CONFIDENTIAL EH/JAN 2013/CPE553

UNIVERSITI TEKNOLOGI MARA

FINAL EXAMINATION

COURSE CHEMICAL ENGINEERING THERMODYNAMICS

COURSE CODE CPE553
EXAMINATION JANUARY 2013
TIME 2 HOURS

INSTRUCTIONS TO CANDIDATES

1. This question paper consists of three (3) questions.

2. Answer ALL questions in the Answer Booklet. Start each answer on a new page.

3. Do not bring any material into the examination room unless permission is given by the
invigilator.

4. Please check to make sure that this examination pack consists of:

) the Question Paper

) a one - page Appendix 1
) a one - page Appendix 2
iv) a two - page Appendix 3
v) an Answer Booklet - provided by the Faculty

DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO

This examination paper consists of 5 printed pages
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CONFIDENTIAL 2 EH/JAN 2013/CPE553

QUESTION 1
(P02, C01.C2, C4)

a) Figure 1 shows P - x ^ diagram for benzene(1)/ethylbenzene(2) at 363.15 K. Determine

the following values from the figure,
i) Saturation pressure for benzene and ethylbenzene at 363.15 K.
(2 marks)

ii) Pressure and vapor phase compositions of the system that is in equilibrium with
liquid phase composition of 60 mole % benzene at 363.15 K.
(3 marks)

iii) Pressure and liquid phase compositions of the system that is in equilibrium with
vapor phase composition of 55 mole % benzene at 363.15 K.
(3 marks)

T = 363.15 K
IOU •-

14f) -

19f) --

mn —

an —

fin -

/ °-y
AC\ .-

9f) - I >-,
' •

0 - ]
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

*i,yi

Figure 1

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CONFIDENTIAL 3 EH/JAN 2013/CPE553

b) An effluent from a reactor consists a mixture of acetone, ethanol and acetonitrile with
flow rate of 150 kmol/h, 120 kmol/h and 30 kmol/h respectively. The mixture is to be
separated in a phase column at 333.15 K. By assuming Raoult's law is applied to the
system, determine the range of pressures that this system can exists as two phases.
(12 marks)

QUESTION 2
(P01.P02, C02, C2.C3, C5)

a) Figure 2 shows a plot of molar volume, V vs. liquid composition, x t for a binary system at
constant temperature and pressure. The tangent line shown extends across the figure
intersecting the edges (at x^ = 1 and Xi = 0) at points labeled Zi and Z2.

Constant T, P

V <>-

Xi

Figure 2

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CONFIDENTIAL 4 EH/JAN 2013/CPE553

i) Express two equivalent equations for the slope (dV/cfx,) of this tangent.
(2 marks)

ii) From equations in i), show that

Z, = V, and Z 2 = V2

(6 marks)

iii) Explain how to obtain the values of partial molar volume at infinite dilution for species
1 and 2 from the plot.
(4 marks)

b) Fugacity coefficient for pure gases can be estimated from method adopted by Lee and
Kesler as the following equation:

Determine the fugacity and fugacity coefficient for sulphur dioxide at 500 K and 250 bar.
Given that Tc = 430.8 K, Pc = 78.84 bar and co = 0.245.

(10 marks)

QUESTION 3
(P02, C03, C4, C6)

a) Relation of equilibrium constant to composition for an equilibrium mixture that behaves

as an ideal gas is given by:

The equilibrium constant is dependent on temperature as the following equation:

d l n K _ AH°
dT ~ RT2

By referring to the above equations, if the pressure is constant, conclude in words the
effect of temperature on equilibrium constant, direction of reaction, equilibrium
conversion and composition.
(8 marks)

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CONFIDENTIAL 5 EH/JAN 2013/CPE553

b) For the following reaction:

CO{g) + 3H2(g)->CHA{g) + H20(g)

Initially the feed mixture consists of carbon monoxide and hydrogen in stoichiometric
proportion. The reaction takes place at 300 kPa and the equilibrium constant is 2.723.
Determine the equilibrium conversion for this reaction by assuming that the system
behaves as non-ideal gas and the equilibrium mixture is non-ideal solution. Given that
the fugacity coefficient for each component as follow:

4 , =0.90 4=0.84 4 4 =0.93 4 o =0.81

[Hint: Range of equilibrium conversion is in between 0.7 and 0.75]

(10 marks)

END OF QUESTION PAPER

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CONFIDENTIAL APPENDIX 1 EH/JAN 2013/CPE553

FORMULA LIST

1- yiP = xiPi sat 14.

