Lesson 3.1: Electrochemical Reactions

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For instructional purposes only • 1 Semester SY 2020-2021 3
Lesson 3.1: Electrochemical Reactions
Lesson Summary
Interconversion of chemical energy and electrical energy involved
electrochemical reactions which is an example of redox reactions. Redox
reactions are a bit tricky to balance compared to other types of reactions. A
balanced redox reaction is the sum of the two half-reactions thus making also
the cell potential equal to the sum of the individual potential of each
electrode. Scientists have compiled a list of standard reduction potentials of
electrodes which is useful for computing the Eocell and comparing the relative
strength of an oxidant and reductant. The Ecell at non-standard condition is
calculated using the Nernst equation. A high concentration of the reactant will
equate to a large value of Ecell.
Learning Outcomes
1. Write and balance redox equations;
2. Distinguish between a galvanic cell and an electrolytic cell;
3. Predict the relative strength of oxidant and reductant and;
4. Calculate the Eocell and Ecell of a cell.
Motivation Question
How can you generate electricity using two different metals? Can you predict
which will be reduced and oxidized between the two metals?
Discussion
Redox Reactions
Electrochemistry is the study of the interconversion of electrical

energy and chemical energy. Interconversion of electrical energy and
chemical energy involves electrochemical reactions. The electrochemical
reaction is an example of a reduction-oxidation or redox reaction. Electricity is
generated when the energy is released by a spontaneous electrochemical
reaction or you can use electricity to make a nonspontaneous reaction
happen.
Electrons are transferred from one substance to another in a redox
reaction. You have here the burning of magnesium as an example:
0 0 +2 -2
2 Mg (s) + O2 (g)  2 MgO (s)
Look at the charge of Mg on the reactant side and compare it with its
charge on the product side. From a charge of zero (0), it increases to two (2)
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so, it means it undergoes oxidation. The opposite happens to oxygen; it

decreases from 0 to -2 which means it is the one being reduced. With this
observation you can now write a half-reaction equation:
Oxidation: 2 Mg  2 Mg2+ + 4 e- (lose electrons)

- 2-
Reduction: O2 + 4 e  O (gain electrons)
The 4 electrons lose by the Mg (that is 2 moles of Mg then each mole
has a +2 charge) are transferred to the oxygen.
Figure 1. Redox Reaction of Mg and O
How will you know what will be the charge of a given element? Why
does Mg have a charge of 0 then it became +2, as well as in oxygen, from 0 to
-2? The charge of the atom has in a molecule or ionic compound when
electrons were completely transferred is called an oxidation number. You
have here the rules in assigning the oxidation number of an element:
1. Elements that are not combined will have an oxidation number of 0.

EXAMPLE: Na, C, H, O, Mg, Cl and Fe = 0
2. Elements in monoatomic ion will have an oxidation number equal to
its charge.
EXAMPLE: Li+, Li = +1 Fe2+, Fe = +2 Pb 4+, Pb = +4
3. The oxidation number of oxygen is usually -2, except in peroxide (O2-2),
it is -1.
EXAMPLE: H2O, O = -2 H2O2, O = -1
4. The oxidation number of H is +1 except if bonded to metals in a binary
compound it will be -1.
EXAMPLE: NaH, H = -1 H2O, H = +1
5. The GIA will have a charge of +1, GIIA will have +2, and fluorine will
also have a charge of -1.
6. The charge on the molecule or ion is equal to the sum of the oxidation
number of all atoms in it.
SAMPLE PROBLEM: Give the oxidation number of all the elements in the
molecule HCO3-:
ANSWER: Familiarize and understand the rules first.

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o H is not bounded to any metal so it will have a charge of +1

o O is not in peroxide (O22-) so it will have a charge of -2
o The charge of the molecule is -1, with that we can compute the
oxidation number of C based on the last rule:
HCO3- : (+1) (X) (3x-2) = 1
so solving for X, X=charge of C= +4
Then the oxidation number of C is +4.
Balancing Redox Equations
Compared to balancing ordinary chemical equations, redox equations

are a bit tricky. The one method used in balancing redox equations is the ion-
electron method. In this method, the overall reaction is split into half-
reactions – reduction and oxidation. The half-reactions are separately
balanced and after added together to give a balanced overall reaction.
Let us balance the redox reaction between dichromate and iodide ions
forming chromium (III) ion and solid iodine, which occurs in acidic solution.
1. Write the unbalanced equation of the reaction:

