Republic of the Philippines

CAGAYAN STATE UNIVERSITY

Carig Campus, Tuguegarao City
College of Engineering

Course CHEM111E (Chemistry for Engineers)

Title of the Unit II. ENERGY
Module I. Electrochemical Energy
At the end of this module, the student shall be able:
a. To discuss the driving force in concentration cells.
Learning
Objectives b. To quantify the relationship between cell potential and cell concentration.
c. To show how to calculate equilibrium constants from cell potentials.

Content E. EFFECT OF CONCENTRATION ON CELL EMF: THE NERNST EQUATION

E. EFFECT OF CONCENTRATION ON CELL EMF: THE NERNST EQUATION

Electromotive Force (emf): The force or electrical potential that pushes the negatively charged electrons
away from the anode (− electrode) and pulls them toward the cathode (+ electrode). It is also called the cell
potential (E) or the cell voltage.

1J=1C×1V
joule (J) coulomb (C) volt (V)
SI unit of energy Electric charge SI unit of electric potential

1 coulomb is the amount of charge transferred when a current of 1 ampere (A) flows for 1 second.

E.1 RELATIONS BETWEEN EO, ∆GO, AND K

The value of the standard cell voltage, Eo, is a measure of the spontaneity of a cell reaction. The
standard free energy change, ∆Go, is a general criterion for reaction spontaneity. These two
quantities have a simple relation to one another and to the equilibrium constant, K for the cell
reaction.

faraday or Faraday constant

The electric charge on 1 mol of electrons and is equal to
96,500 C/mol e−

FREE ENERGY CHANGE

Cell potential
o o
∆G = - n F E

Number of moles of electrons transferred in the reaction

Chemical Engineering Department Unit II: Module 3: Page 1

 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

❑ Work done in a redox reaction: ∆G = - n x F x Ecell

-
Where: n= moles of e transferred
Ecell = voltage of the cell
F = Charge of 1 mole of e- = 1 Faraday = 96,485 coulombs (c)
❑ Notes:
o Units: Joules = moles x (coul/mole) x volts
o 1 coulomb x 1 volt = 1 joule
o Since batteries are spontaneous redox rxns the sign is -: ∆G = - nFEcell
❑ Free Energy, ΔG = maximum useful work done
o ΔG = - nFEcell
o At 1M concentrations, 1 atm pressure & 25 oC: ΔG = ΔGo
o ΔGo = - nFEocell

_____________________________________________________________________________
Learning Activity:
The standard cell potential at 25 °C is 1.10 V for the reaction:
Zn(s) + Cu2+(aq → Zn2+(aq) + Cu(s)
Calculate the standard free-energy change for this reaction at 25 °C.

Solution:

∆G° = −nFE°
 96,000C   1J  1KJ 
= − (2mole) (1.1V )  
 mole   1CV  1000 J 
∆G° = −212 kJ

Redox reactions, like all reactions, eventually reach a state of equilibrium. It is possible to calculate
the equilibrium constant for a redox reaction from the standard voltage.

ΔGo = - RTln K

We have just seen that ∆G° = −nFE°. It follows that

- nFEo = - RT ln K
RT
Eo = ln K
nF
RT
The quantity is readily evaluated at 25oC, the temperature at which standard potentials are
F
tabulated.

Chemical Engineering Department Unit II: Module 3: Page 2

 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

RT 8.31J / [Link] 298K

= 4
= 0.0257V
F
9.648 x10 J / mol.V

0.0257V
Eo = ln K (at 25 o C )
n
Notice that if the standard voltage is positive, lnK is also positive, and K is greater than 1.
Conversely, if the standard voltage is negative, lnK is also negative, and K is lea than 1.
______________________________________________________________________________
Learning Activity :
Consider the following reaction at 25oC:
3 Ag(s) + NO3-(aq) + 4H+(aq) → 3 Ag+(aq) + NO(g) + 2H2O

a. Find ∆Go
Strategy:
1. Assign oxidation numbers.
2. Split the redox reaction into oxidation and reduction half-reactions and solve for Eo.
3. Determine the number of electrons cancelled out when balancing the equation to find n.
4. Substitute into the equation. Note that ∆Go will be in joules since the Faraday constant is in
joules.
Solution:
1. Oxidation numbers. N: +5 → +2 reduction
Ag: 0 → +1 oxidation

