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CHM431/432 FUNDAMENTAL TO PHYSICAL CHEMISTRY

At the end of this chapter , students should be able to
1. Write balanced half-cell reaction and overall cell reaction for
electrochemical processes.
2. Explain the differences between voltaic and electrolytic cell.
3. Understand the relationship between chemical energy (Gibbs free energy
change for a redox reaction) and electrical,energy (electromotive force or
cell potential) in an electrochemical cell.
4. Calculate cell potentials for electrochemical cells using the Nernst
equation.
5. Relate the concentration of solutes to the cell potential
6. Explain the nature of electrolysis and use the electrolysis information
quantitatively

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▪ All electrochemical processes involve the movement of electrons from
one chemical species to another species
▪ Oxidation (electron loss) always accompanies reduction (electron
gain).
▪ The number of electrons gained by the oxidizing agent always equals
the number lost by the reducing agent.

Zn loses electrons. Hydrogen ion gains

electrons.
Zn is the reducing
agent and becomes Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) Hydrogen ion is the oxidizing agent
oxidized. and becomes reduced.
The oxidation number The oxidation number of H
of Zn increases from 0 decreases from +1 to 0.
to +2.
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1. Free elements have an oxidation state of 0. (e.g., He, N2, O2 has an oxidation state of 0)
2. The oxidation state of one atom ion must equal the net charge. (e.g., F- oxidation state
is -1, K+ oxidation state is +1)
3. The sum of the oxidation state has to equal the total net charge for a compound. (e.g.,
MnO4- has a net charge of -1, Mn(+7)O4(-8)= -1)
4. The alkali metals (Group I elements) have an oxidation state of +1. (e.g., Li2O, Li= +1)
5. The alkaline earth metals (Group II elements) always have an oxidation state of +2.
(e.g., CaO, Ca=+2)
6. Oxygen has an oxidation state of -2 in a compound
7. Fluorine has an oxidation state of -1 in a compound
8. Hydrogen has an oxidation state of +1 in a compound.
9. Transition metals and other metals may have more than one common ionic charge.
(e.g., Chromium's common ionic charges are Cr+2 and Cr+3)

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 Balancing Redox Reactions in Acidic Solution

Cr2O72-(aq) + I-(aq) Cr3+(aq) + I2(aq)

1. Divide the reaction into half-reactions -

Determine the O.N.s for the species undergoing redox.
How to calculate oxidation
number of Cr in Cr2O72-?
+6 -1 +3 0
2Cr + 7(-2) = -2
Cr = +6
Cr2O7 (aq) + I-(aq)
2- Cr (aq) + I2(aq)
3+

Cr2O72- Cr3+ Oxidation number of Cr is decreased from +6 to +3 → reduction

I- I2 Oxidation number I is increased from -1 to 0 → oxidation

2. Balance atoms and charges in each half-reaction -

14H+(aq) + Cr2O72- 2 Cr3+ + 7H2O(l)

Net charge: +12 Net charge: +6 Add 6e- to left.
6e- + 14H+(aq) + Cr2O72- 2 Cr3+ + 7H2O(l)
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net: +6 net: +6
 Balancing Redox Reactions in Acidic Solution

6e- + 14H+(aq) + Cr2O72- 2 Cr3+ + 7H2O(l)

2 I- I2 + 2e-

Cr(+6) is the oxidizing agent and I(-1) is the reducing agent.

3. Multiply each half-reaction by an integer, if necessary -

2 I- I2 + 2e- X3

4. Add the half-reactions together -

6e- + 14H+ + Cr2O72- 2 Cr3+ + 7H2O(l)
6 I- 3 I2 + 6e-

14H+(aq) + Cr2O72-(aq) + 6 I-(aq) 2Cr3+(aq) + 3I2(s) + 7H2O(l)

Do a final check on atoms and charges.

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 Balancing Redox Reactions in Basic Solution

Balance the reaction in acid and then add OH- so as to neutralize

the H+ ions.

14H+(aq) + Cr2O72-(aq) + 6 I-(aq) 2Cr3+(aq) + 3I2(s) + 7H2O(l)

+ 14OH-(aq) + 14OH-(aq)

14H2O + Cr2O72- + 6 I- 2Cr3+ + 3I2 + 7H2O + 14OH-

Reconcile the number of water molecules.

7H2O + Cr2O72- + 6 I- 2Cr3+ + 3I2 + 14OH-

Do a final check on atoms and charges.

