Preface The concept of University Chemistry grew from my experiences in teaching Honors General Chemistry at the University of Kansas for a number of semesters. It is my attempt to inform and challenge the well-prepared student to discover and learn the diverse but related topics within general chemistry. This text includes the core topics that are necessary for a solid foundation of chemistry. The Basic Features Organization—In this text, I adopt a “Molecular to Macroscopic” approach in which the quantum theory of atomic and molecular structure and interaction is outlined in Chapters 1 – 4. Building on this molecular foundation the presentation moves on to the macroscopic concepts such as states of matter, thermodynamics, physical and chemical equilibrium and chemical kinetics. This organization is based on “natural prerequisites”; that is, the position of each topic is determined by what other topics would be required to be understood it. For example, to understand the structure and interaction of atoms and molecules, knowledge of thermodynamics or equilibrium chemistry is not needed; whereas, to understand deeply the application of thermodynamics to chemical systems or the material properties of liquids and solids, knowledge of how energy is stored in chemical bonds and how molecular structure and bonding affect intermolecular forces is desirable. Calculus based presentation— Where appropriate, calculus is used in presenting chemical concepts in quantum theory, thermodynamics, and kinetics. The level of calculus is similar to that in other chemistry texts at this level; however, it is not, as is often done, relegated to secondary boxed text, but is integrated into the primary discussion. To supplement this approach, a few calculus-based problems are included in each of the relevant chapters. Appendix 1 includes a short review/tutorial of the basic concepts from elementary differential and integral calculus. Problem-Solving Model—Worked Examples are provided in every chapter for students to use a base for learning problem solving around the concept discussed. The examples present the problem, a strategy, a solution, a check, and a practice problem. Every problem is designed to challenge the student to think logically through the problems. This problem-solving approach is used throughout the text. Organization and Presentation Review— Students with a strong background in high-school chemistry have already been exposed to the concepts of the structure/classification of matter, chemical nomenclature and stoichiometry. Because of this assumed background, I have condensed the standard introductory chapters in a typical general chemistry text into a single chapter (Chapter 0). Chapter 0 provides the student a refresher of the subject matter they covered in their high school chemistry courses. Early coverage of quantum theory—To lay a molecular-level foundation for the later chapters on states of mater, thermodynamics and equilibrium, the quantum theory of atoms and molecules is treated early on. In Chapters 1 and 2, elementary quantum theory is used to discuss the electronic structure of atoms and the construction of the periodic table. Chapters 3 and 4 cover molecular bonding, structure and interaction, including molecular-orbital theory. In a change from most general chemistry texts, intermolecular forces are discussed at the end of the chapter on molecular structure (Chapter 4) instead of being part of a later chapter on liquids and solids. This is a more natural position that allows for a molecularlevel discussion of the forces that influence real gas behavior in Chapter 5. States of Matter—Phase diagrams, equations of state and states of matter (gases, liquids and solids) are treated in a unified manner in Chapters 5 and 6, with an emphasis on the role of molecular interaction in the determination of material properties. Thermochemistry, Entropy and Free Energy—The basic principles of thermodynamics are treated together in Chapters 7 (thermochemistry) and 8 (entropy and free energy). This allows for a more sophisticated discussion of physical and chemical equilibrium from a thermodynamic perspective. In particular, the central role of the entropy and free energy of mixing in colligative properties and chemical equilibrium is explored in detail. Physical and Chemical Equilibrium—The principles of physical equilibrium (phase boundary prediction and solubility) are discussed in Chapter 9, followed by a discussion of chemical equilibrium in Chapter 10. Chapters 11, 12 and 13 present applications of chemical equilibrium to acid-base chemistry, aqueous equilibria and electrochemistry, respectively. Chemical Kinetics —Unlike many General Chemistry texts, chemical kinetics (Chapter 14) follows the presentation of chemical equilibrium, allowing for full discussion of transition-state theory and detailed balance. Final chapters—Chemistry of Transitions Metals (Chapter 15), Organic and Polymer Chemistry (Chapter 16) and Nuclear Chemistry (Chapter 17) are each an entity of itself. Every instructor and student can choose to assign and study the chapters according to time and preference. Pedagogy