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CHEMISTRY
-1-
THERMODYNAMICS
Problems
1. 1.25 m3 of air at 1800C at 8 bar is undergoing a constant pressure until the volume is doubled. Determine the
change in the entropy and enthalpy of air. , Given CP = 1.005 kJ/kg 0K, Cv = 0.718 kJ/kg 0K and R = 0.287 kJ/kg
0
K
1 Solution: Assuming air behaves like a perfect gas we have, CP = 1.005 kJ/kg 0K,
Cv = 0.718 kJ/kg 0K and R = 0.287 kJ/kg 0K
Given: V1 = 1.25 m3, T1 = 180 + 273 = 4530 K, P1 = P2 = 8 x 105N/m2 and V2 = 2V1
For a constant pressure process, change in entropy is
T
S 2 S1 mC P ln 2
T1
8 x10 5 x1.25
7.69kg
287 x 453
PV
PV
Also 1 1 2 2
T1
T2
2 x1.25 x 453
T2
906 0 K
1.25
m
906
453
= 5.596 kJ/0K
Change in enthalpy = Q1-2 = mCP (T2 T1) = 3500.99 kJ
1kg of air initially at 270C is heated reversibly at constant pressure until the volume is doubled, and then is heated
at constant volume until the pressure is doubled. For the total path find i) Work transfer, ii) Heat transfer, iii)
Change in entropy
2. Solution: Given: m = 1 kg, T1 = 3000 K V2 = 2V1,
P3 = 2P2 = 2P1
2.
P
2
1
V
Process 1-2: Constant pressure process
i) Work done, W1-2 = P (V2 V1)
= PV2 PV1
= mR (T2 T1)
P1V1 P2V2
T1
T2
V V
But P1 = P2 1 2
T1 T2
Also
But V2 2V1
= 86.1 kJ
-2-
ii) From first law of TD, Heat Transfer, Q1-2 = W1-2 + (U2 U1)
= W1-2 + mCv (T2 T1)
= 86.1 + 1 x 0.718 x (600 300)
= 301.5 kJ
iii) Change in entropy,
S 2 S1 mC P ln
T2
T1
1(1.005) ln
600
300
= 0.6966 kJ/0K
P2V2 P3V3
T2
T3
T P T x 2 P2
T3 2 3 2
P2
P2
We have
But V2 V3
= 2 x T2 = 12000K
i) Work done, W2-3 = 0
ii) Heat transfer, Q2-3 = W2-3 + (U3 U2)
= mCv (T3 T2)
= 430.8 kJ
iii) Change in entropy
S 3 S 2 mC P ln
T3
T2
= 0.4977 kJ/0K
Therefore work transfer in total path, W1-3 = W1-2 + W2-3
= 86.1 + 0
= 86.1 kJ
Heat transfer in total path, Q1-3 = Q1-2 + Q2-3
= 301.5 + 430.8
= 732.3 kJ
Change in entropy for the total path = (S3 S1) = (S3 S2) + (S2 S1)
= 0.4977 + 0.6966
= 1.1943 kJ/0K
A mass of air is initially at 2600C and 700 kPa, and occupies 0.028m3. The air is expanded at constant pressure to
0.084m3. A polytropic process with n = 1.5 is then carried out, followed by a constant temperature process which
completes a cycle. All the processes are reversible. (i) sketch the cycle in the P-v and T-s diagrams. (ii) find the
heat received and heat rejected in the cycle. (iii) find the efficiency of the cycle.
3 Solution: P1 = 700 kPa, T1 = 533K = T3, V1 = 0.028m3, V2 = 0.084m3
3.
-3-
700 x 0.028
0.128kg
0.287 x533
T
PV
0.084
3
Now 2 2 2
T1
P1V1 0.027
Therefore T2 = 3 x 533 = 1559 K
n
Again
P2 T2 n 1 1599 0.5
3
(3) 27
P3 T3
533
1.5
Q2 3 U pdv
mc v T3 T2
mc v
mR T2 T3
n 1
n
T3 T2
n 1
But dU = 0, i.e.,
P
v1
mRT1 ln 3
v3
P1
cycle 1
Q2
84.12
1
0.39 or 39%
Q1
137.13
1 kg of air at a pressure of 7 bar and a temperature of 900C undergoes a reversible polytropic process which may be
represented by PV1.1 = C, final pressure is 1.4 bar. Evaluate i) The final specific volume, temperature and increase
in entropy, ii) Work done and heat transfer.
