CHEMICAL AND PHASE

EQUILIBRA
COURSEWORK
Name: Yap Wei Khang
Student ID:UNIMKL-007852
Lecturer: Dr.Sergey Sportar
Module Code:H82CPE
Due Date:13th December 2011

Part#1: Example Sheet #1, Part B

Question 8

( )

{(

------

[ (

) ]}

*(

) +

(
(

[(

) (

)
) ]

(
(

) (

Question 9
To determine value of
(

, the following equation must be applied

( )

can be found by plotting graph of specific volume of gas ( ) versus temperature ( ). Value

( )

is determined by calculating the gradient of the graph.

From steam table, at 100

and 1 atm, value of

is 1.673

Table 1: Values specific volume of superheated steam,

pressure of 1 atm
Temperature (K)
373.15
398.15
423.15
448.15
473.15
498.15
523.15
548.15

, at different temperatures (K) at a constant

Specific volume,
1.673
1.793
1.912
2.039
2.145
2.260
2.375
2.490

Specific Volume(Vg) vs. Temperature (T)

Specific volume (m3/kg)

3
2.5
2
y = 0.0047x - 0.0592

1.5

Data Points

1
Linear (Data Points)

0.5
0
370

420

470

520

570

Temperature (K)

Figure 1: Graph of specific volume, vg, against temperature, K, is shown as above.

Comment: Specific volume of superheated steam increases with temperature (K) and behaves in a
linearity pattern.
3

From Figure 1, the gradient of the graph, ( )

Then substitute the value ( )
(

back into equation (2) giving,

To determine the value of , using the equation of =

1 1 (PV)

P P V P T

(PV)
(PV)
2 2

can be found by plotting graph of PV (m /s ) versus pressure (KPa). Value

is
P T
P T

determined by calculating the gradient of the graph.

Table 2: Values of PV and specific volumes at different pressure (KPa) under constant temperature of
100
Pressure (KPa)
1
10
20
30
40
50
75
100
101.325

Specific volume,
(
172.1800
17.1900
8.5847
5.7144
4.2792
3.4181
2.2698
1.6955
1.6730

PV (m2/s2)
172.180
171.900
171.694
171.432
171.168
170.905
170.235
169.550
169.517

Example calculations when determining PV

If pressure =

and specific volume,

, therefore the units of pressure x volume (PV) will be:

For first data, P= 1KPa and Vg =172.1800

PV (m2/s2) vs. Pressure (KPa)

172.5
172
PV, m2/s2

171.5
y = -0.0265x + 172.21

171

Data Points

170.5

Linear (Data Points)

170
169.5
169
0

20

40

60

80

100

120

Pressure, KPa

Figure 2: Graph of PV (m2/s2) against pressure (KPa) is shown as above.

Comment: Values of PV decreases in terms of pressure, KPa. The graph shows a linear negative slope
with a gradient of -0.0265.
(PV)

P T

From Figure 2, the gradient of the graph

1 1 (PV)
(PV)
Next, substitute the value of
back into equation of =

P P V P T
P T

Question 10

To show that ( )

( ) , a graph consists of specific volume against temperature must be

plotted. From the graph, its gradient can be determined and will be the value for ( )
Table 3: Values of specific volume at different temperature (K) at a constant pressure of 1 bar
Specific volume, V (m3/kg)

Specific Volume (m3/kg)

Temperature, T (K)
423.15

1.937

448.15

2.055

473.15

2.173

498.15

2.290

523.15

2.406

548.15

2.523

573.15

2.639

623.15

2.871

673.15

3.103

723.15

3.334

773.15

3.565

Specific Volume(Vg) vs. Temperature (K)

y = 0.0046x - 0.0269

3
2

Data Points

Linear (Data
Points)

0
0

100

200

300

400

500

600

700

800

900

Temperarture (K)

Figure 3: Graph of specific volume (Vg) against temperature (K) is shown as above
Comment: Specific volume increases directly with temperature, K. The graph shows a linear positive
slope with a gradient of 0.0046, approximately.
6

From Figure 3, the gradient of the graph, ( )

Since ( )
graph, (

/kg.K

) at 1 bar, a graph of entropy, S, against Ln P is plotted and gradient of the

) can be determined.

