ION EXCHANGE

2
Definition
A reversible chemical reaction where
an ion from a solution is exchanged
for a similarly charged ion attached to
an immobile solid particle
3
Ion Exchange
Chemical reactions between ions in solution
and ions in an insoluble solid phase
Example: Water softening (to remove
calcium ions)
Mechanisms
4
The techniques used in ion exchange so closely resemble
those used in adsorption that for the majority of
engineering purposes ion exchange can be considered as a
special case of adsorption

5
Water softening
Hardness in water, caused by calcium and magnesium ions,
which form insoluble compounds, is removed by ion
exchange.

Ca
2+
+ Na
2
R Ca R + 2 Na
+
(12.4-1)
(solution) (solid) (solid) (solution)

The water is filtered through an artificial zeolite (ion
exchange resin) , such as Permutite, and the sodium in the
zeolite replaces the undesirable ions that are in the water.
The positively charged ions in solution such as Ca
2+
diffuse
into the pores of the solid and exchange with the Na
+
ions
in the mineral
When the zeolite is saturated with these metallic ions, it is
washed with salt solution, which restores the sodium.

6
Advantages

Increased value of a product because of improved
properties
Recovery of valuable components
Recovery of water for re-use
Better quality control due to elimination of process
variability
Reduced waste disposal costs due to elimination of
objectionable components or reduced volume
Reduction of corrosion or scaling in subsequent
equipment


7
Disadvantages
Capital cost of equipment
Resin costs which may be either capitalised or expensed
depending on resin life
Cost of chemical regenerants
Operating labour
Disposal costs for regenerant wastes


8
Ion Exchange Resin
Synthetic resins predominant can be tailored to specific
applications
Provides cation/anions to be exchanged
Generally solid gels in spherical or granular form
consists:
polymeric network
ion functional group attachment
counterions (exchangeable ions)
solvent


9
Ion Exchange Resin
Fixed and mobile ions in a cation exchanger
(ref 1, pg 791)
10
Ion Exchange Resin
--SO
3
-
groups permanently fixed to the polymeric
network to give a negatively charged matrix and
exchangeable, mobile hydrogen cations, H
+
This condition exist when solvent (e.g. water, methanol)
is added.

The H
+
ion can be exchanged with other cations eg.
Na
+
, Ca
2+
, K
+
or Mg
2+
to maintain neutrality of polymer.
Resin
Each resin has a distinct number of mobile ion sites that set
the maximum quantity of exchanges per unit of resin.

11
Solid ion exchange particles
An organic ion exchange resin is composed of high-
molecular-weight polyelectrolytes that can exchange their
mobile ions for ions of similar charge from the surrounding
medium.
e.g : Zeolites
Resin types
Ion exchange resins are classified as cation exchangers, which have
positively charged mobile ions available for exchange, and anion
exchangers, whose exchangeable ions are negatively charged.


12
Both anion and cation resins are produced from the same
basic organic polymers.
Classification of resin
Strong Acid
Cation Resins.
Weak
Acid
Cation
Basins
Strong Base
Anion Resins.
Weak
Base
Anion
Resins
13
Ion Exchangers (types)
1.Natural: Proteins, Soils, Lignin, Coal, Metal
oxides, Aluminosilicates (zeolites) (NaOAl
2
O
3
.
4SiO
2
).





2.Synthetic zeolite
gels and most common -polymeric resins
(macroreticular, large pores).

14
15
Ion Exchangers
Commercial ion exchangers

Amberlite
Duolite
Dowex
Ionac
Purolite

Form of spherical beads from about 40m to
1.2mm diameter.
16
Equilibrium Relations
Ion exchange differs from adsorption in that
one ion is exchanged for a solute ion.
The exchange is governed by a reversible,
stoichiometric chemical-reaction equation.

17
Equilibrium Relations
Na
+
+ HR Na R + H
+
(12.4-2)
(solution) (solid) (solid) (solution)

(12.4-4)


Total ionic concentration, = [NaR] + [HR] = constant

(12.4-6)



] ][ [
] ][ [
HR Na
H NaR
K

] [ ] [
] ][ [
] [
_

Na K H
Na R K
NaR
R
(Ref. 1)
18
Ion-exchange process for strong acid or strong base
exchangers by replacing ions in a solution with either:
H
+
OH
-

