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| Chemical Analysis, What, Who, and Why | |
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| Chemical Quantites | |
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| Units Involved in the Expression of Amount | |
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| The Differentiating Characteristic | |
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| Devising a Probe for the Differentiating Characteristic | |
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| Anticipating the REsponse to the Probe | |
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| Measuring the Response to the Probe | |
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| Quantitation | |
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| Assessing Errors and Interferences | |
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| Detection | |
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| Assessing Confidence in the Results | |
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| Identification | |
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| Identification by Deductive Reasoning | |
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| "Analyze This for Me!" | |
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| Separation | |
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| Single-Step Separation | |
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| Separation by Dispersion | |
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| Chemical Analysis in Science and Society | |
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| Challenges and Rewards | |
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| The Evolution of Chemical Analysis | |
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| Practice Questions and Problems | |
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| The Elements of Measurement | |
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| Measurement, Interpretation, and Observation | |
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| Measurements and Interpretations | |
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| Information from Sets of Measurement Data | |
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| Sources of Measurement Numbers | |
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| Measurement Qualities | |
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| Elements of Measurement Systems | |
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| Conversion Devices | |
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| Input/Output Relationships | |
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| Examples of Measurement Systems | |
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| The Analog Thermometer | |
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| The Ammeter | |
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| The Analog Clock | |
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| pH Paper | |
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| Characteristics of Scalar Readouts | |
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| Linear Scales | |
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| Scalar Readout Characteristics | |
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| Interpolation Errors | |
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| Verniers | |
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| Scales in Arcs or Circles | |
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| Volume-to-Length Converters | |
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| The Graduated Cylinder | |
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| Scale Indication by Liquid Level | |
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| The Buret | |
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| The Volumetric Flask | |
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| The Pipet | |
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| Effects of Temperature on Volumetric Measurements | |
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| Characteristics of Digital Readouts | |
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| The Number Register | |
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| The Stepwise form of the Transfer Function | |
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| Range and Resolution | |
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| Measurements Involving ADCs | |
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| The Discrete Nature of the Data | |
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| Stimulus-Response Measurements | |
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| Null Measurements and Conversion Devices | |
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| Double-Pan Balance | |
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| Null Measurement Characteristics | |
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| Null Conversion Devices | |
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| The Electronic Analytical Balance | |
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| Measurement Accuracy and Precision | |
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| Measures of Precision | |
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| Confidence Intervals | |
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| Significant Figures | |
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| Measurement Precision in Data Processing | |
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| Comparing Means and Deviations | |
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| Comparing the Mean with an Accepted Value | |
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| Comparing the Means of Two Data Sets | |
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| Limit of Detection | |
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| Comparing the Deviations of Two Data Sets | |
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| Rejection of Data | |
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| Least Squares Method for Linear Plots | |
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| The Straight Line | |
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| Linear Regression | |
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| Precision of the Regression Results | |
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| Precision of Values Calculated from the Working Curve | |
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| Practice Questions and Problems | |
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| Acidity, Activity, and pH | |
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| Acids, Bases, and Their Reactions | |
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| Conjugate Acid-Base Pairs | |
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| Relative Strengths of Acids and Bases | |
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| Equilibrium Constants | |
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| Acids and Bases in Water | |
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| Reactions of Acids with Water | |
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| Relationship Between [H subscript 3 O superscript +] and [OH superscript -] in Water | |
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| Reactions of Bases with Water | |
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| Logarithmic Concentration Expressions | |
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| Other Amphiprotic Solvents | |
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| Concentrations, Activities, and pH | |
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| Chemical Potential | |
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| Chemical Activity | |
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| Activity Coefficients | |
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| Mean Ionic Activities | |
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| Activity Coefficients of Neutral Species | |
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| Equilibrium Constants | |
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| The Equilibrium State | |
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| Thermodynamic and Formal Equilibrium Constants | |
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| The Effect of Ionic Strength on K'[subscript a] | |
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| Using Formal Equilibrium Constants | |
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| pH Electrode and the Definition of pH | |
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| The pH Electrode | |
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| pH Standards | |
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| The Definition of pH | |
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| The Measurement of pH | |
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| Practice Questions and Problems | |
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| Analysis by Acid--Base Reactivity | |
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| Equilibrium Concentrations | |
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| The Fraction of the Conjugate Pair in Each Form | |
