CHEE3320 THERMODYNAMICS

ASSIGNMENT # 3
RESIDUAL ENTHALPY

Question 1

The ideal gas heat capacity for water vapour on a molar basis is:
`

= 3.470 + 1.450 10

+ 0.121 10

[1]

ENTHALPY CHANGE AS AN IDEAL GAS

Overall, on a molar basis,

`=

[2]

i) Calculation the Enthalpy change for a temperature increase from 273.16

K to 823.15 K. The molecular weight of water, M = 18.0152 kg/kmol.
.
! . "

`=

H`=

.
#$
! . "

+% +&

'

[$ + 0.5%

&

.
! . "

[#3.470 823.15 + 0.5 #1.450 10 ' #823.15' #0.121 10 ' #823.15' '

[#3.470 273.16 + 0.5 #1.450 10 ' #273.16' #0.121 10 ' #273.16' ']

H` = 1096.15641 kJ/kg
ii) For the pressure change from 0.611 kPa to 9000 kPa, H` = 0

iii) Calculating the residual enthalpy, HR

Method_1 Calculating the residual enthalpy by application of Virial
Equation.
Firstly, we need to know the values of some variables.
Reduced temperature is

[3]

, 1234 57 8594 :8;97 <=:7 => 57 ?97@5=3>

647.3 A 8>

= 823.15 A.

7> BC =

DEF.GH
IJK.F

= G. EKGIIK.

Reduced pressure is
L. =

, 1234 57 8594 :8;97 <=:7 => 57 ?97@5=3> L = 220.5 M82 =

22050 NL8 8> L = 9000 A.

7> PC =

QRRR

EERHR

= R. JRDGIF.

By Generalized Virial-Coefficient Correlation, we can know the B0

and B`;
% = 0.083

0.422
."

Thus, SR = R. RDF

% ` = 0.139

R.JEE
#G.EK'G.I

= R. ERJEQ

0.172
.

+.

Thus, S` = R. GFQ

R.GKE
#G.EK'J.E

= R. RKIFGH

This way it is possible to calculate the HR by Direct Application of the Virial

Equation,
TU

= L. [%

VWX
. V
Y

= [ \ L. [%

+ Z#% `

VWX
. V
Y

VW`
. V ']
Y

+ Z#% `

VW`
. V ']
Y

[4]
[5]

Where,
]SR
R. IKH
=
= R. FIGFHJ
]BC
BE.I
C
]S`
R. KEE
=
= R. ERIQGK
]BC
BH.E
C

8> Z =@ 57 8^^7>52=^ 18^532, _=^ =@ `723 132 >3M;7 <8@7@ 8> 0.344 132 _8572.
Hence, substituting the values above in the equation [5]
= 8.314 647.3 0.408163[0.20429 1.271667 0.36135
+ 0.344#0.076315 1.271667 0.206917']

= 1599.28

Na
N43;

de

Divided by molecular weight of water, bc = DD. KKFD df

For calculation of the actual enthalpy is.
H = H`0 + H` + HR
H = (2501.6 + 1096.15641 + 0 88.7738) kJ/kg
H = 3508.983 kJ/kg

Method_2 Calculating the HR by Numerical Integration of PVT Data

Firstly, we need to calculate the J #P',
a #L' = ij

kj
|Lm
k

According to values on Table 1,

a #9000' = #0.039822 #823.15' ##0.042798 0.036737'/100''

a #9000' = 0.010069

Now that the J1(P) is knows it is possible to calculate the HR,

=

oj

pq
p

|Lr L =

a #L' L

[6]

According to what was asked in Question 1, we must solve the integral in

the equation [6] using the trapezium rule.

Then the trapezium rule was applied by equation below,

a #L ' + a #L '
#L2 L1'
2
a #9000' + a #8600'
=
#9000 8600'
2
0.010069 + #0.010022'
#9000 8600' = 4.0182365 Na/N<
=
2

$278 =

After calculating the value of HR related to each pressure and J1(P) was

done the summation of these values. All values related to the above
calculations can be checked on Table 1.
The Trapezoidal Rule Graph can also be checked, where the areas of each
section according to the trapezium rule can be seen in the Graph 1.

P (kPa)
50
1700
3500
5500
7600
8600
9000

Volumes (m3/kg)
500
550
600
7.1335 7.595500 8.057400
0.20704 0.221090 0.235060
0.099088
0.10617
0.11315
0.062002 0.066694 0.071289
0.044056 0.047603 0.051045
0.038586 0.041787
0.04488
0.036737 0.039822 0.042798

dV/dT|P

(V-TdV/dT|P)

0.009239
0.000280
0.000141
0.000093
0.000070
0.000063
0.000061

-0.009583
-0.009557
-0.009581
-0.009752
-0.009927
-0.010022
-0.010069
Total:

HR
-0.4791425
-15.790071
-17.224185
-19.333294
-20.662839
-9.9745073
-4.0182365
-87.482274

Table 1. Calculating the HR using Steam Table Data.

1000

2000

3000

-0.009499

-0.009599

J1(P)

-0.009699

-0.009799

-0.009899

-0.009999

-0.010099

Graph 1. Trapezoidal Rule Graph

Pressure, P (kPa)
4000 5000 6000 7000

8000

9000 10000

Then, using Steam Table PVT, the actual value for H is:

H = H`0 + H` + HR
H = (2501.6 + 1096.15641 + 0 87.482274) kJ/kg
H = 3510.274 kJ/kg

From Steam Table, for P = 9000 kPa and T = 823.15 K the H = 3509.8 kJ/kg.

In the Table 2 it is shown the comparison between the values found for HR and H
for both methods used.
HR (kJ/kg)
-88.7738
-87.482274

H (kJ/kg)
3508.983
Using Virial Eqn of State
3510.274
Using Steam Tables PVT
3509.8
Results from Steam Table
Table 2. Comparison between the values found for HR and H and the value of the
steam table for H.

Therefore, according to values on table 2 it is perceptible a percentage error

related to the H values found to the H value from Steam Table respectively
0.023% and 0.013%. A range of error that can be acceptable.

REFERENCES
Gavin, K., and Moreno-Atanasio, R., CHEE3320 Thermodynamics Course
Notes. University of Newcastle. 2014.
Smith, J.M., and Van Ness, H.C., Introduction to Chemical Engineering
Thermodynamics, 6th Ed., 2001, McGraw Hill.