L-3/T-lICHE Date: 19/08/2017

BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY, DHAKA

L-3/T-1 B. Sc. Engineering Examinations 2016-2017

Sub: CHE 307 (Chemical Engineering Thermodynamics)

Full Marks: 210 Time: 3 Hours

The figures in the margin indicate full marks.
USE SEPARATE SCRIPTS FOR EACH SECTION

SECTION -A
There are FOUR questions in this section. Answer any THREE.
Symbols have their usual meanings. A data booklet will be supplied.

1. (a) For a system that exhibits VLE, at least one of the k-values must be greater than 1.0
and at least one must be less than 1.0. True/False. Explain your answer. (8)
(b) For a binary system that exhibits VLE, show that, (12)
1- k2
x]=---
k] - k2

2 z] (k] -k )-(1-k2)
v=--------
, (k] -1)(1- k2)
(c) The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is

represented by the equation, (15)

H = 400Xl + 600X2 + XIX2(40XI + 20X2)
where H is in l/mo!.
(i) Show that
- 2 3
HI = 420 - 60x] + 40x]
- 3
H2 = 600 + 40x]
(ii) Find the numerical values of pure species properties, and
(iii) Determine the numerical values for partial enthalpies at infinite dilution.

2. (a) A liquid mixture of cyclohexanone(l)/ phenol(2) for which XI = 0.6 is in equilibrium

with its vapor at 144°C. Determine the equilibrium pressure and vapor pha.se composition
from the following information (20)
2 2
In y] = A X2 In Y2= A x]

P satj = 80 kPa P satl = 40 kPa

] 1440C I 2 144°C

and xa azl = 0.304

144°C

(b) The molar volume of a binary liquid mixture at T and P is given by (15)
V = 120x] + 70X2 + (l5x] + 8X2)X]X2
(i) Find the expression for the partial molar volume of species 1 and 2 at T and P.
(ii) Show that these expressions satisfy the Gibbs/Duhen equation.

Contd : P/2
 =2=

CHE 307

3. (a) The virial equation of state for a gas mixture is represented by (20)
nBP
nz=n+--
RT
where the second virial co-effiCient

B = IIYiYj Bij
i j

Show that for binary mixture, fugacity co-efficient of species 1,

In<Pl=~(Bll +Y/ 812)

RT
(b) Estimate z for an equimolar mixture of propane(1 )In-pentane(2) at 50°C and 2 bar.

Where, (15)
3
Bll = -331 cm Imol
3
B12 = -558 cm Imol
3
B22 = -980 cm Imol

4. (a) A single effect evaporator operating at atmospheric pressure concentrates a 15% (by
weight) LiCI solution to 40%. The feed enters the evaporator at the rate of 2 kg/s at 25°C.
The normal boiling point of a 40% LiCl solution is about 132°C and its specific heat is
estimated as 2.72 kJ/kg.°C. What is the heat transfer rate in the evaporator? The change
of enthalpy for water [from 25°C (I) to 132°C (g)] is 2635 kJ/kg. (18)
(b) The excess Gibbs energy of a binary liquid mixture at T and P is given by (17)
GE
--- = A21xl + A12x2
XlX2 RT
Show that

SECTION -B
There are FOUR questions in this section. Answer any THREE.

5. (a) With a schematic diagram write the working principle of a Linde liquefaction process. (15)
(b) Consider the vapor compression refrigeration cycle with tetrafluoroethane as
refrigerant. If the evaporation temperature is -12°C, show the effect of condensation
temperature on the coefficient of performance by making calculation for condensation
temperatures of 38°C and 27°C.
(i) Assume isentropic compression of vapor. (10)
(ii) Assume a compressor efficiency of 75%. (10)
Contd P 13
 =3=

CHE307

6. (a) Discuss on the choice of refrigerant. (10)

(b) Write different ways of cooling process on a T-S diagram. (10)
(c) A system formed initially of 2 mol C02, 5 mol H2 and I mol CO undergoes the

reactions: (15)
C02 + 3 H2 ~ CH30H + H20

C02 + H2 ~ CO + H20
Develop expressions for the mole fractions of the reacting species as function of the
reaction coordinates for the two reactions.

7. The feed gas to a methanol synthesis reactor is composed of75% mol H2, 15 mole% CO,

5 mole% C02 and 5 mole% N2. The system comes to equilibrium at 550 K and 100 bar

with respect to the reactions: (35)

2H2 + CO ~ CH30H

H2 + CO2 ~ CO + H20

Assuming ideal gases, determine the composition of the equilibrium mixture.

8. (a) For calculating the effect of temperature on the equilibrium constant, derive the

following equation: (20)

L1C 0
L10
o 0

= L100 -
0

L1HO
0

+ L1HO +! fTOTL1Cp dT _ f -L dT
RT RTo RT T To R To R T

(b) Oil refineries frequently have both H2S and S02 to dispose of. The following

reactions suggests a means of getting rid of both at once: (15)

For reactants in the stoichiometric proportion, estimate the percent conversion of each
I
reactant if the reaction comes
I
to equilibrium at 450°C and 8 -bar.
 •

-70

\
-60 ' \

!::l
'0
.•..0
CI) •

(5
-50
\1
E...
Ql
a. ..
.
'I .I P-.
~;

. Itt:. -40
<1, . . Ll::JJ:lillIJHI"I"lIIl1l1l1l11ll1l1mlllllllllllllllllllll~ I 1.1IIHIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII 11. - I '.IIIIIIIHIIIIIIIIIIII
'.. . 1II1I1I11I11II11I11m~
111111111111 . I
\1
-30
I

-20
1. 2 3 4 6 8 10 20. .30 40 60 80 1()2
. .200 '300 400 600 800 103
~ moleso/H20 pe~mole of solute

Figure 12.14: Heats of solution at 25°C. (Based on data from 'The NBS Tables of Chemical Thermodynamic Properties," J. Phys: Chern. Ref Data;

"I n,,"PP~}, '?82) T="'G'-" &v Q. 1 (cD

•

L-3ff -lICHE Date: 04/02/2017

BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY, DHAKA
L-3/T-l B. Sc. Engineering Examinations 2015-2016

Sub: eRE 307 (Chemical Engineering Thermodynamics)

Full Marks: 210 Time: 3 Hours

The figures in the margin indicate full marks.
USE SEPARATE SCRIPTS FOR EACH SECTION

SECTION-A
There are FOUR questions in this section. Answer any THREE.
A Data booklet is to be provided. Assume any missing data.

1. (a) With a neat sketch, describe a absorption refrigeration system. (15)

(b) Fifty kmol/h of liquid toluene. at 1.2 bar is cooled from 100°C to 20°e. A vapor
compression refrigeration cycle is used for the purpose. Ammonia is the working fluid.
Condensation in the cycle is affected by an air-cooled fin-fan heat exchanger for which

the air temperature may be assumed essentially constant at 20°C. Determine the

circulation rate of ammonia. (20)

Data for ammonia:

~Hlv = 23.34 k~ol

InpSat = 45.3 _ 4104.6 _ 5.14 T + 615 pS;t

T T
where pSat in bars and T in Kelvin.

2. (a) A refrigeration system requires 1.5 kW of power for a refrigeration rate of 4 kJ/s. (5+5)
(i) What is COP and how much heat is rejected in the condenser.
(ii) If heat rejection is at 40°C, what is the lowest temperature the system can possibly
maintain?

(b) Find the relation between standard Gibbs-Energy change and the equilibrium constant. (15)

(c) Derive the relationship of IT (Xi ti = K. (10)

i

3. A bed of coal (assume pure carbon) in a coal gasifier is fed with steam and air, and

produces a gas stream containing H2, CO, 02, H20, C02 and N2. If the feed to the

gasifier consists of 1 mol of steam and 2.38 mole of air, calculate the equilibrium

composition of the gas stream at P = 20 bar for temperature of 1000 and 1500 K. (35)

Contd P/2
 •
..

=2=

CHE307

4. (a) Write a block diagram for the calculation of DEW T, by using Gamma-Phi

formulation. Write necessary equations clearly. (15)

(b) For the cracking reaction,

C3Hg (g) ~ C2H4 (g) + CH4 (g)

The equilibrium conversion is negligible at 300 K, but becomes close to equilibrium at
temperature above 500 K. For a pressure of 1 bar, determine the

(i) fractional conversion of propane at 625 K. (10)

(ii) temperature at which fractional conversion is 85%. (10)

SECTION -B
There are FOUR questions in this section. Answer any THREE.

