Subject Geology: Paper No and Title Metamorphic and Igneous Petrology

Subject Geology
Paper No and Title Metamorphic and Igneous Petrology

Binary and Ternary Systems and their Relationship to
Module No and Title Magma Genesis and Crystallization in the Light of Modern
Experimental Work
Module Tag Vb
Principal Investigator Co-Principal Investigator Co-Principal Investigator

Prof. Talat Ahmad Prof. Devesh K Sinha Prof. P. P. Chakraborty
Vice-Chancellor Department of Geology Department of Geology
Jamia Millia Islamia University of Delhi University of Delhi
Delhi Delhi Delhi
Paper Coordinator Content Writer Reviewer
Prof. Pulak Sengupta Dr. Indra Sekhar Sen Prof. Pulak Sengupta
Department of Geological Department of Earth Department of Geological
Sciences, Sciences,
Sciences,
Jadavpur University Jadavpur University
Kolkata IIT Kanpur Kolkata
Paper: Metamorphic and Igneous Petrology

GEOLOGY Module: Binary and Ternary Systems and their Relationship to Magma
Genesis and Crystallization in the Light of Modern Experimental Work
Table of Content
1. Binary Phase Diagrams
2. Ternary Phase Diagrams
3. List of Abbreviations

1. Binary Phase Diagrams
A system with two components is termed as a Binary system. Binary phase relations
can be of different types such as a solid solution, eutectic system, and a eutectic
system with a peritectic reaction. Here we will investigate each of the above
mentioned phase relation with common igneous minerals such as Plagioclase,
Pyroxene and Olivine. We will only discuss few cases of equilibrium and fractional
melting, as well as fractional crystallization.
1.1 Binary Solid solutions

Minerals with very similar mineral lattice structure can easily mix on the
atomic scale, a phenomenon defined as solid solution of one phase with the
other phase. The most common igneous minerals that show such behavior are
olivine and plagioclase. Here we only discuss olivine, which is a solid
solution between forsterite (Mg2SiO4) and fayalite (Fe2SiO4). Figure 1 shows
the forsterite-fayalite phase diagram. This is an isobaric (constant pressure)
phase diagram on T-X space (Temperature on y axis, and Composition on x
axis). The diagram has two loops that intersect on a single point on the T-X
space. These two points are the melting point of forsterite- and fayalite. The
higher temperature curve is the liquidus, which mean anything above that
particular temperature will be liquid, while the lower temperature curve is
solidus below which all are solid phases. In between the solid and liquid
phases, both liquid and solid phases will coexist.


' %(%) *

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1550
1500

1450

+

1400

1350
1300
0 20 40 60 80 100

Figure 1: Equilibrium crystallization of a liquid of composition “BC” in the
system forsterite-fayalite at 1 atmosphere pressure. The y axis is in weight
percent.

1.1.1 Equilibrium crystallization and Equilibrium Melting in the
Forsterite -Fayalite System
Consider a melt with BC composition in Figure 1 (i.e., 60% fayalite,
40% forsterite, or, Fo40Fa60). BC melt composition will start
crystallizing as soon as it reaches the liquidus temperature of 1590oC
[stage (1)]. The composition of the crystal in equilibrium with the melt
composition at (1) (Figure 1) can be obtained by drawing a straight
horizontal line from the liquidus intersection point to the solidus curve,
which will be hereafter called as a “tie-line”. Figure 1 shows the
composition of the first crystals that were crystallized when a melt of
BC composition intersected the liquidus curve at 1590oC. As the
temperature drops, the liquid composition will follow the liquidus
curve towards (2) and (3) in Figure 1a, and its corresponding crystal
composition can be obtained by drawing a tie-line. One can also
constrain the proportions of solid and melt phase using the lever rule.
The lever is a tie-line connecting the coexisting phases (melt and solid)
at a given temperature, and the bulk composition is the “fulcrum” of
the lever. Figure 1b shows how lever rule can be used to quantify the
proportions of solid and melt at a given temperature. For example, at
1525˚C [stage (2) in Figure 5a, b], a “lever” x – z is drawn, where x
and z are coexisting solid and melt compositions, respectively. Since
BC is the bulk composition, it follows that it can be defined by the sum
of the proportions of the solid x and melt z. In our example, we can
calculate the percentage of melt using the lever rule as:
liq% = 100x l
[l+s]
Where l is the distance between x and y, and s is the distance between
y and z [Figure 1b]. Since this is a binary system, %crystals = 100 – %
melt. Thus, using the lever rule one can calculate %melt (or solid) as a
function of temperature for a given bulk composition (Figure 1c). The
melt composition will change from (1) to (4), which is the melt path,
and the corresponding tie lines provide the solid path (Figure 1). The
final crystal composition must have the same starting bulk composition
(BC). The equilibrium melting will just be the opposite of equilibrium
crystallization. BC solid composition will start melting as soon as it
reaches the solidus temperature of 1380oC. The compositional change
in the melt will be through (4) through (1). As discussed above, the
melt proportion at a given temperature can be obtained using lever rule.
BC solid composition will completely melt at 1590oC.
1.1.2 Fractional Crystallization

