5.

8 Liquid-Liquid phase diagrams

Key points
1.  Phase separation of partially miscible liquids
may occur when T is below UCST or above
LCST
2.  UCST is the highest T at which phase separation
occurs. LCST is the lowest T at which phase
separation occurs
3.  The outcome of a distillation of a low-boiling
azeotrope depends on whether the liquids
become fully miscible before they boil or boiling
occurs occurs before mixing is complete
4.  Consider partially miscible liquids
 5.8 Liquid-Liquid phase diagrams
(a) Phase separation
•  Suppose a small amount of liquid B is
added to a sample of another liquid B
at T’. Liquid B dissolves completely
forming a single phase
•  As more B is added, a stage comes at
which no more dissolves. The sample
consists of two phases in equilibrium;
A-rich phase (a’’) and B-rich phase (a’)
•  Lever rule is still applied
•  As more B is added, a stage comes at
so much B is present and it can
dissolve all the A forming a single
phase
 5.8 Liquid-Liquid phase diagrams
(b) Critical solution temperature
•  Upper critical solution temperature
(UCST) : the highest temperature at
which phase separation occurs
•  The phase boundary: ∂∆mixG/∂x = 0
x
ln + ξ (1− 2x ) = 0
1− x
•  Lower critical solution temperature
(LCST) : below LCST they mix in all
proportions and above which they
form two phases
•  Some systems have both upper and
lower critical solution temperatures
(Figure 5.47)
 5.8 Liquid-Liquid phase diagrams
(c) The distillation of partially miscible liquids
•  Consider a pair of liquids that are
partially miscible and form a low-
boiling azeotrope
•  This combination is quite common
because both properties reflect the
tendency of A and B to avoid each
other
•  (1) The liquids become fully miscible
before they boil and (2) the boiling
occurs before mixing is complete
•  Distillation of a1 leads to a vapor of
composition b1
•  b1 condenses to the completely
miscible single-phase solution at b2
•  When this distillate is cooled to b3,
phase-separation occurs
 5.8 Liquid-Liquid phase diagrams
(c) The distillation of partially miscible liquids
•  Distillate obtained from a liquid of
composition of a1 has composition b3
•  The distillate is a two-phase mixture
of b3’ and b3’’
•  A system at e1 forms two phases,
which persist up to the boiling point at
e2. The vapor of this mixture has the
same composition as liquids
(azeotrope)
•  Condensing a vapor of composition e3
gives a two-phase liquid of the same
overall composition
 5.9 Liquid-solid phase diagrams
Key points
1.  At the eutectic composition the liquid phase
solidifies without change of composition
2.  The phase equilibria of binary systems in which
the components react may also be summarized
by a phase diagram
3.  In some cases, a solid compound does not
survive melting
 5.9 Liquid-solid phase diagrams
(a) Eutectics
•  a1 → a2 : The system enters the two-phase
region labeled ‘Liquid+B’. Pure solution
begins to come out of solution and remaining
liquid becomes richer in A
•  a2 → a3 : More of the solid B forms
•  a3 → a4 : At the end of this step, there is less
liquid a3, and its composition is given by e2.
This liquid now freeze to give a two-phase
system of pure B and pure A
•  The isopleth e2 corresponds to “the eutectic
composition”: a liquid with the eutectic
composition freezes at a single temperature,
without previously depositing solid A or B
•  Thermal analysis is a powerful way of
detecting eutectics
•  Eutectic halt
 5.9 Liquid-solid phase diagrams
(b) Reacting systems
•  Many binary mixtures react to produce
compounds
•  For example, Ga + As ⇌ GaAs
•  Although three constituents are present,
there are only two components
•  Consider A + B ⇌ C
•  Consider a system prepared by mixing an
excess of B with A that consists of C and
unreacted B
•  The solid deposited on cooling along the
isopleth a is C
•  Below a4 there are two solid phases:
solid B and solid C phases
•  The pure compound C melts congruently,
that is the composition of the liquid it
forms is the same as that of the solid
 5.9 Liquid-solid phase diagrams
(c) Incongruent melting
• C is not stable as a liquid
(Liquid Na2K is unstable)
• a1 → a2 : A solid solution
rich in Na is deposited
• a2 → just below a3 : The
sample is entirely solid
and consists of a solid
solution rich in Na and
solid Na2K
•  b1 → b2 : Solid solution rich in Na begins to deposit
•  b2 → b3 : A solid solution rich in Na deposits, but a reaction occurs
to form Na2K
•  b3 : Three phases are in mutual equilibrium; liquid + Na2K + a solid
solution rich in Na (peritectic line)
•  b3 → b4 : The amount of solid compound increases until at b4 the
liquid reaches its eutectic composition. It solidifies to give a two-
phase solid of a solid solution rich in K and solid Na2K
 5.10 The solvent activity
Key points
1.  The activity is an effective concentration that
preserves the form of the expression for the
chemical potential
 5.10 The solvent activity
•  The general form of the chemical potential of a real or ideal
solvent is given by a straightforward modification of µA = µA* +
RTln(pA/pA*)
•  For an ideal solution, the solvent obeys Raoult’s law and µA = µA*
+ RTln(xA)
•  The form of this relation can be preserved when the solution does
not obey Raoult’s law
pA
µ A = µ ∗A + RT ln aA aA =
p∗A
•  The quantity aA is the activity of A (an “effective” mole fraction)
•  The activity coefficient, ϒ

a A = γ A x A and γ A →1 as x A →1
µ A = µ∗A + RT ln x A + RT ln γ A
 5.11 The solute activity
Key points
1.  The chemical potential of a solute in an ideal-
dilute solution is defined on the basis of Henry’s
law
2.  The activity of a solute takes into account
departures from Henry’s law behavior
3.  An alternative approach to the definition of the
solute activity is based on the molality of the
solute
4.  The biological standard state of a species in
solution is defined as pH = 7 (and 1 bar)
 5.11 The solute activity
(a) Ideal-dilute solutions

