Voltaic or Galvanic Cells

Electrochemical cells in which a spontaneous chemical

reaction produces electrical energy.
Th half-cells are physically separated so that electrons
(from redox reaction) are forced to travel through wires
Electrochemistry Lecture 1.2 (external circuit) and this creates a potential difference.
Chem 17
2015 A useful electrical energy is obtained.
Examples of voltaic cells include: car batteries, computer
References/Sources for Pictures and images
batteries, flashlight batteries, etc.
(1) Petrucci
Car batteries consists of voltaic cells connected in series
(2) Whitten (Voltages add up).

Construction of A Simple Voltaic Cell Voltaic Cell (Cell Construction)

Voltaic cells consist of two half-cells which A voltmeter can be inserted into the circuit to measure the
contain the oxidized and reduced forms of an potential difference between the 2 electrodes. (The total cell
potential, Ecell, is measured.)
element (or other chemical species) in contact
with each other. A simple half-cell consists of:
A piece of metal immersed in a solution of its ions. An ammeter can also be inserted to measure the current flow**.
A wire to connect the two half-cells.
And a salt bridge to complete the circuit, maintain
neutrality, and prevent solution mixing.
**Note: the electric current is the result of the spontaneous redox
Zn |Zn+2(1M) || Cu+2(1M) | Cu reaction that occurs in each cell.

Half-cell#1 Bridge Half-cell#2

Voltaic Cell: Purpose of Salt The Zinc-Copper Cell

Bridge Zn |Zn+2(1M) || Cu+2(1M) | Cu *

Salt Bridge= any medium through w/c ions can slowly pass. (e.g.
a piece of a bent tubing w/c is U-shaped. This could be filled with
hot sat. salt/5% agar solution. The ions can still pass through the
gel).
Functions of a salt bridge:
 Allows electrical contact between the two solutions
 Prevents mixing of the electrode solutions
 Maintains the electrical neutrality in each half-cell as ions flow into and out
of the salt bridge. From Petrucci_2010

Standard cell: In which all reactants and products are in their

thermodynamic standard states (1M for dissolved species and 1atm
partial pressure for gases).

1
 The Zn-Cu Cell = Daniel Cell The Zinc-Copper Cell
Zn |Zn+2(1M) || Cu+2(1M) | Cu
Experimental Observation: e- are release in the anode and consumed on the cathode.
Therefore, the e- flow through the wire from Anode to Cathode, as
 Initial voltage is 1.100 volts.
in all electrochemical cells.
 Mass of the Zn electrode decreases. The concentration of
Zn+2 in solution increases as the cell operates.
 The mass of the Cu electrode increases. The concentration

of the Cu+2 ions in solution decreases as the cell operates.

Anode Cathode
e-
- +
Zn Zn+2 + 2e- (Oxidation, anode)
Zn |Zn+2(1M) || Cu+2(1M) | Cu
Cu + 2e  Cu(0) (Reduction, cathode)
+2
2Cl- per every Zn+2 formed 2K+ per every Cu+2 reduced
Overall cell reaction: Zn + Cu+2 Zn+2 + Cu(0)
Zn+2 
|| SO4-2

Voltaic Cell Copper-Silver Cell

As the redox reaction proceeds consuming the reactants, the cell
voltage decreases. When the cell Voltage reaches zero, the
reaction has attained equilibrium and no further net reaction
occurs. As this point, however, the Cu ion concentration in the
cathode cell is not zero.

