QUANTITATIVE DETERMINATION OF TOTAL ION

CONCENTRATION BY ION EXCHANGE

Chemical analysis has long been an interest, and this interest lead to the
development of different made especially for separation of substances. This
experiment aims to show how Ion Exchange Chromatography works. The
concentration of the metal ion being studied was also calculated as well as its
percent purity. This experiment used a burette as an improvised ion exchange
column. Dowex 50, a strong acid cation exchanger was used as the stationary
phase, distilled water as the mobile phase, and the 10 mL of CuSO 4 which was the
analyte was pipetted into the column. Continuous washing was of the resin was
done using a distilled water until the pH containing the eluate was nearly equal to
pH 7. It was titrated with 0.1004 M NaOH. After calculations the cation
concentration was 0.7343 ppm. The RSD value obtained was 0 and the confidence
interval measured was 0.7343 + 0, and the calculated percent purity was 50.93%.
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INTRODUCTION
The classical titrimetric and gravimetric methods have been essential to analytical
chemistry. Analytical methodologists have been advancing their chemical analysis
since the twentieth century, and this advancements lead to the development of
instrumental methods for analysis. Chromatography is an instrumental method that
separates, identifies, determines and quantifies the chemical components of a
mixture. In general, chromatography can be planar meaning that it uses a porous
paper support, or chromatography may be columnar meaning it uses a narrow tube
support. The set up is composed of a stationary phase that is fixed in as the support
and the mobile phase which moves through the stationary phase. [1]
Among all of the techniques for chromatography, the
ion
exchange
chromatography is considered to be a versatile method that is very useful for the
separation of ions that have similar properties. It is also called the column technique
because the material for the ion exchange is usually packed into the column. Elution
chromatography is one columnar chromatography technique that involves washing
the solute through a stationary phase by quantitative additions of a mobile phase.
The basic process of chromatography using ion exchange is eluent loading, sample
injection, separation of sample, elution of analyte A and B. Elution is the process

where a compound is moved through a column. This the the solution used as the
solvent, also known as the eluent is constantly pumped through the column. [1]
The term ion exchange refers to the separation techniques in analytical chemistry
that allows different ionic materials to be selectively retained on an ion exchange
resin. It is described as the process of reversible stoichiometric exchange of ions of
the same charge. This is between a mobile liquid phase and an insoluble
stationary solid phase. An ion exchanger is an insoluble material that liberates
the mobile ions through electrolytic dissociation.
As mentioned above, a resin is used when doing an ion exchange chromatography.
Resins are also known as polymers, they are insoluble material larger than other
compounds. It is made of exchangeable ions at different sites in a polymer chain.
Functional groups, usually made of sulfonic acids for cations and trialkylamines for
anions and are attached to the polymer chain. [1]
This experiment aims to understand the principles of ion exchange chromatography,
its use as a separation technique and determine the purity Cu 2+ sample using this
specific technique.
METHODOLOGY
Before introducing the cation exchange resin (Dowex 50) to the ion-exchange
column, the resin was already soaked in water and concentrated acid. An ionexchange resin is very spherical made from an ionic polymeric material that is
insoluble in water, but has an exchangeable ion at several exchange sites. It is
important to have the resin soaked in water for an hour first because of the
presence of water-filled channels inside the beads. They allow for the waters of
hydration to become part of the bead structure hence they play a critical role in ion
exchange. This water allows ions in the eluent to migrate through a continuity of
water molecules so that exchange can take place with the functional groups inside
the resin bead. The water level must be maintained above the resin. A dry resin
cannot be used because they will crack and break which will cause non-uniform
spaces between the beads. Consequently, blockage and channeling will occur that
will cause ineffective ion exchange due to limited contact time between the eluent
and that will lead to band spreading resulting in poor separation, or cross
contamination of the eluted ionic species [1].
The column was prepared by placing a wad of absorbent cotton at the bottom of a
clean 50 mL burette that should still allow liquid to flow at a controllable rate. Onefourth of the burette was filled with the prepared resin as it is suspended in HCl in
order to regenerate the cationic resin to replace any bound ions and replenish the
supply of the hydrogen ion. Thus, this step would make the resin exclusively
covered in hydrogen ions. The level of the liquid should not fall below the resin level
at any time because this usually causes channels to develop in the resin column
and greatly reduces its efficiency, as explained earlier when a dry resin is used [2].

