Saul Guerra Razo

ID 2077645
:

Problem Set 3
Due: 10/1/2021

Problem 1:
Assuming the van der Waals equation of state applies, consider the following systems at 470 K:

a. 1000 mol of pure methanol in a 300 L vessel

b. 1000 mol of pure 1-propanol in a 300 L vessel

Recall that the van der Waals equation has the following form:

RT a 9RTC vC vC
P= − 2 , where a = and b=
v −b v 8 3

Use the following critical parameters:

€ € Methanol € Propanol
TC (K) 513 537
vC (m3/mol) 1.16 x 10-4 2.17 x 10-4

For each system (hint: Maxwell construction):

a. How many stable phases are predicted AT EQUILIBRIUM by the equation of state?
b. Estimate the density of each stable phase.
c. Estimate the fraction of the system’s mass that will be in each phase.
d. Estimate the equilibrium pressure.
 >
a) How many stables phases
Below the critical temperature (Ta) the stable states
given
on a
,

isotherm are divided into two

groups .
Above the Tc
,
the distinct
liquid
and to exist ; therefore
gas
fluid state
states cease ,
there is
only a
single stable
.

of
b) Density each
phase
f ¥ =
; u = It
mm
.

1
M -

- n -

mm

Therefore
f- n.fm
fmetauol =
110010m¢) ( 32.04 Excl) = 106.8g
3/0/0 L I

f propanol ( 1000 not ) ( 60.09 Eno D=

200.39g
=

300L

fraction of that will

'

c) The the
system 's mass be in each
phase
Mmetauol + M
propanol =
(32.04 + 60-09) 91m01
= 92 .
13 91m01
1

3,2%0,4-3%11.4=0-3477
Xm +
Xp
=

✗ metanot =

Therefore
✗ propanol = 1- ✗metanot = 1- 0-3477
= 0 . 6522
 F-
R÷ ,
-

Ii a=9Rf i. b-
-

¥
d) Estimate the
equilibrium pressure

Metauolt -YE.j-m.g.fi#)- 3.xio-4nIo ,

a =9( 8.31451 Ñ¥÷ , ) ( 513K) ( 1.16×10-4m¥ ) , =

0.5566Pa ( m3 )2( mol
-

1)
2

b.
¥ (1.163110-4)-1%1 Ennio
-

= = =
3.867×10
,

p= . / 8.31451717T¢ )( 470kt) -
0 -5566Pa (m#( mom
( (3×10-4) syzygy m÷
-

13.867×10 ( 3×10-4
P= (14953582 -

6184444.444) Pa
P= 8769138 Pa

P= 86.54 atm

propanol
a= 918.31451m¥:P:D ) (537*112.17×10-414)=1 .

oqpq (mm÷)2
8

b = (2.17×10-4) Ñmol = 7.23×10 -5M¥

p= 18.3145 ?m¥¥md ) (470×1) -
1.09Pa l¥
( (3×10-4)
-

17-23×10-51 ]%¥ ( 3×10-41T¥

p= 5057030.742Pa
P= 49.84 atm
Problem 2:
At 5°C and 1 bar partial pressure, the solubility of carbon dioxide in naphthalene is very low; the
mole fraction of CO2 in naphthalene at equilibrium at that temperature is xCO2 = 0.6 x 10-4. At
5°C, the saturation pressure of pure carbon dioxide is 41 bar and that of pure naphthalene is
5x10-5 bar. Also at 5°C, the molar volume of carbon dioxide is given by the empirical relation:

#1 &
v = RT % − 6.89x10 −3 − 7.27x10 −5 P (
$P '

where P is in bar.
€ of carbon dioxide in naphthalene at 5°C when the partial pressure of CO2
Calculate the solubility
is 37 bar (assume Henry's constant is the same at 1 bar).
Partial Pressure of CO2 = 37bar
R =
0.08314511m¥.Ñ
T = 5°C =
278.15K

(¥ 6.89×10-3 SP
)
-

V =
RT -
-

7.27×10

✓ = 10.0831451
t.bar-11278.IS/k)z1zb-a
Mo / 14
'
,
-

(6-89×10-3) (7.27×10-5) 137bar )

-

)
✓ =
0.4034
Jo ,
This correspond to the
total naphtalene
d
molar
solubility =

f- ,÷zy±-
=
=
2.478 MI
L

hid
0-6×10-4
✗ coz =

Molar solubility of CO2 in naphthalene =

(0.6×10-4) ( 2.478m¥ )
1.487×10-4
44 91m01
=

YI
Mmco ,
=

Solubility )( mouth )
(
44¥
= 1.487×10-4 =
6.5428×10--31
, L
Problem 3:
Some experimental data for the region from 0 to 50 bar indicate that the fugacity of a pure gas is
given by the empirical relation:

f
ln( ) = −cP − dP 2
P

Where P is the pressure in bar and c and d are constants that depend only on temperature. For
the region 60 to 100°C, the data indicate that:
€
30.7
c = −0.067 +
T

0.416
d = 0.0012 −
T
€
Where T is in Kelvin. At 80°C and 30 bar, what is the molar enthalpy of the gas relative to
that of the ideal gas at the same temperature? (Hint: Gibbs-Helmholtz equation)
€
 In
1¥ ) = -
op -
d P2

[0 to 50 bar
]
where

30¥
c =
-
0.067 -1

0--416-1
d = 0.0012 -

For temperature 7--80 c 353 K

•
=

C = -
0.067 + 30.7-a =
0 . 0 199
353

D= 5-

0j4glg6_
-

0.0012 -

=
2- 15297×10

(Ip )
In at 30 bar & 80°C

In ( Ip ) =
-
0.0199 ( 30 ) -

(2.15297×10-5) ( 3012
=
-
O -

616

Molar be related with

enthalpy can Gibbs energy :

For ideal
gas
Gif =
ELT) + RT In P
Formal
gas
Gi =
ri (7) + RT In fi
Relative Gibbs energy Th " valid for molar
Ypres"on is

(g)
for
Gi Gi'T -

=p -1 In enthalpyes Entropy0 .

pure
substance =
Si =

Mi Mi - -

- Mln
(F)
(8.3142*-1*1/3534) (-0-616) 1807.86 I
=
=

Mol