A TEXTBOOK OF CHEMISTRY
CONTENTS 1 BASIC ELECTRICAL PRINCIPLES OVERVIEW BASIC CONCEPTS VOLT DEFINED CURRENT DEFINED OXIDATION AND REDUCTION CURRENT AND FARADAY’S LAW POTENTIAL, WORK, AND GIBBS’ FREE ENERGY CHANGE METHODS BASED ON VOLTAGE MEASUREMENT VERSUS CURRENT MEASUREMENT ELECTROCHEMICAL CELLS ELECTRODES CELL RESISTANCE SUPPORTING ELECTROLYTE THE ELECTRIFIED INTERFACE OR ELECTRICAL DOUBLE LAYER STRUCTURE OF THE DOUBLE LAYER THE RELATIONSHIP BETWEEN DOUBLE LAYER CHARGE AND THE POTENTIAL AT THE ELECTRODE INTERFACE CONDUCTANCE MASS TRANSPORT BY CONVECTION AND DIFFUSION LIQUID JUNCTION POTENTIALS PROBLEMS REFERENCES 2 POTENTIOMETRY OF OXIDATION–REDUCTION PROCESSES MEASURING “OPEN CIRCUIT” POTENTIALS SOLUTION REDOX POTENTIAL THE DEVELOPMENT OF A CHARGE SEPARATION THE NERNST EQUATION FORMAL POTENTIAL ACTIVE METAL INDICATOR ELECTRODES REDOX TITRATIONS OXIDATION–REDUCTION POTENTIAL (ORP) OR EH ENVIRONMENTAL APPLICATIONS OF REDOX MEASUREMENTS 3 POTENTIOMETRY OF ION SELECTIVE ELECTRODES LIQUID MEMBRANE DEVICES SELECTIVE ACCUMULATION OF IONS INSIDE AN ORGANIC LIQUID THEORY OF MEMBRANE POTENTIALS LIQUID MEMBRANE IONOPHORES GLASS MEMBRANE SENSORS HISTORY OF THE DEVELOPMENT OF A GLASS SENSOR OF PH GLASS STRUCTURE AND SENSOR PROPERTIES SELECTIVE ION EXCHANGE MODEL THE COMBINATION PH ELECTRODE GAS-SENSING ELECTRODES CRYSTALLINE MEMBRANE ELECTRODES CALIBRATION CURVES AND DETECTION LIMITS A REVOLUTIONARY IMPROVEMENT IN DETECTION LIMITS MORE RECENT ION SELECTIVE ELECTRODE INNOVATIONS THE FUNCTION OF THE INNER REFERENCE ELECTRODE ALL SOLID-STATE REFERENCE ELECTRODES ELIMINATING THE INNER REFERENCE ELECTRODE SUPER-HYDROPHOBIC MEMBRANES ION SELECTIVE FIELD EFFECT TRANSISTORS (ISFETS) PRACTICAL CONSIDERATIONS IONIC STRENGTH BUFFERS POTENTIAL DRIFT 4 APPLICATIONS OF ION SELECTIVE ELECTRODES CASE I AN INDUSTRIAL APPLICATION WILL THE SAMPLE CONCENTRATIONS BE MEASURABLE? IONIC STRENGTH ADJUSTMENT BUFFER SAMPLE PRETREATMENT SALT BRIDGES CALIBRATION TEMPERATURE CONTROL SIGNAL DRIFT VALIDATING THE METHOD STANDARD ADDITIONS FOR POTENTIOMETRIC ANALYSIS CASE II A CLINICAL APPLICATION CASE III ENVIRONMENTAL APPLICATIONS US EPA METHOD FOR NITRATE DETERMINATION BY ISE FIELD MEASUREMENTS GOOD LAB PRACTICE FOR PH ELECTRODE USE ELECTRODE MAINTENANCE STANDARD BUFFERS INFLUENCE OF TEMPERATURE ON CELL POTENTIALS CALIBRATION AND DIRECT SAMPLE MEASUREMENT EVALUATING THE RESPONSE OF A PH ELECTRODE CALIBRATING A COMBINATION ELECTRODE AND PH METER LOW IONIC STRENGTH SAMPLES SAMPLES CONTAINING SOIL, FOOD, PROTEIN OR TRIS BUFFER PH TITRATIONS 4 5 10 GRAN PLOTS 5 CONTROLLED POTENTIAL METHODS SIMILARITIES BETWEEN SPECTROSCOPY AND VOLTAMMETRY CURRENT IS A MEASURE OF THE RATE OF THE OVERALL ELECTRODE PROCESS RATE OF ELECTRON TRANSFER THE SHAPE OF THE CURRENT/VOLTAGE CURVE RATE OF MASS TRANSPORT ELECTROCHEMICAL REVERSIBILITY VOLTAMMETRY AT STATIONARY ELECTRODES IN QUIET SOLUTIONS METHODS FOR AVOIDING BACKGROUND CURRENT WORKING ELECTRODES MERCURY ELECTRODES SOLID WORKING ELECTRODES ULTRAMICROELECTRODES FAST SCAN CV PULSE AMPEROMETRIC DETECTION STRIPPING VOLTAMMETRY SPECIAL APPLICATIONS OF AMPEROMETRY FLOW-THROUGH DETECTORS DISSOLVED OXYGEN SENSORS ENZYME ELECTRODES KARL FISHER METHOD FOR MOISTURE DETERMINATION ION TRANSFER VOLTAMMETRY CONTENTS 6 CASE STUDIES IN CONTROLLED POTENTIAL METHODS CASE I EVALUATING THE FORMAL POTENTIAL AND RELATED PARAMETERS CASE II EVALUATING CATALYSTS – THERMODYNAMIC CONSIDERATIONS CASE III STUDYING THE OXIDATION OF ORGANIC MOLECULES CASE IV EVALUATING CATALYSTS – KINETIC STUDIES 7 INSTRUMENTATION A BRIEF REVIEW OF PASSIVE CIRCUITS OPERATIONAL AMPLIFIERS PROPERTIES OF AN IDEAL OPERATIONAL AMPLIFIER THE VOLTAGE FOLLOWER CURRENT FOLLOWER OR CURRENT-TO-VOLTAGE CONVERTER INVERTER OR SIMPLE GAIN AMPLIFIER A POTENTIOSTAT FOR A THREE-ELECTRODE EXPERIMENT NOISE AND SHIELDING MAKING ELECTRODES AND REFERENCE BRIDGES VOLTAMMETRIC WORKING ELECTRODES REFERENCE ELECTRODES