Chapter 14.

Fundamentals of Electrochemistry

Electrochemistry is a branch of analytical chemistry that uses electrical

measurements.

Applications of Electrochemistry
Batteries
Fuel Cells
Electroanalysis
Electrocatalysis
Corrosion
Metal Coatings
The basis of biochemistry across cell membranes
Photoelectrochemistry
 14-1, Basic Concepts

A redox reaction: transfer of electrons from one species to another

Oxidation: loss of electrons

Reduction: gain of electrons

Fe3+ + V2+ -->Fe2+ + V3+ ---- (14.1)

electron
oxidizing agent (oxidant) : takes electrons from others and reduces
reducing agent (reductant) : oxidizes itself

Chemistry and Electricity

When electrons from a redox reaction flow through an

electric circuit
Current ∝ the rate of the electrochemical reaction

Voltage ∝ the free energy change for the electrochemical

reaction
 Electric Charge (q)
Unit: coulomb (C)

The magnitude of the charge of a single electron = 1.602 x 10-19 C

Charge of 1 mol of electrons = 9.649 x 104 C/mol ; Faraday constant (F)

(1.602 x 10-19 C x 6.02x1023 /mol)
Relation between charge and moles:

q=nxF

Example: Relating Coulombs to Quantity of Reaction

Q: If 5.585 g of Fe3+ were reduced in rxn 14-1,

how many coulombs of charge must have been transferred from V2+ to Fe3+ ?
Sol:
Atomic weight of Fe = 55.85 g/mol
5.585g of Fe3+ = 0.100 mol of Fe3+
Each Fe3+ ion requires one electron in the reaction
→ 0.100 mol of electrons must have been transferred

(0.100 mol e-)(9.649x104 C/mol e-) = 9.649 x 103 C

 Current (I)

Current: the quantity of charge flowing each second through a circuit, I = q/t

Unit: ampere, 1 A = 1 C/s

Q: If Sn4+ is reduced to Sn2+ at a constant
rate of 4.24 mmol/h,
how much current flows ?

Sol:

Example: Relating Current to Rate of Reaction Sn4+ + 2e- Sn2+

Sn4+ reduction rate = 4.24 mmol/h

(-) → Electron flows at a rate of 2 x (4.24 mmol/h )
Power (+)
e-
Supply (8.48 mmol/h)/(3600s/h) = 2.356 x10-3 mmol/s

e- Current = (2.356x10-6 mol/s)(9.649x104 C/mol)

= 0.227C/s = 0.227 A
(-) KCl (+) (Current ∝ the rate of the electrochemical reaction)
Pt Cu
Salt bridge

K+ Cl-
2e-
2e-
SO42- Cu2+
Cu
Zn2+ Cu2+
Sn2+ Sn4+ SO 2- SO42- Cu
2+
4

Cathode Anode
 Voltage (E), Work, and Free Energy

The difference in electric potential (E) between two points is a measure of the work

that is needed when an electric charge moves from one point to the other.

When a charge, q, moves through a potential difference, E, the work done is

Work = E x q
(jouls) = (volts) x (coulomb)

1 volt = 1 J/C

Example: Electrical Work

Q: How much work is needed to move 2.36 mmol of electrons

through a potential difference of 1.05 V ?

S: To get coulombs of charge, q = n x F = (2.36 x 10-3 mol)(9.649

x 104 C/mol) = 2.277 x 102 C

The work required = E x q = (1.05 V) x (2.277 x102 C) = 239 J

 Relationship between Free Energy Difference and Electric Potential Difference

At constant T, P

The free energy change (ΔG) for a chemical reaction =

the maximum possible electrical work that can be done by the reaction on its surroundings

Work done on surroundings = - ΔG ------- (14.4)

From equations (14-2, 14-3, 14-4)

ΔG = - work = - E x q = - nFE

ΔG = - nFE ------- (14.5)

 Ohm’s Law

I=E/R ------- (14.6)

cf: Electrical conductance = 1/resistance (1/ohm)  siemens (S)