5. (a) Prepare a t-x-y diagram for a pressure of 90 kPa for Benzene (1)/Ethylbenzene (2)

system. Assume the Raoult's law is valid. The parameter for Antoine equation (15)
A B C
Benzene 13.86 2774 220
Ethylbenzene 14.00 3279 213

(b) A concentrated binary solution containing mostly species 2 (but X2 #- 1) is in

equilibrium with a vapor phase containing both species 1 and 2. The pressure of this two

phase system is 1 bar. The temperature is 25°C. Determine the good estimate of Xl and

YI. HI = 200 bar and p~at = 0.1 bar. State and justify all assumptions. (15)

(c) Helium-laced gases are used as breathing media for deep-sea divers. Why? (5)

6. (a) A binary system of species 1 and 2 consists of vapor and liquid phases in equilibrium

at temperature T, for which (25)

2 2
In YI = 1.8 X2 In Y2 = 1.8 Xl
PI Sat = 1.24 b ar P2Sat = 0.89 bar

Assuming the modified Raoult's law is valid.

(i) for what range of values of the overall mole fraction ZI can this two phases system

exist with a liquid mole fraction Xl = 0.65?

(ii) What is the pressure P and vapor mole fraction YI within this range?
(iii) What are the pressure and composition of azeotrope at temperature T?
(b) Show that the partial properties are readily calculated directly from an expression for

the solution property as a function of composition at constant T and P. (10)

Contd P/3
•

=3=

CHE307

7. (a) Define fugacity. How would you estimate fugacity of a pure liquid? (10)
(b) The excess Gibbs energy of a binary liquid mixture at T and P is given by (25)

GhT = (Axi + BX2)XIX2

(i) Find expressions for InYIand InY2at T and P.

(ii) Show that these expressions satisfy the Gibbs-Duhem equfl,tion.

Yl)
"') Sh owt h at (d-- In
(111 = (d-- InY2) =.0
dXl xl=}
dx} xl=O

8. The following is a set ofVLE data for the system acetone (l)/methanol (2) at 55°C. (35)
PlkPa Xl Yl PlkPa Xl Yl
68.73 0.000 0.000 98.46 0.543 0.617
75.28 0.057 0.129 99.95 0.633 0.677
78.95 0.104 0.219 100.46 0.733 0.738
86.76 0.217 0.363 101.06 0.792 0.787
93.20 0.358 0.478 99.80 0.945 0.934
96.36 0.448 0.551 96.88 1.00 1.00

(a) Find the parameter values for the two parameters Margules equation that provide the
E
best fit of G IRT to the data.

(b) Prepare a P-x-y diagram that compares the experimental points with the curves
determined from the correlation.

.. ".,
L-3/T-1ICHE Date: 26/0112016
BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY, DHAKA
L-3/T-1 B. Sc. Engineering Examinations 2014-2015

Sub: eRE 307 (Chemical Engineering Thermodynamics II)

Full Marks : 210 Time: 3 Hours

The figures in the margin indicate full marks.
USE SEP ARA TE SCRIPTS FOR EACH SECTION

SECTION-A
There are FOUR questions in this section. Answer any THREE.
Data booklet for CHE 307 to be supplied.

1. (a) Explain the tenn Retrograde condensation using P-T diagram in the critical region. (10)

(b) A liquid mixture of cyclohexanone (l)/Phenol (2) for which XI = 0.6 is in equilibrium

with its vapor at 144°C. Detennine the equilibrium pressure P and vapor composition YI

from the following infonnation: (15)

2 2
In YI = AX2 InY2= AXI
Sat P2Sat = 40 kPa
At 144°C, PI = 80 kPa

The system fonns an azeotrope at 144°C for which XIaz = 0.3.

(c) Prove that an equilibrium liquid/vapor system described by Raoult's law cannot

exhibit an axeotrope. (10)

2. (a) Define Partial Molar Properties and show that for a binary system (10)

where M is solution properties

Mi is partial properties.

(b) The molar volume of a binary liquid mixture at T and P is given by (25)
V = 120 XI + 70 X2+ (15 XI + 8X2)XIX2
(i) Find the expression for the partial molar volume of species 1 and 2 at T and P.
"''1

(ii) Show that V = LXi Vi .

(iii) Show that the expressions of partial molar properties satisfy the GibbslDuhem
equation.

( - J = ( --dV2
- J
. dVI
(IV) Show that -- = O.
dXI Xl
-1
-.
dXI Xl-
- 0

- -00 -00
(v) Plot values of V, VI and V2 versus XI and label points VI and V2 and show

their values.
Contd P/2
 =2=
eRE 307

3. (a) The excess Gibbs energy of a particular ternary liquid mixture is represented by
empirical expression (20)
GE . .
- = A12xlx2 + A13xlx3 + A23x2x3
RT
(i) Detennine the expression for the activity coefficient of species 1, 2 and 3.
(ii) How do you calculate limiting value of activity coefficient of species I?
(iii) What does the limiting case represent?
(b) Show that fugacity co-efficient for a binary mixture, (15)

~1 = exp [:T (B11 + y~812)]

p
where, In ~i= f (~i-1) dP
o . P
BP !
z=I+-
RT
and B = LLYiYj Bij
I J

4. (a) Draw the schematic diagram of an adsorption refrigeration unit. Discuss the working

principle and find the expression for (Q%c\nin. Estimate (Q/6c)min if the surrounding
temperature is 30°C and Tc = -10°C and TH = 100°e. (15)
(b) A refrigerator with tetrafluoroethane as refrigerant operates with an evaporation
temperature of -15°F and a condensation temperature of 80°F. Saturated liquid
refrigerant from the condenser flows through an expression valve into the evaporator
from which it emerges as saturated vapor. (20)
(i) Estimate the circulation rate ofthe refrigerant for a cooling rate of 5 Btu/s.
(ii) By how much would the circulation rate be reduced if the throttle valve were
replaced by a turbine in which refrigerant expands isentropically.
(iii) Determine COP for isentropic compression of vapor for case (i) and (ii).

SECTION -B
There are FOUR questions in this section. Answer any THREE.

5. The following is a set of VLE data for the system methanol (1)/water (2) at 60°C.
PlkPa Xl YI PlkPa XI YI
19.95 0.00 0.00 60.61 0.53 0.81
39.22 0.17 0.57 63.99 0.60 0.84
42.98 0.22 0.63 67.92 0.68 0.87
48.85 0.30 0.70 70.23 0.73 0.89
52.78 0.37 0.73 72.83 0.78 0.91
56.65 0.45 0.77 84.56 1.0 1.0
eontd P/3
 =3=

CHE307
Contd ... Q. No.5

(a) Find parameter values for the Margules equation that provide the best fit of GE/RT to

the data. (20)

(b) Prepare a P xy diagram that compares the experimental points with curves determined

from the correlation. (15) ,.,

6. (a) Prove that Henry's law is related to the Lewis/Randall rule through the Gibbs-Duhen
equation. (10)
(b) For liquid-phase reactions, find the relation of equilibrium constants to composition. (10)
(c) For the ammonia synthesis reaction written as (15)
1 3
- N2 (g) + - H2 (g)~ NH3 (g)
2 2
with 0.5 mol N2 and 1.5 mol H2 as the initial amounts of reactants and with the
assumption that the equilibrium mixture is an ideal gas, show that

-M
ce = 1- ( 1 + 1.299 K ~
J
2

7. Hydrogen gas is produced by the reaction of steam with 'water gas', an equimolar mixture
of H2 and CO obtained by the reaction of steam with coal. A stream of 'water gas' mixed

with steam is passed over a catalyst to convert CO to C02 by reaction:

H20 (g) + CO (g) ~ H2 (g) + C02 (g)

Subsequently unreacted water is condensed and carbon dioxide is absorbed, leaving a
product that is mostly hydrogen. The equilibrium conditions are 1 bar and 8000K.
(a) Determine the molar ratio of steam to 'water gas' (H2 + CO) required to produce a
product gas containing only 2 mole % CO after cooling to 20°C, where the unreacted
H20 has been virtually all condensed. (22)
(b) What happens if solid carbon will form at the equilibrium conditions by the reaction: (13)
2 CO (g) ~ C02 (g) + C (s)

