Prof. José A.

Pérez

IDEAL DILUTE SOLUTIONS

Solute in ideally dilute solutions : μ i =μ ° i (T , P)+ RT lnx i
Solvent in ideally dilute solutions : μ B=μ ° B + R T lnx B
Equilibrium criteria μ lA =μ vA
P
( )
μ vA =μ °A, v + R T ln A°
P
μ lA =μ °A, l + R T lnx A
μ°A, l is magic or hypothetic standard state
P
( )
μ °A, v +R T ln A° =μ °A, l + R T lnx A
P
P
° ,l °,v
( )
(μ A −μ A )=R T ln ° A
P xA
(μ °A, l −μ°A, v ) P
RT ( )
=ln ° A
P xA
μ°A, l−μ °A, v P A
°
P exp ( RT ) =
xA
The exponential termis a constant .
μ°A, l−μ °A, v
°
P exp ( RT ) =K A (T , P)
P A =K A x A ;( Henry ' s law )
1
Exercise 1.
For the Chloroform (A)-Acetone (B) system at 35 °C the following data have
been obtained (table 1). Base on the experimental information shows that the
solute and solvent obey the Henry’s law and Raoult’s law respectively.

Table 1. Equilibrium data of Chloroform (A)-Acetone (B) system at 35 °C

Chloroform (A) Acetone (B)

xA PA [Torr] PB [Torr]
0.0 0.0 347.0
0.2 35.0 270.0
0.4 82.0 185.0
0.6 142.0 102.0
0.8 219.0 37.0
1.0 293.0 0.0

2
 Answers
K A =145Torr
K B =155 Torr

3
 Non-ideal Solutions

Fugacity and activity Fugacity of a pure gas

Pure Gas A residual property is define
fi
Gi =μ i=μ i ° +R T ln
( )
fi°
R
ζ = ζ −ζ
∂ G=V ∂ P−S ∂ T
real idg

Mixture of gases Process at constant temperature .

f^i ∂G real =∂ μ =V real ∂ P
Gi =μ i =μ i °+ RT ln
( )
^f °
i
idg idg
∂G =∂ μ =V ∂ P
ig

P
f^i : fugacity of i compound in mixture . (μ −μ ) −(μ −μ ) =∫ (V real −V idg )∂ P
* real * idg

Fugacity coefficient is define( ϕ^ i ): P*

f^i f^i Reference point P* where real gas

^
ϕi = =
Pi y i P properties are the same to an ideal gas .
P* →0 y μ *real =μ* ideal
P
Lewis−Randall rule real id real idg
μ −μ =∫ (V −V ) ∂ P
ϕ^i = ϕi 0

ϕ^i y i P= f^i fi
ϕ i y i P= f^i
G ireal =μ real
i =μ i ° +R T ln
( ) f i°
For anideal gas P
ϕ =1.0 : y i P=Pi = f^i
G idi =μidi =μ i ° +R T ln ( )
P°
4
 °
Standard state of real gas real is the hypothetic state like an ideal gas f i = P °
P
fi
R real id
G =μ −μ =R T ln
P 0 ( )
=∫ (V real −V idg )∂ P
P real idg
(V −V )
ln ϕ =∫ ∂P
0 RT
real Z RT idg RT
V = and V =
P P
P
(Z −1)
ln ϕ =∫ ∂P
0 P
f
For a pure gas : ϕ = i
P
For an ideal gas : ϕ =1.0→ f idg
i =P

Exercise 2.
Determine the fugacity of the nitrogen at 50 bar and 298.15 K. Ans : ϕ =0.965 ; f N =48.2 bar :
2

