Andrew Nico S.

Lozano
CHEM 112.1 2L
2
nd
Semester A.Y. 2009-2010
Gibbs Phase Rule
formulated by J. Willard Gibbs of
Yale University
A general expression for the
number of intensive variables
that have to be specified for a
multiphase system at equilibrium
A rule for discussing phase
diagrams; applicable for all
phase diagrams


Gibbs Phase Rule
Basic formula:

2 F C P = +
Where:

F = degrees of freedom
= number of variables that can be varied
C = Number of components in a system
P = Number of phases
2 = means that temperature and pressure
are varied
Gibbs Phase Rule
If either temperature or pressure is held
constant:


If both temperature and pressure are
held constant:

1 F C P = +
F C P =
Ternary System
A system having three (3) components
C = 3
Gibbs Phase Rule:

2
5
F C P
F P
= +
=
Ternary System
Problem:
Cannot be illustrated graphically, since there
are four (4) or more parameters that can be
varied
Solution for this case:
Keep the temperature and pressure
constant
Ternary System
By keeping temperature and pressure
constant:



In any number of phases, one can
already illustrate the system using what
was called a Gibbs-Roozeboom
Diagram
3
F C P
F P
=
=
Gibbs-Roozeboom Diagram


An equilateral triangle representing a
ternary system at constant temperature
and pressure

Gibbs-Roozeboom Diagram
The components are in pure
state at the apices:

Apex A:
Component A is pure

Apex B:
Component B is pure

Apex C:
Component C is pure
Gibbs-Roozeboom Diagram
The Binary systems (only 2
components as the third
component is absent) are
illustrated at the edges of
the triangle.

i.e.

Edge A-B
- mixture consists only of
components
A and B
- %C=0, meaning C is
absent
Edge A-B
Gibbs-Roozeboom Diagram
Any point inside the triangle
would mean a ternary
system of composition X
A,

X
B
and X
C

X
A
+ X
B
+ X
C
= 1

X
A
= %A/100

X
B
= %B/100

X
C
= %C/100
Other important parts of the
diagram
Binodal Curve
The area below such curve represents a
region of immiscibility
Region where which a system will not exist as
a homogeneous mixture.
Tie Line
A line with which its endpoints determine the
composition of the two phases
determined experimentally and drawn within
the binodal curve
Other important parts of the
diagram
Delta point
Serves as a guide for finding the plait point
Plait Point
In this point, the two phases will have
identical compositions
Usually not located on the maximum of the
binodal curve
The tie lines are not horizontal

A sample Gibbs-Roozeboom
diagram
Plait
Point
Binodal Curve
Tie lines
Delta point
Apparatus
Separatory funnels
Erlenmeyer Flasks
Burets and Buret holders
Beakers
Reagents
H
2
O
CHCl
3

CH
3
COOH
NaOH
KHP
phenolphthalein

Construction of the binodal curve for the
H
2
O-CHCl
3
-CH
3
COOH System



Method used: Turbidimetric method
Sample is titrated until the first sign of
turbidity or cloudiness is observed
Scattering of light by the very small droplets of
a second phase that forms upon titration of
sufficient amounts and shaking results to the
cloudiness of the mixture

Construction of the binodal curve for the
H
2
O-CHCl
3
-CH
3
COOH System

Solutions of CH
3
COOH
and H
2
O at different
concentrations of 15,
30, 45, 60 and 70 %
(v/v) were subjected to
turbidimetric analysis
using CHCl
3
as titrant
The % composition by
weight was
determined for each
mixture after
turbidimetry
Points were
plotted on
the diagram

