Basics of Analytical Chemistry and Chemical Equilibia

BRIAN M. TISSUE, PhD, is Associate Professor of Chemistry at Virginia Tech, where he teaches analytical chemistry at both the undergraduate and graduate levels. In addition to curriculum development, Dr. Tissue oversees a research program in nanomaterials and analytical spectroscopy, preparing and testing nanocomposites for catalytic activity. Among his honors, Dr. Tissue has received an NSF Career Award and a Cottrell Scholar Award from the Research Corporation for Science Advancement.

PREFACE ix I QUANTITATIVE ANALYSIS USING REACTIONS THAT GO TO COMPLETION 1 1 MAKING MEASUREMENTS 3 1.1 Introduction / 3 1.2 GLP and a Few Other Important Acronyms / 10 1.3 Precision and Random Error / 15 1.4 Discarding a Suspected Outlier / 25 1.5 Calibration / 28 1.6 Maintaining Accurate Results / 43 Practice Exercises / 48 2 SAMPLE PREPARATION, EXTRACTIONS, AND CHROMATOGRAPHY 53 2.1 Sampling and Control Samples / 53 2.2 Sample Preparation / 58 2.3 Solvents and Solutions / 64 2.4 Introduction to Solubility / 69 2.5 Extraction / 71 2.6 Stationary Phases / 82 2.7 Solid-Phase Extraction (SPE) / 88 2.8 Introduction to Chromatography / 91 2.9 Immunoassays / 96 Practice Exercises / 97 3 CLASSICAL METHODS 103 3.1 Introduction / 103 3.2 Review of Chemical Reactions / 105 3.3 Reactions in Aqueous Solution / 111 3.4 Gravimetry / 120 3.5 Titration / 124 3.6 Titration Curves / 132 3.7 Coulometry / 134 Practice Exercises / 137 4 MOLECULAR SPECTROSCOPY 141 4.1 Introduction / 141 4.2 Properties of EM Radiation / 142 4.3 Electromagnetic Spectrum / 146 4.4 Spectroscopic Transitions / 147 4.5 UV/Vis Absorption Spectroscopy / 154 4.6 UV/Vis Instrumentation / 156 4.7 Beer Lambert Law / 159 4.8 Molecular Fluorescence / 167 Practice Exercises / 171 II REACTIONS THAT DO NOT GO TO COMPLETION. EQUILIBRIA IN AQUEOUS SOLUTIONS 177 5 ACID BASE EQUILIBRIA AND ACTIVITY 179 5.1 Acids and Bases / 179 5.2 Weak Acids and Weak Bases / 186 5.3 Water and Kw / 190 5.4 Acid Strength / 196 5.5 The Concept of Activity / 199 5.6 Acid Base Equilibrium Calculations / 212 Practice Exercises / 218 6 BUFFER SOLUTIONS AND POLYPROTIC ACIDS 221 6.1 Buffer Solutions / 221 6.2 Alpha Fraction Plots / 226 6.3 Weak Acid Titration Curve / 230 6.4 Polyprotic Acids / 233 Practice Exercises / 242 7 COMPLEXATION AND PRECIPITATION EQUILIBRIA 245 7.1 Complex Terminology / 246 7.2 Complex Equilibria / 249 7.3 Competing Equilibria / 256 7.4 Stepwise Complexation / 263 7.5 Precipitate Equilibrium / 267 7.6 Molar Solubility / 275 7.7 Precipitation and Competing Equilibria / 282 Practice Exercises / 287 III INSTRUMENTAL METHODS AND ANALYTICAL SEPARATIONS 293 8 ELECTROANALYTICAL CHEMISTRY 295 8.1 Introduction / 295 8.2 Standard Reduction Potentials / 298 8.3 Using Half Reactions / 302 8.4 Background on Spontaneous Reactions and Equilibrium / 308 8.5 Reaction Energies, Voltages, and the Nernst Equation / 311 8.6 Electrochemical Cells / 314 8.7 Potentiometry / 319 8.8 Ion-Selective Electrodes (ISE) / 322 8.9 Voltammetry / 328 Practice Exercises / 336 9 ATOMIC SPECTROMETRY 340 9.1 Atomization / 342 9.2 Atomic Absorption Spectrometry (AAS) / 346 9.3 Atomic Emission Spectrometry (AES) / 354 9.4 Introduction to Mass Spectrometry (MS) / 357 9.5 ICP-MS Measurements / 361 9.6 Summary / 362 Practice Exercises / 364 10 ANALYTICAL SEPARATIONS 367 10.1 Thin-Layer Chromatography / 368 10.2 Chromatogram Terminology / 372 10.3 Column Selection / 375 10.4 High Performance Liquid Chromatography / 380 10.5 Gas Chromatography / 388 10.6 Molecular Mass Spectrometry / 390 10.7 Electrophoresis / 398 Practice Exercises / 402 INDEX 407