From Petrucci_2010

Cu | Cu+2(1M) || Ag+ (1M) | Ag *

The Copper-Silver Cell Comparison

Cu |Cu+2(1M) || Ag+(1M) | Ag *
Experimental Observation:
 Initial voltage of the cell is 0.462 Volts.
 Mass of Cu electrode decreases. The Cu+2 ion increases in
the solution around the Cu electrode.
 The mass of the Ag electrode increases. The Ag+ ion
concentration decreases in the solution around the Ag
electrode.
Cu Cu+2 + 2e- (Oxidation, anode, negative)
2{Ag+ + 1e  Ag(0)} (Reduction, cathode, positive)
Overall cell reaction: Cu + Ag+ Cu+2 + Ag
Ions from the salt bridge migrate to maintain electroneutrality. Some
NO3- ions ) from the cathode vessel and Cu+2 ions from the anode
vessel also migrate into the salt bridge.
Cu|Cu+2(1M) || Ag+(1M) | Ag
Zn|Zn+2(1M) || Cu+2(1M) | Cu
Cu+2 ions is more easily reduced (a stronger oxidizing agent) than Zn+2, so Cu+2 oxidizes
metallic Zinc to Zn+2.
Ag+ ion is more easily reduced (stronger oxidizing agent) compared to Cu+2.
Metallic Zn(0) is a stronger reducing agent than metallic Cu(0).
Metallic Cu(0) is a stronger reducing agent than metallic Ag.
Zn+2 < Cu+2 < Ag+ (increasing strength as oxidizing agents).
Ag < Cu < Zn (increasing strength as reducing agents).
There is an activity series (see table Whitten 4/14)
(Li, K, Ca, Na) > Mg, Al, Mn, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, H, Sb, Cu, Hg, Ag, Pt,
Au. (metals above H would readily displace H (H2 gas is produced and the metal is
oxidized).

2
 20-1 Electrode Potentials and
Their Measurement Anode

Cu(s) + 2Ag+(aq) Cu(s) + Zn2+(aq)

Cu2+(aq) + 2 Ag(s) No reaction Cathode

FIGURE 20-1 FIGURE 20-2

Behaviour of Ag+(aq) and Zn+(aq) in the presence of copper An electrochemical half cell
From Petrucci_2010
From Petrucci_2010
Copyright © 2011 Pearson
Canada Inc.

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Measurement of the electromotive force (potential or Ecell = 1.103 V

voltage) of an electrochemical cell The reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) in an
From Petrucci_2010
electrochemical cell
Copyright © 2011 Pearson Copyright © 2011 Pearson
Canada Inc. Canada Inc.
General Chemistry: Chapter 20 Slide 16 of 53

Cell Diagrams and Terminology

Electromotive force, Ecell
The cell voltage or cell potential.
Cell diagram
Shows the components of the cell in a symbolic way.
Anode (where oxidation occurs) on the left.
Cathode (where reduction occurs) on the right.
Boundary between phases shown by |.
Boundary between half cells Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
(commonly a salt bridge) shown by ||. Ecell = 1.103 V

The reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) in an

electrochemical cell

3
 Activity Series of Elements
Galvanic (or voltaic) cells
Produce electricity as a result of spontaneous reactions. There is an activity series (see tables on Gen Chem Books)
(Li, K, Ca, Na) > Mg, Al, Mn, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, H,
Electrolytic cells Sb, Cu, Hg, Ag, Pt, Au.
Non-spontaneous chemical change driven by electricity.
Couple, M|Mn+ (metals above H would readily displace H+; H2 gas is then
A pair of species related by a change in number of e-. produced and the metal is oxidized.
Mg0 + 2H+  Mg 2+ + H2
However, Cu + 2H+  No spontaneous reaction

Copyright © 2011 Pearson

Canada Inc.
General Chemistry: Chapter 20 Slide 19 of 53

Standard Electrode Potentials Standard Electrode Potentials

To measure relative electrode potentials, we
Cu|Cu+2(1M) || Ag+(1M)
| Ag Ecell= 0.462volts must establish an arbitrary standard.
Zn|Zn+2(1M) || Cu+2(1M) | Cu Ecell= 1.100volts
That standard is the Standard Hydrogen
Electrode (SHE).
The magnitude of the total cell’s potential is a
measurement of spontaneity of the redox reaction.
The SHE is assigned an arbitrary voltage of
Higher (more positive) cell potentials indicate greater 0.0000 V
driving force for the reaction as written.

SHE: conventional reference Zinc-SHE Cell

electrode
Contains: Metal coated with Pt
immersed in 1M H+ solution. H2 gas
is bubbled at 1 atm pressure.

H2  2H+ + 2e- Eo=0.0000v Anode

2H+ +2e-  H2 Eo=0.0000v Cathode
From Petrucci_2010

The standard electrode potential of
the other half cell can thus be
determined in reference to SHE.
From Petrucci_2010
SHE (Standard
Hydrogen Electrode
With E= 0.0000volts
For this cell the components are:
A Zn strip immersed in 1.0 M zinc (II) sulfate.
The other electrode is the Standard Hydrogen Electrode.
A wire and a salt bridge to complete the circuit.
The initial cell voltage is 0.763 volts.

