ELECTROCHEMISTRY

Chemical energy  Electrical

energy
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Electrochemical processes are oxidation-reduction reactions
in which:
• the energy released by a spontaneous reaction is
converted to electricity or
• electrical energy is used to cause a nonspontaneous
reaction to occur

0 0 2+ 2-
2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-)

19.1
Oxidation Numbers

• oxidation number, or oxidation

state, of an element in a simple
binary ionic compound is the
number of electrons gained or lost
by an atom of that element when it
forms the compound.
 Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation

number of zero.

Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to
the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1.
4.4
4. The oxidation number of hydrogen is +1 except when
it is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.

5. Group IA metals are +1, IIA metals are +2 and fluorine is

always –1.

6. The sum of the oxidation numbers of all the atoms in a

molecule or ion is equal to the charge on the molecule
or ion.
HCO3-
Oxidation numbers of all O = -2 H = +1
the atoms in HCO3- ?
3x(-2) + 1 + ? = -1
C = +4
4.4
• Elements by itself = 0
• Gr 1A: Always +1
• Gr 2A: Always +2
Halogens usually -1 ;positive with oxygen
Monoatomic ion = ion charge
H = +1 with non metals
= -1 with metals
O usually -2 ; -1 in peroxide H2O2 F always -1
Sum of ON’s for neutral compound =0
Sum of ON’s for polyatomic ion= ion charge
 Example
Determine the oxidation numbers of each element
following species:
1. N2O4
2. NH3
3. HNO3
4. N2O3
5. N2
6. H2SO4
7. KMnO4
8. H3PO4
 ReDox Reactions

• In redox reactions electrons are transferred from one

substance to another.
1. N20 + 3H20  2N-3H3+1
2. Mg0 (s) + 2H+1Cl (aq)  Mg+2Cl2 (aq) + H2 0(g)
3. Fe+2 + Cr+5  Fe+3 + Cr+3
Review

Oxidation reduction reactions involve a transfer of

electrons.
• OIL- RIG
• Oxidation Involves Loss
• Reduction Involves Gain
• LEO-GER
• Lose Electrons Oxidation
• Gain Electrons Reduction
DEFINITION OF TERMS

• Electrochemistry is the branch of chemistry that deals

with the interconversion of electrical energy and chemical
energy.
• Electrochemistry deals with the chemical changes produced
by electric current and with the production of electricity by
chemical reactions.
• Electrochemical processes are redox (oxidationreduction)
reactions in which the energy released by a spontaneous
reaction is converted to electricity or in which electrical
energy is used to cause a nonspontaneous reaction to occur.
Classification Of Electrochemical
Cells

1. Voltaic or Galvanic Cells

•electrochemical cells in
which spontaneous oxidation–
reduction reactions produce
electrical energy.
•after the Italian scientists
Luigi Galvani and Alessandro
Volta, who constructed early
Components of a Galvanic Cell

the anode cathode is

is the the
electrode at electrode
which at which
oxidation reduction
occurs occurs.
 DEFINITION OF TERMS

• oxidation-reduction reactions (redox reactions)

• Reactions that involve oxidation of one reactant and
reduction of another.
• Oxidation is an increase in oxidation number and
corresponds to the loss, or apparent loss, of electrons.
• Reduction is a decrease in oxidation number and
corresponds to a gain, or apparent gain, of electrons.
ELECTRODES
•are surfaces on which oxidation or
reduction half-reactions occur.
•cathode - electrode at which
reduction occurs as electrons
are gained by some species.
•anode -electrode at which
oxidation occurs as electrons
are lost by some species.
 DEFINITION OF TERMS
Oxidizing agents are species that
• oxidize other substances
• contain atoms that re reduced
• gain (or appear to gain) electrons.
Reducing agents are species that
• reduce other substances,
• contain atoms that are oxidized,
• Lose (or appear to lose) electrons.
• Connected this way the reaction starts
• Stops immediately because charge builds up.

eee
e
- - e
-
ZnSO4 CuSO
- 4-
Electricity travels in a complete circuit
An electric current flows from the anode
to the cathode because there is a
difference in electrical potential energy
A salt bridge
between the electrodes. serves three
functions.
1. It allows
electrical
contact
between the
two solutions.
2. It prevents
mixing of the
electrode
solutions.
3. It maintains
the electrical
• The voltage across the electrodes of a galvanic cell
• is called the cell voltage, or cell potential.
Experimentally, this is measured by a voltmeter
• Another common term for the cell potential is the
electromotive force or emf (E), which, despite the
name, is a measure of voltage, not force.

