Analytical Chemistry 2.1

Citation

Harvey, D. T. (2016). Analytical Chemistry 2.1. David T. Harvey (open access, CC BY-NC-SA 4.0). Free official edition: https://sites.google.com/depauw.edu/dth/analytical-curriculum-projects/analytical-chemistry-2-1

Chapter Summary

The text is a digital reworking of the author's print book Modern Analytical Chemistry (McGraw-Hill, 2000), whose copyright returned to him; version 2.1 is the summer 2016 release. Its preface sorts the fifteen chapters into four groups: a general introduction (Chapters 1–3), topics that explain how methods work (4–7), the major families of methods (8–13), and the design and maintenance of methods (14–15). Each chapter ends with key terms, a summary, problems and worked solutions to the in-text practice exercises.

Chapters 1–3: Introduction to Analytical Chemistry; Basic Tools of Analytical Chemistry; The Vocabulary of Analytical Chemistry

Chapter 1 separates analytical chemistry, which improves and invents methods, from routine chemical analysis, and presents a five-step "analytical approach" with a feedback loop. It also sorts problems into qualitative, quantitative, characterization and fundamental analyses, and states that qualitative work gets no further treatment. Chapter 2 reviews units, significant figures, concentration scales, stoichiometry, glassware, solution preparation, spreadsheets and the laboratory notebook. Chapter 3 defines the working vocabulary (analyte and matrix, technique, method, procedure and protocol) and the criteria for choosing a method. The preface says later chapters assume familiarity with all three.

Chapter 4: Evaluating Analytical Data

A statistics chapter built around the mass of a United States penny. It covers central tendency and spread, determinate and indeterminate error, propagation of uncertainty, probability distributions and confidence intervals, significance tests (t, F, outlier tests), and detection limits. A closing section shows the same calculations in Excel and in R.

Chapter 5: Standardizing Analytical Methods

Starts from the relationship between signal and amount of analyte and asks how to find the method's sensitivity and the reagent blank. It compares external standards, standard additions and internal standards, then treats linear regression in some depth (unweighted, weighted, and with errors in both variables), again with Excel and R.

Chapter 6: Equilibrium Chemistry

A review of precipitation, acid–base, complexation and redox equilibria, followed by two ways of working with them: ladder diagrams for quick, semi-quantitative reasoning and a systematic approach to full equilibrium calculations. It ends with buffers, activity effects and spreadsheet solutions, and closing thoughts on choosing between ladder diagrams and rigorous calculation.

Chapter 7: Collecting and Preparing Samples

Treats sampling as a source of error: designing a plan (where, what type, how much, how many), collecting solutions, gases and solids, and then separating analyte from interferents. The separation sections classify techniques by size, mass or density, masking, change of state and partitioning, and work through liquid–liquid extraction with acid–base and metal–ligand equilibria.

Chapters 8–9: Gravimetric Methods; Titrimetric Methods

Gravimetry covers precipitation, volatilization (including thermogravimetry) and particulate methods. Titrimetry covers acid–base, complexation (EDTA), redox and precipitation titrations; each type follows the same pattern of titration curves, choice of end point, quantitative applications and an evaluation of the method.

Chapter 10: Spectroscopic Methods

Begins with the nature of electromagnetic radiation and the components of an instrument, then absorption (Beer's law, UV/Vis and IR, atomic absorption), photoluminescence, atomic emission and scattering (turbidimetry and nephelometry), again ending each method with an evaluation.

Chapter 11: Electrochemical Methods

Concentrates on interfacial techniques: potentiometry (reference, metallic and membrane electrodes), coulometry (controlled-potential and controlled-current) and voltammetry, including polarography, stripping methods and amperometry.

Chapters 12–13: Chromatographic and Electrophoretic Methods; Kinetic Methods

Chapter 12 builds a general theory of column chromatography (resolution, retention factor, selectivity, efficiency) before gas chromatography, HPLC, other liquid-chromatographic forms and capillary electrophoresis. Chapter 13 moves from equilibrium to nonequilibrium measurements: chemical kinetic methods, radiochemistry and flow injection analysis.

Chapters 14–15: Developing a Standard Method; Quality Assurance

Chapter 14 follows a method from optimization (response surfaces, simplex searches, factorial designs) through verification and ruggedness testing to validation by collaborative studies and analysis of variance. Chapter 15 returns to the analytical approach of Chapter 1 and covers quality control, internal and external quality assessment, and control charts. The appendices hold statistical tables, constants and a review of kinetics; an "Additional Resources" section lists further reading and experiments by chapter.

Key Concepts

Chapters 1–3: Perspective and vocabulary

• Analytical approach: a five-step cycle from defining the problem to proposing a solution, with design, experiment and data analysis forming a feedback loop.
• Analyte and matrix: the species of interest versus everything else in the sample.
• Method selection criteria: accuracy, precision, sensitivity, selectivity, robustness, ruggedness, scale, time and cost.

Chapters 4–5: Data and calibration

• Propagation of uncertainty: how errors in individual measurements combine in a calculated result.
• Significance testing: t-tests, F-tests and outlier tests to compare results with known values or with each other.
• Standardization strategies: external standards, standard additions and internal standards, with regression to fit the calibration.

Chapters 6–7: Chemistry and samples

• Ladder diagrams: a graphical shortcut for judging which species dominate under given conditions.
• Sampling plan: decisions about type, size and number of samples so that sampling error does not limit precision.
• Liquid–liquid extraction: separation by partitioning, described with distribution ratios.

