QUANTITATIVE DETERMINATION OF TOTAL ION

CONCENTRATION BY ION EXCHANGE

CHROMATOGRAPHY
E. CALDERON1 and N. CASTOR2
1INSTITUTE

OF BIOLOGY, COLLEGE OF SCIENCE

OF BIOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 6 May 2015
DATE PERFORMED: 24 April 2015
2INSTITUTE

ABSTRACT
The copper (II) concentration of an unknown sample was determined by ion exchange chromatography,
with resin as its stationary phase. The NaOH titrant was standardized with KHP as the primary standard
and phenolphthalein as the indicator. The eluate acquired from the column was titrated using the
standardized titrant and the same indicator. The procedure involved the concept of ion-exchange in
resins which is used for the separation and determination of chemical components in complex mixtures.
It was shown in the results of the sample analysis that the concentration was 783.28 ppm Cu2+.

INTRODUCTION
Chromatography is widely utilized for the
separation, identification, or determination of
the chemical components in many complex
mixtures. This is an analytical technique
wherein the components are separated based
on the differences in the rates at which they
are carried through the stationary or mobile
phases. [1]
The flow of a mobile phase is used to carry the
components of a mixture through the
stationary phase, and the separations are
based on the differences in migration rates
among the mobile-phase components.
The two basic types of chromatographic
methods are column chromatography, in
which the stationary phase is held in a narrow
tube, and the mobile phase is forced through
the tube by gravity or pressure; and planar
chromatography, in which the stationary
phase is supported on a flat plate or in the

pores of a filter paper, and the mobile phase

moves through the stationary phase by
capillary action or the influence of gravity.
The concept behind the retention in ionexchange chromatography relies on the
attraction between solute ions and charged
sites bound to the stationary phase. [2] Ions
are held on a porous, insoluble solid, and are
exchanged for ions in a solution that is brought
in contact with the solid. [1]
The most common materials with ionexchange properties are clays, zeolites, and
resins. Ion-exchange resins are heavy,
amorphous (non-crystalline) polymers that
contain large numbers of an ionic functional
group per molecule, and are widely used in the
softening and deionization of water, solution
purification and ion separation. [2] In
addition, these materials are also used to
separate
charged
species
in
liquid
chromatography, in which they are used as
stationary phases.

In anion exchangers, solute anions are

attracted by positively charged groups on the
stationary phase. Strong-base anion exchange
resins are composed of hydroxyl ions attached
to the basic group RNH3+ on the resin, as
shown in the general reaction (1).
n RNH3+OH- + An- (RNH3)nA + n OH- (1)
where An- represents a cation, and RNH3+
represents the part of the resin molecule that
contains an attached hydroxyl group.
Cation exchangers, on the other hand, attract
solute cations using covalently-bound,
negatively-charged sites. Cation exchange
resins contain acidic functional groups
attached to the aromatic ring of the insoluble
organic molecule. The active sites on the resin
are made up of a polymeric matrix with
attached sulfonic acid groups, -SO3H, which
after treatment with HCl forms ionizable RSO3H+on the resin, as shown in the general
reaction (2). [2]
n RSO3-H+ + Mn+ (RSO3)nM + n H+

(2)

where Mn+ represents a cation and R

represents the part of the resin molecule that
contains one sulfonic acid group.
In the study, a strongly acidic cation exchanger
was used, Dowex 50, which is made up of
sulfonic acid gropus attached to styrene and
divinylbenzene copolymers. The ion content
of unknown samples can then be determined
by titrating and neutralizing the eluate which
contains the displaced ions from the resin.

Erlenmeyer flasks, each weighing 0.1008 g,

0.127 g, and 0.1002 g. The primary standard in
each flask was then dissolved in 50 mL of
distilled water and then added with 2-3 drops
of phenolphthalein indicator.
For the standardization of NaOH, the primary
standard was titrated using the basic titrant
until a color change from a clear to pink
solution was observed.
At the bottom of a 50-mL burette, a wad of
absorbent cotton, that was large and enough
to support the resin without blocking the flow
of liquid, was placed. The prepared resin,
which was suspended in concentrated acid
solution, was poured gently into the burette
until it was quarter-full. The level of the liquid
was made sure not to fall below the level of the
resin at any time. The sides of the column were
washed with water once some of the resin
adhered to the sides. The column stopper was
opened in order to allow some of the liquid to
flow out of the column.
A sample of unknown concentration was
procured and placed in a 100-mL beaker.
Using a pipette, 10 mL of the sample was
poured into the prepared column. A 250-mL
Erlenmeyer flask was then placed under the
column as the receiver of the eluate. The
stopcock was opened and adjusted
accordingly until the rate of flow of liquid was
about 30 drops per minute. The remaining
solution was then poured into the column.