4 Solution: Given, m = 1 kg,
P1 = 7 bar,
T1 = 3630K,
PV1.1 = C,
P2 = 1.4 bar
Air is perfect gas i.e., P1V1 = mRT1
4.
v1
1( 287)(363)
0.14883m 3 / kg
7 x10 5
-4-
V
n
R. ln 2
S 2 S1
1
V1
P1V1 P2V2
n 1
cp
cv
Or
vdp
pdv
dp
dv
0
p
v
Or
d (ln p) + d (ln v) = d (ln c)
Therefore ln p + ln v = ln c
i.e., pv = constant
A mass of 0.25 kg of an ideal gas has a pressure of 300 kPa, a temperature of 800C, and a volume of 0.07 m3. The
gas undergoes an irreversible adiabatic process to a final pressure of 300 kPa and final volume of 0.1 m3 during
which the work done on the gas is 25 kJ. Evaluate the cp and cv of the gas and increase in entropy of the gas.
6 Solution: We have, P1 V1 = mRT1
6.
300 x 0.07
0.238kJ / kgK
0.25 x353
PV
300 x 0.1
Final temperature T2 2 2
505 K
mR
0.25 x 0.238
S 2 S1 mcv ln
P2
V
mc p ln 2
P1
V1
-5-
V2
0.10
0.25 x0.896 ln
V1
0.07
= 0.08 kJ/kg-K
7.
An ideal gas cycle consisting of three processes uses Argon (M = 40) as a working substance. Process 1-2 is a
reversible adiabatic expansion from 0.014m3, 700 kPa, 2800C to 0.056m3. Process 2-3 is a reversible isothermal
process and process 3-1 is a constant pressure process. Sketch the cycle on P-v and T-s diagrams and determine (i)
work transfer in each of the three processes (ii) heat transfer in each of the three processes and (iii) net work output
from the cycle. Assume for Argon = 1.67.
Solution: M = 40, V1 = 0.014m3, P1 = 700 kPa, T1 = 553 K
V2 = 0.056m3, = 1.67
R 8.3143
0.208kJ / kg K
M
40
R
0.208
cv
0.311kJ / kg K
1 1.67 1
V
i.e., P V P2V or P2 P1 1
V2
or P2 69.13kPa
1 1
W12
0.014
700 x
0.056
1.67
V
0.014
Also T2 T1 1 553 x
218.45 K
0.056
V2
P V P2V1 700 x10 3 x0.014 69.13x10 3 x0.056
1 1
J
1
1.67 1
0.67
But
P
V
P
W2 3 mRT2 ln 3 mRT2 ln 2 mRT2 ln 2
V2
P1
P3
3
PV
700 x10 x0.014
m 1 1
0.2157 kg
RT1 0.208 x10 3 x 218.45
-6-
69.13
W2 3 0.2157 x 0.208 x10 3 x 218.45 x ln
700
= - 22.69 x 103J = - 22.69 kJ
By first law of TD Q2-3 = (U3 U2) + W2-3
But U3 U2 = mcv (T3 T2) = 0
Therefore Q2-3 = W2-3 = - 22.69 kJ
Q W
or Q1 2 Q2 3 Q31 W
A mass of an ideal gas exists initially at 200 kPa, 300K and 0.5 m3/ kg. The value of is 1.4. (i)Determine the
specific heats of the gas. (ii)What is the change in entropy when the gas is expanded to a pressure of 100 kPa
according to the law pv1.3 = constant (iii) What will be the change in entropy if the process is according to the law
pv1.5 = constant (iv) What inference you can draw from this example.
Solution: P1 = 200 kPa, T1 = 300 K, v1 = 0.5 m3/kg, =1.4, P2 = 100 kPa
(i) For an ideal gas P1v1 = RT1 or
P1v1
T1
333.33 J / kg K
cv
R
833.33 J / kg K
1
c p c v 1166.66 J / kg K
(ii) For the given process
P1v1n P2 v 2n
1
n
P
or v 2 1 v1 0.852m 3 / kg
P2
P v
Also T2 2 2 255.6 K
R
Change in entropy per unit mass is given by
T
S 2 S1 c v ln 2
T1
v
R ln 2
v1
= 44.18J/K
(iii) For the process for which the index n = 1.5 we have
1
200 1.5
3
v2
x0.5 0.764m / kg
100
1-D-10 Talwandi & B-7. JAWAHAR NAGAR, KOTA.(RAJ) Ph-0744-2422383 .Mo-93149-05055
-7-
300
0 .5
= - 38.07 J/K
(iv) It can be seen from the results of (ii) and (iii) above that entropy increases when n < and it decreases when n
> .
A closed rigid cylinder is divided by a diaphragm into two equal compartments, each of volume 0.1 m3. Each
compartment contains air at a temperature of 200C. The pressure in one compartment is 2.5 MPa and in the other
compartment it is 1 MPa. The diaphragm is ruptured so that the air in the compartments mix to bring the pressure to
a uniform value through the insulated cylinder. Find the net change in entropy due to mixing process.
