SAMPLE CALCULATION

A)

P-X-Y diagram
90
80
70
60
50
Pressure (kPa)

40
30
20
10
0
0.05 0.15 0.25 0.35 0.45 0.55 0.65 0.75 0.85 0.95 1.05
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
X1, Y1

From the graph

X1

= 0.1686

Y1

= 0.57

Pressure = 39.5 kPa

VAN LAAR METHOD

P(kPa x1
y1
ln(1) x2
y2
ln(2) GE/RT GE/x1x
x1x2RT/
)
2RT
GE
19.95
0
0
1
1
0
3
39.22 0.168 0.571 0.452 0.831 0.428 0.013 0.087
0.6229
1.6053
3
6
4
3
4
6
3
3
42.98 0.216 0.626 0.385 0.783 0.373 0.026 0.103
0.6123
1.6332
4
7
8
5
3
2
0
9
48.85 0.303 0.694 0.277 0.696 0.305 0.072 0.134
0.6373
1.5691
2
9
3
5
1
7
5
8
52.78 0.368 0.734 0.219 0.631 0.265 0.105 0.147
0.6346
1.5757
4
1
5
6
9
5
7
6
56.65 0.446 0.774 0.150 0.553 0.225 0.146 0.148
0.5999
1.6670
2
1
2
7
9
8
2
2
60.61 0.528 0.808 0.092 0.471 0.191 0.209 0.147
0.5932
1.6859
4
2
5
7
8
5
5
8
63.99 0.604 0.838 0.048 0.395 0.161 0.270 0.136
0.5707
1.7523
8
4
3
5
6
7
8
5
67.92 0.680 0.873 0.030 0.319 0.126 0.299 0.116
0.5360
1.8656
4
4
3
5
6
7
8
6
70.22 0.725 0.892 0.021 0.274 0.107 0.323 0.104
0.5231
1.9118
9
5
2
1
5
8
7
2
72.83 0.777 0.914 0.012 0.222 0.085 0.343 0.086
0.4975
2.0102
2
6
1
4
4
9
5
0
84.56
1
1
0
0
0
2

9.
60
8.
40
7.
20
6.
00
4.
80
0.
00

1.
20

2.
40

3.
60

x1x2RT/GE

0 f(x) = 0.2
R = 0

0.4

0.6
X1

( yi ) ( Pi)
( xi ) ( P 1 sat)

( 0.5714 ) (39.223)
( 0.1686 ) (84.562)

= 1.5720

ln 1 = ln 1.5720
= 0.4523

( yi ) (Pi)
( xi ) ( P 2 sat )

( 0.4286 ) (39.223)
( 0.8314 ) (19.953)

0.8

1.2

= 1.0134
ln 1 = ln 1.0134
= 0.0133

RT

= (X1) (ln 1) + (X2) (ln 2)

= (0.1686) (0.4523) + (0.8314) (0.0133)
= 0.0873

X 1 X 2 RT

= 0.0873 / (0.1686)( 0.8314)

= 0.6229

X 1 X 2 RT

= 1 / 0.6229

= 1.6053

From graph
Gradient

= 0.576

Y intercept = 1.494

Y intercept =

1
A ' 12

1
A ' 12

= 1.494

A12 = 0.6693
Gradient, m =

0.576 =

1
1

A ' 21 A ' 12

1
1

A ' 21 0.6693

A21 = 0.4831

ln1 = X22[A12 + 2(A21 A12)X1]

ln1 = (0.8314)2[0.6693 + 2(0.4831 0.6693)0.1686]
ln1 = 0.4192
1

= 1.5208

ln2 = X12[A21 + 2(A12 A21)X2]

ln2 = (0.1686)2[0.4831 + 2(0.6693 0.4381)0.8314]
ln2 = 0.0225
2

= 1.0228

P = X1 1P1sat + X2 2P2sat
P = (0.1686)(1.5208)(84.562) + (0.8314)(1.0228)(19.953)
P = 38.65 kPa

Y1 =

X 1 1 P 1 sat
P

( 0.1686 )( 1.5208 ) ( 84.562)

38.65

Y1 = 0.561

WILSON METHOD
X1

= 0.1686

X2

= 0.8314

= 333.15 K

P1 sat = 84.562 kPa

P2 sat = 19.953 kPa

Methanol (1) / water (2)

From table 12.5
A12

= 107.38 cal/mol

A21

= 469.55 cal/mol

V1

= 40.73 cm3/mol

V2

= 18.07 cm3/mol

12

V2
V1

18.07
40.73

exp

a12
RT

107.38
exp ( 1.987 ) (333.15)

