M ASDAR I NSTITUTE OF S CIENCE AND T ECHNOLOGY

CHE501 - Chemical Engineering

Thermodynamics
Assignment 2

Author: Supervisor:
Aravind Muthiah Dr. Simo Pehkonen

February 27, 2012

Problem 1
Rapid discharge of a fire extinguisher results in cooling of the gas inside the cylinder. Consider a
fire extinguisher containing 0.1 m3 of CO2 initially at 20 MPa and 300 K. Assume that CO2 is an
ideal gas with Cp = 29 J/(mol K). The valve on the extinguisher can be modelled as an ideal orifice
with molar flow rate given by
P
n = C0 a0 f ()
T
where C0 = 0.8 is the orifice coefficient, a0 = 103 m2 is the orifice area, P is the difference
between the pressure in the cylinder and the ambient pressure, and f () = 0.5 mol K/s Pa m2 is
the heat capacity function. Assuming that heat transfer to the cylinder is negligible, develop an
expression for the gas pressure in the cylinder as a function of time.
(a) At what time will the pressure in the cylinder be 5 bar?
(b) What will the temperature of the gas in the cylinder be at that time?
(c) Make plots of P versus t and T versus t.

Solution:
Energy balance:
dE + PE +
X
= Q + W + KE ni Hi
dt
Now,
W =0 (now work done)
Q =0 (assuming Adiabatic process with no heat loss)
KE =0 (Stationary cylinder)
PE =0
No inlet gas i.e. no inlet enthalpy
dE
= nexit Hexit
dt
Where,
nexit = dn
dt
= C0 a0 f () P P
T
ext

E = nU
d(nU ) dn
= Hexit
dt dt
But U = CV T and H = CP T
d(nCv T ) dn
= CP T
dt dt
 
n dT T dn dn
Cv + = CP T
dt dt dt
 
dT dn CP dn
n +T = T
dt dt CV dt

1
 dn dT
( 1)T =n (1)
dt dt
Upon integrating this we get,
   
nf inal Tf inal
( 1)ln = ln
ninitial Tinitial
PV
Using n = RT
where V is constant we get,
!  
Pf inal Tinitial Tf inal
( 1)ln = ln
Pinitial Tf inal Tinitial

  1
Tf inal Pf inal
= (2)
Tinitial Pinitial
Thus the system shows that the gas behaves like it is undergoing reversible adiabatic expansion.
Now substituting n = dn
dt
= C0 a0 f () P
T
back in ( 1) gives
P dT
( 1)T C0 a0 f () =n
T dt
PV
Substituting n = RT
;
P P V dT
( 1)T C0 a0 f () =
T RT dt
C0 a0 f ()R P
dt = dT (3)
V P T ( 1)
Substituting for T from (2)

1

1
C0 a0 f ()R P PT
dt = ! 1 d i
V P i
P Ti1
P ( 1) Pi

P  1 
= 1 d P
P ( 1)P

1
P ( 1)P
1
= 1 dP
P ( 1)P

1 1
( 1)P 1 +1
= dP
P ( 1)
( 1) 1
= dP = dP
P ( 1) P
1
= dP
(P Pext )

2
 t P2
C0 a0 f ()R
Z Z
1
dt = dP
0 V P1 (P Pext )

P2
C0 a0 f ()Rt 1 
= ln(P Pext ) (4)
V P1

This is the required equation relating P to t.

 
C0 a0 f ()Rt 1 P1 Pext
= ln
V P2 Pext
Solving for P1 = 200 bar and P2 = 5 bar, we get;

t = 84seconds

Temperature at the time;

  1
P2
T2 = T1
P1
Substituting = 1.4, T1 = 300K, P1 = 200 bar and P2 = 5 bar
 0.4
 1.4
5
T2 = 300
200

T2 = 104.6K
Now for the equation relating T to t, substituting 2 in 4;

 1 !T2
C0 a0 f ()Rt 1 T 
= ln P1 Pext 
V T1 
 
T1
1
1 P1 TT1 Pext
= ln

 T  1
P1 T11
Pext

1 P1 Pext
= ln


  1
T
P1 T1 Pext

This is the equation relating T to t.

200 1.013
0.04656t = ln
T 3.5


200 300 1.013

3
This is the equation relating P to t.
 
200 1.013
0.04656t = ln
P 1.013

Thus the plot of T and P vs t is shown below

Temperature

Pressure

320
300
200
280
260
240 150
220
Temperature (K)

Pressure (bar)
200
180 100
160
140
120 50
100
80
0
60
40
0 50 100 150 200
Time (s)

Problem 2
Two Hilsch vortex tubes are advertised for sale on E-bay. Both claim to take a stream of nitrogen
at 2.4 bar and 298 K split the stream into two equimolar streams at 1.2 bar, but at different tem-
peratures. Seller ntropee claims his machine will produce streams at 455 K and 141 K. Another
seller, karknow is offering a version that produces streams at 475 K and 121 K. Should I bid on
either of these devices? If so, which one and why? Assume for simplicity that nitrogen is an ideal
gas with a constant pressure heat capacity of 29.3 J/(mol K).

