CHM520

Solutions of Electrolyte

General Properties of
Aqueous Solutions
Solution - a homogeneous mixture
Solute: the component that is dissolved
Solvent: the component that does the
dissolving
Generally, the component present in the
greatest quantity is considered to be the
solvent. Aqueous solutions are those in
which water is the solvent.
2

 Electrolytes and Nonelectrolytes

Electrolyte: substance that dissolved
in water produces a solution that
Free
conducts electricity
moving
ion
Contains ions

Nonelectrolyte: substance that

dissolved in water produces a solution
that does not conduct electricity
Does not contain ions

 Dissociation - ionic compounds

separate into constituent ions
when dissolved in solution

Ionization - formation of ions by

molecular compounds when
dissolved

 Strong and weak electrolytes

Strong Electrolyte: 100%
dissociation
All water soluble ionic compounds,
strong acids and strong bases
Weak electrolytes
Partially ionized in solution
Exist mostly as the molecular form
in solution
Weak acids and weak bases

 Examples of weak electrolytes

Weak acids
HC2H3O2(aq)
Weak bases
NH3 (aq) + H2O(l)

C2H3O2

(aq)

+ H+

NH4+

(aq)

+ OH

(aq)

(aq)

(Note: double arrows indicate a

reaction that occurs in both directions a state of dynamic equilibrium exists)
7

Method to Distinguish Types of Electrolytes

nonelectrolyte

weak electrolyte

strong electrolyte
8

Classify the following as

nonelectrolyte,
weak electrolyte or strong
electrolyte
H2SO4
strong electrolyte
CH3OH
nonelectrolyte
H2CO3
weak electrolyte
9

Precipitation Reactions
Precipitation (formation of a solid from
two aqueous solutions) occurs when
product is insoluble
Produce insoluble ionic compounds
Double replacement (or metathesis
reaction)
Solubility is the maximum amount of a
solid that can dissolve in a given amount
of solvent at a specified temperature
Prediction based on solubility rules

 Hydration: process by which

water molecules remove and
surround individual ions from the
solid.

Identify the Precipitate

(?)
3

Pb(NO3)2(aq) + 2NaI(aq) 2NaNO

(aq)
PbI2

(?)
(s)

Mixing Solutions of Pb(NO3)2 and NaCl

14

Classify the following as soluble or

insoluble in water
Ba(NO3)2
soluble
AgI
insoluble
Mg(OH)2
insoluble

types of electrochemical
cell

Galvanic cell or voltaic cell,

Electrolytic cell
Galvanic cell Chemical rxn Generate electrical
current
Electrolytic cell Use electric current Causes
chemical rxn

An electrolytic cell is a cell, which an electric current is

applied to drive a non-spontaneous reaction.

In electrolytic cell:
electrical energy is converted into chemical
energy.
Anode is positive electrode and cathode is
negative electrode
Electron flow from anode to cathode.
During conduction of electricity through
electrolytes, oxidation occurs at anode whereas
reduction occurs at cathode

AAL

CCG

2 steps are involved in electrolysis:

a) Ion movement towards electrodes (cations move toward
cathode & anions travel toward anode)
b) Ion discharged at electrodes / metal deposited

Reactions at the electrodes:

a) Products of electrolysis of
When the salts
battery (Example:
is connected, electrons
are
molten
PbBr
)
2
moved from anode to cathode.
Pb2+ions migrate to cathode to undergo
reduction. Metallic lead (Pb) is produced.
Cathode: Pb2++ 2e- Pb

Br-ions migrate to anode to undergo oxidation.

Bromide molecules (Br2) are produced.
Anode: 2Br- Br2+ 2e- Due to the high temperature, Br2escapes as
gas.

Half cell equation

Anode:

2Br-(aq) Br2(g)+ 2e-

Cathode:
Pb2+(aq) + 2e- Pb(s)
Overall reaction:
Pb2+(aq) + 2Br-(aq) Pb(s) +
Br2(g)

Galvanic & Electrolytic Cells - A Comparison

In galvanic cells the reactions are separated so electrons can

be used as they are transferred.
Electrolytic cells have two electrodes and an electrolyte.
Electrolytic cells differ from galvanic cells in that the
anode is the positive electrode while the cathode is the
negative electrode.
The polarities of the anode and cathode change because in
galvanic cells the polarity is imposed by the reactions
themselves.
At the anode, electrons are produced and at the cathode
electrons are consumed.
In electrolytic cells the polarity is imposed by the power
source.
This pulls electrons from the anode and forces electrons onto
the cathode.

Electrolytic Cells

Regardless of which cell, electron

flow is always the same from
anode to cathode!
Oxidation always occurs at the
anode and reduction always occurs
at the cathode!

Electrolytic Cells

Predicting Electrolytic Reactions

When electrons are forced into the cell, the oxidants

present at the surface of the electrode compete with
one another to accept them.
The strongest of the oxidants present preferentially
accepts the electrons and is discharged, i.e. the
oxidant highest on the electrochemical series accepts
the electrons.
Similarly, at the anode where the electrons are being
withdrawn, the reductants present at the anode
surface compete to donate electrons.
The strongest of the reductants is preferentially
discharged.

Predicting Electrolytic Reactions

Note that if two competitors have very similar E

values, they will probably both be discharged
simultaneously.
In aqueous solutions, the water may be involved in
either the oxidation or the reduction reaction or both.

