DETERMINATION OF TOTAL ION CONCENTRATION USING ION

EXCHANGE CHROMATOGRAPHY

A.O. DE LA SERNA
INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
OCTOBER 1, 2010

ABSTRACT

This affirms the importance of the employment of ion exchange chromatography, including its concept of
isocracy and electroneutrality, resin polymerization and sulfonation, stoichiometric ratio, hydration and
particulates, in chemical analysis and determination of total ion concentration of Cu II in samples
provided by instructor. This report discusses basic mechanisms and materials of specifically cation
exchange columnar chromatography. Dowex 50 cation exchange resin was the stationary phase and the
solvent containing the analyte ion was the mobile phase. IC conditions were kept paramount during the
duration of the experiment. 10 mL of the analyte sample was then eluted to the preconditioned column for
three trials. Per trial, the eluate was allowed to flow to a fresh Erlenmeyer flask until its pH = 5. This
fresh pool was then titrated with previously standardized sodium hydroxide NaOH against a primary
standard KHP. Cu2+ concentration in ppm was then calculated using the titrimetric data. The actual
concentration was 1250 ppm Cu2+, the entire class reported a substantially accurate experimental value –
1260 ppm Cu2+ of 0.8% error. The highly accurate value affirms the feasibility of IC as a means of
determining total ion concentration.