Power, P work done per unit time, J/s or watt (W)

work Eq q
P= = =E
s s s
= EI
 14-2, Galvanic Cells (Voltaic Cells)
A galvanic cell : uses a spontaneous chemical reaction to generate electricity
To accomplish this: 1. One reagent must be oxidized
2. The other must be reduced
3. The two reagents must be physically separated
→ electrons are forced to flow through external circuit to go from one reagent to the other
Digital
voltmeter
Anode reaction Cd(s) Cd2+ (aq) + 2 e-
: oxidation
e-
0.777V Cathode reaction 2 AgCl(s) + 2 e- 2Ag(s) + 2Cl-(aq)
(ΔG = -150kJ) : reduction
e-
(-) (+) Cd(s) + 2 AgCl(s) Cd2+ (aq) +2Ag(s) + 2Cl-(aq)
Cd Ag

Cathode: where reduction occurs

0.0167M CdCl2(aq) Anode: where oxidation occurs
AgCl
Cd2+ (aq)
Cl- (aq)
When electrons flow from the
left electrode to the right
Anode Cathode electrode : positive voltage

Fig. 14-3 A simple galvanic cell

 Salt Bridge Fig. 14-6 A cell that works
Digital
voltmeter
Digital
voltmeter A
A
B e-
B e-
e- Negative Positive
e- ions ions
(-) NO3- K+ (+)
(-) (+) Cd Ag
Cd Ag Salt bridge
NO3-
K+
Physical
Cd2+, NO3-(aq) separation 2e- e-

NO3-
Ag+, NO3-(aq) Ag
Cd
Cd2+ Cd2+ Ag+
Anode Cathode
Anode Cathode
Fig. 14-4 A cell that will not work Cd(NO3)2 (aq) AgNO3(aq)
Positive ions increase Positive ions decrease
The Ag+
ions in solution can directly react
at Cd(s) surface

→ No flow of electrons through the external circuit

The purpose of salt bridge is to maintain

electroneutrality (no charge buildup) through the cell
Line Notation

Phase boundary Salt bridge

Cd(s) CdCl2(aq) AgNO3(aq) Ag(s)

Digital
voltmeter

A
B e-

e- Negative Positive
ions ions
(-) NO3- K+ (+)
Cd Ag
Salt bridge
NO3-
K+

2e- e-

NO3-
Cd Ag

Cd2+ Cd2+ Ag+

Anode Cathode

Fig. 13-6 A cell that works

 Li-ion battery

2.5 V
4.2 V (discharged)
(charged)
Eo = 0.0V Eo = 1.229 V
(Hydrogen Oxidation Reaction) (Oxygen Reduction Reaction)
H2→2H+ + 2e- O2 + 4H++4e-→ 2H2O
①
② ②
① ④

③
14-3. Standard (reduction) Potentials (activities of all species = 1)

A quantitative description of the relative driving force for a half-cell reaction.

A relative quantity vs standard hydrogen electrode
assigned to zero volt. E0(SHE)=0

Reduction :
H+ (aq, A = 1) + e- ½ H2 (g, A = 1) spontaneous
E0(SHE)=0

SHE

Oxidation:
Spontaneous
 14-4. Nernst Equation
Le Chatelier’s principle:
increasing reactant concentrations drives the reaction to the right

The net driving force of the reaction is expressed by the Nernst equation

The Nernst equation describes the relationship between potential and

concentration

Nernst Equation for a Half-Reaction R: gas constant = 8.314 J/Kmol

T: temperature (K)

aA + ne- bB

b
RT A
E = Eo − ln Ba
nF AA
ΔG = ΔGo + RT lnQ (Q; reaction quotient)
-nFE = -nFEo + RT lnQ
E = Eo –(RT/nF) lnQ
 b
RT A RT
E=E −
o
ln a = E −
B o
ln Q
nF AA nF
Q
When all activities are unity, Q = 1 and ln Q = 0, thus E = E o