Predicting Electrolytic Reactions - Questions

Predict the products at each electrode during

electrolysis for the following 1 M solutions (unreactive
electrodes used) . The nitrate ion is not involved in
any of the reactions.
a. Copper(II) bromide
b. Sodium iodide
c. Lead nitrate
d. Zinc chloride
e. Aluminium nitrate

Predicting Electrolytic Reactions - Solutions

a. 1 M copper(II) bromide
Species present at the electrodes are Cu2+ (aq), Br- (aq) and
H2O (l)
Possible reductions:
Cu2+ (aq) + 2e- Cu (s)
+0.34 V
2H2O (l) + 2e- H2 (g) + 2OH- (aq)
-0.83 V
Here the strongest oxidant (most positive Eo value) is Cu2+.
Thus, at the cathode Cu forms.
Possible oxidations:
Br2 (g) + 2e- 2Br- (aq)
+1.09 V
O2 (g) + 4H+ (aq) + 4e- 2H2O (aq)

+1.23 V

Here the strongest reductant (least positive Eo value) is 2Br-.

Thus at the anode Br2 forms.
Overall equation: Cu2+ (a) + 2Br- (aq) Cu (s) + Br2
(g)

Predicting Electrolytic Reactions - Solutions

b. 1 M sodium iodide
Species present at the electrodes are Na+ (aq), I- (aq) and H2O
(l)
Possible reductions:
Na+ (aq) + e- Na (s)
-2.71 V
2H2O (l) + 2e- H2 (g) + 2OH- (aq)
-0.83 V
The strongest oxidant (most positive Eo value) is H2O.
Thus at the cathode H2 and 2OH- form.
Possible oxidations:
I2 (g) + 2e- 2I- (aq)

+0.54 V

O2 (g) + 4H+ (aq) + 4e- 2H2O (aq)

+1.23 V

The strongest reductant (least positive Eo value) is 2I-.

Thus at the anode I2 forms.
Overall equation: 2H2O (l) + 2I- (aq) H2 (g) + 2OH(aq) + I2 (g)

Predicting Electrolytic Reactions - Solutions

c. 1 M lead(II) nitrate
Species present at the electrodes are Pb 2+ (aq) and H2O (l)
Possible reductions:
Pb2+ (aq) + 2e- Pb (s)

+0.13 V

2H2O (l) + 2e- H2 (g) + 2OH- (aq)

-0.83 V

The strongest oxidant (most positive E o value) is Pb2+.

Thus, at the cathode Pb forms.
Possible oxidations:
O2 (g) + 4H+ (aq) + 4e- 2H2O (aq)

+1.23 V

The strongest reductant (least positive E o value) is 2H2O.

Thus at the anode O2 and 4H+ form.
Overall equation: 2Pb2+ (aq) + 2H2O (l) 2Pb (s) + O2
(g) + 4H+ (aq)

Predicting Electrolytic Reactions - Solutions

d. 1 M zinc chloride
Species present at the electrodes are Zn2+ (aq), Cl- (aq) and
H2O (l)
Possible reductions:
Zn2+ (aq) + 2e- Zn (s)
-0.76 V
2H2O (l) + 2e- H2 (g) + 2OH- (aq)
-0.83 V
The strongest oxidant (most positive Eo value) is Zn2+.
Thus, at the cathode Zn forms.
Possible oxidations:
Cl2 (g) + 2e- 2Cl- (aq)
+1.36 V
O2 (g) + 4H+ (aq) + 4e- H2O (l)

+1.23 V

The strongest reductant (least positive Eo value) is 2H2O.

Thus at the anode O2 and 4H+ form.
Overall equation: 2Zn2+ (aq) + 2H2O (aq) 2Zn (s) + O2
(g) + 4H+ (aq)

Predicting Electrolytic Reactions - Solutions

e. 1 M aluminium nitrate
Species present at the electrodes are Al3+ (aq) and H2O (l)
Possible reductions:
Al3+ (aq) + 3e- Al (s)

-1.71 V

2H2O (l) + 2e- H2 (g) + 2OH- (aq)

-0.83 V

The strongest oxidant (most positive Eo value) is 2H2O.

Thus at the cathode H2 and 2OH- form.
Possible oxidations:
O2 (g) + 4H+ (aq) + 4e- 2H2O (aq)

+1.23 V

The strongest reductant (least positive Eo value) is 2H2O.

Thus at the anode O2 and 4H+ form.
Overall equation: 6H2O (l) 2H2 (g) + 4OH- (aq) + O2
(g) + 4H+ (aq)

Electrolysis has a variety of industrial applications.

These include electroplating and electrorefining
as well as the recharging secondary cells.
Non-spontaneous reactions are forced to occur in
electrolytic cells by passing an electric current from
an external power source through an electrolyte.
The potential energy of the system is increased as
electrical energy is forced into the cell.

Applied Electrolysis - Electroplating

In this application, the cathode is coated with a thin layer

of metal from a solution containing ions of the metal.
This is done to improve the appearance or to prevent
corrosion by the application of a protective layer.
The object to be plated is attached to the negative
terminal of a power supply and becomes the cathode.
It is then placed in an electrolyte solution containing ions
of the metal that forms the plating.
The anode is made from the metal that is to form the
plating.
To ensure the coating on the surface is strongly bonded
and smooth, the electrolyte is a complex mixture of ions
and the conditions (voltage, current, time) carefully
controlled.