In fractional crystallization, the crystals formed are instantaneously
removed from the melt and a result a new melt composition is
produced. Figure 2 shows how the liquid and sold path will evolve if
perfect fractional crystallization processes in active. If we start with a
BC melt composition, finally this melt will evolve towards a pure
fayalite composition. The melt path during fractional crystallization is
show in Figure 2 as LP. The solid paths can be of two types in
fractional crystallization: (1) instantaneous solid path (ISP) - one that
tracks the compositions of solids that are in equilibrium with melt at
each instant of crystallization, and (ii) total solid path (TSP), which
tracks the integrated compositions of all solid fractions. In fractional
crystallization the ISP falls on the solidus and can reach pure fayalite
composition; but the TSP follows a curved path (which can be
calculated but beyond the scope of this discussion) below the solidus
and reaches the bulk composition when the last drop of melt runs out
(Figure 2).


Figure 2: Fractional crystallization of a liquid in the system forsterite-
fayalite at 1 atmosphere pressure.
1.2 Binary Eutectic Systems: Diopside-Anorthite at one atmosphere

In a binary eutectic system, a new melting point (called the eutectic point, E
in Figure 3) occurs where melt of a fixed composition (called eutectic
composition) forms when mixtures of two minerals are heated at a fixed
pressure. The temperature at which eutectic melting occurs is called the
eutectic temperature. Let us consider the equilibrium melting of bulk
composition BC. As stated above the first melt will be produced at E, the
eutectic temperature. If we apply Phase Rule at E (remember pressure if
fixed at 1 atm), the degree of freedom at E is zero [c = 2, = 3 (diopside
and anorthosite crystalline phases and melt), so ƒ = 2 – 3 +1 = 0.]. The liquid
path will only move up along the liquids curve when one of the phase gets
exhausted and the degree of freedom becomes 1 (c = 2, = 2 (anorthosite
crystalline phase and melt), so ƒ = 2 – 2 +1 = 0.]. In Figure 3, diopside
crystals will all be dissolved in the melt phase and solid path has reached the
anorthite composition axis (Figure 3). As the temperature is raised further,
the melt will move up the liquidus of anorthite from E to 3’ while the
corresponding solid composition will move from 2 to 3. When the melt
reaches 3’, the starting mixture will be fully molten. Lever rule can be
applied in the same manner as discussed before to find out the proportions of
anorthite crystals and melt phase.
Figure 3: The “system” diopside-anorthite at 1 atmosphere pressure.
The equilibrium crystallization will be will be just the reverse of equilibrium

melting. If we consider the same bulk composition BC at 1500 oC, the first
crystals to be produced will be anorthite crystals when melt intersects the
liquidus curve at 3/. The corresponding solid path can be obtained by
drawing tie lines i.e. 3/-3. As the temperature is further cooled the liquid path
will evolve along the liquidus curve towards the Eutectic point (E), At E
(Figure 3), diopside will start crystallizing, and the solid path will move
towards 1. The final crystal composition must have the same starting bulk
composition (BC). The compositional change in the melt will be from3 /to E,
where 321 will define the solid path.