Cr2O72- (aq) + I-1 (aq)  Cr3+ (aq) + I2 (s) [acidic solution]
2. Separate the reactions into two half-reactions. One half-reaction is

consisting of the two chromium species and the other half of the two
species of iodine.
Cr2O72- (aq)  Cr3+ (aq)
I-1 (aq)  I2 (s)
3. Balance every atom in each half-reaction:

a. For Cr2O72- (aq)  Cr3+ (aq)
 Balance atoms aside from O and H.
You have 2 moles of Cr on the reactant side so we need to add
2 on the Cr on the product side.
Cr2O72- (aq)  2 Cr3+ (aq)
 Balance O atoms by adding H2O.

There are 7 O atoms on the reactant side and in every molecule
of water you have one O atom. Thus, you need to add 7 moles of
water to have 7 moles of O atoms.
Cr2O72- (aq)  2 Cr3+ (aq) + 7 H2O (l)
 Balance H atoms by adding H+ ions.
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In every water molecule, we have 2 H atoms, since we add 7

moles of water that will give us a total of 14 H atoms. The
number of H+ needed to balance is 14.
14 H+ (aq) + Cr2O72- (aq)  2 Cr3+ (aq) + 7 H2O (l)
 Balance the charge by adding electrons.

Every H+ has a charge of 1+, so we will a total charge of 14 for
H+ and a -2 for the dichromate ion. The total charge on the
reactant side is 12. For the product side, the one that has a
charge is only the Cr (III) so a total of 6 since we have 2 moles
of Cr3+and the H2O have no charge.
14 H+ (aq) + Cr2O72- (aq)  2 Cr3+ (aq) + 7 H2O (l)
12  6
So to balance, we need to add 6 electrons to the reactant side,
12 + -6  6
66
+ 2-
14 H (aq) + Cr2O7 (aq) + 6e-  2 Cr3+ (aq) + 7 H2O (l)
This half-reaction is already balanced, and we see that this is a
reduction reaction (gain of electrons).
b. For I-1 (aq)  I2 (s)
 Balance atoms aside from O and H.
You have 2 moles of iodine atoms on the product side and only
1 on the reactant side. To balance, we need to add 2 on the
reactant side.
2 I-1 (aq)  I2 (s)
 Balance O atoms by adding H2O.

Not needed since there are no O atoms.
 Balance H atoms by adding H+ ions.

Not needed since there are no O atoms.
 Balance the charge by adding electrons.

To balance the -2 on the reactant side we need to add two
electrons on the product side.
2 I-1 (aq)  I2 (s) + 2 e-
This half-reaction is now balanced, and we see that this is an
oxidation reaction (loss of electrons).
4. If necessary, multiply the reaction by an integer.
This step is only needed if the number of e- lost and gained in the
reaction are not the same. So you need to think of an integer that
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when you multiply will give a common number of electrons since it

must be canceled.
Six electrons are gained in the reduction reaction and two electrons are
lost in the oxidation reaction. So an integer that we can use is 3, in
which we can multiply it to the reduction reaction.
REDUCTION: 14 H+ (aq) + Cr2O72- (aq) + 6e-  2 Cr3+ (aq) + 7 H2O (l)
OXIDATION: 3 (2 I-1 (aq)  I2 (s) + 2 e-) so,
6 I-1 (aq)  3 I2 (s) + 6 e-
5. Add the half-reactions together and cancel the species that can be
found on both sides.
We can cancel the electrons here since it appears on the reactant side
as well as on the product side.
14 H+ (aq) + Cr2O72- (aq) + 6e-  2 Cr3+ (aq) + 7 H2O (l)
6 I-1 (aq)  3 I2 (s) + 6 e-
6 I-1 (aq) + 14 H+ (aq) + Cr2O72- (aq)  3 I2 (s) + 2 Cr3+ (aq) + 7 H2O (l)
6. Check if the atoms and charges are balanced.

