Chapter 14a

Zn-Ag battery
invented by
Alessandro Volta
in 1799

Electrode
Potentials
Saturated
calomel
electrode
(S.C.E)

Silver-silver chloride Lithium-ion battery

reference electrode
Ch14-1 CHEM 3369
 In this chapter…
Ø Chemical reactions that generate electricity
Free energy change
of redox reaction Potential

ΔG = −nFE < 0, so E > 0 (spontaneous

Moles of e
in Faraday reactions)
redox reaction constant

Ø Relative strengths of oxidizing and reducing agents (redox

couples)
ü Electrochemical Series
Ø Using electricity to produce chemical change — electrolysis

ΔG > 0, so Eapplied > ΔG/nF (non-spontaneous

reactions)
Ch14-2 CHEM 3369
 14-1 Redox Chemistry
and
Electricity

Ch14-3 CHEM 3369

 Basic Concepts and Terminology
Redox Reactions:
Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s)
Ø transfer of e– from one species to another
Ø involve two half-reactions:
Product
Oxidation Half-Reaction:
Zn(s) ¾® Zn2+(aq) + 2e−
Ø electron loss
Ø increase in oxidation number
Reactant
Reduction Half-Reaction:
Cu2+(aq) + 2e− ¾® Cu(s)
Ø electron gain
Ø decrease in oxidation number
Ch14-4 CHEM 3369
 Basic Concepts and Terminology (cont’d)
Overall Redox Reaction — sum of two half-reactions:
e
transfer

Zn(s) + Cu2+(aq) « Zn2+(aq) + Cu(s)

Reducing Oxidizing
agent agent

Reducing Agent or reductant

Ø gives electron(s)
Ø becomes oxidized

Oxidizing Agent or oxidant

Ø takes electron(s)
Ø becomes reduced
Ch14-5 CHEM 3369
 Chemistry and Electricity (1)
Electric Charge (q):
Ø measured in coulombs (C)
Ø charge of 1 e− = 1.602
10–19 C
Ø charge of 1 mol e− = 9.649
104 C = Faraday constant (F )
Ø the quantity of electrons that flow from a redox reaction is
proportional to the quantity of analyte that reacts

q = n
N
F
Coulombs Unit charges Moles Coulombs
per molecule —————
Mole

Moles of e− in balanced redox reaction

(moles of charge)
Ch14-6 CHEM 3369
 EXAMPLE Relating Coulombs to Quantity of Reaction
PROBLEM If 6.539 g of Zn(s) were oxidized in the reaction
Cu2+(aq) + Zn(s) ® Zn2+(aq) + Cu(s), how many coulombs
of charge must have been transferred from Zn to Cu2+?

Ch14-7 CHEM 3369

 EXAMPLE Relating Coulombs to Quantity of Reaction
PROBLEM If 6.539 g of Zn(s) were oxidized in the reaction
Cu2+(aq) + Zn(s) ® Zn2+(aq) + Cu(s), how many coulombs
of charge must have been transferred from Zn to Cu2+?
SOLUTION
6.539 g
6.539 g Zn(s) = —————— = 0.1000 mol Zn(s)
65.39 g/mol

Because Zn(s) ® Zn2+(aq) + 2e–

nN = 2
(mol Zn) = 2(0.1000 mol) = 0.2000 mol e–

q = nNF = (0.2000 mol) (9.649
104 C/mol) = 1.930
103 C

Ch14-8 CHEM 3369

 Chemistry and Electricity (2)
Electric Current (I ):
Ø the quantity of charge flowing
each second through a circuit
Figure 14-2
Ø measured in amperes (A)
1 A = 1 C / s
Ø is proportional to the
rate of a redox reaction
Figure 14-1

Current = F
Rredox
Coulombs Coulombs Moles
————— ———— ————
Second Mole Second

Ch14-9 CHEM 3369

 EXAMPLE Relating Coulombs to Rate of Reaction
PROBLEM If Te is created at the rate of 1.00 g/h in the reaction
2S2O42– + TeO32– + 2OH– « 4SO32– + Te(s) + H2O,
how much current is flowing?

Ch14-10 CHEM 3369

 EXAMPLE Relating Coulombs to Rate of Reaction
PROBLEM If Te is created at the rate of 1.00 g/h in the reaction
2S2O42– + TeO32– + 2OH– « 4SO32– + Te(s) + H2O,
how much current is flowing?
SOLUTION +4 0
TeO32– + 3H2O + 4e– « Te(s) + 6OH−
4 electrons are required to reduce 1 TeO32–(aq) to 1 Te(s)
1.00 g/h
Rate(Te) = 1.00 g/h = —————— = 7.837
10–3 mol/h
127.6 g/mol
Rate(e–) = 4
Rate(Te) = 4(7.837
10–3) = 3.135
10–2 mol/h
3.135
10 –2 mol/h
Rate(e–) = ———————— = 8.708
10–6 mol/s
3600 s/h

I = (8.708
10–6 mol/s)(9.649
104 C/mol) = 0.840 C/s = 0.840 A

Ch14-11 CHEM 3369
 Chemistry and Electricity (3) – –
Repulsions
Voltage (E ) and Electrical Work: + +
Ø it costs energy to move like charges toward each other
Attraction
Ø energy is released when opposite charges move
– +
toward each other
Ø hence, electrons in redox reactions either can do useful work
along the way or need force to push them along

Ch14-12 CHEM 3369

 Chemistry and Electricity (3) – –
Repulsions
Voltage (E ) and Electrical Work: + +
Ø it costs energy to move like charges toward each other
Attraction
Ø energy is released when opposite charges move
– +
toward each other
Ø hence, electrons in redox reactions either can do useful work
along the way or need force to push them along
work = q
E Figure 14-2
Joules Coulombs Volts

E = electric potential difference (voltage)

Electric potential represents how much energy a charged
particle can acquire as it moves through the electric field.
ü E is measured in volts (V) 1 V = 1 J / C
ü is related to the identity and concentrations
of reactants and products
Ch14-13 CHEM 3369
 EXAMPLE Calculating Electrical Work
PROBLEM Hydrogen ions can carry out useful work in a living cell
(such as synthesis of the molecule ATP that provides energy for
chemical synthesis) when they pass from one region of high
potential to a region of lower potential. How many joules of work
can be done when 1.0 µmol of H+ crosses a membrane and goes
from potential of +0.075 V to a potential of –0.090 V?

Ch14-14 CHEM 3369

 EXAMPLE Calculating Electrical Work
PROBLEM Hydrogen ions can carry out useful work in a living cell
(such as synthesis of the molecule ATP that provides energy for
chemical synthesis) when they pass from one region of high
potential to a region of lower potential. How many joules of work
can be done when 1.0 µmol of H+ crosses a membrane and goes
from potential of +0.075 V to a potential of –0.090 V?

