Part Two

Electrochemical Methods

Dr. Professor: Zhang, Chengxiao E-mail: cxzhang@snnu.edu.cn Tel: 85307567

Chapter 6 Introduction to Electrochemistry Chapter 7 Potentiometry Chapter 8 Bulk Electrolysis: Electrogravimetry and Coulometry Chapter 9 Voltammetry

Course Introduction
Bilingual Course

Analytical Electrochemistry
2004. 10; 2005. 10.31; 2006. 10.23; 2007. 2.10 -4.27; 2008. 4.5-6.27.

Instrumental Analysis
2008.9 2009.9

A conversation with Allen J. Bard

Education: Ph.D. in Chemistry, 1958, Harvard University M.A. in Chemistry, 1956, Harvard University B.Sc. in Chemistry, 1955, City College of New York Hackerman-Welch Regents Chair in Chemistry, The University of Texas, 1985-present. Research Interests: Electro-organic Chemistry Photoelectrochemistry Electrogenerated Chemiluminescence Electroanalytical Chemistry SECM Editor-in-Chief JACS. 20 years Ma Fen. PhD. Candidate, ( SNNU, Anal. Chem. My Lab).

Chapter 6 Introduction to Electrochemistry

6.1 Characterizing oxidation/reduction reactions
6.2 Electrochemical cells

6.3 Electrode Potentials

6.4 Nernst Equation 6.5 Applications of Standard Electrode Potentials

Chapter 6

Aim: Master
Classification of Electrochemical Methods Advantages of Electroanalysis Electrochemical Cell Electrodes

Nernst Equitation
Trends in Analytical Chemistry

Electrochemistry is the branch of chemistry

concerned with the interrelation of electrical and chemical effects. A large part of this field deals with the study of chemical changes caused by the passage of an electric current and the production of electrical energy by chemical reactions. In fact, the field of electrochemistry encompasses a huge array of different phenomena (e.g., electrophoresis and corrosion), devices (electrochromic displays, electroanalytical sensors, batteries, and fuel cells), and technologies (the electroplating of metals and the largescale production of aluminum and chlorine). While the basic principles of electrochemistry discussed in this course apply to all of these, the main emphasis here is on the application of electrochemical methods to the study of chemical systems.

Electroanalytical methods are concerned with the

interplay between electricity and chemistry, namely the

measurements of electrical quantities, such as current, potential, or and their relationship to chemical

parameters.
Such use of electrical measurements for analytical p urposes has been found a vast range of applications, i ncluding environmental monitoring, industrial quality, a nd biomedical analysis. Electrochemistry Analytical Electrochemistry; Electrochemical Ananlysis; Electroanalysis

Variables affecting the rate of an electrode reaction

Classification of Electrochemical Methods

V I R
(1) Electrical parameter: R: Conductometry; V: Potentiometry; I: Bulk Electrolysis Electrogravimetry and Coulometry Voltammetry (2) Current Value Zero: Small: Large:

(3) IUPAC recommendation 1976

A. No Involving double layer: Conductometry B. Involving double layer; No electrode reaction: Potentiometry C. Involving electrode reaction: Electrolysis; Voltammetry

Advantages of Electroanalysis

Electroanalysis as a representative of wet-chemical method has many attractive advantages, such as selectivity and sensitivity, notwithstanding its inexpensive equipment; ample choice of possibilities; and direct accessibility, especially to electronic and hence automatic control even at distance; automatic data treatment; and simple insertion, if desirable, into a process-regulation loop. 3S+2A

6.1 Characterizing oxidation/reduction reactions

In an oxidation/reduction reactions, electrons are transferred from one reactant to another. For example:

Ce4+ + Fe2+

Ce3+ + Fe3+

Cerium Ce4+: an oxidizing agent/oxidant, electron acceptor. Iron Fe2+ : an reducing agent/reductant, electron donor.

6.1 Characterizing oxidation/reduction reactions

Oxidation/Reduction reactions are sometimes called redox reactions. So we can write a generalized equation for a redox reaction as:

Ared + Box

Aox+ Bred

(1)Ared reductant, reduced form, having given up electrons, becomes an oxidizing agent, Aox. (2) Box, the oxidized form of species B, accepts electrons from Ared to form the new reductant Bred.

6.2 Electrochemical cells

Constitute

What is electrode? First type conductor, S econd type conductor.

