TITLE: Application of Ion-Exchange Resins: The Separation of Cations

OBJECTIVES OF THE EXPERIMENT:

After completing this experiment, the students should be able to:

1. Describe the process of ion exchange chromatography

2. Draw the schematic diagram of the apparatus used in the experiment

3. Perform the calculations involved ion exchange chromatography

INTRODUCTION:

An ion-exchange resin or ion-exchange polymer is an insoluble matrix (or support

structure) normally in the form of small (1–2 mm diameter) beads, usually white or yellowish,

fabricated from an organic polymer substrate. The material has highly developed structure of

pores on the surface of which are sites with easily trapped and released ions. The trapping of ions

takes place only with simultaneous releasing of other ions; thus the process is called ion-

exchange. There are multiple different types of ion-exchange resin which are fabricated to

selectively prefer one or several different types of ions.

Ion-exchange resins are widely used in different separation, purification, and

decontamination processes. The most common examples are water softening and water

purification. In many cases ion-exchange resins were introduced in such processes as a more

flexible alternative to the use of natural or artificial zeolites.

Most typical ion-exchange resins are based on crosslinked polystyrene. The required

active groups can be introduced after polymerization, or substituted monomers can be used. For

example, the crosslinking is often achieved by adding 0.5-25% of divinylbenzene to styrene at

the polymerization process. Non-crosslinked polymers are used only rarely because they are less

stable. Crosslinking decreases ion- exchange capacity of the resin and prolongs the time needed

to accomplish the ion exchange processes. Particle size also influences the resin parameters;

smaller particles have larger outer surface, but cause larger head loss in the column processes.

Besides being made as bead-shaped materials, ion exchange resins are produced as

membranes. The membranes are made of highly cross-linked ion exchange resins that allow

passage of ions, but not of water, are used for electrodialysis.

Several cations can form negatively charged (anionic) chloro complex with hydrochloric

acid. The anion complex can adsorbed by an anion exchanger. Every metal is adsorbed at certain

pH range and property can be used as the basis for separation. For example, zinc can be adsorbed

from 2 M of acidic solution but not magnesium and aluminium. Therefore, if a solution

containing Zn and Mg being introduced to column, only Zn will be adsorbed. Mg is thus

separated from Zn which can then be eluted with dilute nitric acid. The amount of separated Mg

and Zn can be determined through EDTA titration.

The advantages of ion exchange processes are the very low running costs. Very little

energy is required, the regenerant chemicals are cheap and if well maintained resin beds can last

for many years before replacement is needed. There are, however, a number of limitations which

must be taken into account very carefully during the design stages. When itemized these

limitations appear to represent a formidable list and the impression can be given that ion-

exchange methods might have too many short comings to useful in practice. However, this is not

the case as the advantages mentioned above are very great and compensation can readily be

made for most restrictions.

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PROCEDURE:

RESULTS:

Conical flask

1
2

CALCULATION:
Initial reading (cm3)

2.50
1.00
Final reading (cm3)

78.90
76.30
Volume of EDTA
used (cm3)
76.40
75.30
 i. Mg2+ ions

1. Equation of Mg and EDTA

Mg2+ + (EDTA)4- → [Mg(EDTA)]2-

2. n Mg 2+ ¿
¿ = n EDTA

MV ( 0.025 M ) (76.40 cm3 )

n EDTA = = = 0.0019 mol
1000 1000

ii. Zn2+ ions

1. Equation of Mg and EDTA

Zn2+ + (EDTA)4- → [Zn(EDTA)]2-

2. nZn 2+¿
¿ = n EDTA

MV ( 0.025 M ) (75.30 cm3 )

n EDTA = = = 0.0019 mol
1000 1000

iii. Ratio of Zn to Mg

Zn : Mg

nZn
2 +¿ 0.0019 mol 1
= ¿= =
n Mg ¿
2+¿ 0,0019 mol 1

=1:1

iv. Mass of Mg = n × Mr

= 0.0019 mol × 24.3050 g mol-1

= 0.0462 g

v. Mass of Zn = n × Mr

= 0.0019 mol × 65.409 g mol-1

= 0.1243 g
DISCUSSION:

Experiment of ion-exchange resins carried out using a column of bed called resins.

Resins in this experiment are very small orange round crystal beads. This cross-linked polymers

always related with divinylbenzene in its chain. The resins sometime changed its colour as seen

in the experiment, from dark orange to lighter orange after elucidating with a solution. This

condition is because of the resins properties, which is acid-base indicator property in addition to

its ion-exchange property.