8. (a) By using Gamma/Phi fonnulation of VLE, derive necessary equations for Dew Point
and Bubble Point calculations. (10)
(b) Write a block diagram for the calculation of Dew P. (15)
(c) If pure liquid H2S04 at 27°C is added adiabatically to pure liquid water at 27°C to

form a 40 mass % solution, what is the final temperature of the solution? (10)
 =~

Table 9.1: Thermodynamic Properties of Saturated Tetraftuoroethane l'

Volume Enthalpy Entropy

(ft)'(lbm)-1 (Blu)(lbm )-1 (B1U)(lbm)-1 (R)-I

1(°10) P(psia) Vi V" H' H" S' S"

-40 7.429 0.01132 5.7X2 0,000 97,050 000000 0,23125

-35 X.577 0.01139 5,053 IAX9 <)H04 0,00352 0.23032
-30 9862 0.01145 4.432 2,9X4 98.556 0.00701 0,22945
-25 11.297 0,01152 3.<)01 4AM 99.306 O,OlO4X O,22Xh3
-20 12.X95 0,01158 3.445 5.991 100.054 0.01392 0.227Xli

~- 15 14.667 001165 3.052 7.505 100.799 (l.01733 022714

.C 10 1("b2h 001172 2.7'12 1),02(, If) 15-'12 OO?O7.\ 022647
--5 (X.7X7 O,OIIXO 2,411) 11I.5.~,:j I02.2XO 0.02'111') 1I.':',','5X'1
0 21,162 0.01187 2.159 12,U90 10301S OOn ..I.1 O.2.,52:i
5 23.767 0.01194 1.934 13,634 103.74:i 0.03077 0,22470

10 2().617 0.01202 1.73r. 15,IX7 104.471 0.0.\40X 11.2241X

15 29.72() 0.01210 1,51>3 lil,748 105.11)2 0.03737 022:170
20 33110 0.0121X 1.410 18J IX 105.907 0,0401,5 O,22Y2.')
25 36.7X5 0.0 I ?21, 1.275 I I).Wi? 106.617 1l.(431) I 0.2'22XJ
30 .ol0.7(,X 0.1l12.l5 1.IS'i 214X6 I07.J20 Oo,n!5 O.2,,2H

35 45.075 0.01243 1.04X 23.0X5 IOX.OII, O,050lX 0.2'2207

40 49.724 0,012.)2 O()S3 2,1.('94 IOX,705 O.053'i') 0.2'2172
45 54.732 0.012(,2 O.81,X 2<1.314 109,:JXI, IUl51,7') 0221411
50 (,0.116 0.01271 0.792 27.944 110.0.'iX II.O.'i')')X 11,2'21111
55 h5.X,)5 0.012X I 0724 2').')X6 110.722 IUII,:1 II, 1I,22I1XI

60 72.0X7 O.O!?'») O.(,ld 3111') IIU71, o ()(,I,:n 11.'2'2(15.1

65 7X.712 0.01301 O,WX 32,90.'i 11?OII) O.OliN') 0.2202X
70 X5,7X7 0,01312 0.55X 34 ..)X3 112.1,52 0,07264 O.2201U
75 93,3.13 0,111323 0,512 36,274 II,J27? O,07.'i7X 0'21')7')
XO 101,37 0,01335 0.472 37,978 I I.\.XXO O.07X')2 0,21')57

X5 10').1)2 001347 0.4:\4 39.1>'>7 11'1.47.'1 O,OX211S O,? 1'I."\-I

')0 119,00 0,0 I 3'i') 0,400 41 A:\() I 1.'iOSS O,OXSIX O.':!I ') 12
')5 12X'(d 0,01372 0.369 43,17') 115.1"9 0.OXX30 (,),2IX')1I
100 13X.X3 0,11138(, OJ41 44,9'1.\ I 11,,1(,I, 0,0')14'2 O,218(,~
lOS 14<)./1:J 0,01400 0.31.'1 4h.725 1II"h94 0,0')454 1l.218,tS

110 11,1.05 (U)1415 0.292 48,.'124 117,203 0,0')7(,1, 0,2 I lQ','

II.) Inll 0.01430 0.270 50.343 117.1,')0 ().I007~ 0,217~J7.
120 18.'1.84 0.01447 0250 .'12, IX I II X.IS3 0,10391 0,21772
125 199,25 0.014M O,DI 54,040 II X..'i') I 0,10704 0,217,1,1
130 21:J.3X 0.014X2 0,214 55.'i2,J 119,000 0.11018 0,21715

135 22X.25 0.01502 0.198 .'17,830 11')377 0,113.1:\ O,211,X3

140 243,X8 0.01522 O,IX4 5'l,7M II')?;'O o IIh50 02/('48
ISO 277.57 0.01.'167 0,157 63,722 120.284 O,I22XX O,21.'iI,!>
I riO 314.69 0,01(,20 O.I.H 1,7.X2.I 120,650 O,12')JX 0,214(,3
170 355.5 I 0,0 I (,X:\ 0.114 72.10(, 120,753 O,I31i03 O,21:\!.')
_._----_. __
._----------_ ..__ ._---_ ..- . ... _--_._._ ..- --- -_.-. _
i' Adapted by permission from I\SJ1I?AE flolld/wok.- FUI1t!ulIll'Jlla/s. p. 17,29. t\mcrican
Society of Heating, Refrigerating ancl Air-Conditioning I;ngineers, Inc .. Atlanta. 19')J,
\)

..

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-20 20 50 100 140 180 220 260
3000 i IN I ill/I: II / :,' <: I' 'I} :~rx~~'-r'~:-1:::;~~~~~--=-];:;~r-~;:'--l\;
,~\1 I\ I 1
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 --
; L-3/T-lICHE Date: 08/0812015
BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY, DHAKA
L-3IT-l B. Sc. Engineering Examinations 2013.2014

Sub: CHE 307 (Chemical Engineering Thermodynamics II)

Full Marks: 210 Time: 3 HOll""

The figures in the margm mdicate full marh.
USE SEPARATE SCRIPTS FOR EACH SECTTON

SECTlO~-A
There are FOUR questions in this section, Answer any THREE.

1. (a) Show that the Linde process is a limiting case of the claude process with necessary
diagrum and equation. (15)
(b) A remgemlor wllh telra Iluorodhanc as refrigerant operates \~ilh an evaporation
tempemture of -26"C and a condensation temperature of 27°C. Saturated liquid
refrigerant from the condcll5cr flows through an expansion valve into the evaporator,
from which it emerges as satunlted vapor. (20)
i) For cooling rate of 5.3 kW, what is the circl.liation nlte of the rdiigerunt?
ii) Sl.Ippose the cycle of (i) is modified by the incil.lsion of U cOl.lnter el.lrrent heat
exchanger between the condenser and the throttle valve in whIch heut is tramterred to
vapor returning from the evaporator, If liquid from the C<Jndenserenters the ex~hanger lit
2TC and ifvapor from the evaporator enters the exchanger at _26°C and leaves at 21°(',
what is the cir~ulation rate of the rerri gerant?
iii) Determine COP for isentropi~ ~ompres;ion of the vapor for cuse (i) and (ii).

2, (a) Derive a relation hetween standard Glhh~-energy change and the eqUllihritLlTIconstant. (10)

(b) Prove that for gas phase reaction: (10)

(~) The reed gus to a methanol synthesis reactor is composed on5 mole % Hz, 15 mole
% CO, 5 mole % C02 and 5 mole % N2, The system comes to equilibrium at 550 k and

100 har with respecllo the reaetl(ln$: (15)

2H,(g )+CO(t;) ---.ClI,Gll(g)

CO,(,,)+ II,v:) ---.co(,,)+ H,O(g)

Assuming ideal gases, determine the composition of the equilibrium mrxture~.