Table 4: Values of entropy at different pressures at a constant temperature of 250

Pressure, KPa
0.6112
1
5
10
50
75
100
101.325
150

Entropy, Sg (KJ/KgK)
10.390
10.163
9.420
9.100
8.355
8.167
8.033
8.027
7.843

Ln P
-0.4923
0.0000
1.6094
2.3026
3.9120
4.3175
4.6052
4.6183
5.0106

Entropy (Sg) vs. ln P

Entropy (KJ/KgK)

12

y = -0.4626x + 10.164

10
Data Points

8
6

Linear (Data
Points)

4
2
0

-1

ln P

Figure 4: Graph of entropy, Sg, against ln P is shown as above

Comment: Values of entropy of gas decreases as the values of Ln P increases. The graph shows a
linear negative slope with a gradient of -0.04626.
From Figure 4, the gradient of the graph, (
Having the value of (

) , then substitute it into equation ( )

m3/kg K

( )
Thus, ( )

( ) is proven
7

Part#2: Example Sheet#2, Part B, Question A

Coefficient of fugacity, , must be determined first before calculating the fugacity, . Therefore, to calculate
the coefficient:

However, the compressibility factor,

must be determined from P=0 bar to the saturation

pressure, which in this case, 146.11 bar before calculating for .

Table 5: Values of pressure and specific volume for gas at 340

P( bar)
0
0.006112
0.01
0.05
0.1
0.5
0.75
1
1.01325
1.5
2
3
4
5
6
7
8
9
10
15
20
30
40
50
60
70
80
90
100

Vg (m3/kg)
0
463
282.98
56.592
28.294
56.592
3.7678
2.8246
2.7872
1.881
1.4092
0.93764
0.70194
0.5416
0.45036
0.38516
0.33628
0.2982
0.2678
0.17642
0.13074
0.08992
0.06184
0.04794
0.0386
0.03178
0.02899
0.02486
0.02149

Vg (m3/kmol) z
0
8340.945
5097.885
1019.505
509.7164
1019.505
67.87692
50.88517
50.21141
33.88622
25.38674
16.89158
12.64545
9.756924
8.113235
6.938657
6.058084
5.372073
4.824417
3.178206
2.355281
1.619909
1.114048
0.863639
0.695379
0.572517
0.522255
0.447853
0.387142

(z-1)/P
0
0.988
1
0.9999
0.9998
0.9999
0.9986
0.9982
0.998
0.9971
0.996
0.9941
0.9922
0.9569
0.9549
0.9528
0.9507
0.9484
0.9464
0.9352
0.9241
0.9533
0.8742
0.8471
0.8185
0.7862
0.8196
0.7907
0.7594

0
8.23E-05
3.09E-05
-8.01E-06
-1.11E-05
-4.00E-06
-1.82E-05
-1.81E-05
-1.95E-05
-1.94E-05
-2.00E-05
-2.97E-05
-1.94E-05
-8.60E-05
-7.51E-05
-6.74E-05
-6.16E-05
-5.73E-05
-5.36E-05
-4.32E-05
-3.80E-05
-1.56E-05
-3.15E-05
-3.06E-05
-3.03E-05
-3.05E-05
-2.26E-05
-2.33E-05
-2.40E-05

P (KPa)
0
0.6112
0.3888
4
5
40
25
25
1.325
48.675
50
100
100
100
100
100
100
100
100
500
500
1000
1000
1000
1000
1000
1000
1000
1000

((z-1)/P)

0
5.03134E-05
1.19953E-05
-0.00003203
-0.000055425
-0.000160148
-0.000455
-0.0004525
-2.58375E-05
-0.000941861
-0.0009995
-0.0029675
-0.0019395
-0.0086025
-0.0075128
-0.0067444
-0.0061611
-0.0057294
-0.0053614
-0.0216055
-0.018987
-0.015563
-0.031462
-0.030584
-0.030257
-0.030549
-0.022551
-0.023258
-0.024046