Nernst Equation at 25 oC

aA + ne- bB

b
0 . 05916 V A
E = Eo − log( Ba )
n AA

If Q changes 10-fold, the potential changes by (59.16/n)mV

Example: Writing the Nernst Equation for a Half-Reaction

Reduction of phosphorus to phosphine gas

1/4 P4 (s, white) + 3H+ + 3e- PH3 (g) Eo = -0.046 V

0.05916 PPH3
Sol: E = −0.046 − log( + 3
)
3 [H ]
Box 14-4

Eo and Cell Voltage (E)

Ag+ + e- Ag(s) Eo = 0.799 V

2Ag+ + 2e- 2Ag(s) Eo = ?

E = work/charge

- 0.1 C, 0.2 C, 0.3 C

- Total work is different
 Nernst Equation for a Complete Reaction

Q: Find the voltage of the cell in Fig. 14-6

if the right cell contains 0.50M AgNO3(aq) and the left cell contains 0.010M Cd(NO3)2(aq)

Sol: Look at the next page Digital

voltmeter

A
B e-

e- Negative Positive
ions ions
(-) NO3- K+ (+)
Cd Ag
Salt bridge
NO3-
K+

2e- e-

NO3-
Cd Ag

Cd2+ Cd2+ Ag+

Anode Cathode
0.010M Cd(NO3)2 Fig. 14-6 A cell that works 0.50 M AgNO3
 Example: Nernst Equation for a Complete Reaction

Q: Find the voltage of the cell in Fig. 14-6

(Step 1)
Right electrode: 2Ag+ + 2e 2Ag(s) Eo+ = 0.799V
Left electrode: Cd2+ + 2e Cd(s) Eo- = – 0.402V
(Step 2)
Nernst equation for right electrode:
E+ = (Eo+) – (0.05916/2) log (1/[Ag+]2) = 0.799 – (0.05916/2) log(1/0.52) = 0.781 V
(Step 3)
Nernst equation for left electrode:
E- = (Eo-) – (0.05916/2) log (1/[Cd2+]) = – 0.402 – (0.05916/2) log(1/0.010) = – 0.461 V
(Step 4)
Cell voltage: E = E+ – E- = 0.781 – (– 0.461) = + 1.242 V
(spontaneous in the forward direction)
Right electrode: 2Ag+ + 2e 2Ag(s) Eo+ = 0.799V
( ) Left electrode: Cd2+ + 2e Cd(s) E0- = – 0.402V

Cd(s) + 2Ag+ Cd2+ + 2Ag(s)

Different Description of the Same Reaction

(Fig. 14-4) right electrode

(1) AgCl(s) + e- Ag(s) + Cl- Eo+ = 0.222 V

E+ = Eo+ − 0.05916 log [Cl-]

CdCl2 Cd2+ + 2Cl- Why different E+ values ?

0.0167 M 0.0334 M 1. Activity coefficient: neglected

2. Inaccurate Ksp
E+ = 0.222− 0.05916 log (0.0334) = 0.3093 V

(2) Ag+ + e- Ag(s) Eo+ = 0.799 V

E+ = 0.799 − 0.05916 log(1/ [Ag+])

AgCl Ag+ + Cl-

0.0334
x x+0.0334

x(x+0.0334) = Ksp= 1.8 x 10-10, x = [Ag+] = 5.4 x 10-9 M

E+ = 0.799− 0.05916 log (1/5.4 x 10-9) = 0.3099 V
 Advice for Finding Relevant Half-Reactions

Your choice of reactions depend on whether concentrations of reactants is easier to figure out

The Nernst Equation is Used in Measuring Standard Reduction Potentials

It is nearly impossible to construct a standard electrochemical cell

because we have no way to adjust the concentrations and ionic strength
to give unit activities

In reality, activities less than unity are used in each half-cell, and
the Nernst equation is used to extract the value of Eo from the cell voltage
 14-5. Eo and Equilibrium Constant
• A galvanic cell produces electricity because the cell reaction is not at equilibrium
• The potentiometer allows negligible current to flow
→The concentration in each half-cell remains unchanged