2. Half-reactions: NO3-(aq) + 4H+(aq + 3e- → NO (g) + 2H2O Eored = 0.96V

Ag(s) + e- → Ag+ (aq) Eoox = -0.80V
Eo = 0.96V + (-0.80V) = 0.16V

3. Multiply the oxidation half-reaction by 3 to cancel out the three electrons in the reduction half-
reactions.
Three electrons cancel out: n = 3

J
∆Go = − nFE o = (−3mole)(9.648x10 4 )(0.165) = −4.78 x10 4 J = −47.8KJ
mol.V

b. Find K

Chemical Engineering Department Unit II: Module 3: Page 3

 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

Substitute into the equation

0.0257V
Eo = ln K
n
0.0257V
0.165V = ln K ; ln K = 19.3
3
K = e19.3 = 2.4 x10 8

_________________________________________________________________________________

Self-Assessment Activity:
1. Consider a cell reaction at 25oC where n =2. Fill in the following table
∆Go Eo K
a. 19 KJ
b. 0.035 V
c. 0.095
d. -5.8KJ

2. For a certain cell, Eo = 1.08V. Calculate ∆Go if n is

a. 1 b. 2 c. 3
o o o
3. Calculate E , ∆G ,and K at 25 C for the reaction
2MnO4-(aq) + 4H+ (aq) + Cl2(g) → 2 Mn2+(aq) + 2ClO3- (aq) + 2H2O

Chemical Engineering Department Unit II: Module 3: Page 4

 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

NERNST EQUATION
• Electrochemistry deals with cell potential as well as energy of chemical reactions.

• The energy of a chemical system drives the charges to move, and the driving force give rise to
the cell potential of a system called galvanic cell.

• The energy aspect is also related to the chemical equilibrium.

• All these relationships are tied together in the concept of Nernst equation.

Walther H. Nernst (1864-1941) received the Nobel prize in 1920 "in recognition of his work in
Thermochemistry". His contribution to Chemical Thermodynamics led to the well known
equation correlating chemical energy and the electric potential of a galvanic cell or battery
The general Nernst equation correlates the Gibb's Free Energy ΔG and the EMF of a chemical
system known as the galvanic cell.
RT
Ecell = E o cell − ln Q
nF
In this equation, Ecell is the cell voltage, Eocell is the standard voltage, n is the number of moles of
electrons exchange in the reaction, and Q is the reaction quotient. Notice that:
• If Q>1, which means that the concentrations of products are high relative to those of reactants,
ln Q is positive and Ecell < Eocell.
• If Q< 1(concentrations of products low relative to reactants), lnQ is negative and Ecell > Eocell.
• If Q = 1, as is the case under standard conditions, ln Q = 0 and Ecell = Eocell.

Remember that gases enter Q as their partial pressures in atmospheres. Species in water solution
enter as their molar concentrations. Pure liquids and solids do not appear in the expression for Q.
For example,

[C ]c ( PD ) d
aA(s) + bB(aq) → cC(aq) + dD(g)
Q=
[ B ]b
_________________________________________________________________________________
Learning Activity:
Consider a voltaic cell in which the following reaction occurs:
O2(g, 0.98atm) + 4H+(aq, pH =1.24) + 4Br-(aq, 0.15M) → 2H2O + 2Br2(l)
a. Calculate E for the cell at 25oC.
Strategy:
1. Change pH to [H+] and find Q
2. Assign oxidation numbers, write the oxidation and reduction half-reactions, and cancel

Chemical Engineering Department Unit II: Module 3: Page 5

 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

electrons to find n
3. Find Eo ,( Eored, Eoox)
4. Substitute in the Nernst Equation

Solution:
1. pH = -log [H+]; 1.24 = -log [H+]
[H+] = 0.058 M
1 1
Q= + 4 − 4
= 4 4
= 1.8 x10 8
( PO )[ H ] [ Br ] (0.98)(0.058) (0.15)

2. O: 0 → -2 (reduction); Br-: -1 → 0 (oxidation)

Half-reactions: O2 (g) + 4H+(aq) + 4e- → 2H2O
2Br- (aq) → Br2 (l) + 2e-
The oxidation half-reaction must be multiplied by 2 to cancel out the four electrons in the
reduction half-reaction.
n=4
3. E red, for O2 = 1. 23 V; Eoox for Br- = -1.09 V
o

Eo = 1.23V + (-1.09V) = 0.14V

0.0257
0.14V − ln(1.8 x10 8 ) = 0.018V
Ecell = 4

b. When the voltaic cell is at 35oC, E is measured to be 0.039 V. What is Eo at 35oC?