Reactants: 6 I, 14 H, 2 Cr and 7 O charge = 6(-1) + 1(14) + 1(-2) = +6
Products: 6 I, 14 H, 2 Cr and 7 O charge = 0 + 2(+3) + 0 = +6
Based on the steps, we can treat any redox reaction as the sum of
reduction and oxidation half-reaction, in which electrons are lost in one half-
reaction and gained in the other. Although we treated the half-reactions
separately, reduction and oxidation occur simultaneously.
Why do you need to deal with the balancing of redox reactions? This is
because it gives us an insight regarding the redox processes and it is
essential in understanding electrochemical cells.
Electrochemical Cells
The electrochemical cell is an apparatus that generates electricity

from a spontaneous redox reaction or it uses electricity to cause a
nonspontaneous redox reaction to occur. There two types of electrochemical
cells based on the general thermodynamic nature of the reaction:
a. Galvanic Cell or Voltaic Cell named after Luigi Galvani is an
electrochemical cell that generates electricity from the
spontaneous redox reaction (ΔG < 0). The chemical potential
energy difference between the high energy reactants and low
energy products are converted into electrical energy. We can
say that the system does some work on the surrounding.
Galvanic cells are found in all batteries which are used to light
your flashlight, load your gadgets, and other electrical devices.
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b. Electrolytic Cell is an electrochemical cell in which electricity is

needed to make a nonspontaneous reaction (ΔG > 0) to occur.
The low energy reactants are being converted into high energy
products using electricity. Thus, the surrounding does some
work on the system.
Electroplating and recovering metal in ores use this type of
electrochemical cell.
The two electrochemical cells may be different but they have some
common features as shown in the figure. You have two electrodes that
conduct electricity between the cell and surrounding, which was dipped in an
aqueous solution of ions that are involved in a reaction called an electrolyte.
The electrode is indicated as anode or cathode depending on what half-
reaction occurs in it:
 In the anode, an oxidation reaction occurs in which electrons are lost

by the substance being oxidized (or also referred to as a reducing
agent) and leave the cell.
 In the cathode, a reduction reaction occurs in which electrons are
gained by the substance being reduced (referred to as an oxidizing
agent) and enter the cell.
Figure 2. Two Types of Electrochemical Cell
Galvanic Cells
Let us focus first on the galvanic cell. To demonstrate the galvanic

cell, let us have the reaction of Zn metal with Cu2+ ion to give Zn2+ ion and
metallic Cu:
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Zn(s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s)
Figure 3. Galvanic Cell
The bar of zinc and copper is called electrodes. The specific

arrangement of the electrode (Zn and Cu) and solutions (ZnSO4 and CuSO4) is
called the Daniell cell. The cell operates as the Zn is being oxidized to Zn2+
and the Cu2+ being reduced in a separated location but occurs simultaneously
with the use of wire for transferring electrons. The anode in a galvanic cell is
the electrode at which oxidation occurs and at which reduction occurs is the
cathode. The mnemonic for this one is REDCAT, ANOX = (Red)uction
(Cat)hode, (An)ode (Ox)idation. The half-reaction that occurs in each
electrode is:
ANODE (Zn electrode): Zn (s)  Zn2+ (aq) + 2e-

CATHODE (Cu electrode): Cu2+ (aq) + 2 e-  Cu(s)
The inverted U tube called a salt bridge contains a KCl solution that
provides an electrically conducting medium between the two solutions. The
inverted U tube’s openings are loosely plugged with cotton balls to prevent
KCl solution from flowing into containers thus letting the anions and cations
travel across. The ions in the electrolyte solution should not react with the
other ions in the solution or with the electrode. In the solutions, the cations
Zn2+, Cu2+, and K+ move toward the cathode while the anions SO42- and Cl-
move toward the anode. Without your salt bridge that connects the two
solutions, the positive charge will build up in the anode compartment due to
the formation of Zn2+ ions and the negative charge in the cathode which is
due to the formation of solid Cu will make the cell not to function.
The electrons are transferred directly from the reducing agent (Zn) to
the oxidizing agent (Cu2+) in solution. The bulb (instead of voltmeter being
attached) lit as the electrons flow externally from the Zn electrode (anode) to
the Cu electrode (cathode).
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Why does electric current flow from anode to cathode? It is because