M2=M - x.,
GfX 1

2- YiP = Xlyfi« 15. y/(p_p«rf\

<;=^r/rexp ,v/?r' }
sat 16. P / , \
i ln^=—(ei1+y22£12)

4. sat
m4=-^r(e22 + y^12)

1 18. ^ . 2 8 , , - ^ - ^
P=
sat
i
6. 1 19. 1
^ = exp ^(8° + «e )
T,y,/r,pr
7 20.
- \ny,=Axl 0.422
8° - 0.083 -1.6

8 21.
- \ny2=Ax* 0.172
8 1 =0.139 -4.2

9. 22.
K,= y, "/ _nio+vi£
y/=rr
n nQ+vs

10. z,K, 23. -AG0

y—tiih— =1 InK
V 1 + V(K,-1) RT

11. 24.
nwM£ «
12. 25.
£X,C/M, = O
no^r = K

13. - dM 26.
M. = M + x,
1 2
dx.
n(*r =p° K

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CONFIDENTIAL APPENDIX 2 EH/JAN 2013/CPE553

Table 1 Constants for the Antoine equation for vapor pressures of pure species

In P ""/kPa = A - [B/(T/K + C)]

Latent heat of vaporization at the normal boiling point {AH„) and normal boiling point (T„)
Parameters for Antoine Equation Temperange Range A//„ T„
1
Name Formula A** B C K kJ/mol K
From To
Acetone C3H60 14.3145 2756.22 -45.090 247.15 350.15 29.10 329.35
Acetic acid C2H4O2 15.0717 3580.80 -48.500 297.15 415.15 23.70 391.05
Acetonirrile* C2H3N 14.8950 3413.10 -22.627 246.15 354.15 30.19 354.75
Benzene CeHfi 13.7819 2726.81 -55.578 279.15 377.15 30.72 353.15
/jo-Butane C4H10 13.8254 2181.79 -24.280 190.15 280.15 21.30 261.25
n-Butane C4H10 13.6608 2154.70 -34.361 200.15 292.15 22.44 272.65
1-Butanol QH10O 15.3144 3212.43 -90.411 310.15 411.15 43.29 390.75
2-Butanol* C4H10O 15.1989 3026.03 -86.650 298.15 393.15 40.75 372.65
uo-Butanol C4H10O 14.6047 2740.95 -106.480 303.15 401.15 41.82 380.95
rert-Butanol C4H10O 14.8445 2658.29 -95.500 283.15 374.15 39.07 355.45
Carbon tetrachloride CCI4 14.0572 2914.23 -41.002 259.15 374.15 29.82 349.75
Chlorobenzene C6H5C1 13.8635 3174.78 -61.450 302.15 432.15 35.19 404.85
1-Chlorobutane C4H9C) 13.7965 2723.73 -54.885 256.15 352.15 30.39 351.65
Chloroform CHCb 13.7324 2548.74 -54.598 250.15 357.15 29.24 334.25
Cyclohexane C6H12 13.6568 2723.44 -52.532 282.15 378.15 29.97 353.85
Cyclopentane C 5 Hio 13.9727 2653.90 -38.640 238.15 344.15 27.30 322.35
n-Decane C10H22 13.9748 3442.76 -79.292 338.15 476.15 38.75 447.25
Dichloromelhane CH2CI2 13,9891 2463.93 -49.910 235.15 333.15 28.06 312.85