SOLUTION

ΔE = (+0.075 V) – (–0.090 V) = +0.165 V = 0.165 J/C

q = nNF = (1)(1.0
10–6 mol)(9.649
104 C/mol) = 9.649
10–2 C

Moles of charge

work = q ΔE = (9.649
10–2 C)(0.165 J/C) = 0.016 J

Ch14-15 CHEM 3369

 Two Types of Electrochemical Cells
1. Galvanic Cell (or voltaic cell ) — uses a spontaneous reaction
(DG < 0) to generate electricity (flow of electrons). Examples:
rechargeable Ni-metal hydride and Li-ion batteries.
Overall (cell) reaction
X + Y+ « X+ + Y; ΔG < 0

ANODE: e– + X+ Y+ + e– CATHODE:
source of sink of
electrons from electrons for
oxidation X Y reduction
half-reaction half-reaction

Ch14-16 CHEM 3369

 Two Types of Electrochemical Cells
2. Electrolytic Cell — uses electrical energy to drive an otherwise
non-spontaneous reaction (DG > 0). Examples: production of
aluminum metal from Al3+ and of chlorine gas from Cl– in
seawater. Overall (cell) reaction
A – + B + « A + B ; Δ G > 0

ANODE: e– + A B+ + e– CATHODE:
sink of source of
electrons from electrons for
oxidation A– B reduction
half-reaction half-reaction

Ch14-17 CHEM 3369

 14-2 Voltaic Cells:
Using Spontaneous
Reactions to Generate
Electricity

Ch14-18 CHEM 3369

 Construction of a Voltaic Cell A voltaic cell involves
two half-reactions of a
Electrodes redox process occurring
at two separate places
Salt bridge within the cell.
Anode
U Cathode
T A
Oxidation Reduction

Anode where Cathode where

oxidation occurs Electrolyte Electrolyte reduction occurs

Ø The metal conductors at which the half-reactions take place are called
electrodes:
ü Oxidation takes place at the anode (left side)
ü Reduction takes place at the cathode (right side)
Ø The solution in which the redox reaction occurs is called an electrolyte; it
conducts electrons by the process of ionic conduction
Ø A salt bridge (e.g., a gel containing saturated aqueous KCl, Na2SO4) through
which ions can migrate to maintain electroneutrality on each side
Ch14-19 CHEM 3369
 Charges of the Electrodes Negative terminal

Ø Anode is labeled as negative electrode ANODE:

source of e−
as electrons are produced here by the from oxidation
oxidation reaction. half-reaction

Ø Cathode is labeled as positive Positive terminal

electrode as electrons are consumed
here (by positive ions in solution) in CATHODE:
sink of e− for
the reduction reaction. reduction half-
reaction
Ø Electrons flow from the anode to the
cathode, in the external circuit.

Ø Salt bridge keeps the two half-cells in

contact with one another so that there
can be a flow of electrons.
Ch14-20 CHEM 3369
 A Galvanic Cell in Action
5. Potentiometer (voltmeter) measures the 4. Migration
voltage difference between the two half-cells. of ions
2. Electrons through a
from the Zn salt bridge
metal flow exactly
through the offsets
potentiometer the charge
into the Cu buildup.
electrode.

1. Oxidation
of Zn(s) at
3. Cu2+(aq) is
the anode
reduced to
produces
Cu(s) at the
Zn2+(aq)
cathode.
and
electrons.
Zn(s) ® Zn2+(aq) + 2e− Cu2+(aq) + 2e− ® Cu(s)
Cell reaction: Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s)
Ch14-21 CHEM 3369
 If a Voltaic Cell Had No Salt Bridge …

1. ANODE 2. CATHODE
electrolyte Zn2+ SO42− electrolyte
SO42−
would build Zn2+ would build
Zn2+ SO42−
up positive Zn2+ up negative
SO42−
charge from charge by
Zn2+ SO42−
excess of depletion of
Zn2+(aq). Cu2+(aq).

Zn(s) ® Zn2+(aq) + 2e− Cu2+(aq) + 2e− ® Cu(s)

Cell reaction: Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s)
Ch14-22 CHEM 3369
 If a Voltaic Cell Had No Salt Bridge …
3. This charge buildup would oppose the otherwise energetically favorable
chemical reaction, and the process would stop (no e– flow; ΔG = 0).

1. ANODE 2. CATHODE
electrolyte Zn2+ SO42− electrolyte
SO42−
would build Zn2+ would build
Zn2+ SO42−
up positive Zn2+ up negative
SO42−
charge from charge by
Zn2+ SO42−
excess of depletion of
Zn2+(aq). Cu2+(aq).

Zn(s) ® Zn2+(aq) + 2e− Cu2+(aq) + 2e− ® Cu(s)

Cell reaction: Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s)
Ch14-23 CHEM 3369
 Flow of a Charge in a Voltaic Cell
By convention, Electrons flow through the wire from
a voltaic cell is anode to cathode.
shown with the
anode on the
left and the
cathode on
the right.

Cations
move Anions move
through the through the
salt bridge salt bridge
from the from the
anode cathode
solution to solution to
the cathode the anode
solution. solution.

Zn(s) ® Zn2+(aq) + 2e− Cu2+(aq) + 2e− ® Cu(s)

Cell reaction: Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s)
Ch14-24 CHEM 3369
 Flow of a Charge in a Voltaic Cell
By convention, Electrons flow through the wire from
a voltaic cell is anode to cathode.
shown with the
anode on the
left and the
cathode on
the right.

Cations
move Anions move
through the through the
salt bridge salt bridge
from the from the
anode cathode
solution to solution to
the cathode the anode
solution. solution.

Zn(s) ® Zn2+(aq) + 2e− Cu2+(aq) + 2e− ® Cu(s)

Cell reaction: Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s)
Ch14-25 CHEM 3369
 Cell Line Diagrams: Conventions
Ø A cell diagram is a shorthand way of writing the essential
chemistry and components of the electrochemical cell.
Ø It is written as
Components of anode components of cathode
compartment compartment
(oxidation half-cell) (reduction half-cell)

Ø The double vertical bar ( || ) represents the salt bridge

Ø Each compartment is written to show the electrodes and any
chemicals present
Ø The electrode is written first for the anode compartment and
last for the cathode compartment
Ø A single vertical line ( | ) represents a boundary between phases
Ø Chemicals present in a single phase are separated by commas ( , )
Ch14-26 CHEM 3369
 Diagramming Galvanic Cells
Recall line notation: The anode is written on the left, the cathode is
written on the right, and the two are separated by a double
vertical line ( || salt bridge).
EXAMPLE : A galvanic cell in Figure
14-3 is abbreviated as:

Zn(s) | ZnCl2(aq) || CuSO4(aq) | Cu(s)

Figure 14-3

Ch14-27 CHEM 3369

 Diagramming Galvanic Cells
Recall line notation: The anode is written on the left, the cathode is
written on the right, and the two are separated by a double
vertical line ( || salt bridge).
EXAMPLE : A galvanic cell in Figure EXAMPLE : A galvanic cell in Figure
14-3 is abbreviated as: 14-5 is abbreviated as:
Pt(s) | HBr (aq, 0.10 M) | Br2(l)
Zn(s) | ZnCl2(aq) || CuSO4(aq) | Cu(s)
|| Al(NO)3(aq, 0.010 M) | Al(s)

Figure 14-3 Figure 14-5

Ch14-28 CHEM 3369

 EXAMPLE Writing Cell Diagrams (1)
PROBLEM Write the cell diagram for a redox reaction in which the
Cu2+(aq) ion is reduced to Cu+(aq) by magnesium metal, forming
Mg2+(aq) as the oxidized product.

