Chemistry of Igneous Rocks

• Characterization of different types (having

different chemistries):
– Ultramafic  Mafic  Intermediate  Felsic

• Composition commonly presented in

weight % of the oxides
– 40-78% SiO2
– 12-18% Al2O3
 Melts
• Liquid composed of predominantly silica and oxygen.
Like water, other ions impart greater conductivity to
the solution
• Si and O is polymerized in the liquid to differing
degrees – how ‘rigid’ this network may be is
uncertain…
• Viscosity of the liquid  increases with increased
silica content, i.e. it has less resistance to flow with
more SiO2… related to polymerization??
• There is H2O is magma  2-6% typically – H2O
decreases the overall melting T of a magma, what
does that mean for mineral crystallization?
 Thermodynamic definitions
• Gi(solid) = Gi(melt)
• Ultimately the relationships between these is related to the
entropy of fusion (S0fus), which is the entropy change
associated with the change in state from liquid to crystal

 dT  RT fus
   0
dX
 i S fus

• These entropies are the basis for the order associated with
Bowen’s reaction series  greater bonding changes in
networks, greater entropy change  lower T equilibrium
 • Minerals which form are
thus a function of melt
composition and how fast it
cools (re-equilibration?) 
governed by the stability of
those minerals and how
quickly they may or may not
react with the melt during
crystallization

Mg2+ Na+
Ca 2+
Fe2+
O2- Mg2+ Fe2+
Liquid hot O
2-
cooling rock
O2- MAGMA O 2-
O2- Si4+ O2- O2-
Si4+ Mg2+
O2- O2- O2- Si4+
Processes of chemical differentiation
• Partial Melting: Melting of a different solid
material into a hotter liquid

• Fractional Crystallization: Separation of

initial precipitates which selectively
differentiate certain elements…

• Equilibrium is KEY --? Hotter temperatures

mean kinetics is fast…
 Melting
• First bit to melt from a solid rock is generally
more silica-rich
• At depth in the crust or mantle,
melting/precipitation is a P-T process,
governed by the Clausius-Clapeyron
Equation – Slope is a function of entropy and
volume changes!
• But with water… when minerals precipitate
they typicaly do not pull in the water, melt left
is ‘diluted’  develop a negative P-T slope
 Melt-crystal equilibrium 1
• Magma at composition
X (30% Ca, 70% Na) X
cools  first crystal
bytownite (73% Ca,
27% Na)
• This shifts the Y
composition of the
remaining melt such that
it is more Na-rich (Y)
Z
• What would be the next
crystal to precipitate?
• Finally, the last bit
would crystallize from Z
 Melt-crystal equilibrium 1b
• Precipitated crystals
react with cooling
liquid, eventually will
re-equilibrate back,
totally cooled magma
xstals show same
composition
• UNLESS it cools so
quickly the xstal
becomes zoned or the
early precipitates are
segregated and
removed from contact
with the bulk of the melt
 Why aren’t all feldspars
zoned?
• Kinetics, segregation

• IF there is sufficient time, the crystals will re-

equilibrate with the magma they are in – and
reflect the total Na-Ca content of the magma
• IF not, then different minerals of different
composition will be present in zoned
plagioclase or segregated from each other
physically
• What about minerals that do not
coexist well – do not form a solid
solution – are immiscible??
• More than 1 crystal can precipitate from a melt –
different crystals, different stabilities…
– 2+ minerals that do not share equilibrium in a melt are
immiscible (opposite of a solid solution)
– Liquidus  Line describing equilibrium between melt and
one mineral at equilibrium
– Solidus  Line describing equilibrium with melt and solid
– Eutectic  point of composition where melt and solid can
coexist at equilibrium

Diopside is a pyroxene Solidus

Anorthite is a feldspar Eutectic

Liquidus
• Melt at composition X cools to point Y where anorthite
(NOT diopside at all) crystallizes, the melt becomes more
diopside rich to point C, precipitating more anorthite with
the melt becoming more diopside-rich
• This continues and the melt continues to cool and shift
composition until it reaches the eutectic when diopside
can start forming
A
At eutectic, diopside
AND anorhtite crystals B S1
precipitate C S2
Lever Rule 
diopside/anorthite
(42%/58%) crystallize
until last of melt Z
precipitates and the rock
composition is Z
• Melting  when heated to eutectic, the
rock would melt such that all the heat goes
towards heat of fusion of diopside and
anorthite, melts so that 42% diopside /
58% anorthite…
• When diopside gone, temperature can
increase and rest of anorthite can melt
(along liquidus)
 Melt-crystal equilibrium 2 -
miscibility
• 2 component mixing
and separation 
100
chicken soup analogy,
SOUP
cools and separates

Temperature (ºC)
• Fat and liquid can X
crystallize separately if
cooled slowly
50
• Miscibility Gap – no
single phase is stable 0 Y
fats
• SOUP of X ice Miscibility Gap
composition cooled in Z
-20
fridge Y vs freezer Z 10 30 50 70 90
Water
Fat
% fat in soup
 Melt-crystal equilibrium 2 -
miscibility
• 2 component mixing
and separation  anorthoclase
monalbite

chicken soup 1100

analogy, cools and high albite

Temperature (ºC)
separates 900
sanidine
intermediate albite
• Fat and liquid can
crystallize separately 700
orthoclase
if cooled slowly
• Miscibility Gap – no 500
microcline low albite

single mineral is Miscibility Gap

stable in a 300
composition range for 10 30 50 70 90

x temperature Orthoclase Albite

% NaAlSi3O8
KAlSi3O8 NaAlSi3O8
 Combining phase and composition
diagrams for mineral groups
Mica ternary
Muscovite
KAl2(AlSi3O10)(OH)2

