Binary System

 The Crystallisation of bicomposed magma can be

easily understood if the fundamental principle in
kept in mind that, the specific properties of each
constituents are modified in the presence of others.
Most important is the fact that freezing point are
lowered. A study of bi-component Systems or binary
system is much helpful in understanding the salient
features of crystallisation behaviour of magma.
When two component are present their mutual
relation may vary as represented by corresponding
binary system.
Congruent Melting

 melting wherein a phase melts to a liquid with the

same composition as the solid.
 For an Example Wollastonite(casio3) and
caAl2O4 , There exists an Intermediate
compound Gehlenite(Ca2Al2SiO7).
 When Heated Gehlenite melts completely at
15950c to form a liquid of same composition as
the liquid.
 Melting of this type might be regarded as
“normal” is termed as “Congruent”.
(1) Without reaction relation and having
eutectic relation between the phases.
(2) Having Peritectic reaction relation that is
discontinous reaction phenomenon.
(3) Having complete solid solution relation that
is continuos reaction phenomenon.
(4) Having Limited solid solution relation.
Binary system With Eutectic
Relation
 The Crystalisation of magma consists of 2
independent constituents may be illustrated
by the use of the temp-composition diagram.
 Temp is represented in the ordinate and
composition in the abiscica.
 Suppose a magma consists of a mixture
of minerals A & B. If the system contains
only pure A, the melting temperature is
TmA. If the system contains only pure
B,the melting temperature is TmB
 The curves
separating the fields of A + Liquid from
Liquid and B + Liquid from Liquid are
termed liquidus curves. The horizontal
line separating the fields of A + Liquid
and B + Liquid from A + B all solid, is
termed the solidus. The point, E, where
the liquidus curves and solidus intersect,
is termed the eutectic point.
 . At the eutectic point in this two component
system, all three phases, that is Liquid, crystals of A
and crystals of B, all exist in equilibrium. Note that
the eutectic is the only point on the diagram where
this is true .
 Since we looking at a system at constant pressure,
the phase rule in this case is F = C +1 - P.  The eutectic
point is therefore an invariant point.  If we change
the composition of the liquid or the temperature,
the number of phases will be reduced to 2 .
 For all compositions between pure A and pure
B, the melting temperature is drastically
reduced, and melting begins at the eutectic
temperature TE. Note that for all compositions
between A and B the melting also occurs over a
range of temperatures between the solidus and
the liquidus. This is true for all compositions
except one, that of the eutectic. The eutectic
composition melts at only one temperature, TE.
 Rule 1 -  In equilibrium crystallization or
melting in a closed system, the final
composition of the system will be identical
to the initial composition of the system.
 Therefore, according to rule 1, composition X,
which is made up of a mixture of 80% A and
20% B, will have, as its final crystalline
product a mixture of 80% crystals of A and
20% crystals of B.
 Composition X will be all liquid above the temperature
T1, because it will lie in the field of all Liquid. If the
temperature is lowered to T1, at T1 A starts to crystallise.
 Further lowering of the temperature causes more
crystals of A to form. As a result, the liquid composition
must become more enriched in B as more crystals of A
form out of the liquid. Thus, with lowering of
temperature, the liquid composition will change from
point 1 to point 2 to point 3 to point E as the temperature
is lowered from T1 to T2 to T3 to TE respectively.
 At the eutectic temperature, TE, crystals of B will
begin to form, and three phases will coexist;
crystals of A, crystals of B, and liquid. The
temperature must remain at TE until one of the
phases disappears. Thus when the liquid
crystallizes completely, only pure solid A and
pure solid B will remain and mixture of these
two solid phases will be in the proportions of the
original mixture, that is 80% A and 20% of B.
 The Crysatallisation history of composition of
x can be written in abb. Form is as follows.
(1) T>T1- All Liquid
(2) T1-TE –Liquid + A solid
(3) T<TE – A+B (all solid)
(4) At TE –Liquid + A + B
 % of A & B can be calculated at any point by
using of Lever rule.
 % crystals of A = b/(a + b) x 100
 % liquid = a/(a + b) x 100
 Vogt has determined the following eutectic
proportions for certain pairs of rock forming
minerals :-
Orthoclase:Quartz::72.5:27.5
Orthoclase : Albite:: 42:58
Anorthite : Olivine ::70:30
Diopside:Enstatite :: 45:55
Significance

 Some Binary Systems characteristic

Intergrowth textures Results due to
crystallisation of melts at Eutectic Pt.
 Intergrowth of Orthoclase & Quartz
produces the graphic granite.
 Perthite & Micro perthite are
corresponding terms for course and
fine Intergrowth of Orthoclase &
Albite.
Intermediate Compound

