Electrochemical

Energy
Advincula, Lea Mae DC.
del Rosario, Kris-Anne Louise Gail T.
Gulapa, Eldrin B.
Marcelino, Alexis Luvinne O.
Martinez, Shiena Marie P.
Vijandre, Joshua Angelo S.

Industrial Engineering Department

 I. ELECTRODE POTENTIAL MEASUREMENT

Electrode potential for any given electrode is the voltage or potential difference of a cell
assembled from a standard hydrogen electrode and the given electrode with the potential that is
being defined. It is the resultant potential difference between a point on the electrode surface and
the point in the bulk of electrolyte, due to transfer of charged particles as well as the adsorption of
some polar molecules.

As per convention, the standard hydrogen electrode is always at zero potential.

Electrode potential has uses such as:

• Prediction of corrosion-related chemical or electrochemical reactions

• Used for choosing substances and devices for controlling reactions

• Helps the study of crevice corrosion and pitting, as electrode potential in crevices and pits
is studied for controlling reactions

In any electrochemical process, electrons flow from one chemical substance to another, driven
by an oxidation–reduction (redox) reaction.

Redox Reaction- occurs when electrons are transferred from a substance that is oxidized to one
that is being reduced.

Reductant- is the substance that loses electrons and is oxidized in the process.

Oxidant- is the species that gains electrons and is reduced in the process.

A redox reaction can be described as two half-reactions, one representing the oxidation
process and one the reduction process. For the reaction of zinc with bromine, the overall
chemical reaction is as follows:

reduction half-reaction:
 oxidation half-reaction:

Each half-reaction is written to show what is actually occurring in the system; Zn is the
reductant in this reaction (it loses electrons), and Br is the oxidant (it gains electrons). Adding the
two half-reactions gives the overall chemical reaction. A redox reaction is balanced when the
number of electrons lost by the reductant equals the number of electrons gained by the oxidant.
Like any balanced chemical equation, the overall process is electrically neutral; that is, the net
charge is the same on both sides of the equation.

Electrochemical Cell- an apparatus that is used to generate electricity from a spontaneous redox
reaction or, conversely, that uses electricity to drive a nonspontaneous redox reaction.

There are two types of electrochemical cells: galvanic cells and electrolytic cells.

Galvanic (voltaic) cell- uses the energy released during a spontaneous redox reaction (ΔG < 0) to
generate electricity. This type of electrochemical cell is often called a voltaic cell after its inventor,
the Italian physicist Alessandro Volta (1745–1827).

Electrolytic cell- consumes electrical energy from an external source, using it to cause a
nonspontaneous redox reaction to occur (ΔG >0).

Both types contain two electrodes, which are solid metals connected to an external circuit that
provides an electrical connection between the two parts of the system. The oxidation half-reaction
occurs at one electrode (the anode), and the reduction half-reaction occurs at the other (the
cathode).

The potential (𝐸𝑐𝑒𝑙𝑙 ) of the cell, measured in volts, is the difference in electrical potential between
the two half-reactions and is related to the energy needed to move a charged particle in an electric
field.

A galvanic (voltaic) cell converts the energy released by a spontaneous chemical reaction to
electrical energy. An electrolytic cell consumes electrical energy from an external source to drive
a nonspontaneous chemical reaction.
Example 1.

A chemist has constructed a galvanic cell consisting of two beakers. One beaker contains
a strip of tin immersed in aqueous sulfuric acid, and the other contains a platinum electrode
immersed in aqueous nitric acid. The two solutions are connected by a salt bridge, and the
electrodes are connected by a wire. Current begins to flow, and bubbles of a gas appear at the
platinum electrode. The spontaneous redox reaction that occurs is described by the following
balanced chemical equation:

a. Write the half-reaction that occurs at each electrode.

b. indicate which electrode is the cathode and which is the anode.

c. indicate which electrode is the positive electrode and which is the negative electrode.

Tip: Identify the oxidation half-reaction and the reduction half-reaction. Then identify the anode
and cathode from the half-reaction that occurs at each electrode. Then, from the direction of
electron flow, assign each electrode as either positive or negative.
Solution:

a. In the reduction half-reaction, nitrate is reduced to nitric oxide. (The nitric oxide would
then react with oxygen in the air to form NO2, with its characteristic red-brown color.) In
the oxidation half-reaction, metallic tin is oxidized. The half-reactions corresponding to
the actual reactions that occur in the system are as follows:

Thus, nitrate is reduced to NO, while the tin electrode is oxidized to 𝑆𝑛2+ .

b. Because the reduction reaction occurs at the Pt electrode, it is the cathode. Conversely, the
oxidation reaction occurs at the tin electrode, so it is the anode.

c. B Electrons flow from the tin electrode through the wire to the platinum electrode, where
they transfer to nitrate. The electric circuit is completed by the salt bridge, which permits the
diffusion of cations toward the cathode and anions toward the anode. Because electrons flow
 from the tin electrode, it must be electrically negative. In contrast, electrons flow toward the
Pt electrode, so that electrode must be electrically positive.

Example 2.

Consider a simple galvanic cell consisting of two beakers connected by a salt bridge. One beaker
contains a solution of MnO4− in dilute sulfuric acid and has a Pt electrode. The other beaker
contains a solution of 𝑆𝑛2+ in dilute sulfuric acid, also with a Pt electrode. When the two electrodes
are connected by a wire, current flows and a spontaneous reaction occurs that is described by the
following balanced chemical equation:

For this galvanic cell,

a. Write the half-reaction that occurs at each electrode.

b. indicate which electrode is the cathode and which is the anode.

c. indicate which electrode is positive and which is negative.

Answer:

a.
b. The Pt electrode in the permanganate solution is the cathode; the one in the tin solution is
the anode.
c. The cathode (electrode in beaker that contains the permanganate solution) is positive, and
the anode (electrode in beaker that contains the tin solution) is negative.
 II. OXIDATION-REDUCTION HALF REACTION

Oxidation-Reduction Reactions (Redox)

It is a type of chemical reaction that involves a transfer of electrons between two species.
Any chemical reaction in which the oxidation number of a molecule, atom, or ion may
change by gaining or losing an electron.

