Thermodynamic Models

of Magmas

Introduction to Kinetics
Lecture 13
 Silicate Magmas
Basic structural unit of
silicates (solid & liquid) is
the silica tetrahedron

• These are variously joined by

shared, or bridging, oxygens, to
form various structures in solids and
liquids.
• Basic difference between solids
and liquids is lack of long-range
structure in the latter.
• Liquids structure can be studied by
quenching them to glass.
Liquid Structures
• Bridging oxygens and
joining tetrahedra results in
polymerization of the melt,
changing its properties.
• Al3+, Ti, and Fe3+ can
promote polymerization
and, along with Si, are
called network-forming ions.
• Other ions, Ca2+, Mg2+, Fe2+,
Na+, K+, and H+ tend to
break up this structure and
are called network
modifiers.
 Modeling Silicate Liquids
• Silicate liquids are • Problems are:
o Decide on the components
complex solutions of o Determine the nature of the model

many components. • Ghiorso et al. adopt a regular solution

model for their MELTS model.

• Solids crystallizing from • Determine the interaction

parameters from experimental
them are generally data.
solutions themselves. • The resulting program then
• Generally these solutions iteratively computes free energy
of the liquid plus free energy of
cannot be treated as
all possible precipitating solids
ideal. and calculates the equilibrium
• Crystallization (or melting) assemblage based on the
principles that
occurs over a wide range o the stable assemblage is the one with the
of T (400-500˚C). o
lowest free energy.
The chemical potentials of components in
coexisting phases are equal.
 MELTS Model
• For network modifiers, • Free energy of the
Ghiroso et al. chose
silicate components such liquid solution is:
as CaSiO3, Mg2SiO4, 1 æ ö
Na2SiO3, KAlSiO4, etc. G = å Xi µio + RT å ln Xi + å å i j G ÷ø
2 i çè j
X X W i, j

because mole fractions i

of individual oxides tend

to be small numbers, • Activity coefficients
reducing influence of calculated as:
interaction parameters.
• Network formers RT ln li = å X jWGi, j -
1
å å X j XiWGi,k
generally just the oxides i 2 i k
(e.g., Al2O3).
• Eleven components, plus
water treated separately.
 Components &
Interaction Parameters
 Will Plagioclase
Precipitate?
• For anorthite, reaction of interest is:
CaSiO3(l) + Al2O3(l) + SiO2(l) ⇋ CaAl2Si2O8(plag)
• But plag is usually a solid solution, so:
• x[½NaSiO3 + ½Al2O3(l) + 2½SiO2(l)] + y[CaSiO3(l) + Al2O3(l) +
SiO2(l)] ⇋ [yCaAl2Si2O8–xNaAlSi3O8](plag)
• What thermodynamic condition must be met for
plagioclase to precipitate?
o ∆Gr is negative.
o The negative of ∆Gr is often referred to (particularly in MELTS lingo) as the
affinity of reaction, Ar.
o MELTS calculates affinities for all possible reactions.
• If a plagioclase crystal has precipitated from a magma
under equilibrium conditions, what can we say about
the component?
o Chemical potentials of components must be equal in both solid and liquid.
MELTS Iterations
Calculate
∆G for all possible
reactions

Recalculate liquid and Precipitate any phases

all solid compositions where ∆Gr is negative

Otherwise
increment T, P

Recalculate liquid comp

Precipitate any phases
and Calculate ∆G for all
where ∆Gr is negative;
possible reactions
 pMELTS
Predicted and actual SiO2
Predicted and actual
concentrations in experimental
pyroxene compositions in
melts of peridotite as a
lavas.
function of melt percent.
Introduction to Kinetics
Lecture 14
 Reading in Chapter 5
Read sections 5.1 through 5.5.4 (p.160 to p. 199) and section 5.7
(p. 207-211).
We will probably skip the intervening sections – or cover them
briefly.

Book errata:
http://bcs.wiley.com/he-bcs/Books?action=index&itemId=0470656670&bcsId=8017
 Kinetics
• Whereas thermodynamics concerns itself with
equilibrium and the distribution of components
between species and phases at equilibrium, kinetics
concerns itself with the pathway to equilibrium,
including the rates and mechanisms of reaction.
• Rates depend on temperature and at the surface
of the Earth reaction rates are often so slow that
equilibrium is never achieved. This can also be true
at higher temperature - and we have mentioned
one example (the spinodal).
• The microscopic perspective becomes somewhat
more important in kinetics than it was in
thermodynamics.
 Overall & Elementary
Reactions
• The reaction:
CaAl2Si2O8 + 3H2O + CO2 = CaCO3 + 2Al(OH)3 + 2SiO2
describes a key process at the surface of the Earth, namely weathering igneous
minerals (plagioclase) to form common sedimentary ones (calcite, gibbsite, and
quartz). But does this overall reaction describe what actually happens?
NO.