Example 1:
“The assemblage of nepheline and quartz are not found together in igneous
rocks”. Can you provide an explanation by looking at the nepheline
(NaAlSiO4)-quartz (SiO2) phase diagram (Figure 4) that why we don’t
expect nepeheline and quartz to co-exist? The nepheline-quartz system looks
complex because of the presence of many different SiO 2 polymorph phases,
two eutectic point – E1 and E2, and limited solid solution albite and
carnegieite/nepheline. However, you can simply ignore all these complexities
and consider the phase systematic is composed of two simple eutectic
system- Albite-Nephelene and Albite-Quartz, and apply our learning so far.
Figure 4: Nepheline – silica system.
Solution: Consider two melt composition M1 and M2 (Figure 5), and draw
their liquid paths for equilibrium crystallization. M2 will form nepheline and

albite as its final assemblage, whereas M1 will form albite and quartz. A bulk
composition right above the Albite composition will only produce Albite
crystals. Therefore, any bulk composition towards the right of 100% Albite
composition will move towards right (SiO2), and any bulk composition
towards the left of the 100% Albite composition line will move towards left.
This shows why nepheline and quartz do not co-exists in igneous rock. Here
the melting point of albite serves as a thermal divide. The Ne-SiO2 diagram
with a thermal divide is the experimental proof of the recognition of two
genetically distinct classes of magmas in the field – (a) alkalic magmas,
which are SiO2—deficient magmas that can potentially crystallize nepheline;
and (b) subalkalic magmas (magmas that can potentially crystallize quartz or
tridymite or any other silica polymorph).
Figure 5: Melt M1 and M2 in Nepheline – silica system.

2. Ternary Phase Diagrams
Ternary phase diagrams are three component systems. Ternary diagrams are more
complex than binary systems due to the presence of an additional component. Before
we start our discussion, it is very important to understand how to plot compositions on
a ternary diagram. Plotting compositions on a triangular diagram requires the
knowledge of the percentage of any two components because the third is then
automatically fixed, i.e., if % of A and B are 25 and 35 in a starting melt composition
then C must be equal to 100 – (25+35) or 40%. The apices of the triangle have 100%
A, B and C composition respectively, and as we move away from the apices, say if we
move away from A100, percentage of A decreases. Figure 6 shows a triangular graph,
on which the percentages along A - C are labeled to show how the percentage of A
and C change. Also plotted is the composition A40B30C30 in order to illustrate how the
plotting inside the triangle is done. Horizontal lines represent %A, increasing in 10%
steps from 0% along B – C boundary to 100% at the apex A. Similarly, %B is 0 at the
A – C boundary and increases in 10% steps along the lines parallel to the A – C
boundary, increasing to a maximum of 100% B at the B apex. And, %C lines are
parallel to the A – B boundary. So, A40B30C30 plots where the three lines representing
A40, B30, and C30 intersect.
Figure 6: Plotting a ternary composition in a triangular graph.

The other important thing the readers should be aware is how the temperature is
plotted. Figure 7 is an example of a 3-D perspective diagram of a hypothetical
ternary system at a fixed pressure with A, B and C component. Each side of the
triangle is basically a binary system. Therefore, E1, E2 and E3 are the eutectic points
in between B-C, A-C and A-B respectively. The three sloping surfaces (shaded)
represent the liquidus surfaces for each of the three crystalline phases A, B, and C.
Isotherms (i.e., constant temperature contours) are shown as dashed contours on the
three liquidus surfaces. The boundary line where the two liquidus surfaces intersect
is called the cotectic boundary, for example, the liquidus surface of A and B merge
at the cotectic E3  E.

Figure 7: (a) Perspective sketch of the nature of the liquidus surfaces (differently
shaded) in temperature-composition space for the hypothetical ternary eutectic
system A-B-C at a fixed pressure. The three bounding eutectic points are E 1, E2, and
E3; and the ternary eutectic point is located at E. The dashed curves are isotherms.
Arrows indicate down-temperature directions of the cotectic curves. The inset shows
the liquidus surface of C; with dashed arrows indicating movement paths of various
liquid compositions as they cool. (b)The temperature-composition diagram in (a) is
projected onto the base of the triangle A-B-C.
Ternary phase diagram has 3-cotectic boundaries E1  E, E2  E, and E3  E.