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| Solving for [H subscript 3 O superscript +] in Solutions of Acids | |
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| Solving for [H subscript 3 O superscript +] in Solutions of Bases | |
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| Exact Equilibrium Expressions | |
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| Quantitation by Acid-Base Titration | |
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| Making the Standard Titrant | |
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| Adding Known Volumes of Standard Solution | |
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| Detecting the Response to the Titrant | |
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| Using an Indicator | |
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| Using a pH Meter | |
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| Concentration Effect in Strong Acid-Base Titration | |
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| Weak Acids, Weak Bases, and Buffers | |
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| Titration of Weak Acids | |
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| Buffer Solutions | |
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| Titration of Weak Bases | |
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| Logarithmic Concentration Plots | |
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| Constructing Logarithmic Concentration Diagrams | |
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| Solving Problems with Log Plots | |
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| Obtaining Titration Curve Points from Log Plots | |
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| Quantitation in Polyprotic Systems | |
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| Alpha Plots for Polyprotic Systems | |
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| Logarithmic Concentration Diagrams | |
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| Titration Curves in Polyprotic Systems | |
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| Titrations of Acid Mixtures | |
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| Other Analyses by Acid-Base Reaction | |
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| Identification by Acid-Base Reactivity | |
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| Detection by Acid-Base Reactivity | |
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| Separation by Acid-Base Reactivity | |
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| Practice Questions and Problems | |
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| Analysis by Absorption of Light | |
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| Colored Solutions and White Light | |
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| The Wave Nature of Light | |
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| The Particle Nature of Light | |
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| Sources of Light | |
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| Light Absorbing Solutions | |
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| Measuring the Absorption of Light | |
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| Developing the Probe | |
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| Anticipating the Response to the Probe | |
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| Detecting the Response to the Probe | |
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| Obtaining the Fraction of Light Transmitted | |
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| Relating Light Absorption to Concentration | |
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| Rationalizing the Working Curve | |
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| The Absorbance-Concentration Relationship | |
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| Calibration of the Working Curve | |
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| Instruments for Absorption Measurements | |
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| Photometers | |
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| Spectrometers | |
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| Flow Injection Analysis | |
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| The Absorbance Spectrum | |
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| Rationalizing the Absorbance Spectrum | |
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| Obtaining an Absorbance Spectrum | |
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| Scanning Spectrometers | |
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| Array Detector Spectrometers | |
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| Fourier Transform Spectrometers | |
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| Attenuated Reflectance Spectroscopy | |
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| Spectral Precision and Accuracy | |
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| Identification by the Absorption of Light | |
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| Compound Identification by Spectral Matching | |
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| Deduction of Molecular Structure and Composition | |
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| Separation by the Absorption of Light | |
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| Mixture Spectra | |
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| Resolution by Simultaneous Equations | |
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| Study Questions, Section I | |
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| Practice Questions and Problems | |
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| Analysis by Photon Emission | |
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| Photon Excitation of Molecular Species | |
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| Photon Absorption | |
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| Scattering of the Excitation Radiation | |
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| Vibrational Relaxation | |
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| Molecular Fluorescence | |
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| Phosphorescence | |
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| Fluorescence and Phosphoresence Spectrometry | |
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| Quantitation | |
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| Excitation and Emission Spectra | |
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| Phosphorescence Measurements | |
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| Raman Spectrometry | |
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| Excitation from Chemical Reactivity | |
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| Chemiluminescence Measurements | |
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| Chemiluminescence Applications | |
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| Thermal Excitation and Atomic Emission | |
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| Flame Excitation | |
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| Plasma Excitation | |
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| Creating the Aerosol | |
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| Photon Excitation of Atomic Species | |
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| Flames for use with Photon Excitation | |
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| Furnaces for Sample Atomization | |
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| Atomic Fluorescence Spectroscopy | |
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| Atomic Absorption Spectroscopy | |
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| Practice Questions and Problems | |
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| Analysis by Complexation Reactivity | |
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| Complexation Reactions | |
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| Bonds Formed in Complexation | |
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| Complexing Species | |
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| Reaction Rates | |
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| Equilibrium Concentrations | |
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| Formation of a 1:1 Complex | |
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| Solving for Concentrations in Complexation Systems | |
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| Formation of Higher Order Complexes | |
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| Alpha Plots | |
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| The Effect of [H subscript 3 O superscript +] on Complex Equilibria | |
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| Hydrolysis of the Coordination Center | |
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| Hydrolysis of the Ligand | |
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| Hydrolysis of Ligand and Coordination Center | |
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| Quantitation by Complexation Titration | |
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| Standard Titrants | |
