INTRODUCTION

Ion exchange is a process in which ions attached to a high molecular weight polymer are
exchanged for other ions in solution. The high molecular weight polymer is normally in the form
of small, round spheres called beads. Ion exchange resins are used to demineralize water and
to separate mixtures of ions. One important characteristic of ion exchange resin is its capacity,
expressed in terms of milli equivalents of exchangeable ion per gram of resin.
An ion-exchange resin or ion-exchange polymer is an insoluble structure normally in the form of
small beads. The color is usually white or yellowish and the resin is fabricated from an organic
polymer substrate. The material has highly developed structure of pores on the surface which
are sites where ions are trapped and released. The trapping of ions takes place only with
simultaneous releasing of other ions, thus the process is called ion-exchange process. 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.
The ion exchange process is widely used for the removal of hardness which is also known as
softening, removing of heavy metals as in waste treatment, removal of radionuclides which is
usually from power plants, and municipal water feeds (removal of nitrates, arsenic, perchlorate,
hexavalent-chrome and others). Since most ion exchange processes are reversible, the ion
exchangers can be regenerated or put back into their original salt form and used over and over.
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 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.

OBJECTIVES
1. To study the effect of calcium chloride concentration on water softening by using cationic
resin.
2. To determine the breakthrough time of the process.
3. To determine the volume of test water softened.

THEORY
The electrical charge on an ion can be either positive (+) or negative (-). Valence is the term that
describes the category of the electrical charge on a dissolved ion such as positive 2 or positive
3. If the contaminant has a positive charge, it would be called a cation, and would be removed
by use of an IE media called a cation exchange resin. If the contaminant has a negative charge,
it would be called an anion, and the appropriate treatment media would be called an anion
exchange resin.
Ion exchange is a process in which mobile ions from an external solution are exchanged for ions
that are electrostatically bound to the functional groups contained within a solid matrix. When
the functional groups are negatively charged, the exchange will involve cations and when they
are positively charged they involve anions. By taking advantage of the fact that, under certain
conditions, ion exchange media have a greater affinity for certain ionic species than for others, a

separation of these species can be made. For example, the hydrogen form of a cation
exchanger will release its hydrogen ion into solution and pick up a caesium ion from the solution
according to the following equation:
R H + Cs+ R Cs + H+
where R represents the insoluble matrix of the ion exchange resin. The negative counter ion of
the caesium salt is not affected by the exchange since every caesium ion removed from solution
is replaced by a hydrogen ion and the solution become neutral [1].
Ion Exchange Resins

These are very small plastic beads, with a diameter of about 0.6 mm. These beads are porous
and contain invisible water inside the beads, measured as humidity or moisture content. The
structure of the resin is a polymer similar like all plastics on which a fixed ion has been
permanently attached. This ion cannot be removed or displaced; it is part of the structure. To
preserve the electrical neutrality of the resin, each fixed ion must be neutralised with a counter
ion. This counter ion is mobile and can get into and out of the resin bead. Figure 3 shows
schematic cation and anion exchange resin beads. The dark lines represent the polymeric
skeleton of the resin bead: it is porous and contains water. The fixed ions of this cation

exchange resin are sulphonates (SO3-) that are attached to the skeleton. In this picture, the
mobile ions are sodium (Na+ ) cations. Cation exchange resins such as Amberjet 1200 are often
delivered in the sodium form.

The anion resin bead has a very similar skeleton. The functional groups are here quaternary
ammonium cations shown in the picture as N+R3. The mobile ions in the anion resin bead are
chloride anions (Cl). This is also the standard delivery form for many anion resins. Each ion
going into the bead has to be replaced by an ion getting out of the bead, again to preserve
electrical neutrality. This is what is called ion exchange. Only ions of the same electric sign are
exchanged. You cannot make a resin that can exchange cations as well as anions, because the

fixed cations inside the resin beads would neutralise the fixed anions and no exchange with the
outside world would be possible. Therefore you need separate cation exchange resins and
anion exchange resins [2].

Water Softening
Among the substances dissolved in water, hardness is very commonly found. Hardness is a
popular word to represent principally calcium and magnesium dissolved in the water; these ions
can precipitate under certain conditions and form the scale that you may have seen in your
boiling pan, and that can obstruct pipes and damaged water boilers. The softening of water is
the exchange of the hardness cations (Ca++ and Mg++) for another cation that cannot form
scale because it is much more soluble: the sodium ion Na+ .
To soften water, you take a cation exchange resin on which the mobile ion inside the beads is
sodium (Na+ ) and you pass the hard water through a column filled with the sodium form resin.
The hardness ions Ca++ and Mg++ move into the resin beads and each of these divalent

cations is replaced by two sodium ions getting out of the resin. The exchange reaction can be
written as:
2 RNa + Ca++ -> R2Ca + 2Na+
Figure 4 illustrates the reaction: the resin beads are initially loaded with sodium (Na+ ) ions. As
shown schematically, each calcium or magnesium ion entering the resin bead is compensated
by two sodium ions leaving it. Anions from the water (not shown) cannot enter the resin bead
because they would be repelled by the fixed sulphonate (SO3 ) anions inside the beads.