3. Ethanol is produced from ethylene via the gas phase reaction

C,H, (g)+ H,O(g)-) C,H,GH(g)
Reaction eondition$ are 400K and 2 bar,
a) Determine a Ilumerieal value for the equilibrium constant K for thi~ reaction at 25°C. (15)

Contd " P/2

 ,
CHE307
Could ... Q. No.3

(b) Dctenninc the value ofK at 400K. (5)

(e) Determine the compos1llon of the eql1illhrium gus mixture for an equimolar feed
containing only ethylene and H20. (10)
(d) For the same feed as in part (e), but for P ~ I bar. would the oquihhrill1TImole rradion
of elbano1he hither OT lnwer~ Explain. (5)
;

4 (aJ By clearly showing all the necessary equations, wrile a block diagram for the
calculatIOn of Dew T, (15)
(b) With a neal ~kelch, wrile the workmg principle of an absorption refrigeration system.
Derive necessary eqUBtiOIlS. (l0)

(e) A system initially containing 2 mol C:!H. and 3 mol O2 llndergoing the reactions (l0)

C,H, (g)+io, (g)--+(CfJ, ),O{g)

C,H, (g)+ 30, (g)-. 2CD, (g)+ 2H,O(g)

Develop expression for the mole fractions or the reading species as function of the
reaction coordinates,

SECTION-B
There are FOUR qlle~lions m th,~ sedion. Answer any THREE,

5, (a) Of the following fine binary Jiquidivapor systems, whieh ean he approximately
modeled by Raoult's la\\-! Explain your answer. (Hmt: Table B.l of App B may be
useful) ( 15)
i) Benzene/toluene at 1 atm.
ii) n-Hexanc/n-hcptane at 25 bar
iii) Hydrogen/propane at 200K
iv) lso-Oetane/n-Oetane at 373.15 K
v) \Vater/n-de<:an~ at 1 bar.
(h) A binary ~y-"lemor 8pe~)~S I and 2 ~onsists of vapor and liquid phase in equillbnum
at t~mperature T, for which (20)
InYI=l.Sx2' lnY2~I,SxL2
P,""= 1.24 bar r;"=0.89bar
(i) for what range of values of the overall mole fi-action /1 can this two-phase system
exist with a liquid mole fraction x,= 0.65,
(Ii) what is the pressure P Andvapor mo1c fraction y, within this nmge?
(Iii) What are the pressure And composition of the azeotrope at temperature 1"?

Contd .. ,.... ,. P/3

 =3=

CHE 307

6. (a) Define fugacity. What" it, physi~al ~ignitican~e? (8)

(b) The excess Gibbs energy of a binary liquid mixture at T and P i~ given by (27)
G'
RT = (- 2.6x, -1.8x,) x,x,

(i) Fmd ~xpr~ssillns fllr InYIand Inn <ItT and P

(ii) Show that these expre~sion<;~ati~fy the Gibb,,/Duhem ~quatiun.
(ili) Plat InYI<lndInn versus Xl, Label points InYlu, InY2"and show thcirvalue~.

7, (a) "Henry's law applies to a speeies a<; it approaehes infinite dlll.ltion in a binary
solution, and the Gibbs/Duhem equation insures validity of the LewislRandall rule for the
oth~r spe~)~s at it upprouch~~ purity" -ju~tify this statement with necessary equation<;, ( I 8)
(b) FigClre Jor QCl~8tillnNo. 7(b) pr~senl'; the plot8 of excess properties of two binarv
mixtures, Draw the corresponding plots of In'fl and Iny, vs X, qual1tativcly. (Hints: tor XL

--+ I, Iny,--+0 and i generally have the same sign as G F,) (1 0)

(e) What is the basic critcrion to check whether the cxperimental value" or uetlvlty
c()dli~1~nt8 ~llnt<lin8y~temutic ~lTor? (07)

8. (a) A concentrated binary solution containing mostly species 2 (but x, oF I) is in

cqmlibrium wIth a vapor phase containing both ~pecie~ 1 and 2. The pre,8Ure of this two-
phas~ .<'y~temi~ 1 har; the lemperatur~ i~ 298.15 K. Detennine from the following data
good e~tilTIat~.'or x I and YI
H,- 200 har P2S,"= 0.1 0 bar
State and justi£)' all assmuptions. (15)
Gil
(b) For 502 at 600K <lnd300bar. make good estimates of the fugacity and -" (14)
RT
(Hint: use the supplied data book and figure fo1'Qucstion No, 8(b))
, (e) Di<;tinguish hetwecn excess properties und re,idual properties, (6)

I,,
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,

i
I,
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I ..i< •
It"
•
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/
/
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Flgur(' for Question 7 b) excess properties at 323,15 K for i) chloroform(1)/n-

heptane (2) and ii) acetone(1)jchloroform(2)

----,._ ..._--- ------- ----

L:_:~ '. ~ . _
C0tl1pan30n of correi"'!lol,S for Z~.',lEo viriai-coeff,clcr.t correi-,tlcn is
i'epresen,ed b:1;\1.;.straight lin~s: ;1,,=L"oiKes ier ccrr"latlor., by L1i'e points, _

Figure for Question NO.8 (b)

---------------------------- ._- ..-_ ~-----------

-----------'"
L..3rr-lICHE Date: 17/05/2014
BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY, DHAKA
L-3/T-1 B. Sc. Engineering Examinations 2012.,.2013

Sub: CHE 307 (Chemical Engineering Thermodynamics II)

Full Marks: 210 Time: 3 Hours
The figures in the margin indicate full marks.
USE SEPARATE SCRIPTS FOR EACH SECTION

" SECTION - A
There are FOUR questions in this section. Answer any THREE.

1. (a) How Henry's law is related to the Lewis-Randal rule through Gibbs-Duhem equation. (7)
(b) Derive the equations of Margules and VanLaar equations and describe the procedures
for evaluating the parameters of the two equations. (20)
(c) What is the heat effect when 150 Ibm of H2S04 is mixed with 350 Ibm of an aqueous

solution containing 25% wL H2S04 in an isothermal process at lOO°F? . (8)

2.. (a) Prove, that, II )i/ ]Vi =

(
.f
fiO .. exp
(- AGo
R:r
J. (10)

(b) Fm liquid Phas~reactions, show that, IT. (~iYi)Yi = K exp [(~O_pRT )L:(viVd].
.
(8)
. 1 1

(c) The following reaction reaches equilibrium at 650°C and.atmospheric pressure: (17)

. 'C6HSCH: CH2 (g) + H2 (g) = C6HS .'C2HS (g)

If the system initially contains 1.5 mol H2 for each mol of styrene, what IS the,
coinposition of the system at equilibrium?
Assume ideal gases. Use the following data:
J J
AH298= -'- 117440 -, AG298= - 830} 0 -.
mol mol
M = - 4.175, AB = 4.766 xI0~3, L\C == - 1.81 x IO-{i
5
AD = - 0.083 x 10
[Hint: Calculate the K value by using IDCPH and IDCPS concepts.]

3. For the methanol synthesis reaction,

CO (g) + 2 H2 (g) ~ CH30H (g)
the equilibrium conversion to methanol is large at 300 K, but decreases rapidly with
increasing T. However, reaction rates become appreciable only at higher temperatures.
For a feed mixture of carbon monoxide and hydrogen in the stoichiometricproporlions,
(a) What is the equilibrium mole fraction of methanol at 1 bar and 300 K? (20)
(b) At what temperature does the equilibrium mole fraction of methanol equal 0.50

for a pressure of I bar? (10)

Contd P/2
 =2=

CHE307
Contd ..• Q.No. 3

(c) At what temperature does the equilibrium mole fraction of methanol equal 0.50

for a pressure of 100 bar, assuming the equilibrium mixtur~ is an ideal gas? (5)
Ml298 = - 90135 llmol, 80298 = - 24791 llmol '
.'; -3 -6
M=-7.663;8B=1O.815xlO; 8C=-3.45xlO ;
5
8D = - 0.135 x 10

4. (a) Derive the expression of poynting factor. (5)

(b) Derive all the equations of Gama/Phi formulation of VLE required for Dew and

Bubble point calculations. (8)

(c) For multicomponent system, write block diagrams for the calculation of Bubble T and

a P-T-flash calculations. (11+11=22)

SECTION-B
There are FOUR questions in this section. Answer any THREE.
••

5. (a) A refrigeration system requires 2.5 kW of power for a refrigeration rate of 6 kJ s-I. Ifheat

rejection is at 40°C, what is the lowest temperature the system can possibly maintain? (10)
(b) Describe a vapor-compression refrigeration system with appropriate diagram. (7)
(c) You may consider a vapor c0!Upression refrigeration system where tetrafluoroethane

is used as refrigerant in a cycle and the refrigeration rate is 200 Btu s-1. If the refrigerator

operates with compressor efficiency 0.75, an evaporation temperature of -15°F and a

condensation temperature of 80°F, determine the (18)

(i) Circulation rate of refrigerant
(ii) Heat transfer rate in the condenser
(iii) Power requirement
(iv) Coefficient of performance of the cycle
(v) Coefficient of performance of a Carnotrefrigeration cycle operating between the
same temperature levels.

