Experiment 5

Phase Diagram of a Three-

Component Liquid System
Gibbs’ Phase Rule

 “provides the theoretical foundation, based

in thermodynamics, for characterizing the
chemical state of a (geologic) system, and
predicting the equilibrium relations of the
phases (minerals, melts, liquids, vapors)
present as a function of physical conditions
such as pressure and temperature.”
(Mogk, 2011)
Assumptions

 Systems under study should be in a state of

EQUILIBRIUM.
 Systems should be of the CLOSED type.
 Only P-V WORK should be involved.
Variance (F)

F = C-P+2
 Degrees of freedom (F) – minimum number
of intensive variables needed to define the
system at equilibrium.
 Components (C) – minimum number of
chemical constituents required to define the
phases in the system.
 Phases (P) – number of physically separable
constituents.
Variance

 F=0 (invariant)
 F=1 (univariant)
 F=2 (divariant)
 F=3 (trivariant)
Phase Diagram

 Used to represent phase equilibria

One-Component System

 F = 2-P+1 = 3-P
 eg: CO2
 Areas: P=1, F=2
 Curves: P=2, F=1
 TP: P=3, F=0
▪ T=216.55 K
▪ P=5.17 bar

Source: http://en.wikipedia.org/wiki/File:Carbon_dioxide_pressure-temperature_phase_diagram.svg
Two-Component System

 eg: boiling point-composition diagram

Source: http://en.wikipedia.org/wiki/File:Binary_Boiling_Point_Diagram_new.svg
Three-Component System

 F = 3-P+2 = 5-P
 T and P = constant
 F=3-P
 Use Stokes and Roozeboom Triangle Method
Three-Component System

 eg: CHCl3-HOAc-H2O system

Source: http://2.bp.blogspot.com/_d7L3szdZ5Ns/SlCtEEY7FkI/AAAAAAAAALM/mrzNFxh2ZCo/s1600-h/Phase+Diagram.bmp
Objective

 To prepare the phase diagram of a three-

component liquid system
 To construct a solubility curve for the DCM-HOAc-
H2O system
 To draw tie lines
 Methodology
Prepare the f ollowing mixtures using a buret in a 1 25-mL E.
flask:
1 mL H2O + 9mL DC M ( 10% by volume H2O)
2mL H2O + 8mL DC M ( 20% by volume H2O)
3 mL H2O + 7 mL DC M ( 30% by volume H2O)
4mL H2O + 6mL DC M ( 40% by volume H2O)
5mL H2O + 5mL DC M ( 50% by volume H2O)
6mL H2O + 4mL DC M ( 60% by volume H2O)
7 mL H2O + 3 mL DC M ( 70% by volume H2O)
8mL H2O + 2mL DC M ( 80% by volume H2O)
9mL H2O + 1 mL DC M ( 90% by volume H2O)

Ti
tr
at
e
wi
th
H
O
A
c
u
nt
il
cl
ea
r
Methodology

MIXTURE Comp. HOAc DCM H2O

1 % by vol 15 25 60
Prepare the following mixtures:
volume 3 5 12
2 % by vol 30 25 45
volume 6 5 9
3 % by vol 45 25 30
volume 9 5 6
4 % by vol 60 25 15
volume 12 5 3
 Methodology
Transfer
No layer? to
Add
separatory
H2O until layer
appears
funnel

W
ei
g
h
25
0
m
L
E.
Fl
as
ks
 Methodology
Transfer 5.0mL of
Weigh
Add
each to E.
50mL
layer
separate 250mL E.
H2O
flasks
Flasks

Titr
ate
aqu
eou
s
wit
h
0.5
M
Na
OH,
org
anic
wit
h
0.2
5M
Na
OH
(ind
icat
or:
phe
nol
pht
hal
ein)
Results
Table 1. Results for the solubility curve
V liquid (ml) W liquid (g) % Weight
Mixture
H2O HOAc DCM H2O HOAc DCM H2O HOAc DCM
1 1 5.5 9 1 5.77 11.97 5.3 30.8 63.9
2 2 6.5 8 2 6.82 10.64 10.3 35.0 54.7
3 3 7.7 7 3 8.08 9.31 14.7 39.6 45.7
4 4 8.2 6 4 8.60 7.98 19.4 41.8 38.8
5 5 9.5 5 5 9.97 6.65 23.1 46.1 30.8
6 6 9.4 4 6 9.86 5.32 28.3 46.6 25.1
7 7 8.8 3 7 9.23 3.99 34.6 45.7 19.7
8 8 7.6 2 8 7.97 2.66 42.9 42.8 14.3
9 9 5.6 1 9 5.87 1.33 55.5 36.3 8.2
Computation
V liquid (ml) W liquid (g) % Weight
Mixture
H2O HOAc DCM H2O HOAc DCM H2O HOAc DCM
1 1 5.5 9 1 5.77 11.97 5.3 30.8 63.9
Results
Table 2. Results for the tie lines
Mixture No. 1 2 3
Weight 2.0 2.0 2.0
Aqueous V NaOH
Layer (mL) 12.7 24 37
% HOAc 19.07% 36.05% 55.5%
Weight 2.66 2.66 2.66
Organic V NaOH
Layer 13.3 14.2 16.2
% HOAc 9.98% 10.66% 12.2%
Computation
Mixture No. 1
Weight 2.0
Aqueous Layer V NaOH (mL) 12.7
% HOAc 19.07%
References

 http://www.d.umn.edu/~mille066/Teaching/5
310_09/1.phase_rule.pdf
 http://www.chem.arizona.edu/~salzmanr/480
a/480ants/gibbspr/gibbspr.html
 http://serc.carleton.edu/research_education/
equilibria/phaserule.html
 http://chemhail.wordpress.com/2009/07/05/a
pplication-of-phase-rule-to-three-componen
t-systems/
 http://www.whitman.edu/geology/winter/Pet
rology/Ch%2006%20Binary%20Phase.ppt