there is a difference in electric potential energy between your anode and
cathode. An analogy of this one is like the diffusion of a smell, the smell
travels from high concentrated area to the low concentrated area.
The difference in electric potential between the electrode is measured
experimentally using a voltmeter. The measurement of electric potential
difference is in voltage and called cell voltage, cell potential, or electromotive
force (emf).
We have a convenient way of representing a galvanic cell called a cell
diagram. Based on the Daniell cell (Figure 39) and the solutions are in 1 M
concentration, we can write a cell diagram for that as:
Zn (s) | Zn2+ (aq) (1 M) || Cu2+(aq) (1 M) | Cu (s)
The single bar represents a phase boundary; the Zn in a solid phase
while Zn2+ is in an aqueous solution the same concept as the Cu and Cu2+.
The double bar represents the salt bridge. The anode is written first, to the left
to the double lines and the rest components appear in the order we encounter
them from anode to cathode.
Standard Reduction Potentials
The cell potential of a Daniel cell made up of 1 M Cu2+ and Zn2+ ions
are 1.10 V at 25 oC. The voltage and the redox reactions are related directly.
Recall that the redox reaction is the sum of the two half-cell reactions, with
that we can also treat the emf as the sum of the individual electrical
potentials of the Zn and Cu electrodes. If one of these electrode potentials is
given, we can obtain the other one by subtracting it from the emf value. It is
impossible to measure the potential of just a single electrode, but if we can
set the potential value of a specific electrode (or reference electrode) at zero
then we can determine the relative potentials of other electrodes.
Figure 4. Standard Hydrogen Electrode
The H electrode (Fig.40) serves this purpose as a reference electrode in

which H2 gas is bubbled into HCl at 25 0C. The platinum electrode has two
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functions – to provide the hydrogen molecules a surface for dissociation and

to serve as an external conductor for the circuit.
Under standard state conditions where pressure is at 1 atm, the
temperature at 25oC and concentration of HCl at 1 M, the electric potential for
reduction of H+ is equal to 0 V:
2 H+ (1 M) + 2e-  H2 (g) (1 atm) Eo = 0 V

The Eo denotes the standard reduction potential or the voltage
associated with a reduction reaction at standard conditions (concentration at
1 M, the temperature at 25 OC, and gases at 1atm).
The hydrogen electrode is called the standard hydrogen electrode
(SHE) and this is used to measure the reduction potential of other electrodes.
Let us have a sample problem for this one.
SAMPLE PROBLEM: A galvanic cell made up of a Zn electrode and SHE,
calculate the reduction potential of the Zn electrode.
Figure 5. Galvanic Cell of Zn and H
ANSWER:
a.) First, identify the anode and cathode. The anode is preferably written at
the left side so that will be your Zn electrode and the cathode will be the SHE.
You can write the cell diagram as:
Zn(s) |Zn2+ (1 M) || H+ (1 M) | H2 (1 atm)
b.) Now you can write each half-reaction and take note that the Pt serves as a
surface for the dissociation of hydrogen.
ANODE (oxidation): Zn(s)  Zn2+ (1 M) + 2e-