Solution:

dU = T dS P dV

4
 dU P dV Cv dT P dV
dS = + = +
T T T T
RT
(Cp R) dT PdP (Cp R) dT dT P RT dP
= + = +R
T T T T TP2
Cp dT R dP
=
T P
S = Cp ln(T2 /T1 ) Rln(P2 /P1 )
Now for the 2 streams a and b the total entropy would be

S = Sa + Sb
   
Ta Pa Tb Pb
= Cp ln Rln + Cp ln Rln
Tin Pin Tin Pin
   
Ta Tb Pa Pb
= Cp ln 2
Rln 2
Tin Pin
Now fluid properties at inlet: Tin = 298K, Pin = 2.4 bar
ntropees machine
Ta = 455 K, Tb = 141 K, Cp = 29.3J/(mol K)
   
455 141 1.2 1.2
S = Cp ln Rln
2982 2.42
= 1.99 > 0

karknows machine
Ta = 475 K, Tb = 121 K, Cp = 29.3J/(mol K)
   
475 121 1.2 1.2
S = Cp ln Rln
2982 2.42
= 1.22 < 0

In the 2nd machine the total change in entropy, S < 0. This is in violation of the 2nd law where
Stotal >= 0. Thus the machine should be bought from NTROPEE.

Problem 3
An elastic hard sphere gas obeys the equation of state
RT
P =
V b
where b = 20 cm3 /mol is the second virial coefficient. Compute U, S, H, q, and w, for
compression of this gas from a volume of 600 cm3 /mol to 300 cm3 /mol isothermally at 300 K.

5
Solution:
Internal Energy change
! !
U U
dU = dT + dV
T V
V T
!
S
= CV dT + T P dV
V T
!
P
= CV dT + T P dV
T V
RT
P= V b
and for isothermal process dT = 0. Now upon integrating
Z 600 "   #
R RT
U = 0 + T dV
300 V b V b
=0
U = 0
Enthalpy change
dH = T dS + V dP
Upon solving and obtaining equation from notes,
!
Z P2
V
H = V T dP
P1 T
P
" #
P2  Z P2
RT R
Z
= +b T dP = b dP
P1 P P P1
" #
1 1
= b(P2 P1 ) = bRT
V2 b V1 b
= 92.15J/mol
H = 92.15J/mol
Work done
V2 V2
RT
Z Z
W = P dV = dV
V1 V1 V b
 
V2 b
= RT ln = 1816.4J
V1 b
W = 1816.4 J i.e Work is done on the system

6
 Heat transferred
Now U = Q + W but U = 0,
Q = W = 1816.4 J
Entropy change
V2
dQ P dV
Z Z
Ssystem = =
T V1 T
V2  
R V2 b
Z
= dV = Rln
V1 V b V1 b
= 6.05J/mol
Ssystem = 6.05 J/mol

Problem 4
Tester and Modell - 4.5

Solution:
The maximum work that can be extracted from the energy cylinders described in the problem is
actually the amount of shaft work Ws done in compressing the air from Ambient conditions to the
required Conditions in the cylinder. For frictionless adiabatic compression, this is called reversible
work and is given by Eq. 4.66(Pg 95)
Z P2
Ws
= V dP
n P1
So here Initial conditions are that in the cylinder; P1 , T1 , V1
Final conditions are those of the atmosphere; P2 , T2
V1
Also, n represents the decrease in amount of gas in the tank and is given by n = RT1
P1
Now, since the process is adiabatic P V = P1 V1
Z P2
Ws = n V dP
P1
 1 1
P2 P2
P1 V1

P1 V1
Z Z
= n dP = n 1 dP
P1 P P1 P
1
!P2
1
1 P 
= nP1 V1 
1 1 
P1
1  
nP1 V1
1 1 1 1
= P2 P1
1 1

7
Now = CCP = 29/20.7 = 1.4
V
V1
Also n is given by n = RT 1
P .
Now subsituting all of it back in the previous equation,
1
V1
P P11.4 V1
 
1 1
RT1 1 1.4 1 1.4
Ws = 1 P2 P1
1 1.4
R
But P = P2 P1
1  
V1 (P2 P1 )P11.4 V1 1
1 1.4 1
1 1.4
Ws = 1 P2 P1
RT1 (1 1.4 )
V 2 (P2 P1 )P10.714
= 1 P20.286 P10.286


0.286RT1

Substituting for values : P2 = 105 Pa, V1 = 1m3 , R = 8.314 J/molK

0.42(105 P1 )P10.714
26.915 P10.286


Ws =
T1
This is the equation required by the customer when out shopping for energy cylinders.
Now for P1 = 8x105 Pa and T = 300K;

WS = 252.85MJ

i.e. 252.85 MJ of work can be extracted from the given cylinder.

0.32
Unit cost of produced work = Cost
Ws
= 252.85

= 0.00127$/MJ