Ch14-29 CHEM 3369

 EXAMPLE Writing Cell Diagrams (1)
PROBLEM Write the cell diagram for a redox reaction in which the
Cu2+(aq) ion is reduced to Cu+(aq) by magnesium metal, forming
Mg2+(aq) as the oxidized product.
SOLUTION
Anode (left): Mg(s) ® Mg2+(aq) + 2e–
oxidation Magnesium metal serves as an electrode

Cathode (right): Cu2+(aq) + e– ® Cu+(aq)

reduction Redox couple in solution — need an inert metal electrode

Cell Diagram: Mg(s) | Mg2+(aq) || Cu+(aq), Cu2+(aq) | Pt(s)

Anode Bridge Cathode

Ch14-30 CHEM 3369

 EXAMPLE Writing Cell Diagrams (2)
CourseKey Write the cell diagram for a cell that uses the reaction
Mg(s) + 2H+(aq) ® Mg2+(aq) + H2(g).

Ch14-31 CHEM 3369

 EXAMPLE Writing Cell Diagrams (2)
PROBLEM Write the cell diagram for a cell that uses the reaction
Mg(s) + 2H+(aq) ® Mg2+(aq) + H2(g).
SOLUTION

Anode (left): Mg(s) ® Mg2+(aq) + 2e–

oxidation Magnesium metal serves as an electrode

Cathode (right): 2H+(aq) + 2e– ® H2(g)

reduction Need phase boundary and an inert metal electrode

Cell Diagram: Mg(s) | Mg2+(aq) || H+(aq) | H2(g) | Pt(s)

Anode Bridge Cathode

Ch14-32 CHEM 3369

 EXAMPLE Writing Cell Diagrams (3)
PROBLEM Write the cell diagram for a cell that uses the following
half-reactions:
Fe3+(aq, 1 M) + e– ® Fe2+(aq, 1 M) Ø reduction, cathode, right
H2(g, 1 atm) ® 2H+(aq, 1 M) + 2e– Ø oxidation, anode, left

Ch14-33 CHEM 3369

 EXAMPLE Writing Cell Diagrams (3)
PROBLEM Write the cell diagram for a cell that uses the following
half-reactions:
Fe3+(aq, 1 M) + e– ® Fe2+(aq, 1 M) Ø reduction, cathode, right
H2(g, 1 atm) ® 2H+(aq, 1 M) + 2e– Ø oxidation, anode, left
SOLUTION
Anode (left): H2(g, 1 atm) ® 2H+(aq, 1 M) + 2e–
oxidation Need phase boundary and an inert
metal electrode

Cathode (right): Fe3+(aq, 1 M) + e– ® Fe2+(aq, 1 M)

reduction Redox couple in solution, so also need an
inert metal electrode
Cell Diagram:
Pt(s) | H2(g, 1 atm) | H+(aq, 1 M) || Fe3+(aq, 1 M), Fe2+(aq, 1 M) | Pt(s)
Anode Bridge Cathode
Ch14-34 CHEM 3369
 EXAMPLE Interpreting Line Diagrams of Cells
PROBLEM Identify the anode and cathode half-reactions and write
the reaction for the cell:
Cd(s) | Cd2+(aq) || H+(aq) | O2(g) | Pt(s)

Ch14-35 CHEM 3369

 EXAMPLE Interpreting Line Diagrams of Cells
PROBLEM Identify the anode and cathode half-reactions and write
the reaction for the cell:
Cd(s) | Cd2+(aq) || H+(aq) | O2(g) | Pt(s)
Anode Cathode
SOLUTION
Anode (left): Cd(s) ® Cd2+(aq) + 2e–
{ }
2
oxidation
Cathode (right): O2(g) ® 2H2O(l)
reduction
O2(g) + 4H+(aq) ® 2H2O(l)
O2(g) + 4H+(aq) + 4e– ® 2H2O(l)

Cell Reaction: 2Cd(s) ® 2Cd2+(aq) + 4e–

O2(g) + 4H+(aq) + 4e– ® 2H2O(l)
2Cd(s) + O2(g) + 4H+(aq) ® 2Cd2+(aq) + 2H2O(l)
Ch14-36 CHEM 3369
 Chapter 14b
Zn-Ag battery
invented by
Alessandro Volta
in 1799

Electrode
Potentials
Saturated
calomel
electrode
(S.C.E)

Silver-silver chloride Lithium-ion battery

reference electrode
Ch14-37 CHEM 3369
 Cell Potential::
14-3
Output of
a Galvanic Cell

Ch14-38 CHEM 3369

 Cell Potentials, Ecell
Ø The kinetic energy of electrons moving through an external
circuit of electrochemical cell is called an electrical energy.
Ø This electrical energy is proportional to the difference in
electrical potential between the two electrodes, which is called
the cell potential (Ecell); it is also called the voltage of the cell
or the electromotive force (emf).
Ø Electrons flow from the negative to the positive electrode, that
is toward the electrode with the more positive electrical
potential.
Ø Consequently,
Ecell > 0 (positive potential) for a spontaneous process (DG < 0)
Ecell < 0 (negative potential) for a nonspontaneous process (DG > 0)
Ecell = 0 (zero potential) for a process at equilibrium (DG = 0)
Ch14-39 CHEM 3369
 Relating Ecell to Energy and Charge
Ø The cell potential, which is measured in units of volts (V), is a
measure of how
hard the electrons in the external circuit of
the cell are pushed from the anode to the cathode.
1 joule of heat
Heater given off

1 V = 1 J/C
+1.0 V + Flow of 1 coulomb of charge
(1.04´10–5 moles of electrons)
Voltage
source
– e–

Ø The SI units of volts is defined such that when 1 coulomb (C)

of charge moves from the anode to cathode, with a potential
difference of 1 volt between the two electrodes, 1 joule (J) of
energy is released.
Ch14-40 CHEM 3369
 Standard Cell Potentials, !°"#$$
Just as for other
thermodynamic properties,
we define a standard cell
potential (!°"#$$ ), the
measured cell potential at 1M
a specific temperature 1M
(usually 298 K) and
standard state conditions:
1 atm for gases, 1 M for
solutions, the pure solid
The zinc-copper cell, operating at 298 K
for electrodes. under standard state conditions, produces
a voltage of +1.10 V.