Chapters 8–11: Classical and instrumental methods

• Gravimetric and titrimetric signals: mass and volume as the measured quantities.
• Equivalence point and end point: the stoichiometric point of a titration versus where it is observed to finish.
• Beer's law: absorbance proportional to concentration, the basis of absorption spectroscopy.
• Potentiometry, coulometry, voltammetry: measuring potential, charge or current as the analytical signal.

Chapters 12–15: Separations, kinetics and method quality

• Resolution, retention factor, selectivity and efficiency: the quantities that describe a chromatographic separation.
• Response surface: the dependence of a method's response on its experimental factors, searched to find optimum conditions.
• Statistical control: the state, monitored with control charts, in which a routine analysis is behaving as validated.

Critical Analysis

Strengths

• A deliberate balance of method and method design. The preface says the aim is to balance theory and practice, classical and modern methods, and analysis with sampling and sample preparation. In practice this means separate chapters on statistics, calibration, sampling, method development and quality assurance, topics that many first courses treat briefly.
• A consistent structure for the methods chapters. The gravimetry, titrimetry, spectroscopy, electrochemistry and chromatography chapters each close their techniques with quantitative applications and an evaluation, which makes methods easy to compare. The preface adds that the first technique in each chapter is generally the one most often taught in an introductory course.
• Flexible use. The preface describes the later chapters as mostly independent of Chapters 4–7, and the preface says there is more material than any one semester can cover, so instructors and students can select.
• Equilibrium kept in proportion. The preface warns against letting equilibrium calculation stand in for analytical chemistry and pairs rigorous methods with ladder diagrams. Chapter 6 closes by discussing which tool suits which question and noting that equilibrium says nothing about reaction rate.
• Computing built in. Excel and R are used for statistics, regression, equilibrium and analysis of variance, so the calculations in Chapters 4, 5, 6 and 14 can be reproduced by the reader.
• Free and reusable. The text, a solutions manual and per-chapter files are offered by the author under a Creative Commons licence, with an errata list on the same page.

Limitations

• Scope by design. Qualitative analysis is excluded in Chapter 1 on the grounds that it is covered elsewhere in the curriculum, and the spectroscopy chapter concentrates on optical methods. Nuclear magnetic resonance and mass spectrometry have no chapters of their own; mass spectrometry appears, for example, as a detector in the gas chromatography section.
• Very long. The PDF runs to over 1,100 pages, and the preface itself says it holds more than one course can use; a reader needs a syllabus or a selective plan, such as the one below, to avoid getting lost.
• Format dated in places. The preface describes embedded QuickTime and Flash movies and Acrobat-specific features (commenting tools, hyperlink navigation), which many current readers will not be able to use as described.
• Small inconsistencies. Chapter and section titles differ between versions (Chapter 7 is "Collecting and Preparing Samples" in the PDF but "Obtaining and Preparing Samples for Analysis" on the author's chapter list and LibreTexts), a few section numbers repeat or skip in the contents, and the author's page lists seven errata items. Check the errata list before relying on a specific worked answer.
• Answers are split. Answers to the in-text practice exercises are at the end of each chapter, but checking the end-of-chapter problems requires the separate solutions manual.

Where It Fits in the Course

This is the free, openly licensed main text for a first analytical chemistry course. Harris and Lucy's Quantitative Chemical Analysis is the commercial comprehensive alternative at a similar level, and Harris's Exploring Chemical Analysis is a shorter, less mathematical companion to it; either can supply a second set of explanations and problems when a topic in Harvey is unclear. Harvey's distinguishing choices are the early chapters on statistics and calibration and the final chapters on method development and quality assurance.

For the instrument side, Rouessac and Rouessac's Chemical Analysis: Modern Instrumentation Methods and Techniques is an introduction to instrumental methods, and Skoog, Holler and Crouch's Principles of Instrumental Analysis is the upper-level treatment; Harvey's Chapters 10–12 are a sensible preparation for either. Bard, Faulkner and White's Electrochemical Methods is a graduate text that picks up where Chapter 11 stops.

How to Use This Book

It suits students who have finished general chemistry. The author site's prerequisite note (algebra and logarithms, no calculus) matches what the text demands: the mathematics is arithmetic, logarithms and statistics, with calculus appearing only in passing, for example in the derivation of Beer's law and in the integrated rate laws of Chapter 13 and its kinetics appendix.

A practical plan for one semester:

• Core: Chapters 1–3 quickly, then Chapter 4 (at least sections 4A–4F), the first parts of Chapter 5, the Chapter 6 sections on acid–base, complexation and ladder diagrams, and the first technique in each of Chapters 8–12 (precipitation gravimetry, acid–base and EDTA titrations, UV/Vis absorption, potentiometry, gas chromatography and HPLC).
• Optional or second pass: weighted regression in Chapter 5, activity effects in Chapter 6, atomic and luminescence methods in Chapter 10, voltammetry in Chapter 11, capillary electrophoresis in Chapter 12, and Chapter 13 on kinetic methods.
• For laboratory courses: Chapters 14 and 15 pair naturally with a project or a quality-assurance exercise.

Work the practice exercises as they appear, since their answers are at the end of each chapter, and use the Excel and R sections for the statistics and regression problems. The "Additional Resources" section lists experiments and in-class activities that go with each chapter. Download the single PDF for searching, or individual chapter files for lighter reading.

Edition and Sources

This guide is based on the author's free PDF of Analytical Chemistry 2.1 (summer 2016 release, 1,122 pages), downloaded from the author's website at https://sites.google.com/depauw.edu/dth/analytical-curriculum-projects/analytical-chemistry-2-1, which is also hosted on LibreTexts. It draws on the preface, the full detailed table of contents, the opening pages and chapter summaries of all fifteen chapters, and the Additional Resources section.