 - A phase that has a composition

intermediate between two other phases.
Incongruent Melting

 melting wherein a phase melts to a liquid with a

composition different from the solid and produces a
solid of different composition to the original solid.
 For the case of incongruent melting, we will use the
system forsterite (Mg2SiO4) - silica (SiO2), which has
an intermediate compound, enstatite (MgSiO3).
 This system is a prime example of the phenomena of
incongruent melting in rocks, and therefore gives
insights into many aspects of mineral formation.
 Composition X is a mixture
of 13 wt. % SiO2 and 87 wt. %
Mg2SiO4. Because this
composition falls between
the compositions of pure
forsterite and pure enstatite,
it must end its crystallization
history containing only
crystals of forsterite and
enstatite. i.e. no quartz will
occur in the final crystalline
mixture
 If a mixture such as
composition X is taken
to a temperature
above its liquidus (i.e.
above 1800oC in Figure
2) it will be in an all
liquid state. We now
trace the cooling
history of composition
of X.
 As a liquid of composition X is cooled, nothing
will happen until the temperature is equal to
the liquidus temperature at 1800o. At this point
crystals of forsterite (Fo) begin to precipitate
out of the liquid. As the temperature is further
lowered, the composition of the liquid will
change along the liquidus toward the peritectic
(P), and the crystals forming from the liquid will
always be pure Fo until P is reached.
 At the temperature of the peritectic, about
1580o, note that three phases must be in
equilibrium Fo, liquid, and enstatite (En). At
this point some of the crystals of Fo react
with the liquid to produce crystals of En. The
reaction that takes place can be written as
follows:
 Mg2SiO4 + SiO2 = 2MgSiO3
 Fo + liq = 2En
 After all of the liquid is consumed by this
reaction, only crystals of Fo and En will
remain. The proportions of Fo and En in the
final crystalline product can be found by
applying the lever rule.
 %Fo crystals = [d/(c + d)] x 100
 %En crystals = [c/(c + d)] x 100
 %liquid = [a/(a + b)] x 100
Crystallisation of
composition of Y
 Composition Y is equivalent to pure En. Thus only En may
appear in the final crystalline product if perfect equilibrium
is maintained.
 If composition Y is cooled from an all liquid state it first
begins to crystallize at about 1650o. At 1650ocrystals of Fo
will begin to precipitate from the liquid. This will continue
with further cooling until the temperature of the peritectic
is reached. In this interval, the composition of the liquid
must become more enriched in SiO2 and will thus change
along the liquidus until it has the composition of the
peritectic, P.
 At the peritectic temperature (1580o) all of the
remaining liquid will react with all of the
previously precipitated Fo to produce crystals
of En. The temperature will remain constant
until this reaction has gone to completion, after
which the only phase present will be pure En.
 Thus, it can be seen that enstatite melts
incongruently. If pure enstatite is heated to a
temperature of 1580o it melts to Fo plus liquid.
Crystallisation of
Composition Z
 Since composition Z lies between En and SiO2, it must end up with
crystals of En and Qz (Quartz). If such a composition were cooled
from some high temperature where it is in the all liquid state, it
would remain all liquid until it reached the liquidus temperature at
about 1600o. At this temperature crystals of Fo would begin to
precipitate and the composition of the liquid would begin to change
along the liquidus toward the peritectic, P. At P, all of the Fo
previously precipitated would react with the liquid to produce
crystals of En. After this reaction has run to completion, and all of
the previously precipitated Fo is consumed, there would still remain
some liquid. With decreasing temperature, more crystals of En
would form, and the liquid composition would change along the
liquidus toward the eutectic, E.
 At E crystals of Qz would begin to form, the
temperature would remain constant until all of the
liquid was used up, leaving crystals of Qz and En as
the final solid. Note that because composition Z
lies very close to the composition of pure En, the
final crystalline product would consist mostly of En
with a very small amount of Qz.
 For all compositions between P and 100% SiO2 the
system would behave in an identical fashion to the
simple Eutectic system discussed previously.
 Mg2SiO4-SiO2 is a typical ex. of such binary
systems with silica which exhibit liquid
immscibility. Within the area shown as “2
liquids”, single liquid unmixes in to two
fractions with contrasting composition; one is
almost pure, the other is enriched in
magnesian component.
 The miscibility gap protrudes the cristobalite
liquidous and develops at very high temp under
isobaric condition.
 A liquid above the miscibility gap on cooling
reaches the immiscibility field and splits into
two liquids one of which progressively
becomes more silica rich and other one is
magnesium rich.
 With progressive cooling the relatively silica
rich liquid crystalises as cristobalite at 16890c
where as the magnesium rich liquid cools
down the liquidus to the Eutectic.
Solid Solution:-