Prior to standardization, using a pipette, 100

mL of 1.0 M NaOH was quantitatively
transferred using a pipette into a 1-L
volumetric flask and diluted to mark with
distilled water.

A drop of eluate from the column was caught

on a watch glass and was tested for pH using
pH paper. The column was washed with
distilled water until the pH of the latest drop
of eluate showed a pH equal to that of the
distilled water. The washings and the eluate
were then combined in the same flask. Once
the pH of the eluate was already equal to the
pH of the distilled water, the acid solution was
then titrated with the standardized NaOH
using phenolphthalein as the indicator.

Three sets of the primary standard KHP of

99.8% purity were weighed in different

For the storage of resin, 3.0 M HCl was poured

into the column until the blue color of the resin

METHODOLOGY

disappeared and changed back to the original

yellowish-brown color. The burette was
inverted and the resin with acid was poured to
the original container until all the resin was
transferred.
RESULTS AND DISCUSSION

copper (II) ions were bound to the exchange

sites within the resin. A higher rate of flow
would result in an incomplete exchange
process, wherein less Cu2+ ions are bound to
the sites. A lower rate, however, would be
inefficient as it would require a greater
amount of time to complete the method.

For the column preparation and resin storage,

the resin was soaked in acid in order to supply
the resin with excess amounts of H+ ions that
it required for the exchange of ions. This
process also allows the resin to displace and
free any other bound ions present in the case
it was used previously.

During the column preparation and sample

analysis, the column was washed until the
eluate and the distilled water had equal pH so
that excess H+ ions would not occupy the
pockets of the resin. This procedure ensured
that all the cations have been exchanged
completely with H+ in the resin.

In contrast, the resin was soaked in water

before it was introduced to the ion-exchanged
column in order to allow it to swell. As the
resin swelled, the possible sites of ion
exchange were opened up. The water inside
the resin allowed the ions from the sample to
diffuse into the resin, and reach the bindingexchange sites within the structure of resin,
instead of just the surface.

There are a number of factors that may affect

the efficiency of ion-exchange between the
resin and the solution which is usually
measured by the time of elution. The factors
include: charge, which increases the affinity of
the resin to the ions as it increases; radius,
which decreases the hydration of the resin as
it increases; and pH, as it affects the hydration
of weak acid salts and metal ions.

In addition, water-soluble impurities were

dissolved and the functional groups present in
the structure of resin were ionized as the resin
was soaked in water. These water-soluble
impurities may block the exchange sites in the
resin.

Similarly, the degree of cross-linking of the

resin polymer also affects the exchange of ions
within the column. Resin is known to be
composed of styrene polymers. Cross-linking
must occur between monomers in order to
form a polymer. A high degree of cross-linking
would indicate the presence of less pores and
less exchange sites. Conversely, a low degree
would indicate more exchange sites in the
polymer.

If the resin used was dry, the solution will

occupy the spaces in between the resins,
resulting in a low volume of eluate and
consequently a lower calculated value of total
ion concentration.
The water level was kept above the top of the
resin in order to avoid the formation of air
channels or pockets around the resin particles.
The air bubbles may prevent the access of the
ions from the solution to the column binding
sites. In consequence, these may decrease the
number of available binding sites and the
amount of ions bound to them.
The rate of flow of the column was maintained
at 30 drops per minute to ensure that all

The
standardization
procedure
was
performed in triplicate and upon calculation,
the molarity of the basic titrant was found to
be 0.124 M NaOH. The results of the procedure
are shown in table 1.
The sample analysis was also performed in
triplicate, as shown in table 2, and the total ion
concentration of the sample was determined
to be 783.28 ppm Cu2+ on average. The percent
purity of the sample was calculated to be at
31.33%.

