CATION EXCHANGE

I.

Introduction
In most cases the term ion exchange is used to denote the processes of
purification, separation, and decontamination of aqueous and other ion-containing
solutions with solid polymeric or mineralic 'ion exchangers' [Zagorodni, 2006].
Ion exchangers are insoluble solid materials, which carry exchangeable cations or
anions. These ions can be exchanged for a stoichiometrically equivalent amount of other
ions of the same sign when the ion exchanger is in contact with an electrolyte solution
[Helfferich, 1962].
The most common industrial ion exchangers are ion exchange resins (functionalized
porous or gel polymer), zeolites, montmorillonite, clay, and soil humus [Dorfner, 1991].
These could either be cation exchangers or anion exchangers that exchange
positively charged ions (cations) and exchange negatively charged ions (anions),
respectively. There are also amphoteric exchangers that can exchange both cations
and anions simultaneously. However, the simultaneous exchange of cations and anions
can be more efficiently performed in mixed beds, which contain a mixture of anion and

Cation Exchange

cation exchange resins, or passing the treated solution through several different ion
exchange materials [Muraviev et al., 2000].
Ion exchangers have binding preferences for certain ions or classes of ions,
depending on their chemical structure. This can be dependent on the size of the ions,
their charge, or their structure [Muraviev et al., 2000]. Typical examples of ions that can
bind to ion exchangers are:

H+ (proton) and OH (hydroxide)

Single charged monoatomic ions like Na+, K+, or Cl

Double charged monoatomic ions like Ca2+ or Mg2+

Polyatomic inorganic ions like SO42 or PO43

Organic bases, usually molecules containing the amino functional group -NR2H+

Organic acids, often molecules containing -COO (carboxylic acid) functional

groups

Biomolecules, which can be ionized: amino acids, peptides, proteins, etc.

Ion exchange is a reversible process and the ion exchanger can be regenerated or
loaded with desirable ions by washing with an excess of these ions.
Cation-exchange equilibiria are usually determined by equilibrating the cation
exchanger with a solution containing both competing counter-cation species and
analyzing the ionic composition of the cation exchanger after separation from the
solution. The exchange between cations say, A and B, can be represented by the
following mass-action equation:

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zA

z B +z B RA

zB zA B

(1)

z A +z A RB

zB A

where R refers to the resin matrix with fixed negative charges, zi is the species charges,
and the over bar denoting the solid phase [Helfferich, 1962].
Solid-liquid adsorption is usually described through isotherms, that is, the amount of
adsorbate on the adsorbent as a function of its concentration at constant temperature.
The quantity adsorbed is nearly always normalized by the mass of the adsorbent to
allow comparison of different materials [Helfferich, 1962].
Single-component distribution data of a solid-liquid adsorption can be well described
by either Langmuir or Freundlich adsorption isotherms. The most common mathematical
fit to an isotherm was published by Irving Langmuir in 1916. Langmuir isotherm has a
theoretical basis and is given by the following:

q=

qoC
K +C

(2)

Cation Exchange

where

is the liquid phase concentration in kg/m3 or meq/ml,

qo

is an empirical

constant with the unit kg adsorbate/kg solid or meq adsorbate/g adsorbent, and

is

also an empirical constant with the unit kg/m3 or meq/ml. This is based on assumption
that there are only a fixed number of active sites available for adsorption, that only a
monolayer is formed, and that the adsorption is reversible and reaches equilibrium

condition. The parameters can be determined by plotting

the slope is

K
qo

and the intercept is

1
qo

versus

where

[Geankoplis, 2003].

Freundlich isotherm equation is empirical. This equation often approximates data for
many adsorption systems and is particularly useful for liquids:

q=K C

where

and

(3)

are constants and must be determined experimentally. The

parameters can be determined by plotting

versus

where the slope is

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the dimensionless exponent

. The dimensions of

depend on the value of

[Geankoplis, 2003].
The Langmuir adsorption isotherm describes quantitatively the build up of a layer of
molecules on an adsorbent surface as a function of the concentration of the adsorbed
material in the liquid in which it is in contact. The shape of the isotherm (assuming the xaxis represents the concentration of adsorbing material in the contacting liquid) is a
gradual positive curve that flattens to a constant value. The Freundlich isotherm curves
in the opposite way and is exponential in form. It often represents an initial surface
adsorption followed by a condensation effect resulting from extremely strong solutesolute interaction [Muraviev et al., 2000].
The subject of this experiment is the cation-exchange involving hydrogen ion (H+)
and sodium ion (Na+) in an aqueous solution.