e e
ZnSO4 CuSO
-
- 4
The voltage across the electrodes of a
galvanic cell
is called the cell voltage, or cell
potential. Experimentally, this is
measured by a voltmeter
Another common term for the cell
potential is the electromotive force or
emf (E), which, despite the name, is
a measure of voltage, not force.
 Standard Reduction Potentials
Eo
The superscript “Eo” denotes standard-
state conditions, and Eo is the
standard reduction potential, or
the voltage associated with a
reduction reaction at an electrode
when all solutes are 1 M and all gases
are at 1 atm. Thus, the standard
reduction potential of the hydrogen
electrode is defined as zero. The
hydrogen electrode is called the
standard hydrogen electrode (SHE).
Standard Hydrogen Electrode
• This is the reference all other
oxidations are compared to
• Eº = 0 H2 in
• º indicates standard states
of 25ºC, 1 atm, 1 M
solutions.

H+
Cl-
1 M HCl
 Half cell
• A half-cell contains the oxidized and reduced forms of
an element, or other more complex species, in contact
with one another. A common kind of half-cell consists of a
piece of metal (the electrode) immersed in a solution of its
ions.
The zinc–copper voltaic cell utilizes the reaction
• Zn(s) + Cu+2(aq)  Zn+2(aq) + Cu(s)
Anode: Oxidation (Zn  Zn+2 + 2e–)
Cathode: Reduction (Cu+2 + 2e–  Cu)
• The standard cell can be represented as
Zn/Zn+2 //Cu+2/Cu
 Cell Potential
• Zn(s) + Cu+2 (aq)  Zn+2(aq) + Cu(s)
• The total cell potential is the sum of the potential at each
electrode.
Eºcell = Eºred - Eºox
Anode: Oxidation (Zn  Zn+2 + 2e–) Eº= - 0.76
Cathode: Reduction (Cu+2 + 2e–  Cu) Eº= 0.34

• Eºcell = 0.34 – (- 0.76)

= 1.1 volts
• Cell Potential
Determine the cell potential for a galvanic cell based on
the redox reaction.
• Cu(s) + Fe+3(aq) ® Cu+2(aq) + Fe+2(s)

• Fe+3(aq) + e-® Fe+2(s) Eº = 0.77 V red

• Cu(s)® Cu+2(aq) +2e- Eº = 0.34 V ox
Cell Potential

• Determine the cell potential for a galvanic cell based on

the redox reaction.
Cu(s) + 2Ag+(aq) Cu+2(aq) + 2Ag(s)
• Ag+(aq) + e-® Ag(aq) Eº = 0.79 V
• Cu (s) ® Cu +2
(aq) +2e
-
Eº = 0.34 V
Determine the oxidation numbers of each element in the
following compounds.
1. CaCO3
2. K2Cr2O7
3. Fe2O3
4. H2CO3
Show that the reaction below is a Redox Reaction. Determine
the reducing and oxidizing agents.
Zn + 2HCl  ZnCl2 + H2
• Reduction Potentials (E) at varying conditions
standard –state conditions are often difficult, and
sometimes impossible to maintain.
there is a mathematical relationship between the emf of a
galvanic cell and the concentration of reactants and
products in a redox reaction under nonstandard-state
conditions.
E= Eº cell - RT/nF log Q
E= Eº cell - 0.0821 li-atm/mol-k X 298 K /n 96,485 C/
mol- e- log Q
E = Eºcell – 0.0591 log Q

n
• Q = the ratio of concentration = product/reactant
• E= reduction potential
• Eº = standard potential
• R = universal gas constant = 0.0821 li-atm/mol-K
• T= temperature in Kelvin = 298 k
• N = iron charge ( moles of electrons)
• F= Faraday constant= 96, 485 c /mol-e-
• Q= reaction quotient
•
 By using Nernst Equation
What is the reduction potential of the reaction shown below
at 298 K
2 Al(s) + 3Cu+2(aq)  2Al+3(aq) + 3Cu(s)
Eºcell = 2.00v ; Al+3 = 0.1 M ; Cu+2 = 2.5M
E= Eºcell – 0.0591 log Q  Nernst Equation
n

In order to get the value of n & Q balance the redox reaction

Example No.1
• Al(s) + Cu+2(aq) )  Al+3(aq) + Cu(s)
( Al(s)  Al+3(aq) + 3e– ) 2
Cu+2(aq) + 2e–  Cu(s) ) 3
2Al(s)  2 Al+3(aq) + 6e n= 6
3Cu+2(aq) + 6e–  3Cu(s)
Q= product/ reactant
= (conc’n of Al+3)exp ; exp = coefficient of AL+3 = 2
( conc’n of Cu+2)exp ; exp = coefficient of Cu+2 = 3

