ELECTROCHEMISTRY

RULES FOR ASSIGNING OXIDATION STATES

(Review) 

Rule # 1: Group one elements are always 1+ in

compounds or as free (aq) ions.
 
Example
in NaCl EACH Na has an oxidation state of 1+.
in K2SO4 EACH Na has an oxidation state of 1+.
A Li+1 (aq) free ion has an oxidation number of 1+.
 
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 

Rule # 2: Group two elements have an oxidation

state of 2+ in compounds and as free (aq) ions.

Example:
in BaCl2 EACH Ba has an oxidation state of 2+
in Ca3(PO4)2 EACH Ca has an oxidation state of 2+.
A free Mg+2 has an oxidation state of 2+.
 
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 

Rule # 3: The oxidation state of any ion is its charge.

Example:
a Fe+3(aq) ion has an oxidation state of 3+.
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 

Rule # 4: Any atom that is uncombined and has a neutral

charge has an oxidation state of 0, this is called the
elemental state
Example
Cu(s) has an oxidation state of 0, as does Fe(s):
IMPORTANT - remember if no charge is shown,
assume it is 0 – not one as is algebra.
the exceptions H2, O2, N2, Cl2, Br2, I2, F2 exist as diatomic
molecules in the elemental state and have oxidation
states of 0.
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 
Rule # 5: The oxygen rules: Oxygen USUALLY has an
oxidation state of 2- in compounds, 0 in O2.
EXAMPLE: in H2O oxygen is 2-
In H2SO4 EACH oxygen is 2-
EXCEPTION #1– when oxygen is contained in a
PEROXIDE, it has an oxidation state of 1-.
o       H2O2, Li2O2, K2O2 are peroxides, each O is 1-
EXCEPTION #2 – when oxygen is combined with Fluorine,
its oxidation state is 1+ or 2+. Fluorine is electronegative
enough to oxidize oxygen
EXAMPLE in FO the oxygen is 1+
in F2O each oxygen is 2+
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 

Rule # 6: Fluorine is always 1- in its compounds

Rule #7 Halogens (Group 17) are usually 1- EXCEPT

when in table E polyatomic ions, where their oxidation
states can vary (multiple oxidation states).
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 

Rule # 8: The sum of the oxidation states of all the

elements in a compound MUST equal the charge of the
compound, even if it is neutral.
Example:
in NaOH all the oxidation states equal neutrality, 0
Na = +1
O = -2
H = +1
total = 0
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 

Rule # 9: The hydrogen rule: the oxidation state of

hydrogen is usually 1+
EX in H2O each hydrogen is 1+

EXCEPTION – in metal hydrides the hydrogen is 1-,

hydrogen is electronegative enough to oxidize
group one metals.
Example: NaH, KH etc the hydrogen is 1-
 RULES FOR ASSIGNING OXIDATION STATES
(Review) 

Rule # 10: ELEMENTS WITH MULTIPLE

OXIDATION STATES LISTED ON THE PERIODIC
TABLE Some elements have many oxidation
states, determined by what other elements they
combine with.

For example N, Mn, Cr have multiple oxidation states

in their compounds. NOTE elements like Zn only
have one state from your periodic table, so just look
it up!
KMnO4
(NOTE, this is a neutral compound, charge is 0)

K = +1 (Rule 1) = +1
O = -2 (Rule 2) = 4(-2)
Mn = ? (Rule 10) = X .
total = 0
Mn - +1 + 4(-2) + X = 0 (solve for X)
+1 + (-8) + X =0
(-7) + X = 0
X = 7 , Mn = +7
 Electrochemistry
• Electrochemistry is the study of chemical
processes that cause electrons to move. This
movement of electrons is called electricity,
which can be generated by movements of
electrons from one element to another in a
reaction known as an oxidation-reduction
 ("redox") reaction.
 Redox Reaction
• A redox reaction is a reaction that involves
a change in oxidation state of one or more
elements.
• When a substance loses an electron, its
oxidation state increases; thus, it is
oxidized. When a substance gains an
electron, its oxidation state decreases, thus
being reduced. For example, for the redox
reaction 
 Redox Reactions
• Examples of Redox Reactions:
Zn(s) + CuSO4(aq)  ZnSO4(aq) + Cu(s);
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)