The species undergoing oxidation is referred to as a reducing agent.

The species undergoing reduction is referred to as an oxidizing agent.

For oxidation, it loses an electron

For reduction, it gains an electron
In the oxidation-reduction reaction, electrons move between atoms.

e-

Atom A Atom B atom A

loses electron atom B gains electron atom A is
oxidized atom B is reduced

To remember which atom belongs to oxidation and which belong to reduction. Just remember,

OIL means oxidation is the Loss of electron

RIG means reduction is a Gain of electron
GER means Gain of Electron is Reduction

Example: Na + Cl → NaCl
 Na and Cl are electrically neutral on their own, but when Na donates. One electron to
Sodium, the result is Na becomes Na+ ion, and when Cl accepts the donated 1 electron from Na,
the result is Cl becomes Cl- ion.

Na (Sodium) is oxidized; it loses an electron.

Cl (Chlorine) is reduced; it gains an electron.

Na → Na+ + e- Sodium undergo oxidation process

Cl + e-→ Cl- Chlorine undergo reduction process

Na→ Na+ + e- Oxidation half-reaction for Na

Oxidation Cl + e- → Cl- Reduction Half-reaction for Cl

Na 0 + Cl 0 → Na + Cl -

Reduction

➢ How to calculate oxidation number?

Steps to calculate oxidation number:

1. The oxidation number of the element by itself is equal to zero (0). Ex. Na, Cl,
oxidation number = 0
2. For group 1 A: always = +1
3. For group 2A: always = +2
4. For halogen 7A: Usually = -1 and positive with oxygen
5. Monoatomic ion: ion Charge
H: +1 with non-metals
H: - 1 with metals
 O: usually -2
F: always -1
6. Sum of Oxidation numbers (ON’) for a neutral compound = 0
Examples: K+Cl- = 0, KCl as neutral compound, ON = 0
Mg+2O2- = 0, MgO as neutral compound, ON = 0

HNO3
H with non-metal N and 03

H+1N+5O3-2 = 0, 1+ 5 -6 = 0 HNO3 is neutral compound

H with metal Zn

Zn+2 H2-1 = +2 -2 =0 ZnH2 is a neutral compound

7. Polyatomic ion of having charge of -1 Example:

Br+5 O3-2, Br+5 O-6 = -1 BrO3-1 Oxidation number = -1

➢ BALANCING REDOX HALF- REACTIONS EQUATIONS:

Steps on how to balance REDOX half-reaction equations in acidic solution using the half-reaction
method:
1. Determine the oxidation number
2. Figure out what is being oxidized and reduced.
3. Write the half-reactions equations.
 4. Balance atoms other than O and H.
5. Add H2O to balance O and H+ to balance H.
6. Add electrons to balance charges.
7. Multiply half-reactions by any number to make the number of electrons equal half-
reaction equations.
8. Add the half-reactions, cancelling out stuff that appears on both sides of the equations.
9. Do the final checking to make sure everything balances.

For basic solutions, just add no.10 and no.11 steps.

10. For each H+, add one OH- to both sides of the equation.
11. Subtract H2O from both sides of the equation, if possible.

➢ CELL DIAGRAMS/NOTATION AND TERMINOLOGY

Figure 1: The reaction Zn(s) + Cu2+ (aq) → Zn2+(aq) + Cu(s)

Occurring in an electrochemical cell.
A cell diagram shows the components of an electrochemical cell in a symbolic way.

• The anode, the electrode at which oxidation occurs, is placed on the diagram's
left side.
• The cathode, the electrode at which reduction occurs, is placed on the
diagram's right side
• A single vertical line is represented by a boundary between different phases (for
example, an electrode and a solution). ( │)
• The boundary between half- cell compartments, often 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
• Different species in the same solution are separated from each other by a comma.

Example: The cell diagram of figure 1.

anode→ Zn(s) │ Zn2+(aq) ║ Cu2+(aq) │ Cu(s) ← cathode

The electrochemical cell of figure 4 produces electricity due to a spontaneous chemical reaction;
this is called a voltaic or galvanic cell.
Non-spontaneous chemical change.

• Voltaic Cell – It is a cell which produces electricity because of spontaneous chemical

reaction.
• Electrolytic cell – an electrochemical cell that drives a non-spontaneous redox reaction
through the application of electrical energy.
 III. STANDARD ELECTRODE POTENTIAL

Standard electrode potential, commonly denoted as E°, is the measurement of the potential for
equilibrium. It is the potential of the half – reaction measured against SHE.

E°cell = E° red - E° ox

Standard electrode potential occurs under the following standard conditions:

➢ Temperature = 298 K (25 ° C)

➢ Pressure = 1 atm
➢ Concentration = 1M
One of the uses of this standard electrode potential is that it can be used in determining the
spontaneity of a given redox reactions.

A standard hydrogen electrode (SHE) is a gas – ion electrode that is commonly used as a
reference electrode for determination of standard electrode potential of elements and other half
cells. It is assigned a value of 0.00 V.

It consists of a platinum wire which is commonly connected to the Pt surface that has a contact
with an aqueous solution that contains 1 M H+ in equilibrium with H2 gas at a pressure of 1 atm.
 Figure 3.3.1. The Standard Hydrogen Electrode

STANDARD ELECTRODE POTENTIAL (E°) at 298 K

The list of standard electrode potential values is also known as the electrochemical series.

