GibbsPhaseRule PDF

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Gibbs Phase Rule: f = c p + 2

f = Intensive Degrees of freedom = variance


Number of intensive variables that can be changed independently without
disturbing the number of phases in equilibrium
p = number of phases
gas, homogeneous liquid phases, homogeneous solid phases
c = components
Minimum number of independent constituents
Case I. No chemical reactions: c = constituents
Example 1: start with methanol and water 2 components
Case II With chemical reactions:
Example 2: start with NaH2PO4 in water --
Ka2 Ka3
- 2- +
H2PO4 HPO4 + H PO43- + H+
Constituents: Na+, H+, H2PO4-, HPO42-, PO43-, H2O
but only 2 components -- NaH2PO4 and H2O.
Example 3: start with NaH2PO4 and Na2HPO4 in water --
Same constituents: Na+, H+, H2PO4-, HPO42-, PO43-, H2O
but now 3 components -- NaH2PO4, Na2HPO4, and H2O.
Need to know: T, P, yA, yB, xA, xB
total intensive variables = c p + 2
yA + yB =1 A&B A(g) B(g)
vapor =
=

A&B A(xA) B(xB)


But yA + yB = 1 liquid
xA + xB =1
xA + xB = 1
Get p such equations, one for each phase:
Independent variables = c p + 2 p

But, chemical potential is everywhere equal: f'=cp+1 P = cst

A(xA) = A(g) *
TbB
vapor A & B
f'=2
B(xB) = B(g)
Get p1 for each component T f'=1
Get c( p1) such equations:
liquid A & B
Independent variables = c p + 2 p c( p1) f'=2
*
TbA

0 1
f=cp+2 xA, yA

Colby College
f' = c p + 1 cst. P
f "= c p cst. T&P

Binary solid-liquid Equilibrium


Melting Point Variation with Composition
c=2
p=3 A&B
liquid

liquid, pure solid A, pure solid B


Solid A
Solid-liquid 2-phase region: & Solid B
f'=22+1 =1

Eutectic: f'=c p+1 P = cst

f' = 2 3 + 1 =0 liquid A & B


T f ' =2
invariant at cst P
f ' =1 f ' =1
liq. & solid B liq. & solid A
f ' =0
solid A & solid B

0 1
xA
For NaCl in water:
Eutectic -21.1 oC at 23% wt/wt giving NaCl2H2O

Add One Extensive Independent Variable for Each Phase:


Gibbs energy is extensive:
Degrees of freedom:
D=f+p
Binary Solid-Liquid at constant T & P:
Solid-liquid 2-phase region:
f" = 2 2 = 0
D" = f" + p = 0 + 2 = 2

dG = A dnA + B dnB dnA and dnB: totals for both phases

since: A(s) = A(l), and B(s) = B(l) (doesnt matter which phase)

Colby College

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