INTRODUCTION is fixed in the support and the mobile phase that

The classical titrimetric and gravimetric
methods have long been solely tantamount to
analytical chemistry until the early Twentieth
century. Chemical analysis is such a trending
pursuit that analytical methodologies have been
advancing exponentially. [1] Hence, instrumental
methods for analysis were developed. This
report features ion exchange chromatography as
a chromatographic instrumental method for
analytical chemistry and as a separation science.
Chromatography, as an instrumental method,
separates, identifies, determines and quantifies
the chemical components of a mixture.
Methodologically, it can be planar using porous
paper support or columnar using narrow tube
support. It is composed of a stationary phase that
moves through the stationary phase.
Elution chromatography is one columnar
chromatography technique involving washing
the solute through a stationary phase by
quantitative additions of the mobile phase. [2]
In 1850, forty years prior to Arrhenius’ proposal
of the ionization theory, a primordial notion
about ion exchange was discovered by two
Englishmen, J.T. Way and H.S. Thompson. The
concept was described by the liberation of
Calcium and Magnesium ions by treating earths
with ammonium sulfate. Ion exchange is a
meristem henceforth. [3]
The impeccable promise for analysis of the ion
exchange concept underwent further harnessing.
It was inculcated and formally tagged in
chromatography in 1905 by M. Tswett. [3] The
term “ion chromatography” has then been
shortened by the common usage of the acronym
IC. It has become a formidable advancement
after its formalization as a novel analytical
method by Small, Stevens and Bauman of the
Dow Chemical Company. The technique was
then commercialized in 1975 by the Dionex
Corporation, the leader of ion-exchange
equipment today. [4]
The experiment aimed to determine the
concentration in ppm of Cu2+ in a given sample
using IC as a separation technique. In the
experiment, Dowex 50 cation exchange resin
was the stationary phase and the solvent
containing the analyte ion was the mobile phase.
A column previously inserted with a wad of
absorbent cotton for resin support and packed
with sulfonated resin was kept hydrated with
distilled water washings in an improvised IC
burette tube. A flow rate of 15 drops per minute
was maintained by precise manipulation of the
stopcock. The mobile phase was allowed to flow
until the pH of the eluate = pH distilled water =
pH of 5. These particulates are discussed
intently in the remainder of this report. 10 mL of
the analyte sample was then eluted to the
preconditioned column for three trials. Per trial,
the eluate was allowed to flow to a fresh
Erlenmeyer flask until its pH = 5. This fresh
pool was then titrated with previously
standardized sodium hydroxide NaOH against a
primary standard KHP. Cu2+ concentration in
ppm was then calculated using the titrimetric
data.
The copper cation was separated from the
sample at par with the displacement of hydrogen
protons from the column. Separation is made
possible by the adsorption of charged analyte
molecules to immobilized resin ion exchange
function group of opposite charge. The displaced
ions from the column exist in a stoichiometric
ratio or factor with the analyte ion. [1] Hence, the
displaced ion will be titrated and the calculated
amount multiplied by the said propagated ratio
or factor will be the amount of analyte
constituents. There is an exchange of ions,
hence the name, “ion exchange
chromatography”.
An intent discussion about IC, its processes,
chemical concepts, stoichiometric calculations
for analysis, limitations, conditions, separation
phases and other particulates are found in the
remainder of this report.
Be guided that the discussions give more
emphasis on cation exchange columnar
chromatography as it has been employed
throughout the course of the experiment.
RESULTS AND DISCUSSION
As its name suggests, ion exchange
chromatography is a chromatographic science
concerned with the separation of various type of
charged species in a system. This system is
usually comprised of separate phases. Since it
explicitly meddles with ion exchange, to
maintain the ionic integrity of the system, a
stoichiometric reaction must be paramount at all
analyses. [1]
To further substantiate and affirm the
importance of this stoichiometric ionic reaction,
look intently to these chemical equations
(a) nrSO3 – H+ + Mn+ (rSO3)nM + nH+
(b) 2rSO3 – H+ + Cu2+ (rSO3)2Cu + 2H+
(c) 2H+ + 2OH-  2H2O
Equation (a) shows the general chemical
reaction in cationic exchange. (Anionic
exchange works analogously except that OH -
species are involved, not H+). nrSO3 – H+ refers to
the sulfonated cation exchanger resin, M n+refers
to the metal / cation analyte species, and H +
refers to the displaced proton ion. Most
importantly, n refers to that stoichiometric
factor, the defining number in our calculation.
Equation (b) is the particular reaction in the
experiment. Dwelling on the stoichiometry of
the equation, for every 1 mole of copper II
species, 2 moles of the cation exchanger reacts,
therefore, 2 moles of H+ are displaced. These
displaced H+ are then titrated with any strong
base, NaOH for example, and both species react
with each other in one-to-one correspondence.
Therefore, twice the amount of OH- and
transitively twice the amount of H+ , is equal to
one amount of Cu 2+
Analogously, thrice of an amount of H + is equal
to one amount of Aluminum 3+. All of which can
be explained by the interplay of ionic charges
during the stoichiometric reaction.
Now grounded to the notion that the calculations
are dependent on that stoichiometric ratio, this
working equation for determination of the
amount of Cu2+ concentration in a given sample
is derived:
(d)Ppm Cu2+ =
Now we have a stoichiometric foothold for the
ion exchange process, we are now ready to look
intently on the explanations of the materials and
mechanism of IC at par with the experiment
performed (cationic exchange columnar
chromatography).
Standard Conditions. Prior to conducting the IC,
a set of parameters must be paramount and
maintained throughout the duration of the
experiment. That is why a pH of 5 (the pH of
distilled water must be observed. A pH of 5
means that the system is isocratic and therefore
is highly deprotonated from H+ after the cation
exchanger has fully reacted with the cation
analyte (all H+ have been displaced and are now
ready for titration with strong base). [4]
Isocracy or electroneutrality. The stationary
adsorbent phase or the site of exchange, the
column of resins, must be solvated with
deionized and distilled water. [4]
Ultrapure Reagents should be used in cleaning
the IC tube. Impurities can accumulate on the
column which reduce the ion exchange capacity
and reacts drastically with the system chemicals.
[4]
Flow rate should occur between 0.7 and 4.5 mL
or 15 drops per minute. Flow rate is crucial for
the ion exchange to take place. Water is the
medium for reaction. Rapid flow will never
assure the optimum completion of the reaction
and the total liberation of H+. A modest rate of
flow neutralizes the turbulence and high fluid
pressure at the narrow end of the tube. [3]
Resins. The resin used is Dowex – 50. Cation
exchanger contain sulfonic acid groups nSO3 – H+
attached / chelated to the aromatic ring of
insoluble inorganic molecule nR.[5] Gel-based
resins are produced by polymerizing with
usually styrene-divinylbenzene S-DVB
copolymer. The cross linkages with the
copolymer give the resin physical strength to
withstand subsequent ion reactions. The
spherical shape narrows particle size allotment.
The polymerization yields inactive resins and
must be activated. [4]
Sulfonation by nrSO3–. Inactive resins have
hydrophobic spheres and must be introduced to
sulfonic acid nrSO3 – to expose the functional
hydrophilic sites for exchange. As the resins
react with the acid, water forms and swells the
beads making it a suitable medium for reaction.
Other acids like carboxylic acid and other bases
like quaternary ammonium can functionalize
resins. [4] Notice that a resin functional group is
written with H+ written posteriorly (nrSO 3 – H+).
This shows that the resin is activated and the H+
are now ready to be exchanged with another
cation species. The resins are also perforated
with micropores for liquid pathways to increase working equation (d), the concentration of Cu 2+
surface area of adsorption. These pores are in ppm was determined per sample. See
generated by poragens like toluene. appendix B, table 2 for detailed titration data of
trials 1, 2 and 3 per group.
Regenration of cationic resin exchangers by 2M
H2SO4. Sulfuric acid is such a strong acid that it Table 3. Cu 2+ppm per group
prolongs the activity of the cation exchanger.
Divalent and Trivalent organic and carboxylic
are more strongly held making them a less
activator for the resins. Their stronger cohesion
prevents the resin ions from approaching the ion
exchange sites. [4] Transition ions from the
previous usage of the resin might still be left in
the column. Sulfuric acid displaces these cations
as explained by IC mechanism making the
column isocratic and ready for another usage.