The three-cotectic boundaries intersect at a single point, which is called the ternary
eutectic point. The ternary eutectic point is the lowest possible temperature at which
melt can exist with A, B and C crystals, and melting will always start at ternary
eutectic point.
Example 2:
What will be the degree of freedom along the cotectic boundary and at the ternary
eutectic point for ternary phase diagram at a fixed pressure?
Solution: The ternary eutectic point E has a variance of zero, which can be shown as
follows. Since pressure is fixed, the phase rule reduces to f = c – +1. At E, c = 3,
and = 4 (melt, A, B, and C crystals); therefore, f = 0. Similarly, at the cotectic
boundary c = 3, and = 3 (melt, and any two solid crystals i.e. either A-B, or B-C,
or A-C); therefore, f = 1 and the degree of freedom is one.
2.1 Equilibrium Crystallization and Melting
Figure 8: Equilibrium crystallization of a melt M in the hypothetical ternary

eutectic system A-B-C. Solid and liquid paths are shown as bold lines and tie-
lines are shown as dashed lines.
By now you all are familiar with the ternary phase diagram and its various
components such as eutectic points, liquidus surface, cotectic boundaries,
ternary eutectic points, and the isotherms. The system anorthosite-forsterite-
diopside shows ternary eutectic behavior, however to keep things simple,
here we only consider them as A, B and C phases. The idea is to explain the
fundamentals of a ternary system. Consider a melt composition M with a
liquidus temperature of 1600oC (Figure 8) undergoing equilibrium
crystallization process. As the melt will begin to crystallize B crystals, its
composition will begin to move away from the B corner. The melt will start
crystallizing A as soon as it intersects the E3-E cotectic curve at (1).

Therefore, at (1), there will be three phases A, B and melt and liquid path
will move towards the ternary eutectic point (E). The liquid path will be M-
1-2-3-E. The sold path can be obtained by drawing tie lines through the bulk
composition M. For example, when the melt composition has reached (2), its
corresponding solid phase will be at 2/, which is obtained by drawing a tie
line between 2-M-2/. The solid path will be B-2/-3/-4/-M. As we applied lever
rule in binary systems, the same concepts can be applied here as well.
The equilibrium melting paths for solid residue and melt generated are
exactly the opposite of equilibrium crystallization. The bulk composition M
(Figure 8) will start to melt at the ternary eutectic point E. The degree of
variance will be zero at E, and when all B crystals gets consumed the liquid
path will move away along the E-E3 cotectic curve. At (1) all A crystals will
be consumed and the liquid will move towards M. The liquid path will be
given by E-3-2-1-X, while the solid path will be given by M-4/-3/-2/-B. The
lever rule can be applied here as well to calculate the proportions of different
solid phases present along E-3-2-1-M.
2.2 Fractional Crystallization

In fractional crystallization, the crystals formed are instantaneously removed
from the melt and a result a new melt composition is produced. Consider a
bulk composition X that is undergoing fractional crystallization (Figure 9).
As soon as the first crystals of B are produced at the liquidus temperature of
X, B crystals will be removed and the residual melt composition will start
moving from the B corner. As the B crystals are removed, the melt
composition will start moving towards the cotectic boundary E 3-E and at any
given instance the new liquid composition is a new bulk composition.

Figure 9: Fractional crystallization of starting liquid X.
As the melt reaches (1), crystals of A and B will be produced. The mixture of
A and B crystals will have its composition at the point where a tangent (1 –
1’) to the cotectic E-E3 at 1 meets the binary side A-B of the triangle. This is
a “solid hop”. The melt at 1 will move towards the ternary eutectic point (E),
and as it reached E crystals of A will be produced. The total solid path (1’--
>2’) can be found out by drawing a tangent of the cotectic curve on to the A-
B line. The sold path will be defined by a series of “hop” B, 1’->2’, E. The
new bulk composition of the rock will be at E.

Example 3:
The following diagram is a phase diagram for a hypothetical ternary eutectic system
A-B-C. M and N are two starting liquid compositions.
a. What are the liquidus temperatures of M and N?
b. In the top diagram draw liquid path for equilibrium crystallization of M.
Solution:
a) 1600oC and 1650oC
b) Draw a straight line away from A corner and it will intersect on the E2-E
curve, and after that it will move down towards E.