4
 Zinc-SHE Cell Copper-SHE Cell
E0
Anode reaction Zn 0  Zn 2 + + 2 e - 0.763 V
Cathode reaction 2 H + + 2 e -  H 2 g  0.000 V
Cell reaction Zn 0 + 2H +  Zn 2 + + H 2 g  E 0cell  0.763 V

The cathode is the Standard Hydrogen Electrode.

Zn reduces H+ to H2.
The anode is Zn metal.
The cell components are:
A Cu strip immersed in 1.0 M copper (II) sulfate.
Zn| Zn(1M) || H+ (1M) |Pt|H2(1atm) The other electrode is a Standard Hydrogen Electrode.
anode cathode A wire and a salt bridge to complete the circuit.
The initial cell voltage is 0.337 volts.

Copper-SHE Cell Uses of Standard Electrode

E0 Potentials, Eo
Anode reaction H 2g   2 H + 2 e
+ -
0.000 V Electrodes that force the SHE to act as an anode are assigned
positive standard reduction potentials.
Cathode reaction Cu 2+
+ 2e  Cu
- 0
0.337 V Electrodes that force the SHE to act as the cathode are assigned
Cell reaction H 2g  + Cu 2+  2H + + Cu 0 E 0cell  0.337 V negative standard reduction potentials. (that is H2 is produced).
Standard electrode (reduction) potentials tell us the tendencies of
half-reactions to occur as written.
In this cell the SHE is the anode
The Cu 2+ ions oxidize H2 to H+. For example, the half-reaction for the standard potassium
The Cu is the cathode. electrode is:
 
The Cu2+ ions are reduced to Cu metal. K e  K 0 0
E = -2.925 V
Pt(s)| H2(1atm)|H+(1M)||Cu+2(1M)| Cu(s) The large negative value tells us that this reaction
Anode. Negative electrode will occur only under extreme conditions.
Cathode, Positive electrode

Uses of Standard Electrode

Potentials, Eo
Reducing
F20 + 2 e-  2 F- E0 = +2.87 V Agents

Oxidation
Positive E0 values denote that the reaction tends to occur Is favored
to the right. 
The larger the positive value, the greater the tendency to
occur to the right. (as written, thus as a reduction
reaction).

It is the opposite for negative values of Eo. Oxidizing

 A larger negative reduction potential, thus mean, it is the Agents
oxidation reaction which is more favored. From Petrucci_2010
Reduction is favored. 

5
 Uses of Eo values
• Use standard electrode potentials to predict
whether an electrochemical reaction at standard
state conditions will occur spontaneously.
• Question: Will Ag+ ions oxidize metallic Zn to
Zn2+ ions, or will Zn2+ ions oxidize metallic Ag
to Ag+ ions?
You do it!
• Steps for obtaining the equation for the
From Petrucci_2010 spontaneous reaction. 

Steps for obtaining the equation for

Deciding which half-reaction the spontaneous reaction.
Choose the appropriate half-reactions from a
would represent the anode table of standard reduction potentials.
versus the cathode Write the equation for the half-reaction with the
more positive E0 value first, along with its E0
Eocell = Eocathode – Eoanode value.
Write the equation for the other half-reaction as
an oxidation with its oxidation potential, i.e.
reverse the tabulated reduction half-reaction and
change the sign of the tabulated E 0.

