At sea level At top of a mountain

Water boils at 100C Water boils at < 100C

b.P = f(P)
P = 1.0133 bar
bp = 100C
elevation = 8848 m
P = 0.26 bar
bp = 69C
P = 2 atm , b.p = 124C
+ EG 50/50 (v/v), b.p =129.5  C => b.p = f(P, c)
 If I specify P, T, and c, what are the stable phases?

Phase diagram

stability map

stability of the state of aggregation

Depending on the circumstances, molecules aggregate to form

solid, liquid, or gas
Phase = region of a substance that is:
 Uniform in chemical composition
 physically distinct
 mechanically separable

Examples of single-phase system ( = 1):

 Pure water (l)
 White gold (alloy of Au-Ag-Ni) => Ag and Ni substitute Au
in its FCC lattice => homogeneous composition throughout
=> solution
 Air (N2, O2, Ar, CO2)

Examples of dual-phase system ( = 2):

 Ice cubes in liquid water
 Milk (fat globules in aqueous solution)
Equilibrium =
 the condition which represents the lowest energy level
 the properties are invariant with time

Component = the measure of chemical complexity

 1 2
N
Water (l) Ice cube in liquid water
1 diamond (slush)
White gold
>1 CCl4 – H2O
(Au-Ag-Ni)
 s = l coexistence curve
=2 Critical point
P (atm) (374C, 218 atm)
Liquid
=1
1 l = v coexistence curve
=2
4.58 mm Hg Solid
=1 Gas
=1
s=v Triple point
coexistence =3
curve
=2

0 0.01 100 T (C)

Phase diagram of water

 POLYMORPHS

Different atomic arrangement

at constant composition

B : 95,5C and 0,51 Pa

C : 115C and 2,4 Pa
E : 151C and 1,31108 Pa

Phase diagram of sulfur

The transformation from one polymorph to another can
be :
1. Reversible : two crystalline forms are said to be
enantiotropic
2. Irreversibel : two crystalline forms are said to be
monotropic
Pressure-temperature diagram for dimorphous
substances: (a) enantiotropy, (b) monotropy
 There are tree variables that can affect the phase
equilibria of a binary system: T, P, and C
P

c
T
 Two-component phase diagram

3 dimension 2 dimension
T-P-c

T-P P-c T-c

Crystallization: liquid and solid

The effect of P can be ignored T-c Diagram

  Complete solubility in solid and liquid states
 Change of state (s = l)
Metal (Hume-Rothery Rule)
Similar crystal structure
Similar atomic volumes
Small values of electronegativity

For interstitial solid solutions, the Hume-Rothery rules are:

1. Solute atoms must be smaller than the pores in the solvent
lattice.
2. The solute and solvent should have similar electronegativity.
For substitutional solid solutions, the Hume-Rothery rules are:

1. The atomic radii of the solute and solvent atoms must

differ by no more than 15%:

2. The crystal structures of solute and solvent must match.

3. Maximum solubility occurs when the solvent and solute
have the same valency. Metals with lower valency will
tend to dissolve in metals with higher valency.
4. The solute and solvent should have similar
electronegativity. If the electronegativity difference is too
great, the metals will tend to form intermetallic
compounds instead of solid solutions.
T Liquid
=1
Liquidus B
Tmp
Liquid + solid
=2
A Solidus
Tmp

Solid
=1

A c B
 Liquidus : l  s + l : the lowest T for only liquid (at any c)
 Solidus : s  s + l : the highest T for only solid (at any c)
 The diagram represents the phase behavior of two
components having many similarities (type of bonding,
atomic size, crystal structure, etc), we call it
ISOMORPHOUS DIAGRAM.
 The shape of the diagram looks like a lens  lens-shape
diagram / lenticular diagram.
 Example: naphthalene - -naphthol
 Similar 

Solid solution of naphthalene - -naphthol

  >

Solid solution of naphthalene - -naphthylamine

 Partial or limited solubility  miscibility gap
 No change of state  always liquid or always solid

T l
= 1
s

l1 + l2 Coexistence curve
=2
+

A c B
upper critical
solution temperature
(upper consolute
temperature)

Hexane - nitrobenzene
lower critical solution
temperature (lower
consolute temperature)
  Partial or limited solubility
 Change of state

EUTECTIC DIAGRAM
T B
Tmp
Liquid solution

A
Tmp l
=1
l+
l+ =2 Solid solution
=2 (B rich)
Solid solution  
(A rich)
=1 =1

=2 Eutectic
l

A c B
 Freezing point depression of both components (A and B)
 Eutectic point is equilibrium of , , and l
 Eutectic point is unique; it only happens at one T, P, and c
Phase diagram for the simple eutectic system naphthalene - benzene
Phase diagram for system NaCl – H2O
Solution A having composition of xA and enthalpy of HA is mixed
adiabatically with solution A having composition of xB and
enthalpy of HB.
The composition and the enthalpy of the mixture is calculated
using material balance:

Total balance: mC  m A  m B

Component balance: mC xC  m A x A  m B x B

Combining both equations yields:

m A x A  mB xB
xC 
m A  mB
Similarly, if mixture A were to be removed adiabatically from
mixture C, the enthalpy and composition of residue B can be
located on the straight line through points A and C by means of
the equation:

mC xC  m A x A
xB 
mC  m A
EXAMPLE
Calculate (a) the quantity of heat to be removed and (b) the
theoretical crystal yield when 5000 lb of a 30 per cent solution of
MgSO4 by mass at 110F is cooled to 70F. Evaporation and
radiation losses may be neglected.

SOLUTION

(a) Initial solution (A) xA = 0.3 HA = - 31 Btu/lb

Cooled system (B) xB = 0.3 HB = - 75 Btu/lb
Enthalpy change H = - 44 Btu/lb
Heat to be removed = (- 44) (5000) = - 220000 Btu

(b) The cooled system B is located in the region where

MgSO4.7H2O is in equilibrium with solution.
The crystal MgSO4.7H2O contains:

MWMgSO4 120.3
Weight fraction of MgSO4  
MWMgSO4 .7H2O 120.3  126

xC = 0.49

From the graph: xA = 0.26

xB  x A 0.3  0.26
mC  mB  5000  869.6
xC  x A 0.49  0.26

The MgSO4.7H2O crystal yield is 869.6 lb