Applied Electrolysis - Electroplating

http://youtu.be/BZGDxL9pBC4

Applied Electrolysis - Electrorefining

Metals can be purified by electrolysis.

The impure metal is used as the anode and oxidised.
Metals that are stronger reductants will also be discharged
at the electrode surface.
Any constituents of the anode that are weaker reductants
are not oxidised but fall as uncharged metal atoms to the
bottom of the cell.
This leaves an electrolyte solution containing ions of the
metal to be refined and a small amount of other ions.
The mixture of metal ions in solution compete for electrons
at the cathode surface.
As the dissolved impure ions are weaker oxidants, the
metal to be refined is preferentially reduced at the
cathode, and is in a much purer form.

Applied Electrolysis - Electrorefining

Applied Electrolysis
Sodium from Molten Sodium Chloride The Downs Cell

Applied Electrolysis

Sodium from Molten Sodium Chloride The Downs Cell

Products

Sodium metal and chlorine gas must be

kept separate otherwise they will
spontaneously react

Anode reaction
Cathode reaction
Overall reaction

2Cl- (l) Cl2 (g) + 2eNa+ (l) + e- Na (l)

2Na (l) + 2Cl- (l) 2Na (l) + Cl2 (g)

Anode (+)
Cathode (-)

Carbon in centre of cell

Cylindrical iron near edge of the cell

Conditions

Molten NaCl and CaCl2 electrolyte added to the

melt to lower the melting point from 801oC to
below 600oC
7 Volts, 30 000 Amps, electric current melts
electrolyte

Applied Electrolysis

Aluminium from Molten Alumina

The Hall-Hroult Process

Applied Electrolysis

Aluminium from Molten Alumina

The Hall-Hroult Process
Products

Aluminium metal and carbon dioxide gas must be

kept separated otherwise they will spontaneously
react

Anode reaction
Cathode reaction
Overall reaction

C (s) + 2O2- (l) CO2 (g) + 4eAl3+ (l) + 3e- Al (l)

2Al2O3 (l) + 3C (s) 4Al (l) + 3CO2 (g)

Anode (+)
Cathode (-)

Graphite, lowered into top of cell and consumed during

reaction
Graphite lining and aluminium metal at the bottom of the
cell

Conditions

Al2O3 dissolved in cryolite, Na3AlF6, which lowers the melt

point of alumina from 2045oC to ~1000oC
5 Volts, 150 000 Amps, electric current melts electrolyte

Applied Electrolysis

Sodium Hydroxide and Chlorine from Brine

The Membrane Cell

Applied Electrolysis

Sodium Hydroxide and Chlorine from Brine

The Membrane Cell
Products

Sodium hydroxide, chlorine gas and hydrogen

gas must be kept separated otherwise they will
spontaneously react

Anode reaction
Cathode reaction
Overall reaction

2Cl- (l) Cl2 (g) + 2e2H2O (l) + 2e- H2 (g) + 2OH- (aq)
2H2O (l) + 2Cl- (l) H2 (g) + 2OH- (aq) + Cl2 (g)

Anode (+)
Cathode (-)

Graphite
Steel mesh

Conditions

Cells separated by plastic semipermeable membrane

that prevents mixing of products and allows Na+ ions
to migrate but neither Cl- or OH- ions. Ensures a purer
NaOH solution.
3.5 5 Volts, up to 80 000 Amps, electric current
heats electrolyte

Faradays Laws of Electrolysis ( Electrolytic deposition)

If you wished to electroplate an object, you might ask

yourself the following questions:
How can I determine how much metal is being
plated?
How long should I leave the object being plated in the
electroplating cell?
What size electric current should be used?

Faradays Laws of Electrolysis

Michael Faraday was a 19th century English chemist.

Faraday studied the quantitative relationships between
amount of current and amount of material released from
solution (mass of product formed at the electrode).
His results (Faradays laws of electrolysis) are stated in
two laws of electrolysis:
These laws enable us to:
Work out the amount of energy required to discharge a
metal ion and place it out on an object or
To calculate the amount of metal produced in an
electrolytic cell.

Faradays Laws of Electrolysis First Law

The mass of metal produced at the cathode is directly

proportional to the quantity of electricity passed through
the cell
mQ
Electric charge, Q, = coulomb (C)
The electric charge passing through a cell may be
calculated from measurements of the current, I, through
the cell and the time, t, for which the current flows.
Charge (coulombs) = current (amps) x time
(seconds)
Q = I t OR
Charge (C)= current(A) x time (s)

Faradays Laws of Electrolysis Second Law

The mass of an element liberated at an electrode is

proportional to the equivalent weight of the
element

Faraday found that there was a certain charge

associated with one mole of electrons.
This amount of charge is now called the Faraday
and is equivalent to 96 487 (96 500) Coulomb.
1 Faraday = 96 500 Coulomb

 Example: 96 485 C will liberate 1 mol of Ag

Faraday constant is the magnitude of electric charge per
mole of electrons
If a constant current I is passed for a period of time t, the
amount of substance deposited is It / (96 485 C mol-1)
m = It/F
Since the charge on one mole of electrons is 96,485
Coulombs, the number of moles of electrons passess
through the cell is
Mole electrons = charge x 1 mol electron
96485 C
The charge on 1 electron is = 96485 C mol-1
6.022 x 1023 mol-1