Steps for obtaining the equation for Electrode Potentials for

the spontaneous reaction. Other Half-Reactions
Balance the electron transfer. (Do not multiply the E0 value with Example: Will permanganate ions, MnO4-, oxidize Fe (II) ions to
the factor used for balancing the equation). Fe(III) ions, or will Fe(III) ions oxidize Mn(II) ions to MnO4- in
Add the reduction and oxidation half-reactions and their acidic solution?
potentials. This produces the equation for the reaction for which Follow the steps outlined in the previous slides.
E0cell is positive, which indicates that the forward reaction is Note that E0 values are not multiplied by any stoichiometric
spontaneous (product-favored). E0 relationships in this procedure.
MnO4-  Mn+2 E0 =+1.510 V
Reduction 2(Ag+ + e -  Ag 0 ) + 0.7994 V
Fe+3  Fe+2 E0 =+0.771V
Oxidation 1(Zn  Zn 2+ + 2 e- ) - (-0.7628 V)
Eocell = Eocathode – Eoanode = [Eo MnO4- /Mn+2] − [Eo Fe+3/Fe+2] = 1.510 - 0.771 = 0.741 V
Cell reaction 2Ag + + Zn 0  2Ag 0 + Zn 2+ E 0cell = +1.5662 V
We put a negative sign, because we reverse the reduction equation and made into an oxidation The more positive value Eo M+n/M is set to be the cathode, less negative value the anode.
reaction. The Eocell we obtain for this process should be equal to that obtain from equation:
Eocell=Eocathode-Eoanode

6
 Standard Electrode Potentials Standard Electrode Potentials
Calculation of E0Cell Calculation of E0Cell
Example: Will permanganate ions, MnO4-, oxidize Fe Example: Will nitric acid, HNO3, oxidize arsenous
(II) ions to Fe(III) ions, or will Fe(III) ions oxidize acid, H3AsO3, in acidic solution? The reduction product
Mn(II) ions to MnO4- in acidic solution? 0 of HNO3 is NO in this reaction.
E
E0
Reduction 1(MnO -4  8H  + 5e -  Mn 2  4H 2 O) + 1.51 V Reduction 2(NO-3  4H  + 3e -  NO  2H 2 O) + 0.96 V
Oxdation 5(Fe 2  Fe 3+ + e - ) - (0.771 V) Oxidation 3(H 3 AsO 3  H 2 O  H 3 AsO 4  2H  + 2e - ) - ( 0.58 V)
2  2
Cell reaction MnO  5Fe  8H  Mn  4H 2 O + 5Fe
-
4
3+
E 0
cell = +0.74 V Cell reaction 2NO -3  3H 3AsO 3  8H   3H 2 O  2NO  4H 2 O + 3H 3 AsO 4  6H 
2NO 3-  3H 3 AsO 3  2H   2NO  H 2 O + 3H 3 AsO 4  6H  E 0cell = +0.38 V

Thus MnO4-, permanganate ions will oxidize Fe(II) ions Eo HNO3/NO= +0.96 V; E0 H3AsO4/H3AsO3= +0.58V
to Fe(III) and are reduced to Mn(II) ions in acidic Eocell = Eocathode – Eoanode = [Eo HNO3/NO] − [Eo H3AsO4/H3AsO3] =
= 0.96− 0.58 = 0.38 V
solution.

Standard Electrode Potentials Standard Electrode Potentials

Extra Exercises: Predict the overall reactions Predict the overall spontaneous reactions for the following
(spontaneous process) for the following combinations of combinations of half-reactions:
half-reactions: Cr2O72-Cr3+; F2 2F-
(a) Fe+3Fe+2/Sn+4Sn+2 (see next few slides for answer) E°Cr2O7/Cr+3= +1.330V; E°F2/F-= +2.870V
E°Fe+3/Fe+2 = +0.771V; E°Sn+4/Sn+2= +0.150V E °cell = +2.870V – 1.330V = 1.540V
3(F2 + 2e-  2F-) +2.870V
(b) SO42-SO2/H3AsO4H3AsO3 HOMEWORK! 2Cr + 7H2O  14H+ + Cr2O72- +6e-
3+ -1.330V
Eo H3AsO4/H3AsO3 = +0.58V 3F2 + 2Cr3+ + 7H2O  6F- + 14H+ + Cr2O72 E °cell = 1.540V
E° SO4-2/SO2 = +0.20V
G o   zFE o cell  6mol e * 96485 J *1.540 V  892kJ
mol eV

Standard Electrode Potentials Reminder: “Standard Conditions”

