Nucleation, Chemical

Equilibrium, Recrystallization
Why do rocks change?
Why Metamorphism?
Why Reactions?
 Answer : Thermodynamics
• Theromodynamics : deals with relation b/w
energy and work
• the energy that determines the direction in
which a chemical reaction proceeds is known
as Gibbs free energy.
• Any reaction that can take place naturally
must lower the Gibbs free energy, and the
reaction does not reach equilibrium until the
free energy reaches a minimum.
Natural systems tend toward states of minimum energy
 Equilibrium
• Minimizing the free energy brings about other
conditions that must be met at equilibrium
• At equilibrium: No temp gradient, No pressure
gradient, No chemical potential gradient

DG for any reaction = 0 at equilibrium

The amount of energy needed to cross the
threshold is known as the activation energy .

The activation energy required to start

metamorphic reactions is commonly provided
by slight overheating or mechanical
deformation.

Material that is prevented from reacting by a

large activation energy are said to be
metastable.
 Rate of Met Reactions: Kinetics
• Thermodynamics explains why reactions should take place
and what is required to achieve equilibrium, but it does not
tell us how rapidly the reaction takes place; this is a
question of kinetics.
• In general, reaction rates increase dramatically with
increasing temperature, because of increased diffusion
rates .
• Prograde metamorphic reactions are, therefore, more
rapid than retrograde ones because temperatures are rising
and fluids are being released by reactions.
• Retrograde reactions, in contrast, are very much slower
because temperatures are falling and fluids are generally
lacking.
 Nucleation theory suggests that the rate of
heterogeneous nucleation of a new phase
should show a very sharp dependence on the
amount by which the equilibrium temperature
for a metamorphic reaction is overstepped, so
that nucleation begins suddenly after a certain
critical overstep is achieved.
The interaction between nucleation rate and
mineral growth rate (interface- or diffusion-
controlled) may take two forms, depending on
the rate of heat supply.
At low heating rate, mineral growth rates are
rapid relative to heat supply when the critical
overstep is reached, so that crystals appear
only at the most favourable nucleation sites,
and reaction runs to completion over a small T
(temperature) interval.
At a high rate of heat supply, mineral growth
cannot keep pace with T increase, and
abundant nuclei form over a wide interval of T
and site energy.
 Development of Metamorphic minerals
For a new mineral to appear by a chemical reaction, a number of
processes have to operate in concern:

 Nucleation: nuclei (embryo crystals) of the

new mineral appear
 Interface reactions - dissolution: reactant
minerals break down
 Interface reactions - growth: material is
added onto the nuclei to build larger crystals
 Mass transfer: material is transported through
the rock from sites of breakdown to sites of
growth
 Recrystallization
• Metamorphism brings about the growth of new mineral grains that
generate characteristic textures that can be used to distinguish
metamorphic rocks from igneous and sedimentary rocks. New
grains may appear as a result of recrystallization of former grains in
the protolith or as products of metamorphic reaction. In either
case, grain growth can occur under lithostatic pressure (pressure
equal in all directions), directed pressure, or even a shear stress.
Grain growth is a natural process and, therefore, must involve a
decrease in the Gibbs free energy; that is, once a grain has grown,
the free energy of the rock must be lower than it was before. Grains
have all sorts of energy associated with them other than the simple
chemical energy. For example, a detrital mica grain in a sedimentary
rock that was bent during compaction of the sediment would have
stored elastic energy. Twins in crystals are another source of excess
energy. By recrystallizing, these excess energies are released
 Recrystallization
• All grains have boundaries, which are sources of excess
energy. At grain boundaries, the crystal structure of a
grain must terminate and come in contact with the
crystal structure of adjoining grains. The mismatch of
structures across boundaries results in surface free
energies. The surface area of a large grain is less than
the combined surface area of two smaller grains with
the same total volume. Thus, by recrystallizing to a
coarser-grain size, rocks reduce their surface free
energies. This explains why metamorphic rocks
typically become coarser grained during
metamorphism
 Recrystallization
• Although recrystallization decreases the free energy of a rock by
eliminating energies associated with strain, twinning, and grain
surfaces, the process typically has an activation energy that must
be overcome before new strain-free grains can begin to form. The
energy needed to overcome this threshold may come from rocks
being overheated. In regional metamorphic rocks, deformation
associated with folding and thrusting may supply the activation
energy. Deformation of mineral grains can create small regions of
intense strain that have a much greater tendency to recrystallize
than do less deformed regions. These high-strain regions are the
sites of nucleation of new grains. Once a new strain-free grain has
nucleated, material diffuses to it from nearby deformed grains.
Recrystallization generally coarsens metamorphic rocks, but in
zones of intense shear, so many new nucleation sites may form that
the eventual strain-free rock contains so many grains that it
becomes finer grained.
 Metamorphic reactions at the grain-boundary scale
Elementary reactions
Practical approximations to elementary
reactions are probably of two kinds:
• Replacement reactions B A
Grain boundary (with fluid present?) moves through solid phases,
material is transferred across the boundary and reassembled.
• Coupling between breakdown of one phase and growth of other
• Not usually isochemical
• Constrained to conserve volume approximately

