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CHEM 111LEC CHEMISTRY FOR ENGINEERS

Electrolysis/Electroplating

Electrolysis - is the passage of electricity through an electrolyte, with cations moving to


the cathode to get reduced, and anions moving towards the anode to get oxidized.
An electrolyte is a liquid that conducts electricity.

Take note: Faraday's Constant: 1 mole e- = 96,485 C (where C measures Coulombs)

Take Note:

Electric current arises whenever there is a flow of charges (for example, electrons) and
is defined as the rate at which charge flows. The formula is as follows:
Current = Quantity of charge/Time, or
Mathematically,
I = Q/t
Where
I- is the current in Ampere (A), which is the flow of 1 Coulomb of charge per second, or
C/s,
t -is time in seconds, and
Q -is quantity of electricity in Coulombs

Faraday's Constant
The charge of a single electron is 1.6023 x 10 -19 C.
1 mole of electrons is represented by the Avogadro's Number, L = 6.022 x 1023 electrons.
Therefore, 6.022 x 1023 electrons carries a charge of 6.022 x 1023 x 1.6023 x 10-19 C/mol
= 96,485 C/mol.
96,485 C/mol, or one Faraday, denoted by the symbol F, is the amount of electricity that
is carried by one mole of electrons and is known as the Faraday constant
Chemical Equivalent or Equivalent Weight

Equivalent weight or equivalent mass is another quantity which is often used in


electrolytic calculations and is given by:
Equivalent weight, or E = Atomic weight/Valency = MW/charge
where atomic weight or atomic mass is in g/mol and the value is usually
provided. Valency is an atom's ability to combine with other atoms, and equivalent
weight or equivalent mass is measured in grams.
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CHEM 111LEC CHEMISTRY FOR ENGINEERS

Example 1 - Find the equivalent weight for silver.

Atomic mass of Ag is given as 108.


Valency = 1, since only 1 mole of electron can be used to combine with another atom.
Equivalent weight = Atomic weight of silver/Valency of silver= 108/1=108g

Example 2 - Find the equivalent weight for aluminum

Atomic mass of Al is given as 27.


Valency = 3, since 3 moles of electrons can be used to combine with another atom.
Equivalent weight = Atomic weight of aluminum/Valency of aluminum = 27/3 = 9g
The Faraday’s First Law of Electrolysis
“The mass of the substance (m) deposited or liberated at any electrode is directly
proportional to the quantity of electricity or charge (Q) passed.”
In the mathematical form, this law can be represented as follows:

m = ZQ --- removing proportionality constant


Where: m is the mass in grams (g)
Q is measured in Coulombs ©
Z is the proportionality constant in g/C (in grams per coulomb) and is also
known as the electrochemical equivalent, which is the mass of a substance
produced at the electrode during electrolysis by one Coulomb of charge.
Z = Equivalent weight/96,485, or Z = E/96,485
m = E x I x t /96,485

Summarize Formulas:

 amperes x time = Coulombs


 96,485 coulombs = 1 Faraday
 1 Faraday = 1 mole of electrons

Equivalent weight, E = Atomic weight/Valency = MW/Charge

m = E x I x t /96,485

PV = nRT

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CHEM 111LEC CHEMISTRY FOR ENGINEERS

Example:
1. During an electrolysis of molten sodium chloride, a 4A current is passed through
electrodes for 1 hour. Calculate the mass of sodium that is produced during this time.
Given I = 4A, t = 1 x 60 x 60 = 3,600s, and E of sodium is 23/1 = 23g
Mass of sodium produced = E x I x t/96,485
= (23 x 4 x 3,600)/96,485
= 3.43g
2. What mass of nickel metal can be plated on to cathode from Nickel Sulfate solution
using a current of 8 amp for 15 mins?
Ni 2+ + 2e- → Ni(s)
3. How much current is needed to plate 5 g of copper metal on the cathode from a copper
sulfate solution in 2hrs?
4. Molecular masses can be determined through electroplating. Determine the molecular
mass and identity of a +2 metal, X, that plates 46.3g of X in 6.75 hours at a current of 2
A.
5. How long will it take for 1.25 L of a 1.0 M CuSO4 solution being electrolyzed with a
current of 3.40 A to reach a concentration of 0.25 M?
6. How long must a 20.0 amp current flow through a solution of ZnSO4 in order to
produce 25.00 g of Zn metal.
7. A 40.0 amp current flowed through molten iron(III) chloride for 10.0 hours (36,000
s). Determine the mass of iron and the volume of chlorine gas (measured at 25oC and 1
atm) that is produced during this time.
8. What current is required to produce 400.0 L of hydrogen gas, measured at STP, from
the electrolysis of water in 1 hour (3600 s)? Calculate the number of moles of H2.
(Remember, at STP, 1 mole of any gas occupies 22.4 L.)