Construction of the binodal curve for the
H
2
O-CHCl
3
-CH
3
COOH System

Solutions of CH
3
COOH
and CHCl
3
at different
concentrations of 15, 30,
45, 60 and 70 % (v/v) with
respect to CH
3
COOH
were subjected to
turbidimetric analysis,this
time using H
2
O as titrant.
The %
composition by
weight was
determined for
each mixture
after
turbidimetry
Points were
plotted on the
diagram as
well.
Construction of Tie Lines
Four 100g g mixtures
containing the H
2
O-CHCl
3
-
CH
3
COOH were prepared
such that there will be
approximately equal volumes
of conjugate phases.
Each was equilibrated in a
250-mL separatory funnel at
25 C.
The conjugate phases were
separated and transferred
into 125-mL Erlenmeyer
flasks, properly labeled.
The density of each phase
was measured using a
pycnometer.
5.0 mL aliquots of each
conjugate phase was titrated
with 1.0M NaOH, previously
standardized with KHP, up to
the phenolphthalein end
point.
The values of the %w/w
CH
3
COOH were located on
the binodal curve of the
diagram for each conjugate
phase.
Drawing a straight line along
the two points corresponding
to each prepared sample
gave the tie lines
Determination of delta and plait
points
Each tie line was
extended until the
tie lines intercept
at a certain point
The point of
intersection
gave the
delta point
A tangential line
was drawn along
the binodal curve,
starting from the
delta point
The point where
the binodal curve
and the
tangential line
meet gives the
plait point
Titration of A-B with C
Solution
number
%A
(v/v)
vol A,
ml
mass A,
g
vol B,
ml
mass B,
g
vol C,
ml
mass C,
g
total
mass, g
%(w/w)
A
%(w/w)
B
%(w/w)
C

total %
(w/w)
1 15 3.75 3.94 0.2 0.20 21.25 31.32 35.46 11.10 0.56 88.33 100.00
2 30 7.50 7.88 0.4 0.40 17.50 25.80 34.07 23.11 1.17 75.71 100.00
3 45 11.25 11.81 2.2 2.19 13.75 20.27 34.27 34.47 6.40 59.13 100.00
4 60 15.00 15.75 5.4 5.38 10.00 14.74 35.87 43.90 15.01 41.09 100.00
5 75 17.50 18.38 8.4 8.38 7.50 11.06 37.81 48.60 22.15 29.24 100.00
where: A=CH
3
COOH, B=H
2
O, C=CHCL
3

Titration of A-C with B
Solution
number
%A(v/v)
vol A,
ml
mass A,
g
vol B,
ml
mass B,
g
vol C,
ml
mass C,
g
total
mass, g
%(w/w)
A
%(w/w)
B
%(w/w)
C
total %
1 15 3.75 3.94 21.25 21.19 0.8 1.18 26.30 14.97 80.55 4.48 100.00
2 30 7.50 7.88 17.50 17.45 1.0 1.47 26.80 29.39 65.11 5.50 100.00
3 45 11.25 11.81 13.75 13.71 1.6 2.36 27.88 42.37 49.17 8.46 100.00
4 60 15.00 15.75 10.00 9.97 4.2 6.19 31.91 49.36 31.24 19.40 100.00
5 75 17.50 18.38 7.50 7.48 10.4 15.33 41.18 44.62 18.16 37.22 100.00
where: A=CH
3
COOH, B=H
2
O, C=CHCl
3

Computed data for the Construction
of the Binodal Curve
Sample Layer
Volume
A, ml
vol B, ml vol C, ml
mass
pycnome
ter, g
mass
pycnome
ter +soln,
g
mass
soln, g
mass
pycnome
ter+wate
r, g
mass
water, g

water
,
g/mol

soln
,
g/mol
P1
upper 9.52 35.15 37.31 16.461 27.046 10.585 26.768 10.307 0.99704 1.023932
lower 9.52 35.15 37.31 16.461 31.425 14.964 26.768 10.307 0.99704 1.447531
P2
upper 14.29 30.13 37.31 16.15 26.8 10.65 26.398 10.248 0.99704 1.036151
lower 14.29 30.13 37.31 16.15 30.834 14.684 26.398 10.248 0.99704 1.428624
P3
upper 19.05 25.11 37.31 15.788 26.342 10.554 26.338 10.55 0.99704 0.997418
lower 19.05 25.11 37.31 16.616 31.171 14.555 26.906 10.29 0.99704 1.410293
P4
upper 23.81 20.09 37.31 16.616 28.44 11.824 26.906 10.29 0.99704 1.145676
lower 23.81 20.09 37.31 15.788 30.39 14.602 26.338 10.55 0.99704 1.379979
Determination of the Delta and
Plait points
Sample Layer
Volume of
aliquot, mL

soln
, g/ml
mass of
aliquot, g
NaOH
concentrati
on, mol/L
volume of
NaOH
used, ml
MM A,
g/mol
mass A, g %(w/w)
A