Strategy: Substitute into the Nernst Equation

Solution:
RT
Ecell = E o cell − ln Q
nF

(8.31J / mol.K )(308K )

0.039V = E 0 − 4
ln(1.8 x108 )
4(9.648x10 J / mol.V )

E 0 = 0.039V + 0.126V = 0.165V

Chemical Engineering Department Unit II: Module 3: Page 6

 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

USE OF THE NERNST EQUATION TO DETERMINE ION CONCENTRATIONS

In chemistry, the most important use of the Nernst equation lies in the experimental determination
of the concentrations of ions in solution. Suppose you measure the cell voltage E and know the
concentration of all but one species in the two half-cells. It should then be possible to calculate the
concentrations of that species by using the Nernst equation.
_________________________________________________________________________________
Learning Activity:
Consider the voltaic cell at 25oC in which the reaction is

Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)

It is found that the voltage is +0.56V when [Zn2+] = 0.85M and PH2 = 0.98 atm. What is the pH in the
H2-H half-cell?

Strategy:
1. Assign oxidation numbers, write oxidation and reduction half-reactions, and cancel electrons to
find n.
2. Find Eo
3. Substitute into the Nernst equation for T= 25oC and find Q.
4. Write the Q expression and substitute given concentrations and pressures to find [H +]. Change
[H+] to pH.

Solution:
1. Oxidation numbers Zn: 0 → +2 oxidation; H+: +1 → 0 reduction
2H+ (aq) + 2e- → H2(g)
Half-reaction Zn(s) → 2e- + Zn2+ (aq)

N 2 electrons cancel out so n =2

2. Eo Eo = EooxZn + EoredH+ = 0.76V + 0 V = 0.76V

3. Q 0.0257 0.0257
E = E0 − ln Q;0.56V = 0.76V − ln Q
n 2
0.0257
ln Q = 0.76V − 0.56V ; ln Q = 15.56
2
Q = 5.72 x10 6
4. [H+]
Q=
Zn ( P ) ; H  =  (0.85)(0.988) 
2+
H2 +
1/ 2

= 3.83x10 −4
H  + 2  5.72 x10 
 
6

5. pH pH = − log 10 (3.83 x10 −4 ) = 3.42

Chemical Engineering Department Unit II: Module 3: Page 7

 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

Self-Assessment Activity:
1. Consider a voltaic cell at 25oC in which the following reaction takes place.
3H2O2(aq) + 6H+(aq) + 2Au(s) → 2Au3+(aq) + 6H2O
a. Calculate Eo
b. Write the Nernst equation for the cell.
c. Calculate E when [Au3+] =0.25M; [H+] = 1.25M; [H2O2] = 1.5 M
2. Consider the voltaic cell at 25oC in which the following reaction takes place:
MnO2(s) + 4H+(aq) + 2Br-(aq) → Br2(l) + Mn2+(aq) + 2H2O
a. Calculate Eo
b. Write the Nernst equation for the cell.
c. Calculate E at 25oC under the following conditions: [Mn2+] =0.60M; [Br-] = 0.83M; pH = 3.17

References:

1. Brown, L. S & Holmes, T. A. (2015). Chemistry for Engineering Students. CENGAGE Learning
2. Chang, R. (2010). Chemistry. McGraw-Hill Companies, Inc.
3. Masterton, William L, et al. (2018).Principles and Reactions: Chemistry for Engineering Students.
C&E Publishing, Inc.
4. Zumdahl, S.S, Zumdahl, S.A.& DeCoste, D.J. (2018) Chemistry. CENGAGE Learning

Chemical Engineering Department Unit II: Module 3: Page 8