Element Half-Reaction E° (V)

Lithium Li+ + e‾ → Li -3.05

Potassium K+ + e‾ → K -2.93
Calcium Ca2+ + 2e‾ → Ca -2.87
Sodium Na+ + e‾ → Na -2.71
Magnesium Mg2+ + 2e‾ → Mg -2.37
Aluminum Al3+ + 3e‾ → Al -1.66
Manganese Mn2+ + 2e‾ → Mn -1.18
Zinc Zn2+ + 2e‾ → Zn -0.76
Chromium Cr3+ + 3e‾ → Cr -0.74
Gallium Ga3+ + 3e‾ → Ga -0.53
Iron Fe2+ + 2e‾ → Fe -0.41
Cadmium Cd2+ + 2e‾ → Cd -0.40
Cobalt Co2+ + 2e‾ → Co -0.28
Nickel Ni2+ + 2e‾ → Ni -0.25
Tin Sn2+ + 2e‾ → Sn -0.14
Lead Pb2+ + 2e‾ → Pb -0.13
Hydrogen 2H+ + 2e‾ → H2 0.00
Copper Cu2+ + e‾ → Cu+ (aq) +0.15
Copper Cu2+ + 2e‾ → Cu(s) +0.34
Iodine I2 + 2e‾ → 2I‾ +0.54
Mercury Hg2+ + 2e‾ → Hg +0.79
Silver Ag+ + e‾ → Ag +0.80
 Bromine Br2 + 2e‾ → 2Br‾ +1.08
Platinum Pt2+ + 2e‾ → Pt +1.20
Oxygen O2+ 4H+ + 4e‾ → 2H2O +1.23
Chlorine Cl2 + 2e‾ → 2Cl‾ +1.36
Gold Au3+ + 3e‾ → Au +1.50
Fluorine F2 + 2e‾ → 2F‾ +2.87

Note: The more negative the E° value, the stronger the reducing agent and more likely to undergo
oxidation. The more the value is positive, the stronger the oxidizing agent and more likely to
undergo reduction.

Example 1:

Figure 3.3.2. Standard electrode potential of a zinc electrode with the help of the standard
hydrogen electrode

In the figure above, we can see that the given potential of zinc is measured with the given
standard conditions where in it is under the temperature of 298K (25° C), pressure of 1 atm and
the concentration of electrolytes is 1M.
 The half-reactions that actually occur in the cell and their corresponding electrode
potentials are as follows:

• Oxidation:
Zn(s) → Zn2+(aq) + 2e− E° ox = − 0.76V

• Reduction:

2 H+(aq) + 2e− → H2(g) E° red = 0 V

• Overall:
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)

E°cell = E° red - E° ox

E°cell = 0 V - (-0.76 V)

E°cell = +0.76 V

Example 2

0.34 V
 Figure 3.3.3. Standard electrode potential of a copper electrode with the help of the
standard hydrogen electrode

• Oxidation:
H2(g) → 2 H+(aq) + 2e− E° ox = 0 V

• Reduction:

Cu2+ (aq) + 2e‾ → Cu(s) E° red = +34 V

• Overall:
H2(g) + Cu2+ (aq) → 2 H+(aq) + Cu(s)

E°cell = E° red - E° ox

E°cell = + 0.34 V - 0 V

E°cell = + 0.34 V

Calculating Standard Cell Potentials

Standard Cell Potential (E°cell) is the measure of the tendency of reactants in which is it
also the potential difference between the cathode (where reduction occurs) and anode (where
oxidation occurs).

The two standard electrode potentials above can be used to solve the standard potential of
Zn/Cu cell.
 Figure 3.3.4. Zinc | Copper Cell

• Oxidation:
Zn(s) → Zn2+(aq) + 2e− E° ox = − 0.76V

• Reduction:

Cu2+ (aq) + 2e‾ → Cu(s) E° red = +34 V

• Overall:
Zn(s) + Cu2+ (aq) → Zn2+(aq) + Cu(s)

E°cell = E° red - E° ox

E°cell = +0.34 V - (-0.76 V)

E°cell = + 1.10 V

Note: If the value of the E°cell is positive, the reaction occurs spontaneously and a negative value
of E°cell means that it is non-spontaneous.
 IV. ECELL AND SPONTANEOUS CHANGE

The cell potential (Ecell) is the measure of the potential difference between the two half cells in an
electrochemical cell. This is caused by the ability of the electrons to flow from one half cell to
the other half cell. The cell potential (Ecell) is measured in voltage (V).

If E°cell > 0, then the process is spontaneous (galvanic cell/voltaic cell).

If E°cell < 0, then the process is nonspontaneous (electrolytic cell).

Note:

E°cell is the standard state cell potential, which means that these conditions; Activity = 1, Pressure
= 1 atm, and Concentration = 1M, are met.

Ecell is the cell potential at nonstandard state conditions, which means that the conditions are:
Activity ≠ 1, Pressure ≠ 1 atm, and Concentration ≠ 1M.

THE NERNST EQUATION AND NON-STANDARD CONDITIONS

The standard cell potential of an electrochemical cell must meet the standard cell
conditions for all the reactants. However, if there are differences from the standard conditions,
the cell potential will deviate from the standard cell potential. The Nerst equation can be used to
describe the cell potential under nonstandard conditions. It is named after the German physical
chemist who first formulated it, Walther Nernst.

At T = 25°C:

0.0592 [𝑃 𝑖𝑜𝑛]𝑥
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
𝑛 [𝑅 𝑖𝑜𝑛]𝑦

At T > 25°C:
 𝑅𝑇 [𝑃 𝑖𝑜𝑛]𝑥 (𝑃𝑔 )
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑛
𝑛𝐹 [𝑅 𝑖𝑜𝑛] 𝑦

Where:

Ecell = cell potential at nonstandard conditions

E°cell = cell potential at standard conditions

n = number of electrons lost or gained/ number of moles

F = Faraday’s constant = 96485 J/V mol

R = universal gas constant = 8.314 J/mol K

T = absolute temperature at Kelvin unit = °C + 273

Pg = pressure of gas

[P ion] = product ion concentration

[R ion] = reactant ion concentration

x and y = coefficients of ions in the balanced cell reaction

EXAMPLE:

1. Find the cell potential of a voltaic cell based on the following reduction half-reactions
where [Mg2+] = 0.1 M and [Ag+] = 0.25 M at 25°C.
Mg2+ + 2e- → Mg E°cell = - 2.37 V