Electrochemical Cells - An electrochemical cell is a device that produces an electric


current from energy released by a spontaneous redox reaction. This kind of cell includes
the galvanic, or voltaic, cell, named after Luigi Galvani and Alessandro Volta. These
scientists conducted several experiments on chemical reactions and electric current
during the late 18th century. One important application of oxidation and
reduction reactions are used to provide useful electrical energy in batteries.

Electrode - is a solid electric conductor that carries electric current into non-metallic
solids, or liquids, or gases, or plasmas, or vacuums. Electrodes are typically good electric
conductors, but they need not be metals. Electrodes can be made from any sufficiently
conductive materials, such as metals, semiconductors, graphite, and even conductive
polymers. In between these electrodes is the electrolyte, which contains ions that can
freely move.

Electrolyte- substances that become ions in solution and


acquire the capacity to conduct electricity.

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CHEM 111LEC CHEMISTRY FOR ENGINEERS

Two conductive electrodes of Electrochemical Cell

1. Anode- defined as the electrode where oxidation occurs.


2. Cathode - electrode where reduction takes place.

Two types Electrochemical Cell

1. Voltaic Cell / Galvanic Cell


2. Electrolytic Cell

Voltaic Cell / Galvanic 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).

Voltaic Cell / Galvanic Cell- The voltaic cell uses two different metal electrodes, each in
an electrolyte solution. The anode will undergo oxidation and the cathode will undergo
reduction. The metal of the anode will oxidize, going from an oxidation state of 0 (in the
solid form) to a positive oxidation state, and it will become an ion. At the cathode, the
metal ion in the solution will accept one or more electrons from the cathode, and the ion’s
oxidation state will reduce to 0. This forms a solid metal that deposits on the cathode. The
two electrodes must be electrically connected to each other, allowing for a flow of
electrons that leave the metal of the anode and flow through this connection to the ions at
the surface of the cathode. This flow of electrons is an electrical current that can be used
to do work, such as turn a motor or power a light.

Electrolytic Cells

Electrolysis uses electrical energy to induce a chemical reaction, which then takes place
in an electrolytic cell.

In chemistry and manufacturing, electrolysis is a method of using a direct electric current


(DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is
commercially important as a stage in the process of separating elements from naturally
occurring sources such as ore.

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CHEM 111LEC CHEMISTRY FOR ENGINEERS

Electrolysis is the passage of a direct electric current through an ionic substance that is
either molten or dissolved in a suitable solvent, resulting in chemical reactions at the
electrodes and separation of the materials.

Electrolysis can sometimes be thought of as running a non-spontaneous galvanic cell.


Depending on how freely elements give up electrons (oxidation) and how energetically
favorable it is for elements to receive electrons (reduction), the reaction may not be
spontaneous. By externally supplying the energy to overcome the energy barrier to
spontaneous reaction, the desired reaction is “allowed” to run under special
circumstances.
The main components required to perform electrolysis are:

 An electrolyte: a substance containing free ions that carry electric current. If the
ions are not mobile, as in a solid salt, then electrolysis cannot occur.
 A direct current (DC) supply: provides the energy necessary to create or discharge
the ions in the electrolyte. Electric current is carried by electrons in the external
circuit.
 Two electrodes: an electrical conductor that provides the physical interface
between the electrical circuit providing the energy and the electrolyte.
CELL POTENTIALS
electrochemistry: The science of the chemistry associated with the flow of electricity,
especially at the surface of an electrode.
electrochemical cell: A container containing an electrolyte and two electrodes; used to
produce direct current electricity. One or more of them constitute a battery.
voltage: The amount of electrostatic potential between two points in space.
electromotive force:EMF, Voltage generated by a battery or by a varying magnetic
field,
NOTE: Spontaneous Reaction the Eo = positive

Cell Notation:
In Cell Notation, we always follow Anode // Cathode format.
For Example,
1. What is the cell notation for [Ni2+] = 0.030 M and [Pb2+] = 0.300 M.
Ni2+ (aq)+ 2 e- → Ni(s), E0 = -0.25 V
Pb2+ (aq)+ 2 e- → Pb(s), E0 = -0.13 V
Anode: Ni(s) → Ni2+ + 2 e- [Ni2+] = 0.030 M
Cathode:Pb2+ + 2 e- → Pb [Pb2+] = 0.300 M.
Ni(s) / Ni2+ (aq) (0.030M) // Pb2+ (aq) (0.3 M)/ Pb(s)

Note: Anode has an Eo lower than the cathode.


Reduction: mas naging negative, e- nasa reactant side
Oxidation: Mas Naging positive, e- nasa product side

The Nernst Equation

In electrochemistry, the Nernst equation can be used to determine the reduction potential
of an electrochemical cell.

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CHEM 111LEC CHEMISTRY FOR ENGINEERS

The Nernst equation gives a formula that relates the electromotive force of a nonstandard
cell to the concentrations of species in solution:

0.05914
E= Eo - log Q
n -----For 1 Molar Solution and @ T=25oC

RT
ln Q
E= E -o nF -------for T higher than 25

R= 8.314 J/mol.K

Eo= Eocathode - Eoanode

In this equation:

 E is the electromotive force of the non-standard cell


 Eo is the electromotive force of the standard cell
 n is the number of moles of electrons transferred in the reaction, Electrons from
half cell reaction., Mol e-/Mol

for the reaction: aA+bB→cC+dD

Mathematically,

C ^ c.D ^ d
Q= = Products/Reactants
A^ a.B ^ b

Example:

1. Find the cell potential of a galvanic cell based on the following reduction
half-reactions where [Ni2+] = 0.030 M and [Pb2+] = 0.300 M.

Ni2+ + 2 e- → Ni, E0 = -0.25 V


Pb2+ + 2 e- → Pb, E0 = -0.13 V
First, find the electromotive force for the standard cell, which assumes concentrations of
1 M.

Take Note: Pure Solids has a concentration of 1.

2. Find the cell potential of a galvanic based on the following reduction half reactions at
25 oC

Cd 2+ + 2e- → Cd E0 = -0.403 V

Pb2+ + 2e- → Pb E0 = -0.126 V

Where [Cd2+] = 0.020 M and [Pb2+] = 0.200 M.

3. What is the cell potential of the reaction shown below at 298 K?


2Al (s) + 3Cu2+ → 2Al3+ + 3Cu(s)
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CHEM 111LEC CHEMISTRY FOR ENGINEERS

Eo = 2v ,Where [Al3+] = 0.10 M and [Cu2+] = 2.5 M

4. Determine the cell potential when Ni2+ = 0.01, Cl- = 0.20 M and the Cl2=1.0 atm
Given the reaction: Ni + Cl2 → Ni2+ + 2Cl-
5. A galvanic cell is made using 0.25M ZnSO4 and an unknown amount of CuSO4. The
cell potential is 1.05V at 50 C. a. what is the concentration of CuSO4 in the Cathode
compartment? How many grams of CuSO4 are dissolved if the cathode compartment
contains 250 mL solution?
Zn(s) + Cui2+ → Zn2+ + Cu(s)

Batteries and Fuel Cell


Battery (storage cell) - is a galvanic cell (or a series of galvanic cells) that contains all
the reactants needed to produce electricity.
Fuel cell is a galvanic cell that requires a constant external supply of one or more
reactants to generate electricity.