Diethyl ether C4H10O 14.0735 2511.29 -41.950 230.15 328.15 26.52 307.55
1,4-Dioxane QHgOz 15.0967 3579.78 -32.813 293.15 378.15 34.16 374.45
n-Eicosane C20H42 144,575 4680.46 -141.050 481.15 652.15 57.49 616.75
Ethanol C2H60 16.8958 3795.17 -42.232 276.15 369.15 38.56 351.35
Ethylbenzene C8HI0 13.9726 3259.93 -60.850 306.15 436.15 35.57 409.35
Ethylene glycol* C2H6O2 15.7567 4187.46 -94.500 373.15 495.15 50.73 470.45
n-Heptane C7HI6 13.8622 2910.26 -56.718 277.15 396.15 31.77 371.55
n-Hexane C6H.4 13.8193 2696.04 -48.833 254.15 365.15 28.85 341.85
Methanol CH4O 16.5785 3638.27 -33.650 262.15 356.15 35.21 337.85
Methyl acetate C3H6O2 14.2456 2662.78 -53.460 250.15 351.15 30.32 330.05
Methyl ethyl ketone C4HgO 14.1334 2838.24 -54.460 265.15 376.15 31.30 352.75
Nitromethane* CH3NO2 14.7513 3331.70 -45.550 329.15 419.15 33.99 374.35
n-Nonane C9H20 13.9854 3311.19 -70.456 319.15 451.15 36.91 423.95
wo-Octane C 8 Hi 8 13.6703 2896.31 -52.383 275.15 398.15 30.79 372.35
n-Octane C 8 H, 8 13.9346 3123.13 -63.515 299.15 425.15 34.41 398.75
n-Pentane C 5 H 12 13.7667 2451.88 -41.136 228.15 331.15 25.79 309.15
Phenol C6H60 14.4387 3507.80 -97.750 353.15 481.15 46.18 454.95
1-Propanol C3HgO 16.1154 3483.67 -67.343 293.15 389.15 41.44 370.35
2-Propanol C3H80 16.6796 3640.20 -53.540 281.15 373.15 39.85 355.35
Toluene C7H8 13.9320 3056.96 -55.525 286.15 409.15 33.18 383.75
Water H20 16.3872 3885.70 -42.980 273.15 473.15 40.66 373.15
o-Xylene C 8 H, 0 14.0415 3358.79 -61.109 313.15 445.15 36.24 417.55
m-Xylene C 8 Hio 14.1387 3381.81 -57.030 308.15 439.15 35.66 412.25
p-Xylene C 8 H, 0 14.0579 3331.45 -58.523 308.15 439.15 35.67 411.45

Based primarily on data presented by B. E. Poling, J. M. Prausnitz and J. P. O'Connell,

The Properties of Gases and Liquids, 5th ed., App. A, McGraw-Hill, New York, 2001.
•Antoine parameters adapted from Gmehling et al. See footnote 2, p. 791.
**Antoine parameters A are adjusted to reproduce the listed values of Tn.

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CONFIDENTIAL EH/JAN 2013/CPE553