Ag+ + e- → Ag E°cell = + 0.80 V

Oxi: Mg → Mg2+ + 2e- E°cell = + 2.37 V

Red: Ag+ + e- → Ag E°cell = + 0.80 V

Cell rx: Mg + 2 Ag+ → Mg2+ + 2 Ag E°cell = + 3.17 V

 0.0592 [𝑃 𝑖𝑜𝑛]𝑥
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
𝑛 [𝑅 𝑖𝑜𝑛]𝑦

0.0592 [𝑀𝑔2+ ]1
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
2 [𝐴𝑔+ ]2

0.0592 [0.1]1
𝐸𝑐𝑒𝑙𝑙 = +3.17 − 𝑙𝑜𝑔
2 [0.25]2

𝐸𝑐𝑒𝑙𝑙 = +3.17 − [(0.0295)(0.2041)]

𝐸𝑐𝑒𝑙𝑙 = +3.17 − 0.00604

𝐸𝑐𝑒𝑙𝑙 = +3.164 𝑉

2. Find the cell potential of the galvanic cell based on the redox equations given, where
[Ni2+] = 0.03 M and [Pb2+] = 0.30 M.
Ni2+ + 2e- → Ni E°cell = - 0.25 V

Pb2+ + 2e- → Pb E°cell = - 0.13 V

Oxi: Ni → Ni2+ + 2e- E°cell = + 0.25 V

Red: Pb2+ + 2e- → Pb E°cell = - 0.13 V

Cell rx: Pb2+ + Ni → Ni2+ + Pb E°cell = + 0.12 V

0.0592 [𝑃 𝑖𝑜𝑛]𝑥
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
𝑛 [𝑅 𝑖𝑜𝑛]𝑦

0.0592 [𝑁𝑖 2+ ]1
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
2 [𝑃𝑏 2+ ]1

0.0592 [0.03]1
𝐸𝑐𝑒𝑙𝑙 = + 0.12 − 𝑙𝑜𝑔
2 [0.30]1
 𝐸𝑐𝑒𝑙𝑙 = +0.1496 𝑉 = +0.15 𝑉

3. Assume that the cell has an iron (II) concentration of 0.015 M and an H+ concentration of
0.0010 M. The temperature is 38°C, and the pressure of the hydrogen gas is maintained at
0.4 atm. Determine the cell potential based on the given reduction half-reactions under
these conditions.
Given:

[Fe2+] = 0.015 M

[H+] = 0.0010 M

T = 38°C + 273 = 311 K

PH2 = 0.04 atm

Fe2+ + 2e- → Fe E°cell = - 0.44 V

2H+ + 2e- → H2 E°cell = 0.00 V

Oxi: Fe → Fe2+ + 2e- E°cell = + 0.44 V

Red: 2H+ + 2e- → H2 E°cell = 0.00 V

Cell rx: Fe + 2H+ → Fe2+ + H2 E°cell = + 0.44 V

𝑅𝑇 [𝑃 𝑖𝑜𝑛]𝑥 (𝑃𝑔 )
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑛
𝑛𝐹 [𝑅 𝑖𝑜𝑛] 𝑦

𝐽
8.314 × 311 𝐾 [0.015]1 (0.04)
𝐸𝑐𝑒𝑙𝑙 = +0.44 − 𝑚𝑜𝑙 𝐾 𝑙𝑛
𝐽 [0.0010]2
2 × 96485
𝑉 𝑚𝑜𝑙

𝐸𝑐𝑒𝑙𝑙 = +0.35 𝑉
GIBBS FREE ENEGY AND THE NERNST EQUATION

In the late 19th Century, Josiah Willard Gibbs formulated a theory in order to predict
whether a chemical reaction would be spontaneous on free energy.

∆𝐺 = ∆𝐺° + 𝑅𝑇 × ln 𝑄

Where:

ΔG = change in Gibbs free energy

ΔG° = standard change in Gibbs free energy

R = universal gas constant = 8.314 J/mol K

T = absolute temperature at Kelvin unit = °C + 273

Q = reaction quotient

In the late 20th Century, Walther Nernst extended Gibbs’ theory in order to include the
contribution from the electric potential on the charged species. This change can be related to the
cell potential (see Gibbs free energy and Cell potential), thus resulting to this equation:

−𝑛𝐹∆𝐸𝑐𝑒𝑙𝑙 = −𝑛𝐹∆𝐸°𝑐𝑒𝑙𝑙 + 𝑅𝑇 × ln 𝑄

Where:

n = number of moles of electrons

Ecell = cell potential at nonstandard conditions

E°cell = cell potential at standard conditions

F = Faraday’s constant = 96485 J/V mol

Note: The negative sign is required to indicate that the process is spontaneous.

Walther Nernst divided the whole equation by the amount of charge transferred and the
Faraday’s constant, thus, arriving at a new equation, the Nerst Equation.
 𝑅𝑇
∆𝐸𝑐𝑒𝑙𝑙 = ∆𝐸°𝑐𝑒𝑙𝑙 − × 𝑙𝑛𝑄
𝑛𝐹

Where:

Ecell = cell potential at nonstandard conditions

E°cell = cell potential at standard conditions

n = number of electrons lost or gained/ number of moles

F = Faraday’s constant = 96485 J/V mol

R = universal gas constant = 8.314 J/mol K

T = absolute temperature at Kelvin unit = °C + 273

Q = reaction quotient

GIBBS FREE ENERGY AND CELL POTENTIAL

The free energy is the maximum amount of work that can be done by the system. In the
case of a galvanic cell, there is electrical work done, thus, the relationship between Gibbs free
energy and the cell potential is stated as:

∆𝐺° = −𝑛𝐹𝐸°𝑐𝑒𝑙𝑙

Where:

ΔG° = standard change in Gibbs free energy

n = number of electrons transferred

F = Faraday’s constant = 96485 J/V mol

E°cell = cell potential at standard conditions

 The negative sign is required because the voltaic cell has a positive cell potential and it
generate electrical work spontaneously. The standard change in Gibbs free energy must be
negative to be a spontaneous process.

If the ΔG° is (-), then the process is spontaneous.