Problem-Solving. The development of problem-solving skills is a major objective of this text. Each problem is broken down into learning steps for the student to increase their skill set on logical critical thinking skills. When appropriate, calculus is used in the problem-solving of chemical process in quantum theory, thermodynamics, and kinetics. There are numerous end-of-chapter problems to continue skill building and then practice solving problems. Many of these same problems are in the electronic homework program, ARIS, providing a seamless homework solution for the student and instructor. Text ARIS End-of-Chapter Material. At the end of every chapter, you will find a summary of all the material that was presented in the chapter to use as a study tool. The summary provides the highlight of each section within the chapter. Key Words are also listed along with the page on which the term was introduced as reference. Applications Throughout the text, applications are used to reinforce students’ grasps for concepts and principles and to provide grounding to real-world experiences. The applications focus on key industrial chemicals, drugs and technological advances in chemistry. 360° Development Process A key principle in the development of any chemistry text is its ability to adapt to teaching specifications in a universal way. The only way to do so is by contacting those universal voices—and learning from their suggestions. We are confident that our book has the most current content the industry has to offer, thus pushing our desire for accuracy and up-to-date information to the highest standard possible. In order to accomplish this, we have moved through an arduous road to production. Extensive and open-minded advice is critical in the production of a superior text. Here is a brief overview of the initiatives included in the 360° Development Process of University Chemistry, First Edition by Brian B. Laird. Symposia Every year McGraw-Hill conducts a general chemistry symposium which is attended by instructors from across the country. These events are an opportunity for editors from McGraw-Hill to gather information about the needs and challenges of instructors teaching these courses. This information helped to create the book plan for University Chemistry. They also offer a forum for the attendees to exchange ideas and experiences with colleagues they might have not otherwise met. Manuscript Review Panels Over 50 teachers and academics from across the country and internationally reviewed the various drafts of the manuscript to give feedback on content, pedagogy, and organization. This feedback was summarized by the book team and used to guide the direction of the text. Developmental Editing In addition to being influenced by a distinguished chemistry author, the development of this manuscript was impacted by three freelance developmental editors. The first edit in early draft stage was completed by an editor who holds a PhD in chemistry, John Murdzek. Katie Aiken and Lucy Mullins went through the manuscript line-by-line offering suggestions on writing style and pedagogy. Accuracy Check and Class Test Cindy Bierre at the University of Kansas worked hand-in-hand with the author checking his work and providing detailed comments to him as she and her students did a twosemester class test of the manuscript. The students provided the author with comments on how to improve the manuscript so the content was acceptable to their variety of learning styles. Shawn Phillips at Vanderbilt University reviewed the entire manuscript after the developmental edit was completed and checked all the content for accuracy and provided the author suggestions for further improvement. A select group reviewed manuscripts and art in draft and final form, review page proofs in first and revised rounds, and oversaw the writing and accuracy check of the instructor’s solutions manuals, test bank, and other ancillary materials. List of Applications Distribution of Elements on Earth and in Living Systems 18 Important Experimental Technique: The Mass Spectrometer 46 Laser—The Splendid Light 92 Important Experimental Technique: Electron Microscopy 109 The Third Liquid Element? 156 Discovery of the Noble Gases 163 Major Experimental Technique: Microwave Spectroscopy 186 Just Say NO 198 Major Experimental Technique: Infrared Spectroscopy 238 cis-trans Isomerization in the Vision Process 254 Buckyball, Anyone? 262 Super-Cold Atoms 316 Why Do Lakes Freeze from the Top Down? 340 High- Temperature Superconductors 358 Fuel Values of Foods and Other Substances 390 The Efficiency of Heat Engines: The Carnot Cycle 438 The Thermodynamics of a Rubber Band 456 The Killer Lake 483 Life at High Altitudes and Hemoglobin Production 545 Antacids and the pH Balance in Your Stomach 602 Maintaining the pH of Blood 620 Dental Filling Discomfort 680 Femtochemistry 753 Coordination Compounds in Living Systems 784 Cisplatin—an Anticancer Drug 795 Important Experimental Technique: Nuclear Magnetic Resonance Spectroscopy 824 Sickle Cell Anemia: A Molecule Disease 840 DNA Fingerprinting 843 Nature’s Own Fission Reactor 881 Food Irradiation 888