Distilled water is added into the column to wash the excess acid until the pH of the
latest drop of eluate is equal to the pH of the distilled water being used. Excess acid
should be removed in order to obtain an accurate [Cu 2+] for the selectivity
coefficient, Kd. If the excess acid is not removed, the excess H + will be read as the
hydrogen ions displaced by the exchange ion, thus reflecting a higher concentration
of Cu2+. Once the both pH are equal, the column is ready for use to determine the
total cation concentration of Cu2+ (CuSO4).
Ten mL of the sample (CuSO 4) was poured into the prepared column(burette). A 250
mL Erlenmeyer flask was placed under the burette as receiver of the eluate. The
solution was allowed to flow at about 30 drops per minute. This controlled flow rate
ensures that effective diffusion into and out of the ion exchange beads can occur
[1]. However, it would be impractical if the flow rate is too slow since it would take a
longer time. Then, the column was washed with distilled water until the pH of the
eluate is equal to the pH of the distilled water used to ensure that all displaced H +
are removed, hence an accurate [Cu2+] for Kd. The eluate and the washings were
combined in the same Erlenmeyer flask. Once the pH eluate is equal to the pHdistilled water,
collection of the eluate is stopped and the acidic solution is then titrated twice with
standard 0.1000 M NaOH solution using phenolphthalein. This is done to know the
total Cu(II) concentration in the sample solution.
After performing titration, 3.0 M HCl solution is poured into the column to replace
the copper ions with H+ and move the ions down the column. It is also done to
regenerate H+, the same as when HCl was added to the column during the
preparation of the resin. It is important to note however that Cu(II) ions displace H+ ions when
a resin in the hydrogen form is exposed to a copper sulfate solution. However, the reverse happens when a
resin in the copper form is exposed to hydrochloric acid. This is because of the higher concentration of
HCl. Diffusion takes place due to chemical potential where ions migrate from a region of solution of
higher concentration to a region of solution of lower concentration [1]. Finally, the remaining resin
with the acid was transferred to the original container.
RESULTS AND DISCUSSION
After two trials of titrating the NaOH solution to the copper solution the following
results in table 1 were obtained.
Table 1. Determination of Total Cation Concentration

Trial

Volume of 10
Sample, mL

10

Final

4.6

2.3

Volume of
NaOH, mL
Initial
0
Volume of
NaOH, mL

2.3

Net Volume 2.3

2.3

The balanced exchange reaction between resin and copper sulfate is:
2RSO3-H+ + Cu2+ + 2H2O -> (RSO3)2Cu + 2H3O+
Two hydrogen ions are replaced for every copper ion. As the small amount (10.00
mL) of CuSO4 solution is used and washed down the column with distilled water, the
exchange between Cu2+ and the bound H+ is evident in the appearance of the blue
stationary adsorbed band at the top of the resin. A narrow and concentrated band
was observed which reflects a lower value of K d. The larger the size of the
equilibrium constant, the better retained the ion will be on the resin [3].
The factors that affect ion exchange between the resin and the solution that were
discussed earlier are concentration and flow rate. However, other factors that may
also affect this ion exchange. First, the larger the charge of the ions being analyzed
then the greater the affinity of the resin. The higher charged ion will take longer to
be analyzed because of its attraction to the resin. the ion exchange between Cu 2+
and H+ explains that polyvalent ions are much more strongly retained than singly
charged species. Differences in the values of K are also related to the size and ionic
charge of the hydrated ion [3]. For a typical sulfonated cation-exchange resin,
decreasing values of K are given in the order: Zn 2+ > Cu2+ > Ni2+ > Co2+ for divalent
cations while Ag+ > Rb+ > Cs+ > K+ > NH4+ > Na+ > H+ > Li+ for univalent ions [4].
Second, the size is also a factor such that for cations of the same charge the affinity
is inversely proportional to the radius of the hydrated ion [5]. Simply, the larger the
size of the ion the greater its affinity for the resin.
Third, in this experiment, only one ion (Cu 2+) is analyzed with the ion-exchange
chromatography. However, when two or more ions are analyzed the degree of crosslinking could affect ion selectivity. The acidic cation resin used has a high degree of
cross-linking which means it has a smaller pore size. Hence it has less exchange
sites and the resin made more selective towards smaller ions and diffusion would
become less rapid than that with low degree of cross-linking [4].