If the ΔG° is (+), then the process is nonspontaneous.

EXAMPLE:

1. Calculate the free energy change for the cell: Ga(s) | Ga3+ (aq) || Ag+ (aq) | Ag (s)
Oxi: Ga → Ga3+ + 3e- E°cell = + 0.53 V

Red: 3 Ag+ + 3e- → 3 Ag E°cell = + 0.80 V

Cell rx: Ga + 3 Ag+ → Ga3+ + 3 Ag E°cell = + 1.33 V

∆𝐺° = −𝑛𝐹𝐸°𝑐𝑒𝑙𝑙

𝐽
∆𝐺° = −3 𝑚𝑜𝑙 × 96485 × 1.33 𝑉
𝑉 𝑚𝑜𝑙

∆𝐺° = −384975.15 𝐽

2. Determine the free energy change based on the given reduction half-reaction below.
Zn2+ (aq) + 2e- → Zn (s) E°cell = - 0.763 V

Ag+ (aq) + e- → Ag (s) E°cell = + 0.800 V

Oxi: Zn (s) → Zn2+ (aq) + 2e- E°cell = + 0.763 V

Red: 2 Ag+ (aq) + 2e- → 2 Ag (s) E°cell = + 0.800 V

 Cell rx: Zn (s) + 2 Ag+ (aq) → Zn2+ (aq) + 2 Ag (s) E°cell = + 1.563 V

∆𝐺° = −𝑛𝐹𝐸°𝑐𝑒𝑙𝑙

𝐽
∆𝐺° = −2 𝑚𝑜𝑙 × 96485 × 1.563 𝑉
𝑉 𝑚𝑜𝑙

∆𝐺° = −301612.11 𝐽

3. Determine the free energy change of the redox reaction given below.
Zn2+ (aq) + Cr (s) → Cr2+ (aq) + Zn (s)

Oxi: Cr (s) → Cr2+ (aq) + 2e- E°cell = + 0.910 V

Red: Zn2+ (aq) + 2e- → Zn (s) E°cell = - 0.763 V

Cell rx: Cr (s) + Zn2+ (aq) → Cr2+ (aq) + Zn (s) E°cell = +

0.147 V

∆𝐺° = −𝑛𝐹𝐸°𝑐𝑒𝑙𝑙

𝐽
∆𝐺° = −2 𝑚𝑜𝑙 × 96485 × 0.147 𝑉
𝑉 𝑚𝑜𝑙

∆𝐺° = −28366.59 𝐽

EQUILIBRIUM CONSTANT AND CELL POTENTIAL

The value of the equilibrium constant of a redox reaction can be calculated by relating it
to the cell potential. It can be derived from the Nernst equation.

𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − × 𝑙𝑛𝑄
𝑛𝐹
 Where:

Ecell = cell potential at nonstandard conditions

E°cell = cell potential at standard conditions

n = number of electrons lost or gained/ number of moles

F = Faraday’s constant = 96485 J/V mol

R = universal gas constant = 8.314 J/mol K

T = absolute temperature at Kelvin unit = °C + 273

Q = reaction quotient

The cell potential is zero at equilibrium (Ecell = 0), and the reaction quotient (Q) can now
be assigned as the equilibrium constant (K). Deriving the Nernst equation:

𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − × 𝑙𝑛𝑄
𝑛𝐹

𝑅𝑇
0 = 𝐸°𝑐𝑒𝑙𝑙 − × ln 𝐾
𝑛𝐹

𝑅𝑇
𝐸°𝑐𝑒𝑙𝑙 = × ln 𝐾
𝑛𝐹

𝑛𝐹𝐸°𝑐𝑒𝑙𝑙 = 𝑅𝑇 × ln 𝐾

𝑛𝐹𝐸°𝑐𝑒𝑙𝑙
ln 𝐾 =
𝑅𝑇

Where:

E°cell = cell potential at standard conditions

n = number of electrons lost or gained/ number of moles

F = Faraday’s constant = 96485 J/V mol

R = universal gas constant = 8.314 J/mol K

 T = absolute temperature at Kelvin unit = °C + 273

K = equilibrium constant

The equilibrium constant can also be determined using Gibbs free energy. The free
energy is zero at equilibrium (G = 0), and the reaction quotient (Q) can now be assigned as the
equilibrium constant (K). Derving the Gibbs free energy:

∆𝐺 = ∆𝐺° + 𝑅𝑇 × ln 𝑄

0 = ∆𝐺° + 𝑅𝑇 × ln 𝐾

∆𝐺° = −𝑅𝑇 × ln 𝐾

∆𝐺°
ln 𝐾 =
−𝑅𝑇

Where:

ΔG° = standard change in Gibbs free energy

R = universal gas constant = 8.314 J/mol K

T = absolute temperature at Kelvin unit = °C + 273

K = equilibrium constant

A large value of the equilibrium constant means that the forward reaction is spontaneous
which indicates that most of the reactants are converted into products. On the other hand, a small
value of the equilibrium constant shows that the reaction is nonspontaneous, which means that
most of the reactants remain unreacted and only small amounts of products are formed.

If K > Q, the reaction is spontaneous.

If K < Q, the reaction is nonspontaneous.

EXAMPLE:

1. Determine the equilibrium constant based on the following reaction studied at 298 K.
Zn2+ + 2e- → Zn E°cell = - 0.763 V

Cu2+ + 2e- → Cu E°cell = + 0.337 V

Oxi: Zn → Zn2+ + 2e- E°cell = + 0.763 V

Red: Cu2+ + 2e- → Cu E°cell = + 0.337 V

Cell rx: Zn + Cu2+ → Zn2+ + Cu E°cell = + 1.10 V

𝑛𝐹𝐸°𝑐𝑒𝑙𝑙
ln 𝐾 =
𝑅𝑇

𝐽
2 𝑚𝑜𝑙 × 96485 × 1.10 𝑉
ln 𝐾 = 𝑉 𝑚𝑜𝑙
𝐽
8.314 × 298 𝐾
𝑚𝑜𝑙 𝐾

ln 𝐾 = 85.67541125

𝐾 = 𝑒 85.67541125

𝐾 = 1.61569113 × 1037

Since the value of the equilibrium constant is particularly high, this indicates that the
equilibrium strongly favors the formation of products.