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| Titration Curves | |
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| Achieving Selectivity with EDTA Titrations | |
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| Equivalence Point Detection | |
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| Indicators | |
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| Displacement Titration | |
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| Back Titrations | |
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| Specific Ion Electrodes for Equivalence Point Detection | |
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| Light Absorption for Equivalence Point Detection | |
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| Log Concentration Plots | |
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| 1:1 Complex Formation | |
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| Stepwise Complex Formation Systems | |
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| Prediction of Titration Curves | |
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| Spot Tests, Test Strips, Flow Injection Analysis and Immunoassays | |
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| Spot Tests | |
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| Test Strips | |
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| Flow Injection Analysis | |
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| Immunoassays | |
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| Practice Questions and Problems | |
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| Analysis by Precipitation Reactivity | |
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| Precipitation Reactions | |
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| The Equilibrium Expressions | |
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| The Crystallization of Precipitates | |
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| The Nucleation of Precipitates | |
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| Equilibrium Concentrations | |
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| Simple Solubility Calculations | |
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| Effect of Hydrolysis on Solubility | |
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| Effect of Complexation on Solubility | |
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| Quantitation by Precipitation Titration | |
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| Frequently Used Reactions | |
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| Titration Curves | |
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| Equivalence Point Detection | |
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| Logarithmic Concentration Plots | |
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| Unsymmetrical Log Plots | |
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| Estimation of Titration Curves | |
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| Separation by Precipitation | |
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| Quantitation by Weighing the Precipitate | |
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| Spot Tests and Test Strips | |
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| Practice Questions and Problems | |
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| Analysis by Electrode Potential | |
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| Electron Exchange at Metals | |
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| The Equilibrium Potential Difference | |
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| Metal-Solution Potentials from Two Related Ionic Species | |
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| Calculating Redox Equilibrium Electrode Potentials | |
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| Formal and Thermodynamic Standard Potentials | |
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| Relating Redox Concentrations to Equilibrium Potentials | |
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| The pH Dependence of Equilibrium Potentials | |
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| The Hydrogen Electrode | |
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| Measurement of Electrode Potentials | |
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| The Necessity of a Reference Electrode | |
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| Calculating the Expected Measurement Voltage | |
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| Relating Electrode Voltage to Activity and Concentration | |
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| Electrodes of the Second Kind | |
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| Log Concentration Plots for Redox Couples | |
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| Lines for the Case Where Ox and Red are Dissolved | |
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| Lines for the Case Where Only Ox or Red is Dissolved | |
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| Lines for Secondary Reaction Species | |
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| Using Log Plots for Cell Equilibrium Potentials | |
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| Log Plots of Unsymmetrical Couples | |
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| Ion Reactions on Membrane Surfaces | |
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| H[superscript +] Reaction with a Glass Surface | |
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| Calculation of the Interfacial Potential | |
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| Measurement of Interfacial Potential | |
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| Use of the Measured Voltage to Calculate pH | |
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| Transistor Chemical Sensors | |
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| Interfering Electrode Reactions | |
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| Gas-sensing Electrodes | |
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| The Use of Ion-Surface Interactions for Ions Other than H[superscript +] | |
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| Ion Diffusion Through Porous Membranes | |
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| Development of Electrical Potential Difference | |
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| Measurement of Membrane Potential | |
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| Electrode Types and Interferents | |
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| Liquid Junction Potentials | |
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| The Equivalence of Response Function for all Electrodes | |
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| Selectivity and Detection With Electrodes | |
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| Practice Questions and Problems | |
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| Analysis by Oxidation--Reduction Reactivity | |
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| Oxidation-Reduction Reactions | |
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| Combining Electron Half-Reactions | |
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| Balancing Complete Redox Reactions | |
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| Equilibrium Constants for Redox Reactions | |
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| Formal and Thermodynamic Equilibrium Constants | |
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| Equilibrium Concentrations | |
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| Approximation Method for Equilibrium Concentrations | |
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| Algebraic Method for Equilibrium Calculations | |
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| Quantitation by Redox Titration | |
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| Titration with Ce(IV) | |
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| Assuring Analyte Oxidation State Before Titration | |
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| Titration Curves | |
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| Multiple Equivalence Point Titrations | |
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| Equivalence Point Detection | |
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| Iodine and Thiosulfate | |
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| Log Concentration Plots | |
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| Redox Log Plots with a Constant Activity Reactant | |
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| Log Plots with Asymmetry and pH Complications | |
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| The Iodine, Iodide System | |
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| Points on Titration Curves from Log Concentration Plots | |
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| Karl Fischer Titration for Water | |
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| Quantitation by Electrolytic Redox Reaction | |
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| Electrolytic Reactions | |
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| Coulombs and Moles | |
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| Coulometry | |
