Atkins & de Paula:

Elements of Physical Chemistry

Electrochemistry

Terms, Units, & Symbols

Build Yourself a Table

TERM

UNITS

SYMBOL

Potential

volts

Resistance

ohms

Current

amp

Siemens

-1 (ohm-1)

Resistivity

ohm meter

Conductivity

ohm-1 meter-1

Molar
conductivity

S m2 mol-1

Ionic
conductivity

mol/dm3
mS m2 mol-1

is an uppercase

Foundational concepts
What is the most important
difference between solutions of
electrolytes and solutions of nonelectrolytes?
Long-range (Coulombic)
interactions among ions in
solutions of electrolytes

The Debye-Hckel theory

Activity, a, is roughly effective
molar concentration
aJ = JbJ
treating b as the numerical value of
molality

If a is known, you can calculate

chemical potential:
J = J* + RT ln aJ

The mean activity

coefficient
Mean activity coefficient = (+ )
For MX, = (+ )
For MpXq, = (

q)1/s

s=

p+q

So for Ca3(PO4)2, = (

2)1/5

Debye-Hckel theory
Fig 9.1 (203)
A depiction of the
ionic
atmosphere
surrounding an ion
The energy of the
central ion is
lowered by this
ionic atmosphere

Debye-Hckel theory
Debye-Hckel limiting law:
log = A|z+ z| I

is the mean activity coefficient

I = ionic strength of the solution
I = (z+2 b+ + z2 b )
[b = molality]
A is a constant; A = 0.509 for water
z is the charge numbers of the ions

p.203

The extended Debye-Hckel

law
log

A |z+ z| I
=
1 + B. I

+ C.I

is the mean activity coefficient

I = ionic strength of the solution
I = (z+2 b+ + z2 b )
A is a constant; A = 0.509 for water
B & C = empirically determined
constants
z = the charge numbers of the ions
p.203

Debye-Hckel theory
Fig 9.2 (203)
(a) the limiting law
for a 1,1-electrolyte
(B & C = 1)
(b) the extended
law for B = 0.5
(c) the extended
law extended
further by the
addition of the
CI term
[in the graph, C=0.2]

The migration of ions

Ions move
Their rate of motion indicates:
Size, effect of solvation, the type of
motion

Ion migration can be studied by

measuring the electrical resistance
in a conductivity cell
V = IR

The migration of ions

V = IR
Resistivity () and conductivity ()
And = 1/
Drift velocity, s = uE
Where u (mobility) depends
on a, the radius of the ion and
, the viscosity of the solution

Conductivity cell
Fig 9.3 (204)
The resistance is
typically compared
to that of a solution
of known
conductivity
AC is used to avoid
decomposition
products at the
electrodes

Conductivity
bridge

T9.1 Ionic conductivities, /(mS m2/mol)*

Do you see any trends?

T9.2 Ionic mobilities in water at 298 K, u/

(10-8 m2 s-1 V-1)

Do you see any trends?

The hydrodynamic radius

The equation for drift velocity
(s) and the equation for
mobility (u) together indicate
that the smaller the ion, the
faster it should move

s=
uE

But the Group 1A cations increase in

radius and increase in mobility! The
hydrodynamic radius can explain this
phenomenon.
Small ions are more extensively hydrated.

Proton conduction through

water
Fig 9.4 (207) The Grotthus mechanism
The proton leaving on the right side is not
the same as the proton entering on the left
side

Determining the
Isoelectric Point
Fig 9.5 (207)
Speed of a
macro-molecule
vs pH
Commonly
measured on
peptides and
proteins (why?)
Cf isoelectric
focusing

Types of electrochemical
rxns
Galvanic cella spontaneous
chemical rxn produces an electric
current
Electrolytic cella nonspontaneous
chemical rxn is driven by an
electric current (DC)

Anatomy of electrochemical
cells

Fig 9.6 (209)

Fig 9.7 (209) The salt

bridge overcomes
difficulties that the liquid
junction introduces into
interpreting measurements

Half-reactions
For the purpose of understanding and
study, we separate redox rxns into two
half rxns: the oxidation rxn (anode)
and the reduction rxn (cathode)
Oxidation, lose e, increase in oxid #
Reduction, gain e, decrease in oxid #
Half rxns are conceptual; the e is
never really free

Fig 9.8 (213)

Direction of e fow in electrochemical
cells

Reactions at electrodes
Fig 9.9 (213)
An electrolytic cell
Terms:
Electrode
Anode
Cathode

A gas electrode
Fig 9.10 (213)
Standard
Hydrogen
Electrode
Is this a good
illustration of
the SHE?
Want to see a
better one?