= 1.602 x10-19

Faradays work: suggest a relationship between matter and electricity

Faradays Laws of Electrolysis Second Law

In order to produce one mole of metal, one two or

three moles of electrons must be consumed.
Ag+ (aq), Cu2+ (aq) and Cr3+ (aq) require 1, 2 and 3
moles of electrons for discharge.
The quantity of electricity required will be:
Amount of charge = no. of moles of metal
ions x charge
on an ion x 1 Faraday
Q = nzF

and

It = nzF

Q = It

Suppose a current of 0.452 A is passed through the cell

for 1.5 hr. How much product will be formed at the
anode and
at the cathode?
-

Anode (oxidation)

: 2Cl (l)

Cl2 (g) + 2e

Cathode (reduction) : Ca2+ (l) + 2e-

Ca (s)
Overall
: Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)

Mass (g) Cl2?

Charge (C) = Current (A) x time (s)
Charge = 0.452 A x 1.50 hr x 3600 s x 1C = 2.44 x 103 C
1 hr
1As
1 mol e = 96,485 C

 Mole electrons = charge x 1 mole electron

96485 C
Mole electrons = 2.44 x 103 C x 1 mole electron
96485 C
= 0.025 mol of e
Mol of Cl2 = 0.025 mol of e x 1 mol Cl2= 0.0125 mol of Cl2
2 mol e
Mass of Cl2 = 0.0125 mol of Cl2 x 70.90 g/mol
= 0.886 g
_______________________________________________
Mass (g) of Ca?
Ans; 0.501 g

A dilute solution of HNO3 is electrolyzed by passing 2.30 A of current

for 5.6 hr. Write the half-reactions at anode and cathode. Calculate
the volume of gases generated at standard temperature and
pressure, STP.

Volume of O2 gas?
Charge (C) = Current (A) x time (s)
Charge = 2.3 A x 5.6 hr x 3600 s x 1C = 4.637 x 104 C
1 hr
1As
1 mol e = 96,485 C
Mole electrons = charge x 1 mole electron
96485 C
Mole electrons = 4.637 x 104 C x 1 mole electron
96485 C
= 0.48 mol of e

Volume of H2 gas?
Ans: 5.38 L

Mol of O2 =0.48 mol of e x 1 mol O2= 0.12 mol of O2

4 mol e

At STP: 1 mol of O2 gas = 22.4 L

0.02 mol of O2 gas = ? L

Volume of O2 gas = 0.12 mol of O2 x 22.4 L

1 mol O2
= 2.69 L.

Calculate the number of mole of copper produced

in an electrolytic cell if a current of 5.0 A at a
voltage of 6.0 V flows through a solution of copper
ions for 10 minutes.

Cu

2+

(aq)

+ 2 e Cu (s)

n (Cu) = I t / z F
n (Cu) = 5.0 x 10 x 60 / 2 x 96 500
n (Cu) = 1.6 x 10-2 mol
That is, 1.6 x 10-2 mole of copper
would be produced

Calculate the time taken to deposit 1.00 g of

copper onto an object that is placed in a solution of
copper nitrate, Cu(NO3)2, and has a current of 2.50
A flowing through it.

t=nzF/I
t = (1.00 / 63.5) x 2 x 96 500 / 2.5
t = 1216 seconds
That is, it takes 20 minutes 15
seconds to deposit 1.00 g of copper

Faradays Laws of Electrolysis Questions

1. In an operating Hall-Hroult cell, a current of 150 000

A is used at 5.0 V. Calculate the mass of aluminium
that would be produced if this cell operates
continuously for 1 day.
Ans: m (Al) = 1 208 705 g
That is, 1.2 tonne of aluminium is produced per day
2. The electrolysis of a solution of chromium ions using a
current of 2.2 A for 25 minutes produced 0.60 g of
chromium. Calculate the charge on the chromium ion.
Ans: As the charge on an ion is a small integer, it must
be 3+.
The ion is Cr3+.

The process of conduction:

A great difficulty when dealing with
electrolytes is to ascribe individual
properties to individual ions.
Individual thermodynamic properties
cannot be determined, only mean
ionic quantities being measurable.

Electrolytic conduction
- Nature properties of solutions

Based on measurements of their conductivities

A solution of sucrose in H2O does not dissociate into ions & has the same
electrical conductivity as H2O itself. Such substances are known as
nonelectrolytes

A solution of NaCl or CH3COOH forms ions in solution & has a much higher
conductivity. These substances are known as electrolytes.

Some electrolytes in aqueous solutions of the same molality conduct better

than others. This suggest that some electrolytes exist as ions in solution to a
greater extent than do others.
Such substances are known as strong electrolytes.

Other substances, including CH3COOH and NH3 are present only partially as
ions.
- CH3COOH exists in solution partly as CH 3COOH and partly as CH3COO- + H+.
These substances are known as weak electrolytes.

