Q83.

From the sketch given above determine the recycle ratio R and the amount of water
evaporated in the evaporator.

Ans:
Recycle Ratio = R/F
Overall solid balance
10,000 𝑋 20
= 0.96 𝐶
100
C = 2083.33 kg
Crystallizer:
Overall material balance
V=R+C
V = R + 2083.33 ----- (1)
Solid balance
50 0.6
𝑉= 𝑅 + 0.96 𝑋 2083.33 ---- (2)
100 1.6

Solving 1 and 2
V = 9750.01 kg and R= 7666.68 kg
Recycle ratio = R/F = 7666.68/10000 = 0.767
Junction balance
F +R = B
B = 10000 + 7666.68
B = 17666.68 kg
Water evaporated in evaporator
Water evaporated = B – V
= 17666.68 – 9750.01
= 7916.67 kg
Q84. A distillation column separates 10,000 kg/h of 50% Benzene and 50% toluene mixture.
The product removed from the condenser contains 95% Benzene and the bottom product
contains 96% toluene. The vapour stream leaving the top of the column is 8000 kg/h. A portion
of the product is recycled back to the column. Find the reflux ratio.
Ans:
Basis: feed 10,000 kg/h
Reflux Ratio = L/D
Overall material balance
F=D+W
10,000 = D + W --------- (1)
Benzene Balance
10000 x 0.5 = 0.95 D + 0.04 W ---- (2)
Solving 1 and 2
D = 5054.95 kg
W = 4945.055 kg
Junction Balance
8000= L + D
L = 8000 – 5054.95
 = 2945.05 kg
𝐿 2945.05
R = 𝐷 = 5054.95 = 0.583

Q85. A distillation column separates feed mix containing 30 mole% Benzene, 50 mole %
Toluene and 20 mole % Xylene into an overhead containing 95 mole% Benzene, 4 mole%
toluene and 1 mole % xylene and bottom product containing 2 mole % Benzene. The reflux
ratio is 2.5.
On the basis of 1000 moles of feed/h Calculate:
i. Mass of top and bottom product
ii. Recovery of benzene in top product and recovery of xylene in the bottom product
iii. Recycle ratio

Ans:
Overall material balance
F=D+W
1000 = D + W --- (1)
Benzene Balance
0.3 x 1000 = 0.95 D + 0.02 W --- (2)
Solving,
D = 301.075 moles/h W = 698.925 moles/h
Toluene balance
0.5x1000 = 0.04 D + xW T W
xW T = 0.698
Xylene Balance
0.2 x 1000 = 0.01 D + xW X W
xW X = 0.282
Top product
mass of top product = mass of Benzene + mass of toluene + mass of xylene
=0.95 x 301.07 x 78 + 0.04 x 301.07x 92 + 0.01 x 301.07 x 106 = 23736.36 g/h
Bottom product
Mass of bottom product = 0.02 x 698.925 x 78 + 0.698 x 698.925 x 92 + 0.282 x
698.925 x 106
= 66864.75 g/h
𝑥𝐵,𝐵 𝐷 0.95 𝑋 301.075
𝑋100 = 𝑋 100 = 95.35 %
𝑥𝐹,𝐵 𝐹 1000 𝑋 0.3
𝑥𝑊,𝑋 𝑊 0.282 𝑋 698.925
𝑋100 = 𝑋 100 = 98.55 %
𝑥𝐹,𝑋 𝐹 1000 𝑋 0.2
Reflux Ratio R =L/D
L = R. D
= 2.5 x 301.075
= 752.6875 moles
Recycle ratio
Recycle ratio = L/F = 752.685/1000 = 0.7526
 RECYCLE WITH CHEMICAL REACTIONS

Q86. Methanol is produced by the reaction

CO+ 2H2 → CH3OH
Only 15 mole% CO entering the reactor is converted to methanol so that the recycle of the
unconverted gases is required. The feed gas is at 40oC and 300 atm. Calculate:
i. Volumetric flowrate of feed in m3/h to produce 100 kg/h of methanol.
ii. Volumetric flowrate of recycle stream at this product rate.
iii. Recycle to feed ratio.
Ans:
Basis: 100 kg/h of methanol.
100/32 = 3.125 kgmoles methanol
3.125
CO to be fed to reactor = 𝑋 100 = 20.833 kg moles of CO
15

H2 required = 2 x 20.833 kgmoles =41.67 kgmoles

In kgmoles
a b c
CO = CH3OH = 3.125 CO=17.708
20.833
H2 = 41.67 CO = 20.833 x 0.85 = H2 = 35.42
17.708
H2 = 41.67 – 3.125 x 2 =
35.42
Σ = 62.503 Σ = 56.253 Σ= 53.13

F = a-c
= 62.503-53.13
= 9.375 kgmole
i. PV=nRT
300 x V = 9.375 x 0.08206 x 313
V = 0.8206 m3/h
ii. 300 x V = 53.13 x 0.08206 x 313
V = 4.55 m3/h
iii. c/F = 53.13/9.375 = 5.67