Pr= 1.0000 1.2000 1.5000 2.0000 3.0000 5.0000 7.0000 10.000

Tr
0.30 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.35 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.40 0.0003 0.0003 0.0003 0.0002 0.0002 0.0002 0.0002 0.0003
0.45 0.0016 0.0014 0.0012 0.0010 0.0008 0.0008 0.0009 0.0012
0.50 0.0055 0.0048 0.0041 0.0034 0.0028 0.0025 0.0027 0.0034
0.55 0.0146 0.0127 0.0107 0.0089 0.0072 0.0063 0.0066 0.0080
0.60 0.0321 0.0277 0.0234 0.0193 0.0154 0.0132 0.0135 0.0160
0.65 0.0611 0.0527 0.0445 0.0364 0.0289 0.0244 0.0245 0.0282
0.70 0.1045 0.0902 0.0759 0.0619 0.0488 0.0406 0.0402 0.0453
0.75 0.1641 0.1413 0.1188 0.0966 0.0757 0.0625 0.0610 0.0673
0.80 0.2404 0.2065 0.1738 0.1409 0.1102 0.0899 0.0867 0,0942
0.85 0.3319 0.2858 0.2399 0.1945 0.1517 0.1227 0.1175 0.1256
0.90 0.4375 0.3767 0.3162 0.2564 0.1995 0.1607 0.1524 0.1611
0.93 0.5058 0.4355 0.3656 0.2972 0.2307 0.1854 0.1754 0.1841
0.95 0.5521 0.4764 0.3999 0.3251 0.2523 0.2028 0.1910 0.2000
0.97 0.5984 0.5164 0.4345 0.3532 0.2748 0.2203 0.2075 0.2163
0.98 0.6223 0.5370 0.4529 0.3681 0.2864 0.2296 0.2158 0.2244
0.99 0.6442 0.5572 0.4699 0.3828 0.2978 0.2388 0.2244 0.2328
1.00 0.6668 0.5781 0.4875 0.3972 0.3097 0.2483 0.2328 0.2415
1.01 0.6792 0.5970 0.5047 0.4121 0.3214 0.2576 0.2415 0.2500
1.02 0.6902 0.6166 0.5224 0.4266 0.3334 0.2673 0.2506 0.2582
1.05 0.7194 0.6607 0.5728 0.4710 0.3690 0.2958 0.2773 0.2844
1.10 0.7586 0.7112 0.6412 0.5408 0.4285 0.3451 0.3228 0.3296
1.15 0.7907 0.7499 0.6918 0.6026 0.4875 0.3954 0.3690 0.3750
1.20 0.8166 0.7834 0.7328 0.6546 0.5420 0.4446 0.4150 0.4198
1.30 0.8590 0.8318 0.7943 0.7345 0.6383 0.5383 0.5058 0.5093
1.40 0.8892 0.8690 0.8395 0.7925 0.7145 0.6237 0.5902 0.5943
1.50 0.9141 0.8974 0.8730 0.8375 0.7745 0.6966 0.6668 0.6714
1.60 0.9311 0.9183 0.8995 0.8710 0.8222 0.7586 0.7328 0.7430
1.70 0.9462 0.9354 0.9204 0.8995 0.8610 0.8091 0.7907 0.8054
1.80 0.9572 0.9484 0.9376 0.9204 0.8913 0.8531 0.8414 0.8590
1.90 0.9661 0.9594 0.9506 0.9376 0.9162 0.8872 0.8831 0.9057
2.00 0.9727 0.9683 0.9616 0.9528 0.9354 0.9183 0.9183 0.9462
2.20 0.9840 0.9817 0.9795 0.9727 0.9661 0.9616 0.9727 1.0093
2.40 0.9931 0.9908 0.9908 0.9886 0.9863 0.9931 1.0116 1.0568
2.60 0.9977 0.9977 0.9977 0.9977 1.0023 1.0162 1.0399 1.0889
2.80 1.0023 1.0023 1.0046 1.0069 1.0116 1.0328 1.0593 1.1117
3.00 1.0046 1.0069 1.0069 1.0116 1.0209 1.0423 1.0740 1.1298
3.50 1.0093 1.0116 1.0139 1.0186 1.0304 1.0593 1.0914 1.1508
4.00 1.0116 1.0139 1.0162 1.0233 1.0375 1.0666 1.0990 1.1588

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CONFIDENTIAL APPENDIX 3 (2) EH/JAN 2013/CPE553