 Interionic and ion-solvent interactions are so

numerous and important in solution that, except
in the most dilute cases, no ion may be regarded
as behaving independently of others.
On the other hand, there is no doubt that certain
dynamic properties and transport numbers may
be determined, although values for such
properties are not absolute by vary with ion
environment.

conductivity
A measure of how well a solution conducts
electricity

Water with absolutely no impurities

(does not exist)
Conducts electricity very poorly
Impurities in water increase conductivity
So, when measure conductivity of water can
estimate the degree of impurities

 The current is carried by dissolved

ions
The ability of an ion to carry current
is a function of:
Ions charge (more charge, more current)
Ions mass or size (larger ions, conduct
less)

Ohms law
The fundamental measurement used to study the motion of
ions is that of the electrical resistance (R) of the solution repulsion of a current within a circuit. It explains the
relationship between voltage (amount of electrical pressure)
and the current (flow of electricity).

the resistance R of a slab of material is equal to the electric

potential difference V divided by the electric current,
R = Resistance in V/A = (Ohm)
V = Voltage or potential difference in Volts, V
I = Current in Amperes, A

V
R
I

If a material has a resistance of 1 , it means that when applying

a potential difference of 1 V, the current in the material is 1 A.

Resistance measurement

Conductance , G

The electrical conductance of material measures how easily

electricity flows along a certain path through an electrical
element or capacity of a substance to conduct electricity:
The electrical conductance of material of length and crosssectional area A is proportional to A and inversely proportional
to

G (conductance) = A

A=
cross-sectional area
l = length of medium
=
electrolytic conductivity/ specific conductance/ electrical
conductivity (S m-1) (in the case of a solution of an
electrolyte) measure of its ability to conduct electricity

 SI unit of is -1m-1 S m-1 , but unit

more commonly used is -1cm-1 S cm-1
- The electrical conductance is
proportional to A (the conductance is
increase to cross-sectional area, A)
- The electrical conductance is inversely
proportional to l (the conductance of a
sample decreases with its length, l)

 The conductance of a sample decreases with its length l and increases

with its cross-sectional area A:

A = cross-sectional area
l = length of the medium
= electrolytic conductivity (S m-1)-siemens per metre (in the case of a
solution of an electrolyte)

For electrolytic conductivity (), whose SI units is S m-1 (or -1 m-1), the
values of increase with temperature and concentration.

Note:
The electrolytic conductivity () is not a suitable quantity for
comparing the conductivities of different solutions
If a solution of one electrolyte is much more concentrated than another,
it may have a higher conductivity simply because it contain more ions

cell

Conductance and
measurement

 is the conductivity (Sm-1). The unit most commonly used is S

cm-1.The molar conductivity is defined as the electrolytic
conductivity, divided by the concentration C
The conductivity of a solution depends on the nmber of ions
present, and it is normal to introduce (m )- capital lambda

1m 2 mol 1

m = molar conductivity (SI unit =

or
= 10-3 S)
k= electrolytic conductivity
C = molar concentration to the added electrolyte

S m 2 mol 1

) (where 1 mS

Molar conductivity

Example

Molar conductivity gives information about conductivity of ion

produced in solution by 1 mol of substance.

Imagine two
electrodes
held aat
separation
1 m. apart,
If athe
solution
Suppose
that a cell we construct
cella
having
parallel plates a of
unit distance
plates being of such
area thatm
for-3a),
particular
mol of electrolyte
HCl,
has a concentration
Can(mol
thensolution
the1volume
of(e.g
solution
CuSO ) is present in it (Figure 7.1b)
containing one mole = 1/C m3 and both electrodes would have to
The molar conductivity, is the conductance (the reciprocal of the resistance) across the
2
have an area
plates 1/C m , for a separation of 1 m.
4

If the concentration of the solution is C, the volume of the hyphothetical molar conductivity cell
must be (1 mol)/C in order for 1 mol to be between the plates (Figure 7.1b)

Figure 2.1: (a) The relationship between conductance and electrolytic conductivity
(b) The relationship between molar conductivity & electrolytic conductivity

 The molar conductivity, of an

electrolyte would be independent of
concentration if were proportional to
the concentration of the electrolyte.

is found to vary with the concentration. Reasons:

1) The number of ions in solution might not be proportional
to the concentration of the electrolyte.

- Example: the concentration of ions in a solution of a
weak acid depends on the concentration of the acid in a
complicated way & doubling the concentration of the acid
added does not double the number of ions

2) Because ions interact strongly with one another, the

conductivity of solution is not exactly proportional to the
number of ion present

 Calculation:

The molar conductivity of 0.0050 M KCl is 144 -1 cm2 mol-1. Calculate its electrolytic
conductivity in SI units.

Solution:

ans=0.072
In a given electrolyte solution of strong electrolytes, the number of ions depends on
the concentration

Solutions of weak electrolytes it is also dependent on the degree of dissociation or
ionization and on the temperature.

 Measurement:
Bridge circuit for conductivity
determination.

A: Conductivity cell

B: Oscillator

C: Capacitance (variable) to
balance capacitance of cell.

D: Detector

Measuring conductance of a solution is based on a

Wheatstone bridge circuit.
The conductivity of a solution is measured in a cell that is
one arm of a Wheatstone bridge. They actually measure
resistance. The electrolytic conductivity is calculated from:

since l and A are difficult to measure, the usual procedure is to treat

l/A as a cell constant, Kcell and to calibrate the cell by using of KCl,
having a known molar conductivity. Then

Calculation:
2
1
110 1cmthe
molresistance
A student measured
of a 0.100 M NaCl solution to
be 19.9 . Calculate the experimental value of the molar
conductivity of this solution.(cell constant, Kcell = 0.2120 cm-1)

ans=

The concentration of electrolyte dependence of (molar

conductivities) indicates that there are two classes of electrolyte:

Characteristic : its molar conductivity decrease only slightly as its

concentration is increased (strong)
Characteristic : its molar conductivity is normal at concentration close to zero,
but fall sharply to low value as concentration increases (weak)

The weak electrolytes produce fewer ions & exhibit a much

more fall of molar conductivity with increasing concentration, as
shown by the lower curve in Figure above

Strong electrolytes are substances that are virtually fully ionized in

solution, and include ionic solids and strong acids.

