Electrochemistry

Reading Assignment:
Chapter 21 of Silberberg
Chapter 20 of Brown et al.
 Reduction-Oxidation Reaction

What is difference between these two reactions?

Ag+ + Cl- AgCl(s) Ag+ + Cu(s) Cu2++ Ag(s)

Reduction-Oxidation Reaction
Reduction-Oxidation Reaction
Reduction-Oxidation Reaction
 Reduction-Oxidation Reaction

In a redox reaction, both oxidation and reduction are necessary

Oxidation involves loss of electrons

Reduction involves gain of electrons

OLI
O = oxidation
L = loss electrons LEO/GER
I = increase in oxidation number Lose electrons = oxidation
Gain electrons = reduction
RGD
R = reduction
G = gain electrons
D = decrease in oxidation number
 Identifying Oxidation Number (Review)

Assign oxidation numbers to all of the elements in the following compounds:

a. O2
b. NaCl
c. KMnO4
d. CaC2O4
e. (NH4)2CO3
f. OF2
g. Fe3+
h. Al
 Identifying Redox Reaction

Identify whether each of the following is an oxidation-reduction reaction:

1. Fe2O3 + 3CO 2Fe + 3CO2
2. MnO2 + 4 H+ + 2 Cl Mn2+ + 2 H2O + Cl2
3. H2PO4 + OH HPO4 + H2O
4. Al3+ + OH Al(OH)3
5. 2H2O2 2H2O + O2
6. 2O2 O22 + O2
 Electrochemistry

Electrochemistry is the study of the relationships between electricity and chemical

reactions

Study of chemical reactions that produce electrical currents or voltages and of the
chemical reactions that are caused by the action of currents or voltages.
 Voltaic Cell

Voltaic (or galvanic) cell uses spontaneous redox reaction to generate electricity
Voltaic Cell
Voltaic Cell
Voltaic Cell

Components of the half-cells include

electrode materials, electrolyte ions, and
other species involved in the reaction.

Electrode name (anode or cathode) and

charge are shown. By convention, the
anode compartment appears on the left.

Each half-reaction and the overall cell

reaction are given.

Direction of electron flow in the external

circuit is from anode (left) to cathode (right)

Nature of ions and direction of ion flow in

the salt bridge are shown, with cations
moving right and anions moving left.
 Notation for a Voltaic Cell

The components of the anode compartment (oxidation half-cell) are written to the left of the components of the cathode compartment
(reduction half-cell).

A double vertical line indicates the half-cells are physically separated.

A single vertical line represents a phase boundary.

A comma separates the half-cell components that are in the same phase.

If needed, the concentrations of dissolved components are given in parentheses;

e.g.

Half-cell components usually appear in the same order as in the half-reaction, and electrodes appear at the far left (anode) and far right
(cathode) of the notation.

Ions in the salt bridge are not part of the reaction so they are not in the notation.
 Example

The oxidationreduction reaction

is spontaneous. A solution containing K2Cr2O7 and H2SO4 is poured into one beaker,
and a solution of KI is poured into another. A salt bridge is used to join the beakers. A
metallic conductor that will not react with either solution (such as platinum foil) is
suspended in each solution, and the two conductors are connected with wires
through a voltmeter or some other device to detect an electric current. The resultant
voltaic cell generates an electric current. Indicate the reaction occurring at the
anode, the reaction at the cathode, the direction of electron migration, the direction
of ion migration, and the signs of the electrodes.
The following two half-reactions occur in a voltaic cell:

Which one of the following descriptions most accurately describes what is occurring
in the half-cell containing the Cu electrode and Cu2+(aq) solution?

(a) The electrode is losing mass and cations from the salt bridge are flowing into the
half-cell.
(b) The electrode is gaining mass and cations from the salt bridge are flowing into
the half-cell.
(c) The electrode is losing mass and anions from the salt bridge are flowing into the
half-cell.
(d)The electrode is gaining mass and anions from the salt bridge are flowing into the
half-cell.
 Your Turn!
The two half-reactions in a voltaic cell are:

(a) Indicate which reaction occurs at the anode and which at the cathode. (b) Does
the zinc electrode gain, lose, or retain the same mass as the reaction proceeds? (c)
Does the platinum electrode gain, lose, or retain the same mass as the reaction
proceeds? (d) Which electrode is positive?
 Cell Diagram

Aluminum metal displaces zinc(II) ion from aqueous solution.

(a) Write oxidation and reduction half-equations and an overall equation for this redox
reaction.
(b) Write a cell diagram for a voltaic cell in which this reaction occurs.

The cell diagram for an electrochemical cell is written as

Ni(s)|NiCl2(aq)||Ce(ClO4)4(aq),Ce(ClO4)3(aq)|Pt(s)
Write the equations for the half-reactions that occur at the electrodes. Balance the
overall cell reaction.
 Cell Potentials
2+
Why do electrons transfer spontaneously from a Zn atom to a Cu ion?
 Cell Potential

The potential difference between the two electrodes of a voltaic cell is called the cell
potential, denoted Ecell (electromotive (causing electron motion) force, or emf)

For Zn/Cu cell, potential is +1.10 V at 25 C and when [Zn2+] and [Cu2+] = 1.0 M.
This is the STANDARD CELL POTENTIAL, Eo

a quantitative measure of the tendency of reactants to proceed to products when all

are in their standard states at 25 C.
 Standard Electrode Potential

How do we calculate the cell potential?

If we know Eo for each half-reaction, we could get Eo for net reaction.