Q= (Al+3)2 = (0.1) 2
= 6.4x10-4
(Cu+2)3 (2.5)3
E= Eºcell – 0.0591 log Q
n
E= 2.00 v– 0.0591 log 6.4x10-4
6
E= 2.03 V // ans.
 Example:
Zn(s) + Ag+ (aq)  Zn+2(aq) + Ag(s)
Zn  Zn+2 + 2e–

(e
-
+ Ag+1 ® Ag) 2
Zn  Zn+2 + 2e–

2e
-
+2 Ag+1 ® 2Ag
Zn +2 Ag+1 ® Zn+2 + 2Ag
• EXERCISES
• 1. Al(s) + Fe+2(aq) → Al+3(aq) + Fe(s)
• [Fe+2]=0.40M Fe+2 + 2e= -0.409V
• [Al+3]=0.55M Al+3 + 3e= -1.706V
• 2. Mg(s) + Ag+1(aq) → Mg+2(aq) + Ag(s)
• [Mg+2]=0.35M Mg+2 + 2e= -2.37V
• [Ag+1]=0.67M Ag+1 + 1e= 0.79V
•
Classification of
Electrochemical
2. Electrolytic Cell
Cells
- those in which electrical energy from an external
source causes nonspontaneous chemical reactions to
occur.
• ELECTROLYSIS- The process whereby an electric
current passes through a substance to cause a
chemical change; produces an oxidation–reduction
reaction.
• Lysis means “splitting apart.” In many electrolytic
cells compounds are split into their constituent
elements.
Electrolysis
If you melt or dissolve an ionic compound
(such as NaCl or CuCl2), then the ions become
free to move around – and carry electrical
current.
Molecule of solid
copper chloride
CuCl2 (s)

Molecule of solid
copper chloride
after being
chlorid Copper dissolved
e ion
27/10/2024
ion CuCl2 (aq)
 Electrolysis
Electrolysis is used to separate a metal
from its compound.
When we electrolysed
copper chloride the
NEGATIVE chloride
ions moved to the
POSITIVE electrode
and the POSSITIVE
copper ions moved to
the NEGATIVE
electrode – OPPOSITES
ATTRACT!!!
= chloride ion

= copper ion
27/10/2024
 Purifying Copper

Impure
copper
+ -- Pure
copper
+ Cu 2+ --
Solution
+ Cu 2+

containing + Cu 2+
copper
ions
At the anode: At the cathode:
Cu(s)
27/10/2024 Cu2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)
BATTERIES
A battery is a device that stores chemical
energy and converts it to electrical energy.
The chemical reactions in a battery involve to
flow of electrons from one material
(electrode) to another
through an external circuit.
Types of battery
[Link] cell – batteries are single use and
cannot be recharged. Dry cells and alkaline
batteries
b. Secondary cell – rechargeable batteries
Secondary cell
 Batteries

Lead storage
battery

Anode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e-

Cathode: PbO2 (s) + 4H+ (aq) + SO42- (aq) + 2e- PbSO4 (s) + 2H2O (l)

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42- (aq) 2PbSO4 (s) + 2H2O (l)

19.6
 Batteries

Solid State Lithium Battery 19.6

Electrolysis is the process in which electrical energy is used
to cause a nonspontaneous chemical reaction to occur.

19.8
Electrolysis of Water

19.8
Electrolysis and Mass Changes

charge (C) = current (A) x time (s)

1 mole e- = 96,500 C

19.8
 How much Ca will be produced in an electrolytic cell of
molten CaCl2 if a current of 0.452 A is passed through the
cell for 1.5 hours?

Anode: 2Cl- (l) Cl2 (g) + 2e-

Cathode: Ca2+ (l) + 2e- Ca (s)

Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)

2 mole e- = 1 mole Ca

C s 1 mol e- 1 mol Ca
mol Ca = 0.452 x 1.5 hr x 3600 x x
s hr 96,500 C 2 mol e-
= 0.0126 mol Ca

= 0.50 g Ca
19.8
Voltaic cell vs Electrolytic cell

It is a source of It requires a source

energy. of external energy.
Converts chemical energy to Converts electrical energy to
electrical energy. chemical energy.

Cathode is the positive Cathode as the negative

electrode ( gain electrons) electrode attracts cations
toward it.
Anode is the negative electrode Anode as the positive electrode
( loss electrons) attracts anions toward it.

Oxidation in the anode and Oxidation in the anode and

reduction in the cathode. reduction in the cathode.
Example
Determine the oxidation
numbers of each
element following
species:
1.MnO4
2. HNO3
3. N2
4. H2SO4
The end