MODERN ANALYTICAL CHEMISTRY
CONTENTS CONTENTS CHAPTER INTRODUCTION 1A WHAT IS ANALYTICAL CHEMISTRY? 1B THE ANALYTICAL PERSPECTIVE 1C COMMON ANALYTICAL PROBLEMS 1D KEY TERMS 1E SUMMARY 1F PROBLEMS 1G SUGGESTED READINGS 1H REFERENCES CHAPTER BASIC TOOLS OF ANALYTICAL CHEMISTRY 2A NUMBERS IN ANALYTICAL CHEMISTRY FUNDAMENTAL UNITS OF MEASURE SIGNIFICANT FIGURES 2B UNITS FOR EXPRESSING CONCENTRATION MOLARITY AND FORMALITY NORMALITY MOLALITY WEIGHT, VOLUME, AND WEIGHT-TO-VOLUME RATIOS CONVERTING BETWEEN CONCENTRATION UNITS P-FUNCTIONS 2C STOICHIOMETRIC CALCULATIONS CONSERVATION OF MASS CONSERVATION OF CHARGE CONSERVATION OF PROTONS CONSERVATION OF ELECTRON PAIRS CONSERVATION OF ELECTRONS USING CONSERVATION PRINCIPLES IN STOICHIOMETRY PROBLEMS 2D BASIC EQUIPMENT AND INSTRUMENTATION INSTRUMENTATION FOR MEASURING MASS EQUIPMENT FOR MEASURING VOLUME EQUIPMENT FOR DRYING SAMPLES 2E PREPARING SOLUTIONS PREPARING STOCK SOLUTIONS PREPARING SOLUTIONS BY DILUTION 2F THE LABORATORY NOTEBOOK 2G KEY TERMS 2H SUMMARY 2I PROBLEMS 2J SUGGESTED READINGS 2K REFERENCES THE LANGUAGE OF ANALYTICAL CHEMISTRY 3A ANALYSIS, DETERMINATION, AND MEASUREMENT 3B TECHNIQUES, METHODS, PROCEDURES, AND PROTOCOLS 3C CLASSIFYING ANALYTICAL TECHNIQUES 3D SELECTING AN ANALYTICAL METHOD ACCURACY PRECISION SENSITIVITY SELECTIVITY ROBUSTNESS AND RUGGEDNESS SCALE OF OPERATION EQUIPMENT, TIME, AND COST MAKING THE FINAL CHOICE ERRORS IN SIGNIFICANCE TESTING 4F STATISTICAL METHODS FOR NORMAL DISTRIBUTIONS COMPARING –X TO µ COMPARING TWO SAMPLE VARIANCES COMPARING TWO SAMPLE MEANS OUTLIERS 4G DETECTION LIMITS 4H KEY TERMS 4I SUMMARY 4J SUGGESTED EXPERIMENTS 4K PROBLEMS 4L SUGGESTED READINGS 4M REFERENCES CALIBRATIONS, STANDARDIZATIONS, AND BLANK CORRECTIONS 5A CALIBRATING SIGNALS 5B STANDARDIZING METHODS REAGENTS USED AS STANDARDS SINGLE-POINT VERSUS MULTIPLE-POINT STANDARDIZATIONS EXTERNAL STANDARDS STANDARD ADDITIONS INTERNAL STANDARDS 5C LINEAR REGRESSION AND CALIBRATION CURVES LINEAR REGRESSION OF STRAIGHT-LINE CALIBRATION CURVES UNWEIGHTED LINEAR REGRESSION WITH ERRORS IN Y WEIGHTED LINEAR REGRESSION WITH ERRORS IN Y WEIGHTED LINEAR REGRESSION WITH ERRORS IN BOTH X AND Y CURVILINEAR AND MULTIVARIATE REGRESSION 5D BLANK CORRECTIONS 5E KEY TERMS 5F SUMMARY 5G SUGGESTED EXPERIMENTS 5H PROBLEMS 5I SUGGESTED READINGS 5J REFERENCES 3E DEVELOPING THE PROCEDURE COMPENSATING FOR INTERFERENCES CALIBRATION AND STANDARDIZATION SAMPLING VALIDATION 3F PROTOCOLS 3G THE IMPORTANCE OF ANALYTICAL METHODOLOGY 3H KEY TERMS 3I SUMMARY 3J PROBLEMS 3K SUGGESTED READINGS 3L REFERENCES EVALUATING ANALYTICAL DATA 4A CHARACTERIZING MEASUREMENTS AND RESULTS MEASURES OF CENTRAL TENDENCY MEASURES OF SPREAD 4B CHARACTERIZING EXPERIMENTAL ERRORS ERROR AND UNCERTAINTY 4C PROPAGATION OF UNCERTAINTY A FEW SYMBOLS UNCERTAINTY WHEN ADDING OR SUBTRACTING UNCERTAINTY WHEN MULTIPLYING OR DIVIDING UNCERTAINTY FOR MIXED OPERATIONS UNCERTAINTY FOR OTHER MATHEMATICAL FUNCTIONS IS CALCULATING UNCERTAINTY ACTUALLY USEFUL? 