CONDUCTANCE
- Flow of electricity through a conductor involves a
transfer of electrons from a point of higher
negative potential to one of lower negative
potential
- The mechanism varies for different conductors.
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Conductors
2. ELECTROLYTIC CONDUCTORS
- Include solutions of strong and weak electrolytes
- Electron transfer takes place by migration of ions
(accomplished by a transport matter)
- (+) and (-) ions do not carry equal portions of the
current, thus, a concentration gradient develops
- Current flow in electrolytic conductors is
accompanied by a chemical reaction (electrolysis)
at each electrode.
3 4
Conductors
1. ELECTRONIC CONDUCTORS
- Include solid/molten metals and certain solid salts
- Example: CuS and CdS
- Conduction takes place by direct migration of
electrons through the conductor under the
influence of an applied potential
- Atoms and ions composing the conductor are not
involved in the process
Electrolysis
- The splitting of a substance by the input of
electrical energy
- Often used to decompose a compound into its
elements
- In predicting the product, the general rule is that
▪ the more easily oxidized species (stronger reducing
agent) reacts at the anode and
▪ the more easily reduced species (stronger oxidizing
agent) reacts at the cathode
 Identification of Reaction at the Electrode
Electrolytic Cell
in an Electrolytic Cell

- A cell in which non-spontaneous redox reaction

1. ELECTROLYSIS OF PURE MOLTEN SALT
is made to occur by the action of an external - Predicting the product is simple because the
potential electrolyte is the molten salt itself
CATION – Reduction; ANION – Oxidation
- Involved in key industrial - Example: Industrial preparation of metallic calcium
production steps for isolating and Cl2 from CaCl2
some of the most commercially
Anode: 2Cl-(l) → Cl2(g) + 2e-
important elements, including
chlorine, aluminum, copper, etc. Cathode: Ca2+(l) + 2e- → Ca(s)
OCR* Ca2+ + 2Cl-(l) → Ca(s) + Cl2(g)
*OCR: Overall Cell Reaction
Photo from: By © Nevit Dilmen, CC BY-SA
5 3.0, 6
https://commons.wikimedia.org/w/index.php?curid=10959462

continuation… continuation…
2. ELECTROLYSIS OF MIXED MOLTEN SALT 2. ELECTROLYSIS OF MIXED MOLTEN SALT
- Electrolyte is a mixture of molten salts which is
then electrolyzed to produce a specific metal CATION – Reduction ANION - Oxidation
- knowledge of PERIODIC ATOMIC TRENDS is Periodic Atomic Trend:
significant in predicting which ion gains or loses IONIZATION ENERGY (IE) ELECTRONEGATIVITY (EN)
electrons more easily
If a metal holds its electrons If a nonmetal holds its electrons
more tightly than the other less tightly than the other
- NOTE: Tabulated E° values cannot be used to tell the relative • then it has a higher IE • then it has a lower EN
strengths of oxidizing and reducing agents since those values • as a cation, it gains electrons • as an anion, it loses more
refer to the change from aqueous ion to free element under more easily electrons more easily
standard state conditions • it is the stronger oxidizing • it is the stronger reducing
▪ ex. Mn+(aq) + ne- → M(s) agent agent
▪ there are no aqueous ions in the molten salt • and is reduced at the cathode • is oxidized at the anode
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Sample Problem:
1. A chemist and a chemical engineer melt a
naturally occurring mixture of NaBr and MgCl2 and
decompose it in an electrolytic cell. Predict the
substance formed at each electrode and write the
balanced half-reactions and the overall
electrolytic reaction.
2. A sample of AlBr3 contaminated with KF is melted
and electrolyzed. Determine the electrode
products and the overall cell reaction.
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Sample Problem:
- What reaction occur at each electrode in the
electrolysis of aqueous copper fluoride (CuF2)?
SOLUTION:
- Species: Cu2+, F-, and H2O
1. Identify species that could be oxidized or reduced
- Oxidized? F- and H2O
- Reduced? Cu2+and H2O
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continuation…
3. ELECTROLYSIS OF AQUEOUS SOLUTIONS
- Water may participate in the reduction/oxidation
half-reactions
- Tabulated E° values can be used to identify the
relative strengths of oxidizing and reducing agents
because those values refer to the change from the
aqueous ion to free element:
Mn+(aq) + ne- → M(s) (under std state condition)
continuation…
2. Identify possible anode and cathode reactions
from reduction potential table (follow the link
Electrochemical Series)
Possible cathode reactions:
• Cu2+(aq) + 2e- → Cu(s) E° = 0.34 V
• 2H2O(l) + 2e- → H2(g) + 2OH-(aq) E° = -0.83 V at pH 14
• 2H2O(l) + 2e- → H2(g) + 2OH-(aq) E° = -0.41 V at pH 7
At the cathode, reduction of copper generates
some voltage, while the reduction of water uses
electrical energy. Copper metal is deposited at the
cathode due to the difference in potential.
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continuation…
Faraday’s Law of Electrolysis
Possible anode reactions:
- Michael Faraday (1791-1867); the great English
• 2F-(aq) → F2(s) + 2e- E° = -2.87 V
physicist and chemist
• 2H2O(l) → O2(g) + 4H+(aq) + 4e- E° = -1.23 V at pH 0
- Determines the amount of electrolysis product that
• 2H2O(l) → O2(g) + 4H+(aq) + 4e- E° = -0.82 V at pH 7 will be produced by passage of a given amount of
electrical current
At the anode, oxygen gas is evolved, because less
voltage is required to oxidize water than to oxidize
fluoride ion.