Cu(s) + 2AgNO3(aq)  CuSO4(aq) + 2Ag(s);

Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) 

Mn2+(aq) + 5Fe3+(aq) + 4H2O
 Balancing Redox Equations
• Review of Terms:
– Oxidation–reduction (redox) reaction – involves a
transfer of electrons from the reducing agent to the
oxidizing agent
– Oxidation – loss of electrons
– Reduction – gain of electrons
– Reducing agent – electron donor
– Oxidizing agent – electron acceptor
 Balancing Redox Equations

• Half–Reactions Method:
• The overall reaction is split into two half –
reactions, one involving oxidation and one
reduction.
8H+ + MnO4 + 5Fe2+  Mn2+ + 5Fe3+ + 4H2O

Reduction: 8H+ + MnO4 + 5e  Mn2+ + 4H2O

Oxidation: 5Fe2+  5Fe3+ + 5e
Giventhe redox reaction

Which species is oxidized?

Which is reduced?
Identify the reducing agent and the oxidizing
agent.
 Balancing Redox Equations
• The Half–Reaction Method for Balancing
Equations for Oxidation–Reduction Reactions
Occurring in Acidic Solution
1. Write separate equations for the oxidation
and reduction half–reactions.
2. For each half–reaction:
A. Balance all the elements except H and O.
B. Balance O using H2O.
C. Balance H using H+.
D. Balance the charge using electrons.
 Balancing Redox Equations:
The Half-Reaction Method
1. Write separate equations for oxidation and
reduction half–reactions.
2. For each half–reaction:
Balance all the elements except H and O.
Balance O using H2O.
Balance H using H+.
Balance the charge using electrons.
3. If necessary, multiply one or both balanced half–
reactions by an integer to make the number of
electrons in both half–reactions equal.
4. Add half–reactions and cancel identical species.
 Balancing Redox Equations

Example:

Cr2O72-(aq) + HSO3-(aq)  Cr3+(aq) + HSO4-(aq)

• How can we balance this equation?

• First Steps:
 Separate into half-reactions.
 Balance elements except H and O.
 Balancing Redox Equation:
The Half-Reaction Method

• Cr2O72-(aq)  2Cr3+(aq)  
• HSO3-(aq)  HSO4-(aq)

• How many electrons are needed to balance the

charge in each half-reaction?
 Balancing Redox Equation:
The Half-Reaction Method

• Adding electrons:
• 6e- + Cr2O72-(aq)  2Cr3+(aq) 
• HSO3-(aq)  HSO4-(aq) + 2e-

• How can we balance the oxygen atoms?

 Balancing Redox Equation:
The Half-Reaction Method

• 6e- + Cr2O72-(aq)  Cr3+(aq) + 7H2O 

• H2O + SO32-(aq)  + SO42-(aq) + 2e-

• How can we balance the hydrogen atoms?

 Balancing Redox Equation:
The Half-Reaction Method

• This reaction occurs in an acidic solution.

• 14H+ + 6e- + Cr2O72-  2Cr3+ + 7H2O 
• H2O + HSO3-  HSO4- + 2e- + 2H+

• How can we balance the electrons?

 Balancing Redox Equation:
The Half-Reaction Method

• 14H+ + 6e- + Cr2O72-  2Cr3+ + 7H2O

• 3[H2O + HSO3-  HSO42- + 2e- + 2H+]

• The final balanced equation:

Cr2O72- + 3HSO3- + 8H+  2Cr3+ + 3HSO4- + 4H2O

 Sample Exercises

Balance the following redox reactions in acidic

solution.

1) Br–(aq) + MnO4–(aq)  Br2(l) + Mn2+(aq)

2) Cr2O72-(aq) + H2O2(aq)  Cr3+(aq) + H2O(l) + O2(g)

The Half–Reaction Method for Balancing Redox
Equations in Basic Solution

1. Use the half–reaction method as specified for acidic

solutions to obtain the final balanced equation as if
H+ ions were present.
2. To both sides of the equation, add a number of OH–
ions that is equal to the number of H+ ions present.
(You want to eliminate H+ by turning is into H2O)
3. Form H2O on the side containing both H+ and OH–
ions, and eliminate the number of H2O molecules
that appear on both sides of the equation.
4. Check that elements and charges are balanced.
 Sample Exercises

