CHEMISTRY FOR ENGINEERS NOTES
ELECTROCHEMICAL CELL
 a device or a mechanism that can either
generate electrical energy from a chemical
reaction or utilize electrical energy to produce a
chemical reaction.
TYPES OF ELECTROCHEMICAL CELL
1. Voltaic or Galvanic Cell
 spontaneous reaction generates electricity
 named after Alessandro Volta and Luigi Galvani
who pioneered in the development of voltaic
cells/galvanic cells
 common examples are dry cells, lead-acid
batteries and fuel cells
2. Electrolytic Cell
 a type of cell which uses electricity to cause a
non-spontaneous reaction to take place.
 application of an electrolytic cell is in the field of
electrolysis
Components of an Electrochemical Cell
1. Electrode – a piece of metal immersed in a
solution containing ions of the same metal.
Anode- an electrode where oxidation occurs.
Cathode – an electrode where reduction
occurs.
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An electrode immersed in a solution containing ions
of the same metal is called a half-cell.
 in the above electrochemical cell,
anode: Zn(s)Zn2+(aq)+2e-
cathode: Cu2+(aq) + 2e-  Cu(s)
2. Salt bridge- an inverted porous U-tube plug
that “bridges” two half cells. It contains an inert
electrolyte solution (like KNO3, KCl) to maintain
charge balance because the electrons are
moving from one-half cell to the other
3. Voltmeter- measures the electrical potential
energy difference between the two half-cells.
The reading in a voltmeter is called cell voltage
often called as electromotive force (emf) or the
cell potential. The unit for measuring cell
potential is the volt (V).
notes:
 flow of electrons is from the anode going to
the cathode
 anions from the salt bridge migrate toward
the anode & cations toward the cathode
Cell Diagrams & Writing Cell Notations
 shows the components of an
electrochemical cell in a symbolic way
 below is the convention used in writing cell
diagrams:
A. the anode is placed at the left side of the
diagram
B. the cathode is placed at the right side of
the diagram
C. a boundary between different phases
(ex: an electrode & a solution) is represented
by a single vertical line ().
D. the boundary between half-cell
compartments, usually a salt bridge, is
represented by a double vertical line ().
Species in aqueous solution are placed on
either side of the double vertical line, and a
comma separates different species in the
same solution from each other.
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CHEMISTRY FOR ENGINEERS NOTES
 for the cell diagram above, it is customarily
written as:
EXERCISES:
1. For the following cell
Zn l Zn+2 ll Ag+ l Ag
a.) Give the anode and cathode reactions
b.) Write the overall equation for the chemical
reaction
c.) Give the direction of the current in the
external circuit
2. The following reactions take place in an
electrochemical cell:
Fe →Fe +3 + 3 e
Fe+2 + 2e →Fe
a.) Which is the oxidation half-reaction?
b.) Which is the reduction half-reaction?
c.) name the reducing agent
d.) name the oxidizing agent
e.) write cell diagram for the reaction
3. Aluminum metal displaces zinc (II) ion from
aqueous solution.
a.) Write oxidation & reduction half equations
and a net equation for this redox reaction
b.) Write a cell diagram for a voltaic cell in
which this reaction occurs
4. Write the net equation for the redox reaction
that occurs in the voltaic cell:
Sc(s) Sc3+(aq)  Ag+(aq)  Ag(s)
5. Draw a voltaic cell in which the displacement of
silver ion from solution by aluminum metal
occurs. Label the cathode, the anode and other
features of the cell. Show the direction of the
flow of electrons. Also, indicate the direction of
flow of cations and anions form a KNO3(aq) salt
bridge, write a balanced equation for the overall
reaction and write a cell diagram.