9 Solution: Let suffix 1 denote the condition of air in the left half of the cylinder, suffix 2 the conditions in the right
half of the cylinder and suffix 3 the condition after mixing
It if given that,
V1 = V2 = 0.1 m3, T1 = T2 = 20 + 273 = 293K, P1 = 2.5 MPA, P2 = 1.0 MPa
After mixing the temperature is given by
9.
T3
m1 c p1T1 m2 c p 2T2
m1c p1 m 2 c p 2
T
v
T
v
m1 cv ln 3 R ln 3 m2 cv ln 3 R ln 3
T1
v1
T2
v2
6
Pv
2.5 x10 x0.1
m1 1 1
2.973kg
RT1
287 x 293
p
s 2 s1 s 20 s10 R ln 2
p1
0
From table C-21 at T1 = 300 K, s1 2.5153kJ / kg K and
(i) We have change in entropy per kg of air,
at T2 = 450 K, s 2 2.9245kJ / kg
Therefore on substituting, s2 s1 = - 0.02508 kJ/kg-K
0
s 2 s1 c p ln
T2
P
R ln 2
T1
P1
-8-
450
4 .5
0.289 ln
0.0252kJ / kg K
300
1
11 a) A gaseous mixture contains 21% by volume of N2, 50% by volume of H2 and 29% by volume of CO2. Calculate
the gas constant of the mixture and the ratio of specific heats. If the mixture pressure is at 1 bar and the mixture
temperature is 100C, calculate the partial pressures and mass fractions of the constituents.
b) A cylinder contains 0.085m3 of this mixture at 1 bar and 100C. The gas undergoes a polytropic process according
to the law Pv1.2 = constant to a final volume which is one fifth of the initial volume. Determine i) the magnitude and
direction of work transfer, ii) magnitude and direction of heat transfer and iii) the change in entropy.
11 Solution: From tables C-6, MN2 = 28.02, MH2 = 2.016 and MCO2 = 44
From table C-11, CPN2 = 1.039 kJ/kg-K, CPH2 = 14.15 kJ/kg-K and CPCO2 = 0.818 kJ/kg-K
a) Given VN2 / V = VfN2 = 0.21, VH2 / V = VfH2 = 0.5, VCO2 / V = VfCO2 = 0.29
P = 1 bar, T = 283 K
We have R N 2
R
8.3143
0.297kJ / kg K
M N 2 28.013
RH 2
R
8.3143
4.124kJ / kg K
MH2
2.016
RCO 2
R
8.3143
0.189kJ / kg K
M CO 2
44
Mass fraction of N2
m fN 2
mN 2 nN 2 M N 2
M
yN 2 N 2
mm
nm M m
Mm
28.013
0.21x
0.2993
19.654
Similarly m fH 2 0.5 x
m fCO 2
2.016
0.0513
19.654
44
0.29 x
0.6494
19.654
For the mixture Cvm = MfN2 CvN2 + MfH2 CvH2 + MfCO2 CvCO2
= 0.2993 x 0.742 + 0.0513 x 10.026 + 0.6494 x 0.629
= 1.145 kJ/kg-K
CPm = Cv + Rm
= 1.145 + 0.423
= 1.568 kJ/kg-K
Therefore the ratio of specific heat for the mixture is m = CPm / Cvm
= 1.568 / 1.145
= 1.369
1-D-10 Talwandi & B-7. JAWAHAR NAGAR, KOTA.(RAJ) Ph-0744-2422383 .Mo-93149-05055
-9-
p V 1x10 5 x0.085
m 1 1
0.071kg
423 x 283
RT1
1.2
1. 2
For the given process, p1V1 p 2V2
V
p 2 1
V2
p1 5 x1 6.9 bar
1. 2
1.2
p1V1 p 2V2
n 1
5
5 1
1x10 x 0.085 6.9 x10 x 5 x 0.085
1.2 1
16150 J
W1 2 Wd 1 2
Negative sign indicates that work is done by the surroundings on the gas mixture.
Temperature of the mixture at the end of the process is,
1
6.9 x10 5 x x0.085
pV
5
T2 2 2
mR
0.071x 423
390.6 K
p
T
Or 2 2
T1 p1
n 1
n
0.2
6.9 1.2
i.e., T2 283
390.5 K
1
390.6
1
0.0711.145 x ln
0.423 x ln
283
5
0.02214kJ / K
12. Calculate the constant volume and constant pressure specific heats of a gas mixture consisting of 1 kg of
oxygen and 2 kg of nitrogen at a pressure of 1.5 bar and temperature 200C. Also determine the change in internal
energy, enthalpy and entropy of the mixture when it is heated under constant volume to a temperature of 1000C.
