples of the application of physical chemistry to other disciplines, but this is not the case. No special attempt has been made to present problems or discussions relevant to biology, geology, engineering, or any other field outside of chemistry. One of the special features of this text is the "considerable number of worked out examples." These examples are described as "quite easy, involving little more than substitution of numerical data into equations." There is a vast gulf between the level of difficulty of the examples and the problems at the chapter ends. This may lead to frustration among students who understand the former, but have difficulty solving the latter. No answers are provided for any student problems, nor have the problems been sorted by degree of difficulty. Many excellent, thought-provoking problems are provided, but students will need a considerable amount of help to work their way through them. A chapter on symmetry is included, but it appears so late in the text that it is followed by only one illustrative application of symmetry: a three-page discussion of normal mode vibrations. It is unfortunate that the powerful concepts of group theory could not have been presented early enough to allow ample discussion of their applications.
Michael D. Ryan and Quintus Fernando, Harcourt Brace Jovanovich, New York, NY, 1982. x 241 pp. Figs. and tables. 23 X 27 cm.
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This book presents a unique and carefully thought out approach to the equilibrium calculations underlying analytical titrations. The authors state that it is intended to be a workbook, rather than a textbook. However, there is considerable useful discussion of principles as well as many worked out examples. The special character of the book lies in the close relationship of the problems to precise plots of titration curves and species distribution diagrams. Each problem provides sufficient information to deduce the coordinates (e.g., pH and fraction titrated) for one point on a curve. The emphasis on plots is valuable for the constant overview of a given system. The book begins with a sound treatment of basic concepts such as concentration and stoichiometry calculations are related to gravimetric analysis and titrations. Succeeding chapters treat acid-base equilibria and titrations including polyprotic systems, metal-ligand complex systems, precipitation equilibria, and redox systems including galvanic cells. The discussion is brief by design but unusually comprehensive in scope. For example, a discussion of acid-base buffer capacity is well presented including its calculus-based derivation. The treatment of metal-ligand titrations includes the complexities of metal indicator equilibrium theory. Theoretical treatments of titration error are also included. Although the reader is cautioned that "all equilibrium constants must be corrected for ionic strength effects if meaningful answers to problems are desired," the authors have largely left this up to the user rather than repeatedly showing how this is done. The use of "Gran plots" for determination of titration endpoints is referred to repeatedly, but only from the overall view instead of thorough practical application of data near the endpoints. Assuming that most students will be studying introductory chemistry from a more conventional text, this novel workbook can be quite useful m providing a different look