Zn(s) + Cu2+(aq; 1 M) ¾® Zn2+(aq; 1 M) + Cu(s) !°"#$$ = +1.10 V

Ch14-41 CHEM 3369
 Standard Electrode Potentials, !°"#$$
Just as a cell reaction can be thought of as the result of two half-
reactions, a cell potential can be thought of as the sum of the two
half-reaction potentials. & ° = + 1.10 V
'())

The half-cell potentials are

called electrode potentials or, if Figure 14-3

the cell is at standard Anode Cathode

conditions, standard electrode (−) (+)
°
potentials (&'()) ).
°
To obtain &'()) , we sum
° ° (1 M) (1 M)
&-./0( and &'-12/0( :
° ° °
&'()) = &-./0( + &'-12/0(
Zn(s) ® Zn2+(aq) + 2e– Cu2+(aq) + 2e– ® Cu(s)
° °
= &/340-14/. + &5(06'14/. °
&-./0( = + 0.76 V °
&'-12/0( = + 0.34 V
E
ce= 0.76 + 0.34 = + 1.10 V (oxidation) (reduction)
Ch14-42 CHEM 3369
 Standard Hydrogen Electrode, S.H.E.
Since an electrode represents only a half-reaction, it is not
possible to measure the absolute
potential of an electrode.
The standard hydrogen electrode (S.H.E.)
provides a reference for measurement of other
electrode potentials.
In the S.H.E. electrode, hydrogen gas at
exactly 1 atm pressure is bubbled over an
inert platinum electrode and into a 1 M
aqueous solution of a strong acid, H+(aq)
[or H3O+(aq)].
The S.H.E. is arbitrarily assigned a potential of 0.000 V:

2H+(aq, 1 M) + 2e– ® H2(g, 1 atm) 1°234323563 = 0 V (exactly)

Ch14-43 CHEM 3369
 Figure 14-6 Determining Unknown !°"#$%&'($$ with S.H.E
Oxidation half-reaction Reduction half-reaction
H2(g) ® 2H+(aq) + 2e– Ag+(aq) + e– ® Ag(s)

°
-./00 = + 0.799 V
Anode Cathode
(−) (+)

-1° = 0 V -.° = + 0.799 V

Overall (cell) reaction

H2(g) + Ag+(aq) ® 2H+(aq) + Ag(s)
° ° ° ° °
-./00 = -45 + -6/7 = -8.:.; + -<=0>/6 = + 0.799 V
Ch14-44 CHEM 3369
 °
Tabulated Values of !"#$%&'($$
Standard electrode potentials are always recorded and tabulated
(Appendix C) as standard reduction potentials.
For instance, for the Zn2+/Zn(s) redox couple:
Zn2+(aq) + 2e– ® Zn(s) E
= – 0.76 V
Reduction potential
Zn(s) ® Zn2+(aq) + 2e– E
= + 0.76 V
Oxidation potential
Reversing a half-reaction changes the sign of the electrode
potential. Thus, for any redox couple,

Oxidation potential = – reduction potential

=>?@@ = =A?HI>EBJK + =JLBHMEBJK
=>?@@ = =ABCDE − =@?GE
Ch14-45 CHEM 3369
 Observed Voltages Can Be Ranged…
oxidant + 2e− ⟶ reductant The more positive
the $° value, the
more readily the
reactant will act as
Cu2+ will Cu will not reduce
oxidize H2 and H+ and Zn2+
an oxidizing agent.
Zn
Strength as an oxidant:
Cu 2 + > H + > Z n 2 +
H+ will oxidize H2 will reduce
Zn but not Cu Cu2+ but not Zn2+

Strength as a reductant:
Z n > H 2 > C u

Zn2+ will not Zn will reduce The more negative

oxidize H2 and Cu H+ and Cu2+ the $° value, the
more readily the
product will act as
a reducing agent.

Ch14-46 CHEM 3369

Electrochemical Series:
Strengths of Oxidizing and Reducing Agents
Table 14-1 Ordered standard reduction potentials
Oxidizing agent Reducing agent E
(V)
F2(g) + 2e– « 2F– 2.890

Reducing power
O3(g) + 2H+ + 2e– « O2(g) + H2O 2.075
MnO4– + 8H+ + 5e– « Mn2+ + H2O 1.507

increasing
Ag+ + e– « Ag(s) 0.799
Oxidizing power

Cu2+ + 2e– « Cu(s) 0.339

2H+ + 2e– « H2(g) 0.000
increasing

Cd2+ + 2e– « Cd(s) –0.402

K+ + e– « K(s) –2.936
Li+ + e– « Li(s) –3.040
the higher (positive) the electrode reduction potential, the stronger the
oxidizing agent the electrode material is
the lower (negative) the electrode reduction potential, the stronger the
reducing agent the electrode material is
Ch14-47 CHEM 3369
 EXAMPLE Relative Oxidizing Strength (Top Hat)
Which is the stronger oxidant under standard conditions, an
acidified KMnO4 solution or an acidified K2Cr2O7 solution?

E
(MnO4–, H+/Mn2+) = +1.507 V

E
(Cr2O72–, H+/Cr3+) = +1.36 V

Ch14-48 CHEM 3369

 EXAMPLE Relative Oxidizing Strength
PROBLEM Which is the stronger oxidant under standard conditions,
an acidified KMnO4 solution or an acidified K2Cr2O7 solution?
E
(MnO4–, H+/Mn2+) = +1.507 V Ø larger E

+ stronger oxidant
E
(Cr2O7 , H /Cr ) = +1.36 V
2– 3+
will be reduced
When you multiply half-reaction by a factor, do not multiply its E

SOLUTION
MnO4– + 8H+ + 5e– ⟶ Mn2+ + 4H2O E
= +1.507 V
Red: { } 6

Ox: { } 5
2Cr3+ + 7H2O ⟶ Cr2O72– + 14H+ + 6e– E
= –1.36 V

Cell: 6MnO4– + 10Cr3+ + 11H2O ⟶ 6Mn2+ + 5Cr2O72– + 22H+

°
;<=>> = (+1.507 V) + (–1.36 V) = + 0.147 V
°
Since ;<=>> > 0, the reaction is spontaneous (ΔG
< 0) and
MnO4– ions will oxidize Cr3+ ions in acidified solution.

