Experiment 13.

QUANTITATIVE DETERMINATION OF TOTAL ION CONCENTRATION

BY ION EXCHANGE CHROMATOGRAPHY

Chem 26.1 WFQR1

Mandaing, Shejay G.
15 March 2013

Introduction
Chromatographic techniques have been valuable in the separation and analysis of highly
complex mixtures and revolutionized the capabilities of analytical chemistry. These techniques
involves the physical method of separation in which the components to be separated are
distributed between two phases, one of which is stationary (stationary phase), and the other
which moves in a definite direction (mobile phase). Ion exchange chromatography is one of
these techniques, which uses an ion exchange resin as stationary phase (Christian, 2004)
Cation-exchange resins contain acidic groups, while anion-exchange resins contain basic groups
(Skoog, 2004). In this experiment, the total ion concentration of Cu (II) from a provided sample
was determined using cation ion exchange column chromatography. A wad of absorbent cotton
was placed at the bottom of a clean ion-exchange column (in this case a burette was used as
the column). A prepared Dowex 50 cation exchange resin was gently poured to the column
while suspended in the concentrated acid solution until ¼ of the column was filled up. The
stopper was opened to allow some liquid to flow out and the excess acid was washed out of the
column with distilled water until the pH of the eluate was equal to the pH of the distilled water
being used. This was checked using pH paper. To determine the total cation concentration of
the unknown sample, a 16 mL aliquot of the sample was diluted to 50 mL. 10 mL of this
working solution was poured into the column and an Erlenmeyer flask was placed under the
column to collect the eluate. The stopcock was opened until the rate of the flow of the eluate is
about 30 drops per minute. The column was washed with distilled water until the pH of a drop
of the eluate is equal to the pH of the distilled water being used. The washings and the eluate
were combined in the same Erlenmeyer flask, which was then titrated with the standardized
sodium hydroxide (NaOH) solution, using phenolphthalein as indicator (ACAG, 2012).
Results and Discussion
Table 1 below shows the data obtained from the standardization of NaOH. From these data
obtained, the average concentration of NaOH was calculated from the stoichiometric reaction of
NaOH with KHP as follows:

NaOH + KHP NaKP + H2O (1)

Table 1. Standardization of Sodium Hydroxide

Trial 1 2 3
Primary standard weight, g 0.1 g 0.0999 0.1026
Final volume of NaOH, mL 3 6 9.2
Initial volume of NaOH, mL 0 3.1 6.1
Net volume of NaOH, mL 3 2.9 3.1
M NaOH 0.1624 0.1679 0.1613
Average M NaOH 0.1639
This average concentration was then used to calculate the equivalent moles of H+ from the
volume of NaOH used in titration througt the stoichiometric reaction:

2OH- + 2H+  2H2O (2)

Now, the equivalent moles of Cu2+ can be calculated from the number of moles of H+
following the equation
2rSO3 – H+ + Cu2+ (rSO3)2Cu + 2H+ (3)

which shows that for every 1 mole of Cu2+, 2 moles of H+ are displaced.

Table 2 gives us the computed confidence interval and RSD for the data results. The calculated
experimental Cu(II) concentration of ppm showed a deviation from the theoretical
value of ppm of Cu(II). This gives us a percentage error of % for the
experiment.
Table 2. Determination of the total cation concentration
Trial 1 Trial 2 Trial 3
Volume of sample, mL 50 50 50
Net volume of NaOH, mL 2.175 2.075 2.2
[H+], mol 3.56 x 10^-4, 3.401 x 10^-4, 3.6058 x 10^-4,
[Cu2+] , mol 1.78 x 10^-4 1.700 x 10^-4 1.8029 x 10^-4
2+
Average [Cu ] , mol 1.7953 x 10^-4,
RSD
Confidence Interval

Answers to Questions
1. Discuss the basic principles of ion-exchange chromatography.
All chromatographic techniques are based on an equilibrium between stationary and mobile
phase. In ion exchange chromatography, a small volume of sample is placed at the top of the
column which is filled with chromatographic particles (stationary phase) and solvent as it is
moved along the column(Christian, 2004). Here, the stationary phase is a porous, essentially
insoluble solid that is exchanged for ions in the sample solution that is brought into contact with
the solid stationary phase, usually an ion exchange resin. This synthetic ion-exchange resin is a
high-molecular-weight polymer that contains a large numbers of an ionic functional group per
molecule. A Cation exchange resin contains acidic groups, while anion exchange resins have
basic groups (Skoog, 20040). Anions such as —SO3- or cations such as —N(CH3)# 3 are
covalently attached to the resin and solute ions of the opposite charge are attracted to the
stationary phase (Harris, 2010). In cation exchange, the resin contains acidic functional groups
added to its aromatic ring. The strong-acid cation excahngers have sulfonic acid groups-SO3H,
which are strong acids much like sulphuric acid. The protons on these groups can exchange
with other cations (Christia, 2004). The exchange reaction that is followed by the cation
exchange is given by:

xRSO-3H+ + Mx+  (RSO-3)xMx+ + xH+ (4)