II. Objective of the Experiment

This experiment aimed to characterize Dowex Monosphere 650C (H) cationexchanger and to establish Na+- H+ exchange isotherm at 30 C.

III. Methodology
2.1 Materials
Solutions of different concentration of sodium chloride (NaCl) were used as the
cation (Na+) source. Dowex Monosphere 650C (H) was used as the cation exchange
resin. Hydrochloric acid (0.1 N) and sodium chloride (0.1 N) solutions were used for
conditioning the cation exchange resin. Reagents used were all analytical grades
manufactured by Ajax Finechem (Australia).

Cation Exchange

2.2 Equipment and Apparatus

Erlenmeyer flask of 125 ml capacity was used to contain the cation exchange
mixture. A rotary shaker (New Brunswick Scientific rotary shaker model G25) was used
to agitate the mixture of cation exchange resin and NaCl solution. A pH meter (ORION
210-A) was also used in measuring the initial and equilibrium pH of the samples and
were converted later to H+ concentration (in meq/ml) using the following equation:

[H+] = 10-pH

(4)

2.3 Procedures
2.3.1 Resin Preparation
The Dowex Monosphere 650C (H) cation exchanger is supplied in H+-form. Prior to
use in the experiments, about 50 g of wet resin was placed in a 125-ml Erlenmeyer flask.
The resin was conditioned by 5 cycles of rinsing with de-ionized water, bringing to H+
form using 0.1 N HCl, rinsing, and then back again to Na+-form using 0.1 N NaCl. Per
cycle, 500 ml of NaCl and HCl was used to condition 50 g of resin.
Each rinsing cycle lasted for one hour. A rotary shaker was used in agitating for
better contacting of resin and conditioning solution. Then, the conditioned resin in H+-

Cation Exchange

form was rid of adhering moisture by suction filtration. Finally, resin was placed in a
media bottle, covered with a paraffin film, and stored in the refrigerator at 4C to prevent
dehydration.

2.3.2 Resin Characterization

Water content. The water content of the hydrated resin in H+-form is determined by
noting the decrease of the weight of the resin placed in an evaporating dish upon ovendrying (Memmert Um 500F Nr Oven) at 105C for 24 hours.

Resin Density. The density of Dowex Monosphere 650C (H) resin is given by the
manufacturer as approximately equal to 1.2 g / ml. However, experimental determination
of the density of Dowex Monosphere 650C (H) was still conducted in order to
countercheck the quoted value. First, 2 grams of resin was equilibrated with 50 ml of 0.1
N HCl solution for 24 hours and then the swollen resin was weighed. BOD bottle of
known volume (determined experimentally) was filled with 50 ml solution and the resin
was allowed to settle into the bottom of the bottle. After that, the bottle was weighed at
thermal equilibrium. The volume, V of the ion exchanger resin was computed using the
following equation:

(5)

V=V b

(W b W )

where Vb is the volume of the bottle, Wb is the weight of the bottle content, W is the dry
weight of the Dowex Monosphere 650C (H) resin, and is the density of the solution.

Cation Exchange

Density of the solution was determined experimentally at room temperature using

electronic balance (KERN EW150-3M) and densitometer (SARTORIUS YDK O1).
The volume of the bottle was determined using the following procedure:
First, BOD bottle was dried with the cover in the oven for two hours at 105 oC. After
that, the empty bottle was weighed with the cover and filled with distilled water of known
temperature. The volume of the bottle was then determined using Equation 7.

Finally, the density of the resin,

was computed using the following equation:

(6)

where W as defined previously, is the dry weight of the Dowex Monosphere 650C (H)
resin while V is the corresponding volume of it.

Resin Capacity. The total exchange capacity of the resin was given by the
manufacturer as equal to 1.9 equivalents / liter or approximately 1.56 milliequivalents /
gram. However, the value was still verified using the procedure given by Helfferich
(1962): 2 grams of hydrated resin was placed in a 125 ml Erlenmeyer flask and then
equilibrated with 1.0 N NaCl solution. Effluent was collected and the pH was determined

using the pH meter. Resin capacity or Na+ uptake of the resin,

through the mass balance equation,

Na
q

was computed

Cation Exchange

,i
,f
C
C
mw W

V
Na+ =
q

where V is the volume of solution in ml,

mw

(7)

is the mass of hydrated ion exchange

resin, W is the gram dry resin per gram hydrated resin,

,i
C

and

,f
C

and final Na+ concentrations in the solution in meq/ml. By mass balance,

are the initial

,i
f
C
C

which

Cation Exchange

is the amount of Na+ taken up by the cation exchanger is equal to

,f
,i
C
C

or the amount

of H+ released.