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Cell Potential
 ability of cell to do electrical work
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
A coulomb is the quantity of charge passing in 1
second when the current is 1 ampere
1C = 1 ampsec
Electrode Potential
 measure of the tendency of a metal to get
oxidized or reduced when it is placed in a
solution of its own salt
Standard Electrode Potential
 measure of the tendency of a metallic electrode
to lose or gain electrons when it is in contact
with a solution of its own salt of 1M
concentration at 25 oC
PRIMARY REFERENCE ELECTRODES
 electrode potential is determined by coupling the
electrode with a primary reference electrode, the
potential of which is arbitrarily fixed as zero.
 important primary reference electrode used is a
standard hydrogen electrode (SHE)
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CHEMISTRY FOR ENGINEERS NOTES
 SHE is made up of platinum wire in an inverted
glass tube. H2 gas is passed through the tube at
1 atm.
 A platinum foil is attached at the end of the
wire. The electrode is immersed in 1M H+
solution at 25oC.
The electrode potential of SHE is zero at all
temperature
 used to measure the potentials of other kinds of
electrodes
STANDARD REDUCTION POTENTIAL
 the potential in volts generated by a reduction
half cell reaction compared to the standard
hydrogen electrode at 25oC and 1 atm and at a
concentration of 1 M
Rules in Using Standard Reduction Potentials
1. Read the half reactions as written
2. The more POSITIVE the reduction potential, the
greater the tendency is for the substance to be
reduced and therefore the better the oxidizing
agent
3. The half-cell reactions ARE reversible. IF you
need to reverse, you MUST change the sign of
the E0 cell.
4. If you change the stoichiometric coefficients,
E0cell remains the same ( Electrode potential is
an intrinsic property; its value is independent of
the amount os species in the reaction)
5. Under standard state conditions: any species
on the LEFT of a given half-reaction will react
spontaneously with a species that is on the
RIGHT and ABOVE it
6. The most positive values for Ecell mean that they
are the strongest OXIDIZING AGENTS and
therefore are themselves reduced.
7. The most negative values for Ecell mean that
they are the strongest REDUCING AGENTS and
therefore are themselves oxidized.
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Calculating Cell Potentials (E Ecell) of A Redox
Reaction
 The following are the steps in determining the
cell potentials from standard reduction potentials
A. Write the reduction half-equation and its
standard reduction potential. This will be
taken directly from the table of standard
reduction potentials.
B. Write the oxidation half-equation. Its potential
will be the negative of the value listed in the
tables of standard reduction potentials.
C. Combine the half equations into a net redox
reaction. Add the potentials for the half-cells
to obtain Ecell.
Example:
1. The following reaction takes place:
Cu(s) + Ag+(aq) → Cu+(aq) + Ag(s)
a. Represent cell using standard notation.
b. Calculate the cell potential of the
electrochemical cell
a. Cu(s) l Cu+(aq) ll Ag+(aq) l Ag(s)
b. Anode: Cu(s) → Cu+(aq) + e- Eo = - 0.34 V
2 { Cathode: Ag (aq) + e → Ag(s) Eo = 0.80 V
+
Cell Rxn: Cu(s) + 2Ag+(aq) → Cu+(aq) +2Ag(s) Ecell =0.46 V
2. Order the following oxidizing agents by
increasing strength under standard state
conditions: Cl2(g), H2O2(aq), Fe+3(aq)
From table of Std. Reduction potential;
Cl2(g) + 2e- → 2Cl-(aq) Eo = 1.36 V
H2O2(aq) + 2H+(aq) + 2e- → 2Cl- Eo = 1.78 V
Fe+3(aq) + e- → Fe+2(aq) Eo = 0.77 V
The order by increasing oxidizing strength is
Fe+3(aq), Cl2(g) , H2O2(aq),
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Exercises:

1. Look at the following half- reactions:

Ca+2(aq)+ 2e- → Ca(s)
Cl2(g) + 2e- → 2Cl-(aq)
Fe+3(aq) + 3e- →Fe(s)
I2 + 2e- →2I-
a. Which substance is the strongest oxidizing
agent?
b. Which substance is the strongest reducing
agent?
2. Calculate the standard cell potential produced by
a galvanic cell consisting of a nickel electrode in
contact with a solution of Ni2+ ions and a silver
electrode in contact with a solution of Ag+ ions.
Which is anode and which is the cathode?
3. What is the voltage produced by a galvanic ell
consisting of an aluminum electrode in contact
with a solution of Al3+ ions and an iron electrode
in contact with a solution of Fe2+ ions. Which is
anode and which is the cathode?
4. What is the voltage produced by a voltaic cell
consisting of a zinc electrode in contact with a
solution of Zn2+ ions and a silver electrode in
contact with a solution of Ag+ ions? Which is
anode and which is the cathode?
5. A new battery system currently under study for
possible use in electric vehicles is the zinc-
chlorine battery. The net reaction producing
electricity in this cell is Zn(s) + Cl2(g)  ZnCl2(aq).
What is the Ecell of this voltaic cell?

Spontaneous Change in Oxidation/Reduction

Reactions
 if Eocell is (+) , spontaneous in forward
direction
 if Eocell is (-) , spontaneous in reverse
direction
 if Eocell is 0, reaction is at equilibrium

Exercise:
1. Will aluminum metal displace Cu2+ ion from
aqueous solution? That is, does a spontaneous
Source: General Chemistry by Ebbing and Gammon, 9th ed reaction occur in the forward direction for the
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following reaction:
2Al(s) + 3Cu2+(aq)  3Cu(s) + 2Al3+ RELATION SHIP BETWEEN ΔG, E and Q
From thermodynamics,
2. Use half-reaction potentials to predict whether
the following reactions are spontaneous or non- ΔG = ΔGo + RTlnQ
spontaneous in aqueous solutions.
ΔG – Gibbs Free Energy - energy associated with a
a. Ca2+(aq) + 2 I-(aq)  Ca(s) + I2(aq)
chemical reaction that can do useful work.
b. H2S(g) + O2(g)  2 H2O(l) + 2 S(s)
c. SO2(g) + MnO2(s)  Mn2+(aq) + SO42-(aq) Q - the mathematical product of the
d. 2 H+(aq) + 2 Br-(aq)  H2(g) + Br2(aq) concentrations of the products of the reaction
divided by the mathematical product of the
3. Four beakers are set up, each of which contains concentrations of the reactants.
one of the following solutions: = [products] coefficient/[reactants] coefficient
a. magnesium nitrate
b. barium nitrate ΔG = -nFE and ΔGo = -nFEo
c. cupric nitrate
-nFE =-nFEo + RT ln Q
d. aluminium nitrate
Iron is added to each of the beakers. In which Simplifying, E =Eo + RT ln Q
beaker will a spontaneous reaction take place? -nF

4. Which one of the following solutions can be E =Eo - RT ln Q

stored in an aluminum container? nF
a. Copper (II) sulfate
Nernst Equation
b. zinc sulfate
c. sodium chloride
 used to calculate cell potentials at non-standard
d. Lead(II) nitrate
conditions.
5. What would happen if you used an aluminum
spoon to stir a solution of FeSO4(aq)? Write a
reaction and calculate Eo .

Ecell and Eºcell where:

Eº cell - the standard state cell potential, which

= cell potential at non-standard
means that the value was determined under conditions
standard states. The standard states include a = standard cell potential
concentration of 1 Molar (mole per liter) and an
atmospheric pressure of 1 and at 25oC = gas constant, 8.314 J/molK
= absolute temperature in K
Ecell is the non-standard state cell potential, which = no. of moles of electrons transferred in
means that it is not determined under a
concentration of 1 M and pressure of 1 atm and the reaction
25oC = Faraday's constant, the charge on a mole
of electrons = 96,485 C/mol
The two are closely related in the sense that the
= reaction quotient
standard cell potential is used to calculate for the
cell potential in many cases.
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CHEMISTRY FOR ENGINEERS NOTES
Since the temperature is generally 25 C (298 K),
three of the terms in the above Nernst equation
can be considered constants: R, T, and F.
Substituting the values of these constants, results
in the following equation:
In terms of logarithm to base 10,
Simplifying,
Sample Calculations:
Calculate the cell potential for the following system:
Anode: Cu(s) → Cu+2(aq) + 2e- Eo = - 0.34 V
2 { Cathode: Ag+(aq) + e → Ag(s) Eo = 0.80 V
Cell Rxn: Cu(s) + 2Ag+(aq) → Cu+(aq) +2Ag(s) Ecell =0.46 V
Exercises:
1. Calculate the cell potential of the following cell at
25oC
Cr(s)lCr+3(1.0 x 10-3M) ll Ni+2 (1.5M)l Ni(s)
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2. Calculate the voltages of the following cells at
25oC under the following conditions:
a. ZnlZn+2(0.50M) ll Cd+2(0.020M) lCd
b. CulCu+2().001 M) ll H+(0.010M)lH2
3. Complete the following cell notation:
ZnlZn+2(1.0M)ll H+ (?)lH2 (1 atm)l Pt Ecell=0.4V
ELECTROLYTIC CELL
 a cell that does work on a chemical system by
driving an electric current through the system
 made up of two electrodes connected to a
battery immersed in an electrolyte.
Battery – source of electric current
Electrolyte – contains ions that conducts
electricity
Electrolytic cells are typically used to:
- plate metals on other metals
- obtain a pure metal from it’s compounds
- recharge batteries
Electrolysis – a non-spontaneous reaction caused
by the passage of an electric current through a
solution
Faraday’s Law of Electrolysis
1. The quantities of substance produced and
consumed at the electrodes are directly
proportional to the amount of electric charge
passing through the cell.
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CHEMISTRY FOR ENGINEERS NOTES
2. When a given amount of electric charge passes
through the cell, the quantity of substance
produced or consumed at an electrode is
proportional to its molar mass divided by the
number of moles of electrons required to
produce or consume one mole of the substance.
 A coulomb (C) is the quantity of charge
passing a point in a circuit in 1 s when the
current is 1 ampere (A)
 If a current of I amperes flows for a period of t
secs, the amount of charge transferred = I
amperes x t sec
Q = It
(coulomb = amperes x seconds)
 Current is the rate of flow of charge
1 A = 1C/sec
The charge on a single electron=1.6022 x 10-19 C
Faraday’s constant - the charge associated with
one mole of electrons
F = 1.6022 x 10-19 C =9.6485x104 C/mol
6.022 x 1023 mole
To use Faraday’s law to calculate the amount of
substance oxidized or reduced:
1. Identify the amount of current passed
through the cell and the time
2. Calculate the quantity of charge transferred-
3. Use the Faraday constant to calculate the
number of moles of electrons that corresponds
to the quantity of charge determined in step 2
4. Relate the number of moles of electrons to the
number of moles of substance oxidized or
reduced
5. Convert moles of substance to grams of
substance
EXERCISES:
1. A manufacturer wants to make gold forks out of
his more cheaply made stainless steel (Fe) forks.
Draw an electrolytic cell that he could use to
accomplish this task. Assume Au forms Au+3.
Label everything fully and specify the oxidation
and reduction half- cell reactions that will take
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place.
2. Sketch a cell for the electroplating of a copper
medal with gold. You will need only one
compartment, a battery, a bar of gold and the
copper medal. Which metal will be your anode,
your cathode? What solution will you need? How
will you hook up your battery? Indicate the flow
of electrons, and the reactions at the anode and
cathode.
3. In the electrolytic cell shown here, an iron nail is
being plated with copper
a. Which object, the iron nail or the copper bar,
should be connected to the negative post of the
battery?
b. Write the equation for the half-reaction that
occurs at the cathode of the electrolytic cell
c. Write the equation for the half-reaction that
occurs at the anode of the electrolytic cell
d. Show on the diagram the flow of electrons both
entering and leaving the battery
4. How long must a current of 2.5 amps be applied
to the solution of Au+ ions to plate out 3 grams
of gold on the metal?
5. A current of 0.452 A is passed thru an
electrolytic cell containing molten CaCl2 for 1.50
hours. Write the electrode reactions and
calculate the quantity of products (in grams)
formed at the electrodes.
6. Calculate the mass of aluminum produced in
1.00 hour by the electrolysis of molten AlCl3 if
the electrical current is 10.0 A.
7. The half reaction for the formation of
magnesium metal upon electrolysis of molten
MgCl2 is Mg2+ + 2e-  Mg. How much current
should pass through the molten solution for
4.00 x 103 seconds to produce 30.2 g Mg?
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