CATHODE (reduction): 2 H+ (1 M) + 2e-  H2 (g) (1 atm)
OVERALL REACTION: Zn(s) + 2 H+ (1 M) Zn2+ (1 M) + H2 (g) (1 atm)
c.) Conventionally, the standard emf of the cell, Eocell (0.76 V based on the
figure above), is given by:
Eocell = Eocathode - Eoanode so,
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Eocell = -
0.76 V = 0 V -
= 0 V – 0.76 V
= – 0.76 V
Thus, the standard reduction potential of zinc, , is – 0.76 V.
Using the SHE, we can get the standard reduction potential of other
electrodes such as we did with the Zn on the previous sample problem.
Scientists have compiled and tabulated the standard reduction potential of
several half-reactions. The Eo of SHE has a value of 0 V, below the SHE the
negative value increases and above the SHE the positive value increases.
Below is the list of standard reduction potentials of selected electrodes:
Half-Reaction E° (V)
F2(g) + 2e−→ 2F−(aq) 2.87
H2O2(aq) + 2H+(aq) + 2e− → 2H2O(l) 1.78
Ce4+(aq) + e− → Ce3+(aq) 1.72
PbO2(s) + HSO4−(aq) + 3H+(aq) + 2e− → PbSO4(s) + 2H2O(l) 1.69
Cl2(g) + 2e− → 2Cl−(aq) 1.36
Cr2O72−(aq) + 14H+(aq) + 6e− → 2Cr3+(aq) + 7H2O(l) 1.23
O2(g) + 4H+(aq) + 4e− → 2H2O(l) 1.23
MnO2(s) + 4H+(aq) + 2e− → Mn2+(aq) + 2H2O(l) 1.22
Br2(aq) + 2e− → 2Br−(aq) 1.09
− + −
NO3 (aq) + 3H (aq) + 2e → HNO2(aq) + H2O(l) 0.93
Ag+(aq) + e− → Ag(s) 0.80
Fe3+(aq) + e− → Fe2+(aq) 0.77
H2SeO3(aq) + 4H+ + 4e− → Se(s) + 3H2O(l) 0.74
O2(g) + 2H+(aq) + 2e− → H2O2(aq) 0.70
MnO4−(aq) + 2H2O(l) + 3e− → MnO2(s) + 4OH−(aq) 0.60
MnO42−(aq) + 2H2O(l) + 2e− → MnO2(s) + 4OH−(aq) 0.60
I2(s) + 2e− → 2I−(aq) 0.54
H2SO3(aq) + 4H+(aq) + 4e− → S(s) + 3H2O(l) 0.45
O2(g) + 2H2O(l) + 4e− → 4OH−(aq) 0.40
Cu2+(aq) + 2e− → Cu(s) 0.34
AgCl(s) + e− → Ag(s) + Cl−(aq) 0.22
Cu2+(aq) + e− → Cu+(aq) 0.15
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Half-Reaction E° (V)
Sn4+(aq) + 2e− → Sn2+(aq) 0.15
2H+(aq) + 2e− → H2(g) 0.00
Sn2+(aq) + 2e− → Sn(s) −0.14
2SO42−(aq) − 2−
+ 4H+(aq) + 2e → S2O6 (aq) + 2H2O(l) −0.22
Ni2+(aq) + 2e− → Ni(s) −0.26
PbSO4(s) + 2e− → Pb(s) + SO42−(aq) −0.36
Cd2+(aq) + 2e− → Cd(s) −0.40
Cr3+(aq) + e− → Cr2+(aq) −0.41
Fe2+(aq) + 2e− → Fe(s) −0.45
Ag2S(s) + 2e− → 2Ag(s) + S2−(aq) −0.69
Zn2+(aq) + 2e− → Zn(s) −0.76
Al3+(aq) + 3e− → Al(s) −1.662
Be2+(aq) + 2e− → Be(s) −1.85
Li+(aq) + e− → Li(s) −3.04
Several key points to keep in mind regarding using the table are:
1. Conventionally, the half-reactions are written as reduction meaning only the

reactants are the oxidizing agents and only the products are reducing agents.
2. The more positive the value of Eohalf-cell the stronger the oxidizing agent and
the more negative the stronger the reducing agent. For example, the F2 is the
strongest oxidizing agent while the weakest oxidizing agent yet the strongest
reducing agent is the Li+.
3. The half-reactions are reversible depending on the conditions whether it is

used as an anode or cathode but its magnitude remains the same.
4. Changing the stoichiometric coefficient doesn’t change the value of Eohalf-cell

since this is an intensive property. For example,
F2 (g) + 2e-  2F- (aq) Eo = 2.87 V
2F2 (g) + 4e-  4F- (aq) Eo = 2.87 V
Let us have an example for some application of using your table of

standard electrode potentials.
SAMPLE PROBLEM: What will happen if molecular F2 is added to a solution

containing NaCl at 25oC? Assume all substances are in standard state
conditions.
ANSWER:
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Using the table, write the standard reduction potentials as:
F2 (g) + 2e-  2F- (aq) Eo = 2.87 V