Two Kinds of Battery Cell


1. Disposable or primary Batteries - electrode reactions are effectively irreversible and
which cannot be recharged.
2. Rechargeable or secondary Batteries - which form an insoluble product that adheres
to the electrodes. These batteries 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.

Three Kinds of Primary (Nonrechargeable) Batteries


1. Leclanché dry cell - actually a “wet cell,” in which the electrolyte is an acidic
water-based paste containing MnO2, NH4Cl, ZnCl2, graphite, and starch. Though
inexpensive to manufacture, the cell is not very efficient in producing electrical energy
and has a limited shelf life.
2. Button battery - the anode is a zinc–mercury amalgam, and the cathode can be either
HgO (shown here) or Ag2O as the oxidant.
3. Lithium–iodine battery - consists of two cells separated by a metallic nickel mesh
that collects charge from the anodes. The anode is lithium metal, and the cathode is a
solid complex of I2. The electrolyte is a layer of solid LiI that allows Li+ ions to diffuse
from the cathode to the anode. Although this type of battery produces only a relatively
small current, it is highly reliable and long-lived.
Leclanché Dry Cell
- is used in flashlights, electronic devices such as the Walkman and Game Boy, and many
other devices.
-In spite of its name, the Leclanché dry cell is actually a “wet cell”: the electrolyte is an
acidic water-based paste containing MnO2, NH4Cll, ZnCl2, graphite, and starch.
The half-reactions at the anode and the 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−
Overall Reaction:
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CHEM 111LEC CHEMISTRY FOR ENGINEERS

2MnO2(s)+2NH4Cl(aq)+Zn(s)→Mn2O3(s)+Zn(NH3)2Cl2(s)+H2O(l)
E cell= 1.55 V
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 cathode and overall reactions and cell output for these two types of button batteries
are as follows:
A)
cathode (Hg):
HgO(s)+H2O(l)+2e−→Hg(l)+2OH−(aq)
anode (oxidation):
Zn(s)+2OH−(aq)→ZnO(s)+H2O(l)+2e−
Overall Reaction:
Zn(s)+2HgO(s)→Hg(l)+ZnO(s)
Ecell=1.35V

B)
cathode (Ag):
Ag2O(s)+H2O(l)+2e−→2Ag(s)+2OH−(aq)
anode (oxidation):
Zn(s)+2OH−(aq)→ZnO(s)+H2O(l)+2e−
Overall Reaction:
Zn(s)+2Ag2O(s)→2Ag(s)+ZnO(s)
Ecell=1.6V

Lithium–Iodine Battery
None of the batteries described above is actually “dry.” They all contain small amounts
of liquid water, which adds significant mass and causes potential corrosion problems.
Consequently, substantial effort has been expended to develop water-free batteries. One
of the few commercially successful water-free batteries is the lithium–iodine battery.
The anode is lithium metal, and the cathode is a solid complex of I2. Separating them is a
layer of solid LiI, which acts as the electrolyte by allowing the diffusion of Li+ ions.
cathode (reduction):
I2(s)+2e−→2I−(Li)
anode (oxidation):
2Li(s)→2Li+(LiI)+2e−
overall:
2Li(s)+I2(s)→2LiI(s)
Ecell=3.5V

Fuel Cells
A fuel cell 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. In principle, this should be a more efficient process than, for
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CHEM 111LEC CHEMISTRY FOR ENGINEERS

example, burning the fuel to drive an internal combustion engine that turns a generator,
which is typically less than 40% efficient, and in fact, the efficiency of a fuel cell is
generally between 40% and 60%.
A. Hydrogen Fuel Cell
These space vehicles use a hydrogen/oxygen fuel cell that requires a continuous input of
H2(g) and O2(g).
cathode (reduction):
O2(g)+4H++4e−→2H2O(g)
anode (oxidation):
2H2(g)→4H++4e−
Overall Reaction:
2H2(g)+O2(g)→2H2O(g)
E cell (theo) = 1.23 V
E cell (actual) = 0.9 V
In the reaction the catalyst used is O2.

Prepared by: Engr. Lachica

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