ANION EXCHANGE

Background
Ion exchange is very similar to adsorption; both processes involve mass transfer from a fluid to a solid phase.
Ion exchange can be described as a sorption process, but ions are sorbed in comparison to electrically neutral
species in adsorption. An important difference between ion exchange and adsorption is that ion exchange
requires that the species removed from the fluid phase is replaced with a species (exchanged) so that
electroneutrality is maintained. Electroneutrality requires that the total charge sorbed and desorbed is the
same.
It is important to note that not all dissolved ions are removed equally and/or completely. Ions that are low on
the selectivity preference order may not be completely removed.

Ion-exchange mechanism
All ion exchangers, whether natural or synthetic, have fixed ionic groups that are balanced by counterions to
maintain electroneutrality. The counterions exchange with ions in solution. As an example, consider the
schematic cation-exchange resin shown with the reaction below.
The resin containing cation B+ is placed in a solution containing cation A+. The cations A+ and B+ will diffuse
due to a concentration gradient between the resin and solution. The chemical equation for this particular
exchange reaction within the ion-exchange resin is:
A+ +(R-)B+↔B+ +(R-)A+
where R- represents the negatively charged functional group of the resin.

Ion-exchange media
Some ion-exchange resins occur naturally and have been used for hundreds of years. They include clay peat,
charred bone, and natural aluminosilicates. The recognition of ion exchange as a process is generally
attributed to H. S. Thompson and J. Thomas Way, who were English agricultural chemists. Thompson
observed in 1848 that soil treated with either ammonium sulfate or ammonium carbonate adsorbed the
ammonia and released lime. He reported his results to Way and then conducted systematic studies, 1850–54.
In 1935, B. A. Adams and E. L. Holmes observed that crushed phenolic phonograph records were capable of
ion exchange. This observation led to the development of synthetic organic ion-exchange resins. With this
development, the industrial use of ion exchange was rapidly increased.
The following factors are important in the choice of an ion-exchange resin:
1. Exchange capacity (loading or productivity).
Capacity is the quantity of the counterion that the resin can exchange. It is a critical factor in
evaluating a resin for a given application. The total capacity is determined by the number and charge on the
fixed ion-exchange groups in the resin. The dry-weight capacity is then determined as the milliequivalents
per gram of dry resin (meq/g). This quantity is a measure of the loading capacity of the resin and is a
constant.
2. Fraction or percent removal of various ions from the liquid phase (selectivity).
Selectivity is primarily dictated by ionic charge and size, with charge having the most significant
effect. The following empirical points was suggested to approximate selectivities.
 a) At low aqueous concentrations and ambient temperatures, the extent of exchange increases with
increasing valence of the exchanging ion:
Th4+> Al3+> Ca2+> Na+
PO43-> SO42- > Cl-
b) At low aqueous concentrations, ambient temperatures and constant valence, the extent of exchange
increases with increasing atomic number (decreasing hydrated radius) of the exchanging ion:
Cs+> Rb+> K+> Na+> Li+
Ba2+> Sr2+> Ca2+> Mg2+> Be2+
c) At high ionic concentrations, the difference in exchange “potentials” of ions of different valence (Na+ vs
Ca2+ or NO3- vs SO42-) diminish and, in some cases, the ion of lower valence has the higher exchange
potential.

3. Particle size and size distribution (flow throughput considerations).

Particle size affects the pressure drop through the column. Smaller particle size leads to higher
pressure drops for a given flowrate. Often, hydraulic limitations are the most important consideration in
design.
4. Chemical and physical stability.
Stability is directly related to the lifetime of the resin. This, in turn, directly affects the cost of the
process. Physical stresses can occur through swelling and shrinking cycles due to osmotic pressure
changes. Mechanical forces, such as static pressure load, and abrasion can cause breakage. Operation
outside the normal temperature range will also add to particle degradation.
5. Regeneration requirements (chemicals, amounts required, loss in capacity).
Regeneration typically involves several steps. At the end of the exchange cycle, a backwash is
typically done. This step serves two purposes. First, trapped particles in the bed are removed. Second, the
backwash serves to remix the bed and reclassify the particles so that there is a gradual increase in particle
size from top to bottom (smaller particles are pushed toward the top). This structure reduces the effect of
channeling. Regeneration is the next step. The regeneration amount is usually given in terms of an acid or
base concentration (6 mol% HCl, for example) at a prescribed flowrate for a minimum contact time. After
regeneration, there are two rinse cycles. A slow rinse to remove excess regenerant from the bed followed by
a fast rinse. The volume of these regenerant fluids is often a major cost for operation and disposal.
The four different types of synthetic ion-exchange resins are: strong acid, weak acid, strong base, and weak
base. Acidic resins have negative fixed charges and can exchange cations; basic resins have positive fixed
charges and can exchange anions. Strong resins are fully ionized and all the fixed groups are available to
exchange counterions, while weak exchangers are only partially ionized at most pHs (this often results in a
lower exchange capacity, but makes regeneration easier).