Cl2 (g) + 2e-  2Cl- (aq) Eo = 1.36 V
We can see that the F2 can oxidize the Cl- because it has a higher value of
standard reduction potentials. With that, the following reaction will occur:
REDUCTION: F2 (g) + 2e-  2F- (aq)
OXIDATION: 2Cl- (aq)  Cl2 (g) + 2e-
OVERALL REACTION: F2 (g) + 2Cl- (aq)  2F- (aq) + Cl2 (g)
SAMPLE PROBLEM: The black tarnish that forms on silver things such as the
silver spoon is primarily Ag2S. To reverse the reaction which means to convert
back the Ag2S to silver by reduction:
a. Predict which species—H2O2(aq), Zn(s), I−(aq), Sn2+(aq)—can reduce Ag2S

to Ag under standard conditions.
b. Suggest an alternative reducing agent that is readily available,

inexpensive, and possibly more effective at removing tarnish.
ANSWERS:
a. Of the four species given in the problem, I−(aq), Sn2+(aq), and

H2O2(aq) lie above Ag2S, and one Zn(s) lies below it. We can therefore
conclude that Zn(s) can reduce Ag2S(s) under standard conditions,
whereas I−(aq), Sn2+(aq), and H2O2(aq) cannot.
Figure 6. Silver Spoon Tarnishing
b. Of the reductants that lie below Zn(s) and therefore are stronger
reductants, only one is commonly available in household products:
Al(s), which is sold as an aluminum foil for wrapping foods.
SAMPLE PROBLEM: A galvanic cell consists of a Cu electrode in a 1.0 M

Cu(NO3)2 solution and an Ag electrode in a 1.0 M AgNO3 solution. Calculate
the standard emf of this cell at 25 oC.
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ANSWER: First assign the electrode which will be the anode or the cathode by
comparing their standard reduction potentials.
Ag+ (aq) + e-  Ag (s) Eo = 0.80 V
Cu2+ (aq) + 2e-  Cu (s) Eo = 0.34V
Since the silver has a higher standard reduction potential, then it means that
Ag+ will oxidize Cu. The Ag electrode will be the cathode and the Cu will be
the anode.
CATHODE (Reduction): 2 Ag+ (aq) + 2e-  2 Ag (s) Eo = 0.80 V
ANODE (Oxidation): Cu (s)  Cu2+ (aq) + 2e- Eo = 0.34V
OVERALL REACTION: 2 Ag+ (aq) + Cu (s)  2 Ag (s) + Cu2+ (aq) Eocell = ?
Note that to balance the overall equation, we need to multiply it by 2 since the
electrons involved in the oxidation are two while only one with the reduction.
Eocell = Eocathode - Eoanode = 0.80 V – 0.34 V = 0.46 V
Spontaneity of Redox Reactions
We can use the sign of Eo just like the ΔGo. A positive Eo means the
redox reaction favors the formation of products at equilibrium. A negative Eo
means favors more of the reactant to form rather than the products.
In a cell, chemical energy is converted into electrical energy to do
electrical work such as the battery of your mobile cellphones. We can say that
the electrical energy production is the product of the emf of the cell and the
total electrical charge (in coulombs) that passes through the cell:
electrical energy = volts (V) x coulombs (C) = joules (J) so,
1 J = 1 C∙V
The total charge is equal to the number of electrons multiplied by the

charge of an electron and it is conveniently expressed in molar quantities.
The charge of one mole of electrons is called the Faraday constant and it is
equal to 96.500 C/mol e-. Using that one, we can express the total charge as
nF where n is the number of electrons involved in the redox reaction.
The maximum work done by the cell is equal to maximum electrical

work which is equal to the electrical energy involved. Since the emf is the
maximum voltage a cell can achieve then we have here:
wmax = welec = -nFEcell
The negative sign in the equation denotes that the electrical work is
done by the system (which is your galvanic cell) on the surroundings. Recall
from the previous topic that we define free energy as the available energy to
do work. The ΔG is then equal to the maximum work so,
wmax = welec = ΔG= -nFEcell
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When ΔG is negative it is a spontaneous reaction, since both n and F

are positive quantities then Ecell must be positive to have a galvanic cell. If all
the components are in standard states, then:
ΔGO= -nFEocell
SAMPLE PROBLEM: Calculate the standard free energy of the following

reaction at 25 OC and identify if this a galvanic cell or an electrolytic cell:
2 Au (s) + 3 Ca2+ (1 M)  2 Au3+ (1 M) + 3 Ca(s)
ANSWER:
Identify which undergo oxidation and reduction, and write the half-reactions
involved:
ANODE (oxidation): 2 Au (s)  2 Au3+ (1 M) + 6 e--