No micas
Miscibility Gap

Biotite series
Annite Phlogopite
KFe3(AlSi3O10)(OH)2 KMg3(AlSi3O10)(OH)2
 SOLID SOLUTION
• Occurs when, in a crystalline solid, one
element substitutes for another.
• For example, a garnet may have the
composition: (Mg1.7Fe0.9Mn0.2Ca0.2)Al2Si3O12.
• The garnet is a solid solution of the following
end member components:
Pyrope - Mg3Al2Si3O12; Spessartine - Mn3Al2Si3O12;
Almandine - Fe3Al2Si3O12; and Grossular -
Ca3Al2Si3O12.
 GOLDSCHMIDT’S RULES
1. The ions of one element can extensively replace
those of another in ionic crystals if their radii differ
by less than approximately 15%.
2. Ions whose charges differ by one unit substitute
readily for one another provided electrical neutrality
of the crystal is maintained. If the charges differ by
more than one unit, substitution is generally slight.
3. When two different ions can occupy a particular
position in a crystal lattice, the ion with the higher
ionic potential forms a stronger bond with the
anions surrounding the site.
 RINGWOOD’S MODIFICATION OF
GOLDSCHMIDT’S RULES
4. Substitutions may be limited, even when the size and
charge criteria are satisfied, when the competing ions
have different electronegativities and form bonds of
different ionic character.
This rule was proposed in 1955 to explain discrepancies
with respect to the first three Goldschmidt rules.
For example, Na+ and Cu+ have the same radius and
charge, but do not substitute for one another.
 INCOMPATIBLE VS. COMPATIBLE
TRACE ELEMENTS
Incompatible elements: Elements that are too large
and/or too highly charged to fit easily into common
rock-forming minerals that crystallize from melts.
These elements become concentrated in melts.
Large-ion lithophile elements (LIL’s): Incompatible owing to
large size, e.g., Rb+, Cs+, Sr2+, Ba2+, (K+).
High-field strength elements (HFSE’s): Incompatible owing to
high charge, e.g., Zr4+, Hf 4+, Ta4+, Nb5+, Th4+, U4+, Mo6+, W6+,
etc.
Compatible elements: Elements that fit easily into rock-
forming minerals, and may in fact be preferred, e.g.,
Cr, V, Ni, Co, Ti, etc.
Changes in element concentration in the magma
during crystal fractionation of the Skaergaard
intrusion: Divalent cations
Changes in element concentration in the magma
during crystal fractionation of the Skaergaard
intrusion: Trivalent cations
THREE TYPES OF TRACE-
ELEMENT SUBSTITUTION

1) CAMOUFLAGE

2) CAPTURE

3) ADMISSION
 CAMOUFLAGE
• Occurs when the minor element has the
same charge and similar ionic radius as
the major element (same ionic potential;
no preference.
• Zr4+ (0.80 Å); Hf4+ (0.79 Å)
• Hf usually does not form its own mineral; it
is camouflaged in zircon (ZrSiO4)
 CAPTURE
• Occurs when a minor element enters a
crystal preferentially to the major
element because it has a higher ionic
potential than the major element.
• For example, K-feldspar captures Ba2+
(1.44 Å; Z/r = 1.39) or Sr2+ (1.21 Å; Z/r =
1.65) in place of K+ (1.46 Å, Z/r = 0.68).
• Requires coupled substitution to balance
charge: K+ + Si4+  Sr2+ (Ba2+) + Al3+
 ADMISSION
• Involves entry of a foreign ion with an ionic
potential less than that of the major ion.
• Example Rb+ (1.57 Å; Z/r = 0.637) for K+
(1.46 Å, Z/r = 0.68) in K-feldspar.
• The major ion is preferred.
 Partition Coefficients
• How can we quantify the distribution of trace
elements into minerals/rocks?
• Henry’s Law describes equilibrium distribution of
a component (we usedit for thinking about gases
dissolved in water recently):
– aimin = kiminXimin
– aimelt = kimeltXimelt  ppmimin   X imin 
– All simplifies to:  melt
   melt   K iD
 ppmi   Xi 
• Often termed KD, values tabulated…
http://www.earthref.org/databases/index.html?main.htm
 Limitations of KD
• What factors affect how well any element
gets into a particular rock???
 Melting and Crystallization
• Considering how trace elements incorporate the
melt or solid:
Cimelt 1
0
 D
Ci (rock ) K i (1  F )  F
• Where KD(rock)=KD(j minerals)Xj
• For consideration of trace elements into a solid,
use Rayleigh fractionation equation:
C melt
C 0
F K D
i 1 
i i ( rock )

• Where F is the fraction of melt remaining

• However, most KD values reported close to
equilibrium T-P values commonly
encountered (?) and are reasonable, at
least in terms of relative values between
different elements…
 Homework
• Chapter 8
• Problems 2, 6