6. (a) Explain the term "retrograde condensation" with appropriate diagram. (9)
L~ (b) "An equilibrium vapor-liquid system described by Raoult's Law cannot exhibit an

azeotrope." True/False. Explain your answer. (6)

Contd P/3
 •
.•
=3=

CHE3Q1
Contd ... Q. No.6

(c} Discuss the modified Raoult's Law and its importance. Applying the modified
Raoult's Law, determine the equilibrium pressure and vapor composition for a binary

liquid hydrocarbon mixture where Xl = 0.6 is in equilibrium with its vapor at 140°C. Use

the following information, ;; (20)

In 1'1 = Axl and In 1'2 = AX12

sat sat
At 140°C, Pl = 75.20 kPa and P2 = 31.66 kPa

The system forms an azeotrope at 140°C for which Xlaz = y 1az = 0.295.

7. (a) Show the block diagram for Dew T calculation with modified Raoult's law. (10)
(b) What relationship will you use for calculation of molar composition of air dissolved

in water? Why do you think that beverage makers use C02 to make fizzy beverage like

soda water instead of using the inexpensive and nontoxic Air? (7)

(c) The molar volume of a binary liquid mixture at T and P is given by, (18)

V = 120Xl + 70X2+ (l5xl + 8X2)XIX2

(i) Find the expression for partial molar volume of species 1 and 2.
-- '

(ii) Show that the expre;ssions satisfie the Gibbs/Duhem equation.

("')
111 Sh owt h at (dV
-
1 J ='. (dV
-, 2 J =.0"
dXl xz;:1 dXl XI =0

(iv) Plot values of V, Viand~:. V 2 with the change of composition and. label the
-00 -00
points VI, V2, V 1 and V 2 and show their values.

8. (a) Define chemical potential. Why is it considered as one on the most important

thermodynamic property? (10)

(b) Define fugacity and fugacity coefficient. Write down the procedure for determination

of fugacity for a pure liquid. (10)

(c) Determine the fugacity coefficient for an equimolar vapor mixture of propane (1) and
3
n-pentane (2) at 75°C and 2 bar. Second virial coefficients, in cm /mol at 75°C and 2 bar:

Bll = - 276, B22 = - 809 and B12 = - 466. (15)

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Wt. % H2S0~
 ----------------------------------:-----------------_ ..

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314
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Table9.l: of Saturated Tetraf1uoroethane'l

~rhe~.110dynamit'Prqptttl~s
--TV6lume~-~---- Etithalpy Entropy

(ft)3(}bm)-,1 (Btu )(lbm )-1 (Btu)(lbm)-t (R)-t

t("F) P'(psia) V' ill' HI Nil Sl SII

-40 7.429 Mri32 5.7i\2 0,000 97.050 0.00000 0.23125

.:0.35 8.577 0,01139 5.0.'n '1.489 97.804 0:00352 Q~23037;
-30 9.862 0'.:01145 4;412 2.'9&4 '. 98S56 0'.00701 O.2294j
+'25: U.297 Q:OllS2 3;~)o1 4,4-84 "99..306 0;01048 0.22863
-20 12.895 0:01158 3,445 5~991 100:Q54 0.013.92 0227:~6

-15 14;667 O,{J1l65 3.052 7.505 100;799 0;01733 0.22'7/14

"';10 115.626 o-on12 2.712 9..0:26 101.541 0.02013. 0.22647
-5 18,787 O;Ql180 2.416 m,554 ionso 0:02409 0.27~584
0 21.162 Q;Oil87 2.159 12.09() 103.015 0;02744 0.22525
5 23,7:67 .0.0],194 I.V34 13.634 103.745 0.d3077 0.'22470
,
-; 10 20.617 .0~O1201 1.7:\6 lS.lj{7 104.47} 0.03408 (\22418
15 29.726 ();Ol210 156,1 16.'74& 105.192 0.03737 IJ.22370
20 33":110 0:01218 '1.4ft) ll\.JI~ 105.90'7 0.04065 0.22325
25 36.78$ 0,01226 1:275 19~97 l.O6.6l1 0.04391 0.22283
30 40.768 .0.01235 1.155 21.486 107320 0.04715 0.22244

35 4-5.Q75 0.01243 LO~ti 23.085 IOS.016 0.05018 0:22207

40 49.72li 6.0125~ n.'»)] 24.694 108.705 0.05359 0.22172
45 54.732 0.01262 OJ;6H .26.3:{4 1.09.386 0.05679 0.22140
50 60.116 0.01271 0.792 21.944 nO.058 O.0599g 0.22110
55 ,65.895 a.Ol28J. 0.724 29.586 110:722 0.06316 0.22081

60 12:0'81 O:OlllJl n.66J 31:239 U1376 0.06633. 0,22054

65 78.712 0.01301 0,608 32:905 111,019 . 0.06949 0.22028
70 '85.787 0.01312. O.5$S 34.5&3 112.652 0,07264 0.22Q01
75 93.333 0:01323 Mi2 3t.274 ,113'.272 '0.07'578 0.21979
-1 80 101.37 0.Jf1335 .00412 37.978 J13.880 0,0'7892 0.21957
j
I
85 10M2 0.01347 OA3'4. 3~H197 114.475 0.08205 0:21934
~ 90 11SJ.(jO <1.01359 (lAOO 4L430 115:055' 0.085]-8 0:21912
95 12'8.63 0.01372 .0.3(;9 43.1'79 115.619 0.08830 0.21890
.JOO 1'38.8'3 0.01386' .0,34J 44.943 116.166 0.09142 0.2lS68
105 149.63 0.01400 {l,lIS 46.7:25 il6.694 0.09454 0:2J845

110 161.0.5 0.01415 ().~\l'2 • 4!t'524 lJ7;203 0,09766 0.21822

ns H3.11 0,01430 0,270 50.343 117.690 0,10078 0.21797
120 185-84 o.oJ447 0,250 .52.181 118.153 0.10391 0.21772
125 199.25, 0,01464 0.251 54.040 118.591. 0.10.704 0.21744
130 213;3.8_ 0.0.l482 0.2J4 55,923. J 19.000 0.11018 0.21715
,'.;'

'I 13$' 228,25' 0..01502 ().198 .S7.~30 } 19.377 0,] 1333 0.21683
" 140; 243;88 0:01522 0;184. 59.164 119.720 O.H650 0.2J.648
is.o 277.5.7 0;01567 0.157 .... '63.72'1 120.284 0.1228& 0.21566
16u 3]4.(1) . '0:01620 0.134 . .6:7.823 HP.65o. 0,12938 0.21463
17U 3.55'.51 0:01683 O:JlA 72:106" 120;'753 0.13603 0.21329

. tAdapteC:Jby;pcrmissiorLfrom:;4Sl1RAElli:ult1qqok .. Fw:uJamentQls, p.17.29, Al'llCritan

S~iciety;oflfeatin~rRe:tri$cratili"gal'ldAiI''-CQnditio.niug Engineers, Inc., Atlanta, '1993. .

••..
 .,

L-3/T-lICHE Date: 23/09/2013

( BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY, DHAKA
L-3/T-1 B. Sc. Engineering Examinations 2011-2012

Sub: CHE 307 (Chemical Engineering Thermodynamics)

. Full Marks: 210 Time : 3 Hours-

USE SEPARATE SCRIPTS FOR EACH SECTION .
The figures in the margin indicate full marks.

SECTION-A
There are FOUR questions in this section. Answer any THREE.