P1
upper 5 1.023932 5.119661 0.9613 17.9 60.052 1.033331 20.1836
lower 5 1.447531 7.237657 0.9613 4.65 60.052 0.268435 3.7089
P2
upper 5 1.036151 5.180755 0.9613 22.3 60.052 1.287334 24.8484
lower 5 1.428624 7.143118 0.9613 7.9 60.052 0.456051 6.3845
P3
upper 5 0.997418 4.98709 0.9613 26 60.052 1.500928 30.0963
lower 5 1.410293 7.051466 0.9613 11.4 60.052 0.658099 9.3328
P4
upper 5 1.145676 5.728378 0.9613 34.6 60.052 1.997388 34.8683
lower 5 1.379979 6.899895 0.9613 16.6 60.052 0.958285 13.8884
Sample Calculations
Construction of the Binodal Curve


,
(1.05 / )(3.75 ) 3.9375 3.94
A A A used
A
m V
m g mL mL g g
=
= = ~
%( / ) 100%
3.94
%( / ) 100% 11.10%
3.94 0.20 31.32
A
A
A B C
A
m
w w
m m m
g
w w
g g g
=
+ +
= =
+ +
Sample Calculations
Construction of the Tie Lines


2 2
2
2
,
, ,
26.768 16.461 10.307
27.046 16.461 10.585
10.585
0.99704 /
H O pycnometer H O pycnometer empty
H O
solution lower pycnometer solution pycnometer empty
solution
solution water
H O
m m m
m g g g
m m m g g g
m g
g mL
m

+
+
=
= =
= = =
| |
= = |
|
\ .
3
, ,
1.023932 /
10.307
5 1.023932 / 5.119661
1
17.9 0.9613 60.052 1.033331
1000
1.03
%( / ) 100%
aliquot aliquot solution
A NaOH used NaOH M CH COOH
A
A
A
aliquot
g mL
g
m V mL g mL g
m V C M
mol g L
m mL g
L mol mL
m
w w
m

| |
=
|
\ .
= = =
=
| || || |
= =
| | |
\ .\ .\ .
= =
3331
100% 20.1836%
5.119661
g
g
=
Resulting Gibbs-Roozeboom
Diagram
where:
A=CH
3
COOH
B=H
2
O
C=CHCl
3

Resulting Gibbs-Roozeboom
Diagram
Delta
point
Tie Lines
Plait point (P)
Tangential line
Point b
1
Point b
2
Arc b
1
-P CHCl3-
rich phase

Arc P-b
2
H
2
O-rich
phase
Overall Inferences
CH
3
COOH-H
2
O; CH
3
COOH-CHCl
3
Miscible; CH3COOH exhibits hydrogen
bonding with water and London interaction
with CHCl
3
H
2
O-CHCl
3
Only partially miscible; the two compounds
are of opposing polarities, hence the great
tendency to form two phases, especially
between points b
1
and b
2
.
Applications
Mining, geological, pharmaceutical,
metallurgical and agricultural studies
and industries

Ex.metallic alloys, such as stainless steel
(metallurgy); Shephards diagram
(agriculture and geology)
Applications
Applications
Notes
The last two Gibbs-Roozeboom Diagrams
were pre-made diagrams print-screened
from the Ternary diagram plotter of the
Chemix School software Trial version:
(URL: http://www.chemix-chemistry-
software.com/chemistry-software.html).
The rest of the ternary diagrams were
drawn using the Ternary diagram plotter of
the Chemix School software and print-
screened to prevent the inclusion of the
software name in the presentation, a
potential eyesore when presented. :P

Alberty, R.A. and R.J. Silbey. 2001.
Physical Chemistry. 3
rd
ed. MA, USA:
John Wiley and Sons, Inc. p. 159.

Tamayo, J.P. 2008. CHEM 112: Physical
Chemistry II Lecture Notes.
UPLB:Institute of Chemistry. p. 64-66.