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| Electrogravimetry | |
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| Coulometric Titration | |
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| Diffusion-Limited Electrodes | |
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| Test Strips, Spot Tests and FIA | |
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| Practice Questions and Problems | |
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| Analysis by Interphase Partition | |
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| The Liquid-Liquid Interface: Extraction | |
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| The Gas-Liquid Interface: Distillation | |
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| The Gas-Solid Interface: Adsorption | |
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| Adsorption Isotherms | |
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| Solid Phase Extraction | |
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| Continuous Partition: Chromatography | |
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| The Fraction of Time Spent in Each Phase | |
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| Moving One of the Phases | |
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| Measures of Effectiveness | |
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| Effect of Mobile Phase Flow Rate | |
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| Gas Chromatography | |
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| The Instrument | |
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| Sample Injection | |
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| The Column | |
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| The Detector | |
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| The General Elution Problem | |
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| Peak Overlap | |
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| Information Obtained from Gas Chromatograms | |
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| High-Performance Liquid Chromatography | |
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| The HPLC System | |
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| Partition Chromatography | |
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| Variations on the Chromatographic Theme | |
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| Planar Chromatography | |
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| Mass Spectrometric Detection | |
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| Multichannel Chromatographic Detection | |
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| Practice Questions and Problems | |
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| Analysis by Biochemical Reactivity | |
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| Enzyme Reactivity | |
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| Varieties of Enzymes and Reactivity | |
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| Enzyme Activation and Inhibition | |
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| The Effect of pH | |
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| Enzyme Stability | |
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| Kinetics of Enzyme Reactions | |
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| First-Order Reaction Rates | |
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| Enzyme-Catalyzed Reactions | |
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| The Michaelis-Menten Equation | |
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| Analytical Significance of K[subscript M] and K[subscript cat] | |
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| Kinetic Methods of Analysis | |
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| Continuous Flow Methods | |
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| Stopped Flow Methods | |
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| Quenching Methods | |
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| Applications of Kinetic Analysis with Enzymes | |
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| Antigen-Antibody Reactivity | |
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| Antibodies and Their Generation | |
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| Detecting the Antibody-Antigen Reaction | |
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| Immobilized Enzymes and Antibodies | |
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| Bonding Biochemical Reagents | |
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| Containing Biochemical Reagents | |
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| Separation with Biochemical Reactions | |
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| Separation on the Basis of Size | |
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| Separation on the Basis of Complexation Reactivity | |
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| Separation on the Basis of Mass and Density | |
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| Immunoassay | |
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| Direct Binding Reactions | |
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| Competitive Binding Reactions | |
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| Enzyme-Linked Immunosorbent Assay (ELISA) | |
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| Enzyme Multiplied Immunoassay Technique (EMIT) | |
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| Applications of Immunoassay | |
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| Biochemically Based Sensors | |
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| Photon Emission Sensors | |
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| Photon Absorption Sensors | |
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| Electrode Potential Sensors | |
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| Electrode Current Sensors | |
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| Practice Questions and Problems | |
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| Background Materials | |
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| Stoichiometric Ratios in Chemical Compounds and Reactions | |
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| Molecular Formulas | |
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| Reaction Stoichiometry | |
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| Ionic Reactions | |
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| Combining Quantities | |
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| Logarithms and Exponents | |
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| Logarithms | |
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| Antilogarithms | |
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| "p" Units | |
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| Logarithmic Scales | |
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| Natural Logarithms | |
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| Operations with Exponents | |
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| Addition and Subtraction | |
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| Multiplication and Division | |
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| Operations with Logarithms | |
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| Electrical Quantities and Their Relationships | |
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| Electrical Conductors and Insulators | |
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| Separation of Charge | |
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| Electrical Current | |
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| Electrical Capacitance | |
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| Electrical Signals | |
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| Appendices | |
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| Tables of Activity Coefficients and a[subscript X] | |
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| Calculated Values of Acitivity Coefficient Using the DHE | |
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| Table of Ion Size Parameters, a[subscript X], for Inorganic Ions | |
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| Table of Ion Size Parameters, a[subscript X], for Organic Ions | |
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| K[deg subscript a] Values for Weak Acids in Water | |
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| Table of Complex Formation (K[deg subscript f] and K'[subscript f]) Values | |
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| K[deg subscript sp] and K'[subscript sp] Values for Some Precipitates | |
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| Standard Reduction Potentials | |
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| International Atomic Weights | |
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| Useful Constants and Conversions | |
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| Prefixes for Units and their Multiplication Factors | |
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| Techniques Discussed and Their Location | |
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| Index | |