1. (a) A heat pump is used to heat a house in the winter and to cool it in the sUmmer.
During the winter, the outside air serves as a heat source: during the summer it acts as ~
heat sink. The heat-transfer rate through the walls and roof of the house is 0.75 kJ/s for
each °c of temperature difference between the inside and outside of the house: summer

and winter. (12)

The heat pump motor is rated at 1.5 kW. Determine the minimum outside temperature
for which the house can be maintained at 20°C during the winter and the maximum
outside temperature for which the house can be maintained at 25°C during the summei.
(b) With a neat schematic diagram, describe the principles of operation of a absorption-

refrigerator. Derive the necessary equations. (13)

(c) With appropriate thermodynamic diagram explain different liquefaction methods. (10)

2. (a) Describe Claude liquefaction process with diagram and obtain the expression for z. (15)
(b) Ob~ain the expression of Lewis-Randall rule starting from Gibbs-Duhem equation. (10)
(c) Determine the expressions for activity co-efficients when the one-parameter

Margules equation is written in the form: (10)

G
hr = AX1X2 where A is dimensionless

3. The following is a set ofVLE data for the system acetone(1)/methanol(2) at 55°C. (35)

P/kPa XI Yl PlkPa Xl Yl
68.728 0.0 0.0 97.64 0.50 0.58
72.278 0.028 0.064 99.81 0.63 0.67
77.524 0.08 0.18 100.27 0.69 0.71
82.52 0.14 0.26 100.99 0.77 0.77
90.08 0.27 0.41 101.05 0.79 0.78
95.01 0.40 0.51 99.79 0.94 0.93
96.36 0.44 0.55 96.8 1.0 1.0

Find parameter values of for the VanLaar eq~ation that provide the best fit of G hr
to the data. .
Contd P/2
 =2=

CHE307

4. (a) By using Gamma/Phi formulation of VLE, show a block diagram for calculation of

DEWP. (16)
(b) It is proposed to cool a stream of 75-wt% sulfuric acid solution -at 1400p by diluting
it with chilled water at 40oP. Determine the amount of water that must be added to
l(lbm) of 75-wt% acid before cooling below 1400p actually occurs. (8)
(c) Demonstrate Henry's Law and Lewis-Randall rule with a diagram of composition
dependence of fugacity for species i in a binary solution. (11)

SECTION -B
There are FOUR questions in this section. Answer any THREE.

5. (a) Write down the assumptions and range of applicability of Raoult's law for
LiquidN apor systems? Which of the following systems cannot be modeled by Raoult's

law? Why? (Use Table 8.1) (15)

(i) Benzene/toluene at 1 atm
(ii) n-Hexane/n-heptane at 25 bar
(iii) Hydrogen/Propane at 200 K
(iv) ISO-Octane/n-Octane at 100°C.
(b) Por the acetone(l)/methanol(2) system a vapor mixture for which Zl = 0.25 and Z2 =
0.75 is cooled to a temperature T in the two-phase region and flows into a separation
chamber at a pressure of 1 bar. If the composition of the liquid product is to -be
Xl = 0.175, what is the required value of T and what is the value of Yl? Given, (20)
InYI = 0.64 xi
Parameters of Antoine "equation

Component A B C
Acetone 14.3916 2,795.82 230.00
Methanol 16.5938 3,644.30 239.76

6. (a) Define fugacity. Prom the following compressibility factor data for C02 at 150°C
calculate fugacity and fugacity coefficient of C02 at 100 bar. (13)
P (bar) 10 20 40 60 80 100
Z 0.985 0.970 0.942 0.913 0.885 0.869

(b) "Excess properties have no meaning for pure species, whereas residual properties
exist for pure species as well as for mixtures" - explain. (10)
(c) If the molar density of binary mixture is given by the empirical expression. (12)

find the corresponding expressions for V; and V2• Here, V; and V2 are partial molar
volume of component 1 and 2, respectively.
Contd P/3
 \ .

=3=

CHE307

7. (a) Assuming ideal gases, develop the chemical-reaction equilibrium equation for the

gas phase isomerization reaction A -t B. (12)

(b) Consider the reactions. . (23)

If these reactions come to equilibrium after combustion in an internal-combustion

engine at 2,000 K and 200 bar, estimate the mole fractions of NO and N02 present for
mole fractions of nitrogen and oxygen in the combustion products of 0.7 and 0.05.

8. (a) Show that "the potential range of separation by distillation decreases as the pressure

increases" with the help ofVLE diagrams. (9)

(b) What is law of mass action? , Write down the limitations of this law. (9)
(c) How are the reactions in heterogeneous systems are different from the reactions in
homogeneous systems? Write down the simplified expression of equilibrium constant,

K for the following reaction (9)

(d) "The Gibbs energy change, AG of mixing is always negative and entropy change AS

of mixing is positive" - do you agree with this statement. Justify your answer. (8)

UOl+ci. -" 'PILt

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 .. "'.": .'

Table B.I Properties of Pure Species

Molar V,
mass (J) - TcIK Pelbar Zc em3 mol-I TnlK
or 10-3 m3 kmol-J
Methane 16.043 0.012 190.6 45.99 0.286 98.6
Ethane IlIA
30.070 0.100 305.3 48.72 0.279 145.5 184.6
Propane 44.097 0.152 369.8 42.48 0.276 200.0 231.1
n-Butane 58.123 0.200 425.) 37.96 0.274 255. 272.7
n-Pentane 72.150 0.252 469.7 33.70 0.276 313. 309.2
n-Hexane 86.177 0.301 507.6 30.25 0.266 371. 341.9
n-Heptane 100.204 0.350 540.2_ 27.40 0.261 428. 371.6
n-Oetane 114.231 00400 568.7 24.90 0.256 486. 398.8
n-Nonane 128.258 0.444 594.6 22.90 0.252 544. 424.0
n-Decane 142.285 0.492 617.7 21.10 0.247 600. 447.3
Isobutane 58.123 0.181 408.1 36048 0.282 262.7 261.4
Isooctane lI4.23 I 0.302 544.0 25.68 0.266 468. 372.4
Cyclopentane 70.134 0.196 511.8 45.02 0.273 258. 322.4
Cyclohexane 84.161 0.210 553.6 40.73 0.273 308. 353.9
Methylcyclopentane 84.161 0.230 532.8 37.85 0.272 - 319. 345.0
Methylcyclohexane 98.188 0.235 572.2 34.71 0.269 368. 374.1
Ethylene 28.054 0.087 282.3 50.40 0.281 131. 169.4
Propylene 42.081 0.140 365.6 46.65 0.289 188.4 225.5
I.Butene 56.108 .0.191 420.0 40.43 0.277 239.3 266.9
. cis-2-Butene 56.108 0.205 435.6 42.43 0.273 233.8 276.9
trans-2-Butene 56.108 0.218 428.6 41.00 0.275 237.7 274.0
I-Hexene 84.161 0.280 504.0 31.40 0.265 354. 336.3
Isobutylene 56.108 0.194 417~9 40.00 0.275 238.9 266.3
1,3-Butadiene 54.092 0.190 425.2 42.77 0.267 220.4 268.7
Cyclohexene 82.145 0.212 560.4 43.50 0.272 291. 356.1
Acetylene 26.038 0.187 308.3 61.39 0.271 113. 189.4
Benzene 78.114 0.210 562.2 48.98 0.271 259. 353.2
Toluene 92.141 0.262 591.8 41.06 0.264 316. 383.8
Ethylbenzene 106.167 0.303 617.2 - 36.06 0.263 374. 409.4
Cumene 120.194 0.326 631.1 32.09 0.261 427. 425.6
o-Xylene 106.167 0.310 630.3 37.34 0.263 369. 417.6
m-Xylene . 106.167 0.326 617.1 35.36 0.259 376 .. 412.3
p-Xylene 106.167 0.322 616.2 35.11 0.260 379. 411.5
Styrene 104.152 0.297 636.0 38040 0.256 352. 418.3
Naphthalene 128.174 0.302 748.4 40.51 0.269 413.
Biphenyl 154.2lI 0.365 789.3 38.50 0.295 502. 528.2
Formaldehyde 30.026 0.282 408.0 65.90 0.223 115. 254.1
Acetaldehyde 44.053 0.291 466.0 55.50 0.221 154. 2,94.0
Methyl acetate 74.079 0.331 506.6 47.50 0.257 228. 330.1
Ethyl acetate 88.106 0.366 523.3 38.80 0.255 286. 350.2
Acetone 58.080 0.307 508.2 47.01 0.233 209. 32904
Methyl ethyl ketone 72.107 0.323 535.5 41.50 0.249 267. 352.8
Diethyl ether 74.123 0.281 466.7 36040 0.263 280. 307.6
Methyl t-butyl ether 88.150 0.266 497.1 34.30 0.273 329. 328.4
-Methanol 32.042 0.564 512.6 80.97 0.224 118. 337.9