110
120
130
140
146.11

0.01866
0.01621
0.01403
0.01238
0.01137

0.33616
0.292023
0.25275
0.22300
0.204831

0.7254
0.6874
0.6446
0.6124
0.5871

-2.50E-05
-2.60E-05
-2.73E-05
-2.77E-05
-2.83E-05

1000
1000
1000
1000
611
Total

-0.024966
-0.026048
-0.027342
-0.027683
-0.017267471
-0.400264564

After calculating all the necessaries, to find fugacity, :

Ln

-0.400264564

= exp(-0.400264564)= 0.6701

Part#2: Example Sheet#2, Part B, Question B

Given values: Temperature (T) = 613.15K and pressure (P) is 146.11 bar
Value of critical temperature of steam, TC = 374.15
Value of critical pressure of steam, PC = 222.12 bar
Source of TC and PC values : http://www.engineeringtoolbox.com/critical-point-water-steam-d_834.html
To find the coefficient of fugacity, , reduced temperature ( Tr) and reduced pressure (Pr) is determined
Tr =

Pr=

Tr = 0.947

Pr= 0.658

Using the generalized fugacity chart, coefficient of fugacity

can be found

0.71

Figure 5: Fugacity coefficients of gases and vapors (from O.A Hougen and K.M. Watson. Chemical Process
Principle Charts)
From Figure 5, at Pr = 0.658 and Tr = 0.947, the value of

is

Since

Percentage error calculated from: http://www.marshu.com/articles/calculate-percent-error-formula.php

10

Part#3 Question A
Given that A12 and A21 values at a constant temperature of 95 ,
Van-Laar equations had shown as below:
A12 = 2.1041
A21= 1.5555

At
To find

and

To find PA* and Pw * Antoine equations are used:

For acetone:

At 95 ,

For water:

At 95
11

and

can be determined using the

To find PA and PW:

To find PTOTAL:

To find Y1 and Y2:

12

Table 6: Values for

X1
0.01
0.04
0.07
0.1
0.13
0.16
0.19
0.22
0.25
0.28
0.31
0.34
0.37
0.4
0.43
0.46
0.49
0.52
0.55
0.58
0.61
0.64
0.67
0.7
0.73
0.76
0.79
0.82
0.85
0.88
0.91
0.94
0.97
0.99

X2
0.99
0.96
0.93
0.9
0.87
0.84
0.81
0.78
0.75
0.72
0.69
0.66
0.63
0.6
0.57
0.54
0.51
0.48
0.45
0.42
0.39
0.36
0.33
0.3
0.27
0.24
0.21
0.18
0.15
0.12
0.09
0.06
0.03
0.01

7.750373
6.589635
5.658159
4.903962
4.288175
3.78145
3.361414
3.010863
2.716454
2.467754
2.256543
2.076297
1.921801
1.788862
1.674083
1.574698
1.488444
1.413455
1.348189
1.291364
1.241907
1.198923
1.161654
1.129465
1.101815
1.078245
1.058367
1.041847
1.028403
1.017792
1.009809
1.004279
1.001051
1.000116

,PTOTAL, Pa, Pw, Pa*, Pw*, Y1, Y2

1.000283
1.004441
1.013379
1.026927
1.044981
1.0675
1.094493
1.126017
1.162176
1.203111
1.249008
1.300088
1.356612
1.418878
1.487224
1.562028
1.643709
1.732726
1.829587
1.934844
2.049099
2.173005
2.307271
2.452666
2.610019
2.780226
2.964252
3.163137
3.378003
3.610053
3.860581
4.130978
4.422736
4.629894

Pa
189.5396
644.6125
968.6135
1199.291
1363.306
1479.639
1561.899
1619.911
1660.809
1689.808
1710.735
1726.417
1738.952
1749.904
1760.446
1771.465
1783.635
1797.475
1813.389
1831.698
1852.663
1876.5
1903.396
1933.518
1967.02
2004.05
2044.752
2089.272
2137.762
2190.378
2247.285
2308.658
2374.682
2421.379