Although the resin used has less exchange sites, the ion exchange process was
done in a short amount of time because ion exchange is done most rapidly when
the sample solution is very small.
Fourth, pH could be a factor. However, the sulfonic acid resin used was not buffered
as compared to weak acid resins because it is a strong cation exchanger that has a
working pH range of 1 to 14. In all pH, they are fully dissociated and will exchange
its protons for other cations [1].
The total Cu(II) concentration was calculated using the molarity of NaOH computed
from a past experiment and the amount of titrant used to determine the mg of
Cu(II) and dividing it by the liters of the solution to get the ppm of the copper. The
calculated ppm of Cu(II) was 0.7343 ppm. Using the ppm the percent purity that
was calculated was 50.93% purity.
SUMMARY AND CONCLUSIONS
After the standardization of NaOH with primary standard KHP the calculated
concentration was 0.1004M.
After excessive washing of the resin to have the pH of the distilled water to be the
same as the eluate, a small volume of copper solution was added to the column.
Two trials of titration of NaOH to the copper solution was done and the amount of
titrant used for both trials was 2.3mL. Using the calculated molarity of NaOH and
the volume of the titrant the concentration of Cu (II) was 0.7343 ppm. With this data
the percent purity was then calculated and the value measured was 50.93%.
There was no longer a need to perform a Grubbs test as there was no outlier. The
RSD was calculated to be 0 and the confidence interval was 0.7343 to 0.7343.
One of the errors in the experiment that was observed was over titration. Although
the same volume of titrant was used for the second trial, it resulted to over titration.
Other sources of error include the addition of liquid in the column below the resin
level at some time. Another is if the pH of the eluate is checked in the receiving
flask instead of the latest eluate drop. Misreading of the pH with the colors indicated
for a specific pH is another source.
REFERENCES
[1] http://www.epa.gov/ogwdw000/radionuclides/training/transcripts/tutorial_3.4.pdf
[2] Chem122Lab1.pdf.16.
[3] Skoog, D., West, D., Holler, F., Crouch, S., 2014. Fundamentals of Analytical
Chemistry (9th ed.). Belmont: Brooks/Cole, Cengage Learning. 859.

[4] Harris, D., 2010. Quantitative Chemical Analysis (8th ed.). New York: W.H.
Freeman and Co. 636.
[5]https://bchem.files.wordpress.com/2010/03/material-guia-en-clase-no1intercambio-ionico1.pdf

APPENDIX A - LIST OF TABLES

= 0.0994M

M NaOH = 0.10g KHP x 1 mol KHP x 1 mol NaOH x .995

= 0.1014M

AVE M = 0.0994 + 0.1014 / 2 = 0.1004M

x 0.1004M x 1 mol CuSO 4 x 1 mol Cu2+ x

2 mol NaOH
0.010L
= 0.7342734463 ppm Cu2+

1 mol CuSO 4

63.546g

1 mol Cu2+

1g

TRIAL 2
2.3 mL x 1L
1000mg
1000mL

x 0.1004M x 1 mol CuSO 4 x 1 mol Cu2+ x

= 0.7342734463 ppm Cu2+

1 mol CuSO 4

63.546g
1 mol Cu2+

x
1g

{[2.3 mL x (L/1000 mL) x (0.100478181 mol/L) x (mol CuSO 4/2 mol NaOH) x (1 mol
Cu2+/1 mol CuSO4) x (63.546 g/mol Cu2+) / (L/3.605 g)]
[(10 mL) x (L/1000 mL) x (3.605 g/L) x (mol CuSO4/159.11 g) x (mol Cu 2+/mol
CuSO4) x (63.546 g/mol Cu2+)]} x 100
= 50.92836875 %