~J.~-- P/6
 --
--:.6--
-

Table B.I (Continued)

Molar V,
mass w TclK Pclbar Z, ' cm3111Ql-t TnlK
or 10-3 mJ ktilOI-1
Ethanol 46.069 0.645 513.9 61.48 0.240 167. 351,4
I-Propanol 60.096 0.622 536.8 51.75 0254 219. 370.4
I-Butanol 74.123 0.594 563.1 44.23 0.260 275. 390.8
I-Hexanol 102.177 0.579 611.4 35.10 0.263 381. 430.6
2-Propanol 60.096 0.668 508.3 47.62 0.248 220. 355.4
Phenol 94.113 0.444 694.3 61.30 0.243 229. 455.0
Ethylene glycol 62.068 0.487 719.7 77.00 0.246 191.0 470.5
Acetic acid 60.053 00467 592.0 57.86 0.211 179.7 391.1
n-Butyric acid ~8.106 0.681 615.7 40.64 0.232 291:7 436.4
Benzoic acid 122.123 0.603 151.0 44.70 0.246 344. 522.4
Acetonitrile 41.053 0.338 5455 48.30 0.184 173. 354.8
Methylamine 31.057 0.281 430.1 74.60 0.321 154. 266.8
Ethylamine 45.084 O~285 456.2 56.20 0.307 207. 289.7
Nitromethane 61.040 0.348 5882 63.10 0.223 ,173. 374.4
Carbon tetrachloride 153.822 0.193 556.4 45.60 0.272 276. 349.8
Chloroform 119.377 0.222 536.4, 54;72 0.293 239. 334.3
Dichloromethane 84.932 0.199 510,0 60.80 0.265 185. 312.9
Methyl chloride 50.488 0.153 416.3 66.80 0.276 143. 249.1
Ethyl chloride 64514 0.190 460A 52,70 0.275 2(}O. 285.4
Chlorobenzene II 2558 0.250 632.4 45.20 0.265. 308. 404.9
Tetrafluoroethane 102.030 0327 374.2 40.60 0.258 198.0 247.1
Argon 39.948 0.000 150.9 48.98 .0.291 74.6 87.3
Krypton 83;800 0.000 209.4 55.02 0.288 91.2 119.8
Xenon 131.30 0.000 289.7 58.40 0.286 118.0 165.0
Helium 4 4.003 -0.390 5.2 2.28 0.302 57.~ 4.2
Hydrogen 2.016 -0.216 33.19 13.13 0.305 64.1 20.4
Oxygen 31.999 ' 0,022 154.6 50.43 0.288 73.4 90.2
Nitrogen 28.014 0,038 126.2 34.00 0;289 89.2 ,77.3
Airl 28.851 0.035 132.2 37.45 0.289 84.8
Chlorine 70.905 0.069 417.2 77.10 0.265 124. 239.1
Carbon monoxide 28.010 0.048 132.9 34.99 0:299 93.4 81.7
Carbon dioxide 44.010 0.224 304.2 73.83 0.274 94.0
Carbon disulfide 76.143 0.111" 552.0 79.00 0.275 160. 319.4
Hydrogen sulfide 34.082 0.094 373.5 89.63 0.284 98.5 212.8
Sulfur dioxide 64.065 0.245 430.8 78.84 0.269 122. 263,]
Sulfur trioxide 80.064 0.424 490.9 82.10 0.255 127. 317.9
Nitric oxide (NO) 30.006 0.583 t80.2 64.80 0.251 58.0 121.4
Nitrous oxideJNzO) 44;013 0.141 309.6 72.45 0.274 97.4 184.7
Hydrogen chloride 36.46.1 0.132 324.7 83.10 0.249 8L 188.2
Hydrogen cyanide 27;026 0.41.0 456.7 53.90 0.197 139. 298.9
Water 18.0t5 0.345 647.1 220.55 0.229 55.9 373.2
Ammonia 17.031 0.253 405.7 112.80 0.242 . 72.5 239.7
Nitric acid 63.013 0,714 520.0 68.90 0.231 145. 356.2
Sulfuric acid 98.080 924.0 64.00 0.147 1.77. 610.0
tPseudoparameters for YNa = 0.79 and YOz = 0.21. See Eqs. (6.88)-(6.90).

c~d ---'pl?
••

28

",

10 12," ' t4,' '

~~.~."..
'. ,. : }~, 104/K'-1 .'," ,
..:~~i;.~:
I'

Figure' Equilibrium constants as a function of temperature

,
F,~ure 1w QW!Stl~ 7(b)
L-3/T-l/CHE Date: 23/02/2012
BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY, DHAKA
L-3/T-1 B. Sc. Engineering Examinations 2010-2011

Sub: .CHE 307 (Chemical Engineering Thermodynamics II)

Full Marks : 210

!
Time : 3 Hours
;

The figures in the margin indicate full marks.

Symbols and notations have their usual meanings.
USE SEPARATE SCRIPTS FOR EACH SECTION

SECTION-A
There are FOUR questions in this section. Answer any THREE.

1. (a) A concentrated binary solution containing mostly species 2 (but X2 * 1) is in

equilibrium with a vapor phase containing both species 1 and 2? The pressure of this two-
phase system is 1 bar; the temperature is 25°C. Estimate Xl and YI from the following data. (15)

HI = 200 bar p~at = 0.1 bar

State and justify all assumptions.
(b) A binary system of species 1 and 2 consists of vapor and liquid phases in equilibrium
at temperature T. The overall mole fraction of species 1in the system is Z] = 0.65. (20)
At temperature T,
2 2
InYI = 0.67 X2 InY2= 0.67 Xl
PI Sat = 32.27 KPa P2Sat = 73.14 KPa

Assuming the validity of modified Raoult's law.

(i) Over what range of pressures can this system exist as two phases at given T and z]?
(ii) Show whether or not the system exhibits an azeotrope.

2. (a) For the ammonia synthesis reaction (17)

.!.N2(g) + ~ H2(g) ~ NH3(g)

2 2
with 0.5 mol N2 and 1.5 mol H2 as the initial amounts of reactants with the assumption
that the equilibrium mixture is an ideal gas, show that:

Ee = 1-
( .
1 + 1.299 K :0 J-~
(b) Carbon black is produced by the decomposition of methane (18)
CH4 (g) ~ C (s) + 2H2 (g)
For equilibrium at 650°C and 1 bar find the gas phase composition ifpure methane enters
the reactor. Use the booklet for,standard enthalpy and Gibbs energy of formation. Ignore
the effect of temperature on enthalpy in your calculation.

Contd P/2
 =2=

CHE307

3. (a) Write down the algorithm for the calculation of BUBL P by gamma/phi formulation.
List the equations needed to execute the algorithm. (15)
(b)Derive the general relation between n, the moles adsorbed and P, the gas pressure in
terms of compressibility factor, z for pure gas adsorption. Find the adsorption isothermal
for z = 1 + f3n,where f3is a function of T only. Write down the condition when it reduces
to Longmuir isotherm. (20)

4. (a) Derive an expression for osmotic pressure for a dilute solution in an osmotic system
using the concept of fugacity. (13)
(b) Determine the number of degrees of freedom F for (i) a system prepared by partially
decomposing CaCo3 into an evacuated space and (ii) a system prepared by partially

decomposing NH4CI into an evacuated space. (14)

(c) Draw the P, x, y diagram of a binary mixture at constant T. Show the P x relation for

Raoult's law by a dashed line on the diagram. (8)

SECTION-B
There are FOUR questions in this section. Answer any THREE.