(Skoog, 2004)

where Mx+ represents the cation, R represents that part of a resin molecule that contains one
sulfonic acid group, and x is the number of moles of ion or charge equivalent (Skoog, 2004). As
the components of the sample solution are carried through the stationary phase by the flow of
a mobile phase, the separations are based on differences in migration rates among the mobile
phase components (Skoog, 2004). Elution is process by which the eluent (the solvent used to
carry the components of the sample)enters the column and is washed through a stationary
phase(fixed in place in the column) by the movement of a mobile phase(the one that moves
over or through stationary phase, carrying with it the analyte). The mobile phase that exits the
column is called the eluate. The column consists of a narrow tubing packed with a finely
divided inert solid that holds the stationary phase on its surface. The mobile phase occupies the
open spaces between the particles of the packing. Initially, a solution of the sample containing
A and B in the mobile phase is introduced at the head of the column. At the start, the two
components distribute themselves between the mobile and stationary phase. Elution then
occurs by forcing the sample components through the column by continuously adding more of
the fresh mobile phase. Further addition of solvent, can carry solute molecules down the
column in a continuous series of transfers between the two phases. Because solute movement
can occur only in the mobile phase, the average rate at which the solute migrates depends on
the fraction of time it spends on that phase. Solutes that are strongly retained by the
stationary phase have slow rate and fast when its retention in the mobile phase is more likely.
Ideally, the resulting differences in rates causes the components in a mixture to separate in to
bands or zones along the length of the column. Isolation of the separated species is then
accomplished by passing a sufficient quantity of mobile phase through the column to cause the
individual bands to pass out the end (to be eluted from the column), where they can be
collected or detected (Skoog, 2004).

2. What are the factors that can affect ion-exchange?

Length and width of the column. Band broadening is inevitable while addition of more mobile
phase in the column takes place. However, this can be lessened if the column width is kept at a
shorter radius. While, separation of bands or zones will be better if the column length is kept
long.

The relative rates at which the two species are eluted, which is determine by the ratio of the
solute concentration in each of the two phases (stationary and mobile) also affects the ion-
exchange since the two species can be better separated if the differences between their rates is
quite appreciable.
The retention time in both phases also affects ion exchange because this affects the elution
rate. If one ion has more retention time in the stationary phase, then it is eluted more slowly
and vice versa, while the other will be eluted more rapidly while travelling down the column.

The selectivity of the resin to the ions also affects ion exchange because this as well contributes
to retention time in the stationary phase.

A proper balance of intermolecular forces among the analyte, mobile phase, and stationary
phase I also required for a success in the separation process. These IMF are described
qualitatively in terms of the relative polarity possessed by each of the 3 components. As a rule,
most chromatographic separations are achieved by matching the polarity of the analyte to that
of the stationary phase, a mobile phase of different polrity is then used. This procedure is
generally more successful than in the one wherein the polarities of the analyte and the mobile
phase are matched but are different from that of the stationary phase. Because here, the
stationary phase, often cannot compete successfully for the sample components and retention
times then become too short. But if the polarity of analyte and stationary phase are too much
alike, retention time become extraordinarily long (Skoog, 2004)

The distribution equilibrium is described by the distribution constant

Kc= [Xs]/[Xm] (5)

where Xs is the solute concentration in the stationary phase and Xm I the solute concentration
in the mobile phase. Kc is governed by the temperature, type of compound, and the stationary
and mobile phase. Solutes with large Kc will be retained more strongly by stationary phase
than those with small value. The result is that the latter will move along the column (be eluted)
more rapidly. Because true equilibrium between the two phases is not truly achieved, there will
be some lag of the analyte molecules between the two phases which depends on the flow rate
of the mobile phase and on the degree of interaction with the stationary phase and results in
band broadening(Christian, 2004).
Lastly, the greater the cross linkage of the resin , the greater the difference in selectivities.
Crosslinkage increases the rigidity of the resin, reduces swelling, reduces porocity, and reduces
the solubility of the resin.(Christian, 2004)

3. Why was resin soaked in water for an hour before introducing to the ion-exchange column?

Why can’t a dry resin be used?

