Electrochemistry II Calculate E° & 'G° for the following galvanic cell:

Au(s) | Au3+(1 M) || Ca2+(1 M) | Ca(s)

“I require a term to express those bodies which can pass to the

electrodes, or, as they are usually called, the poles. I propose to
distinguish these bodies by calling those anions which go to the
anode of the decomposing body; and those passing to the cathode,
cations; and when I have occasion to speak of these together, I shall
call them ions.”

í Michael Faraday

E°cell and Ecell

2

What is the equilibrium constant for the following reaction

at 250C? Fe2+(aq) + 2 Ag(s) Fe(s) + 2 Ag+(aq)

3 4
 Is this rxn thermodynamically favored at 25°C? Standard Reduction Potential
Explain. Fe2+(aq) + 2 Ag(s) Fe(s) + 2 Ag+(aq)
Standard reduction potential (E0) is the voltage associated
with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.

Standard hydrogen electrode

(SHE)

Reduction Reaction
What is the equilibrium constant for the following reaction
at 25°C? Fe(s) + 2 Ag+(aq) Fe2+(aq) + 2 Ag(s) 2e- + 2H+ (1 M) H2 (1 atm)

E0 = 0 V

This is the reference all other

oxidations are compared to
5 6

Determining Standard Reduction Potential of Zn

Standard
Reduction
Potentials
are
Measured
against
the
Standard Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)
Hydrogen
Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Electrode
Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)

7 Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm)8

 Determining Standard Reduction Potential of Zn Determining Standard Reduction Potential of Cu
0 = 0.76 V
Ecell
0 = 0.34 V
Ecell
0 = E0
Ecell 0
cathode - Eanode
0 = E 0 2+
Ecell 0
0 ) Cu /Cu – EH +/H2
Standard emf (Ecell
0 2+
0.34 = ECu /Cu - 0
0
Ecell = 0
Ecathode - 0
Eanode 0 2+
ECu /Cu = 0.34 V

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)
0 = E 0+ - E 0 2+
Ecell H /H2 Zn /Zn
Anode (oxidation): H2 (1 atm) 2H+ (1 M) + 2e-
0.76 V = 0 - EZn 0 2+
/Zn
0 2+
EZn = -0.76 V Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
/Zn

Zn2+ (1 M) + 2e- Zn E0 = -0.76 V 9 H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M) 10

Ecell & Rxn Direction Quantitative Effect of Concentration on Ecell

'G = 'G0 + RT ln Q
2 Cr(s) + 3 Cd2+(aq) ' 3 Cd(s) + 2 Cr3+(aq)
'G0 = -nFE 0 'G = -nFE
Changes in anode or cathode solution
concentration will affect Ecell -nFE = -nFE0 + RT ln Q
If [Cd2+] decreases:
Walther Nernst
Nernst Equation (1864 – 1941)
2 Cr(s) + 3 Cd2+(aq)  3 Cd(s) + 2 Cr3+(aq)
Fewer e– transferred in forward direction o Ecell decreases
q RT q 0.0592
Ecell Ecell  ln Q Ecell Ecell  log Q
If [Cr3+] decreases: nF n
2 Cr(s) + 3 Cd2+(aq)  3 Cd(s) + 2 Cr3+(aq)
more e– transferred in forward direction o Ecell increases T z 298 K T = 298 K
11 Quantitative use of Nernst Equation is no longer assessed on AP Chem 12Exam!
 What is the Ecell for the following rxn at 25°C if
Nernst Equation: E° and K [Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
At equilibrium, forward and reverse reactions Fe2+(aq) + Cd(s) Fe(s) + Cd2+(aq)
occur at equal rates, therefore:
Oxidation: Cd Cd2+ + 2e-
1. The battery is “dead” n=2
Reduction: 2e- + Fe2+ 2Fe
2. The cell potential, E, is zero volts
0
E0 = EFe 0
2+/Fe – ECd2+/Cd