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First Law of Electrolysis Second Law of Electrolysis

- The mass of a substance altered at an electrode during
electrolysis is directly proportional to the quantity of
electricity transferred at that electrode.
- the amount of chemical change produced by current at
an electrode-electrolyte boundary is proportional to
the quantity of electricity used
▪ m = mass of the substance
produced by electrolysis
▪ Q = quantity of electric charge
▪ M = molar mass of the
substance
▪ F = Faraday’s constant
▪ n = electrons transferred per ion
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- when the same quantity of electricity is passed
through several electrolytes, the mass of the
substances deposited are proportional to their
respective chemical equivalence or equivalent
weight.
▪ One equivalence of a chemical reaction is
produced by the passage of one Faraday, F =
96485 C/equiv
▪ An equivalence of a substance is associated with
one mole of electrons
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Sample Problems: Sample Problems:
a. Calculate the mass of Al produced in 30 mins by the a. Calculate the mass of Al produced in 30 mins by the
electrolysis of molten AlCl3 if the electric current is electrolysis of molten AlCl3 if the electric current is
10.0 A. 10.0 A.

b. What mass of copper (in g) is deposited by a current b. What mass of copper (in g) is deposited by a current
of 1.5 A in 1.00 hour in the electrolysis of CuSO4 of 1.5 A in 1.00 hour in the electrolysis of CuSO4
solution? solution?

c. Given a series of electrolytic cells consisting of
chlorides of Al, Mg, Li, iron (II), and copper (I).
Determine the amount of materials that will be
deposited if a mole of electron is passed through this
system.
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c. Given a series of electrolytic cells consisting of
chlorides of Al, Mg, Li, iron (II), and copper (I).
Determine the amount of materials that will be
deposited if a mole of electron is passed through this
system.
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Illustration for part c:

Al3+ Mg2+ Li+ Fe2+ Cu+

MM, g/mol 26.98 24.31 6.94 55.85 63.55
EW, g/eq 8.99 12.155 6.94 27.93 63.55
Mass 8.99 12.155 6.94 27.93 63.55
- Given a series of electrolytic cells. When 1 mole of deposited, g
electrons is passed through the system, different No. of eq, 1 1 1 1 1
quantities of material are generated at each of the
mole e-
cathodes. The quantities of reduced materials are
equal to the equivalent weight of cations being Amount 0.333 0.5 1 0.5 1
reduced. deposited,
mole
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Sample Problems:
d. The platinum crucible used in a silver coulometer
gains 0.500 g in a certain electrolysis. What would
be the gain in weight of copper cathode in a cell
filled with potassium cuprocyanide [KCu(CN)2]
placed in the same circuit?

e. The platinum crucible used in aluminum

coulometer gains 2.35 g in a certain electrolysis.
What would be the gain in weight of iron cathode
in a cell filled with FeCO3 placed in the same
circuit? (MM in g/mol: Al = 26.98, Fe = 55.85)
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