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 ▪ Permanganate ion is a strong oxidizing agent, and its deep purple color makes it useful as an
indicator in redox titrations. It reacts in basic solution with the oxalate ion to form carbonate ion
and solid manganese dioxide. Balance the skeleton ionic reaction that occurs between NaMnO4
and Na2C2O4 in basic solution:
MnO4-(aq) + C2O42-(aq) MnO2(s) + CO32-(aq)

MnO4-(aq) + 4H+ (aq) + 3e- → MnO2(s) + 2H2O(l) ×2 Reduction: oxidation number Mn decreased from +7 to +4
C2O42-(aq) + 2H2O(l) → 2CO 32-(aq) + 4H+(aq) + 2e- ×3 Oxidation: oxidation number of C increased from +3 to +4
2MnO4-(aq) + 3C2O42-(aq) + 2H2O(l) → 2MnO2(s) + 6CO 32-(aq) + 4H+(aq) Overall redox reaction in acidic condition

Additional step: Add equal number of OH- ions both side to make solution basic:

2MnO4-(aq) + 3C2O42-(aq) + 2H2O(l) + 4OH-(aq) → 2MnO2(s) + 6CO 32-(aq) + 4H+(aq) + 4OH-(aq)

2MnO4-(aq) + 3C2O42-(aq) + 2H2O(l) + 4OH-(aq) → 2MnO2(s) + 6CO 32-(aq) + 4H2O(l)

2MnO4-(aq) + 3C2O42-(aq) + 4OH-(aq) → 2MnO2(s) + 6CO 32-(aq) + 2H2O(l) Overall redox reaction in basic condition

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 VOLTAIC CELL ELECTROLYTIC CELL
System
Energydoes
is released
work onfrom
its Surroundings(power
Energy is absorbed tosupply)
drive a
spontaneous
surroundings
redox reaction nonspontaneous redox reaction
do work on system(cell)

Oxidation half-reaction Oxidation half-reaction

X X+ + e- A- A + e-
Reduction half-reaction Reduction half-reaction
Y++ e- Y B++ e- B
Overall (cell) reaction Overall (cell) reaction 9
X + Y+ X+ + Y; DG < 0 A- + B+ A + B; DG > 0
 Electrode

Cell Type DG Ecell Name Process Sign

Anode Oxidation -
Voltaic <0 >0
Cathode Reduction +

Electrolytic >0 <0 Anode Oxidation +

Cathode Reduction -

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Oxidation half-reaction Reduction half-reaction
Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

Overall (cell) reaction

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) 11
Oxidation half-reaction Reduction half-reaction
Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

Overall (cell) reaction

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) 12
 components of components of
anode compartment cathode compartment
(oxidation half-cell) (reduction half-cell)

phase of lower phase of higher phase of higher phase of lower

oxidation state oxidation state oxidation state oxidation state

A single vertical line indicates a phase boundary The double vertical line represents a salt bridge

Examples: Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu (s)

Fe2+(aq),Fe3+ (aq) || Cu2+(aq) | Cu (s)

a comma is used to separate like states of
matter on the same side. 13
Oxidation half-reaction Reduction half-reaction
2I-(aq) I2(s) + 2e- MnO4-(aq) + 8H+(aq) + 5e-
Mn2+(aq) + 4H2O(l)

Inert electrode

graphite | I-(aq) | I2(s) || H+(aq), MnO4-(aq) | Mn2+(aq) | graphite

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▪ The spontaneous reaction occurs as a result of the different abilities of materials (such
as metals) to give up their electrons and the ability of the electrons to flow through the
circuit.

Ecell > 0 for a spontaneous reaction

1 Volt (V) = 1 Joule (J)/ Coulomb (C)

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 Oxidation half-reaction
Zn(s) Zn2+(aq) + 2e-

Reduction half-reaction
Overall (cell) reaction 2H3O+(aq) + 2e- H2(g) + 2H2O(l)
Zn(s) + 2H3O+(aq) Zn2+(aq) + H2(g) + 2H2O(l)
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 DG = wmax = charge x (-Ecell)
charge = n F
DG = -n F Ecell
n = #mols e-
F = Faraday constant In the standard state -

F = 96,485 C/mol e- DG0 = -n F E0cell

1V = 1J/C DG0 = - RT ln K

F = 9.65x104J/V*mol e- E0cell = (RT/n F) ln K

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 DG0 K E0cell Reaction at
DG0
standard-state
conditions
<0 >1 >0 spontaneous
0 1 0 at equilibrium
DG0 = -nFEocell DG0 = -RT lnK >0 <1 <0 nonspontaneous

E0cell = RT lnK
nF
E0cell K
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PROBLEM: Lead can displace silver from solution:

Pb(s) + 2Ag+(aq) Pb2+(aq) + 2Ag(s)

As a consequence, silver is a valuable by-product in the industrial extraction of lead from its
ore. Calculate K and DG0 at 298 K for this reaction.