= 0.3772

21

V1
V2

40.73
18.07

exp

a 21
RT

469.55
exp ( 1.987 ) (333.15)

= 1.1089

ln1

12
= -ln (X1 + X212) + X2 ( X 1+ X 2 12

21
X 2+ X 1 21

0.3772
= -ln (0.1686 + (0.8314)(0.3772)) + (0.8314) ( 0.1686+ ( 0.8314 ) ( 0.3772)
1.1089
0.8314+ ( 0.1686 ) (1.1089)

ln1

= 0.4743

= 1.6069

ln2

12
= -ln (X2 + X121) X1 ( X 1+ X 2 12

21
X 2+ X 1 21

0.3772
= -ln (0.8314 + (0.1686)(1.1089)) - (0.1686) ( 0.1686+ ( 0.8314 ) ( 0.3772)

1.1089
0.8314+ ( 0.1686 ) (1.1089)
ln2

= 0.0335

= 1.0341

P = X1 1P1sat + X2 2P2sat
P = (0.1686)(1.6069)(84.562) + (0.8314)(1.0341)(19.953)
P = 40.0644 kPa
Y1 =

X 1 1 P 1 sat
P

( 0.1686 )( 1.6069 ) ( 84.562)

40.0644

Y1 = 0.5718

P(kPa x1
y1
x2
ln(1) ln(2) 1
2
P calc y1
)
calc
19.95
0
0
1 0.866 0.000 2.377 1.000 19.95 0.000
3
1
0
6
0
30
0
39.22 0.168 0.571 0.831 0.474 0.033 1.607 1.034 40.06 0.571
3
6
4
4
4
5
1
1
68
9
42.98 0.216 0.626 0.783 0.397 0.051 1.488 1.053 43.72 0.623
4
7
8
3
4
8
0
2
77
6
48.85 0.303 0.694 0.696 0.284 0.091 1.329 1.095 49.37 0.691
2
9
3
1
7
3
3
6
84
8
52.78 0.368 0.734 0.631 0.219 0.124 1.245 1.132 53.04 0.730
4
1
5
9
4
2
4
2
13
9
56.65 0.446 0.774 0.553 0.156 0.167 1.169 1.182 57.17 0.771
2
1
2
9
3
4
1
3
02
4
60.61 0.528 0.808 0.471 0.105 0.215 1.110 1.240 61.30 0.809
4
2
5
8
2
8
9
8
17
4
63.99 0.604 0.838 0.395 0.069 0.262 1.071 1.300 65.03 0.842
8
4
3
6
3
6
7
3
93
2

67.92
4
70.22
9
72.83
2
84.56
2

0.680
4
0.725
5
0.777
6
1

0.873
3
0.892
2
0.914
1
1

NRTL METHOD
X1

= 0.1686

X2

= 0.8314

= 333.15 K

P1 sat = 84.562 kPa

P2 sat = 19.953 kPa

Methanol(1) / water(2)
From table 12.5,
B12

= -253.88 cal/mol

B21

= 845.21 cal/mol

= 0.2994

12

b12
RT

12

253.88
( 1.987 ) (333.15)

= -0.3835

0.319
6
0.274
5
0.222
4
0

0.042
5
0.030
3
0.019
1
0.000
0

0.310
5
0.339
5
0.373
2
0.519
4

1.043
4
1.030
7
1.019
3
1.000
0

1.364
2
1.404
2
1.452
4
1.681
1

68.73
37
70.92
63
73.46
87
84.56
20

0.873
4
0.891
6
0.912
3
1.000
0

21

b 21
RT

21

845.21
( 1.987 ) (333.15)

= 1.2768

G12

= exp ((-)( 12))

= exp ((-0.2994)(-0.3835))
= 1.1217

G21

= exp ((-)( 21))

= exp ((-0.2994)(1.2768))
= 0.6823

ln1

G21
= X2 (21( X 1+ X 2 G 21
2

) +

G 12 12
(X 2+ X 1 G12)2

0.6823
= (0.8314)2 (1.2768( 0.1686+ ( 0.8314 ) (0.6823)

ln1

= 0.4733

= 1.6053

)2 +

)
0.8314+(0.16868)(1.1217)2

( 1.1217 ) (0.3835)

ln2

G12
= X1 (12( X 2+ X 1 G 12
2

) +

G 21 21
2
( X 1+ X 2 G21)

)
2

1.1217
2
= (0.1686) (0.3835( 0.8314+ ( 0.1686 ) (1.1217)

ln2

= 0.0325

= 1.0330

)2 +

0.1686+(0.8314)(0.6832)