Standard Hydrogen Electrode

Reduction Reaction
2e- + 2H+ (1 M)

2H2 (1 atm)

E0 = 0 V

Standard hydrogen electrode (SHE)

19.3

Standard Hydrogen Electrode

Oxidation Reaction
H2 (1 atm)

2H+ (1 M) + 2eE0 = 0 V

Standard hydrogen electrode (SHE)

19.3

Standard Hydrogen Electrode

H2 gas, 1 atm

Pt electrode

SHE acts as cathode

SHE acts as anode

Metal-insoluble-salt
electrode
Fig 9.11 (214)
Silver-silver
chloride electrode
Metallic Ag coated
with AgCl in a
solution of Cl
Q depends on aCl
ion

Variety of cells
Electrolyte concentration cell
Electrode concentration cell
Liquid junction potential

Redox electrode
Fig 9.12 (215)
The same element in two nonzero oxidation states

The Daniell cell

Fig 9.13 (215)

Zn is the anode
Cu is the
cathode

The cell reaction

Anode on the left; cathode on the
right
Cell Diagram

Zn (s) + Cu2+ (aq)

Cu (s) + Zn2+ (aq)

[Cu2+] = 1 M & [Zn2+] = 1 M

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode
cathode

Measuring cell emf

Fig 9.13 (217) Cell
emf is measured
by balancing the
cell against an
opposing external
potential. When
there is no current
fow, the opposing
external potential
equals the cell emf.

The electromotive force

The maximum non-expansion work
(wmax) equals G [T,p=K] (9.12)
Measure the potential difference (V)
and convert it to work to calculate G
rG = nFE
(F = 96.485 kC/mol)
E=

rG
nF

The electromotive force

rG = nFE
rG = rGo + RT ln Q
RT
E=E
nF
o

rG
Eo =
nF
At 25C, RT
F
o

ln Q

= 25.693 mV

E is independent of how the

rxn is balanced

Cells at equilibrium
At equilibrium, Q = K and a rxn at
equilibrium can do no work, so E = 0
So when Q = K and E = 0, the Nernst
equation
RT
E = E nF ln Q , becomes.

ln K =

nFE
RT

Cells at equilibrium
ln K =

nFE
RT

Is simply an electrochemical expression of

rG = RT ln K

Cells at equilibrium
If E > 0, then K > 1 and at
equilibrium the cell rxn favors
products
If E < 0, then K < 1 and at
equilibrium the cell rxn favors
reactants

Standard potentials
SHE is arbitrarily assigned E = 0 at
all temperatures, and the standard
emf of a cell formed from any pair of
electrodes is their difference:
E = Ecathode Eanode OR
E = Eright Eleft
Ex 9.6: Measure E, then calculate K

The variation of potential

with pH
If a redox couple involves
H3O+,
then the potential varies
with pH

Table 9.3 Standard reduction potentials at 25C (1)

Table 9.3 Standard reduction potentials at 25C (2)

The determination of pH
The potential of the SHE is
proportional to the pH of the solution
In practice, the SHE is replaced by a
glass electrode (Why?)
The potential of the glass electrode
depends on the pH (linearly)

A glass electrode
Fig 9.15 (222)
The potential of a
glass electrode varies
with [H+]
This gives us a way to
measue pKa
electrically, since pH
= pKa when [acid] =
[conjugate base]

The electrochemical series

A couple with a low standard
potential has a thermodynamic
tendency to reduce a couple
with a higher standard potential
A couple with a high standard
potential has a thermodynamic
tendency to oxidize a couple
with a lower standard potential

E0 is for the reaction as written

The more positive E0 the

greater the tendency for the
substance to be reduced

The more negative E0 the

greater the tendency for the
substance to be oxidized

Under standard-state conditions, any species on the left of

a given half-reaction will react
spontaneously with a species
that appears on the right of any
half-reaction located below it in
the table (the diagonal rule)

The half-cell reactions are

reversible

The sign of E0 changes

when the reaction is
reversed

Changing the stoichiometric coefficients of a

half-cell reaction does not
change the value of E0

The SHE acts as a cathode with metals below it,

and as an anode with
metals above it

The determination of thermodynamic

functions
By measuring std emf of a cell, we
can calculate Gibbs energy
We can use thermodynamic data
to calculate other properties (e.g.,
rS) nF(E E)
rS =

TT

Determining thermodynamic
functions
Fig 9.16
(223)
Variation of
emf with
temperature
depends on
the standard
entropy of
the cell rxn

Key
Ideas

Key
Ideas

Key
Ideas

Consider the cell Zn ZnCl2(0.02 m) AgCl(s) Ag(s) , the cell

potential is 1.140 v
a. Write the cell reaction.
b. Determine the standard potential.

The End
of this chapter