CuSO4(0.0200M) Cu

Two conductors (called electrodes), Electrolyte solution , Salt bridge.

Zn ZnSO4(0.0200M)

Half-cell

Ecell=Eright-Eleft Types of electrochemical cells: 1Galvanic (or voltaic) cells store electrical energy. Batteries. 2Electrolytic cell requires an external source of electrical energy for operation. Cathodes and Anodesgalvanic or electrolytic cell The cathode reduction The anode oxidation

Figure 6-1

Alessandro Volta (1745-1827), Italian physicist. He was the inventor of the first battery, the so-called voltaic pile (shown on the right). It consisted of alternating disks of copper and zinc separated by disks of cardboard soaked with salt solutions.

6.3 Electrode Potentials

The Standard Hydrogen Reference Electrode (SHE)
The Standard Hydrogen Electrode(abbreviated SHE) is the universal ref
erence for reporting relative half-cell potentials. It is a type of gas ele ctrode and was widely used in early studies as a reference electrode. The SHE is also called the Normal Hydrogen Electrode
What is Reference Electrode ( RE)?

To provide the reference standard for measuring

potential.

Figure 6-3

6.3 Electrode Potentials How to make SHRE?

The platinum electrode (Pt) is made of a small square of platinum foil which is platinized (known as platinum black). Hydrogen gas, at a pressure of 1 atmosphere, is bubbled around the platinum electrode. The platinum black serves as a large surface area for the reaction to take place, and the stream of hydrogen keeps the solution saturated at the electrode site with respect to the gas.

The potential of the standard hydrogen electrode is assigned a value of 0.000V at all temperatures.

Ag/AgCl electrode

Calomel electrode

6.3 Electrode Potentials

Standard Electrode Potential (E0)
Pt, H2 (1.00 atm) | H+(a=1.00|| Ag+(a=1.00) | Ag or SHE || Ag+(a=1.00) | Ag

When the silver ion activity() is 1.00, the cell potential E is the standard electrode potential of th e Ag+/Ag. E0Ag+/ Ag =0.799V
Electrode Potential of Silver Electrode: Ecell=Eright-Eleft=EAg-ESHE = EAg-0.000= EAg
Figure 6-4

6.3 Electrode Potentials

Name of electrodes 1. Cathodes and Anodes;

2. Positive Electrode and Negative Electrode.

3. Working electrode WR ( response electrode) Reference electrode RE Auxiliary electrode; Counter electrode CE; supporting electrode

4. Polarized electrode and unpolarized electrode

(nonpolarizable electrode).

6.4 The Nernst Equation

Oxne0

Red

RT o E=E + ln nF R
E0: Standard Electrode Potential R: ideal gas constant, 8.314J K -1 mol-1 T: temperature, K F: the faraday=96,485C n: number of moles of electrons ln: natural logarithm=2.303log

6.4 The Nernst Aquation

If we substitute numerical values for the constants, convert to base 10 logarithms, and 25 for the temperature. We get:

0.059 o E=E + log n R

0

6.4 The Nernst Equation

Walther nernst(1864-1941)received the 1920 Nobel Prize in chemistry for his numerous contributions to the field of chemical thermodynamics. Nernst (far left) is see here with Albert Einstein, Max Planck, Robert A. Millikan, and Max von Laue in 1982.

6.5 Applications of Standard Electrode Potentials

Calculation redox equilibrium constants For example: biological redox systems

The scheme Cytochrome c

Cytochromes are ironheme proteins in which a porphyrin ring is coordinated through nitrogen atoms to an iron atom. They undergo one-electron redox reactions, and their physiological function is to

facilitate electron transport. Cytochromes are intimately involved in the formation of water from H2. Reduced pyridine nucleotides deliver hydrogen to flavoproteins. The reduced flavoproteins are reoxidized by the Fe3+ of Cytochromes b or c. The chain is completed when cytochromes oxidase transfers electrons to oxyge n. The resulting oxide ion(O2-) is unstable and immediately picks up two H+ ions to produce H2O. How to measure the potential?

Trends in Electroanalysis: Micro-; NanoIn vive; On line Bio-

Robert Hillman

Home Work
Questions and Problems P 628-631 1. Why is it that half-reactions in electrochemical cells

proceed spontaneously in one direction and furnish

current? 2. What is the effect of the salt bridge? 3.. What is the effect of ion migration? 4. What is absolute and relative potential differences?