10: Electrochemical Methods
- Page ID
- 540056
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\(\newcommand{\avec}{\mathbf a}\) \(\newcommand{\bvec}{\mathbf b}\) \(\newcommand{\cvec}{\mathbf c}\) \(\newcommand{\dvec}{\mathbf d}\) \(\newcommand{\dtil}{\widetilde{\mathbf d}}\) \(\newcommand{\evec}{\mathbf e}\) \(\newcommand{\fvec}{\mathbf f}\) \(\newcommand{\nvec}{\mathbf n}\) \(\newcommand{\pvec}{\mathbf p}\) \(\newcommand{\qvec}{\mathbf q}\) \(\newcommand{\svec}{\mathbf s}\) \(\newcommand{\tvec}{\mathbf t}\) \(\newcommand{\uvec}{\mathbf u}\) \(\newcommand{\vvec}{\mathbf v}\) \(\newcommand{\wvec}{\mathbf w}\) \(\newcommand{\xvec}{\mathbf x}\) \(\newcommand{\yvec}{\mathbf y}\) \(\newcommand{\zvec}{\mathbf z}\) \(\newcommand{\rvec}{\mathbf r}\) \(\newcommand{\mvec}{\mathbf m}\) \(\newcommand{\zerovec}{\mathbf 0}\) \(\newcommand{\onevec}{\mathbf 1}\) \(\newcommand{\real}{\mathbb R}\) \(\newcommand{\twovec}[2]{\left[\begin{array}{r}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\ctwovec}[2]{\left[\begin{array}{c}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\threevec}[3]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\cthreevec}[3]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\fourvec}[4]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\cfourvec}[4]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\fivevec}[5]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\cfivevec}[5]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\mattwo}[4]{\left[\begin{array}{rr}#1 \amp #2 \\ #3 \amp #4 \\ \end{array}\right]}\) \(\newcommand{\laspan}[1]{\text{Span}\{#1\}}\) \(\newcommand{\bcal}{\cal B}\) \(\newcommand{\ccal}{\cal C}\) \(\newcommand{\scal}{\cal S}\) \(\newcommand{\wcal}{\cal W}\) \(\newcommand{\ecal}{\cal E}\) \(\newcommand{\coords}[2]{\left\{#1\right\}_{#2}}\) \(\newcommand{\gray}[1]{\color{gray}{#1}}\) \(\newcommand{\lgray}[1]{\color{lightgray}{#1}}\) \(\newcommand{\rank}{\operatorname{rank}}\) \(\newcommand{\row}{\text{Row}}\) \(\newcommand{\col}{\text{Col}}\) \(\renewcommand{\row}{\text{Row}}\) \(\newcommand{\nul}{\text{Nul}}\) \(\newcommand{\var}{\text{Var}}\) \(\newcommand{\corr}{\text{corr}}\) \(\newcommand{\len}[1]{\left|#1\right|}\) \(\newcommand{\bbar}{\overline{\bvec}}\) \(\newcommand{\bhat}{\widehat{\bvec}}\) \(\newcommand{\bperp}{\bvec^\perp}\) \(\newcommand{\xhat}{\widehat{\xvec}}\) \(\newcommand{\vhat}{\widehat{\vvec}}\) \(\newcommand{\uhat}{\widehat{\uvec}}\) \(\newcommand{\what}{\widehat{\wvec}}\) \(\newcommand{\Sighat}{\widehat{\Sigma}}\) \(\newcommand{\lt}{<}\) \(\newcommand{\gt}{>}\) \(\newcommand{\amp}{&}\) \(\definecolor{fillinmathshade}{gray}{0.9}\)In Chapter 10 we examined several spectroscopic techniques that take advantage of the interaction between electromagnetic radiation and matter. In this chapter we turn our attention to electrochemical techniques in which the potential, current, or charge in an electrochemical cell serves as the analytical signal.
Although there are only three fundamental electrochemical signals, there are many possible experimental designs—too many, in fact, to cover adequately in an introductory textbook. The simplest division of electrochemical techniques is between bulk techniques, in which we measure a property of the solution in the electrochemical cell, and interfacial techniques, in which the potential, current, or charge depends on the species present at the interface between an electrode and the solution in which it sits. The measurement of a solution’s conductivity, which is proportional to the total concentration of dissolved ions, is one example of a bulk electrochemical technique. A determination of pH using a pH electrode is an example of an interfacial electrochemical technique. Only interfacial electrochemical methods receive further consideration in this chapter.
- 10.1: Overview of Electrochemistry
- This chapter focuses on analytical electrochemistry, which uses measurements of potential, current, or charge to determine analyte concentration or chemical reactivity. Key concepts include the relationship between electrode potential and analyte form, differences in surface and bulk concentrations, current's role in measuring redox rates, and the balance between controlling current and potential.
- 10.2: Potentiometric Methods
- The page provides a comprehensive overview of potentiometry, which is a method for measuring the potential of electrochemical cells under static conditions. This technique facilitates quantitative analysis by relating a cell???s potential to the concentration of electroactive species using the Nernst equation. It also covers different types of electrodes used in potentiometry, such as ion-selective electrodes, the significance of reference electrodes, and the impact of junction potentials.
- 10.3: Redox Titrations
- The text provides a comprehensive overview of analytical titrations using redox reactions, tracing its evolution from the 18th century when chlorine-based analysis was introduced. It delves into the mechanisms of redox titrations, highlighting important oxidizing agents such as \(\text{MnO}_4^-\) and \(\text{Cr}_2\text{O}_7^{2-}\), and the use of auxiliary agents to adjust oxidation states.
- 10.4: Problems
- This document entails a series of advanced electrochemistry problems that cover various aspects of electrochemical cells, ion-selective electrodes, potentiometry, controlled-potential coulometry, and voltammetry.
- 10.5: Additional Resources
- The page outlines various experiments designed to introduce students to electrochemistry applications. The experiments are organized into categories including general electrochemistry, electrode preparation, potentiometry, coulometry, voltammetry, and amperometry.
- 10.6: Chapter Summary and Key Terms
- This chapter covers three electrochemical analysis methods: potentiometry, coulometry, and voltammetry. Potentiometry involves measuring potential without significant current and using the Nernst equation to calculate analyte activity. Coulometry is based on Faraday???s law to determine analyte quantity through electrical charge or current.