2 −2 −1 bar L
Van der Waals constant: a = 1.408 L bar⋅mol and b = 0.03913 L⋅mol ; R=0.083145
mol K

a a P
( P+
V )
2 (V −b)= RT

P
⇒
[ ( )]
Z =1+ b−
RT RT
a 1
ln ϕ =∫ b−
0
[ ( )] RT RT
∂P

a P
[ ( )]
ln ϕ = b−
RT RT 5
Fugacity and Activity of Solutions

For an ideal solution

μ i=μ i ° +RT ln x i
For non−ideal solution
f^i
G i =μ i=μ i ° +R T ln
( )
f^i °
An ideal solution as a function of fugacity:
f^ ids
ln x i =ln i ids
f^ ° ( ) i

x i f^ i ° ids = f^ ids ^ ids ids

i ; Lewis−Randall rule→ f i ° =f i =f i °

f^ ids f^ ids
( )
ln x i =ln i
f i°
⇒ μi =μ i °+ RT ln i( ) f i°
A new property called activity a i
μ i=μ i °+RT ln a^i
f^li f^li
The activity coefficient is define : γ i= ids =
( )
f^ i f i ° xi
a^i = γ i x i
ids
For ideal solutions γi =1.0
μ i =μi °+ RT ln γ i x i
6
 Fugacity of a Pure Liquid
f li
l
μ =μi °
i
, sat
+RT ln
( )
f i ° , sat
sat
fi
μ sat
i =μ i °
, sat
+R T ln
( )
fi°
, sat

f li
l
μ −μ =R T ln
i
sat
i
( )
f isat
d G=V l dP
l sat l sat
μ i−μ i =V ( P−Pi )
l
fi
R T ln
( ) f isat
=V l (P−Pisat )

l
l
f =f
i
sat
i exp
V
RT [ ( P−P sat
i ) ]
sat f isat
ϕi = sat
Pi
Vl
l
f =ϕ P exp
i
sat
i
RT
sat
( P−P sat
i i ) [ ]
The exponential factor is known as the Poyting ' s factor .

7
Exercise 3.
Calculate the fugacity for pure water at

1. P=1.1 bar (110 kPa) and T=47 °C.

2. P=10 bar (1000 kPa) and T=47 °C.
3. P=50 bar (5000 kPa) and T=47 °C.
4. P=100 bar (10000 kPa) and T=47 °C.
5. P=1000 bar (100000 kPa) and T=47 °C.
l
l sat
f =ϕ P exp
i i i
V
sat

RT [
sat
( P−P i )
3
] 3
m 18 kg −3 m kJ
sat
i
l
At T =320.15 K ; P =10.61 kPa ;V =1.011 x 10
−3
( )( )
kg kmol
=18.20 x 10
kmol
; R=8.3145
kmol⋅K

* *
ΔG i=Gi −G i =μi −μ i
* *
μ i=μ i °+ RT ln f i and μ i =μ i ° +RT ln f i
f
( )
RT ln *i =Δ G=Δ H −T Δ S
fi
Taking as the reference state the lower pressure on superheated vapor tables at 320.15 K .
* * * kJ * kJ
f i = P =10 kPa ; H =2586.2 ; S =8.1560
kg kg K
kJ kJ
For saturation conditions at 320.15 K ; H sat =2586.9 ; S sat =8.1302
kg kg K
kJ kJ kJ
Δ H =0.7 and Δ S=−0.0258 ⇒ Δ G=8.9599
kg kg K kg
8
 kJ kg kJ f^li
Δ G=8.9599 ∗18 =161.28
kg kmol kmol Recall that a^i =
sat fi°
fi ΔG
RT ln * =Δ G ⇒ f isat =f *i exp
fi RT ( ) f
For a pure substance : ai = i
fi°
l

sat
fi
f isat =10.62 kPa ⇒ ϕ sat
i = sat
≈1.0
Pi Exercise 4.

P=110 kPa ⇒ f i =10.62 kPa Calculate the activity of pure water at :

P=1000 kPa ⇒ f i =10.68 kPa
P=5000 kPa ⇒ f i =10.98 kPa
P=10000 kPa ⇒ f i =11.36 kPa
P=100000 kPa ⇒ f i=21.02 kPa
1. P=1.1 bar and T =47 ° C .
2. P=10 bar and T =47 ° C .
3. P=50 bar and T =47 ° C .
4. P=100 bar and T =47 ° C .
5. P=1000 bar and T =47 ° C .

Activity of a pure liquid Answers :

μ i=μ i °+RT ln a i 1. a w =1.000
P
2. a w =1.006
μ i−μ i °=G−G °=∫ V ∂ P , at constant temperature .
P° 3.a w =1.034
V ( P−P °)=RT ln ai 4. a w =1.070
V 5. a w =1.980
a i=exp [
RT
( P−P °) ]
9