Lecture 5

Crystal Chemistry

Part 4:
Compositional Variation of Minerals
1. Solid Solution
2. Mineral Formula Calculations
Solid Solution in Minerals

Where atomic sites are occupied by variable

proportions of two or more different ions
Dependent on:
 Similar ionic size (differ by less than 15-30%)
 Must have electrostatic neutrality
 Atomic sites are more accommodating at higher
temperatures … BUT as temperatures cool
exsolution can occur
Types of Solid Solution

1) Substitutional Solid Solution

Simple cationic or anionic substitution
e.g. Olivine (Mg,Fe)2SiO4; Sphalerite
(Fe,Zn)S
Coupled substitution
e.g. Plagioclase (Ca,Na)Al(1-2)Si(3-2)O8
(Ca2+ + Al3+ = Na+ + Si4+)
neutrality preserved
 Types of Solid Solution Yellow, green (SiO4)-4
Purple Be tetrahedra
Blue Al+3 in voids
2) Interstitial Solid Solution
Occurrence of ions and molecules within
large voids within certain minerals (e.g.,
Beryl)

Beryl, arguably considered a ring silicate (a Cyclosilicate)

Types of Solid Solution

3) Omission Solid Solution

Exchange of single higher charge cation for two
or more lower charged cations which creates a
vacancy (e.g. Pyrrhotite Fe(1-x)S) with x = Fe++
ranging 0-0.2 within regions of the crystal
Where Fe+2 absent from some octohedral sites,
some Iron probably Fe+3 to restore electrical
neutrality

Two Ferric Fe+3 ions

balance charge for
each three missing
Ferrous Fe+2 ion
Mineral Formula Calculations

 Chemical analyses are usually reported

in weight percent of elements or
elemental oxides
 To calculate mineral formula requires
transforming weight percent into
atomic percent or molecular percent
Ion Complexes of Important Cations
(with cation valence in parentheses)
 SiO2 TiO2 (+4)
 Al2O3 Cr2O3 Fe2O3 (+3)
 MgO MnO FeO CaO(+2)
 Na2O K2O H2O (+1)
Problem 1
Calculate a formula for these Weight Percents

 Oxide Wt% MolWt Moles Moles Moles

Oxide Oxide Cation Oxygen
 SiO2 59.85 60.086 .996* .996 1.992
 MgO 40.15 40.312 .996 .996 .996
 total 100% 2.998

 Mole ratios Mg : Si : O = 1 : 1 : 3
 Formula is: MgSiO3 Enstatite

Checked 9 Sept 2011 CLS

*59.85/60.086
 Problem 2
Formula to weight percents

 Kyanite is Al2SiO5
 Calculate the weight percents of the
oxides:
– SiO2
– Al2O3
 Problem 2 p2 Kyanite: Al2SiO5

 Oxide Moles MolWt Grams Wt%

PFU Oxide Oxide

• SiO2 1 60.086 60.086 60/162 37.08

• Al2O3 1 101.963 101.963 102/162 62.92

• Formula weight 162.049 100%

Checked 9 Sept 2011 CLS

Problem 3: Solid Solutions
Weight percents to formula

 Alkali Feldspars may exist with any

composition between NaAlSi3O8 (Albite)
and
KAlSi3O8 (Sanidine, Orthoclase and Microcline)
 Formula has 8 oxygens:
(Na,K)AlSi3O8
 The alkalis may substitute in any
ratio, but total alkalis (Na + K) to Al is
1 to 1.
Problem 3 (cont’) Solid Solutions
Weight percents to Formula
 Oxide Wt% MolWt Moles Moles Moles
Oxide Oxide Cation Oxygen
 SiO2 68.20 60.086 1.1350 1.1350 2.2701
 Al2O3 19.29 101.963 0.1892 0.3784 .5676
 Na2O 10.20 61.9796 0.1646 0.3291 .1646
 K2O 2.32 94.204 0.0246 0.0493 .0246
 100.00 3.0269

 Units: Wt% [g/FU] / MolWt [g/mole]  moles\FU

 3.0269 oxygens is wrong for this mineral. Multiply

cations by 8.000/ 3.0269 oxygen correction
 Mole ratios Na 0.87, K 0.13, Al 1.000, Si ~3.0,
calculated as cations per 8 oxygens
 Notice, now Na + K = 1.00, as required

Checked 9 Sept 2011 CLS Answer (Na.87,K.13)AlSi3O8

 Various Simple Solid Solutions

 Alkali Feldspars
 NaAlSi3O8 - KAlSi3O8
 Orthopyroxenes:
 MgSiO3- FeSiO3 Enstatite - Ferrosilite (opx)
 MgCaSi2O6-FeCaSi2O6 Diopside-Hedenbergite (cpx)
 Olivines: Mg2SiO4- Fe2SiO4 Forsterite - Fayalite
 Garnets:
 Mg3Al2Si3O12- Fe3Al2Si3O12 Pyrope - Almandine
Problem 4: Orthopyroxenes
Solid Solution Weight Percent Oxides from Formula