CATHODE (reduction): 3 Ca2+ (1 M) + 6 e--  3 Ca(s)
Eocell = Eocathode - Eoanode = -2.87 V – 1.50 V = -4.37 V
ΔGO= -nFEocell = - (6) (96,500 J/ V∙mol) ( -4.37 V) = 2.53 x 103 kJ/mol
Therefore, the ΔGO of this cell is 2.53 x 103 kJ/mol and this is an electrolytic
cell since has a positive value of ΔGO and a negative value of Eocell.
The Effect of Concentration on Cell Emf
We tackled a redox reaction in a standard condition but how about if it

is not in standard condition? What if you have a concentration that is lower or
higher than 1 M?
A German physicist and chemist, Walter Nernst is the first one to

derive the most important relationship equation in electrochemistry called the
Nernst equation:
or
This equation is used to determine the value of Ecell as well as the

direction of spontaneity for any redox reaction under any conditions. The n in
the equation is equal to the number of electrons being transferred in the
redox reaction and the Q is the equilibrium constant (concentration of product
over-concentration of reactant). Let us have an example here:
SAMPLE PROBLEM: Calculate E for this reaction under the following non-
standard conditions and determine whether it will occur spontaneously:
Co (s) + Fe2+ (aq)  Co2+ (aq) + Fe (s)
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No. DOPAC-IM-SC002
st
[Co2+] = 0.15 M and [Fe2+] =0.68 M, pressure at 1 atm and temperature at 298
K.
ANSWER:
First, write the half-reactions and compute the Ecell:
OXIDATION (anode): Co (s)  Co2+ (aq) + 2e -

REDUCTION (cathode): Fe2+ (aq) + 2e -  Fe (s)
Eocell = Eocathode - Eoanode = -0.44 V – (-0.28 V) = - 0.16 V
Using the Nerst Equation, we can then calculate the Ecell:
Since the Ecell is negative, the reaction is not spontaneous for the forward
direction.
The Nernst equation showed to us that Ecell depends on the Eocell as

well as on the Q. The Q is affected by the concentration, with that Ecell is high
when the value of Q is small (high concentration of reactant). At equilibrium,
G and Ecell are equal to zero which also means that Q = K.
Learning Task/Activities
The Pain of Dental Voltaic Cell: Have you ever felt a jolt of pain when biting
down with a filled tooth on a scrap of foil left on a piece of food? Explain the
reason behind that. [Note: Aluminum act as an anode and the filling as an
inactive cathode.]
Assessment
1. Balance the skeleton ionic equation for the reaction between NaMnO4
and Na2C2O4 in basic solution: [Make sure to show all the steps
needed and box the final equation.]
MnO4—(aq) + C2O42 –(aq)  MnO2 (s) + CO32—(aq) [basic solution]
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No. DOPAC-IM-SC002
2. A voltaic cell is constructed with an Sn/Sn2+ half-cell and a

Zn/Zn2+ half-cell.
a. Draw a diagram of the cell, labeling electrodes with their
charges and showing the directions of electron flow in the
circuit and cation and anion flow in the salt bridge.
b. Write the balanced half-reactions, the overall reaction, and cell
notation.
c. Calculate the standard cell potential in V and show all
necessary solutions.
3. Use the following half-reactions to write three spontaneous

reactions, calculate E°cell for each reaction and rank the strengths
of the oxidizing and reducing agents:
i. Au+ (aq) + e--  Au (s) Eo = 1.69 V
+ --
ii. N2O (g) + 2 H (aq) + 2 e  N2 (g) + H2O (l) Eo = 1.77 V
3+ o
iii. Cr (aq) + 3e—  Cr (s) E = 0.74 V
4. A voltaic cell consists of an Mn/Mn2+ half-cell and a Pb/Pb2+ half-cell.

