Electrochemistry Equilibria

By
Lilik Miftahul Khoiroh
Electrochemistry Equilibria
Oxidation
states and
oxidation-
reduction
Reactions
FREE
ENERGY AND
Electrode
REDOX
Potentials
REACTIONS

CELL EMF
UNDER Electrochemis
STANDARD try Cells
CONDITIONS
 Fundamental Concept
An electrochemical Reaction is a
heterogeneous chemical process involving the
transfer of charge to or from an electrode,
generally a metal, carbon or a semiconductor
The charge transfer can be a cathodic or
anodic process
Some typical cathodic and anodic processes
Fundamentals of Electrochemistry

Electrical Measurements of Chemical Processes

Redox Reaction involves transfer of electrons from one species to another.
- Chemicals are separated

Can monitor redox reaction when electrons flow through an electric current
- Electric current is proportional to rate of reaction
- Cell voltage is proportional to free-energy change

Batteries produce a direct current by converting chemical energy to electrical energy.

Fundamentals of Electrochemistry
A Redox titration is an analytical technique based on the transfer of electrons
between analyte and titrant
Reduction-oxidation reaction

A substance is reduced when it gains electrons from another substance

- gain of e- net decrease in charge of species
- Oxidizing agent (oxidant)

A substance is oxidized when it loses electrons to another substance

- loss of e- net increase in charge of species
- Reducing agent (reductant)

(Reduction)

(Oxidation)

Oxidizing Reducing
Agent Agent
Fundamentals of Electrochemistry

The first two reactions are known as 1/2 cell reactions

Include electrons in their equation
The net reaction is known as the total cell reaction
No free electrons in its equation

cell reactions:

Net Reaction:

In order for a redox reaction to occur, both reduction of one compound and
oxidation of another must take place simultaneously
Total number of electrons is constant
Fundamentals of Electrochemistry

Electric Charge (q)

Measured in coulombs (C)
Charge of a single electron is 1.602x10-19C
Faraday constant (F) 9.649x104C is the charge of a mole of electrons

q nF
Relation between
charge and moles:
Coulombs
Coulombs moles
mol e

Electric current
Quantity of charge flowing each second
through a circuit
- Ampere: unit of current (C/sec)
 Fundamentals of Electrochemistry

Electric Potential (E)

Measured in volts (V)
Work (energy) needed when moving an electric charge
from one point to another
- Measure of force pushing on electrons

Higher potential
Relation between
difference
free energy, work G work E q
and voltage:
Joules Volts Coulombs

Higher potential difference requires

more work to lift water (electrons) to
higher trough
 Fundamentals of Electrochemistry

Basic Concepts

Electric Potential (E)

Combining definition of electrical charge and potential

G work E q q nF

Relation between free energy difference

and electric potential difference:
G nFE

Describes the voltage that can be generated by a chemical reaction

 Fundamentals of Electrochemistry

Basic Concepts

Ohms Law
Current (I) is directly proportional to the potential difference (voltage) across a
circuit and inversely proportional to the resistance (R)
- Ohms (W) - units of resistance

E
I
R

Power (P)
Work done per unit time
- Units: joules per second J/sec or watts (W)

q
P E EI
s
 Fundamentals of Electrochemistry

Galvanic Cells

1.) Galvanic or Voltaic cell

Spontaneous chemical reaction to generate electricity
- One reagent oxidized the other reduced
- two reagents cannot be in contact
Electrons flow from reducing agent to oxidizing agent
- Flow through external circuit to go from one reagent to the other

Reduction:
Oxidation:

Net Reaction:
AgCl(s) is reduced to Ag(s)
Ag deposited on electrode and Cl-
goes into solution Electrons travel from Cd
electrode to Ag electrode

Cd(s) is oxidized to Cd2+

Cd2+ goes into solution
 Fundamentals of Electrochemistry

Galvanic Cells

1.) Galvanic or Voltaic cell

Example: Calculate the voltage for the following chemical reaction

G = -150kJ/mol of Cd

Solution: n number of moles of electrons

G
G nFE E
nF

150 103 J
E 0.777 J 0.777V
4 C
C
(2 mol ) 9.649 10
mol
 Fundamentals of Electrochemistry