Ch14-49 CHEM 3369

 EXAMPLE Direction of Chemical Reaction
PROBLEM Using the electrochemical series, calculate the standard
free energy change (∆" ° in kJ) for a galvanic cell constructed of tin
metal and a solution containing Fe3+ and Fe2+ ions.
E
(Fe3+/Fe2+) = + 0.771 V
E
(Sn2+/Sn(s)) = – 0.141 V

Ch14-50 CHEM 3369

 Using the electrochemical series, predict which species will be
oxidized on Anode in a galvanic cell constructed of tin metal and a
solution containing Fe3+ and Fe2+ ions.
E
(Fe3+/Fe2+) = + 0.771 V
E
(Sn2+/Sn(s)) = – 0.141 V
Click or tap on the species being oxidized on Anode.

Fe3+ Fe2+ Sn2+ Sn(s)

Ch14-51 CHEM 3369

 EXAMPLE Direction of Chemical Reaction
PROBLEM Using the electrochemical series, calculate the standard
free energy change (∆" ° in kJ) for a galvanic cell constructed of tin
metal and a solution containing Fe3+ and Fe2+ ions.
E
(Fe3+/Fe2+) = + 0.771 V Ø higher E
; Fe3+ stronger oxidant
E
(Sn /Sn(s)) = – 0.141 V
2+ than Sn 2+; will be reduced at the

cathode
SOLUTION
Cathode: { Fe3+(aq) + e– ® Fe2+(aq) }  2 :;° = +0.771 V
Anode: Sn(s) ® Sn2+(aq) + 2e– :>° = +0.141 V
Cell Rxn: 2Fe3+(s) + Sn(s) ® 2Fe2+(aq) + Sn2+(aq)
°
:;?@@ = :;° + :>° = (0.771 + 0.141) V = +0.912 V
n = 2 mol e–
° ° = –(2 mol)(9.649104 C/mol)(0.912 J/C)
∆";?@@ = −KL:;?@@
= – 1.76105 J = – 176 kJ
Ch14-52 CHEM 3369
 EXAMPLE More on How to Use !° Potentials (1)
PROBLEM Write (a) the cell diagram, (b) the observed cell reaction,
and (c) calculate the cell potential for the redox couples Cu2+/Cu(s)
(# ° = + 0.339 V) and PbF2(s)/Pb(s) (# ° = – 0.350 V).

Ch14-53 CHEM 3369

 EXAMPLE More on How to Use !° Potentials (1)
PROBLEM Write (a) the cell diagram, (b) the observed cell reaction,
and (c) calculate the cell potential for the redox couples Cu2+/Cu(s)
(# ° = + 0.339 V) and PbF2(s)/Pb(s) (# ° = – 0.350 V).
PLAN
Ø The two redox couples read as:

Cu2+(aq) + 2e– ® Cu(s) E
= +0.339 V

PbF2(s) + 2e– ® Pb(s) + 2F–(aq) E
= – 0.350 V
Ø The redox couple with more positive # ° will be written
as the cathode (reduction) half-reaction — keep # ° sign
Ø The other redox-couple will then be written as the
anode (oxidation) half-reaction — reverse # ° sign
° ° °
Ø #;<== = #>?@ABC@>D (BD>A<) + #E<AF;C@>D (;BCG>A<)
Ch14-54 CHEM 3369
 EXAMPLE More on How to Use !° Potentials (1)
PROBLEM Write (a) the cell diagram, (b) the observed cell reaction,
and (c) calculate the cell potential for the redox couples Cu2+/Cu(s)
(# ° = + 0.339 V) and PbF2(s)/Pb(s) (# ° = – 0.350 V).
SOLUTION
(a) Cell diagram: Pb(s) | PbF2(s) | F–(aq) || Cu2+(aq) | Cu(s)
Anode Bridge Cathode

(b) Cell reaction:

Anode: Pb(s) + 2F–(aq) ® PbF2(s) + 2e– #;° = + 0.350 V
Cathode: Cu2+(aq) + 2e– ® Cu(s) #0° = + 0.339 V

Cell: Pb(s) + 2F–(aq) + Cu2+(aq) ® PbF2(s) + Cu(s)

°
(c) Cell potential: #0=>> = #;° + #0° = + 0.889 V
Ch14-55 CHEM 3369
 EXAMPLE More on How to Use E
Potentials (2)
CourseKey: Given ! ° (Ag+/Ag(s)) = + 0.799 V and ! ° (Cd2+/Cd(s))
= – 0.402 V, (a) write the observed cell reaction and (b) calculate
its potential.

Ch14-56 CHEM 3369

 EXAMPLE More on How to Use E
Potentials (2)
PROBLEM Given ! ° (Ag+/Ag(s)) = + 0.799 V and ! ° (Cd2+/Cd(s))
= – 0.402 V, (a) write the observed cell reaction and (b) calculate
its potential. Must be cathode, ! ° is greater

SOLUTION When you multiply half-reaction

by a factor, do not multiply its E

(a) Cell reaction:
Ag+(aq) + e– ® Ag(s)
Cathode: { }  2 !0° = + 0.799 V

Anode: Cd(s) ® Cd2+(aq) + 2e– !9° = + 0.402 V

Cell: 2Ag+(aq) + Cd(s) ® 2Ag(s) + Cu2+(aq)

°
(d) Cell potential: !0;<< = !9° + !0° = + 1.201 V

Ch14-57 CHEM 3369

 Formal Potential, Ef
Ø Sometimes, multiple reduction potentials are given in Appendix
C for one reaction, as for the AgCl(s)/Ag(s) redox couple:
+0.222 V
AgCl(s
) + e– ® Ag(s aq)
) + Cl–(
+0.197 V (saturated KCl)
ü 0.222 V — standard potential that would be measured in the
cell
S.H.E. || Cl–(aq, 1 M) | AgCl(s) | Ag(s) E
= +0.222 V

ü 0.197 V — potential measured in a cell containing saturated

KCl solution instead of 1 M Cl–(aq):
S.H.E. || Cl–(aq, saturated) | AgCl(s) | Ag(s) Ef = +0.197 V

Ø The potential for a cell containing a specified concentration of

reagent other than 1 M is called formal potential.
Ch14-58 CHEM 3369
 Chapter 14c
Zn-Ag battery
invented by
Alessandro Volta
in 1799

Electrode
Potentials
Saturated
calomel
electrode
(S.C.E)

Silver-silver chloride Lithium-ion battery

reference electrode
Ch14-59 CHEM 3369
 14-4 The Nernst Equation::
Dependence of Cell
Potential on
Concentration

Ch14-60 CHEM 3369

 The Effect of Concentration on Cell
Potential: Nernst Equation
From the thermodynamic free-energy change equation
DG = DG
+ RT ln Q (all conditions)
we can derive the Nernst equation, which describes the
measured cell voltage under any condition of concentrations
°
−$%&'()) = −$%&'()) + RT ln Q
Solving for Ecell, gives
° ,- (at any T )
&'()) = &'()) − ln 0
$% Cell reaction
or, at 25 °C quotient at any
time
5. 578 9:
12344 = 1°2344 − <=> ?
; (at 25 °C)
Ch14-61 CHEM 3369
 EXAMPLE Nernst Equation for a Half-Reaction
PROBLEM #1 Let’s write the Nernst equation for the reduction of
permanganate ions to Mn(II) ions in acidic solution.
!° (MnO4–, H+/Mn2+) = + 1.507 V.

