Part I Practice

Phase Behavior
 Part II

Fugacity of Gases
 CALCULATING FUGACITY
COEFFICIENTS BY INTEGRATING AN
EOS
Using the van der Waals equation:
RT a
P  2
V  b V
V 1
P
ln       P
0
RT P 

 V  b 2a PV
ln   ln     ln
 V  b  V  b V RT RT
12
 Pr  Z 1
ln      dPr
0
 Pr 
I. We can use this equation together with the
generalized Z charts.
1) Look up Pc and Tc of gas
2) Calculate Pr and Tr values for desired T’s and P’s
3) Make a Table of Z from the generalized charts at
various values of Tr and Pr. Of course, we must have
Pr values from 0 to the pressure of interest at each
temperature.
4) Graph (Z-1)/Pr vs. Pr for each Tr.
5) Determine the area under the the graph from Pr = 0
to Pr = Pr to get ln .
II. Used generalized fugacity charts. 13
14
15
 USE OF TWO-PARAMETER
GENERALIZED FUGACITY
CHARTS
EXAMPLE 1: Calculate the fugacity of CO2 at
600°C (873 K) and 1200 atm.

Tc = 304.2 K; Pc = 72.8 atm

Tr = 2.87; Pr = 16.48
From the chart   1.12
so
f = (1.12)(1200) = 1344 bars

16
EXAMPLE 2: What is the fugacity of liquid Cl2 at
25°C and 100 atm? The vapor pressure of Cl2 at
25°C is 7.63 atm.
For the vapor coexisting with liquid:
Tc = 417 K; Pc = 76 atm
Tr = 0.71; Pr = 0.10
from the chart   0.9
f = (0.9)(7.63) = 6.87 atm
Now we must correct this to 100 atm.
V
ln f 2  ln f1  ( P2  P1 )
RT

V = 51 cm3 mol-1; assume to be constant.

f2 = 8.36 atm 17
 THREE-PARAMETER CORRELATIONS
FOR FUGACITY & H , S , Density
( 0) (1)
f  f   f
Fugacity: log   log     log 
P  P  P
( 0) (1)
H H H H 
0 0
H H 
0
Enthalpy:       
RTc  RTc   RTc 
( 0) (1)
S S S S
0 0
S S 0
Entropy:         ln P
R  R   R 

 1  0.85(1  Tr )  (1  Tr ) (1.89  0.91 )
1
Density: c
3

Tables for these correlations can be found in Pitzer

(1995) Thermodynamics. McGraw-Hill.
18
 THERMODYNAMICS OF IDEAL
MIXING - REVISITED
We have previously shown that:

Gideal mix  RT  X i ln X i
i
using Dalton’s Law we can derive:

Pi
Gideal mix  RT  X i ln
and for entropy we have: i PT

Pi
Sideal mix   R  X i ln
i PT 19
 NON-IDEAL MIXTURES OF NON-
IDEAL GASES
For a perfect gas mixture:
i  io  RT ln Pi  io  RT ln PT  RT ln X i
For an ideal mixture of real gases:
i  io  RT ln fi  io  RT ln fi o  RT ln X i
fi  X i fi o  X ii PT Lewis Fugacity Rule

For a real mixture of real gases:

i  io  RT ln fi
fi  X i i fi o  X i ii PT

Correction for Correction for

non-ideal mixing non-ideal gas 20
 DALTON’S LAW AND
GENERALIZED CHARTS
Calculate reduced pressure according to:
Pi
Pr ,i 
Pc ,i
PAVT  nAZ ART PBVT  nB Z B RT PCVT  nC ZC RT

PA  PB  PC VT  nAZ A  nB Z B  nC ZC RT

 nT  X AZ A  X B Z B  X C ZC RT
 nT Z mixRT
21
 AMAGAT’S LAW AND
GENERALIZED CHARTS
Calculate reduced pressure according to:
PT
Pr ,i 
Pc ,i
PTVA  nAZ ART PTVB  nB Z B RT PTVC  nC ZC RT

PT VA  VB  VC   n AZ A  nB Z B  nC ZC RT
 nT  X AZ A  X B Z B  X C ZC RT
 nT Z mixRT
22
 PSEUDOCRITICAL CONSTANTS

P B
A X
A
1
XA2

L-V curve for A

L-V curve for B

T
23
 KAY’S METHOD
Assumes a linear critical curve between the critical
points for A and B.

Pc '   X i Pc ,i
i

Tc '   X iTc ,i
i

When answers are near the critical point for the mixture, we
cannot be certain that we are not dealing with a liquid-vapor
mixture. 24
PREDICTION OF CRITICAL CONSTANTS
Critical Temperature:
I. All compounds with Tboil (1 atm) < 235 K and all
elements: Tc = 1.70Tb - 2.00.
II. All compounds with Tboil (1 atm) > 235 K.
A. Containing halogens or sulfur
Tc = 1.41Tb + 66 - 11F
F = No. of fluorine atoms
B. Aromatics and napthenes
Tc = 1.41Tb + 66 - r(0.388Tb - 93)
r = ratio of non-cyclic carbon atoms to total carbon
25
atoms.
 C. All other compounds
Tc = 1.027 Tb + 159

20.8Tc
Critical Pressure: Pc 
Vc  9

where Tc is in K and Vc is in cm3 g-1.

Critical Volume: Vc  (0.377 P  11.0)

1.2

where P is a parameter called the Sugten Parachor.

26
SUGTEN PARACHOR VALUES FOR ATOMS
AND STRUCTURAL UNITS

C 4.8 S 48.2 triple bond 46.6

H 17.1 F 25.7 16.7
N 12.5 Cl 54.3 11.6
P 37.7 Br 68.0 8.5
O 20.0 I 91.0 6.1
O (esters) 60.0 double bond 23.2

Pcompound   ni Pi
27
 Part III

Osmosis and Osmotic Pressure

Osmosis and Osmotic Pressure
• Osmosis: The selective passage of
solvent molecules through a porous
membrane from a dilute solution to a more
concentrated one.
• Osmotic pressure (π or ∏): The pressure
required to stop osmosis.
π = iMRT (Approximate Form)

R = 0.08206 (Latm)/(molK)
Osmosis and Osmotic Pressure
Osmosis and Osmotic Pressure
Osmosis and Osmotic Pressure
• Isotonic: Solutions have equal
concentration of solute, and so equal
osmotic pressure.
• Hypertonic: Solution with higher
concentration of solute.
• Hypotonic: Solution with lower
concentration of solute.
 Uses of Colligative Properties
• Desalination:
 End
Thank you