Fundamentals of Electrochemistry - W.H. Freeman

1504T_ch14_270-297 01/30/06 17:08 Page 271
agent, also called an oxidant, takes electrons from another substance and becomes reduced.
A reducing agent, also called a reductant, gives electrons to another substance and is oxidized
in the process. In the reaction
Fe 3 V 2 S Fe 2 V 3
Oxidizing Reducing
agent agent
(14-1)
Fe 3 is the oxidizing agent because it takes an electron from V 2 . V 2 is the reducing agent
because it gives an electron to Fe 3 . Fe 3 is reduced, and V 2 is oxidized as the reaction proceeds
from left to right. Appendix D reviews oxidation numbers and balancing of redox
equations.
Oxidation: loss of electrons
Reduction: gain of electrons
Oxidizing agent: takes electrons
Reducing agent: gives electrons
Fe 3 e S Fe 2
V 2 S V 3 e
Chemistry and Electricity
When electrons from a redox reaction flow through an electric circuit, we can learn something
about the reaction by measuring current and voltage. Electric current is proportional to
the rate of reaction, and the cell voltage is proportional to the free-energy change for the electrochemical
reaction. In techniques such as voltammetry, the voltage can be used to identify
reactants.
Electric Charge
Electric charge, q, is measured in coulombs (C). The magnitude of the charge of a single electron
is 1.602 10 19 C, so a mole of electrons has a charge of (1.602 10 19 C)(6.022
10 23 mol 1 ) 9.649 10 4 C, which is called the Faraday constant, F.
coulombs
Faraday constant (F )
mole of electrons
Relation between
charge and moles:
q n F
Coulombs
mol e
Coulombs
mol e
where n is the number of moles of electrons transferred.
(14-2)
Example Relating Coulombs to Quantity of Reaction
Fe 3
If 5.585 g of were reduced in Reaction 14-1, how many coulombs of charge must
have been transferred from V 2 to Fe 3 ?
Solution First, we find that 5.585 g of Fe 3 equal 0.100 0 mol of Fe 3 . Because each
Fe 3 ion requires one electron in Reaction 14-1, 0.100 0 mol of electrons must have been
transferred. Using the Faraday constant, we find that 0.100 0 mol of electrons corresponds to
C
q nF (0.100 0 mol e ) a9.649 10 4 mol e b 9.649 103 C
Electric Current
The quantity of charge flowing each second through a circuit is called the current. The unit
of current is the ampere, abbreviated A. A current of 1 ampere represents a charge of
1 coulomb per second flowing past a point in a circuit.
Example Relating Current to Rate of Reaction
Suppose that electrons are forced into a platinum wire immersed in a solution containing
Sn 4 (Figure 14-1), which is reduced to Sn 2 at a constant rate of 4.24 mmol/h. How
much current passes through the solution?
Solution Two electrons are required to reduce one ion:
If Sn 4 reacts at a rate of 4.24 mmol/h, electrons flow at a rate of 2(4.24 mmol/h)
8.48 mmol/h, which corresponds to
8.48 mmol e /h
3 600 s/h
Sn 4
Sn 4 2e S Sn 2
mmol e
mol e
2.356 103 2.356 106 s
s
Sn 4+
Sn 2+
Figure 14-1 Electrons flowing into a coil
of Pt wire at which Sn 4 ions in solution are
reduced to Sn 2 . This process could not
happen by itself, because there is no
complete circuit. If Sn 4 is to be reduced at
this Pt electrode, some other species must be
oxidized at some other place.
e –
14-1 Basic Concepts 271