• In thermodynamics ,we might not care, but in kinetics, we

do. The first step in understanding reaction pathways and
reaction mechanics is to breakdown overall reactions
such as this into the elementary reactions.
• An elementary reaction is one that involves only one step
a describes what occurs on the microscopic level.
 Reaction Mechanisms
• We can begin to breakdown the overall reaction.
Some steps are:
CO2(g) + H2O = CO2(aq) + H2O
CO2(aq) + H2O = H2CO3
H2CO3 = H+ + HCO3–
o Producing acidity necessary for weathering.
• Next step is likely absorption of H+ to the surface:
CaAl2Si2O8 + 2H+ = H2CaAl2Si2O82+
• Followed by replacement of the Ca by H:
H2CaAl2Si2O82+ = H2Al2Si2O8 + Ca2+
• etc.
 Defining Reaction Rates
• For a reaction such as:
Ca2+ + Mg2+ + 2CO32– = CaMg(CO3)2
• We define the rate of reaction as the rate of production
of the products, or equivalently, the rate of consumption
of the reactants divided by the stoichiometric
coefficient:

• Equivalently:

• The equation tell us nothing about what the reaction

rate is, we are just defining what it means.
o We’ll shortly see that rates generally do depend on concentrations or
reactants and products, so don’t be confused.
 Reaction Rates &
Concentration
• Consider the gas phase reaction:
• N0 + O2 = NO + O0
• First thing that must happen is we
must bring the reactants
together.
• We can imagine a reference
frame in which the N atom
sweeps out a volume V = v × t ×
πr2 (velocity times time times
area).
• Whether a reaction will occur in
that time will depend on whether
or not the center of an oxygen
molecule is present within that
volume.
• Number of collisions (per N)will
be: C = nO vp (rN + rO ) t
2

• Overall collision rate will be:

C
= nN nO vp (rN + rO )2
t
 Bottom Line:

For an elementary reaction, we expect the

rate of reaction to depend on the
concentration of reactants
 Dependence on
Temperature
• Just because two people
meet on a date, doesn’t
mean they will tie the knot.
o Kinda depends on how ‘hot’ the
date was!
• Similarly, just because two
atoms or molecules collide,
doesn’t mean they will
react.
o Depends on whether the collision is
energetic enough to overcome
coulomb repulsion and the electron
orbits can reorganize.
o An energy barrier, EB, must be
overcome.
o That means it depends on
temperature.
• Hence the date analogy!
 Temperature and Barrier Energy
• Since energy levels are closely
spaced, we can integrate, so the
probability of a molecule having
• We suppose that a E ≥ EB is: ¥

reaction will proceed if ò e-ei /kT

P = e¥B = e-e B /kT
the N atom has at least ò e-ei /kT
certain energy, E ≥ EB. 0

• Our reaction rate is now:

• What function tells us
how energy is
• Maxwell-Boltzmann Law gives
distributed among ave. velocity in a gas as:
molecules? 8kT
v=
Boltzmann Distribution pm

Function. • where µ is reduced mass of gas:

µ = mNmO2/(mN + mO2)
e-ei /kT
Pi =
å e-en /kT
n
 Arrhenius Relation
• Our equation now is:

• Let: 8kT
A= p (rN + rO )2
pµ
• A describes the frequency of opportunity for reaction
and is called the frequency factor.
• We can express the temperature dependence of the
reaction rate as: - e /kT
k = Ae B

• This is known as the Arrhenius relation and describes the

dependence of reaction rates on temperature.
 The Rate Constant
• Arrhenius Relation
- e B /kT
k = Ae
• k is known as the rate constant.
o So many K’s!
o We’ll use upper case roman K for the equilibrium constant
o Lower case roman k for Boltzmann’s constant
o Lower case italic k for the rate constant.

• We can now write the rate of our N+O2 reaction as:

= knN nO2
 Reaction Rates and
Temperature
• The Arrhenius Relation tells us
that reaction rates depend
exponentially on temperature
(fits everyday experience).
• This is reason high-T rocks
survive at the surface of the T = 300K
Earth out of equilibrium.
• In the gas phase reaction, A
depended on square root of
T - much weaker than the
exponential factor.
• Other kinds of reactions show
difference dependence of A
on T. EB = 15kJ
• In many cases we can view A
as a constant independent of
T.
Dependence of the rate
constant on T and barrier energy