• Balance the following redox reactions in basic

solution:

• Br2(aq) + OH-(aq)  BrO3-(aq) + Br-(aq) + H2O;

• Cr(OH)4-(aq) + OH-(aq)  CrO42-(aq) + H2O;

 Electrochemical Cells
Two types of Electrochemical Cell

 Galvanic (Voltaic) Cell

 Electrolytic Cell
 Galvanic Cell
• A device in which chemical energy is
converted to electrical energy.
• It uses a spontaneous redox reaction to
produce a current that can be used to generate
energy or to do work.
A Galvanic Cell
 In Galvanic Cell:
• Oxidation occurs at the anode.
• Reduction occurs at the cathode.
• Salt bridge or porous disk allows ions to flow
without extensive mixing of the solutions.
 Salt bridge – contains a strong electrolyte held in a
gel–like matrix.
 Porous disk – contains tiny passages that allow
hindered flow of ions.
Galvanic Cell
 Cell Potential
• A galvanic cell consists of an oxidizing agent (in
cathode half-cell) and a reducing agent (in anode
half-cell).
• Electrons flows through a wire from the anode half-
cell to the cathode half-cell.
• The driving force that allows electrons to flow is
called the electromotive force (emf) or the cell
potential (Ecell).
 The unit of electrical potential is volt (V).
1 V = 1 J/C of charge transferred.
 Standard Reduction Potentials
• Values of E° in standard table of half-cell potentials
are for reduction half-cell reactions
 Table 18.1 (or 17.1)
 1 M, 1 atm, 25°C
• When a half-reaction is reversed, the algebraic sign of
E° changes.
• When a half-reaction is multiplied by an integer, the
value of E° remains the same.
• A galvanic cell runs spontaneously in the direction
that gives a positive value for E°cell
 Example: Fe3+(aq) + Cu(s)  Cu2+(aq) + Fe2+(aq)

• Half-Reactions:
 Fe3+ + e–  Fe2+ E° = 0.77 V
 Cu2+ + 2e–  Cu E° = 0.34 V
• To balance the cell reaction and calculate the
cell potential, we must reverse reaction 2.
 Cu  Cu2+ + 2e– – E° = – 0.34 V
• Each Cu atom produces two electrons but each
Fe3+ ion accepts only one electron, therefore
reaction 1 must be multiplied by 2.
 2Fe3+ + 2e–  2Fe2+ E° = 0.77 V
 Standard Cell Potential

2Fe3+ + 2e–  2Fe2+ ; E° = 0.77 V (cathode)

Cu  Cu2+ + 2e– ; – E° = – 0.34 V (anode)
• Balanced Cell Reaction:
Cu + 2Fe3+  Cu2+ + 2Fe2+

• Cell Potential: E
E°cell = E°(cathode) – E°(anode)
E°cell = 0.77 V – 0.34 V = 0.43 V
 Calculating Standard Cell Potential

• Given the following reduction potentials:

• Ag+(aq) + e-  Ag(s); E° = 0.80 V
• Zn2+(aq) + 2e-  Zn(s); E° = -0.76 V

• Calculate the cell potential for the following reaction

and predict whether the reaction will take place:
• Zn(s) + 2Ag+(aq)  Zn2+(aq) + 2Ag(s)
 Standard Cell Potentials

• Given the following reduction potentials:

• Cu2+(aq) + 2e-  Cu(s); E° = 0.34 V
• Ni2+(aq) + 2e-  Ni(s); E° = -0.23 V

• Predict whether the following reaction will take

place:
• Cu(s) + Ni2+(aq)  Cu2+(aq) + Ni(s)
 Cell Notations for Galvanic Cells

• Used to describe electrochemical cells.