E °cell = +2.870V – 1.330V = 1.540V Standard Thermodynamic Condition is different
3(F2 + 2e-  2F-) +2.870V from STP (Standard Temperature Pressure for
2Cr + 7H2O  14H+ + Cr2O72- +6e-
3+ -1.330V Gases).
3F2 + 2Cr3+ + 7H2O  6F- + 14H+ + Cr2O72 E °cell = 1.540V Conditions:
G o   zFE o cell  6mol e * 96485 J *1.540 V  892kJ
mol eV T = 25oC (298K) or other indicated Temperature
Electroche mical Notation : Anode || Cathode All reactants and products are at unit activity
2
Pt ( s ) | Cr  3 (1M ), Cr2O7 (1M ), H  (1M ) || F  (1M ) | F2 ( g ,1atm) | Pt ( s) P = 1 atm for gases
1 Molar concentrations for solutions
Reducing Agent: Cr+3 Oxidizing Agent: F2(g)
Pure solids, liquids

7
 The Nernst Equation: Non- The Nernst Equation: Non-
Standard Conditions Standard Conditions
Nernst Equation Nernst Equation
The value of the cell potentials change if conditions are
non-standard (for concentrations or partial pressures).
The Nernst equation describes the electrode potentials at Ecell = Eocell – {(2.303/zF)*RT log Q}
nonstandard conditions. (Ecell)
Ecell = Eocell – {(2.303/zF)*RT log Q}
Or
Where z= no. of mol e- involved in the overall balanced redox
reaction.
F = Faraday’s constant = 96485 J /Volt mol e-
Ecell = Eocell – {(RT ln Q)/zF)}
R = 8.314 J/mol K; T is temperature in K;
Q = reaction quotient

Nernst Equation E for half-reactions

Ecell = Eocell – {(2.303/zF)*(RT log Q)} mOx + ne-  yRed
Therefore, at 25oC E = – (0.0592/z) log [Red]y/[Ox]m
Eo
(2.303) (8.314J/mol-K)(298.15K) = 0.0592 For this half- reaction:
96485 J/V mol-e-

Ecell = Eocell – (0.0592/z) log Q

Cu 2+  e- 
 Cu  E 0 = +0.153 V
The corresponding Nernst equation is:

Note: Use only this equation when T=298.15 K 0.0592

0
Cu +  
 
“n”  #mole electrons transferred in the reaction or half-reaction E=E - log
1 Cu2

Calculation of Half-Cell Potentials

Cu 2+  e- 
 Cu  E 0 = +0.153 V from E0 values.
The corresponding Nernst equation is: What is the electrode potential for a half-cell

E = E0 -
0.0592 Cu   + consisting of a Cd electrode immersed in a
solution that is 0.0150M in Cd+2?
 
log
1 Cu2 Cd2+ + 2e-  Cd E0 Cd+2/Cd(0) = -0.403V
E= E0 – (0.0592/n) log 1/[Cd+2]
If [Cu2+] and [Cu+] are both 1.0 M, i.e. at E= -0.403 – {(0.0592/2) log (1/0.0150) = -0.457V
standard conditions, then E = E0 because the
concentration term equals zero. Negative sign indicates that when this half-cell is coupled with SHE,
the reverse reaction would occur.
Cd|Cd2+(0.0150M) || H+ (1M),H2 (1atm)|Pt Ecell=+0.457V
anode cathode

8
 Nernst Equation is useful to calculate the potential for
Nernst Equation a cell that consists of two nonstandard electrodes

Calculate the electrode potential for a hydrogen

electrode in which the [H+] is 1.0 x 10-3 M and Sample Problem
the H2 pressure is 0.50 atm. Calculate the initial potential of a cell that consists of an
Fe3+/Fe2+ electrode in which [Fe3+]=1.0 x 10-2 M and
log 5.0 10 5 
H
2 H + + 2 e-  0.0592
2 E = E0 - [Fe 2+ ]=0.1 M connected to a Sn4+ /Sn2+ electrode in
2
PH 2

0.50  which [Sn4+]=1.0 M and [Sn2+]=0.10 M . A wire and
Q=
H  1.0 10 
+ 2 3 2 E 0
0.0592
5.699 salt bridge complete the circuit.
2
Q  5.0 10 5 E  0.168 V
Negative Ecell signifies that the reverse reaction is the Pt|Sn+2(0.10M), Sn+4(1.0M) || Fe+3(0.01M), Fe+2(0.1M)|Pt
spontaneous process What is the E for this non-standard conditions?