Modifying the Nernst Equation (at 25 qC): E0 = -0.44 – (-0.40)

[Cd2+]
Q=
E0 = -0.04 V [Fe2+]
0.0592
0 volts E 0  log K E = E0 –
0.0592
log Q
n n
0.0592 0.010
nE° E = – 0.04 V – log
log K = 2 0.60
0.0592 E = 0.013 V
13 14

Qualitative Effect of Concentration on Ecell Qualitative Effect of Concentration on Ecell

• Consider cell potential, E, as the driving force toward H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M)
equilibrium E° = 0.34 V
• The farther a rxn is from equilibrium, the greater the
Q
> products@ K !1
magnitude of E (either + or -)
> reactants@
• As rxn approaches equilibrium, magnitude of E
decreases until… Q<1 Q=1 1<Q<K Q=K Q>K
• …E = 0 at equilibrium (when Q = K) and cell is “dead”
• E° is determined when Q = 1 E > E° E = E° E < E° E=0 E<0
• If rxn is further from equilibrium than Q = 1, then
magnitude of E increases relative to E°
E > 0.34 V E= 0.34 V 0.34 V > E > 0 V E = 0 V E = x V
• If rxn is closer to equilibrium than Q = 1, then
magnitude of E decreases relative to E° 15 16
 What happens to Ecell for the following rxn at Qualitative Effect of Concentration on Ecell
25°C if [Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+(aq) + Cd(s) Fe(s) + Cd2+(aq) • As conditions better enable the thermodynamically
0 0
favorable direction, there is a stronger drive to
Oxidation: Cd Cd2+ + 2e- E0 = EFe 2+/Fe – ECd2+/Cd
transfer electrons (reflected by higher E)
Reduction: 2e- + Fe2+ 2Fe E0 = -0.44 – (-0.40)
• In general, increasing the concentration of reactants
E0 = -0.04 V
or decreasing the concentration of products (such
nFE  RT ln K that Q < K) increases the driving force for the
ª¬Cd 2 º¼ 0.010
(2)(96485)( 0.04) Q reaction, resulting in a higher emf (E).
(8.314)(298) 0.60
K e nFE / RT e ª¬ Fe 2 º¼ • Conversely, decreasing the concentration of
0.044 0.0167 reactants or increasing the concentration of products
(such that Q > K) causes the emf (E) to decrease
Rxn is closer to equilibrium than Q = 1, so from its value under standard conditions.
magnitude of E decreases relative to E°
17 18
(E becomes less negative).

Qualitative Effect of Concentration on Ecell What happens to Ecell for the following rxn at
25°C if [Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Q Thermodynamically Favored E
Fe2+(aq) + Cd(s) Fe(s) + Cd2+(aq)
Rxn Direction
Oxidation: Cd Cd2+ + 2e- 0
E0 = EFe 0
2+/Fe – ECd2+/Cd
<1 forward E > E°
(strongly) Reduction: 2e- + Fe2+ 2Fe E0 = -0.44 – (-0.40)
=1 forward E = E° E0 = -0.04 V
1 <Q<K forward (weakly) E < E° nFE  RT ln K
=K equilibrium E=0 ª¬Cd 2 º¼ 0.010
(2)(96485)( 0.04) Q
(8.314)(298) 0.60
>K reverse E<0 K e nFE / RT e ª¬ Fe 2 º¼
0.044 0.0167
Q < K, so rxn shifts towards the thermodynamically
Watch out for signs of E and E°! favored direction. The magnitude of E decreases
19 relative to E° (becomes less negative). 20
 Concentration Cell Concentration Cell
A galvanic cell in which both compartments The direction of spontaneous electron flow
have the same components but at different can be determined by considering the
concentrations. direction needed to reach equilibrium.
??? ???

Steps to qualitatively and First, determine which side undergoes oxidation,

quantitatively determine Ecell 21 and which side undergoes reduction. 22

??? ???
Concentration Cell II
Concentration Cell III

Concentration Cell

Both sides have

Anode Cathode the same Anode Cathode
components but
at different
concentrations.