4D THE DISTRIBUTION OF MEASUREMENTS AND RESULTS POPULATIONS AND SAMPLES PROBABILITY DISTRIBUTIONS FOR POPULATIONS CONFIDENCE INTERVALS FOR POPULATIONS PROBABILITY DISTRIBUTIONS FOR SAMPLES CONFIDENCE INTERVALS FOR SAMPLES A CAUTIONARY STATEMENT 4E STATISTICAL ANALYSIS OF DATA SIGNIFICANCE TESTING CONSTRUCTING A SIGNIFICANCE TEST ONE-TAILED AND TWO-TAILED SIGNIFICANCE TESTS OBTAINING AND PREPARING SAMPLES FOR ANALYSIS 7A THE IMPORTANCE OF SAMPLING 7B DESIGNING A SAMPLING PLAN WHERE TO SAMPLE THE TARGET POPULATION WHAT TYPE OF SAMPLE TO COLLECT HOW MUCH SAMPLE TO COLLECT HOW MANY SAMPLES TO COLLECT MINIMIZING THE OVERALL VARIANCE 7C IMPLEMENTING THE SAMPLING PLAN SOLUTIONS GASES SOLIDS 7D SEPARATING THE ANALYTE FROM INTERFERENTS 7E GENERAL THEORY OF SEPARATION EFFICIENCY 7F CLASSIFYING SEPARATION TECHNIQUES SEPARATIONS BASED ON SIZE SEPARATIONS BASED ON MASS OR DENSITY SEPARATIONS BASED ON COMPLEXATION REACTIONS (MASKING) SEPARATIONS BASED ON A CHANGE OF STATE SEPARATIONS BASED ON A PARTITIONING BETWEEN PHASES 7G LIQUID–LIQUID EXTRACTIONS PARTITION COEFFICIENTS AND DISTRIBUTION RATIOS LIQUID–LIQUID EXTRACTION WITH NO SECONDARY REACTIONS LIQUID–LIQUID EXTRACTIONS INVOLVING ACID–BASE EQUILIBRIA LIQUID–LIQUID EXTRACTIONS INVOLVING METAL CHELATORS 7H SEPARATION VERSUS PRECONCENTRATION 7I KEY TERMS 7J SUMMARY 7K SUGGESTED EXPERIMENTS 7L PROBLEMS 7M SUGGESTED READINGS 7N REFERENCES EQUILIBRIUM CHEMISTRY 6A REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIA 6B THERMODYNAMICS AND EQUILIBRIUM CHEMISTRY 6C MANIPULATING EQUILIBRIUM CONSTANTS 6D EQUILIBRIUM CONSTANTS FOR CHEMICAL REACTIONS PRECIPITATION REACTIONS ACID–BASE REACTIONS COMPLEXATION REACTIONS OXIDATION–REDUCTION REACTIONS 6E LE CHÂTELIER’S PRINCIPLE 6F LADDER DIAGRAMS LADDER DIAGRAMS FOR ACID–BASE EQUILIBRIA LADDER DIAGRAMS FOR COMPLEXATION EQUILIBRIA LADDER DIAGRAMS FOR OXIDATION–REDUCTION EQUILIBRIA 6G SOLVING EQUILIBRIUM PROBLEMS A SIMPLE PROBLEM: SOLUBILITY OF PB(IO3)2 IN WATER A MORE COMPLEX PROBLEM: THE COMMON ION EFFECT SYSTEMATIC APPROACH TO SOLVING EQUILIBRIUM PROBLEMS PH OF A MONOPROTIC WEAK ACID PH OF A POLYPROTIC ACID OR BASE EFFECT OF COMPLEXATION ON SOLUBILITY 6H BUFFER SOLUTIONS SYSTEMATIC SOLUTION TO BUFFER PROBLEMS REPRESENTING BUFFER SOLUTIONS WITH LADDER DIAGRAMS 6I ACTIVITY EFFECTS 6J TWO FINAL THOUGHTS ABOUT EQUILIBRIUM CHEMISTRY 6K KEY TERMS 6L SUMMARY 