Ch14-62 CHEM 3369

 EXAMPLE Nernst Equation for a Half-Reaction
PROBLEM #1 Let’s write the Nernst equation for the reaction in the preceding
problem, multiplied by 5.
!° (MnO4–, H+/Mn2+) = + 1.507 V.

Ch14-63 CHEM 3369

 EXAMPLE Nernst Equation for a Half-Reaction
PROBLEM #1 Let’s write the Nernst equation for the reduction of
permanganate ions to Mn(II) ions in acidic solution.
!° (MnO4–, H+/Mn2+) = + 1.507 V.
SOLUTION
1. Write a balanced reduction half-cell reaction:

MnO4– + 8H+ + 5e– ® Mn2+ + 4H2O !° = +1.507 V

2. Write the Nernst equation:

0.05916 [Mn2+]
Ecell = +1.507 – ———— log ——————
5 [MnO4–][H+]8

Ch14-64 CHEM 3369

 EXAMPLE Multiplication of a Half-Reaction
PROBLEM #2 Let’s write the Nernst equation for the reaction in
the preceding problem, multiplied by 5.
!° (MnO4–, H+/Mn2+) = + 1.507 V.
SOLUTION
1. Write a balanced half-reaction and multiply all reactants and
products by 5, but do not multiply its !°:
5MnO4– + 40H+ + 25e– ® 5Mn2+ + 20H2O !° = +1.507 V
2. Write the Nernst equation:
0.05916 [Mn2+]5
Ecell = +1.507 – ———— log ———————
25 [MnO4–]5 [H+]40

Ch14-65 CHEM 3369

 EXAMPLE Multiplication of a Half-Reaction
PROBLEM #2 Let’s write the Nernst equation for the reaction in
the preceding problem, multiplied by 5.
!° (MnO4–, H+/Mn2+) = + 1.507 V.
SOLUTION
1. Write a balanced half-reaction and multiply all reactants and
products by 5, but do not multiply its !°:
5MnO4– + 40H+ + 25e– ® 5Mn2+ + 20H2O !° = +1.507 V
2. Write the Nernst equation:
0.05916 [Mn2+]1 5
Ecell = +1.507 – ———— log ——————
(5)(5) [MnO4–]1[H+]8

Ø Take home message: If you multiply half-reaction by any factor,

the value of !° does not change (only n and the exponents in Q
change, but these changes cancel each other).
Ch14-66 CHEM 3369
 EXAMPLE Nernst Equation for a Cell Reaction
PROBLEM #3 Given !°(Cu+/Cu(s)) = + 0.518 V and
!° (Sn2+/Sn(s)) = – 0.141 V, calculate the cell potential when the
concentration of the Cu+ ions is 0.500 M and that of the Sn2+ ions
is 0.0100 M.

Ch14-67 CHEM 3369

 EXAMPLE Nernst Equation for a Cell Reaction
PROBLEM #3 Given !°(Cu+/Cu(s)) = + 0.518 V and
!° (Sn2+/Sn(s)) = – 0.141 V, calculate the cell potential when the
concentration of the Cu+ ions is 0.500 M and that of the Sn2+ ions
is 0.0100 M.
PLAN Step 1. Determine !° (cell):
Ø Write anode (oxidation, change sign of !°) and
cathode (reduction, keep sign of !° unchanged)
reactions.
Ø Multiply the half-reactions as necessary so that
n(anode) = n(cathode). Do not multiply !° ‘s.
Ø Write a net cell reaction and calculate !° (cell).
Step 2. Calculate E (cell):
Ø Write a Nernst equation with Q for the cell reaction
Ø Substitute the values of !° (cell) and concentrations
Ch14-68
and find the E (cell) voltage
CHEM 3369
 EXAMPLE Nernst Equation for a Cell Reaction (cont’d)
PROBLEM #3 Given )°(Cu+/Cu(s)) = + 0.518 V and
)° (Sn2+/Sn(s)) = – 0.141 V, calculate the cell potential when the
concentration of the Cu+ ions is 0.500 M and that of the Sn2+ ions
is 0.0100 M.

SOLUTION Step 1. Determine )° (cell):

Anode: Sn(s) ® Sn2+(aq) + 2e– )<° = +0.141 V

Cu+(aq) + e– ® Cu(s)
Cathode: { }
2 )B° = +0.518 V

Cell: Sn(s) + 2Cu+(aq) ® Sn2+(aq) + 2Cu(s)

°
)BEFF = )<° + )B° = 0.141 + 0.518 = +0.659 V

n = 2 mol e–
Ch14-69 CHEM 3369
 EXAMPLE Nernst Equation for a Cell Reaction (cont’d)
PROBLEM #3 Given 2°(Cu+/Cu(s)) = + 0.518 V and
2° (Sn2+/Sn(s)) = – 0.141 V, calculate the cell potential when the
concentration of the Cu+ ions is 0.500 M and that of the Sn2+ ions
is 0.0100 M.
SOLUTION Step 2. Calculate E (cell):
°
Cell: Sn(s) + 2Cu+(aq) ® Sn2+(aq) + 2Cu(s) 23455 = +0.659 V
[0.500 M] [0.0100 M] n = 2 mol e–

° 0.05916 SnEF
23455 = 23455 − log
C CuF

0.05916 0.0100
23455 = +0.659 − log E = +G. HGG I
2 0.500

Ch14-70 CHEM 3369

 EXAMPLE Different Description of the Same Reaction
Find the voltage of the cell in Figure 14-4 if
the left half-cell contains 0.010 M Cd(NO3)2(aq) and
the right half-cell contains 0.50 M KCl(aq).
!° (Cd2+/Cd(s)) = – 0.402 V and !° (AgCl(s)/Ag(s)) = + 0.222 V.
Cd(s) | Cd2+(aq, 0.010) || AgCl(s) | Cl–(aq, 0.50 M) | Ag(s)

