Electrochemistry

Fundamental Concepts
Oxidation occurs when a chemical species looses an electron. Reduction is
when a species gains an electron. For example, the chemical reaction
can be broken up into two half reactions
The iron is oxidized while the cerium is reduced.
An oxidant species promotes oxidation and a reductant promotes reduction. The
above reaction, cerium is the oxidant or oxidation agent while iron is the
reductant or reducing agent.
Electrical charge, q, is measured in coulombs (C. The charge associated with
chemical species is related to the number o! moles through the Farada" constant,
F#$%,&'(.) (*$%,(++ C,mole.
Electrical current, I, is measured in Amperes (A. Current is the amount o!
charge that passes in a unit time interval (seconds.
Ohm's law relates current to potential (E through the resistance (R o! a circuit.
E = IR
The potential is measured in -olts (- and the resistance in .hms (.
Power (P is measured in /atts (/ # 0,s and is related to the current and
potential b"
P = IE
The work is measured in 0oules (0 and is related to the potential and the amount
o! charge
work = qE
The relationship between the 1ibb2s !ree energ" change, G (0,mole, and the
electro3motive !orce (E4F, E (-, is given b"
G # 3nFE
where F (Coul,mole is Farada"2s constant ( $%,(++ and n is the number o!
electrons trans!erred in the reaction.
The relationship between the 1ibb2s !ree energ" change, G, and the
e5uilibrium constant, K, is given b" is given b"
G # 3RTlnK
where k is 6oltzmann2s constant ('.)7) 0,mole 8 and T (8 is the temperature.
The Nernst Equation gives the cell potentials, E (-,
where is the ratio o! products over reactants t"pical o! e5uilibrium
calculations. For example, the generic reaction
has a
where the ! are activities. For low concentration solutions
Electrochemical Calculations
T"pical E#amples
7 Calculations o! e5uilibrium constants !rom tables o! reduction potentials.
/hat is the K !or ceric oxidation o! !errous iron9
The !ull reaction,
is comprised o! the two hal! reactions
The E are !ound !rom the table o! reduction potentials in the back o! the book.
:otice that when the reaction is reversed, as !or Fe
;$
oxidation, the sign o! E is
changed. The sum o! the two hal! reactions "ields the total reaction and the
reaction potential is the sum o! the two hal! reaction potentials
E # 7.%) - 3 +.<< - # =+.'% -
>sing the !ormulas,
G
o
# 3nFE

G # 3(7($%,(++ Coul,mole(+.'% -
G # 3') k0,mole
G # 3RT ln K
3') k0,mole # 3('.)7& 0,mole 8(;$' 8 ln K
K = 3.5 10
1
Electrochemical Calculations
Calculations o% electrode potentials %or electrodes usin& insolu'le salts(
?@ /hat is the electrode potential !or the electrode !&,!&I(s,I
3
(+.+7 4 9
A@ The overall reaction !or this electrode is
This reaction cannot be !ound in most tables o! reduction potentials. 6ut the
reaction is comprised o! two components,
/e can !ind the E !or the solubilit" product e5uilibrium !rom G #3kTlnK
sp
and
G #3nFE
+.+($log is valid at room temperature. An this case
E # .+($ log K
sp
# .+($ log 7+
37%
# (.+($(37% # 3+.$ -
The electrode potential is E #E
red
=E
Ksp
# +.'-3+.$- # 3+.7-
:ow we use the :ernst E5uation to !ind the electrode potential
E # E 3 .+($ log BI
3
C
E # 3+.7- 3 .+($ log 7+
3;
E = !0.1" ! .05#$!%& .0% "
Electrochemical Calculations
T"pical E#amples
; Another wa" to look at the electrode potential !or !&)!&I*s+)I
,
(+.+7 4
The overall reaction !or this electrode is
The reaction is comprised o! two components,
:ote the change o! sign on the E because it is an oxidation. /e can initiall"
ignore the !act that the electrode contains !&I and !ind E !or the silver ion
reduction.
The electrode potential is based on the concentration o! !&
$
in solution. Dince
and
An this case
An either calculation, the important point to recognize is that the electrode
contains an insoluble salt.