6M SUGGESTED EXPERIMENTS 6N PROBLEMS 6O SUGGESTED READINGS 6P REFERENCES GRAVIMETRIC METHODS OF ANALYSIS 8A OVERVIEW OF GRAVIMETRY USING MASS AS A SIGNAL TYPES OF GRAVIMETRIC METHODS WHY GRAVIMETRY IS IMPORTANT 8B PRECIPITATION GRAVIMETRY THEORY AND PRACTICE QUANTITATIVE APPLICATIONS QUALITATIVE APPLICATIONS EVALUATING PRECIPITATION GRAVIMETRY 8C VOLATILIZATION GRAVIMETRY EVALUATING VOLATILIZATION GRAVIMETRY 8D PARTICULATE GRAVIMETRY 8E KEY TERMS 8F SUMMARY 8G SUGGESTED EXPERIMENTS 8H PROBLEMS 8I SUGGESTED READINGS 8J REFERENCES TITRIMETRIC METHODS OF ANALYSIS 9A OVERVIEW OF TITRIMETRY EQUIVALENCE POINTS AND END POINTS VOLUME AS A SIGNAL TITRATION CURVES THE BURET 9B TITRATIONS BASED ON ACID–BASE REACTIONS ACID–BASE TITRATION CURVES SELECTING AND EVALUATING THE END POINT TITRATIONS IN NONAQUEOUS SOLVENTS REPRESENTATIVE METHOD CHARACTERIZATION APPLICATIONS EVALUATION OF ACID–BASE TITRIMETRY 9C TITRATIONS BASED ON COMPLEXATION REACTIONS CHEMISTRY AND PROPERTIES OF EDTA COMPLEXOMETRIC EDTA TITRATION CURVES EVALUATION OF COMPLEXATION TITRIMETRY 9D TITRATIONS BASED ON REDOX REACTIONS REDOX TITRATION CURVES EVALUATION OF REDOX TITRIMETRY 9E PRECIPITATION TITRATIONS EVALUATION OF PRECIPITATION TITRIMETRY 9F KEY TERMS 9G SUMMARY 9H SUGGESTED EXPERIMENTS 9I PROBLEMS 9J SUGGESTED READINGS 9K REFERENCES SPECTROSCOPIC METHODS OF ANALYSIS 10A OVERVIEW OF SPECTROSCOPY WHAT IS ELECTROMAGNETIC RADIATION MEASURING PHOTONS AS A SIGNAL 10B BASIC COMPONENTS OF SPECTROSCOPIC INSTRUMENTATION SOURCES OF ENERGY WAVELENGTH SELECTION DETECTORS SIGNAL PROCESSORS 10C SPECTROSCOPY BASED ON ABSORPTION ABSORBANCE OF ELECTROMAGNETIC RADIATION TRANSMITTANCE AND ABSORBANCE ABSORBANCE AND CONCENTRATION: BEER’S LAW 11B POTENTIOMETRIC METHODS OF ANALYSIS POTENTIOMETRIC MEASUREMENTS REFERENCE ELECTRODES METALLIC INDICATOR ELECTRODES MEMBRANE ELECTRODES EVALUATION 11C COULOMETRIC METHODS OF ANALYSIS CONTROLLED-POTENTIAL COULOMETRY CONTROLLED-CURRENT COULOMETRY 11D VOLTAMMETRIC METHODS OF ANALYSIS VOLTAMMETRIC MEASUREMENTS CURRENT IN VOLTAMMETRY SHAPE OF VOLTAMMOGRAMS QUANTITATIVE AND QUALITATIVE ASPECTS OF VOLTAMMETRY VOLTAMMETRIC TECHNIQUES 11E KEY TERMS 11F SUMMARY 11G SUGGESTED EXPERIMENTS 11H PROBLEMS 11I SUGGESTED READINGS 11J REFERENCES CHROMATOGRAPHIC AND ELECTROPHORETIC METHODS 12A OVERVIEW OF ANALYTICAL SEPARATIONS THE PROBLEM WITH SIMPLE SEPARATIONS A BETTER WAY TO SEPARATE MIXTURES CLASSIFYING ANALYTICAL SEPARATIONS 12B GENERAL THEORY OF COLUMN CHROMATOGRAPHY CHROMATOGRAPHIC RESOLUTION CAPACITY FACTOR COLUMN SELECTIVITY COLUMN EFFICIENCY BEER’S LAW AND MULTICOMPONENT SAMPLES LIMITATIONS TO BEER’S LAW 10D ULTRAVIOLET-VISIBLE AND INFRARED SPECTROPHOTOMETRY