2. Calculate K for the reaction of O2 with N2 to give NO at 423 K and ΔG° = + 22700
J/mol:
N2 (g) + O2 (g) ⇌ 2 NO (g)

∆𝐺°
ln 𝐾 =
−𝑅𝑇
 𝐽
22700
ln 𝐾 = 𝑚𝑜𝑙
𝐽
−8.314 × 423 𝐾
𝑚𝑜𝑙 𝐾

𝐾 = −6.454691196

Since the value of the equilibrium constant is low, it means that most of the reactants
remain unreacted and only small amounts of products are formed.

3. Find the value of K based on the reaction studied at 298 K.

Zn2+ + 2e- → Zn E°cell = - 0.763 V

2H+ + 2e- → H2 E°cell = 0.00 V

Oxi: Zn → Zn2+ + 2e- E°cell = + 0.763 V

Red: 2H+ + 2e- → H2 E°cell = 0.00 V

Cell rx: Zn + 2H+ → Zn2+ + H2 E°cell = + 0.763 V

𝑛𝐹𝐸°𝑐𝑒𝑙𝑙
ln 𝐾 =
𝑅𝑇

𝐽
2 𝑚𝑜𝑙 × 96485 × 0.763 𝑉
ln 𝐾 = 𝑉 𝑚𝑜𝑙
𝐽
8.314 × 298 𝐾
𝑚𝑜𝑙 𝐾

ln 𝐾 = 59.42758071

𝐾 = 𝑒 59.42758071

𝐾 = 6.442736597 × 1025
 V. BATTERIES PRODUCING ELECTRICITY THROUGH CHEMICAL
REACTIONS

Battery – a galvanic cell or a series of galvanic cells that contains all the reactants needed to
produce electricity.

Fuel Cell – a galvanic cell that requires a constant external supply of one or more reactants to
generate electricity.

Two Basic Kinds of Batteries:

Disposable / Primary – the electrode reactions are effectively irreversible and which cannot be
recharged.

Rechargeable / Secondary – can be recharged by applying an electrical potential in the reverse

direction. (The recharging process temporarily converts a rechargeable battery from a galvanic
cell to an electrolytic cell).

The major difference between batteries and the galvanic cells is that commercial typically
batteries use solids or pastes rather than solutions as reactants to maximize the electrical output
per unit mass. An obvious exception is the standard car battery which used solution phase
chemistry.

Leclanché Dry Cell

It is actually a “wet cell”. The electrolyte is an acidic water-based paste

containing MnO2, NH4Cl, ZnCl2, graphite, and starch.

The half-reactions at the anode and cathode can be summarized as follows:

Cathode (reduction):

2MnO2(s)+2NH+4(aq)+2e−⟶Mn2O3(s)+2NH3(aq)+H2O(l)

Anode (oxidation):

Zn(s)⟶Zn2+(aq)+2e−
The Zn2+ ions formed by the oxidation of Zn(s) at the anode react with NH3 formed at the
cathode and Cl− ions present in solution, so the overall cell reaction is as follows:

Overall reaction:

2MnO2(s)+2NH4Cl(aq)+Zn(s)⟶Mn2O3(s)+Zn(NH3)2Cl2(s)+H2O(l)

Alkaline Battery

It is essentially a Leclanché cell adapted to operate under alkaline, or basic,

conditions.

The half-reactions at the anode and cathode can be summarized as follows:

Cathode (reduction):

2MnO2(s)+H2O(l)+2e−⟶Mn2O3(s)+2OH−(aq)

Anode (oxidation):

Zn(s)+2OH−(aq)⟶ZnO(s)+H2O(l)+2e−

Overall reaction:

Zn(s)+2MnO2(s)⟶ZnO(s)+Mn2O3(s)

Button Batteries

Although some of the small button batteries used to power watches, calculators,
and cameras are miniature alkaline cells, most are based on a completely different
chemistry. In these "button" batteries, the anode is a zinc–mercury amalgam rather than
pure zinc, and the cathode uses either HgO or Ag2O as the oxidant rather than MnO2

The half-reactions at the anode and cathode can be summarized as follows:

Cathode (mercury battery):

 HgO(s)+H2O(l)+2e−⟶Hg(l)+2OH−(aq)

Anode (mercury battery):

Zn+2OH−⟶ZnO+H2O+2e−

Overall reaction (mercury battery):

Zn(s)+2HgO(s)⟶2Hg(l)+ZnO(s)

with Ecell=1.35VEcell=1.35V.

Cathode reaction (silver battery):

Ag2O(s)+H2O(l)+2e−⟶2Ag(s)+2OH−(aq)

Anode (silver battery):

Zn+2OH−⟶ZnO+H2O+2e−

Overall reaction (silver battery):

Zn(s)+2Ag2O(s)⟶2Ag(s)+ZnO(s)

with Ecell=1.6VEcell=1.6V.

Lithium-Iodine Battery

It is one of the few commercially successful water-free batteries. The anode is

lithium metal, and the cathode is a solid complex of I2I2. Separating them is a layer of
solid LiILiI, which acts as the electrolyte by allowing the diffusion of Li+ ions.

The electrode reactions are as follows:

Cathode (reduction):
I2(s)+2e−→2I−(LiI)

Anode (oxidation):
 2Li(s)→2Li+(LiI)+2e−

Overall:
2Li(s)+I2(s)→2LiI(s)

with Ecell=3.5V

Nickel-Cadmium (NiCad) Battery

It is used in small electrical appliances and devices like drills, portable vacuum
cleaners, and AM/FM digital tuners. It is a water-based cell with a cadmium anode and a
highly oxidized nickel cathode that is usually described as the nickel(III) oxo-hydroxide,
NiO(OH).