12 Solution: From tables C-6, MO2 = 32, MN2 = 28
From table C-11, CPN2 = 1.038 kJ/kg-K, CPO2 = 0.917 kJ/kg-K
CvN2 = CpN2 RN2 = 1.038 8.3143 / 28 = 0.741 kJ/kg-K
CvO2 = CpO2 RO2 = 0.917 8.3143 / 32 = 0.653 kJ/kg-K
cv m m fi cv i
i
- 10 -
1
2
x 0.653 x 0.741 0.712kJ / kg K
3
3
m fi c p i
p m
1
2
x 0.917 x1.038 0.998kJ / kg K
3
3
U mm cv m T2 T1
H mm c p m T2 T1
S m
T
mm c v m ln 2
T1
V
Rm ln 2
V1
T
mm c v m ln 2
T1
373
3x 0.712 ln
293
S m
= 0.5156 kJ/K
13. A gaseous mixture consisting of 1 kg of helium and 2.5 kg of nitrogen is compressed isentropically in a closed
system from a pressure of 1 bar, 270C to a pressure of 7 bar. Assuming specific heats of helium and nitrogen to
be constant, determine the specific heats of the mixture, the change in entropy of individual gases, and the
change in internal energy of the mixture. Also find the work required for the compression process. Assume
CvHe = 3.14 kJ/kg-K, CvN2 = 0.741 kJ/kg-K, CpHe = 5.233 kJ/kg-K and CpN2 = 1.038 kJ/kg-K
13 Solution:
cv m m fi cv i
i
p m
1
2 .5
x3.140
x 0.741 1.426kJ / kg K
3 .5
3 .5
m fi c p i
i
1
2 .5
x5.233
x1.038 2.236kJ / kg K
3 .5
3 .5
c p m 2.236
1.568
cv m 1.426
p
T2 T1 2
p1
m 1
m
0.568
7 1.568
300
607 K
1
- 11 -
p He , 2
T
m He c p He ln 2 R He ln
T1
p He,1
p N ,2
p He , 2
p
7
2 2
We know that ,
p He ,1
p N 2 ,1
p1 1
S He
607
7
S He 15.233 ln
2.093 ln
300
1
= - 0.38 kJ/K
Similarly S N 2 2.51.038 ln
0.297 ln
300
1
607
= + 0.38 kJ/K
Internal energy of the mixture
U m mm cv m T2 T1
p N2
pm
v N2
vm
0.85 1
1.7
2
S m
m N 2 R N 2 ln y N 2 mO2 RO2 ln y O2
8.3143 2.5
8.3143 2.5
3.84 x
ln
4.39 x
ln
28
5
32
5
=1.579kJ/K
15. Two kg-mole of CO2 at a pressure of 1.8 bar, 800C is mixed in a thermally insulated vessel with 3 kg-mole of N2 at
2.2 bar, 600C. When the mixture is at equilibrium, determine the final temperature and pressure and the change in
entropy of the mixture. Assume CvCO2 = 0.653 kJ/kg-K, CvN2 = 0.741 kJ/kg-K
1-D-10 Talwandi & B-7. JAWAHAR NAGAR, KOTA.(RAJ) Ph-0744-2422383 .Mo-93149-05055
15 Solution: we have, Tm
cv CO
- 12 -
M CO2 xc v CO2
Now the molal specific heats at constant volume of the constituent gases are
2
= 44x0.653
=28.73 kJ/kg-mole K
cv N
And
M N 2 xcv N 2
=28x0.741
=20.75 kJ/kg-mole K
Tm
=342.6 K
The final pressure of the mixture is
pm
nm R Tm
Vm
nCO2 R TCO2
VCO2
VN2
pCO2
n N 2 R TN 2
p N2
2 x8.3143x353
32.61m 3
100 x1.8
3 x8.3143x333
37.75m 3
100 x 2.2
pm
5 x8.3143 x342.6
2.02 bar
100 x 70.36
pCO2
nCO2
nm
xp m
2
x 2.02 0.808 bar
5
p N2
nN2
S CO2 S N 2
But
nm
xp m
3
x 2.02 1.212 bar
5
pCO2 , 2
T
nCO2 cv CO2 ln m R ln
TCO2
p CO2 ,1
p N ,2
T
n N 2 c v N 2 ln m R ln 2
TN 2
p N 2 ,1
p CO
2
and
p N
2
R c v N 2 8.3143 20.75
- 13 -
342.6
1.212
2 37.04 ln
8.3143 ln
353
1.8
342.6
1.212
529.064 ln
8.3143 ln
333
2.2
=2[-1.108+6.659]+3[0.826+4.957]
=28.45 kJ/ K