 Given the formula En70Fs30 for an

Orthopyroxene, calculate the weight
percent oxides.
 En = Enstatite = Mg2Si2O6
 Fs = Ferrosilite = Fe2Si2O6
 Formula is (Mg0.7Fe0.3)2Si2O6 =
(Mg1.4Fe0.6)Si2O6
Problem 4
Weight Percent Oxides from Formula
Recall formula was (Mg 1.4 Fe 0.6) Si2O6

 Oxide Moles MolWt Grams Wt%

PFU Oxide Oxide
 SiO2 2 x 60.086 = 120.172 54.69
 MgO 1.4 x 40.312 = 56.437 25.69
 FeO 0.6 x 71.846 = 43.108 19.62
 Formula weight tot. 219.717 100.00%

For example 120.172/219.717 = .5469 (i.e. 54.69%)

Checked 23 September 2011 CLS

Problem 5
Weight Percent Oxides
from Formula
 Consider a Pyroxene solid solution of
40% Jadeite (NaAlSi2O6) and 60%
Aegirine (NaFe+3Si2O6).

 Calculate the weight percent oxides

 Formula is Na(Al0.4Fe0.6)Si2O6
 Problem 5 continued
Formula Unit is Na(Al0.4Fe0.6)Si2O6
Calculate Weight Percent Oxides

Oxide Moles MolWt Grams Wt%

PFU Oxide Oxide
 SiO2 2.0 60.086 120.172 54.71
 Al2O3 0.2 101.963 20.393 9.29
 Fe2O3 0.3 159.692 47.908 21.83
 Na2O 0.5 61.980 30.990 14.12
 Formula weight 219.463 100.00
Example: 2x 60.086 = 120.172
120.172/219.463 = .5471 x 100 = 54.71% SiO2
Example: 0.4 moles Al given as Al2O3 is 0.2 moles/per formula unit Al2O3
0.2x101.963 = 20.393; 20.393/219.463 = .0929 x 100 = 9.29%

Checked Sept 9 2011 CLS

Some Coupled Solid Substitutions

 Plagioclase Feldspar CaAl2Si2O8 - NaAlSi3O8

 Jadeite - Diopside NaAlSi2O6 - CaMgSi2O6

 Problem 6
Coupled Substitution
 Given 40% Anorthite; 60% Albite
 Calculate Weight percent Oxides
 First write the formulas
 Anorthite is CaAl2Si2O8
 Albite is NaAlSi3O8
 An40 Ab60 is Ca0.4Na0.6Al1.4Si2.6O8
Ca same as Anorthite, Na Same as Albite

Notice Silica (0.4 x 2 Silica in Anorthite) + (0.6 x 3 in Albite) = 2.6

Aluminum (0.4 x 2 Aluminum in Anorthite) + (0.6 x 1 in Albite) = 1.4

Checked Sept. 9th 2011 CLS

Problem 6
Coupled Substitution
 An40 Ab60 formula is Ca.4 Na.6 Al1.4 Si2.6 O8
Oxide Moles MolWt Grams Wt%
PFU Oxide Oxide

SiO2 2.6 60.086 156.22 58.17

Al2O3 0.7 101.963 71.37 26.57
CaO 0.4 55.96 22.38 8.33
Na2O 0.3 61.980 18.59 6.92
Formula weight 268.58 100.00

Example: Notice Al 1.4 moles/PFU reported as Al2O3 is 0.7 PFU

Checked 9 August 2007 CLS

 Problem 7 Given Analysis Compute Mole percents
Jadeite is NaAlSi2O6 Diopside is CaMgSi2O6
We are given the following chemical analysis of a Px:

Oxide Wt% MolWt Moles Moles Moles Prop. Cations to O6

Oxide Oxide Cation Oxygen

 SiO2 56.64 60.086 .9426 .9426 1.8852 2.00

 Na2O 4.38 61.99 .0707 .1414 .0707 .30
 Al2O3 7.21 101.963 .0707 .1414 .2121 .30
 MgO 13.30 40.312 .3299 .3299 .3299 .7
 CaO 18.46 55.96 .3299 .3299 .3299 .7

2.8278

 But pyroxenes here have 6 moles oxygens/mole, not 2.8278. Multiply moles
cation by 6/2.8278

 As always, Moles Oxide = weight percentage divided by molec weight

 Na .3 Ca.7 Al.3 Mg .7 Si2O6 = 30% Jadeite 70% Diopside

http://www.science.uwaterloo.ca/~cchieh/cact/c120/formula.html

This page checked Sept 2 2007 CLS

Next Lecture

Thermodynamics