Pb(s) Pb2+(aq) + 2e +0.13v

2Ag+(aq) + 2e 2Ag(s) +0.80V
Eo cell = 0.13 + 0.80 = 0.93V
DG0= -n F E0 = -2 mol e x 96500 J/V mol e x 0.93 V = - 179 490 J
DG0= -RT ln K
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-179490 J = - 8.314 J / K mole e x 298K ln K
 DG = DG0 + RT ln Q

-nF Ecell = -nF E0cell + RT ln Q

RT Nernst equation
Ecell = E0 cell - ln Q
nF

•When Q < 1 and thus [reactant] > [product], lnQ < 0, so Ecell > E0cell
•When Q = 1 and thus [reactant] = [product], lnQ = 0, so Ecell = E0cell
•When Q >1 and thus [reactant] < [product], lnQ > 0, so Ecell < E0cell

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PROBLEM:
In a test of a new reference electrode, a chemist constructs a voltaic cell consisting of a
Zn/Zn2+ half-cell and an H2/H+ half-cell under the following conditions:

[Zn2+] = 0.010M [H+] = 2.5M PH = 0.30atm

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Find EO cell
Calculate Ecell at 298 K.
2H+ + 2e → H2(g) 0.00 V
Zn(s) → Zn2+(aq) + 2e 0.76V
2H+ + Zn(s) → H2(g) + Zn2+(aq) +0.76V
EO cell = 0.00 + 0.76 = +0.76V

Ecell = Eocell – RT/nF ln Q

Q = PH2 1 x [Zn2+]1 / [H+]2 = (0.30 x 0.010)/2.5 2
Q = 4.8 e-4
Ecell = 0.76 – 8.314x298/2x96500 ln 4.8e-4
Ecell = 0.86 V 22
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Oxidation half-reaction Reduction half-reaction
Cu(s) Cu2+(aq, 0.1M) + 2e- Cu2+(aq, 1.0M) + 2e- Cu(s)

Overall (cell) reaction Ecell = Eocell – RT/nF ln Q

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Cu2+(aq,1.0M) Cu2+(aq, 0.1M) = 0 – 8.314 x 298 /(2 X 96500) ln (0.1/1)
PROBLEM:
A concentration cell consists of two Ag/Ag+ half-cells. In half-cell A,
electrode A dips into 0.0100M AgNO3; in half-cell B, electrode B dips into
4.0x10-4M AgNO3. What is the cell potential (Ecell) at 298 K? Which
electrode has a positive charge?
A conc, B dilute
A : Ag+(aq,0.01M) + e→ Ag(s) RED-CAT
B: Ag(s) → Ag+(aq, 4e-4M) + e OX-ANODE
O : Ag+(aq,0.01M) → Ag+(aq, 4e-4M) , Q = 4E-4/0.01 = 0.04
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Ecell = 0 – 8.314x298/1x96500 ln 0.04
 Sn(s) → Sn2+(aq) + 2e- Cu(s) → Cu2+(aq) + 2e-
Cu2+(aq) + 2e- → Cu(s) Sn2+(aq) + 2e- → Sn(s)

Cu2+(aq) + Sn(s) → Cu(s) + Sn2+(aq) Sn2+(aq) + Cu(s) → Sn(s) + Cu2+(aq)

voltaic cell electrolytic cell
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The tin-copper reaction as the basis of a voltaic and an electrolytic cell.
o Electrolysis is the splitting (lysing) of a substance by the input of electrical energy.
o Used to decompose a compound into its elements.
o Pure water is hard to electrolyze (low conductivity), so a small amount of a non-reactive salt
(NaNO3) is added (can be neglected)
Reduction half-reaction
2H2O(l) + 2e- → H2(g) + 2OH-(aq) Eo = -0.83 V
(at pH = 7) ⇒ E = -0.42 V

Oxidation half-reaction
2H2O(l) → 4H+(aq) + O2(g) + 4e- Eo = +1.23 V
(at pH = 7) ⇒ E = +0.82 V

Overall (cell) reaction

2H2O(l) → 2H2(g) + O2(g)