• Anode components are listed on the left.
• Cathode components are listed on the right.
• Separated by double vertical lines.
• The concentration of aqueous solutions should be
specified in the notation when known.
• Example: Mg(s)|Mg2+(aq)||Al3+(aq)|Al(s)
 Mg  Mg2+ + 2e– (anode)
 Al3+ + 3e–  Al (cathode)
 Description of a Galvanic Cell

• The cell potential is always positive for a galvanic

cell, where E°cell = E°(cathode half-cell) – E°(anode half-cell) (as
given in the table of half-cell potentials)
• Anode is the negative terminal and cathode is the
positive terminal.
• Electron flows from the anode (-) to cathode (+).
• Current flows from cathode(+) to anode(-).
• Positive ions flows from anode to cathode half-cells
and negative ions flows from cathode to anode
though the “salt bridge”.
 Designation of Anode and Cathode

• Write balanced net ionic equation for the spontaneous

cell reaction.
• The oxidizing agent (one with the more positive or
less negative reduction potential E°) will be the
cathode and the other will be the anode.
• Oxidation occurs in anode half-cell and reduction in
cathode half-cell.
• Anode is negative(-) and cathode is positive(+).
Cell Potential, Free Energy, and Electrical Work

Maximum cell potential and free energy

• Directly related to the free energy difference between
the reactants and the products in the cell reaction.
 ΔG° = –nFE°
F = 96,485 C/mol e–
Work:
• In any real, spontaneous process some energy is
always lost (wasted) – the actual work obtained is
always less than the calculated (maximum) value.
Concentration Cells
 Electrolytic Cell
• an electrochemical cell that drives a non-
spontaneous redox reaction through the
application of electrical energy.

• They are often used to decompose chemical

compounds, in a process called electrolysis
Greek word (lysis) means to break up.
 Applications
• Important examples of electrolysis are the
decompositionof water into hydrogen and
oxygen, and bauxite into aluminium and other
chemicals. Electroplating (e.g. of copper,
silver, nickel or chromium) is done using an
electrolytic cell.
• Electrolysis is a technique that uses a direct
electric current (DC).
 Electrolysis
• A process that forces a current through a cell
to produce a chemical change for which the
cell potential is negative.
 Commercial Electrolytic Processes

• Production of aluminum
• Purification of metals
• Metal plating
• Electrolysis of sodium chloride
• Production of chlorine and sodium hydroxide
The Hall-Heroult Process for Al Production
Electroplating/Silver Plating a Spoon
The Mercury Cell for Production of
Chlorine and Sodium Hydroxide
The Downs Cell for the Electrolysis of Molten
Sodium Chloride
Difference between galvanic
and electrolytic cell
Electrochemical Energy Storage
Electrochemical energy storage is a method
used to store electricity under a chemical
form. This storage technique benefits from
the fact that both electrical and chemical
energy share the same carrier, the
electron. This common point allows to limit
the losses due to the conversion from one
form to another
 Battery
Three categories of batteries

1. Primary (Non rechargeable) Batteries

2. Secondary (Rechargeable) Batteries
3. Fuel Cell
 Primary Batteries
(Non rechargeable)

• A primary battery cannot be recharged, so it is

discarded when the components have reached
their equilibrium concentrations, that is, when
the cell is dead
 Common Dry Cell
• Leclanche’s cell
• Invented in the 1860’s and
become a familiar household
item during the first three
quarters of 20th century
 Drawbacks
• Cathode half cell reaction is not completely
understood
• At a high current drain, the reaction generated
ammonia gas which could build and cause
serious voltage drop
• Zinc anode reacted with the acidic NH4+ , dry
cells had a short shelf life
 Alkaline Battery
Although more expensive, alkaline battery avoids these
drawbacks.

Same electrode materials (Zn and MnO2)

but the electrolyte is a paste of KOH and water.

The half reactions are essentially the same, but the use
of the KOH eliminates the ammonia gas build up and
maintains the Zn electrode.
Alkaline Battery
 Hg & Ag Button Batteries
• Both use a zinc container
as the anode in a basic medium
• Mercury battery employs HgO
as oxidizing agent while Ag2O
for silver battery and both use a steel can around
the cathode.