Calculate [Pb2+] when [Mn2+] is 1.4 M and Ecell is 0.44 V.
Instructions on how to submit student output

For hard copies:
You may submit your outputs via VSU Learning Kiosks (for Baybay City Area)
or mail through concerned LGU partners, may it be handwritten or printed.
Make sure to provide your full name and the assessment number on your
paper.
For e-copies:
You may email your files to mervinjuneg@gmail.com (for students under Mr.
Gasatan) or helengrace.oracion@vsu.edu.com (for students under Ms.
Oracion). Make sure to put your subject as “Assessment [No.] [Name]”.
Remove the brackets, do not put spaces, and the name format must be
[LastName FirstName]. The same formatting also applies to your file name.
Any further inquiries shall be directed to Mr. Gasatan ( Email Address:
mervinjuneg@gmail.com; Contact Number: 09291624464) or Ms. Oracion
(Email Address: helengrace.oracion@vsu.edu.com; Contact Number:
09073118005).
Page 18 of 122
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No. DOPAC-IM-SC002

Lesson 3.1: Electrochemical Reactions

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For instructional purposes only • 1 Semester SY 2020-2021 3

Lesson 3.1: Electrochemical Reactions

Electrochemistry is the study of the interconversion of electrical

so, it means it undergoes oxidation. The opposite happens to oxygen; it

Oxidation: 2 Mg  2 Mg2+ + 4 e- (lose electrons)

Figure 1. Redox Reaction of Mg and O

1. Elements that are not combined will have an oxidation number of 0.

ANSWER: Familiarize and understand the rules first.

o H is not bounded to any metal so it will have a charge of +1

Balancing Redox Equations

Compared to balancing ordinary chemical equations, redox equations

1. Write the unbalanced equation of the reaction:

2. Separate the reactions into two half-reactions. One half-reaction is

3. Balance every atom in each half-reaction:

 Balance O atoms by adding H2O.

 Balance H atoms by adding H+ ions.

In every water molecule, we have 2 H atoms, since we add 7

 Balance the charge by adding electrons.

 Balance O atoms by adding H2O.

 Balance H atoms by adding H+ ions.

 Balance the charge by adding electrons.

when you multiply will give a common number of electrons since it

6. Check if the atoms and charges are balanced.

The electrochemical cell is an apparatus that generates electricity

b. Electrolytic Cell is an electrochemical cell in which electricity is

 In the anode, an oxidation reaction occurs in which electrons are lost

Figure 2. Two Types of Electrochemical Cell

Let us focus first on the galvanic cell. To demonstrate the galvanic

Zn(s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s)

Figure 3. Galvanic Cell

The bar of zinc and copper is called electrodes. The specific

ANODE (Zn electrode): Zn (s)  Zn2+ (aq) + 2e-

Why does electric current flow from anode to cathode? It is because

Standard Reduction Potentials

Figure 4. Standard Hydrogen Electrode

The H electrode (Fig.40) serves this purpose as a reference electrode in

functions – to provide the hydrogen molecules a surface for dissociation and

2 H+ (1 M) + 2e-  H2 (g) (1 atm) Eo = 0 V

Figure 5. Galvanic Cell of Zn and H

Zn(s) |Zn2+ (1 M) || H+ (1 M) | H2 (1 atm)

ANODE (oxidation): Zn(s)  Zn2+ (1 M) + 2e-

Below is the list of standard reduction potentials of selected electrodes:

1. Conventionally, the half-reactions are written as reduction meaning only the

3. The half-reactions are reversible depending on the conditions whether it is

4. Changing the stoichiometric coefficient doesn’t change the value of Eohalf-cell

F2 (g) + 2e-  2F- (aq) Eo = 2.87 V

2F2 (g) + 4e-  4F- (aq) Eo = 2.87 V

Let us have an example for some application of using your table of

SAMPLE PROBLEM: What will happen if molecular F2 is added to a solution

Using the table, write the standard reduction potentials as:

F2 (g) + 2e-  2F- (aq) Eo = 2.87 V

a. Predict which species—H2O2(aq), Zn(s), I−(aq), Sn2+(aq)—can reduce Ag2S

b. Suggest an alternative reducing agent that is readily available,

a. Of the four species given in the problem, I−(aq), Sn2+(aq), and

Figure 6. Silver Spoon Tarnishing

SAMPLE PROBLEM: A galvanic cell consists of a Cu electrode in a 1.0 M

OVERALL REACTION: 2 Ag+ (aq) + Cu (s)  2 Ag (s) + Cu2+ (aq) Eocell = ?

Eocell = Eocathode - Eoanode = 0.80 V – 0.34 V = 0.46 V