SMA SANTA LAURENSIA

Redox Reactions &

Electrochemical Cells
Chapter 3 @1920
CHEMISTRY & YOU
Demo 1
Demo 2
 QuestionS?
• Apa yang anda amati?
• Tuliskan reaksi apa yang terjadi?
• Apa jenis reaksinya? Bagaimana cara
menentukan red-oks?
• Apa reaksi tersebut setara?
Bagaimana cara menyetarakan
reaksi? apa tujuan penyetaraan?
 Outlines:
 Balancing Oxidation–Reduction Reactions
 Galvanic Cells
 Standard Reduction Potentials
 Cell Potential
 Dependence of Cell Potential on Concentration
 Batteries
 Corrosion and Prevention
 Electrolytic Cells
 Commercial Electrolytic Processes
 Redox Basic Concept

CHEMISTRY & YOU

 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)  Cu(NO3)2(aq) + 2Ag(s);

Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

 MnO4-(aq) + 5Fe2+(aq) + 8H+(aq)  Mn2+(aq) +

5Fe3+(aq) + 4H2O
Ex: write the balance redox equation for the
reaction;

1. MnO4-(aq) + Br-(aq) → Mn2+(aq) + Br2(g)

(Acidic solution)

2. Cl2(g) + IO3¯(aq) → IO4¯(aq) + Cl¯ (aq)

(basic solution)
CHEMISTRY & YOU
CHEMISTRY & YOU
The Half-Reaction Method
 The Half-Reaction Method

Example: write the balance redox equation for

the reaction;

S2-(aq) + NO3 -(aq)  SO3(g) + NO(g) (Acidic

solution)
 The Half-Reaction Method
Answer;
 Step 1; write 2 Half-Reactions
- S2-  SO3 (oxidation)
- NO3 -  NO (reduction)
 Step 2;
Balance Elements Other than H & O; (for N and S),
then Balance O with H2O
- S2- + 3H2O  SO3
- NO3-  NO + 2 H2O
then for Acidic solution, Balance H with H+
- S2- + 3H2O  SO3 + 6H+
- NO3- + 4H+  NO + 2H2O
CHEMISTRY & YOU
then balance charge with add electrons
- S2- + 3H2O  SO3 + 6 H+ + 8e-
- NO3- + 4H+ + 3e-  NO + 2H2O
 Step 3; multifly the half reaction to equalize electrons
- 3S2- + 9H2O  3SO3 + 18H+ + 24 8e-e x3

- 8NO3- + 32H+ + 3e 24- e  8NO + 16 H2O x8

 Step 4; Add the 2 half-reaction.
- 3S2- + 9 H2O  3SO3 + 18H+ + 24e-
- 8NO3- + 32H+ + 24e-  8NO + 16 H2O
3S2-(aq) + 8 NO3-(aq) + 14H+ (aq)  3 SO3(g) + 8NO(g)
+ 7H2O(l)

CHEMISTRY & YOU

 The Oxidation-State Method
Step 1. determine the oxidation state of the elements
Step 2. balance the atoms of atoms whose oxidation state
change.
Step 3. determine the total changes of oxidation state of the
elements
Step 4. multiply the total oxidation state
Step 5. balance Elements :
 Other H
 O, H & and charge with H+ , OH- or H2O
Step 6. check the elements and charges are balanced
CHEMISTRY & YOU
 The Oxidation-State Method

Example; Complete and Balance Following Reaction:

CuS (s) + NO3 - (aq)  Cu2+(aq) + SO42- (aq) + NO (g)
(acidic Condition)

STEP 1. Balance the number element with oxidation number

changed
CuS (s) + NO3 - (aq)  Cu2+(aq) + SO42- (aq) + NO (g)
+2 -2 +5 -2 +2 +6 -2 +2 -2

Note: the elements with oxidation number changed are S and N

CHEMISTRY & YOU
 The Oxidation-State Method

Step 3. Determine the total changes of oxidation state of the

elements
CuS (s) + NO3 - (aq)  Cu2+(aq) + SO42- (aq) + NO (g)
+2 -2 +5 -2 +8e +2 +6 -2 +2 -2

-3e
Step 4. Devide/Multiply the total oxidation state
CuS (s) + NO3 - (aq)  Cu2+(aq) + SO42- (aq) + NO (g)
+2 -2 +5 -2 +8e x3 +2 +6 -2 +2 -2

-3ex8
CHEMISTRY & YOU
 The Oxidation-State Method

3CuS (s) + 8 NO3 -(aq)  3Cu2+(aq)+ 3SO42- (aq) + 8 NO(g)

STEP 5. Balance Elements H, O and charge with H+ , OH- or

H2O
- 3CuS (s) + 8NO3 - (aq)  3Cu2+(aq) + 3SO42-(aq) +
8NO(g)