The electrode reactions during the discharge of a NiCad battery are as follows:

Cathode (reduction):
2NiO(OH)(s)+2H2O(l)+2e−→2Ni(OH)2(s)+2OH−(aq)

Anode (oxidation):
Cd(s)+2OH−(aq)→Cd(OH)2(s)+2e−

Overall:
Cd(s)+2NiO(OH)(s)+2H2O(l)→Cd(OH)2(s)+2Ni(OH)2(s)

Ecell=1.4V

Lead-Acid (Lead Storage) Battery

It is used to provide the starting power in virtually every automobile and marine
engine on the market. Marine and car batteries typically consist of multiple cells
connected in series. The total voltage generated by the battery is the potential per cell
(E°cell) times the number of cells.
The electrode reactions in each cell during discharge are as follows:

Cathode (reduction):
PbO2(s)+HSO−4(aq)+3H+(aq)+2e−→PbSO4(s)+2H2O(l)

with E∘cathode=1.685VEcathode°=1.685V

Anode (oxidation):
Pb(s)+HSO−4(aq)→PbSO4(s)+H+(aq)+2e−

with E∘anode=−0.356VEanode°=−0.356V

Overall:
Pb(s)+PbO2(s)+2HSO−4(aq)+2H+(aq)→2PbSO4(s)+2H2O(l)

and E∘cell=2.041V

Fuel Cells

It is a galvanic cell that requires a constant external supply of reactants because

the products of the reaction are continuously removed. Unlike a battery, it does not store
chemical or electrical energy; a fuel cell allows electrical energy to be extracted directly
from a chemical reaction.

The electrode reactions are as follows:

Cathode (reduction):
O2(g)+4H++4e−→2H2O(g)

Anode (oxidation):
2H2(g)→4H++4e−

Overall:
2H2(g)+O2(g)→2H2O(g)
 VI. ELECTROLYSIS CAUSING NON-SPONTANEOUS REACTIONS TO OCCUR

The spontaneous direction of a redox reaction can be exploited in a galvanic cell to provide an
electric current, or we can use an external electric current to force a redox reaction in the non-
spontaneous direction.

Non-spontaneous reaction: it cannot take place on its own, requires an input of energy for it to
occur.

ELECTROLYSIS: the process of passing an electric current through an ionic solution or molten
salt to produce a chemical reaction.

ELECTROLYTIC CELLS can be divided into two categories based on the nature of the electrodes
used.

1. Passive Electrolysis
- A process in which the electrodes are chemically inert materials that simply provide
a path for electrons.
- Used in industry to purify materials that corrode easily.

2. Active Electrolysis
- The electrodes are part of the electrolytic reaction.
- Used in electroplating, a process of depositing a thin coating of one metal on top of
another by using electricity, to provide resistance to corrosion, or for decorative
purposes.

Electrolysis changes the polarity of the electrodes in a system. Instead of the reaction that would
occur spontaneously at the electrodes, the external power supply causes the reverse reaction to
occur. Thus, for reduction, electrons are forced to the cathode in an electrolytic reaction. The
cathode is still the site of reduction, but in electrolysis, it is negatively charged because the external
power supply forces electrons and their negative charges to the location of the reaction. The anode
is still the site of oxidation, but it is positively charged. In forcing oxidation of the material, the
external power supply pulls the electrons away from the region of the oxidation reaction.

ELECTROLYTIC CELLS: an electrochemical cell that uses electrical energy to cause non-
spontaneous chemical reaction to occur. The process in which electrical energy is used to produce
chemical reactions is called electrolysis. Electrolysis is used to purify metals, to plate precious
metals, and to extract metals from their compounds.

EXAMPLE REACTION:

1. A diagram of an electrolytic cell, showing the electrolysis of molten NaCl is shown below.

Oxidation – increases Oxi no.

Reduction – decreases Oxi no.

The cell contains molten NaCl (the electrolyte that conducts the current) and two electrodes
connected to a battery or other source of direct current. When a voltage is applied, one of the
electrodes develops a positive charge and the other, a negative charge. The Cl‾ ions move toward
the anode or positive electrode, where oxidation takes place. The Na+ ions move toward the
cathode or negative electrode, where reduction occurs. The movement of the ions results in the
passage of the electricity.

*** In terms of electron charges, opposite attracts. Charge going from positive (anode) to negative
(cathode).

The half-reactions and the overall reaction for the electrolysis of molten NaCl are:

Oxidation: 2 Cl‾ → Cl2 + 2 e‾

Reduction: 2 Na+ + 2 e‾ → 2 Na
Cell reaction: 2 Na+ + 2 Cl‾ → 2 Na + Cl2
Standard Reduction Potentials
Standard Reduction
Element Reduction Half-Reaction
Potential, Ɛ°red, V
Lithium Li+ + e‾ → Li -3.05
Potassium K+ + e‾ → K -2.90
Calcium Ca2+ + 2e‾ → Ca -2.87
Sodium Na+ + e‾ → Na -2.71
Magnesium Mg2+ + 2e‾ → Mg -2.37
Aluminum Al3+ + 3e‾ → Al -1.66
Manganese Mn2+ + 2e‾ → Mn -1.18
Zinc Zn2+ + 2e‾ → Zn -0.76
Chromium Cr3+ + 3e‾ → Cr -0.74
Gallium Ga3+ + 3e‾ → Ga -0.53
Iron Fe2+ + 2e‾ → Fe -0.44
 Cadmium Cd2+ + 2e‾ → Cd -0.40
Cobalt Co2+ + 2e‾ → Co -0.28
Nickel Ni2+ + 2e‾ → Ni -0.25
Tin Sn2+ + 2e‾ → Sn -0.14
Lead Pb2+ + 2e‾ → Pb -0.13
Hydrogen 2H+ + 2e‾ → H2 0.00
Copper Cu2+ + e‾ → Cu+ (aq) +0.15
Copper Cu2+ + 2e‾ → Cu (s) +0.34
Iodine I2 + 2e‾ → 2I‾ +0.54
Mercury Hg2+ + 2e‾ → Hg +0.79
Silver Ag+ + e‾ → Ag +0.80
Bromine Br2 + 2e‾ → 2Br‾ +1.07
Platinum Pt2+ + 2e‾ → Pt +1.20
Oxygen O2 + 4H+ + 4e‾ → 2H2O +1.23
Chlorine Cl2 + 2e‾ → 2Cl‾ +1.36
Gold Au3+ + 3e‾ → Au +1.50
Fluorine F2 + 2e‾ → 2F‾ +2.87