Galvanic Cells

2.) Cell Potentials vs. G

Reaction is spontaneous if it does not require external energy
 Fundamentals of Electrochemistry

Galvanic Cells

2.) Cell Potentials vs. G

Reaction is spontaneous if it does not require external energy

Potential of overall cell = measure of the tendency of this reaction to proceed to

equilibrium
Larger the potential, the further the reaction is from equilibrium
and the greater the driving force that exists

Similar in concept to balls

sitting at different heights
along a hill
 Fundamentals of Electrochemistry

Galvanic Cells

3.) Electrodes

Anode: electrode where Cathode: electrode where

oxidation takes place reduction takes place
 Fundamentals of Electrochemistry

Galvanic Cells

4.) Salt Bridge

Connects & separates two half-cell reactions
Prevents charge build-up and allows counter-ion migration

Salt Bridge

Contains electrolytes not

involved in redox reaction.
Two half-cell reactions
K+ (and Cd2+) moves to cathode with
e- through salt bridge (counter
balances charge build-up

NO3- moves to anode (counter

balances +charge build-up)

Completes circuit
 Fundamentals of Electrochemistry

Galvanic Cells

5.) Short-Hand Notation

Representation of Cells: by convention start with anode on left

Phase boundary
Electrode/solution interface

anode Zn|ZnSO4(aZN2+ = 0.0100)||CuSO4(aCu2+ = 0.0100)|Cu cathode

2 liquid junctions
Solution in contact with due to salt bridge Solution in contact with
anode & its concentration cathode & its concentration
 Fundamentals of Electrochemistry

Standard Potentials

1.) Predict voltage observed when two half-cells are connected

Standard reduction potential (Eo) the measured potential of a half-cell reduction
reaction relative to a standard oxidation reaction
- Potential arbitrary set to 0 for standard electrode
- Potential of cell = Potential of reaction

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

Potentials measured at standard conditions
- All concentrations (or activities) = 1M
- 25oC, 1 atm pressure

Standard Hydrogen Electrode (S.H.E)

Pt(s)|H2(g)(aH = 1)|H+(aq)(aH+ = 1)||

2
Hydrogen gas is bubbled over a Pt electrode
 Fundamentals of Electrochemistry

Standard Potentials

1.) Predict voltage observed when two half-cells are connected

As Eo increases, the more favorable

the reaction and the more easily
the compound is reduced (better
oxidizing agent).

Reactions always written as

reduction

Appendix H contains a more extensive list

 Fundamentals of Electrochemistry
Standard Potentials

2.) When combining two cell reaction together to get a complete net
reaction, the total cell potential (Ecell) is given by:

Ecell E E
Where: E+ = the reduction potential for the cell reaction at the positive electrode
E+ = electrode where reduction occurs (cathode)
E- = the reduction potential for the cell reaction at the negative electrode
E- = electrode where oxidation occurs (anode)

Place values on number line to

Electrons always flow towards more determine the potential difference
positive potential
 Fundamentals of Electrochemistry

Standard Potentials

3.) Example: Calculate Eo, and Go for the following reaction:

 Fundamentals of Electrochemistry

Nernst Equation

1.) Reduction Potential under Non-standard Conditions

E determined using Nernst Equation
Concentrations not-equal to 1M

For the given reaction:

aA + ne- bB Eo

The cell reduction potential is given by:

b
RT A Where: E = actual cell reduction potential
E Eo ln B Eo = standard cell reduction potential
nF AA a n = number of electrons in reaction
T = temperature (K)
at 25oC R = ideal gas law constant (8.314J/(K-mol)
b
0.05916 V [ B ] F = Faradays constant (9.649x104 C/mol)
E Eo log A = activity of A or B
n [ A]a
 Fundamentals of Electrochemistry

Nernst Equation

2.) Example:
Calculate the cell voltage if the concentration of NaF and KCl were each 0.10 M
in the following cell:

Pb(s) | PbF2(s) | F- (aq) || Cl- (aq) | AgCl(s) | Ag(s)

 Fundamentals of Electrochemistry

Eo and the Equilibrium Constant

1.) A Galvanic Cell Produces Electricity because the Cell Reaction is NOT at
Equilibrium
Concentration in two cells change with current
Concentration will continue to change until Equilibrium is reached
- E = 0V at equilibrium
- Battery is dead
Consider the following cell reactions:
aA + ne- cC E+ o
dD + ne- bB E- o
Cell potential in terms of Nernst Equation is:

0.05916 [ C ] c o 0.05916 [ B ]b

E cell E E E o log E log
n a n d
[ A] [ D ]
Simplify:
0.05916 [C ]c [ D ]d
E cell ( E o E o ) log
n [ A]a [ B ]b
 Fundamentals of Electrochemistry

Eo and the Equilibrium Constant

1.) A Galvanic Cell Produces Electricity because the Cell Reaction is NOT at
Equilibrium

Since Eo=E+o- E-o:

o 0.05916 [C ]c [ D ]d
E cell E log
n [ A]a [ B ]b

At equilibrium Ecell =0:

Definition of
equilibrium constant

0.05916 at 25oC
Eo log K
n

nE o
at 25oC
K 10 0.05916
 Fundamentals of Electrochemistry

Eo and the Equilibrium Constant

2.) Example:
Calculate the equilibrium constant (K) for the following reaction:
 Fundamentals of Electrochemistry

Cells as Chemical Probes

1.) Two Types of Equilibrium in Galvanic Cells

Equilibrium between the two half-cells
Equilibrium within each half-cell

If a Galvanic Cell has a nonzero voltage then the

net cell reaction is not at equilibrium

Conversely, a chemical reaction within a cell will

reach and remain at equilibrium.

For a potential to exist, electrons must

flow from one cell to the other which
requires the reaction to proceed not
at equilibrium.
 Fundamentals of Electrochemistry

Cells as Chemical Probes

2.) Example:
If the voltage for the following cell is 0.512V, find Ksp for Cu(IO3)2:

Ni(s)|NiSO4(0.0025M)||KIO3(0.10 M)|Cu(IO3)2(s)|Cu(s)
 Fundamentals of Electrochemistry
Biochemists Use Eo

1.) Redox Potentials Containing Acids or Bases are pH Dependent

Standard potential all concentrations = 1 M
pH=0 for [H+] = 1M

2.) pH Inside of a Plant or Animal Cell is ~ 7

Standard potentials at pH =0 not appropriate for biological systems
- Reduction or oxidation strength may be reversed at pH 0 compared to pH 7
 The Reaction Gibbs Energy
Relation between the reaction Gibbs energy
and the emf of the cell is

nFE = rG

F = 96,485 kC mol-1
The Work in Transporting Charge

The maximum work

dw e ,max rxn G d

For the passage d electrons from the

anode (LHS) to the cathode (RHS)
n eN A d nF d
 The Nernst equation

RT
E cell E

ln Qcell
F
E represents the standard cell potential, the
potential of the cell when all cell components are
under standard conditions.
f (all gases) = 1
a (solutes) = 1
T = 298.15 K
P = 1.00 bar pressure
 Cells at Equilibrium

When the electrochemical cell has reached

equilibrium
E cell 0 V Qcell K cell
Kcell = the equilibrium constant for the cell reaction.

RT n FE
E

ln K cell ln K cell
nF RT
Knowing the E value for the cell, we can estimate
the equilibrium constant for the cell reaction.
Concentration Effects and the Nernst Equation

Relationship between Gibbs Free Energy and Equilibrium constant:

Gr = Go + RT ln Q

where Q is the reaction quotient = [product]

[reactant]

But G = -n F Ecell and G = - n F Eocell

Ecell = Eocell RT ln Q
nF
 Question
If the standard cell potential at 298 K is 1.10 V for the following
reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s), then what is the change in
Gibbs Free Energy?

G = -n F Ecell
Half reactions: Zn Zn2+ + 2e-
Cu2+ + 2e- Cu
n = no of moles of electrons = 2
F = Faradays constant = 96,500 C/mol
Ecell = 1.10 V = 1.10 J/C
G = - (2) (96500 C/mol) (1.10 J/C)
= - 212300 J/mol
= - 212.3 kJ/mol
 Question
The equilibrium constant for the reaction
Ni(s) + Hg2Cl2(s) 2Hg(l) + 2Cl-(aq) + Ni2+(aq)
is 1.8 1019 at 298K. What is the value of the standard cell
potential Ecell for this reaction?