Solid reactant are compacted with KOH and separated

with moist paper
Anode (oxidation)
Zn(s) + 2OH-  ZnO (s) + H2O + 2e-

Cathode (reduction)
HgO (s) + H2O + 2e-  Hg(ℓ) + 2OH- (aq)
Ag2O + H2O + 2e-  2Ag(s) + 2OH- (aq)

Overall (cell) reaction:

Zn(s) + HgO(s)  ZnO(s) + Hg(ℓ) Ecell= 1.3V
Zn(s) + Ag2O  ZnO(s) + 2Ag(s) Ecell= 1.6 V
 Lithium Batteries
• often used in watches and implanted devices
• The anode is lithium metal foil; cathode is one of the
metal oxide in which lithium ions lies between oxide
layers.
Some implantable medical devices have a silver
vanadium oxide (SVO; AgV2O5.5) cathode
Anode: 3.5 Li(s)  3.5Li+ + 3.5e-
Cathode: AgV2O5.5 + 3.5Li+ + 3.5e-  Li3.5AgV2O5.5
Overall: AgV2O5.5 + 3.5 Li(s)  Li3.5AgV2O5.5
 Secondary Batteries
(Rechargeable)
• Batteries are recharged when it runs down by
supplying electrical energy to reverse the cell
reaction and re-form reactant.

• Voltaic cells are periodically converted to

electrolytic cells to restore non equilibrium
concentrations of the cell components
 Lead-Acid Battery
Contains six cells (each delivers
2.1V)connected in series for a
total of about 12V.

Each cell contains two lead grids high

surface (Pb in the anode and high
surface PbO2 in the cathode).

Grids are immersed in electrolyte

solution of ~4.5M H2SO4.
 Lead-Acid Battery
Anode(oxidation): Pb(s) + HSO4-  PbSO4(s) + H+ + 2e-

Cathode (reduction): PbO2 + 3H+ +2e-  PbSO4 + 2H2O(ℓ)

Overall reaction (discharge):

PbO2(s) + Pb(s) + 2H2SO4(aq)  PbSO4 + 2H2O(ℓ) Ecell= 2.1 V

Overall reaction (recharged):

PbSO4 + 2H2O(ℓ)  PbO2(s) + Pb(s) + 2H2SO4(aq)
Nickel-Metal Hydride(Ni-MH) Battery
• Concerns about the toxicity of Nickel-cadmium batteries
leads to its replacement in the form of Nickel-Metal
Hydride(Ni-MH) batteries.

• The Ni-MH battery is common in cordless razors, camera

flash units, and power tools.

• Lightweight, has high power, and is nontoxic but it may

discharge excessively during long term storage.
Anode (oxidation):
MH(s) + OH-  M(s) + H2O(ℓ) + e-

Cathode (reduction):
NiO(OH)(s) + H2O(ℓ)  Ni(OH)2(s) + OH-

Overall (cell) reaction:

MH(s) + NiO(OH)(s)  Ni(OH)2(s) +M(s)

Ecell= 1.4 V
 Lithium-Ion Battery
• The anode is Li and the atoms lie between sheets of graphite
(designated LixC6) while the cathode is lithium metal oxide,
such as LiMn2O4 or LiCoO2 and a typical electrolyte is 1M
LiPF6 in an organic solvent, such as mixture of dimethyl
carbonate and methylethyl carbonate.

• Li-ion battery powers laptop computers, cellphones and

camcorders.

• Its key drawbacks are expense and

flammability of organic solvent.
 Lithium-Ion Battery
Anode (oxidation): LixC6  xLi+ + xe- + C6(s)

Cathode(reduction): Li1-xMn2O4 + xLi+ + xe-  LiMn2O4 (s)

Overall (cell) reaction:

LixC6 + Li1-xMn2O4(s) LiMn2O4(s) + C6(s) Ecell= 3.7 V

The cell reaction is reversed

during charging.
 Fuel Cells
• In contrast with primary and secondary batteries, fuel cell,
sometimes called flow battery is not self-contained.
• Fuel cells use combustion to produce electricity
• The most common fuel cell developed for use in cars is
the proton exchange membrane (PEM) cell which uses H 2
as the fuel and has an operating temperature of around
80oC
The cell reactions are:
Anode (oxidation)
2H2 (g)  4H+ (aq) + e-
Cathode (reduction)
O2(g) + 4H+ (aq) + 4e-  2H2O (g)
Overall (cell) reaction: 2H2 (g) + O2(g)  2H2O (g)
Mechanism
 Corrosion
• The process that returns metals to their
oxidized state.
• Involves oxidation of the metal.
Electrochemical Corrosion of Iron
 Corrosion Prevention

• Apply coating (such as paint or metal

plating)
 Galvanizing
• Alloying
• Cathodic Protection
 Protects steel in buried fuel tanks and
pipelines.
Cathodic Protection