•  A solute B that satisfies Henry’s law has a vapor pressure pB = KBxB

pB KB
µ B = µ B∗ + RT ln
∗
= µ ∗
B + RT ln ∗
+ RT ln xB
pB pB
•  KB and pB* are characteristics of solute
Θ ∗KB
µ = µ + RT ln ∗
B B
pB
Θ
µ B = µ + RT ln x B
Θ ∗
•  If the solution is ideal, KB = pB* and µ B = µ B
 5.11 The solute activity
(b) Real solutes

•  We now permit deviations from ideal-dilute, Henry’s law behavior

Θ pB
µ B = µ + RT ln aB aB =
KB
•  An activity coefficient : all the deviations from ideality are captured
in the activity coefficient ϒB.
aB = γ B xB
aB → xB and γ B →1 as xB → 0
 5.11 The solute activity
(c) Activities in terms of molalities

•  The selection of a standard state is entirely arbitrary

•  In chemistry, compositions are often expressed as molalities, b, in
place of mole fractions

µ B = µ ΘB + RT ln b B
•  We incorporate the deviations from ideality by introducing an
activity and a dimensionless activity coefficient
bB
aB = γ B Θ where γ B →1 as bB → 0
b
µ = µ Θ + RT ln a
 5.11 The solute activity
(d) The biological standard state

•  The conventional standard state of hydrogen ions : unit activity

corresponding to pH = 0
•  In biochemistry, it is common to adopt the biological standard state,
in which pH = 7
•  G⊕, H⊕, µ⊕, and S⊕ for the biological standard state

µ ( H + ) = µ Θ ( H + ) + RT ln a ( H + ) = µ Θ ( H + ) − ( RT ln10 ) × pH
µ ⊕ ( H + ) = µ Θ ( H + ) − 7RT ln10

•  7RTln10 = 39.96 kJ/mol. The two standard values differ by about 40

kJ/mol
 5.12 The activities of regular solutions
Key points
1.  The Margules equations relate the activities of
the components of a model regular solution to
its composition
2.  The Margules equations lead to expressions for
the vapor pressure of the components of a
regular solution
 5.12 The activities of regular solutions

•  Starting point is the expression for the Gibbs energy of mixing for a
regular solution
Δ mixG = nRT ( xA ln xA + xB ln xB + ξ xA xB )
•  Margules equations
Δ mix G = nRT ( x A ln a A + x B ln a B )
ln γ A = ξ x B2 ln γ B = ξ x A2
2
ξ xB2 ξ (1−x A )
aA = γ A xA = xA e = xA e
2

{
pA = xA e
ξ (1−x A )
} p∗A
p A = x A e ξ p∗A for x << 1
K
 5.13 The activities of ions in solutions
Key points
1.  Mean activity coefficients apportion deviations
from ideality equally to the cations and anions
in an ionic solution
2.  The Debye-Hückel theory ascribes deviations
from ideality to the Coulombic interaction of an
ion with the ionic atmosphere that assembles
around it
3.  The Debye-Hückel theory limiting law is
extended by including two further empirical
constants
 5.13 The activities of ions in solutions
(a) Mean activity coefficients

•  Interactions between ions are so strong that the approximation of

replacing activities by molalities is valid only in very dilute solutions
•  In precise work activities themselves must be used
•  µ+ : the chemical potential of M+
•  µ- : the chemical potential of X-
•  The molar Gibbs energy of an ideal solution of such ions :
Gmideal = µ+ideal + µ ideal
-
•  Real solution of such ions
Gm = µ+ + µ− = µ+ideal + µ ideal + RT ln γ + + RT ln γ − = Gmideal + RT ln γ +γ −
-
•  All deviations from the ideality are contained in the last term
12
γ± = ( γ+ γ− ) : the mean activity coefficient

µ+− = µ+ideal + RT ln γ ± µ− = µ ideal + RT ln γ ±

-
 5.13 The activities of ions in solutions
(a) Mean activity coefficients

•  Generalize the previous approach to the case of a compound MpXq

Gm = pµ+ + qµ− = Gmideal + pRT ln γ + + qRT ln γ −

p q 1s
γ ± = (γ γ
+ − )
s = p+q

•  The chemical potential of eqch ion

µ i = µ iideal + RT ln γ ±
 5.13 The activities of ions in solutions
(b) The Debye-Hückel limiting law

•  The long range and strength of the Coulomb interaction means that
it is likely to be primarily responsible for the departures from
ideality in ionic solutions and to dominate all the other contribution
to non-ideality
•  Oppositely charged ions attract one another
•  Overall, the solution is electrically neutral, but near any given ion
there is an excess of counter ions : ionic atmosphere
•  The chemical potential of any given central ion is lowered as a
result of its electrostatic interaction with its ionic atmosphere by
RTlnϒ±
ln γ± = − z+z− AI1 2 :the Debye-H
uckel limiting law
1
I= ∑ z 2i ( b i bΘ ) :the ionic strength
2 i
•  For a solution consisting of two types of ions,
1
I = (b+ z+2 + b− z−2 ) bΘ
2
 5.13 The activities of ions in solutions
(c) The extended Debye-Hückel law

•  The name ‘limiting law’ was applied

because ionic solutions of moderate
molalities may have activity
coefficients that differe from the
values given by Debye-Hückel
limitingn law
•  When the ionic strength is high
enough,

A z+ z− I 1 2
ln γ ± = − 12
+ CI
1+ BI
•  B and C are dimensionless constants
and are best regarded as an
adjustable empirical parameters