Figure 14-4

ANODE CATHODE
oxidation reduction
occurs occurs
here here

Ch14-71 CHEM 3369

 EXAMPLE Different Description of the Same Reaction
PROBLEM #4 Find the voltage of the cell in Figure 14-4 if the left
half-cell contains 0.010 M Cd(NO3)2(aq) and the right half-cell
contains 0.50 M KCl(aq).
)° (Cd2+/Cd(s)) = – 0.402 V and )° (AgCl(s)/Ag(s)) = + 0.222 V.
Cd(s) | Cd2+(aq, 0.010) || AgCl(s) | Cl–(aq, 0.50 M) | Ag(s)
SOLUTION Step 1. Determine )° (cell):
Anode: Cd(s) ® Cd2+(aq) + 2e– )D° = +0.402 V
AgCl(s) + e– ® Ag(s) + Cl–(aq)
Cathode: { }
2 )G° = +0.222 V

Cell: Cd(s) + 2AgCl(s) ® Cd2+(aq) + 2Ag(s) + 2Cl–(aq)

°
)GHII = )D° + )G° = 0.402 + 0.222 = +0.624 V

n = 2 mol e–
Ch14-72 CHEM 3369
 EXAMPLE Different Description of the Same Reaction
PROBLEM #4 Find the voltage of the cell in Figure 14-4 if the left
half-cell contains 0.010 M Cd(NO3)2(aq) and the right half-cell
contains 0.50 M KCl(aq).
5° (Cd2+/Cd(s)) = – 0.402 V and 5° (AgCl(s)/Ag(s)) = + 0.222 V.
Cd(s) | Cd2+(aq, 0.010) || AgCl(s) | Cl–(aq, 0.50 M) | Ag(s)
SOLUTION Step 2. Calculate E (cell):
Cell: Cd(s) + 2AgCl(s) ® Cd2+(aq) + 2Ag(s) + 2Cl–(aq)
[0.010 M] [0.50 M]
°
56788 = +0.624 V
° 0.05916 n = 2 mol e–
Ecell = 56788 − n log[Cd2+][Cl–]2

0.05916
Ecell = + 0.624 − n log(0.010)(0.50)2 = + 0.701 V

Ch14-73 CHEM 3369

 EXAMPLE Different Description of the Same Reaction
Find the voltage of the cell when given
!° (Cd2+/Cd(s)) = – 0.402 V and !° (Ag+(aq)/Ag(s)) = + 0.799 V.
(Ksp(AgCl) = 1.8
10–10)
Cd(s) | Cd2+(aq, 0.010) || Cl–(aq, 0.50 M), Ag+(aq, ? M) | Ag(s)

ANODE CATHODE
oxidation reduction
occurs occurs
here here

Ch14-74 CHEM 3369

 EXAMPLE Different Description of the Same Reaction
PROBLEM #5 Find the voltage of the cell in Figure 14-4 when given
!° (Cd2+/Cd(s)) = – 0.402 V and !° (Ag+(aq)/Ag(s)) = + 0.799 V.
(Ksp(AgCl) = 1.8
10–10)

CELL Cd(s) | Cd2+(aq, 0.010) || Cl–(aq, 0.50 M) | Ag(s)

SOLUTION Step 1. Determine ! ° (cell):

Anode: Cd(s) ® Cd2+(aq) + 2e– !D° = +0.402 V

Cathode: Ag+(aq) + e– ® Ag(s)
{ }
2 !G° = +0.799 V

Cell: Cd(s) + 2Ag+(aq) ® Cd2+(aq) + 2Ag(s)

°
!GJKK = !D° + !G° = 0.402 + 0.799 = +1.201 V
n = 2 mol e–
Ch14-75 CHEM 3369
 EXAMPLE Different Description of the Same Reaction
Find the voltage of the cell when given
<° (Cd2+/Cd(s)) = – 0.402 V and <° (Ag+(aq)/Ag(s)) = + 0.799 V.
(Ksp(AgCl) = 1.8
10–10)
CELL Cd(s) | Cd2+(aq, 0.010) || Cl–(aq, 0.50 M) | Ag(s)
SOLUTION Step 2. Calculate E (cell):
°
Cell: Cd(s) + 2Ag+(aq) ® Cd2+(aq) + 2Ag(s) <>?@@ = +1.201 V
[0.010 M] n = 2 mol e–
° 0.05916 CDEF
Ecell = <>?@@ − n + log GHF E [Ag+] = Ksp/[Cl–]
[0.50 M]
0.05916 I.IJII
Ecell =+1.201 − 2 + log E = +Q. RQS T
K.L×KNOKN
N.PNN
Both descriptions of the cathode reaction predict the same
voltage, so both are valid — Ag(I) is reduced to Ag(0) in both cases.
Ch14-76 CHEM 3369
 Standard Potential
14-5
and
Equilibrium Constant

Ch14-77 CHEM 3369

 Nernst Equation at Reaction Equilibrium
A galvanic cell produces electricity because the cell reaction is not
at equilibrium
At equilibrium, E(cell) = 0, and Q = K in the Nernst equation
Thus at 25 °C:
E = .° – (0.05916/n) log Q (at any time)
0 = .° – (0.05916/n) log K (at equilibrium)

.° = (0.05916/n) log K
log K = nE°/ 0.05916

K = 10(n.°/0.05916) (at 25 °C)

K = 10(nF.°/2.303RT) (at any temperature)

Ch14-78 CHEM 3369
 PROBLEM Nernst Equation and Reaction Equilibrium
1. Find the equilibrium constant for the reaction.
H2(g) + Cd2+(aq) « 2H+(aq) + Cd(s)
2. At what pH will the reaction above be in equilibrium if we
maintain [Cd2+] = 1 M and PH2 = 1 atm.
3. How can we make the forward reaction spontaneous?
Given .°(Cd2+/Cd(s)) = –0.402 V and .°(H+(aq)/H2(g)) = 0.000 V.

Ch14-79 CHEM 3369

 PROBLEM Nernst Equation and Reaction Equilibrium
Given !°(Cd2+/Cd(s)) = – 0.402 V and !°(H+(aq)/H2(g)) = 0.000 V.
Find the equilibrium constant for the reaction.
H2(g) + Cd2+(aq) « 2H+(aq) + Cd(s)
H2 is oxidized
Cd2+ is reduced
SOLUTION Step 1. Determine !° and n for net reaction:
° = +0.000 V
Ox: H2(g) ® 2H+(aq) + 2e– !9:
n = 2 °
Red: Cd2+ ( aq ) + 2e– ® Cd(s) ! >?@ = −0.402 V
°
Net: H2(g) + Cd2+(aq) ® 2H+(aq) + Cd(s) !>:C = −0.402 V