• Solid-fluid reactions
Precipitation, Dissolution
B
Grain boundary advances or retreats against fluid.
Recrystallization: Minimization of Interfacial Free Energy by Minimizing Surface Area

Sandstone Quartzite

Crack
Recrystallization

Cement Crack Crack

 Effect of heating rate
• Slow heating, sparse nucleation: • Rapid heating, abundant nucleation:
biotite porphyroblasts biotite hornfels

Both photomicrographs at same scale, ca. 2.5 mm across

 pseudotachylite
• In extreme cases, rapid shear can generate
sufficient frictional heat on fault planes to
cause melting. The liquid is injected into
fractures in the surrounding rock where it
freezes rapidly to a glass or extremely fine-
grained rock. This rock is known as
pseudotachylite because it resembles
basaltic glass (tachylite) but has the
composition of whatever rock was frictionally
fused.
 Nucleation, Mineral growth and Grain size
-Completed reaction produces an amount of
product (mineral phases). The microstructure, will
depend on the relative rates of nucleation and
growth of minerals
- Grain size in a metamorphic rocks is a
function of:
- Intensity of P-T conditions,
- nuclation rate, and
-Time interval of metamorphism
-Coarse-grained rocks are the product of long
sustained metamorphic conditions
(possibly over millions of years) at HT
and HP (e.g. in high grade regional
metamorphic rocks)
-Fine-grained rocks are products of LP, LT, in
some cases, short reaction time (e.g. in
contact metamorphiic rocks)
 Types of Metamorphic reactions
- With either progressing or retrogressing metamorphism,
various types of metamorphic reactions are proceeds e.g.:
1- Univarient reactions: reactions that plot as line or curve on
the P-T diagram and depend on temperature and pressure
only e.g:

Al2Si4O10(OH)2  Al2SiO5 + 3 SiO2 + H2O

Pyrophyllite Al-silicate + Qtz + fluid
 Types of Metamorphic reactions
2- Divarient reactions: reactions
occur over wide range of P-T. This
is because most minerals
involved in the reaction exhibit
solid solution (e.g garnet, mica,
plagioclase); therefore, the
reaction boundaries can change
depending on the composition of
solid solution.

KAl2Si3AlO10(OH)2 + SiO2 = KAlSi3O8 + Al2SiO5 + H2O

Ms Qtz Kfs Sill W
 Types of Metamorphic reactions
3- Solid-soild reaction: only involve
the solid-phases for both
reactant and products (with no
fluid phases). So reactions
involves phase transformation
e.g.

Calcite  aragonite,
andalusite  sillimanite,
graphite  diamond
Albite  jadite + quartz
 Types of Metamorphic reactions
4- Dehydration reactions: reactions that
liberate H2O. This always occur in the
prograde reaction, i.e. with increasing
temperature e.g

chlorite + muscovite 
orthoclase + andalusite + H2O

5- Decabonation reaction : reactions that

liberate CO2 e.g
Calcite + quartz  Wallstonite + CO2 
 Types of Metamorphic reactions
6- Oxidation-reduction reaction: reactions that involve change the
valence state of Fe-Ti oxide phases (Fe+2 and Fe+3) e.g: the
breakdown of biotite to K-feldspars and magnetite at high P-T
cinditions
biotite + O2  K-feldspars + Magnetite + H2O

7- Cation exchange reaction: reaction involves ionic substitution of two

or more phases in the system e.g:
Fe-garnet + Mg-biotite  Mg-biotite + Fe-garnet

8- Ionic reactions: reaction that balanced by inferring involvement of

ionic species derived from the fluid phase