Chemical Thermodynamics
CH 201
Phase Equilibria & Phase Diagrams
2/4/2024 CH 201 CHEMICAL tHERMODYNAMICS 1
Binary Isomorphous Systems (I)
Isomorphous system - complete solid solubility of the two
components (both in the liquid and solid phases).
Three phase region can
be identified on the
phase diagram:
➢ Liquid (L)
➢ solid + liquid (α + L)
➢ solid (α)
2
Binary Isomorphous Systems (II)
Liquidus line separates
liquid from liquid + solid.
Solidus line separates
solid from liquid + solid.
There may be a gap
between the solidus and
liquidus.
Within the gap, the
substance consists of a
mixture of crystals and
liquid (like a "slurry").
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Binary Isomorphous
Systems (III)
Example of
isomorphous system:
Cu-Ni (the complete
solubility occurs).
Complete solubility occurs because both Cu and Ni
have the same crystal structure, FCC (face centered
cubic), similar radii and electronegativity.
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Binary Isomorphous Systems (IV)
In one-component system melting occurs at a well-defined melting
temperature.
In multi-component systems melting occurs over the range
of temperatures, between the solidus and liquidus lines.
Solid and liquid phases
are at equilibrium with
each other in this
temperature range.
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Interpretation of a binary phase diagrams
For a given temperature and
composition we can use phase
diagram to determine:
1) The phases that are present,
2) Compositions of the phases,
3) The relative fractions of the
phases.
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Interpretation of a binary phase diagrams…
Finding the composition in a two
phase region:
1. Locate composition and
temperature in diagram.
2. In two phase region, draw the tie
line or isotherm.
3. Note intersection with phase
boundaries.
4. Read compositions at the
intersections. The liquid and solid
phases have these compositions.
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The lever rule
Finding the amounts of phases in a two phase region:
1. Locate composition and temperature in a diagram.
2. In two phase region draw the tie line or isotherm.
3. Fraction (mass or weight fraction) W of a phase is determined
by taking the length of the tie line to the phase boundary for
the other phase, and dividing by the total length of tie line.
The lever rule is a mechanical analogy
to the mass balance calculation.
The tie line in the two-phase region
is analogous to a lever balanced on a
fulcrum.
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Derivation of the lever rule
1) A material must be in one phase (solid, α phase) or the
other (liquid, L): the sum of the mass fractions is
Wα + WL = 1
2) Mass of a component (here Cu or Ni) that is present in
both phases (solid and liquid) equal to the mass of the
component in one phase + mass of the component in
the second phase:
WαCα + WLCL = C0
C is a mass concentration of a given component (here Ni or B in general)
3) Solution of these equations gives us the lever rule.
WL = (Cα – C0) / (Cα – CL)
Wα = (C0 – CL) / (Cα – CL)
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Phase compositions and mass fractions.
An example of Cu-Ni alloy
Given:
C0 = 35 wt. % of Ni
(and 65 wt % of Cu),
CL = 31.5 wt. % of Ni,
t = 1250 °C
Cα = 42.5 wt. % of Ni,
t = 1250 ⁰C
Find: WL, Wα
Mass fractions:
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Development of
microstructure in
isomorphous alloys
(Equilibrium cooling)
➢Solidification in the
solid + liquid phase
occurs gradually
upon cooling from
the liquidus line.
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Development of
microstructure in
isomorphous alloys
(Equilibrium cooling)…
➢The composition of
the solid and the liquid
change gradually
during cooling (as can
be determined by the tie-
line method).
➢Nuclei of the solid
phase form and they
grow to consume all
the liquid at the solidus
line. 12
Binary Eutectic Systems
Eutectic: relating to or denoting
a mixture of substances (in fixed
proportions) that melts and
freezes at a single temperature
that is lower than the melting
points of the separate
constituents or of any other
mixture of them (eutectic means
easy to melt in Greek).
➢At most two phases can be in equilibrium within a phase
field.
➢Three phases (L, α, β) may be in equilibrium only at a few
points along the eutectic isotherm.
➢Single-phase regions are separated by 2-phase regions. 13
Binary Eutectic Systems: systems (alloys) with limited solubility
Three single phase
regions:
• α is the solid
solution of Ag in Cu
matrix,
• β is the solid
solution of Cu in Ag
matrix,
• L is liquid.
Three two-phase
regions:
• α + L, β + L, α + β
Solvus line separates one solid solution from a mixture of
solid solutions. Solvus line shows limit of solubility. 14
Binary Eutectic Systems…
Eutectic or invariant point - Liquid and two solid phases co-exist
in equilibrium at the eutectic composition CE and the eutectic
temperature TE.
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Eutectic isotherm - the horizontal solidus line at TE.
Binary Eutectic Systems…
Eutectic reaction – transition between liquid and mixture
of two solid phases, α + β at eutectic concentration CE.
The melting point of the eutectic alloy is lower than that of
the components. 16
Binary Eutectic Systems …
Compositions and relative amounts of phases are determined
from the same tie lines and lever rule, as for isomorphous alloys.
Task: For points A,
B, and C calculate
i) the compositions
(wt. %) and
ii) relative amounts
(mass fractions) of
phases present.
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How to calculate relative amounts of microconstituents?
Eutectic microconstituent forms from liquid having eutectic
composition (61.9 wt% Sn).
The second microconstituent, in this case, is the primary α phase.
We can treat the
eutectic as a separate
phase and apply the
lever rule to find the
relative fractions of
primary α phase (18.3
wt% Sn) and the
eutectic structure (61.9
wt% Sn):
We = P / (P+Q) (eutectic)
Wα = Q / (P+Q) (primary) 18