0.412 V
At the outset Cell
Potential

Time

[Cu2+] increase
[Ag+] decrease

0V
At equilibrium
Concentrations in the Operating Cell

A high-quality pH meter (voltmeter) → Resistance = 1013 Ω

If we measure 50 mV

Current = E/R = 0.05V/1013 Ω = 5 x 10-15 A

(5 x 10-15 C/s)/(9.649 x104 C/mol) = 5 x 10-20 mol e-/s

The production rate of Cd2+ = 2.5 x 10-20 mol/s ; negligible concentration change

If we replace the potentiometer with a wire, much more current would flow
→ Concentrations would change until the cell reaches equilibrium
 14-5. Eo and Equilibrium Constant

Right electrode: aA + ne- cC : E o+

A+B C+D
Left electrode: dD + ne- bB : Eo-

0.05916 ACc 0.05916 ABb

E = E+ - E- = Eo + − log( a ) − [E - -
o log( d )]
n AA n AD

0.05916 ACc ADd 0.05916

E = E o+ – E o- − n log( a b ) = E −
o
n log Q ----- (14.23)
AA AB
Eo Q

When cell is at equilibrium, nothing would be driving the reaction,

and E = 0 and Q = K (G = -nFE, G = 0 → E = 0)

0.05916
E =o
log K
n
Example: Using Eo to Find the Equilibrium Constant

Q; Find the equilibrium constant for the reaction

Cu(s) + 2Fe3+ 2Fe2+ + Cu2+

Sol; 2Fe3+ + 2e- 2Fe2+ : Eo+ = 0.771 V

(-) Cu2+ + 2e- Cu(s) : Eo- = 0.339 V

Eo = Eo+ − Eo- = 0.771 – 0.339 = 0.432 V

0.05916 0.05916
Eo = log K = log K
n 2

Therefore, K = 10(2x0.432)/0.05916 = 4 x1014

Finding K for Net Reaction that are Not Redox Reactions

Potentiometric measurements allows us to find equilibrium constants

that are too small or too large to measure by determining concentrations of
reactants and products directly

FeCO3(s) + 2e- Fe(s) + CO32- : Eo+ = -0.756 V

(-) Fe2+ + 2e- Fe(s) : Eo- = -0.44

FeCO3(s) Fe2+ + CO32- Eo = -0.756 – (-0.44) = -0.316V

K = Ksp = 10 (2)(-0.316)/(0.05916) = 10-11

Eo for dissolution of iron carbonate is negative

→ Not spontaneous

Not spontaneous simply means K < 1

 14-6. Cells as Chemical Probes
+ 0.503 V was measured

Ag
AgCl(s)
Pt

0.1M KCl
CH3COOH (0.050M), CH3COONa (0.0050 M) What is pH of the left cell ?

AgCl(s) + e- Ag(s) + Cl- (aq, 0.10 M) Eo+ = 0.222V

2H+(aq, ? M) + 2 e- H2(g, 1.0 atm) E o- = 0 V

E = (E+) – (E-) = (0.222 – 0.05916 log[Cl-] )– [0 – (0.05916/2)log(PH2/[H+]2)]

0.503 = (0.222 – 0.0596 log[0.10]) – [0 – (0.05916/2) log (1.00/[H+]2)]

→ [H+] = 1.8 x 10-4 M
→ Also Ka for CH3COOH can be calculated

0.0050 1.8 x 10-4

[CH 3COO ][ H + ] −
Ka = = 1.8 x 10-5
[CH 3COOH ]
0.050
14-7. Biochemists Use Eo’
Most important redox reactions
in living systems :
Respiration
(molecules of food is oxidized by
O2 to yield energy and metabolic
Intermediates)

If H+ is involved in the reaction,

Eo applies when pH = 0 (AH+ = 1)

pH inside a plant or animal cell:

~ pH 7

The Formal Potential (Eo’)

: the reduction potential
under a specified set of
conditions (pH, ionic strength, --)