( 0.6823 ) (1.2768)

P = X1 1P1sat + X2 2P2sat
P = (0.1686)(1.6053)(84.562) + (0.8314)(1.0330)(19.953)
P = 40.0234 kPa
X 1 1 P 1 sat
P

Y1 =

( 0.1686 )( 1.6053 ) ( 84.562)

40.0234

Y1 = 0.5718

P(kPa)
19.95
3
39.22
3
42.98
4

x1

y1

x2

0.168
6
0.216
7

0.571
4
0.626
8

0.831
4
0.783
3

ln(1)
0.8466

1
2.3318

ln(2)
0.0000

2
1.0000

0.4732

1.6052

0.0326

1.0331

0.3958

1.4856

0.0510

1.0523

P calc
19.953
0
40.023
4
43.670
0

y1 calc
0.0000
0.5718
0.6234

48.85
2
52.78
4
56.65
2
60.61
4
63.99
8
67.92
4
70.22
9
72.83
2
84.56
2

0.303
9
0.368
1
0.446
1
0.528
2
0.604
4
0.680
4
0.725
5
0.777
6
1

0.694
3
0.734
5
0.774
2
0.808
5
0.838
3
0.873
3
0.892
2
0.914
1
1

0.696
1
0.631
9
0.553
9
0.471
8
0.395
6
0.319
6
0.274
5
0.222
4
0

0.2810

1.3244

0.0912

1.0955

0.2142

1.2389

0.1249

1.1330

0.1498

1.1616

0.1689

1.1840

0.0985

1.1036

0.2175

1.2429

0.0633

1.0653

0.2634

1.3013

0.0377

1.0385

0.3091

1.3622

0.0264

1.0267

0.3359

1.3992

0.0163

1.0164

0.3664

1.4425

0.0000

1.0000

0.4877

1.6285

49.250
4
52.847
8
56.906
5
60.991
9
64.719
4
68.435
2
70.653
7
73.236
2
84.562
0

0.6911
0.7297
0.7700
0.8082
0.8413
0.8731
0.8915
0.9126
1.0000

B)
P and y for Wilson method

P(kPa)

P calc

y1

y1 calc

y1

x1

19.953

19.9530

39.223

40.0668

0.8438

0.5714

0.5719

0.0005

0.1686

42.984

43.7277

0.7437

0.6268

0.6236

0.0032

0.2167

48.852

49.3784

0.5264

0.6943

0.6918

0.0025

0.3039

52.784

53.0413

0.2573

0.7345

0.7309

0.0036

0.3681

56.652

57.1702

0.5182

0.7742

0.7714

0.0028

0.4461

60.614

61.3017

0.6877

0.8085

0.8094

0.0009

0.5282

63.998

65.0393

1.0413

0.8383

0.8422

0.0039

0.6044

67.924

68.7337

0.8097

0.8733

0.8734

0.0001

0.6804

70.229

70.9263

0.6973

0.8922

0.8916

0.0006

0.7255

72.832

73.4687

0.6367

0.9141

0.9123

0.0018

0.7776

84.562

84.5620

Graph of P and y vs x
1.2

0
0

0.8

P and y

0
0

0.6

0.4

0
0

0.2

0
0

0.2

0.4

0.6
x

0.8

0
1.2

P and y for NRTL method

P(kPa)
19.953
39.223
42.984
48.852
52.784
56.652
60.614
63.998
67.924
70.229
72.832
84.562

P calc
19.953
40.0234
43.67
49.2504
52.8478
56.9065
60.9919
64.7194
68.4352
70.6537
73.2362
84.562

P
0
0.8004
0.686
0.3984
0.0638
0.2545
0.3779
0.7214
0.5112
0.4247
0.4042
0

y1
0
0.5714
0.6268
0.6943
0.7345
0.7742
0.8085
0.8383
0.8733
0.8922
0.9141
1

y1 calc
0
0.5718
0.6234
0.6911
0.7297
0.77
0.8082
0.8413
0.8731
0.8915
0.9126
1

y
0
0.0004
0.0034
0.0032
0.0048
0.0042
0.0003
0.003
0.0002
0.0007
0.0015
0

x1
0
0.1686
0.2167
0.3039
0.3681
0.4461
0.5282
0.6044
0.6804
0.7255
0.7776
1

Graph of P and y vs x

P and y

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

0.01
0.01
0
0
0
0
0

0.2

0.4

0.6
x

0.8

0
1.2