Pw
627.4815
610.9961
597.1696
585.6321
576.064
568.1855
561.7471
556.5223
552.3011
548.8849
546.0813
543.7004
541.5506
539.4351
537.1484
534.4728
531.1754
527.0043
521.6853
514.9182
506.3728
495.6853
482.4536
466.2326
446.5297
422.7993
394.4367
360.7726
321.0659
274.4971
220.1598
157.0533
84.07274
29.33688

13

Pa*
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555
2445.555

Pw*
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405
633.6405

PTOTAL
817.0211
1255.609
1565.783
1784.923
1939.37
2047.824
2123.646
2176.433
2213.11
2238.693
2256.816
2270.117
2280.502
2289.339
2297.594
2305.938
2314.81
2324.479
2335.074
2346.616
2359.035
2372.185
2385.849
2399.751
2413.55
2426.849
2439.188
2450.045
2458.828
2464.875
2467.445
2465.711
2458.754
2450.716

Y1
0.231989
0.513386
0.618613
0.671901
0.702963
0.722542
0.73548
0.744296
0.750441
0.754819
0.75803
0.760497
0.76253
0.764371
0.766213
0.768219
0.770532
0.773281
0.776587
0.78057
0.785348
0.791043
0.797785
0.805716
0.81499
0.825783
0.838292
0.852749
0.869423
0.888637
0.910774
0.936305
0.965807
0.988029

Y2
0.768011
0.486614
0.381387
0.328099
0.297037
0.277458
0.26452
0.255704
0.249559
0.245181
0.24197
0.239503
0.23747
0.235629
0.233787
0.231781
0.229468
0.226719
0.223413
0.21943
0.214652
0.208957
0.202215
0.194284
0.18501
0.174217
0.161708
0.147251
0.130577
0.111363
0.089226
0.063695
0.034193
0.011971

Graph of vs x
9
8
7
6
5
4
3
2
1
0

Y2
Y1

0.2

0.4

0.6

0.8

1.2

Figure 6: Graph of against x at a constant temperature of 95

Comment: The intersection point of the graph is approximately around 0.45. For
the x- values but
shows a decrease in correspond to the increase of x-values.

, the graph increases with

x-y Diagram
1.2
1

0.8
0.6

acetone

0.4

water

0.2
0
0

0.2

0.4

0.6

0.8

Figure 7: Diagram of x-y at a constant temperature of 95

Comment: The graph behaved in an increasing manner values of x and y increases.

14

1.2

P-x-y Diagram for Acetone

3000

Ptotal, bar

2500
2000
1500

acetone

1000

acetone

500
0
0

0.2

0.4

0.6

0.8

1.2

x-y

Figure 8: Diagram of P-x-y for acetone at a constant temperature of 95

Comment: Graph increases as x-y values increases. However, it never crosses through the point (1,2500).

P-x-y Diagram for Water

3000

P total, bar

2500
2000
1500

water

1000

water

500
0
0

0.2

0.4

0.6

0.8

1.2

x-y

Figure 9: P-x-y diagram for water at a constant temperature of 95

Comment: The graph is exactly vice versa from Figure 7. It is decreasing as x-y values increases, however, values
do pass through 2500mmHg benchmark.
Part B
At a given pressure of 1200mm Hg, consider the function T= T(x)
Using the Antoine equation, and by rearrange it in terms of T, we get

15

The T value above, we can assume its value is near

since T(x=0.01) should be approximately close to the
value 0. Then using the Goal Seek tool in Microsoft Excel, the value of T can be calculated by targeting P at the
initial value of
. The equation used for targeting P is shown as below.
(
Table 7: Values for X1, X2,
X1

)
,

0.99
0.96
0.93
0.9
0.87
0.84
0.81
0.78
0.75
0.72
0.69
0.66
0.63
0.6
0.57
0.54
0.51
0.48
0.45
0.42
0.39
0.36
0.33
0.3
0.27
0.24
0.21
0.18
0.15
0.12
0.09
0.06
0.03
0.01