As a result of their complete ionization, the concentration of ions

in solution is proportional to the concentration of strong
electrolyte added.
e.g. solution of salt, strong mineral acids and alkalis, quaternary
salts of amines and etc.

In the
molar
molar
-

19th century, Friedrich Kohlrausch showed that at low concentrations, the

C
conductivities,
of strong electrolytes
vary linearly with the square root of
m
concentration,
:
vary linearly with
(at low concentration of strong electrolyte)

m m
-K

This variation is called Kohlrauschs law

K = non-negative constant depending on the stoichiometry of electrolyte (that is

whether it is of the form MA, or M 2A, etc)

= limiting molar conductivity or molar conductivity at infinite dilution (i.e., the

molarm conductivity in the limit of zero concentration of the electrolyte, when the ions
are effectively infinitely far apart & do not interact with one another).

C = molar concentration

Strong
electrolyte

weak
electrolyte

Consider a strong electrolyte that yields ions A and B in solution,

according to

Kohlrausch assumed that in such a system the molar conductivity

at infinite dilution (limiting molar conductivity) is simply the sum
of the independent contribution of the ions
Kohlrausch was also able to show that can be expressed as the
sum of contribution from its individual ions.

Kohlrauschs law of
independent migration of ions:
Law of the independent migration of ions states that
m
limiting molar conductivity of the cations
limiting molar conductivity of the anions

numbers of cations per formula unit of electrolyte

numbers of anions per formula unit of electrolyte

For example: for

1 HCl, NaCl and CuSO 4

1for
, MgCl
22
This equation has been written for infinite dilution since it is
only under such conditions, when ion-ion interactions are at a
minimum that the law strictly holds.
It is then applicable to both strong electrolyte and weak
electrolytes.

 Limiting ionic conductivity of any

strong electrolyte:

 Calculate the limiting molar

conductivity of BaCl2 in H2O at 298 K.
ans=27.98 mS m2mol-1

Weak electrolyte

Weak electrolytes are not fully ionized in solution. They include

weak Brnsted acids and bases, such as CH3COOH and NH3. The
marked concentration dependence of their molar conductivities
arises from the displacement of the equilibrium towards products
at low molar concentrations.

HA (aq) + H2O (l)

H3O+ (aq) + A- (aq)

a ( H 3O ) a ( A )
Ka
a ( HA)

Initial mole
Change
Amount present at
equilibrium

HA

H3O+

A-

= fraction dissociated

= fraction not dissociated

The conductivity depends on the number of ions in the solution & degree
of ionization,
.

For weak acids (HA) at a molar concentration c, at equilibrium with

degree of ionization () of the electrolyte:

H
O
A
a
(
H
O
)
a
(
A
)
3
3
K
Ka
a
+
HA
[H3O ] = ca ( HA) [A ] = c
[HA] = (1-)c

2c
Ka

1/ 2

K
4
c

If we ignore activity coefficients, the

acidity
K
a is 1
a constant,
1
2c
Ka

From which
it follows that:
1

K
Rearrange aeqn into:

The electrolyte is fully ionized at infinite dilution and its

m
molar conductivity =

Because only a fraction is actually present as ions in the

m solution,
m the measured molar conductivity
actual
is
given by:

K a
4c

1
2c
Ka

Which

1/ 2

PROBLEM:
The molar conductivity of 0.0100 M CH3COOH (aq) at 298 K is
= 1.65 mS
m2 mol1. What is the acidity constant (Ka) of 0.0100 M CH3COOH (aq)?

Ostwald/s dilution law (for weak electrolyte at diluted

1/ 2
concentration)

Ka
4c

and
to1
1
Once we know Ka, we can use equation

2c
Ka

predict the concentration dependence of the

m mThe result agrees quite well with the experimental curve in Fig.
molar conductivity.
2.2:
We can use the concentration dependence
of in measurements of the limiting molar
conductance. First, we rearrange eqn

into
1/ 2

K
4c
a

1
1 using
eqn
Then,
,
2c by
K
a

Ostwalds dilution law:

1
c
1we
obtain

Ka

m m

c
1
c + mx m 2
m m K a ( m )

y 1=

This equation implies that, if

will be

1
m

is plotted against

1
m

, then the intercept

c at c = 0
m

The graph used to determine the limiting value of the molar conductivity of a
solution by extrapolation to zero concentration.