 Standard Electrode Potential
We cannot measure half-reaction directly. Therefore, we measure it relative to a
E o

STANDARD HYDROGEN ELECTRODE (SHE).

 Standard Electrode Potential

A standard electrode potential, Eo, measures the tendency for a reduction process
to occur at an electrode
ionic species at 1 M
gases at 1 bar
when no metal involved, an inert electrode such as Pt

To determine the value of Eo for a standard electrode, such as the one above, we
compare it with SHE
 Standard Electrode Potential

SHE is always the anode, and the compared electrode is the cathode
Standard Electrode Potential
Standard Electrode Potential
 Example
Calculate the standard emf of the cell that employs the following overall reactions:
 Voltaic Cell

In a voltaic cell, the Eo at the cathode is more

positive than the Eo at the anode
 Example

A voltaic cell is based on the two standard half-reactions

Determine (a) which half-reaction occurs at the cathode and which occurs at the
anode and (b) the standard cell potential.

A voltaic cell is based on a Co2+/Co half-cell and a AgCl/Ag half-cell.

(a) What half-reaction occurs at the anode? (b) What is the standard cell potential?
Strengths of Oxidizing and Reducing Agents

Any substance on the right will

reduce any substance higher
than it on the left.

Zn can reduce H + and 2+

Cu .

H2 can reduce Cu2+ but not Zn 2+

Cu cannot reduce H + or 2+
Zn .
 Example

Rank the following in order of increasing strengths of

oxidizing agents:
+
NO3 , Ag , Cr2O7 2

Which of the following species would you expect to

be the strongest oxidizing agent?
+ +
(a) Cl (aq), (b) Cl2(g), (c) O2(g), (d) H (aq), (e) Na (aq)

Rank the following species from the strongest to

weakest reducing agents:

I (aq), Al(s), Fe(s)
 Free Energy and Redox Reactions

n = electron number; number of moles of electrons transferred (no units!)

F = Faradays constant (96, 485 C/mol or 96,485 J/V-mol)

A positive value of E and a negative value of G both

indicate a spontaneous reaction.
 Redox Reactions and Equilibrium
Recall:
 Example

Predict the outcome of the following reaction. Classify each of the reactions as
product-favored or reactant-favored.

(a) Fe(s) + 2+
Sn (aq)
(b) O2(g) + Au(s)
(c) Na(s) + H2O(l)
(d) Al (aq) + Hg(l)
3+
 Example

(a) Combine pairs of the balanced half-reactions (1), (2), and (3) into three
spontaneous reactions A, B, and C, and calculate Ecell for each. (b) Rank the
relative strengths of the oxidizing and reducing agents.
 Example

(a) Use the standard reduction potentials to calculate the standard free-energy
o
change, G , and the equilibrium constant, K, at 298 K for the reaction

(b) Suppose the reaction in part (a) is written

What are the values of o

E, o
G , and K when the reaction is written this way?
 Your Turn!

Will lead metal displace Ag+ ion in aqueous solution?

Calculate K and Go for this reaction at 298 K.
Cell Potential Under Nonstandard Conditions
Example
 Your Turn!

What is the pH of the solution in the cathode half-cell of the voltaic cell:
Zn|Zn2+(aq)(0.10 M)||H2(g)(1 atm)|H+(aq)(? M)|Pt Ecell = 0.542 V
 Concentration Cells

A cell based solely on the emf generated because of a difference in a concentration

is called a concentration cell.
Concentration Cell
Example
 Example

A concentration cell is constructed with two Zn(s) - Zn2+(aq) half-cells. In one half-cell
[Zn2+] = 1.35 M, and in the other [Zn2+] = 3.75 x 104 M. (a) Which half-cell is the
anode? (b) What is the emf of the cell? (c) What is [Zn2+] when the cell ceases to
operate?
 Reading Assignment

Reading Assignment: (Section 21.5 of your text) Electrochemical Processes in

Batteries
Corrosion
Preventing Corrosion
Preventing Corrosion
Corrosion
 Electrolysis

Electrolytic cell uses electricity to produce a nonspontaneous reaction

Voltaic vs. Electrolytic Cell
Voltaic vs. Electrolytic Cell
 Predicting the Products of Electrolysis of Molten Salt

The more easily reduced species (stronger oxidizing agent) reacts at the cathode.

The more easily oxidized species (stronger reducing agent) reacts at the anode.

The most ionic and least ionic of the common alkali halides are, respectively, CsF
and LiI. A solid mixture of these compounds is melted and electrolyzed. Determine
which metal and nonmetal form at the electrodes, and write the overall cell reaction.
Electrolysis of Water
 Electrolysis of Aqueous Solutions

The reduction with the less negative (more positive) electrode potential occurs.

The oxidation with the less positive (more negative) electrode potential occurs.

Predict the product of electrolysis of KI(aq).

 Electrolysis of Aqueous Solutions

The reduction with the less negative (more positive) electrode potential occurs.

The oxidation with the less positive (more negative) electrode potential occurs.

Predict the product of electrolysis of KI(aq).

Possible Reduction Reactions:

Possible Oxidation Reactions:

 Overvoltage

The products predicted from a comparison of electrode potentials are not always the
actual products. For gases to be produced at metal electrodes, additional voltage
(overvoltage) is required.
 Example

Use half-reactions to show which product forms at each electrode during the
electrolysis of aqueous solutions of the following salts:
(a) KBr
(b) AgNO3
(c) MgSO4