Oxidation: 2 Cl‾ → Cl2 + 2 e‾ Ɛ°ox = -1.36 V (opposite sign in reduction

table)
Reduction: 2 Na+ + 2 e‾ → 2 Na Ɛ°red = -2.71 V
Cell reaction: 2 Na+ + 2 Cl‾ → 2 Na + Cl2 Ɛ°cell = -4.07 V

Note that the reaction has a NEGATIVE Ɛ°cell value; thus, the reaction is nonspontaneous and
will not deliver current.
 2.

Oxidation: Cu(s) → Cu2+(aq) + 2 e‾

Reduction: Cd2+(aq) + 2 e‾ → Cd(s)
Cell reaction: Cd2+(aq) + Cu(s) → Cd(s) + Cu2+(aq)

Ɛ°ox = -0.34 V (opposite sign in reduction table)

Ɛ°red = -0.40 V

Ɛ°cell = -0.74 V

Note that the reaction has a NEGATIVE Ɛ°cell value; thus, the reaction is nonspontaneous and
will not deliver current.
ELECTROLYSIS AND STOICHIOMETRY

In electroplating, it is important to use carefully controlled amounts of materials. Fortunately, the

flow of electrons in an electric current provides a ready source of information. So, let us review
some facts about electricity and then apply those to electrolytic cells.
CURRENT AND CHARGE

When the current is measured in an electric circuit, the observation is the flow of charge for a
period of time. The base unit of current is the Ampere (A), which is defined as 1 A = 1 C/s. Devices
called ammeters measure current. If a known current passes through a circuit for a known time,
the charge or the amount of electricity can be easily calculated.

CHARGE FORMULA

Charge = current x time

Q=IXt

Units: Q = Coulombs (C) ; I = Amperes or C/s ; t = seconds (s)

Coulombs (C) and faraday (F) are the units for expressing the charge or amount of electricity. One
faraday is equal to 96,485 C. 1 F = 96,485 C

One mole of electron has a charge of 1 F or 96, 485 C. 1 n e‾ = 96,485 C

The rate at which electric current flows through an electrolytic cell is measured in Amperes (A).
One ampere is the rate at which 1 C of electricity passes through an electrolytic cell in 1 second.
1A=1C/1s
EXAMPLE:

In a process called flash electroplating, a current of 2.50 x 103 A passes through an electrolytic cell
for 5.00 minutes. How many moles of electrons are driven through the cell?

Given:
I = 2.50 x 103 A
t = 5.00 min = 300 s

Solution:
(a) Q = I x t = 2500 C/s x 300 s = 7.50 x 105 C
1 mol e-
(b) mol e‾ = 7.50 x 105 C x = 7.77 mol e‾
96, 485 C

ENERGY CONSUMPTION AND COST

Although current can be measured readily, electricity use is often considered in terms of power.
Electric power is the rate of electricity consumption, and utility charges are based on
consumption. The SI unit for power is the Watt (W). Wattage is the rate of energy use in J/s. To
determine the amount of energy used, we multiply this rate by the time during which it occurs. To
obtain numbers of a convenient magnitude electrical utilities normally determine energy
consumption in kilowatt-hours (kWh) where 1 kWh = 3.60 x 106 J.

Another important relationship to recall between energy and electrical potential:

Energy = charge x voltage = Q x V

Unit: CV or J
EXAMPLE:

Suppose that a batch of parts is plated with copper in an electrolytic bath running at 0.15 V and
15.0 A for exactly 2 hours. If the electric utility charges the company P2.50 per kWh, what is the
energy cost of this process?

Solution:

(a) Determine the charge.

Formula: Q = I x t

Given:
I = 15.0 A = 15.0 C/s
t = 2 hours = 7200 s

Q=Ixt
Q = (15.0 C/s) (7200 s)

Q = 1.08 x 105 C

(b) Determine the energy.

Formula: E = Q x V
 Given:
Q = 1.08 x 105 C
V = 0.15 V

E=QxV
E = (1.08 x 105 C) (0.15 V)

E = 1.62 x 104 J

(c) Convert J to kWh and determine the cost.

1 kWh P 2.50
Energy cost = 1.62 x 104 J × × = P 0.011
3.60 × 106 J 1 kWh

CALCULATIONS USING MASSES OF SUBSTANCES IN ELECTROLYSIS

In problems such as these, we generally encounter one of two questions. First, how much material
is plated, given a specified current or electrical energy expenditure, and second, how long must a
given current pass through the cell to yield a desired mass of plated material?

EXAMPLE:

1. An electrolysis cell that deposits gold from Au+ (aq) operates for 15.0 minutes at a current
of 2.30 amperes. What mass of gold is deposited?

Solution: Au+ (aq) + e‾ → Au (s)

 (a) Q = I x t = (2.3 C/s) (900s) = 2.70 x 103 C

1 mol e‾ 1 mol Au 197 g Au

(b) Mass, Gold = 2.70 x 103 C × × × = 4.23 g Au
96, 485 C 1 mol e‾ 1 mol Au

2. Suppose that you have a part that requires a tin coating. You need to deposit 3.60 g of tin
to achieve an adequate coating. If your electrolysis cell using Sn2+ runs at 2.00 A, how long
must you operate the cell to obtain the desired coating?

Solution: Sn2+ (aq) + 2e‾ → Sn (s)

1 mol Sn 2 mol e‾ 96, 485 C

C = 3.6 g Sn × × × = 5.84 x 103 C
119 g 1 mol Sn 1 mol e‾

5.84 x 103 C
Since Q = I x t; then t = Q/I = = 2920 s = 48. 7 minutes
2.00 C/s