Effects of dilution on specific

conductance

Example 1

Example 2

Calculation of molar
conductivity of a week
electrolyte at infinite dilution

Example:

Ans:

Calculation degree of
dissociation of weak electrolyte

degree of dissociation of weak

electrolyte/weak acid

exercise

Degree of dissociation of weak

electrolyte or weak base

Degree of dissociation of
salt

Determination of the
dissociation constant Ka

For weak electrolyte, we can use Kohlarausch's law

of independent migration to calculate indirectly
value for weak electrolytes as illustrated by the
following example:

Ionic product of water

Solubility and solubility product of sparingly soluble salt

Example 1

Example 2

Ans:

Ions velocity
The individual and independent
conductivities of ions, postulated by
Kohlrausch
are determined by
s u
thezevelocities of those ions.
u
Thef speed of an ion as it moves under
the influence of an electric field is called
its mobility, u.

Question:

m 2 s 1are
v 1 the SI units of mobility?
What

Solution:

s ms 1
1 2 1
u

V
m s
1

=
electrical
field
of magnitude
Vm

= potential diffrence of ion across solution of length 1 cm

drift speed

Since the cation and anion usually have different mobilities, they
usually carry different fraction of the current.

current carried by the cation

z v u
t
z v u z v u

Because

z v z v
t

for all ionic species, this equation simplifies to

u
u u

Because the ionic conductivities are related the mobilities by equation

, it follows that

v
v

v v
m

And hence for each type of ion

v t

or

t m

v

zuF

The mobilites of K+ and acetate ion are 7.61 X 10-4 and 4.23 X 10-4 cm2 V-1 su
u

1, respectively,
at 25 oC. What are their
numbers
in potassium
t CHtransport
t K
3 COO
u

acetateusolution?
u
Solution:

7.61x10 4 cm 2V 1s 1
tK
(7.61x10 4 -4 4.232 x10-14 )-1 cm 2V 1s 1

7.61 X 10 cm V s

4.23x10 4 cm 2V 1s 1
t CH 3COO
(-47.61x210 -14 4-1.23x104 ) cm 2V 1s 1

4.23 X 10 cm V s

t t 0.643 0.357 1
=

0.643

= 0.357

Measurement of transport
number

We can determine transport numbers by several methods, e.g.

Hittorf method and moving boundary method. (These wont be
discussed further)

The importance of transport numbers is that they give a simple

way to obtain molar ionic conductivities. Quantities t and are
related through u:

The limiting transport number, is defined fraction of total

current carried by the ions but for the limit of zero
concentration of the electrolyte solution.

z v u
z v u z v u

The relationz vbetween

z v

u
t
u u
Because
simplifies to

and

is

for all ionic species, this equation

zuF
v
v
t

v the
m
vionic
conductivities
Because
are related the mobilities by
equation
v t m

, it follows that

t m

v

And hence for each type of ion

or

 p , q ,

For infinite dilution,

(Kolhrausch) or
:
m (electrolytes
z u v z u =
v )AFpBq
Strong
- Therefore,
itself in the limit of zero concentration
m z u v for
F the
z u solution
v F
(when there is no interionic interactions):

zuF

m v , v ,
p , q ,
or

The transport numbers of K+ and AC- in a KAc solution are t+ =

2
-1
v -1 tcm
0.643, t- = 0.357. If an experiment yields 114.3
mmol as the
value of o of KAc, what are the experimental molar ionic

v

t
m

conductivities
at infinite dilution?

m
Solution:
t m
t

KAc

K+ + Ac
v
t
z+ = 1, z- = 1, v+ = 1, v- = 1

v 114.3
z u v -1) Fcm2 mol-1
m =( z u =

For ta+ symmetrical

z:z electrolyte:
=
= 0.643

tm= z (=
u 0.357
u )F
-

m zu F zu F

zuF

v of K+ = 1
0.643 x 114 .3 1cm 2 mol 1 = 73.50 -1 cm2 mol-1

1

of CH3COO- = 1
t m

v

0.357 x 114 .3 1cm 2 mol 1

1

m
m (73.50 40.81) -1 cm2 mol-1
= 114.31 -1 cm2 mol-1

= 40.81 -1 cm2 mol-1

The activities of ions in

solution

For dilute solutions of non-electrolytes, it is generally safe to make

the approximation that solute activities can be replaced by their
molarities

In ionic solutions, the interactions between ions are so strong

that the approximation of replacing activities by molalities is valid
only in very dilute solutions (< 10-3 mol/kg total ion concentration)
and, in precise work, activities themselves must be used.

The definition of activity

Chemical potential ( ) which also known aspartial molar free

energy is a form ofpotential energythat can be absorbed or
released during a chemical reaction
The chemical potential of a solute in a real solution is related to
its activity by:
RT ln a

chemical potential

chemical potential at standard state

a = activity of a substance in the mixture

b 1 molkg 1
where the standard state is a hyphothetical solution with
molality
in which the ions are behaving ideally. The activity is related to the molality, b

,by

a b / b
activity
coefficient
b 1 molkg 1

Where

depends on the composition, molality and temperature of the solution.

As the solution approaches ideality (in the sense of obeying Henrys law) at low
molalities, tend toward 1:

a b / b as b 0

and
Henrys Law:
"At a constant temperature, the amount of a given gas that dissolves in a given
type and volume of liquid is directly proportional to the partial pressure
of thatgas in equilibrium with that liquid."
An equivalent way of stating the law is that the solubility of a gas in a liquid
is directly proportional to the partial pressure of the gas above the liquid.