Ecell = Ecath – Eanod = -0.42 – (+0.82 ) = -1.24 V

→ Ecell < 0 ⇒ non-spontaneous reaction

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Overvoltage – the extra voltage (in the case of
water over 1.24) needed to drive the reaction
– For H2O on most inert electrodes, the overvoltage is
0.4 to 0.6 V per electrode
→ Cathode, reduction:
E = -0.42 – 0.6 ≈ -1.0 V
→ Anode, oxidation:
E = +0.82 + 0.6 ≈ +1.4 V
→ Total:
Ecell = -1.0 – (+1.4 ) ≈ -2.4 V

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o The cations(+) are attracted to the cathode(-) and reduced.
o The anions(-) are attracted to the anode(+) and oxidized

Positive electrode (anode): Negative electrode (cathode):

oxidation process reduction process
2 Cl- (l) Cl2(g) + 2 e- Na+ (l) + e- Na(s)
(anion) (cation)

Observation : a pale green Observation : Silvery white

gas , Cl2 sodium form and floats on the
top

Overall reaction of electrolysis :

2 NaCl(l) 2 Na(s) + Cl2(g) 29

Electrolysis of aqueous solutions

Possible cathode half-reactions (reduction)

1. Reduction of H2O
2. Reduction of cations in the solution
→ The half-reaction with the higher Eo value (having
the stronger oxidizing agent) occurs on the cathode

Possible anode half-reactions (oxidation)

1. Oxidation of H2O
2. Oxidation of active metal electrodes
3. Oxidation of anions in the solution
→ The half-reaction with the lower Eo value (having
the stronger reducing agent) occurs on the anode 30
Reduction : cathode (Na+ and H2O)
1. 2H2O(l) → H2(g) + OH-(aq) + 2e- E = -0.83V
2. Na+(aq) + e- → Na(s) E = -2.71 V
(water is still more easily reduced than Na+ ion even if overvoltage of H2 is
considered -0.83V – 0.6V = -1.43V)

Oxidation : Anode (Cl- and H2O)

1. H2O(l) → O2(g) + 4OH-(aq) + 4e- E = +1.23V
2. 2Cl-(aq) → Cl2(g) + 2e- E = +1.36V
The overvoltage for O2 is quite high (E = +1.23V+0.6V = 1.83V)

overal cell reaction

2H2O(l) + 2Cl-(aq)→ 2OH-(aq) + H2(g) + Cl2 (g)
Anode : gas Cl2
Cathode : gas H2
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When an aqueous salt solution is electrolyzed
o The strongest oxidizing agent (most positive electrode potential) is reduced
o The strongest reducing agent (most negative electrode potential) is oxidized

Overvoltage is the additional voltage needed (above that predicted by E° values) to

produce gases at metal electrodes.

Overvoltage needs to be taken into account when predicting the products of electrolysis for
aqueous solutions.

Overvoltage is 0.4 – 0.6 V for H2(g) or O2(g).

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 Summary of the Electrolysis of Aqueous Salt Solutions

• Cations of less active metals (Au, Ag, Cu, Cr, Pt, Cd) are
reduced to the metal.

• Cations of more active metals are not reduced ( K+,Mg2+ ). H2O

is reduced instead.

• Anions (Br-) that are oxidized, because of overvoltage from O2

formation, include the halides, except for F-.

• Anions that are not oxidized include F- and common oxoanions

(SO42- ,CO32-,NO3-, PO43-).. H2O is oxidized instead.

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 A summary diagram for the stoichiometry of electrolysis.

MASS (g) Faraday’s law –the amount of substance produced on

of substance each electrode is directly proportional to the amount of
oxidized or M(g/mol) charge transferred through the cell
reduced

AMOUNT (MOL)
AMOUNT (MOL)
of substance Faraday
of electrons
oxidized or constant
transferred
reduced (C/mol e-)

balanced CHARGE (C)

half-reaction
time(s)
CURRENT (A)

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Relationship Among Current, Time, and Amount of Substance
PROBLEM: A technician is plating a faucet with 0.86 g of Cr from an electrolytic
bath containing aqueous Cr2(SO4)3. If 12.5 min is allowed for the
plating, what current is needed?
PLAN: mass of Cr needed SOLUTION: Cr3+(aq) + 3e- Cr(s)

divide by M
mol of Cr needed 0.86g (mol Cr) (3 mol e-) = 0.050 mol e-
3mol e-/mol Cr (52.00 gCr) (mol Cr)

mol of e- transferred 0.050 mol e- (9.65x104 C/mol e-) = 4.8x103 C

9.65x104C/mol e-
charge (C) 4.8x103 C (min)
= 6.4C/s = 6.4 A
12.5 min (60s)
divide by time
current (A)

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