Table 3 Values of cf

Pr = 1.0000 1.2000 1.5000 2.0000 3.0000 5.0000 7.0000 10.000

Tr
0.30 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.35 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.40 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.45 0.0002 0.0002 0.0002 0.0002 0.0001 0.0001 0.0001 0.000 L
0.50 0.0013 0.0013 0.0013 0.0012 0.0011 0.0009 0.0008 0.0006
0.55 0.0063 0.0062 0.0061 0.0058 0.0053 0.0045 0.0039 0.0031
0.60 0.0210 0.0207 0.0202 0.0194 0.0179 0.0154 0.0133 0.0108
0.65 0.0536 0.0527 0.0516 0.0497 0.0461 0.0401 0.0350 0.0289
0.70 0.1117 0.1102 0.1079 0.1040 0.0970 0.0851 0.0752 0.0629
0.75 0.1995 0.1972 0.1932 0.1871 0.1754 0.1552 0.1387 0.1178
0.80 0.3170 0.3133 0.3076 0.2978 0.2812 0.2512 0.2265 0.1954
0.85 0.4592 0.4539 0.4457 0.4325 0.4093 0.3698 0.3365 0.2951
0.90 0.6166 0.6095 0.5998 0.5834 0.5546 0.5058 0.4645 0.4130
0.93 0.7145 0.7063 0.6950 0.6761 0.6457 0.5916 0.5470 0.4898
0.95 0.7798 0.7691 0.7568 0.7379 0.7063 0.6501 0.6026 0.5432
0.97 0.8414 0.8318 0.8185 0.7998 0.7656 0.7096 0.6607 0.5984
0.98 0.8730 0.8630 0.8492 0.8298 0.7962 0.7379 0.6887 0.6266
0.99 0.9036 0.8913 0.8790 0.8590 0.8241 0.7674 0.7178 0.6546
1.00 0.9311 0.9204 0.9078 0.8872 0.8531 0.7962 0.7464 0.6823
1.01 0.9462 0.9462 0.9333 0.9162 0.8831 0.8241 0.7745 0.7096
1.02 0.9572 0.9661 0.9594 0.9419 0.9099 0.8531 0.8035 0.7379
1.05 0.9840 0.9954 1.0186 1.0162 0.9886 0.9354 0.8872 0.8222
1.10 1.0162 1.0280 1.0593 1.0990 1.1015 1.0617 1.0186 0.9572
1.15 1.0375 1.0520 1.0814 1.1376 1.1858 1.1722 1.1403 1.0864
1.20 1.0544 1.0691 1.0990 1.1588 1.2388 1,2647 1,2474 1.2050
1.30 1.0715 1.0914 1.1194 1.1776 1.2853 1.3868 1.4125 1.4061
1.40 1.0814 1.0990 1.1298 1.1858 1.2942 1.4488 1.5171 1.5524
1.50 1.0864 1.1041 1.1350 1.1858 1.2942 1.4689 1.5740 1.6520
1.60 1.0864 1.1041 1.1350 1.1858 1.2883 1.4689 1.5996 1.7140
1.70 1.0864 1.1041 1.1324 1.1803 1.2794 1.4622 1.6033 1.7458
1.80 1.0839 1,1015 1.1298 1.1749 1.2706 1.4488 1.5959 1.7620
1.90 1.0814 1.0990 1.1272 1.1695 1.2618 1.4355 1.5849 1.7620
2.00 1.0814 1.0965 1.1220 1.1641 1.2503 1.4191 1.5704 1.7539
2.20 1.0765 1.0914 1.1143 1.1535 1.2331 1.3900 1.5346 1.7219
2.40 1.0715 1.0864 1.1066 1.1429 1.2190 1.3614 1.4997 1.6866
2.60 1.0666 1.0814 1.1015 1.1350 1.2023 1.3397 1.4689 1.6482
2.80 1.0641 1.0765 1.0940 1.1272 1.1912 1.3183 1.4388 1.6144
3.00 1.0593 1.0715 1.0889 1.1194 1.1803 1.3002 1.4158 1.5813
3.50 1.0520 1.0617 1.0789 1.1041 1.1561 1.2618 1.3614 1.5101
4.00 1.0471 1.0544 1.0691 1.0914 1.1403 1.2303 1.3213 1.4555

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