INSTRUMENTATION 10E ATOMIC ABSORPTION SPECTROSCOPY 10F SPECTROSCOPY BASED ON EMISSION 10G MOLECULAR PHOTOLUMINESCENCE SPECTROSCOPY MOLECULAR FLUORESCENCE AND PHOSPHORESCENCE SPECTRA QUANTITATIVE APPLICATIONS USING MOLECULAR LUMINESCENCE 10H ATOMIC EMISSION SPECTROSCOPY ATOMIC EMISSION SPECTRA EQUIPMENT 10I SPECTROSCOPY BASED ON SCATTERING ORIGIN OF SCATTERING TURBIDIMETRY AND NEPHELOMETRY 10J KEY TERMS 10K SUMMARY 10L SUGGESTED EXPERIMENTS 10M PROBLEMS 10N SUGGESTED READINGS 10O REFERENCES ELECTROCHEMICAL METHODS OF ANALYSIS 11A CLASSIFICATION OF ELECTROCHEMICAL METHODS INTERFACIAL ELECTROCHEMICAL METHODS CONTROLLING AND MEASURING CURRENT AND POTENTIAL PEAK CAPACITY NONIDEAL BEHAVIOR 12C OPTIMIZING CHROMATOGRAPHIC SEPARATIONS USING THE CAPACITY FACTOR TO OPTIMIZE RESOLUTION USING COLUMN SELECTIVITY TO OPTIMIZE RESOLUTION USING COLUMN EFFICIENCY TO OPTIMIZE RESOLUTION 12D GAS CHROMATOGRAPHY MOBILE PHASE CHROMATOGRAPHIC COLUMNS STATIONARY PHASES SAMPLE INTRODUCTION TEMPERATURE CONTROL DETECTORS FOR GAS CHROMATOGRAPHY 12E HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY HPLC COLUMNS MOBILE PHASES HPLC PLUMBING DETECTORS FOR HPLC 12F LIQUID–SOLID ADSORPTION CHROMATOGRAPHY 12G ION-EXCHANGE CHROMATOGRAPHY 12H SIZE-EXCLUSION CHROMATOGRAPHY 12I SUPERCRITICAL FLUID CHROMATOGRAPHY 12J ELECTROPHORESIS THEORY OF CAPILLARY ELECTROPHORESIS CAPILLARY ELECTROPHORESIS METHODS 12K KEY TERMS 12L SUMMARY 12M SUGGESTED EXPERIMENTS 12N PROBLEMS 12O SUGGESTED READINGS 12P REFERENCES KINETIC METHODS OF ANALYSIS 13A METHODS BASED ON CHEMICAL KINETICS EVALUATION OF CHEMICAL KINETIC METHODS 13B RADIOCHEMICAL METHODS OF ANALYSIS 13C FLOW INJECTION ANALYSIS 13D KEY TERMS 13E SUMMARY 13F SUGGESTED EXPERIMENTS 13G PROBLEMS 13H SUGGESTED READINGS 13I REFERENCES DEVELOPING A STANDARD METHOD 14A OPTIMIZING THE EXPERIMENTAL PROCEDURE RESPONSE SURFACES SEARCHING ALGORITHMS FOR RESPONSE SURFACES MATHEMATICAL MODELS OF RESPONSE SURFACES 14B VERIFYING THE METHOD SINGLE-OPERATOR CHARACTERISTICS BLIND ANALYSIS OF STANDARD SAMPLES RUGGEDNESS TESTING EQUIVALENCY TESTING 15D KEY TERMS 15E SUMMARY 15F SUGGESTED EXPERIMENTS 15G PROBLEMS 15H SUGGESTED READINGS 15I REFERENCES 14C VALIDATING THE METHOD AS A STANDARD METHOD TWO-SAMPLE COLLABORATIVE TESTING COLLABORATIVE TESTING AND ANALYSIS OF VARIANCE WHAT IS A REASONABLE RESULT FOR A COLLABORATIVE STUDY? 14D KEY TERMS 14E SUMMARY 14F SUGGESTED EXPERIMENTS 14G PROBLEMS 14H SUGGESTED READINGS 14I REFERENCES QUALITY ASSURANCE 15A QUALITY CONTROL 15B QUALITY ASSESSMENT INTERNAL METHODS OF QUALITY ASSESSMENT EXTERNAL METHODS OF QUALITY ASSESSMENT 15C EVALUATING QUALITY ASSURANCE DATA PRESCRIPTIVE APPROACH PERFORMANCE-BASED APPROACH