Regeneration, small amount of solution with high
concentration of:
H
+
for cation exchangers
OH
-
for anion exchangers
Originally in the resin
Regeneration shift the equilibrium to the left,
making the regeneration process more favorable
19
Relative-Molar-Selectivity
Coefficients (K)
The equilibrium constant or selectivity coefficient for exchange
of any two ions A and B (Table 12.4-1) and the formula below:
B
A
B A
K
K
K
,
Strong-Base Anion Exchange
(Relative to Cl
-
as 1.0)
Strong-Acid Cation Exchanger
(Relative to Li+ as 1.0)
Cl
-
Iodide
Nitrate
Acetate
Sulfate
Hydroxide
1.0
8.7
3.8
0.2
0.15
0.05 0.07
Li
+
H
+
Na
+
NH
4
+
K
+
Mg
2+
Cu
2+
Ca
2+
1.0
1.27
1.98
2.55
2.90
3.29
3.85
5.16
Table 12-4-1 :Relative molar selectivity coefficient for
polystyrene with 8 % DVB (ref 1)
20
A + BR A R + B
(solution) (solid) (solid) (solution)

K
A,B
= K
A
/K
B


K
A,B
= c
B
q
AR
/c
A
q
BR


(c = ion concentration in equivalents/L volume of solution)
(q = ion concentration in equivalents/L of bulk bed volume)

C = c
A
+ c
B
(total ion concentration in liquid solution)
Q = q
A
+ q
B
(total ion concentration in resin)


21
Example
A waste acidic stream contains copper in solution which is
being removed by a strong acid-cation resin. The cation Cu
2+

(A) is displacing the cation H
+
(B) in the resin. A polystyrene
resin similar to the Table given is being used. The total resin
capacity Q is approximately 1.9 equivalents/l of wet bed
volume. For a total concentration C of 0.10 N (0.10
equivalents/L) in the solution, calculate at equilibrium the
total equivalents of Cu
2+
in the resin when the concentration
is Cu
2+
in solution is 0.02M (0.04 N).
22




Cu
2+
+ 2HR Cu R
2
+ 2H
+

(solution) (solid) (solid) (solution)




23
Design Considerations
Fixed-Bed Ion-Exchange Columns

- Rate depends on

Mass transfer ions from bulk to particle surface

Diffusion in the pores of solid to surface

Exchange of ions at the surface

Diffusion of the exchange ion back to the bulk
solution.
24
Modes of Operation
(Similar to adsorption)








a) Continuous countercurrent: packed bed
25
Modes of Operation









a) Continuous countercurrent: fluidized-bed

26
Ion exchange in water & waste water
Ca, Mg (hardness removal) exchange with Na or H
27
http://www.thewatertreatments.com/water-softener/softner-water-conditioner-water-treatment-filter

Removal of hardness from water
28
The water obtained after passing
through the ion-exchangers is
called deionised water or
demineralised water.
In the ion
exchange process,
hard water is
passed through
two tanks 'A' and
'B'.
Tank- A contains
acid resin and
tank- B is filled
with basic resin.
All the cations
present in hard
water (except
H
+
) are removed
by the acid
resin present
in Tank- A, and
the basic resin
present in
Tank- B removes
all the anions
(except OH
-
)
present in hard
water.
Water obtained after passage
through both the tanks is free from
all the cations and anions that
make it hard.
29
Demineralization in waste water treatment
The effects of hardness in water are:
1.They react with soap to form a scum, which is
unsightly,
2.The reaction of hard water with soap results in
excessive use of soaps and detergents.
3.Hard water may also cause taste problems in
drinking water and may shorten the life of
fabrics washed in hard water.
4.Hard water harms many industrial processes such
as scales inside boilers and pipes.
30
Ion exchange materials
31

Basic resins contain the basic group [(-NH
3
+
)OH
-
], i.e.,
substituted ammonium hydroxide group.

Acid and basic ion exchange resins are represented as RCOO
-
H
+
and RNH
3
+

+ OH
-
respectively.


Giant organic molecules having acidic or basic
groups are known as Ion-exchange resins.
Ion exchange materials
32
Basic resins exchange their OH
-
ions with the other anions such as
HCO
3
-
, Cl
-
, SO
4
2-
, present in hard water.

Basic resins, therefore, are also known as acid exchange resins
Acid resins exchange their H
+
ions with other cations such as Ca
2+
,
Mg
2+
, etc., present in hard water. Acid resins are, therefore known as
base-exchange resins.
Equilibrium relations
in ion exchange
Developed using the law mass of action
General chemical reaction equation in which reactants A and B react to
give product C and D.

a A + b B --> c C + d D

where a, b, c, d are the coefficients for a balanced chemical equation.

The mass action law states that if the system is at equilibrium at a
given temperature, then the following ratio is a constant.
[C]
c
[D]
d

-------- = K
eq
[A]
a
[B]
b

This is the ideal law of chemical equilibrium or law of mass action.
The units for K depend upon the units used for concentrations.

If M is used for all concentrations, K has units
M
c+d-(a+b)

33
Equilibrium relations
in ion exchange
Convenient tables for relative-molar
selectivity coefficient, K for various types of
ion-exchange resins

Table 12.4.1 (textbook) for polystyrene resin
with 8% DVB cross-linking (B8, P4) for strong
acid and base.