More Nernst Equation Nernst Equation

Practice Exercise Practice Exercise
Calculate the E°cell first. E0 Substitute the ion concentrations into Q to
Reduction 2Fe3+ + e  Fe2 +  0.771 V calculate Ecell.
Oxidation 
1 Sn 2+  Sn 4+ + 2 e -  - 0.15V
0.0592
Cell reaction 2 Fe  Sn3+ 2+
 2 Fe  Sn E 0cell  0.62 V
2+ 4+ Ecell = E 0cell - log Q
2
 Sn 
2
Pt|Sn+2(1M), Sn+4 (1.0M)||Fe+3(1M), Fe+2(1M)|Pt E0=0.62V 0.0592 Fe2  4
= 0.62 V - log
 Sn 
2
2 Fe 3 2

Pt|Sn+2(0.10M), Sn+4(1.0M) || Fe+3(0.01M), Fe+2(0.1M)|Pt Ecell = 0.62 V-

0.0592
log
010
.  10
.
2


. 102 010.  
2
What is the E for this non-standard conditions? 2 10

Practice Exercise

E cell = 0.62 V -
0.0592
log
0.10 1.0  2

2 2

1.0 10 2 0.10   How do we relate the constant
E cell  0.62 V -
0.0592
3.00 of equilibrium, K with the Eocell ?
2
E cell  0.62  0.09 V
E cell = 0.53 V

Pt|Sn+2(0.10M), Sn+4(1.0M)||Fe+3(0.01M), Fe+2(0.1M)|Pt E =0.53V

9
 Relationship of E0cell to G0 and K Relationship of E0cell to G0 and K

ΔG0 = -2.303 RT log K When combined together:

or
ΔG = - RT ln K
0

ΔG0 = -z F E0cell
Where
F= 96485 J/V mol e- Lesson: We can solve for the equilibrium constant given the
z= no.of e- involved (in balanced rexn) standard cell potential and the number of e- involved in the redox.

Relationship of E0cell to G0 and K Relationship of E0cell to G0 and K

Calculate the standard Gibbs free energy change, G0 , at Now that we know the E0 then we can calculate
250C for the following reaction. G0
2 2
Pb  Cu  Pb  Cu G 0   n F E 0cell
Calculate E0cell using the appropriate half- reactions
0
 
G 0   2 mol e  96,500 J
V mol e -
0.463 V  
E
G 0  8.94 10 4 J (per " mol of rxn" )
Cu 2   2 e   Cu 0 0.337 V
G 0  -89.4 kJ
2
Pb  Pb  2 e 
- - 0.126 V 
Cu 2   Pb  Pb 2  Cu 0 E0cell  0.463 V

Relationship of E0cell to G0 and K How do we calculate for ΔG or

Calculate the thermodynamic equilibrium constant for
K if the conditions are
the reaction in previous example (at 250C). non-standard?
G 0   RT ln K  Calculate first Q and then using
Nernst Equation the Ecell
G 0  8.94 10 4 J
mol
ln K  

 RT - 8.314 J
mol K
 
298 K 
then use:
ΔG = - z F Ecell
ln K  36.1 K  5 1015 
 
Pb 2 
 
However, K is associated with standard conditions only.
Cu 2 
2 2
Note: ln K = -nFEocell/RT
Pb  Cu  Pb  Cu

10
 1st Step: Calculate E0cell 2nd Step: Calculate Ecell
Calculate the Gibbs Free Energy change, G and the equilibrium constant
at 25C for the following reaction with the indicated concentration
Zn  2 Ag  0.30 M  2Ag  Zn 2 0.50 M 
Use the Nernst equation to calculate E cell for the given
Zn  2 Ag  0.30 M  2Ag  Zn 2 0.50 M  concentrations.

Again, first we calculate the E0 Zn   0 .50   5 .6

2+

Ag  0 .30 
0
E Q=
+ 2 2

2Ag  e  Ag
 - 0
 0.799 V
log 5.6 = 0.748
Zn 0
 Zn  2e 
2 -
- - 0.763 V 
0 . 0592
E cell  E 0cell  log Q
2 Ag  Zn0  2 Ag0  Zn2  E0cell  1.562 V 2

Zn  2 Ag  0.30 M  2Ag  Zn 2 0.50 M  Zn  2 Ag  0.30 M  2Ag  Zn 2 0.50 M 

Ecell = +1.540 V, compared to E0cell = +1.562 V.
Zn  0.50  5.6
2+
We can use this information to calculate G.