, PTotal ,T, PA and Y1

X2
0.01
0.04
0.07
0.1
0.13
0.16
0.19
0.22
0.25
0.28
0.31
0.34
0.37
0.4
0.43
0.46
0.49
0.52
0.55
0.58
0.61
0.64
0.67
0.7
0.73
0.76
0.79
0.82
0.85
0.88
0.91
0.94
0.97
0.99

7.750373
6.589635
5.658159
4.903962
4.288175
3.78145
3.361414
3.010863
2.716454
2.467754
2.256543
2.076297
1.921801
1.788862
1.674083
1.574698
1.488444
1.413455
1.348189
1.291364
1.241907
1.198923
1.161654
1.129465
1.101815
1.078245
1.058367
1.041847
1.028403
1.017792
1.009809
1.004279
1.001051
1.000116

1.000283
1.004441
1.013379
1.026927
1.044981
1.0675
1.094493
1.126017
1.162176
1.203111
1.249008
1.300088
1.356612
1.418878
1.487224
1.562028
1.643709
1.732726
1.829587
1.934844
2.049099
2.173005
2.307271
2.452666
2.610019
2.780226
2.964252
3.163137
3.378003
3.610053
3.860581
4.130978
4.422736
4.629894

PTotal
T
PA
1200.000006 106.4946902 3280.043006
1200.000404 93.56980589 2354.392676
1200.000013 86.45901815 1939.250818
1200.000158 82.17031923 1717.774997
1200.000615 79.44109203 1587.408962
1200 77.64863286 1506.070785
1200 76.44946285 1453.495116
1200.000001
75.6381911 1418.746434
1200.000001 75.08465455 1395.411975
1200.000001 74.70276412 1379.488896
1200.000002 74.43380074 1368.359858
1200.000002 74.23685261 1360.255245
1200.000002 74.08304113 1353.951894
1200.000003 73.95187622 1348.594688
1200.000003 73.82886798 1343.585706
1200.000003 73.70391136 1338.512297
1200.000004 73.57016386 1333.098586
1200.000004 73.42324835 1327.171634
1200.000005 73.26067648 1320.637118
1200.000007 73.08142589 1313.461425
1200.000009 72.88562765 1305.658217
1200.000012 72.67433469 1297.278259
1200.000015 72.44935126 1288.401692
1200.000016 72.21311015 1279.132237
1200.000018
71.9685884 1269.592978
1200.00002 71.71925533 1259.923512
1200.000022 71.46904978 1250.278329
1200.000023 71.22238508 1240.826399
1200.000024 70.98418255 1231.751999
1200.000025 70.75993663 1223.256921
1200.000024 70.55581781 1215.564337
1200.000023 70.37882335 1208.924754
1200.000021
70.2369918 1203.624804
1200.000003
70.1665385 1200.998898

16

Y1
0.211846
0.517153
0.640068
0.701992
0.737434
0.759351
0.773585
0.783136
0.789703
0.794323
0.797672
0.800217
0.802292
0.80415
0.80599
0.807972
0.810232
0.812889
0.816048
0.819809
0.824266
0.829513
0.835645
0.842762
0.850971
0.860387
0.871141
0.88338
0.897272
0.913016
0.930845
0.951043
0.973953
0.990939

T-x-y Diagram
120

Temperature, K

100
80
60

acetone

40

acetone

20
0
0

0.2

0.4

0.6

0.8

1.2

x-y

Figure 10: T-x-y diagram for acetone at a constant pressure 1200mm Hg

Comment: Both graphs are behaving in a decreasing manner. Through the graph, acetone will only reach an
equilibrium around 70K at the highest mole fraction.

x-y Diagram
1.2
1

y(x)

0.8
0.6
Data Points

0.4
0.2
0
0

0.2

0.4

0.6

0.8

1.2

Figure 11: x-y diagram for acetone at a constant pressure of 1200mm Hg

Comment: Overall the graph behaves in an increasing pattern as the x-values increases.

17

Microsoft Excel Screenshots

Part 1
Question 9

18

Question 10

19

Part 2

20

Part 3

21