- 3 CuS (s) + 8 NO3 - (aq) + 8 H+  3 Cu2+(aq) + 3 SO42-

(aq) + 8 NO (g) + 4 H2O

CHEMISTRY & YOU

 Balancing Redox Equations
Exercise:

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

 Quizz
Balance the following redox reactions:
 Cr2O72- + C2O42-  Cr2+ + CO2 (in acidic
solution)

 Br2(aq) + OH-(aq)  BrO3-(aq) + Br-(aq) + H2O

(in basic solution)

 Mn2+ + H2O2  MnO2 + H2O (in basic solution)

CHEMISTRY & YOU

What do you see, think, wonder???
 Electrochemistry Cells
 Two Types of Electrochemical Cells:
1. Galvanic
2. Electrolytic

Galvanic Cell - Converts a Chemical Potential Energy into

an Electrical Potential to Perform Work
Electrolytic Cell- Uses Electrical Energy to Force a
Chemical Reaction to happen that would not otherwise
occur

CHEMISTRY & YOU

 1. Galvanic Cell

The redox reaction of

zinc metal with
aqueous Cu2+ ions.
1. Galvanic Cell
 In Galvanic Cell:

CHEMISTRY & YOU

SHORTHAND NOTATION
FOR GALVANIC CELLS
 CELL POTENTIALS AND FREE-ENERGY
CHANGES FOR CELL REACTIONS
• Directly related to the free energy difference between
the reactants and the products in the cell reaction.
ΔG = –n.F.Ecell, (1F = 96,485C/mol e–)

Note:
• In any real, spontaneous process some energy
is always lost (wasted) – the actual work
obtained is always less than the calculated
(maximum) value
 Standard Reduction Potentials (E°)
A galvanic cell consisting of a Cu2+(1 M)/Cu half-cell and a standard
hydrogen electrode (S.H.E.). The measured standard cell potential at 25 °C
and 1 atm is 0.34 V
Standard Hydrogen Electrode (S.H.E)
Standard Reduction Potentials (E°)
CHEMISTRY & YOU
 USING STANDARD REDUCTION
POTENTIALS
• Calculate Standard Cell Potential (E°cell)
E°cell = E°(cathode) - E°(anode)
Note : E° is standard reduction potential
• ARRANGING OXIDIZING AND REDUCING AGENTS
IN ORDER OF INCREASING STRENGTH
ex; Arrange the following reducing agents in order of increasing
strength under standard-state conditions: Al(s), Na(s), Zn(s).

• PREDICTING WHETHER A REDOX REACTION IS

SPONTANEOUS
ex; Predict whether Pb2+(aq) can oxidize Al(s) or Cu(s) under
standardstate conditions. Calculate for each reaction at 25 °C
 CELL POTENTIALS AND
THE NERNST EQUATION
• At 25oC (for concentration cells).
ΔG = ΔG° + R.T ln Q
Where, ΔG = -n.F.Ecell and ΔG° = -n.F.E°cell

So, -n.F.Ecell = -n.F.E°cell + R.T ln Q

Ecell = E°cell - R.T ln Q
n.F
Ecell = E°cell – 2.303R.T log Q Where,
n.F n = number of electron
Ecell = E°cell – 0.0592 V log Q
Q = quesion for
n equilibrium condition
CHEMISTRY & YOU
 USING THE NERNST EQUATION TO
DETERMINATION pH

The following cell has a potential of 0.55 V at 25 °C:

What is the pH of the solution in the anode compartment?

(answer:pH=4.6)
 STANDARD CELL POTENTIALS AND
EQUILIBRIUM CONSTANTS
ΔG°, K, and E°cell
 STANDARD CELL POTENTIALS AND
EQUILIBRIUM CONSTANTS

Use the standard reduction potentials to calculate the

equilibrium constant at 25 °C for the reaction;

Answer : K = 1 x 1027
 BATTERIES

A battery is an electrochemical cell or series of cells that

produces an electric current. In principle, any galvanic cell could
be used as a battery.
Primary Batteries

a zinc-carbon dry cell Alkaline batteries

CHEMISTRY & YOU

 BATTERIES

d. Lead Storage Battery e. Ni-Cad Battery f. Fuel Cell

CHEMISTRY & YOU

 Corrosion
• The process that returns metals to their oxidized
state.
• Involves oxidation of the metal.

