Railsback's Some Fundamentals of Mineralogy and Geochemistry

Ionic potential
One important way to characterize ions is by their
ionic potential. Ionic potential is an ion's charge divided
by its radius, and it is thus a measure of density of
charge. Ionic potential gives a sense of how strongly or
weakly the ion will be electrostatically attracted to ions of
opposite charge, and to what extent the ion will repel
other ions of like charge. Ionic potential varies greatly for
cations, from 0.75 for K+ to 45 for N5+.
Ionic potential is very useful in understanding the
behavior of relatively hard cations (see below). Cations
of low ionic potential like Na+ are typically soluble and
enter into solids only at relatively low temperatures,
because they make weak bonds to O2-. On the other
hand, cations of high ionic potential, like S6+, bond so
well to O2- that they make oxocomplexes like SO42-
(sulfate) that are soluble. Repulsions between S6+ ions,
and between the S66+ ion and other highly charged
cations, make most sulfate minerals relatively soluble,
and S6+ thus is an incompatible or volatile ion in high-
temperature systems. In between, cations of inter-
mediate ionic potential like Al3+ have sufficient density of
charge to bond strongly to O2- but not such dense
charge as to repel each other, and so they make stable
oxides and/or hydroxides and thus are insoluble. The
cations of intermediate ionic potential also enter into
solids at high temperatures.
The diagrams here show the effect of these trends in
the melting temperatures and solubilites of oxides. The
Earth Scientist's Periodic Table of the Elements and
Their Ions shows many more geoscience trends that
result from variation in ionic potential. In addition, this
book's page on "A bit of the Earth Scientist's Periodic
Table of the Elements and Their Ions as a cross-section
of the Earth" shows the implications of these trends at
even larger scale, the pages on Bowen's Reaction Series
shows how ionic potential affects igneous crystallization,
the pages on solutions and aqueous speciation show
how ionic potential controls the behavior of catons in
solution, and the page on "The Special Siituation of
Silicon" shows the implications of ionic potential for one
important element.

Contours of ionic potential: Conceptual model of the behavior of

Example: oxides of hard (and intermediate) cations
Ca2+ Li N
charge = 2 Li + Be2+ B3+ C4+ N5+ Cations
radius = 1.0 Å 32 H+ 1Å
ionic potential
= 2.0
Na+ Mg2+ Al 3+ Si4+ P5+ S6+
16
K+ Ca2+ Sc3+ Ti 4+ V5+ Cr 6+ High z/r
Strong
Rb O2– bonds, but
charge
Rb+ Sr 2+ Y 3+ Zr 4+ Nb5+ Mo6+ Intermediate
Low z/r cation-cation
radius z/r repulsion
Weak cation-
= ionic Cs+ Ba2+ La3+ Hf4+ Ta5+ W 6+ oxygen bonds
Strong cation- Thus less
potential oxygen bonds stable solids
1 2 4 8 Thus less stable
Thus stable solids
solids
+ 2+
Li
+
Be 2+ B 3+ C 4+ N 5+ Li4.4 Be–7.4 3+
B2.77 C 4+ N 5+
1700 2681 723 216 Bromellite

500
Melting + 2+ 4+ 5+
Na
+
Mg 2+
Al 3+ Si 4+
P 5+ S 6+ temperature Na9.9 Mg –2.4 Al 3+ Si –3.9
–8.1
P–1.37 S 6+
1193 3125 2345 1996 855 290 Periclase
of oxides of Corundum Quartz

hard cations
+
K
+
Ca2+ Sc 3+ Ti 4+ V 5+ Cr 6+ K14.0 Ca2+ Sc3+ Ti 4+ 5+
V –7.6 Cr 6+
3200 Lime 1.4 –9.7
2103 943 Rutile Shcherbinaite
10
00
Solubility + 2+
Rb
+
Sr 2+
Y 3+
Zr 4+
Nb 5+
Mo6+ Rb Sr4.3 Y 3+ Zr 4+ Nb5+ Mo6+
673 2938 3123 1785 1074
of oxide 28.9 Baddeleyite
Molybdite
minerals
of hard
Cs
+
Ba2+ La 3+ Hf 4+ Ta 5+ W 6+
cations 2+
Ba6.7 La 3+ Hf 4+ Ta 5+ W 6+
1500

2286 2580 3173 2058 1745 Mineral Tantite

2000

1500
2500
200

2500

–9.7
4+
3000

300

Th 4+ Th Thorianite
0

Log of activity of cation species

Temperatures in Kelvins in distilled water at 25 °C LBR 2/2007
0

3493
IonicPotential04