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Solid solutions in minerals

Some minerals have variable composition (within fixed limits)


May affect physical properties (density, colour, ..)
May have implications for economic value or environmental hazards (Au,Ag / Cd,Hg)
The compositional extremes end members
1600
1500

Binary solid solution


phase diagram

temperature

1400

liquid

liquidus
solidus

1300

1200
1100

solid

1000
900
0

0.2

0.4

0.6

composition

0.8

Coexisting phases
Melting
point A

(l)

Splits into
liquid & solid phase

Melting
point B
31%A
69%B

100% B
0% A

62%A
38%B

(s)
100% A
0% B

No solid solution formed (eutectic mixture instead)


1600
1500

(l)

1400

This is very different


type of phase
behaviour

1300

1200
1100

Note the solid phase


(l+sA)

1000

(l+sB)

900

E
(sA+sB)

800
0

100%B

0.2

0.4

0.6

0.8

100%A

Completely miscible in (s)

Partially miscible in (s)

Completely immiscible in (s)

Immiscible in (s), forming a compound

Solid solutions are formed by one of these mechanisms


Substitution (complete or incomplete, simple or coupled)
Omission
Interstition

Substitutional solid solution


Involves interchanging one cation for another in a structural site
Requirements to be met
Ion sizes are similar (difference in sizes is less than 15%, higher tolerance
at high temperatures)
Charge neutrality must be maintained
Similar electronegativities and valences

Alloys typical representatives of solid solutions of pure metals.


The solid solution (alloy) often has properties superior to those of pure metals

Simple substitution one for one, e.g., olivine


(solid solution of forsterite & fayalite)
Forsterite
Mg2SiO4

Fayalite
Fe2SiO4
Olivine
(MgxFe1-x)2SiO4

Expression using
end members
Mg0.5Fe1.5SiO4=Fo25Fa75

Complete : covers the whole concentration interval x < 0 ; 1 >

Structure of olivine
(SiO4)2- tetrahedra
with Mg2+, Fe2+ in between

Incomplete substitution
Sphalerite (Zn,Fe)S

Cubic
sphalerite

Hexagonal
wurtzite

Hexagonal
troilite

Caution : mass % vs molar %


e.g., Zn:Fe:S=1:1:1 on atomic basis gives
33.3mol% of each of Zn,Fe,S, thus Zn:Fe=1:1 or 0.5:0.5
42.7w% Zn, 36.4w% Fe, 20.9w% S, thus Zn:Fe=1.17:1 or 0.54:0.46

Common substitution elements in native metals, sulphides and oxides

Sphalerite can contain up to 1.6w% of toxic Cd environmental hazard

Au-Ag
Ag-Cu
Au-Cu

Au Ag Cu system
complete solid solution
no solid solution, eutectic point
three compounds, Au3Cu, AuCu, AuCu3
Cu
1.28

complete sol. sol.

Au
1.44
AuCu3

Ag
1.44

albite
Coupled substitution where two ions are substituted
by other ions so that the charge remains constant
Albite
NaAlSi3O8

Anorthite
CaAl2Si2O8
Plagioclase
Na+ + Si4+ Ca2+ + Al3+

Some other examples


Corundum 2Al3+ Fe2+ + Ti4+ Ilmenite
Biotite, hornblende : Fe2+ + OH- Fe3+ + O2-

anorthite

Ternary solid solutions

x
A

NaAlSi3O8 + KAlSi3O8
NaAlSi3O8 + CaAlSi2O8
CaAlSi2O8 + KAlSi3O8

-- Simple and complete substitution


-- Coupled and complete substitution
-- Coupled and incomplete substitution

Two feldspars region splitting into two solid phases


with composition given by conodes (tielines)

x:
20%A
50%B
30%C

Omission substitution maintains charge balance


when ions of different charge substitute for each other by leaving structural sites vacant
(n+1)Mn+ nM(n+1)+ +

e.g., 3Fe2+ 2Fe3+ +

Pyrrhotite (magnetic pyrite) Fe(1-x)S x<0.17


S

(Fe2+1-3xFe3+2x)xS

Fe2+

Fe3+

FeS hexagonal

Fe(1-x)S -- hexagonal/monoclinic

x=0.167
x=0.125
x=0.100
x=0.091
x=0.083
.
.
.
x=0

Fe5S6
Fe7S8
Fe9S10
Fe10S11
Fe11S12

FeS

Interstitial substitution is a variation of coupled substitution with an ion/atom entering


a cavity in the structure (opposite of omission)

Common in alloys strengthening effect

Beryl (ring of six silicate tetrahedra, Si6O1812-)


Be3Al2Si6O18

Si4+
O2-

Si4+

Al3+

K+

+ Si4+ Be2+ + 2K+

K+ (or Rb+, Cs+)


Al3+

Another example
Chalcopyrite
CuFeS2 ( = Cu4Fe4S8)

Haycockite Cu4Fe5S8

Haycockite
Cu4Fe5S8 ( = Cu4Fe4S8 + Fe)

Mooihoekite Cu9Fe9S16

Known as stuffed derivatives

Talnakhite Cu9(Fe,Ni)8S16

Formation of Ni-rich laterites


Ultramafic (low SiO2) rocks hundreds to thousands metres thick
Olivine typically contains 0.10.2% of nickel in solid solution
Ni2+ (0.69) replaces Mg2+ (0.72) in olivine
Concentration is not enough high for an ore
Ni2+ released from the surface olivine structure by weathering
and is concentrated in goethite (Fe oxide) on the surface
Resulting in (up to few metres) a thick layer of nickelferous laterite
Contains 1-2% of Ni, which is now a ore grade

Solid solutions in sulphides

Many examples of solid solutions in sulphides


Fe, Co, Ni are often interchangeable

Pyrite
FeS2

Cattierite
CoS2

Vaesite
NiS2

Catterite and vaesite not common


but pyrite often contains several to tens of % of Co/Ni

Also arsenopyrite (FeAsS), cobaltite (CoAsS), gersdorffite (NiAsS)


Gersdorffite in nature : (Ni,Fe,Co)(As,Sb)S , e.g., (Ni70Fe20Co10)(As80Sb20)S

Trace elements solid solutions in sulphides


Economical value
Gold in arsenopyrite and pyrite (up to several hundreds of ppm) submicroscopic gold
also called invisible gold)
Refractory gold can be released only by destroying the main sulphide lattice
Methods include roasting, biological oxidation, pressure oxidation
Same phenomenon palladium in pentlandite (Fe,Ni)9S8

Some properties of solid solutions

Specific gravity of olivine


4.4
4.2
4.0
S.G. 3.8
3.6
3.4
3.2

Ideal solution

x M x 2M 2
M x1M1 x2M2

1 1
x1M1 x2M2
V
V1 V2

20

40

60

80

100

% Fo
Refractive index of olivine
1.80
1.75

1
n2

n
1.70
1.65
0

20

40

60

% Fo

80

100

x1 x2
2
2
n1 n2

Some properties of solid solutions


Melting temperature of olivine
1,900

1890

1,700

t / C

1,500
1,300
1205
1,100
0

20

40

60

% Fo

80

100

Variety of pyroxenes