Table 1. Standardization of NaOH

Trial
1
2
1
0.1008
0.1270
Standard
weight, g
Net
volume
of NaOH,
mL
M NaOH

3.85

3
0.1002

5.2

0.128217

Average
M NaOH

3.9

0.119604 0.12582
0.12455

Table
2.
Determination
Concentration
Trial
1
2
Volume of
10
10
sample, mL
Net volume
of NaOH,
mL

2.3

1.1

ppm Cu2+

908.34

434.42

of

Cation
3
10
2.55

1007.07

Average
ppm Cu2+

783.28

RSD

390.82

Confidence
interval

783.28 759.99

The relative standard deviation and

confidence intervals, also shown on table 2,
were computed to be 390.82 and 783.28
759.99, respectively. These calculated
statistical values indicate poor precision in the
procedure due to errors.
The errors could have been from the
subjectivity in the titration using the
phenolphthalein endpoint, erroneous pH

measurement, presence of other substances in

the solution which may have interfered with
the exchange of ions or the presence of air
pockets in the burette as an improvised ionexchange column.
SUMMARY AND CONCLUSIONS
The copper (II) concentration of the unknown
sample was determined using the method of
ion-exchange chromatography. The NaOH
titrant was standardized using KHP as the
primary standard and phenolphthalein as the
indicator.
The sample was made to run through an ionexchange column with resin. The column was
washed until the pH of the latest eluate drop
was equal to the pH of the distilled water. The
eluate and the washings were then titrated
with the standardized NaOH titrant and
phenolphthalein indicator.
The average concentration of Cu2+ was
calculated to be 783.28 ppm. It was then also
determined that the sample was only 31.33%
Cu2+.
REFERENCES
[1] Skoog, D., & West, D. (2013).
Fundamentals of analytical chemistry (9th
ed.). Fort Worth: Saunders College Pub.
[2] Harvey, D. (2000). Modern analytical
chemistry. Boston: McGraw-Hill.
[3] Ion Exchange Chromatography &
Chromatofocusing. (n.d.). Retrieved May 5,
2015, from http://www.gelifesciences.com/
gehcls_images/GELS/RelatedContent/Files/1
314823637792/litdoc11000421_201409262
35100.pdf

APPENDIX A DATA
Standardization of Sodium Hydroxide Solution
Trial
1
1 Standard weight, g
0.1008
Net volume of NaOH, mL
3.85
M NaOH
0.128217
Average M NaOH

2
0.1270
5.2
0.119604
0.12455

3
0.1002
3.9
0.12582

Determination of the Total Cation Concentration

Trial
1
Volume of sample, mL
10
Net volume of NaOH, mL
2.3
ppm Cu2+
908.34
Average ppm Cu2+
RSD
Confidence interval

2
10
1.1
434.42
783.28
390.82
783.28 759.99

3
10
2.55
1007.07

APPENDIX B CALCULATIONS
1. Standardization of NaOH
Trial 1
1
1
1
0.1008

0.998
204.2 1 0.00385
= 0.12796
Trial 2
1
1
1
0.1270

0.998
204.2 1 0.00520
= 0.11936
Trial 3
1
1
1
0.1002

0.998
204.2 1 0.00390
= 0.12557
Average
0.12796 + 0.11936 + 0.12557
= 0.12430
3
2. Determination of total cation concentration
Trial 1
0.12430
1
1 +
1 2+
0.0023

1 1
2 +
2+
2+
63.546
1000
1

= 908.34 2+
2+
2+
1
1
0.010
Trial 2
0.12430
1
1 +
1 2+
0.0011

1 1
2 +
2+
2+
63.546
1000
1

= 434.42 2+
2+
2+
1
1
0.010

Trial 3
0.12430
1
1 +
1 2+
0.00255

1 1
2 +
2+
2+
63.546
1000
1

= 1007.07 2+
2+
2+
1
1
0.010
Average
908.34 + 434.42 + 1007.07
= 783.28 2+
3
3. Percent purity
783.33 2+
1
(

0.01 )

1000
100% = 31.33%
2500 2+
1
(

0.01 )

1000
4. Relative standard deviation
2
2
2
(908.34 783.28 ) + (434.42 783.28) + (1007.07 783.28 )
2
1000 = 390.82
783.28
5. Confidence interval
(908.34 783.28 )2 + (434.42 783.28)2 + (1007.07 783.28 )2
(
) (4.30)
2
783.28
3
= 783,28 759.99