The equilibrium constant/selectivity
coefficient for ions A and B :
K
A,B
= K
A
/K
B

34
Table 12.4.1 (textbook) for polystyrene resin with
8% DVB cross-linking (B8, P4) for strong acid and
base.
35
Equilibrium relations
in ion exchange
For dilute solutions, the equilibrium constant is :
Activity coefficient = CONSTANT

K
A,B
= c
B
q
AR
/c
A
q
BR

= c
H+
q
KR
/ c
K+
q
HR

Resin phase : concentration q
KR
and

q
HR
the unit are in
equivalents/L of bulk bed volume of water-swelled resin

Liquid phase : concentration of c
H+
and c
K+
the unit are in
equivalents/L of volume of solution




36
Equilibrium relations
in ion exchange
Total concentration C in the liquid solution
and total concentration Q is CONSTANT.

C = C
A
+ C
B
Q = q
AR
+ q
BR

37
Example 12.4.1

Removal of Cu
+
Ion From Acid Solution by an Ion-
Exchange Resin

38
Write down the
equilibrium equation
Find the relative molar
selectivity coefficient,
K for Cation and Anion
exchangers
Write down and
calculate the
equilibrium constant
Total concentration, C
in liquid solution
Total concentration, Q
in resin
Solve and calculate
39
a A + b B --> c C + d D
[C]
c
[D]
d

-------- =
K
eq
[A]
a
[B]
b

C = C
A
+ C
B
Q = q
AR
+ q
BR
Table 12-
4-1: if
the resin
used is 8%
DVB
crosslinki
ng
Basic model
in Ion exchange
Rate of ion exchange depends on:
1. Mass transfer of ions from bulk solution to the
particle surface
2. Diffusion of the ions in the pores of solid to
the surface
3. Exchange of ions at the surface
4. Diffusion of the ions back to the bulk solution

Designs method similar to adsorption

40
Concentration profiles
in packed bed
Similar as adsorption

Typical S-shaped curves occur and pass through the bed

Major part of the ion exchange at any time takes place
in narrow mass transfer zone (MTZ)

The MTZ moves down the column

The Breakthrough curve (BC) is similar to BC of
adsorption

41
Mass transfer zone
As MTZ travels down the column, the height of MTZ
becomes constant

The ion to be removed from the feed stream has a
greater affinity for the solid resin than the
ion originally present in the solid.

The constant Height of MTZ allows for scale-up
purposes.
42
Capacity of column
Similar with adsorption process
43
The total/ stoichiometry
capacity
The usable capacity
The length of bed used up to
breakpoint
The length of unused bed
The total bed length
References
1. http://www.tutorvista.com/content/chemistry/chemistry-
iii/hydrogen/methods-hardness-water.php
2. http://www.science.uwaterloo.ca/~cchieh/cact/c123/mas
sacti.html
3. http://www.remco.com/ix.htm
4. ceeserver2.cee.cornell.edu/jjb2/cee6560/9-
Ion%20Exchange.ppt



44
45
Industrial Applications

- Water softening

- Recovery of antibiotics/vitamin
from fermentation broth

- Decolourisation of sugar

46
Chromatorgraphy
Chromatorgraphy - greatest advantage of the
chromatography method over other analytical
procedures is the ability of separating specific
analytes (the entities you are analyzing for), and
gives that ability to discover and analyze unknown
elements and chemical compounds.

All chromatography techniques consists of two
phases; mobile and immiscible stationary phases.



47
Chromatorgraphy

The components that are strongly retained move slowly, while the
components that are weakly retained travel more rapidly. A detector
should be placed at the end of the chromatograph to quantify the
analyte.



Based on the mobile phase, chromatorgraphy can be classified into
major two categories; liquid chromatography and gas
chromatorgraphy.
48
Classification of Chromatorgraphy
General Classification

Specific Method

Stationary Phase

Liquid chromatography (LC)

Liquid-liquid, or partition

Liquid asorbed on soilds

Liquid-bonded surface

Organic species boonded to a
solid surface.

Liquid-solid, or adsorption

Solid

Ion exchange size exclusion

Ion-exchange resin liquid in
interstices of a polymeric solid.

Gas chromatography (GC)

Gas-liquid

Liquid adsorbed on a solid.

Gas-bonded phase

Organic species bonded to a solid
surface

Gas solid

Solid

49
Ion Exchange Chromatorgraphy
Ion exchange chromatography the stationary phase
consists of an insoluble porous resinous material
containing fixed charge-carrying groups.
50
References
1. Geankoplis C. J., Transport Processes and Unit
Operations, 4
th
Edition, Prentice Hall, 2003.
2. Seader J. D. and Henley E. J., Separation Process
Principles, John Wiley, 1998
3. http://pasture.ecn.purdue.edu/~eql/H2Oanalyseanion