At standard conditions, i.e., at pH = 0 ([H+] = 1 M),

this reaction is not spontaneous.
Step 2. Write Nernst equation and solve for K
0.05916 COP
! = !° − logL ⟹ L = 10Q.QRSTU = 2.56884×10ZT[
n
Ch14-80
n =2 CHEM 3369
 PROBLEM Nernst Equation and Reaction Equilibrium
Given !°(Cd2+/Cd(s)) = – 0.402 V and !°(H+(aq)/H2(g)) = 0.000 V.
At what pH will the reaction below be in equilibrium if we
maintain [Cd2+] = 1 M and PH2 = 1 atm.
H2(g) + Cd2+(aq) « 2H+(aq) + Cd(s)
SOLUTION Step 2. Write Nernst equation and solve for [H+]:
0.05916 H, -
! = !° − log
–0.402 V n Cd-, Q
RS
n =2 1M 1 atm
At equilibrium E = 0, therefore
0.05916
! = −0.402 − log H, -
2
– log[H+] = (0.402 V)/(0.05916 V) = pH = 6.80
At pH > 6.80 or [H+] < 1.58
10–7 M,
the forward reaction is spontaneous.
Ch14-81 CHEM 3369
 PROBLEM Finding K for Non-Redox Reactions
Given !°(FeCO3(s)/Fe(s)) = –0.756 V and !°(Fe2+/Fe(s)) = –0.44 V,
calculate the solubility product for FeCO3 at 25 °C.
FeCO3(s) « Fe2+(aq) + CO34 2 (aq) Ksp = ?

Ch14-82 CHEM 3369

 PROBLEM Finding K for Non-Redox Reactions
Given !°(FeCO3(s)/Fe(s)) = –0.756 V and !°(Fe2+/Fe(s)) = –0.44 V,
calculate the solubility product for FeCO3 at 25 °C.
FeCO3(s) « Fe2+(aq) + CO34 2 (aq) Ksp = ?
SOLUTION Step 1. Determine !° for net reaction:
(1) FeCO3(s) + 2e– ® Fe(s) + CO34
2 (aq) !L° = –0.756 V
(2) Fe2+(aq) + 2e– ® Fe(s) !3° = –0.44 V
(3) Modified (2) Fe(s) ® Fe2+(aq) + 2e– !2° = +0.44 V
The dissolution reaction is a sum of (1) and (3):

(4) FeCO3(s) ® Fe2+(aq) + CO34

2 (aq) !F° =– 0.316 V
Step 2. Calculate Ksp from !F° = –0.316 V and n = 2:

Ksp = 10(n!°/0.05916) = 102(–0.316)/0.05916) = 2.08
10–11

Ch14-83 CHEM 3369
 PROBLEM Using !° to Find Equilibrium Constant
Given #°(Cl2(g)/Cl–) = +1.36 V and #°(Br2(g)/Br–) = +1.07 V,
calculate the value of equilibrium constant at 25 °C for the reaction
Cl2(g) + 2Br–(aq) « 2Cl–(aq) + Br2(g)

Ch14-84 CHEM 3369

 PROBLEM Using !° to Find Equilibrium Constant
Given #°(Cl2(g)/Cl–) = +1.36 V and #°(Br2(g)/Br–) = +1.07 V,
calculate the value of equilibrium constant at 25 °C for the reaction
Cl2(g) + 2Br–(aq) « 2Cl–(aq) + Br2(g)
Cl2 is reduced Br– is oxidized

SOLUTION Step 1. Determine #° and n for net reaction:

Ox: 2Br–(aq) ® Br2(g) + 2e– ° = −1.07 V
#?@
n = 2 °
Red: Cl2(g) + 2e– ® Cl–(aq) #GHI = +1.36 V
Net: Cl2(g) + 2Br–(aq) ® 2Cl–(aq) + Br2(g) °
#G@L = +0.29 V

Step 2. Calculate K from #° (at 25 °C):

K = 10(n#°/0.05916) = 102(+0.29)/0.05916) = 6.4
109

Ch14-85 CHEM 3369

 14-6 Reference Electrodes:
Half-Cells That Maintain
Known, Constant Potentials

Ch14-86 CHEM 3369

 Finding the Concentration of an Electroactive Analyte

Reference Electrode Indicator Electrode

maintains constant responds to analyte
(reference) potential concentration

Figure 14-10

Figure 14-9

Oxidation Reduction Cell (net)

Ag(s) + Cl– ® AgCl(s) + e– Fe3+ + e– ® Fe2+ Ag(s) + Cl– + Fe3+ ® AgCl(s) + Fe2+
!"° = –0.222 V !$° = +0.771 V °
!$%&& = +0.549 V

° 0.05916 ,-./
Voltage: !$%&& = !$%&& − n log ,-0/ 123
Ch14-87 CHEM 3369
 Silver – Silver Chloride Reference Electrode
Wire lead
Diagram:
Ag(s)|AgCl(s)|KCl(s)|Cl–(aq)|| Air inlet to allow
electrolyte to drain
slowly through
porous plug
Name:
Ag wire bent
Ag | AgCl electrode: into loop

Aqueous solution
saturated with
Half-Cell Reaction: KCl and AgCl

AgCl(s) + e– ® Ag(s) + Cl– AgCl paste

Solid KCl plus

Potentials: some AgCl

@° = + 0.222 V Porous plug for contact

with external solution
Ef (saturated KCl) = + 0.197 V (salt bridge)

Figure 14-11

Ch14-88 CHEM 3369

 Saturated Calomel Reference Electrode
Wire lead
Diagram:
Pt(s)|Hg(l)|Hg2Cl2(s)|KCl(s)|Cl–(aq)|| Pt wire

Whole to allow
drainage through
Name: porous plug

S.C.E. electrode: Liquid Hg

Hg, Hg2Cl2
+ KCl
Half-Cell Reaction:
Glass wool
½Hg2Cl2(s) + e– ® Hg(l) + Cl– Opening
Saturated KCl
solution
Potentials: Solid KCl
D° = + 0.268 V Glass wall

Porous plug
Ef (saturated KCl) = + 0.241 V (salt bridge)
Figure 14-12

Ch14-89 CHEM 3369

 Voltage Conversions
Figure 14-13 Between Different Reference Scales

Ch14-90 CHEM 3369

 Voltage Conversions
Figure 14-13 Between Different Reference Scales

Point A:
Potential vs. S.H.E. = –0.220 V
Potential vs. Ag|AgCl = –0.220 – 0.197 = – 0.417 V
Potential vs. S.C.E. = –0.220 – 0.241 = – 0.461 V

Ch14-91 CHEM 3369

 Voltage Conversions
Figure 14-13 Between Different Reference Scales

Point B:
Potential vs. S.H.E. = +0.230 V
Potential vs. Ag|AgCl = +0.230 – 0.197 = + 0.033 V
Potential vs. S.C.E. = +0.230 – 0.241 = – 0.011 V

Ch14-92 CHEM 3369