Addition of water. The resin must be hydrated at

Statistics. The actual concentration per 10 mL
all times. Water level should not fall below the
sample was 1250. Table 4 shows the percent
resin level. Aside from maintaining the isocracy
error of the experimental ppm value per group.
of the system, water solvates the system and
serves as a suitable medium for reaction to take
place. It also displaces entrapped gases. [4] The
air pockets cause pulsations in the flow and may Table 4. the percent error of the experimental
react with the resins forming altered canals. ppm value per group.
These canals cause apparent loss in column
capacity and adsorptive power.

Liberation of H+. Since the aforementioned

discussion states that ion exchange explicitly
depends on the ionic interactions, therefore, the
ionic interactions are functions of ionic strength.
Separation is possible due to the differences in
ionic strength. Transition metals like Cu 2+ has
greater ionic affinity with the sulfonic acidic
functional group of the cation exchanger than
H+, therefore, H+ is eluted first.

Titration. As mentioned, the liberated H+ are

titrated with a strong base, NaOH to determine Each group has less than 10% error. This further
the concentration of Cu 2+. Table 1 shows the affirms the feasibility and accuracy of IC in total
standardization data of titrant NaOH of all the ion concentration determination. Appendix C
groups. shows detailed data of statistics per group.

It is grounded on the stoichiometric ratio that 1 Limitations of IC. Like any other instrumental
mole Cu2+ = 2 moles H+. Therefore, using the method and as a still growing chromatographic
science, IC is assailed with a few limitations.
Table 5 lists ions yet analyzable by IC
Table 5. Ions yet analyzable by IC
Not Yet Analyzable
Isocyanite derivatives
Silicate
Large Phosphonates
Nitrilotriacetic acid
EDTA
Ethylenediamine
Toluenediamine
One notable disadvantage is that IC is costly.
The class improvised a burette type IC tube.
Amidst the greater accuracy than that of
classical methods, IC, like any other
instrumental titration, has many demands and
conditions to be observed.
An IC setup may encounter chromatographic
anomalies. An example is water dip, otherwise
known as carbonate water dip. There are also
minor shifts in retention and calibration curves.
Temperature must also be kept constant since
minor fluctuations can alter the ionic kinetic
energy. There are times that to maintain the
isocracy, a buffer is needed. However, buffer
may react with the resin or even the solvent
containing the analyte. The method provides no
direct information on events occurring at the
surface of the stationary phase, because the ion-
exchange equilibrium is always determined by
the balance between the H+ and analyte ion
interaction with active sites of a resin. Impurities
may also affect the data. These limitations may
have lead to these statistical deviations.
However, the standard deviations per group are
very minimal and can still substantiate the
feasibility of IC. Appendix C shows more
statistical data including standard and relative
standard deviations and confidence intervals.
The standard deviations were pooled and the
average ppm was computed. Table 6 shows the
overall class statistics.
Table 6 shows the overall class statistics.
The class got a low percent error with respect to
the actual concentration of 1250 ppm. The class
garnered a value of 1260 ppm (0.8% error). The
pooled sd is also substantially low, meaning, the
class got precise measurements. The actual
concentration of the Cu2+ lies in the interval
1260±7.59 ppm.
SUMMARY AND CONCLUSION
Upon intent analysis of the data, it can be
concluded that since the class has a very small
amount of pooled standard deviation (9.86ppm),
the class garnered a very precise result. The
class got an accurate result basing on the
substantially low percent error of 0.8% with the
reported class value of 1260 ppm. It can be
induced that the interval in which, taking into
account the confidence level, the value of the Cu
2+
concentration from finite number of sources
lies is in 1260±7.59 ppm.
The veracity and feasibility of IC can be
affirmed basing from the experiment results. It
can be concluded that the total ion concentration
can be accurately determined via IC, and that the
mechanism of isocracy of ionic charges and
stoichiometric ratio are of vital importance for
calculations involving IC. The highly accurate
value affirms the feasibility of IC as a means of
determining total ion concentration.
REFERENCES
[1] Dyer A., Hudson MJ.,et al. 1993. “Ion
Exchange Processes: Advances and
Applications”. The Royal Society of Chemistry.
[2] Skoog D., West D., et al. 1996. [4] Smith, Frank. 1983. “The Practice of Ion
“Fundamentals of Analytical Chemistry, 7th Chromatography”. Wiley-Interscience
Edition”. Saunders College Publishing Publications

[3] Walton, Harold. 1976. “Ion Exchange [5] Ballesteros J., Caleja HJ., Carillo KJ.,et al.
Chromatography”. Dowen, Hutchinson & Ross, 2009 ed. “Analytical Chemistry Laboratory
Inc. Manual”. University of the Philippines –
Diliman, Institute of Chemistry.