Because all deviations from ideality are carried in the

be written

, the chemical potential ca

RT ln a

b
RT ln
b

RT ln RT ln

b
b

b 1 molkg 1

RT ln b RT ln

ideal RT ln

b
b

ideal RT ln
= chemical potential of the ideal-solute
solution
of the same molality

ideal

Mean activity coefficients,

Chemical potential of a univalent cation M+ =

Chemical potential of a univalent anion X- =

Total Gibbs energy of ions in the electrically neutral solution is the sum of these
ideal
partial molar quantities. The molar Gibbs energy of an ideal solution,Gm
is:

ideal
m

ideal

ideal

ideal Chemical potential of cation in ideal

solution
ideal Chemical potential of anion in ideal
solution

However, for a real solution of M+ and X- of the same molality, (electrolyte 1:1):

Gm

ideal RT ln
ideal RT ln
Gm ideal ideal RT ln RT ln
Gmideal ideal ideal

Gm Gmideal RT ln

Gm Gmideal RT ln
All the deviations from the ideality are contained in the last term.
There is no experimental way of separating the product +- into contributions
from the cations and the anions.
The best we can do experimentally is to assign responsibility for the
non-ideality equally to both kinds of ion.
Therefore, for a 1,1-electrolyte, we introduce the mean activity
coefficient as the geometric mean of the individual coefficients:

( )1 / s

Example
MX M X
s = p + q or
Thus,
s=1+1=2

( )1 / 2
And express the individual chemical potentials of the ions as

ideal RT ln

ideal

RT ln

The sum of these two chemical potentials is the same as before,

Gm Gmideal RT ln
but now the non-ideally is shared equally (electrolyte 1:2, 2:1)

 H SO
H SO
2H +
EXAMPLE
MpXq
2

p or v = 2
q or

v = 1

z
=1
+
z
=2
-

SO42-

To the case of a compound MpXq that dissolves to give a solution of p cations

and q anions. The total Gibbs energy of the ions:

Gm p q

or

ideal

Gm

pRT ln

ideal qRT ln
Gm ideal ideal pRT ln qRT ln
Gmideal ideal ideal

Gm Gmideal pRT ln qRT ln

If we introduce the mean activity coefficient

( p q )1 / s

s pq

the chemical potential of each ion

i iideal RT ln

Gm p q

We get same expression as in eqn for Gm when we write

However, both
types of ion now share equal responsibility for the
ideal

RT ln

non-ideality

ideal RT ln

Chemical potential of each ion as:

( )

( )

Example:
Answer:
Express mean activity coefficient
in terms of activity
coefficient for cation
and activity coefficient for anion
MgBr
Mg2+ + 2BrMgBr
solution.
2 2

( p q )1 / s

( 2 )1 / 3
s= p + q

p=1, q= 2

( )

for

The DebyeHckel limiting law

(DHLL)
The long range and strength
of the Coulombic interaction
between ions means that it is likely to be primarily responsible for
the departures from ideality in ionic solutions and to dominate all
the other contributions to nonideality.

This domination is the basis of the DebyeHckel theory of ionic

solutions, which was devised by Peter Debye and Erich Hckel in
1923.

Oppositely charged ions attract one another. As a result, anions

are more likely to be found near cations in solution, and vice versa
(Fig. 2.3). Overall, the solution is electrically neutral, but near any
given ion there is an excess of counter ions (ions of opposite
charge).

The environment of a particular ion therefore carries an opposite

charge, and this diffuse, charged environment is known as the ionic
atmosphere.

The energy of a solution of ions distributed in this way will differ

from that of purely random arrangement, and this different energy
will be contribution to the Gibbs free energy of the ions in solution.

The electrical and chemical behavior of ions is determined

thermodynamically by their free energy, and so the dependence of
free energy on concentration is important for both practically and
theoretically.

The calculation of the free energy of an ionic solution by the

Debye- Hckel theory of is involved.

The picture underlying the Debye-Huckel theory is of a tendency

for anions to be found around cations and of a tendency of cations
to be found around anions (one such local clusturing region is
shown by the sphere). The ions are in ceaseless motion and the
diagram represents the time average of their motion

The model leads to the result that at very low concentrations, the mean
activity coefficient can be calculated from the Deybe-Huckel limiting
law.
Some of the assumptions:
2
2
log
=
z
v

z
v
1
/
2

_
z z AI
b
k
I k
2
= mean activity coefficient
b
or
0.509 for an aqueous solution at 25 C
A =
= ionic strength of the solution:
m

or

I I m((vv zz22 vv zz22 ))

22

1
1

zi2 (bi / b )
I

b z 2negative
b z 2 / bfor

charge number of2 an ion (positive for cations and

i
2
I

= molality
z i = molality at standard state
bi

anions)

,
,

2M3+ +

X3
3X2ionicv strength,
, of M2X3 solution
3
z Calculate
3 z 2 vthe
2
2

(3 2 )2 (2 2 )3

I 15

b
b

15

b mo
lality

The table below summarizes the relation of

ionic strength and molality in an easily
usable form,

( )

A = 0.509

1
b z 2 b z 2 / b
2

1
0.005m x (12 ) 0.005m x (12 ) / 1
2

b / b

KCl K+ + Cl?? Estimate the mean activity coefficient

of 0.005
= m KCl (aq) at
z o 1
25 C?
= molality of the solution
z 1
(and b b b )

z z AI 1/ 2

1x1 x 0.509 (5 x10 )

3 1 / 2

Log

=
= -0.036
= 0.92

I 5 x10 3