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Reading Assignment:
Chapter 21 of Silberberg
Chapter 20 of Brown et al.
Reduction-Oxidation Reaction
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)
a. O2
b. NaCl
c. KMnO4
d. CaC2O4
e. (NH4)2CO3
f. OF2
g. Fe3+
h. Al
Identifying Redox Reaction
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
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 comma separates the half-cell components that are in the same phase.
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
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
(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 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 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
Determine (a) which half-reaction occurs at the cathode and which occurs at the
anode and (b) the standard cell potential.
Cu cannot reduce H + or 2+
Zn .
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
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 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
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.
The reduction with the less negative (more positive) electrode potential occurs.
The oxidation with the less positive (more negative) electrode potential occurs.
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