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Cell Emf Under Nonstandard Conditions Lecture 3

This document discusses cell EMF under nonstandard conditions and electrolysis. It covers: 1) The relationship between Gibbs free energy (ΔG) and cell EMF (Ecell), and how both depend on reaction identity, concentrations, and temperature. 2) The Nernst equation, which relates Ecell to standard EMF and reaction quotient (Q) under nonstandard conditions. 3) How electrolytic cells are nonspontaneous and require an external power source, with examples of electrolytic refining and electroplating of metals. 4) Quantitative aspects of electrolysis including electrical current, charge, stoichiometry, electrical work, and illustrative problems calculating unknowns.

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Lyra Gurimbao
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146 views

Cell Emf Under Nonstandard Conditions Lecture 3

This document discusses cell EMF under nonstandard conditions and electrolysis. It covers: 1) The relationship between Gibbs free energy (ΔG) and cell EMF (Ecell), and how both depend on reaction identity, concentrations, and temperature. 2) The Nernst equation, which relates Ecell to standard EMF and reaction quotient (Q) under nonstandard conditions. 3) How electrolytic cells are nonspontaneous and require an external power source, with examples of electrolytic refining and electroplating of metals. 4) Quantitative aspects of electrolysis including electrical current, charge, stoichiometry, electrical work, and illustrative problems calculating unknowns.

Uploaded by

Lyra Gurimbao
Copyright
© © All Rights Reserved
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Download as DOCX, PDF, TXT or read online on Scribd
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CELL EMF UNDER NONSTANDARD CONDITIONS

ELECTROLYSIS
Lecture 3
__________________________________________________________________________________________

Cell EMF under Nonstandard Conditions, Nernst Equation:

The relationship between G and Ecell


Like G, Ecell is a measure of how far the reaction is from equilibrium. It is the “driving force”.

Like G, Ecell depends on:


The identity of the reaction
The initial concentration of reactants and products (Q)
Temperature

There is a simple mathematical relationship between G and Ecell:


G = -nFEcell

n = number of electrons transferred in the balanced equation (unitless)


F = Faraday’s constant = charge on a mole of electrons = 96,500 C/mol e-
What is the unit on G? (remember: 1V = 1 J/C)

For a spontaneous redox reaction: G < 0, Ecell > 0


At equilibrium: G = 0, and Ecell = 0 (For a cell, equilibrium is death!)

EMF of a non-standard cell (Nernst equation)

G = Go + RTln Q

-nFEcell = -nFEocell + RTln Q

Ecell = Eocell – (RT/nF)ln Q (Nernst equation)

By convention, the Nernst equation is written in terms of log Q rather than ln Q:

ln Q = (ln 10)(log Q) = 2.303log Q, so Ecell = Eocell – (2.303RT/nF)log Q

Assuming T = 298 K and combining constants:

2.303RT/F = [(2.303)(8.314 J/mol-K)(298 K)] / 96,500 C/mol = 0.0592 J/C = 0.0592 V

Ecell = Eocell – (0.0592/n)log Q (Nernst equation at T = 298 K)

Illustrative Problems:

1. A voltaic cell is constructed that uses the following reaction and operates at 298 K:
Zn(s) + Ni2+ (aq)  Zn2+ (aq) + Ni(s)
(a) What is the emf of this cell under standard condition?
(b) What is the emf of this cell when [Ni2+] = 3.00 M and [Zn2+] = 0.100 M?
(c) What is the emf of this cell when [Ni2+] = 0.20 M and [Zn2+] = 0.900 M?
2. A voltaic cell utilizes the following reaction:
4Fe2+ (aq) + O2 (g) + 4H+ (aq)  4Fe3+ (aq) + 2H2O(l)

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(a) What is the emf of this cell under standard conditions?
(b) What is the emf of this cell when [Fe2+] = 1.3, [Fe3+] = 0.010 M, 𝑃𝑂2 = 0.50 𝑎𝑡𝑚, and the pH of the solution in
the cathode compartment is 3.50?

Electrolysis or Electrolytic Cells, Nonspontaneous:


Electrolytic Cells are nonspontaneous and need power to react. Ecell is a negative value. Aluminum was once a very
expensive metal to refine since it was originally isolated by electrolysis methods. No salt bridge is necessary since the
reaction will not spontaneously occur. You must separate the products to avoid them spontaneously returning to the
reactants. Anode (+) and cathode (−)

Applications of Electrolysis:
Electrolytic Refining is the most practical, but expensive method to isolate active metals like Na. Chemical reactions can
separate many less active metals from their ores. Usually further refining is still needed for purification. Example: the
anode contains impure copper and the cathode is purified Cu. As power is forced through the system the pure Cu
thickens and grows and the impure Cu thins and drops off a sludge of impurities to the bottom of the vessel.

Electroplating of Metals uses the same method as the refining by electroplating a thin layer of a metal such as Ag or Au
on jewelry.

Quantitative Aspects of Electrolysis:

Electrical current

The amount of charge passing through a circuit (current) is measured in amperes (A): 1 A = 1 C/s

The total charge that passes through an electrolytic cell is given by: charge = (current) x (time)

Volt = Joule/Coulomb
Current is the number of electrons that flow through the system per second, Ampere
Coulomb = Amp . sec (C = A. s) and Faraday's constant = 96500 C/mole e-

Stoichiometry of electrolysis

A balanced reduction half-reaction tells you how many moles of electrons must be pumped into the cathode (or out of
the anode) of an electrolytic cell to produce a mole of product. For example:

Al3+(aq) + 3 e- → Al (s) says that it takes 3 moles of electrons to produce a mole of aluminum.

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Electrical work

Electrical power (rate of energy expenditure) is measured in watts (W): Power = current x potential

1 W = (1 C/s)(1 J/C) = (1 A)(1 V) = 1 J/s

Electrical work = w = (power) x (time).


It is commonly expressed in units of kilowatt-hours (kWh): 1 kWh = 1000 w-h = (1000 J/s)(3600 s) = 3.6 x 106 J

Illustrative Problems:

1. An unknown aqueous iron salt is electrolyzed by a current of 2.75 A for 45 minutes producing 1.43 g of solid Fe.
Solve for the oxidation number for Fe in the salt?

2. Solve for the grams of Cr (s) that will be deposited from CrO4 -2 (aq) using 6.00 amps current for 3 1 /2 hours.
Assume the theoretical yield of Cr (s) is obtained.

3. How many kWh are required to produce 5.00 kg of Mg from the electrolysis of molten MgCl2 if the applied cell
potential is 5.00 V. Assume 100% efficiency.

4. During the electrolysis of molten MgCl2:


a. Calculate the minimum time required to produce 30.0 g of magnesium if the current is 60.0 A.
b. Calculate the minimum number of kilowatt-hours of electricity required to produce 1.00 kg of
magnesium if the applied emf is 5.00 V.

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