The resin was soaked in water to lessen its concentration and to allow more solute from the
concentrated acid to later enter its pores. We should note that because resins are made of
polymers with high molecular weight, it would not dissolve in water. Dry resin cannot be used
because formation of air pockets will cause an uneven flow and poor efficiency of ion-exchange.
Also, in order for the ion-exchange reaction to occur, the ions must be subjected to an aqueous
environment.

4. Why was the water level kept above the top of the resin?
The liquid level of the ion-exchange was kept above the resin level to prevent air pockets to
form and remain inside the column. The air pockets may react with the resins forming altered
canals. These canals can lead to a low column capacity and adsorptive power. It may also
hinder in the interaction of the solution with the resin since it may prevent its contact with the
resin. The resin must be hydrated at all times because water serves as a very good medium for
the reaction to take place and water also displaces entrapped gases.

5. Why was a strong acid added to the column during a) preparation of the resin and b) storage
of the resin?
The resin was soaked in concentrated acid in order to regenerate it with H+ ions needed to
facilitate the ion-exchange. A strong acid added prolongs the activity of the cation exchanger.
The resins are also perforated with very small pores for liquid pathways to increase surface area
of adsorption. As the resins react with the acid, water forms and swells the beads making it a
suitable medium for reaction. The addition of acid shows that the resin is activated and the H+
are now ready to be exchanged with another cation species.

6. Why was the rate flow maintained at 30 drops per minute?

To allow the completion of the replacement of H+ ions of the resin, the solution should be
given enough time to establish an exchange equilibrium and to come in contact with all portions
of the resin. Because of this, the rate of the expelling the solution which have already come in
contact with the resin, should be kept at a certain slow flow rate. This constant flow rate is
crucial for the ion exchange to take place. Water is the medium for reaction and a rapid flow
will never assure the optimum completion of the reaction and the total liberation of H+. A
modest rate of flow will ensure that at the end of the column, equilibrium is ―achieved‖ and that
the flow of the eluate is constant and no pressure or disturbance is observed.

7. Why was the column washed until the eluate has the pH equal to the pH of distilled water
during a) preparation of column and b) sample analysis?
a) The solution was kept at a pH equal to that of the distilled water to be used later on to make
sure that the H+ concentration is not affected with the constant addition of water. B) The same
pH means that the cation exchanger has fully reacted with the cation analyte. It means that all
H+ have been displaced and are now ready for titration with strong base.

8. Give the balanced exchange reaction.

Replacing the general exchange reaction given in equation 1 by the particular species used in
the experiment, the following reaction occurs
2rSO3 – H+ + Cu2+ (rSO3)2Cu + 2H+ (3)
Which tells us that
2 mol H+= 1 mol Cu2+ (6)

9. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.
If the flow rate of the elution (30 drops per minute) was not followed, the solution is not given
enough time for the replacement of H+ ions to be completed. The completion of the reaction
and the total liberation of H+ ions will not be optimized.

If the liquid level fell below the resin level, air pockets might form altered canals which in turn
would interfere with the contact of the ions with the resins. This would cause a low efficiency of
adsorption. This will affect the time for the pH of the eluate to be equal to that of the distilled
water being used.

Overtitration of the sample would cause an increase in the volume of NaOH used, and an
increase in the calculated experimental value of the Cu(II) ion concentration. Also, this would
cause an increase in the percentage error an deviation from the theoretical Cu(II) ion
concentration.

If there was a cotton wad or any other absorbing impurities with the column, above the resin,
same as the air pockets, it would interfere with the contact of the resin to the analyte and this
may absorb either of the ions. This would lead to a lower concentration of the calculated
experimental ion concentration.

If the pouring of water was not gentle that the resin was not tact or was disturbed, the purpose
of the resin acting a sift would be depleted. This would lead to a lower efficiency of the column
and disturbance in the exchange between the cations.

If the pH were not yet equal and titration was already performed, this would lead to a lower
computed value for the Cu(II) concentration since nit all H+ ions have been liberated yet.

Wrong molarity of NaOH. If the molarity of NaOH is too high, less of it will be used for titration
and vice versa. The computed value for Cu(II) ion concentration may increase or decrease if
the molarity of NaOH is too high or too low.

REFERENCES:

Analytical Chemistry Academic Group. (2012). Analytical chemistry laboratory manual. Quezon City:
Institute of Chemistry, University of the Philippines, Diliman.

Christian, G.D. (2004). Analytical chemistry (6th ed.). Somerset, NJ: John Wiley & Sons, Inc.

Harris, D.C. (2010). Quantitative chemical analysis (8th ed.). New York, NY: W.H. Freeman and
Company.

Skoog, D.A., West, D.M., Holler, F.J., & Crouch, S.R. (2004). Fundamentals of analytical chemistry (8th
ed.). Belmont, CA: Thomson-Brooks/Cole