 In the systems we've discussed so far, all of the mineral or

solid phases have been pure phases, that is they have one
and only one possible composition. This is not usually the
case in nature, since substitution of one element for
another often occurs due to the fact that some elements
behave in a chemically similar fashion to other elements.
 When such substitutions occur, the phase can have a
range of possible compositions, depending on the
amount of substitution that takes place. Such solids that
can have various amounts of elemental substitution are
called solid solutions.
 Another good example of a complete solid solution
is displayed in the plagioclase feldspars. In this case
the solid solution is between the end members
albite (NaAlSi3O8) and anorthite (CaAl2Si2O8).
 In order to maintain charge balance we cannot
simply substitute Na+ for Ca+2, so this solid solution
is what is called a coupled solid solution. In this case
Na+Si+4 is substituted for Ca+2Al+3 in the plagioclase
structure to produce intermediate compositions of
plagioclase.
 Since plagioclase is one of the most common minerals in
the earth's crust, we will discuss the phase diagram for the
plagioclase system. The phase relations in the plagioclase
system are shown in Figure 3 at constant pressure equal to
that of the atmosphere (atmospheric pressure is 1 bar).
 In this fig. the upper curve is called the liquidus and the
lower curve is called the solidus. At temperatures above
the liquidus everything is liquid, below the solidus
everything is solid (crystals of plagioclase solid solution).
At temperatures between the solidus and liquidus
crystallisation of Plagioclase solid solution coexist in
equilibrium with liquid.
 Pure albite melts (or crystallizes)
at 1118oC, and pure anorthite
melts (or crystallizes) at 1500oC.
Note that any composition of
plagioclase between the two
end members melts or
crystallizes over a range of
temperatures unlike the pure
end members which have only
one melting point. Thus we can
read from the diagram that a
solid solution containing Ab50
An50 begins to melt at 1220o,
point F, and the melting is
complete at 1410o, point A.
 We will now trace the crystallization history of
composition X, which is Ab50An50. Composition X is
completely liquid above the liquidus (above 1410o). Cooling
to the liquidus at point A results in the crystallization of a
small amount of plagioclase solid solution.
 The composition of this plagioclase can be found by
drawing an isotherm (line of constant temperature, a
horizontal line in this diagram) through the temperature
1410o. Where this isotherm intersects the solidus (at point
B), the composition of the solid can be found by drawing a
vertical line to the base of the diagram.
 Thus it is seen that the first crystals precipitated from
composition X will have the composition Ab10An90. Note
that in this diagram crystals that are in equilibrium with
liquid will always be enriched in anorthite component
relative to the liquid.
 As crystallization continues with lowering of temperature
the composition of the plagioclase will change along the
solidus, continually reacting with the liquid to produce
crystals more enriched in the Ab component. Meanwhile,
the composition of the liquid will change along the
liquidus, thus also becoming more enriched in the Ab
component.
 At a temperature of 1395o the liquid composition
will be at point C, while the solid composition
will be at point D. Crystallization proceeds until a
temperature of about 1220o, at which point the
last remaining liquid will have a composition at
E, and the solid will have a composition equal to
the original starting composition at point F.   
 At this point all of the liquid will be consumed
and the final crystalline product will have the
composition Ab50An50.
 If at any point during the crystallization we wish
to determine the amount of solid and liquid, we
can apply the lever rule. As an example, we will
determine the proportions of liquid and solid in
the system at a temperature of 1395o. At this
point, we measure the distances oC, oD, and CD.
The percentages of liquid and solid are then given
as follows:
 % solid (with composition D) = [x/(x + y)] x 100
 % liquid (with composition C) = [y/(x + y)] x 100
 The foregoing discussion assumes that equilibrium is
maintained throughout the course of crystallization.
 This means that with falling temperature and
continuing crystallization, the earlier-formed, more
calcic crystals must react continuously with the liquid
to produce homogeneous crystals that will become
continuously more enriched in the sodic component.
 If this equilibrium cannot be maintained, then
fractional crystallization will take place.
 Many minerals that show complete solid
solution at higher temperatures do not show
such solid solution at lower temperatures.
 When this is the case, the phenomenon of
exsolution occurs. Since solid solutions are really
one mineral phase dissolved in another mineral
phase to form a single mineral phase, exsolution
implies that one or the other of the mineral
phases in the solution must "exsolve" or come
out of solution with the other mineral phase
 Figure 4 illustrates a phase
diagram (much simplified)
of the alkali feldspar system
which exhibits such
exsolution behavior at low
temperatures. At high
temperatures the diagram
shows that albite (Ab) or
NaAlSi3O8and orthoclase
(Or) or KAlSi3O8 form a
complete solid solution
series.
 . This solid solution series is different from the
plagioclase solid solution series only in that it has a
minimum composition in the middle rather than at
the composition of one of the pure end members.
 At temperatures just below the solidus, alkali
feldspar solid solutions are stable. At lower
temperatures, along the curve labeled "solvus" the
solid solution is no longer.
 In this case the exsolution phenomena occurs below
the solidus and so is a "sub-solidus" reaction stable.