3. List of Abbreviations
kbar: kilobar
atm: atmosphere
0
C: degree Celsius
0
F: degree Fahrenheit
Wt. %: Weight percent
c: component
p: phase
f: degree of freedom
Frequently Asked Questions-
Q1. With suitable example, explain what are invariant point, univariant line, and
bivariant field in a simple ternary system?
Q2. Explain with suitable example how proportions of different phases can be
calculated in a binary phase diagram?
Q3. What is ISP?
Q4. When two phases are mixed, melting temperature of the mixture increases or
decreases?
Q5. What is a cotectic boundary?
Multiple Choice Questions-
1. On a phase diagram a eutectic point indicates which of the following?

a) Both compounds are solid
b) The melting point of the mixture is lower than the melting points of
either of the individual compounds
c) One compound is in the liquid phase whilst the other is in the solid phase
d) It always occurs when the ratio of compound A to compound B is 50:50

2. On a phase diagram an isotherm indicates which of the following?
a) A region where the composition of the system is constant
b) A region where the pressure is constant
c) An area below which only the solid phase exists
d) A region where the temperature is constant
3. On a two-component solid-liquid phase diagram, a tie line indicates which of
the following?
a) A region where the temperature is constant
b) A region where the composition is constant
c) An area below which only the solid phase exists
d) An area above which only the liquid phase exists
4. The boundary line between (liquid) and (liquid+solid) regions of a phase
diagram is known as
a) Solvus
b) Solidus
c) Liquidus
d) Tie Line
5. The degree of freedom at a ternary eutectic point
e) 0
f) 1
g) 2
h) 3
Suggested Readings:
1. Sen, Gautam (2014). Petrology: Principles and Practice, 1st Edn. Springer-
Verlag Berlin Heidelberg. ISBN: 3642387993, 978-3642387999.
2. Philpotts, Anthony R., & Ague, Jay J. (2009). Principles of igneous and
metamorphic petrology, 2nd Edn. Cambridge University Press. ISBN:
0521880068, 978-0521880060.
3. Winter, John D. (2001). An Introduction to Igneous and Metamorphic
Petrology, 1st Edn. Prentice-Hall Inc., New Jersey. ISBN: 0132403420, 978-
0132403429.


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Subject Geology

Paper No and Title Metamorphic and Igneous Petrology

Principal Investigator Co-Principal Investigator Co-Principal Investigator

Paper: Metamorphic and Igneous Petrology

Paper: Metamorphic and Igneous Petrology

1.1 Binary Solid solutions

Paper: Metamorphic and Igneous Petrology

Paper: Metamorphic and Igneous Petrology

1.1.2 Fractional Crystallization

Paper: Metamorphic and Igneous Petrology

1.2 Binary Eutectic Systems: Diopside-Anorthite at one atmosphere

Figure 3: The “system” diopside-anorthite at 1 atmosphere pressure.

The equilibrium crystallization will be will be just the reverse of equilibrium

Paper: Metamorphic and Igneous Petrology

Figure 4: Nepheline – silica system.

Paper: Metamorphic and Igneous Petrology

Figure 5: Melt M1 and M2 in Nepheline – silica system.

Paper: Metamorphic and Igneous Petrology

Figure 6: Plotting a ternary composition in a triangular graph.

Paper: Metamorphic and Igneous Petrology

Paper: Metamorphic and Igneous Petrology

Ternary phase diagram has 3-cotectic boundaries E1  E, E2  E, and E3  E.

2.1 Equilibrium Crystallization and Melting

Figure 8: Equilibrium crystallization of a melt M in the hypothetical ternary

Paper: Metamorphic and Igneous Petrology

2.2 Fractional Crystallization

Paper: Metamorphic and Igneous Petrology

Paper: Metamorphic and Igneous Petrology

a. What are the liquidus temperatures of M and N?

b. In the top diagram draw liquid path for equilibrium crystallization of M.

a) 1600oC and 1650oC

Paper: Metamorphic and Igneous Petrology

Frequently Asked Questions-

Multiple Choice Questions-

1. On a phase diagram a eutectic point indicates which of the following?

Paper: Metamorphic and Igneous Petrology

Paper: Metamorphic and Igneous Petrology

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