Ag  0.30
Q=
+ 2 2

ΔG = - n F Ecell
log 5.6 = 0.748 ΔG = - {(2 mol e-)(96485 J/V mol e-)(1.540V)
0.0592 ΔG = - 2.97x105 Joules
Ecell  E0cell  log Q
2 ΔG = -297 kJ (per mol rxn)
0.0592
Ecell  1.562V - log5.6V The negative ΔG tells us that the reaction
2
Ecell = 1.540V is spontaneous.

We can calculate K. But caution, it is Guide for calculations (Standard

always derived from E0 cell Conditions)
Equilibrium constants do not change with reactant concentration.
We should use the value of E0cell at 250C to get K. Why?
Recall at Equilibrium: ΔG = 0; Ecell=0; therefore,
E0cell = (2.303RT/nF) log K or (RT/nF)ln K

- nFE0cell = - RT ln K
ln K = (nFE0cell)/RT
ln K = (2mol e-)(96485 J/V-mol e)(1.562 V)
(8.314 J/mol K) (298.15K)
K = 6.44x105 = [Zn+2]/[Ag+]

11
 Ecell as a Function of Concentration

Special Topics/Applications ΔG = ΔG° - RT ln Q

related to Voltaic/ -zFEcell = -zFEcell° - RT ln Q

Galvanic Cells RT
Ecell = Ecell° - ln Q
Concentration Cells zF
FIGURE 20-9
Batteries Convert to log10 and calculate constants.
Variation of Ecell with ion concentrations

Corrosion
0.0592 V
Ecell = E°cell - log Q The Nernst Equation
z

Concentration Cells
Two half cells with identical electrodes but different ion concentrations.
2 H+(1 M) → 2 H+(x M) 0.0592 V
Ecell = Ecell° - log Q
Pt|H2 (1 atm)|H+(x M)||H+(1.0 M)|H2(1 atm)|Pt(s) z
E°cell = E°H+/H2 - E°H+/H2 = 0
0.0592 V x2
Ecell = Ecell° - log
2 H+(1 M) + 2 e- → H2(g, 1 atm) z 12
but we can calculate 0.0592 V x2
H2(g, 1 atm) → 2 H+(x M) + 2 e- Ecell = 0 - log
using the Nernst Equation 2 1

2 H+(1 M) → 2 H+(x M) Ecell = - 0.0592 V log x

E°cell = E°H+/H2 - E°H+/H2 = 0 Ecell = (0.0592 V) pH

FIGURE 20-11 Although Eocell is zero, if you vary the
A concentration cell concentrations, then you will get a
positive Ecell

Measurement of Ksp
Ag|Ag+(sat’d AgI)||Ag+(0.10 M)|Ag(s)

Ag+(0.100 M) + e- → Ag(s)

Ag(s) → Ag+(sat’d) + e-

Ag+(0.100 M) → Ag+(sat’d M) 0.22233 V

0.2680 V (sat’d KCl)

or
A concentration cell for determining Ksp of AgI 0.2412 V (1 M KCl)
Schematic diagrams of some common electrodes
Slide 72 of 53

12
 The Glass Electrode and the Electrochemical Measurement of
pH
20-5 Batteries: Producing Electricity
Ag|AgCl(s)|Cl-(1.0M),H+(1.0M)|glass membrane|H+(unknown)|| Cl-(1.0 M)|AgCl(s)|Ag(s)
Through Chemical Reactions
Ag(s) + Cl- AgCl(s) + e- Primary Cells (or batteries).
H+(1.0 M) H+(unknown) Cell reaction is not reversible.
AgCl(s) + e- Ag(s) + Cl-(aq) Secondary Cells (e.g. Rechargeable batteries)
ΔG = G(unknown) – G(1.0M) Cell reaction can be reversed by passing electricity
= G° + RTln[unknown] – G° - RTln(1.0) through the cell (charging).
=RTln[unknown] Flow Batteries and Fuel Cells.
E°cell = -RTln[unknown]/zF Materials pass through the battery which converts
chemical energy to electric energy.
pH = -log[unknown]=zFE°cell/RT