The 1.0 M Zn2+ must decrease in concentration, and For qualitative cell potential relate E with progress
the 0.10 M Zn2+ must increase in concentration in towards equilibrium in thermodynamically favored
order to reach equilibrium. direction. Zn2+ (1.0M) Æ Zn2+ (0.10M)
Zn2+ (1.0M) + 2e- Æ Zn (reduction) Electrons will spontaneously flow from anode to
Zn Æ Zn2+ (0.10M) + 2e- (oxidation) cathode. Ecell starts off greater than 0 V, decreases
as equilibrium is approached, and then becomes 0 24V
Zn2+ (1.0M) Æ Zn2+ (0.10M) 23
once equilibrium is established.
 ???
Concentration Cell III Quantitative Determination of Ecell
Concentration Cell
Zn2+ (1.0M) Æ Zn2+ (0.10M)
Anode Cathode
0.0592
E E0  log Q
n
For quantitative cell potential use the Nernst 0 (0.10)
Equation (assuming 25 qC). E 0.0 Volts n 2 Q
Zn2+ (1.0M) Æ Zn2+ (0.10M)
(1.0)
0.0592 0.0592 0.10
0 E 0.0  log( ) 0.030V
E E  log Q 2 1.0
n 25 26

A Concentration Cell That For the following cell at 25°C:

Contains a Silver Electrode a) Label the anode & cathode. Justify your claim.
and Aqueous Silver Nitrate b) Indicate electron flow
in Both Compartments c) Describe and explain the changes in
i) Ecell
ii) 'G

As long as
[X+] +
anode < [X ]cathode

Ecell > 0.00 V

27 28
 For the following cell at 25°C: For the following cell at 25°C:
a) Label the anode & cathode. Justify your claim. c) Describe and explain the changes in
b) Indicate electron flow i) Ecell
e–

29 30

For the following cell at 25°C: Batteries

c) Describe and explain the changes in

ii) 'G
Dry cell

Leclanché cell

Anode: Zn (s) Zn2+ (aq) + 2e-

Cathode: 2NH+4 (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

31 32
 Batteries II Batteries III

Mercury Battery Lead storage

battery

Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e- Anode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e-

Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq) Cathode: PbO2 (s) + 4H+ (aq) + SO2- - PbSO4 (s) + 2H2O (l)
4 (aq) + 2e

Zn(Hg) + HgO (s) ZnO (s) + Hg (l) Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-
4
(aq) 2PbSO4 (s) + 2H2O (l)

33 34

Batteries IV Fuel Cells

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)

2H2 (g) + O2 (g) 2H2O (l)

35 36
Solid State Lithium Battery
 Chemistry In Action: Bacteria Power
SHE Animation
CH3COO- + 2O2 + H+ 2CO2 + 2H2O http://www.chem.iastate.edu/group/Greenbowe/sections/
projectfolder/animations/SHEZnV7.html

Interactive: Concentration Cells

http://www.chem.iastate.edu/group/Greenbowe/sections/
projectfolder/flashfiles/electroChem/voltaicCellEMF.swf
Battery Animation
http://www.chem.iastate.edu/group/Greenbowe/sections/
projectfolder/animations/ZnCbatteryV8web.html

Lead Battery
http://www.wainet.ne.jp/~yuasa/flash/EngLead_Storage_Battery.swf

Fuel Cell Animation

37 38
http://www.wainet.ne.jp/~yuasa/flash/EngFuel_Cell.swf

For the following cell at 25°C: Answers

b)
a) Label the anode & cathode 0.0592 0.01
b) Calculate Ecell E 0.0  log( ) 0.030V
c) Calculate 'G 2 0.1
c) 'G = -nFE
'G = í(2)(96500)(0.030) = í 5.8 u 103 J

ANODE CATHODE

39 40