Railsback's Some Fundamentals of Mineralogy and Geochemistry

Mineralogical implications of the hardness and softness of ions

Consideration of the concept of hardness and softness (e.g., Na1+, Mg2+, Al3+, etc., all of which have a neon-like
The table presents hardness and softness of cations and
of ions reveals patterns in the chemical compositions of outer shell) all are conventionally considered hard cations.
anions as a spectrum, acknowledging that although cations
minerals. This page plots compositions of minerals on a like Mo6+ and U6+ have nominally lost their six outer-shell
On the other hand, cations with at least some outer-shell
periodic table to make that point. electrons (e.g., Mn2+ and Fe2+) are considered inter-
electrons, they in fact retain some of those electrons, and
Ions can be categorized as hard or "Type A" (behaving mediate in this categorization, and cations with many outer-
their large size also makes them softer than a cation like
as hard spheres and forming more ionic bonds) or soft or shell electrons (e.g., Ag1+ and Hg1+) are considered soft.
Li1+ that is small and has definitely lost all of its outer-shell
"Type B" (deforming from a spherical shape and forming Hardness and softness of ions is shown on the periodic
electrons.
more covalent bonds). Cations with no outer-shell electrons table below with shading for each of the cells of the table.
The table also shows compositional trends among
minerals containing
one cation. The
Anions 4– 3– 2– – colored symbols below
Cations nominally lacking show the result: the C N O F
+ outer-shell electrons harder cations form
H (thus cations with a noble- Hardness and softness of ions 4– 3– 2– – fluoride, oxide, and
gas-like outer shell) oxysalt minerals, Si P S Cl
3– 2– – whereas the softer
+ 2+ 3+ 4+ 5+ Hardest Softest
cations tend more to
As Se Br
Li Be B C N 3– 2– –
form sulfide and
sulfosalt minerals, and
+ 2+ 3+ 4+ 5+ 6+
Cations with some
4+ 5+ 6+
the softest cations Sb Te I
outer-shell electrons 2– form bromide, iodide,
S As Se
Na Mg Al Si P S Po
2–
At
–
and even bismuthide
Bi
3+ 4+ 3+ 3,4+ 3+ 3+ 3+ 2+ 5+ 6+ minerals. Thus we
4+
+ 2+ 3+ 4+ 5+ 6+ Ti V Cr Mn Fe Co Ni Cu
2+ 3+
Ge Sb Te
have an understanding
K Ca Sc Ti 2+ 3+
V Cr 2+ 2+ 2+ 2+ 2+ + 3+ 4+ of why some
Ga
Ti V Cr Mn Fe Co Ni Cu Zn
4+
Sn As Se
substances exist as
minerals and some do
+ 2+ 3+ 4+ 5+ 6+ 4+ 3,4+ 2+ 2+ + 2+ 3+ 2+ 3+ 4+ 5+ not: harder cations
Rb Sr Y Zr Nb Mo Ru Rh Pd Mo Ag Cd n Sn Sb Te
bond well to harder
anions, and softer
4+ + + 2+ 3+ cations bond well to
2+ 3+ 4+ 5+ 4+ 4+ 2+ +
Au Hg Tl Pb Bi
+ 6+ 7+ 4+
Cs Ba La Hf Ta W Re Re Os Ir Pt W softer anions. It also
allows us to predict
2+ 3+ 4+ 5+ what new minerals we
+ 2+ 3+ 4+ 5+ 6+ 4+ Pb Bi Hg Tl might find in the future
Fr Ra Ac Pa Th U U
Cations with many outer-shell electrons
(an SrF2 or Ga2S3
mineral?), and what
minerals we would be
Cations that form simple fluoride minerals of one cation (e.g., Li1+ in griceite, LiF) unlikely to find in the
3+ future (e,g, an MgS or
Cations that form simple oxide minerals of one cation (e.g., Al in corundum, Al2O3) Au2O mineral).
Cations that are the intra-radical cation of oxysalt minerals (e.g., C4+ in calcite, CaCO3)
Legend: Cations that are the intra-radical cation of sulfosalt minerals (e.g., As3+ in proustite, Ag3AsS3)
Cations that form simple sulfide minerals of one cation (e.g., Pb2+ in galena, PbS)
Cations that form simple bromide or iodide minerals of one cation (e.g., Ag1+ in iodargyrite, AgI)
Cations that form simple bismuthide minerals of one cation (e.g., Au1+ in maldonite, Au2Bi)
The hardness-softness concept comes from Pearson, R.G. (1968) Hard and soft acids and bases, HSAB, Part I: Geology, 31, 737-740. The mineral occurrences shown are from that paper, from Figure 1 of Railsback, L.B. (2005)
Journal of Chemical Education, 45, 581-587; Schwarzenbach, G. (1961) The general, selective, and specific A synthesis of systematic mineralogy: American Mineralogist, 90, 1033-1041, and from Figure 2 of Railsback, L.B.
formation of complexes by metallic ions: Advances in Inorganic Chemistry and Radiochemistry, 3, 257-285; and (2007) Patterns in the compositions of oxysalt and sulfosalt minerals, and the paradoxical nature of quartz: American
Stumm, W. & Morgan, J. J. (1996) Aquatic Chemistry (3rd edition), John Wiley & Sons, New York. The periodic table Mineralogist, 92, 356-369. The spectrum of hardness and softness is from Figure 8 of Railsback (2007).
above is based on that of Railsback, L.B. (2003) An earth scientist's periodic table of the elements and their ions: LBR HardnessSoftnessMinsPT03 1/2008