The eluate collected in the experiment is pink in colour which shows the presents of the

metal ion in its complex form. By titrating it with EDTA solution, the indicator was determined

when the colour changed to light blue solution presenting the amount of the metal ion is less than

the EDTA complex which meant the end-point is reached.

By equaling the moles of the cations with moles of EDTA standard solution, 0.0019 mol

of Zn and Mg ions were obtained giving the 1 : 1 ratio of Zn : Mg.

The beads in the column must always covered with liquid as if the liquid level falls below

the bed, separation being made is usually vitiated due to introduction of air to the bead.

Moreover, such air in the column is hard to be removed and tends to cause channeling.

In titration with standard EDTA solution, the burette must be prepared first. The burette

was rinsed and filled with EDTA solution and then a small amount of EDTA solution was

drained through the burette in order to remove any air bubbles and to fill the tip.

The experiment can be more effective by adding the volume of elucidating substance and

adding the substances a little at a time; in this case 2 M of HCl solution to elute Mg ions and 0.5

M of HNO3 to elute Zn ions. The separation of cations need to have complete reaction by the

resins and the substances that passes in the column.

 There are a lot of applications of ion exchange resins in industry that obviously

identified. In water softening,  ion-exchange resins are used to replace

the magnesium and calcium ions found in hard water with sodium ions. For water purification,

ion-exchange resins are used to remove poisonous (e.g. copper) and heavy metal

(e.g. lead or cadmium) ions from solution, replacing them with more innocuous ions, such

as sodium and potassium. In sugar manufacturing, ion-exchange resins are used in the

manufacturing of sugar from various sources. They are used to help convert one type

of sugar into another type of sugar, and to decolorize and purify sugar syrups.

The applications are greatly benefitting in pharmaceuticals industry, ion-exchange resins

are used in the manufacturing of pharmaceuticals, not only for catalyzing certain reactions but

also for isolating and purifying pharmaceutical active ingredients. Ion-exchange resins are also

used as excipients in pharmaceutical formulations such as tablets, capsules, and suspensions. In

these uses the ion-exchange resin can have several different functions, including taste-masking,

extended release, tablet disintegration, and improving the chemical stability of the active

ingredients.

PRECAUTION STEPS:

1. Never let the liquid level below the resins in the columns. This is to avoid channeling of

beads in the column due to introduction to air.

2. Do not touch the nitric acid and concentrated hydrochloric acid with bare hands as they

are toxic, corrosive and poisonous. Use gloves and safety goggle to protect from the

hazards.
 3. Concentrated ammonium hydroxide should never be placed outside the fume cupboard.

Ammonia vapour in harmful amounts is released into the air very rapidly from

concentrated solutions and quickly produces respiratory distress.

CONCLUSION:

1. Ion exchange chromatography involved resins column usage to separate the cations in

same solution by elucidating the cations with suitable eluent.

2. The schematic diagram of the apparatus used in this experiment:

3. The calculations carried out for the ion exchange chromatography. The ratio of Mg : Zn

obtained was 1 : 1.
REFERENCES:

1. Gary D.Christian: Analytical Chemistry Sixth Edition, by John Wiley and Sons Inc.

p (622-625)

2. Odian, G. Principle of Polymerization; McGraw- Hill: New York, 1970; p 713.

3. Tatjana Weiss; Weiss, Joachim (2005). Handbook of Ion Chromatography. Weinheim:

Wiley-VCH.

QUESTIONS:

1. HNO3 is used instead of water in elucidating Zn because Zn ion is likely to stuck within

the resin beads due to its precipitate property. Therefore, HNO3 is used to make sure all

of Zn ions separated from the beads.

2. The concentration of Mg and Zn in the original solution before dilution:

n 0.0019 mol
M Mg 2+ ¿ = = = 0.019 M
v 0.1 dm3
¿

M1 V 1 = M2 V 2

M1 (0.025 dm3) = (0.019 dm3) (0.1 dm3)

M1 = 0.0076 M = initial M Mg 2+ ¿
¿

n 0.0019 mol
M Zn2+ ¿ = = = 0.019 M
v 0.1 dm3
¿

M1 V 1 = M2 V 2

M1 (0.025 dm3) = (0.019 dm3) (0.1 dm3)

M1 = 0.0076 M = initial M Zn 2+ ¿
¿