5. (a) A vapor-compression refrigeration system is conventional except that 'a countercurrent

heat exchanger is installed to subcool the liquid from the condenser by heat exchange with
the vapor stream from the evaporation. The minimum temperature difference for heat
transfer is lOaF. Tetrafluoroethane is the refrigerant [Fig. for Q. 5(a)] evaporating at 20°F
and condensing at 80°F. The heat load on the evaporator is 2000 Btu/s. If the compressor
efficiency is 75%, what is the power requirement? How does this result compare with the
power required by the compressor if the system operates without the heat exchanger? How
do the refrigerant circulation rates compare for the two cases? (24)
(b) What is the more effective way to increase the coefficient of performance of a Carnot
refrigerator: to increase Tc with TH constant or to decrease TH with Tc constant. For a

real refrigerator, does either of these strategies make sense? (11)

6. (a) The excess Gibbs energy of a particular ternary liquid mixture is represented by the
empirical expression with parameters A 12,A 13and A23 functions of T and P only (10+ 10=20)

G%T = Al2 XlX2 + A13 XlX3 '+ A23 x2x3

(i) Determine the implied expressions for InyI. InY2and InY3.

(ii) For species 1 determine expressions for InYl for the limiting cases:

Xl=O, X2=0 and X3=0

What does these limiting cases represent?
Contd P/3
 =3=

CHE307
Contd eo. Q. No.6

E
(b) Given below are values ofG , HE nd e/ for some equimolar binary liquid mixtures

at 298 K. Estimate values of GE, HE and SE at 328 K by two procedures: (i) Use all the

data, (ii) Assume e/ = o. (15)

Compare and discuss your results for the two procedures.
E
Acetone/Chloroform: G = -622 J/mol
E
H = -1920 l/mol
E
Cp = 4.2 J/mol-k

7. The following is a set ofVLE data for the system methanol/water at 333 K (35)
PIKPa Xl YI PIKPa Xl YI
19.95 0.0 0.0 60.6 0.53 0.81
39.2 0.16 0.56 63.9 0.60 0.84
42.9 0.22 0.63 67.9 0.68 0.87
48.8 0.31 0.69 72.8 0.78 0.91
52.7 0.36 0.73 84.56 1.0 1.0
56.6 0.44 0.77

(a) Find parameter values for the Margules equation that provide the best fit ofGE/RT

to the data.

(b) Prepare a Pxy diagram that compares the experimental points with curves

determined from the correlation.

u
Note that: lnYl = AIZ (Xl = 0) and InyzU = AZI (xz = 0) where AIZ and AZI are parameters

of Margules equations.

8. (a) If pure liquid HZS04 at 80°F is added adiabatically to pure liquid water at 80°F to

form a 40 wt% solution, what is the final temperature of the solution? (10)
(b) If a liquid solution of HCl in water, containing 1 mol of HCl and 4.5 mol of HzO

absorbs an additional 1 mol of HCI (g) at the constant temperature of 25°C, what is the

heat effect? . (13).

(c) What is the heat effect when 20 kg of LiCI (s) is added to 125 kg of an aqueous

solution containing 10 wt% Liel in an isothermal process at 25°C? [MW of Lie 1= 42.39] (12)
 ..

~,.'''.''- .~.~." .':~,!

;'.'

Thble 9.1: Th~~~~dynamic properties of saturated tetrafiuoroethanet~l • 'I.f.

.::-l

Volurp.e Enthalpy Entropy

(ft)3{lbm)-1 (Btu)(l,bm)-l (Btu}(lbm)-l(R)-l

t(OF) P(psia) Vi Sl

-40 7.429 0.01132 5.782 0.000 97.050 '0.00000

-35 8.577 0.01139 , 5.053 1.489 97.804 0.00352
-30 9.862 0.01145 4.432 2.984 98.556 0.00701
-25 11.297 0.01152 3.901 4.484 99.306 0.01048
-20 12.895 0.01158 3.445 5.991 100.054 0.01392

-15 14.667 0.01165 3.052 7.505 100.799 0.01733

-10 16.626 0.01172 2.712 9.026 101.542 0.02073
-5 18.787 0.01180 2.416 10.554 102.280 0.02409
o 21.162 0.01187 2.159 12.090 103.015 0.02744
5 23.767 0.01194 1.934 13.634', 103.745 0.03077

10 '26.617 0.01202 1.736 15.187 104.471 0.03408

l5 29.726 .0.01210 . 1.563 16.748 105.192 . 0.03737
20 33.110 0.01218 1.410. 18.318 105.907 0.04065
25 36.785 O.Oi226 1.275 19.897 ,106.617 0.04391
30 40.768 0.01235 1.155 21.486 107.320 0.04715

35 45.075 0.01243 1.048 23.085 108.016 0.05018

40 49.724 0.01252 0.953 24.694 108.705 0.05359
45 54.732 0.01262 0.868 26.314 109.386 0.05679
50 60,116 0.01271. 0.792 27.944 110.058 0.05998
55 65.895 0.01281 .0.724 29.586 110.722 0.06316

60 72.087 , 0.01291 0.663 31.239 111.376 0.06633

65 78.712 0.01301 0.608 32.905 112.019 0.06949
70 85.787 0.01312 0.558 34.583 112.652 0.07264
75 '93.333 0.01323 0.512 36.274 113.272 0.07578
80 101.37 0.01335 0.472 37.978 113.880 0.07892

85 109.92 0.01347 0.434 39.697 114.475 0.08205

90 119.00 0.01359 O.~OO 41.430 115.055 0.08518
95 128.63 0.01372 0.369. 43.179 115.619 0.08830
100 138.83 0.01386 0.341 44;943 116;166 0.09142
105 149.63 0.01400 0.315 46.725 116.694 0.09454

no 161.05 0.01415 0.292 48.524 117.203 0.09766

115 . 173.11 0.01430 0.270 50.343 117.690 0.10018
120 185.84. 0.01447 0.250 52.181 118.153 0.10391
125 199.25 0.01464 0.231 54.040 118.591 0.10704
130 213.38 0.01482 0.214 55.923 119.000 0.11018

.'::~t
.;.t~
-:1
.. ;:,r"
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- 2U :W CIf' r1ti ~.t~) •..•

: .}:.•~.

3000~
2000 I-~/. . :t6
':t1 • /I I
~
1000 1000
~7.2-»-
,sz> 1/
IV

6
400 1\/1 \
/
/~ ~8~1tlJ
~400
11\
/ 2.4JH-j
,\.J\
200 l.k-4H 200
~ /

'--" d 1/ v /
'en
.5
100 ~tjlOO
~ I
/
..-hi. fT :2fE
0.48
~
U) 40. ~ / / ~40
~
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10

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4

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~.
Figure 9.3: PH diagram for tetrafiuoroethane(HFC-134a). (Reprodu.ced by permission. ASHRAE Handbook: Funda.mentals, p. 17.28,
American Society of Heating, Refrigerating, and Air-Conditioning Engineers, Inc., Atlanta, 1993.) "'.
 • .1 ..•••• - •.•• _.

"
Enthalpy-composition diagram for water-sulfuric acid mixtures at 1 atm

200

180
SSO"F
160 2S0"F
270°F
140
+290"F 4S0"F

I! )20

I, 100
310"F
I;

80

20.

o
-20

-40

-60 .

-80
. r-
•)00 -l_'-~>~j'; _.....'..
-120 -_. ~.--.- ~ _--_.
-140 I
o 0.1 0.2 0.3 0.4 . O.S 0.6 0.7 0.8 0.9
weight fraction H2S04

Diagram adapted from Hougen, O. A., Watson, K. M. 1946. Chemical Process Principles Charts, Wiley & Sons.

,
 ,.
~

•• I

-70

-60

•..::l
ll)

r---...... (5 ;:
: t o , •
~ "0
-50

(\X) E
•.. Ql

...,0.
~ """
-40
I~
"il'
'-"
00 -30

QS
>- -20
1 2 3 4 6 8 10
~ 20 30 40, 60 80 10' 200 300 400 600 800 103

. ;;; moles of H20 per mole of solute

~~
1..4-
~.14: Heall>of Solulion aI25°C. ([lased on data frol1l "The NAS Tahles of Chemical Thcfllt/ldynami,' I'llll'cl'licS;'.1. f'hn, Chol/. Ref Data,
')1. 2, 1982.)