This cation exchange can only take place efficiently because the cation exchange resin has a
higher affinity for the hardness ions than for sodium. In plain English, the resin prefers calcium
and magnesium over sodium. The result of the softening process is not a net removal of the
hardness ions from water, it is the replacement of the hardness ions by sodium ions. The salinity
of the water has not changed, only the constituents of the salinity are different at the end of the
softening process. Obviously, this exchange is not unlimited: when the resin has removed so
much hardness from the feed water that no room is left on the resin for removing more, the
exhaustion run has to be stopped. At this stage, the resin will be replaced by a fresh resin, or
regenerated.

Regeneration
When the resins are exhausted, you can bring them back to the fresh state and start over again.
Regeneration of ion exchange resins is a reversal of the exchange reactions shown above. For
instance, the softening resin is regenerated with sodium (Na+ ) ions supplied by a salt (common
salt: NaCl) solution. The regeneration reaction is:
R2Ca + 2 NaCl -> 2 RNa + CaCl2
Regeneration can only be performed when the concentration of the regenerant is high, typically
1000 times higher than the concentration in normal water. For instance, salt is used as a brine
with 10 % (about 100 g/L) concentration. In the case of demineralisation, strong acids such as
hydrochloric acid (HCl) or sulphuric acid (H2SO4) are fully dissociated and can supply H+ ions
to replace the cations that have been exchanged and are sitting in the cation exchange resin
beads at the end of the exhaustion run:
RNa + HCl > RH + NaCl

Limits of ion exchange

For ion exchange to be efficient there must be a difference in affinity between the ion in the
resin and the ion or ions you want to remove from solution. The resin must have a higher affinity
for the ion in solution compared to the ion in the resin. The ion exchange technology is a perfect
tool to remove or exchange contaminants present in low concentrations. In such a case the
running time until the resin column is exhausted can be very long, ranging from a few hours to
several months. When however the concentration of contaminants is high, say several grams
per litre of water, the ion exchange cycles become exceedingly short and the quantity of
regenerants increases to uneconomical levels. In the case of brackish water (underground

water with high salinity as often found in arid countries) or sea water, ion exchange is not
suitable and other technologies must be used, such as reverse osmosis or distillation. Also, any
contaminant that is not ionised cannot be removed by ion exchange. Other technologies are
available for this purpose, using activated carbon, polymeric adsorbents, molecular sieves and
other media.

Selective Ion Exchange

Due to differences of affinity for different ions, common ion exchange resins can be used to
remove selectively ions from water. One of the most obvious examples is softening. You cannot
soften water effectively with reverse osmosis as you have to demineralise it partially [3].
Similarly, you can remove fairly selectively other ions from water, such as nitrate of sulphate,
using an anion exchange resin in the chloride form. This works because the anion resin has
more affinity for the nitrate or sulphate ion than for the chloride ion, the order of affinity being:
SO4= > NO3 > Cl- > HCO3- > OH- > FFor cation resins used in softeners, the affinity is
Pb++ > Ca++ > Mg++ > Na+ > H+
The Pb (lead) is shown here to indicate that any dissolved lead will be removed efficiently by a
softening resin, as well as many other (but not all) heavy metals. Some contaminants are not
easy to remove by conventional ion exchange resins. In many cases, very specific resins have
been developed for these contaminants. Selective resins are available today for the removal of
heavy metal such as Boron, Cadmium, mercury, Chromate, Lead, Nickel, Nitrate, Perchlorate
and some other contaminants

Breakthrough Time Theory

Once the resin in the column is exhausted or used, breakthrough time can be observed. The
majority of hard elements such as calcium are also breaking into the solution. This is
according to a research conducted by Dr Pamela S. William and Dr Gary B. The most common
way or method to detect resin exhaustion is by measuring the change in conductivity. Hence the
ionic breakthrough can be determined. This method is done by having two or more exchange
column tube. The first tube is used to run the process, while other tubes available is used for
regenerating.
In industry, application or process that uses ion exchange process, the ion exchange resin used
normally regenerated every half day to two days. The time taken for regeneration also
depending on the application. It is important to regenerate at first sign of breakthrough. There
are no fully hundred percent or complete regeneration because large amount of regenerate are
needed to restore back the ion in the column. This is not practicable because it is very
expensive and costly. Most ion exchange resin are commonly regenerated to a certain
percentage of their total capacity.

[1]

HARJULA, R., LEHTO, J., BRODKIN, L., TUSA, E., CsTreat highly efficient ion
exchange media for the treatment of cesium-bearing waste waters, Low Level Waste
(Proc. Int. Conf. Providence, RI, 1997), Electric Power Research Institute, Palo Alto, CA
(1997).

[2]

DYER, A., HUDSON, H.J., WILLIAMS, P.A. (Eds), Ion Exchange Processes: Advances
and Applications, Royal Society of Chemistry, Cambridge (1993).

[3]

EBESTA, F., JOHN, J., MOTL, A., STEINEROVA, J., Development and testing of
composite ion exchangers, Proc of the CTU Seminar 94, Prague, 1994