Selectivity

of ion exchange resins

The selectivity coefficient of resins is defined in the ion exchange reactions page. The affinity of
the resin for an ion is governed by the size of its hydrated form as well as its charge. The larger
the ion, the more the resin bead must expand to accommodate it in the structure. The expansion
is opposed by the restraining cross-links, so that large ions require a greater force to penetrate the
resin than small ones. Ions with a higher charge have a higher affinity for the functional group of
a given ion exchange resin.

Although the actual ionic diameter of each ion increases as we increase atomic number, the
number of water molecules that are attracted as the hydration sphere goes down as atomic
number increases. This means that charge density increases with atomic number.

Ion Hydrated diameter (Å) Naked diameter (Å)

Alkaline (monovalent)
Li+ 3.82 0.60
+
Na 3.60 0.95
+
K 3.31 1.33
+
Rb 3.28 1.48
+
Cs 3.27 1.69
Alkaline earths (divalent)
Be++ 4.59 0.31
++
Mg 4.26 0.65
++
Ca 4.11 0.99
++
Sr 4.10 1.13
++
Ba 4.05 1.35
Hydrated ion sizes

Among alkaline metal ions, caesium is thus the most selective and lithium is the least selective.

For carboxylic and chelating resins, the above effect is not applicable, because divalent ions are
complexed and no longer hydrated. On the other hand, the complex increases dramatically the
resin selectivity. See the page about resin structure.

The pore size of a gel type resin is about 10 to 20 Å, which means the pores can accommodate
easily inorganic ions. Resins with a higher degree of cross-linking have less elastic and slightly
smaller pores. Macroporous resins have — in addition to the small gel pores — much larger
pores (200 to 1000 Å or more), which can accommodate large organic ions.
You can see on separate pages selectivity tables for cation and anion exchange