The Leclanché
The alkaline cell
Dry Cell
Reduction: 2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH-
Oxidation: Zn(s) → Zn2+(aq) + 2 e-
Oxidation reaction can be thought of in two steps:
Reduction: 2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH-
Zn(s) → Zn2+(aq) + 2 e-
Acid-base reaction: NH4+ + OH- → NH3(g) + H2O(l)
Zn2+(aq) + 2 OH- → Zn (OH)2(s)
Precipitation reaction: NH3 + Zn2+(aq) + Cl- → [Zn(NH3)2]Cl2(s)
Zn (s) + 2 OH- → Zn (OH)2(s) + 2 e-

The Lead-Acid (Storage) Battery Reduction:

PbO2(s) + 3 H+(aq) + HSO4-(aq) + 2 e- → PbSO4(s) + 2 H2O(l)

Oxidation:
Pb (s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2 e-

PbO2(s) + Pb(s) + 2 H+(aq) + HSO4-(aq) → 2 PbSO4(s) + 2 H2O(l)

E°cell = E°PbO2/PbSO4 - E°PbSO4/Pb = 1.74 V – (-0.28 V) =

2.02 V

FIGURE 20
The lead-acid (storage) cell

Slide 77 of 53

13
The Silver-Zinc Cell: A Button The Nickel-Cadmium Cell: A
Battery Rechargeable Battery

Zn(s),ZnO(s)|KOH(sat’d)|Ag2O(s),Ag(s) A rechargeable nickel-cadmium cell, or nicad battery

Zn(s) + Ag2O(s) → ZnO(s) + 2 Ag(s) Ecell = 1.8 V Cd(s) + 2 NiO(OH)(s) + 2 H2O(L) → 2 Ni(OH)2(s) + Cd(OH)2(s)

The Lithium-Ion Battery Fuel Cells

O2(g) + 2 H2O(l) + 4 e- → 4 OH-(aq)

2{H2(g) + 2 OH-(aq) → 2 H2O(l) + 2 e-}

2H2(g) + O2(g) → 2 H2O(l)

E°cell = E°O2/OH- - E°H2O/H2

= 0.401 V – (-0.828 V) = 1.229 V

FIGURE 20-17 FIGURE 20-18  = ΔG°/ ΔH° =

The electrodes of a lithium-ion battery A hydrogen-oxygen fuel cell
0.83
Copyright © 2011 Pearson
Slide 81 of 53 Canada Inc.
General Chemistry: Chapter 20 Slide 82 of 53

Air Batteries
4 Al(s) + 3 O2(g) + 6 H2O(l) + 4 OH- → 4 [Al(OH)4](aq)
Special Topic: Corrosion
How to prevent corrosion: the
unwanted oxidation oxidation of metals?

A simplified aluminum-air battery

14
 Petrucci FIGURE 20-20
20-6 Corrosion: Unwanted
In neutral solution:
Voltaic Cells Anode Basic Media

O2(g) + 2 H2O(l) + 4 e- → 4 OH-(aq) EO2/OH- = 0.401 V

Cathode
2 Fe(s) → 2 Fe2+(aq) + 4 e- EFe/Fe2+ = -0.440 V
Zn Anode With Zn With Cu Cu Cathode
2 Fe(s) + O2 (g) + 2 H2O(l) → 2 Fe2+(aq) +4 OH-(aq)
Corroded
Ecell = 0.841 V (oxidized)
In acidic solution: Iron at
Anode
O2(g) + 4 H+(aq) + 4 e- → 4 H2O (aq) EO2/OH- = 1.229 V
Demonstration of corrosion and methods of corrosion
protection

Zn is preferentially
oxidized before Fe

Defects allow
penetration of
oxygen and water

Defects allow Magnesium sacrificial anodes

Petrucci FIGURE 20-21 penetration of The small cylindrical bars of magnesium attached to the steel ship
Protection of iron against electrolytic corrosion oxygen and water provide cathodic protection against corrosion.

A more effective way of studying?

ELECTROLYSIS Don’t just read examples, work them!!

If you write:
Information is going through your fingers,

See next file Your muscles,

Your nerves,
Directly to your brain.
Physically experience the solution.
Your eyes and ears are not enough.

15