Electrochemical Corrosion of Iron

CHEMISTRY & YOU
 Corrosion Prevention

• Apply coating (such as paint or metal

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

CHEMISTRY & YOU

Galvanizing
Alloying
 Cathodic Protection

CHEMISTRY & YOU

 2. Electrolysis Cell

• A process that forces a current through a

cell to produce a chemical change for
which the cell potential is negative.
It has the following characteristics :
 Nonspontaneous redox reaction
 Produces chemicals from electricity
 Forces electrolysis to occur

CHEMISTRY & YOU

 Electrolysis of water

Oxidation Half-Reaction 2H2O(l) O2(g) + 4H+(aq) + 4e-

Reduction Half-Reaction 2H2O(l) + 2e- H2(g) + 2OH-(aq)
Overall (cell) Reaction 2H2O(l) 2H2(g) + O2(g)
For electrolysis to work, you need a liquid
sample:
1) molten cells
Melt the crystals (produce a "molten" sample.
This is the only way to electrolyse insoluble
salts, and is the only way to produce, by
electrolysis, pure metals.

2) aqueous cells
Dissolve the ionic substance in water (this is
the most common)
 Type-1 : Electrolysis Cell

• Inert electrodes immersed in a molten

ionic compound
• Things are reversed…meaning:
• The oxidation half reaction is ABOVE
the reduction half-reaction!
• Non-spontaneous…
Draw and completely analyze a molten NaBr electrolytic cell.
Molten or (l) means
Electrons go from
ions but no water DC Power
anode to cathode.
e- Source
- +
e-
The negative is The positive is
reduction oxidation

Pt Pt

_ +
Na+ oxidation
reduction
cathode Br- anode
2Na+ + 2e- → 2Na(l) 2Br- → Br2(g)+ 2e-
-2.71 v cations to cathode -1.09 v
anions to anode

2Na+ + 2Br- → Br2(g) + 2Na(l) E0 = -3.80 v MTV = +3.80 v

The MTV is the minimum theoretical voltage required to start a reaction
 Type-2 : Electrolysis Cell

• Inert electrodes immersed in an

aqueous ionic compound
• Things are different now, you have
water to consider!

Soooo…what do you do if there

is water in the cell?
Pb2+ undergoes reduction
in water

Reduction of water

Treat as if it were here

Water will undergo reduction

above
anything that is below this line.
Below this line, they will
undergo oxidation

Water will undergo

reduction in a K+ solution
Water (lower) undergoes
oxidation before F-

Treat as if here

Oxidation of water

Br- (lower) will undergo

oxidation before water
 Electrolysis Redox
What are the redox reaction in electrolytic cell for the
following molten/solution:
a) Liquid of KBr with electrode carbon
b) Liquid of KBr with electrode magnesium
c) NaCl(aq) with electrode carbon
d) K2SO4(aq) with electrode Carbon
e) FeCl3(l) with electrode C
f) FeCl3(l) with electrode Cu
g) AgNO3(aq) electrode Fe
 Commercial Electrolytic Processes

• Production of aluminum
• Purification of metals
• Metal plating
• Electrolysis of sodium chloride
• Production of chlorine and sodium hydroxide

CHEMISTRY & YOU

 The Hall-Heroult Process for Al Production

 Al2O3 dissolved in molten

cryolite (Na3AlF6) at 950 0C (vs.
2050 0C for pure Al2O3)
Reaction : 2 Al2O3 (sln) + 3C (s)  4 Al (l) + 3CO2 (g)

CHEMISTRY & YOU

 Electroplating/Silver Plating a Spoon

CHEMISTRY & YOU

 The Downs Cell for the Electrolysis of Molten
Sodium Chloride

CHEMISTRY & YOU

 The Mercury Cell for Production of
Chlorine and Sodium Hydroxide

CHEMISTRY & YOU

Faraday’s Law of Electrolysis: the quantity (moles) of product
formed by an electric current is stoichiometrically equivalent to
the amount (moles) of electrons supplied

Faradays Moles
Current + Time Charge constant
of electrons

Using Faradays
Law!

Mass Molar mass Moles

product product
 Faraday’s First law
If W grams of the substance is deposited by Q coulombs of
electricity, then

W  Q
But Q = it, Hence W  I t or W = Z it
I = current in amperes
t = time in seconds.
Z = constant of proportionality
I.t.E
(electrochemical equivalent.) W
E= Equivalent mass of the substance
96500
 Faraday’s second law of electrolysis
When the same quantity of electricity is passed through
different electrolytes the masses of different ions liberated at
the electrodes are directly proportional to their chemical
equivalence

W1 E1 Z1It E1
 or 
W2 E2 Z2It E2
Z1 E1
Hence, 
Z2 E2
 Group Presentation

Topic :
1. Dry Cell Battery and Mercury Cell Battery
2. Ni-Cad Battery and Li-ion Battery
3. Lead Storage Battery and Button Battery
4. Hydrogen Fuel Cell and Microbial Fuel Cell
5. Hall Heroult Process and Platting Process
6. Corrotion and Prevention
7. Down Process and Iron purification Process
 Thank You
see u next chapter...

CHEMISTRY & YOU