2.3.3 Equilibrium Experiment

For the determination of ion-exchange equilibrium, a batch method was employed
and carried out in a single set of eight NaCl concentrations with the set having a
duplicate. This was made by placing 2.0 g of conditioned resin in individual 125- ml
Erlenmeyer flasks containing 20 ml NaCl solution with varied concentrations.
The concentrations of NaCl used in the experiment were 0.2 N, 0.3 N, 0.4 N, 0.5 N,
0.6 N, 0.7 N, 0.9 N and 1.0 N where N is the normality of the solution also expressed as
milli-equivalents per liter (meq/L). Actual concentrations were determined using a
conductivity meter, which are shown in Appendix 7.2.
Twenty milliliters of NaCl solutions with varying concentrations were obtained by
diluting with the stock solution with de-ionized water.
The initial pH of the sample was measured. The flasks were then placed in the
incubator-shaker moving at 200 rpm and 30C. The solution was allowed to reach
equilibrium in 6 hours. The equilibrium pH in each flask was measured again. Initial and
equilibrium pH were converted to H+ concentration using Equation 6 to determine the
amount of H+ released to the liquid which by mass balance is equal to the Na+ taken up

Cation Exchange

by the cation exchanger. The Na+ uptake of the resin,

the mass balance equation in Equation 7.

Na+
q

was computed through

Cation Exchange

Raw Data

7.1 Moisture Content Determination of Swollen Resin

Crucible
#

Wc (g)

, Wro (g)

Wc +
Wr (g)

Wr (g)

Ave.:

%Moisture
Content

Wt.

Wt. water/wt.

wt. dry

water

hydrated

resin/hydrated

(g)

resin (g/g)

resin (g/g), W

Cation Exchange

Notes:

Wc weight condition resin

Wro initial weight of resin
Wr final weight of resin after swelling
Ave. average

W - the gram dry resin per gram hydrated resin

7.2 Resin Density Determination

Volume of BOD bottle

BOD
#

Wbc + Ww
Wb (g)

(g)

Notes: Wb- weight bottle

Wbc weight bottle with cover

Ww, (g)

Vapp (ml)

V app apparent volume

V true true volume

Vtrue@

% rel.

27.5 oC

error

Cation Exchange

Ww weight water

Density of 0.1 N HCl solution using densitometer at

o

27 C

Bouyancy,
W(a), g

W(fl), g

HCl (g/ml)

G (g)

Average

Notes: W(a) weight of the solid plummet

G buoyancy = W(a) W(fl)

W(fl) weight of the fluid

HCl - density of 0.1 N HCl solution =

G/Vtrue

7.3 Volume and density of resin at 27oC

BOD#

Wb (g)

Wro (g)

Wb + Wha

Wb + Wha + Wr

Wha + Wr

(g)

(g)

(g)

Wr (g)

Vr (ml)

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Average:

Notes:

Wc weight condition resin

Wr final weight of resin after swelling

Wro initial weight of resin

Ave. average

7.4 Resin Capacity

12

f (g)

Cation Exchange

Volume,
V of 1.0
Wcr (g)

N NaCl
used

Initial

Initial Na+

Initial

Conductivity

Conc.(meq/ml)

pH

Initial H+

Final H+

conc.

conc.

Amount Na+

(meq/ml)

taken up

(meq/ml)

Final pH

(meq)

(ml)

Average:

Notes: Wf weight flask

Wcr weight conditioned resin
Amount Na+ taken up = Amount of H+ released = V x (Final H+ - Initial
H +)

Cation Exchange

7.5 Na+ - H+ Exchange

13
Wf +
Wsoln. +
Wcr (g)

Wcr (g)

Wdcr
(g)

V
(ml)

CNa+, i,

Initial
+

(meq/ml

Na

(meq)

Initial
pH

Initial H+

Initial

Final pH
+

Conc.

Amount H

(meq/ml)

(meq)

Final H+

Final

H+

Conc.

Amount

release

H+ (meq)
(meq/ml)

d = Na+
taken
up
(meq)

Cation Exchange

CNa+, i initial sodium ion concentration of the solution in the aqueous solution
Notes: Wf weight of flask
Wsoln weight of the solution

Wcr weight

conditioned resin
V volume of the solution

Wdr weight dry resin

CNa+, f - final or equilibrium sodium ion concentration in the aqueous solution;
also expressed as C

14