PURGE

Ammonia synthesis uses syngas generated by steam reforming natural gas (as the feedstock).
However, this reaction also produces a number of other gases that do not contribute to the
ammonia reaction. These purge gases need to be continuously removed from the synthesis loop
and are generally fed back to the reformer furnaces as fuel gas. A typical purge gas contains
about 60% hydrogen, 20% nitrogen, 5% argon, 10% methane and 4% ammonia in varying
concentrations, depending on the process in place at the ammonia plant. Instead of burning
purge gases, it makes good financial sense to recover valuable gases such as ammonia, hydrogen,
nitrogen and argon.
Q87. N2 and H2 mixture in a mole ratio of 1:3 is used for manufacturing NH3 where the
conversion is 18%. Ammonia is separated and the unconverted gases are recycled. The feed
contains 0.2 moles of Argon per 100 moles of N2 and H2 mix by volume. The tolerance limit of
Argon entering the reactor is 6 parts per 100 parts of N2-H2 mix by volume. Calculate
i. The fraction of recycle that must be continuously purged
ii. Recycle Ratio.
Ans:
Basis : 1 mole of N2 and 3 moles of H2 into the reactor
N2 + 3H2 = 2NH3 in moles
a b c
N2 = 1 23.58 % N2= 1-0.18 21.13% N2 23.3 %
=0.82 =0.82

H2 = 3 70.75 % NH3 = 2x 9.28% H2 69.88 %

0.18 =2.46
 =0.36
Argon=0.24 5.67 % H2 = 3- 63.4% Ar= 6.82%
𝐴𝑟 6 3x0.18 0.24
= 100
𝑁2 +𝐻2
=2.46
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓𝐴𝑟 6
= 100
1+3

Argon = 6.18%
0.24
Σ=4.24 100% Σ= 3.88 100% Σ=3.52 100%

Junction balance
Overall mole balance
F+d=a
F + d = 4.24 ---- (1)
Inert balance
0.2 6.82 4.24 𝑋 5.67
100+0.2
𝐹+ 100
𝑑= 100
----- (2)
Solving 1 and 2
F = 0.736 moles
d = 3.503 mole
c=d+e
e=c–d
= 3.52 – 3.503
= 0.016 moles
i. e/c = 0.016/ 3.52 = 4.545 x 10-3 (0.45%)
ii. d/F = 3.503/0.736 = 4.76

Q88. The equation for methanol synthesis is given by the equation

CO2 + 3H2 → CH3OH + H2O
The H2 and CO2 reacting in stoichiometric quantities contain 0.5 % inert by volume. The process
is under steady state. The conc. of inerts going into the reactor must be held 2% by volume.
The conversion is 60% per pass. Calculate:
i. Moles recycled/moles fed
ii. Moles purged/ moles fed

Basis: 1mole CO2 and 3 moles H2 + inert (‘a’ stream)

In moles
a b c
CO2= 1 24.5% CO2= (1- 13.88 % CO2=0.4 23.78%
0.6)=0.4
H2 = 3 73.5% H2= (3- 41.64% H2=1.2 71.36%
1.8)=1.2
I= 2% H2O = 0.6 20.82% I= 4.86%
0.0816 0.0816
CH3OH=0.6 20.82%
I = 0.0816 2.83%
Σ= 100 % Σ = 2.8816 100% Σ 100%
4.0816 =1.6816
I/(1+3+I) X 100 = 2 --> solving for I, we get I =0.0816
Junction Balance
i. F + d =a
F + d = 4.0816
Inert balance
 0.5 4.86
0.02 x a = 100 𝐹 + 100 𝑑

F = 2.6746 moles
d= 1.407 moles
at purge junction
e + d =c
e = 1.6816 -1.407
= 0.2746
d/F = 0.52
e/F = 0.102
 VAPOR PRESSURE
At a given temperature, the vapor pressure of a pure compound is the pressure at which vapor
and liquid coexist at equilibrium. The term "vapor pressure" should be used only with pure
compounds and is usually considered as a liquid (rather than a gas) property. For a pure
compound, there is only one vapor pressure at any temperature.

Vapour pressure or
equilibrium vapor pressure is
defined as the pressure
exerted by a vapor in
thermodynamic equilibrium
with its condensed phases
(solid or liquid) at a given
temperature in a closed
system.
 Variation of vapor pressure of water with
temperature

A few methods for calculating the vapor pressure are discussed below.
i. Clausius Clapeyron Equation
ii. Cox Charts
iii. Antoine equation
 i. Clausius Clapeyron equation (from formulae table 6.1)
dP  dT
 P= Vapour pressure
P RT 2
λ = Latent heat of
vaporization
R= Universal gas constant
T= Absolute temperature
(K)
𝑃2 𝜆 1 1 P1= Initial pressure, P2 =
ln = [ − ]
𝑃1 𝑅 𝑇1 𝑇2 Final pressure
λ = Latent heat of
vaporization,
T1= Initial temperature (K),
T2= Final temperature (K)
Q89. Vapor pressure of ethyl ether at 0oC is 185 mm Hg. Calculate the vapor pressure at 20oC
take R=1.99 cal/gmole K. Mol wt of Ethyl ether = 74. λ=92.5 cal/gm.
Ans:
 𝑃2 𝜆 1 1
ln = [ − ]
𝑃1 𝑅 𝑇1 𝑇2
𝑃2 74 𝑋 92.5 1 1
ln = [ − ]
185 1.99 273 293
Solving P2 = 437.185 mm Hg.

Q90 Vapor pressure of chloroform is 61 mm Hg at 0oC and 526 mm Hg at 50oC Estimate the
vapor pressure at 100oC.
Ans:
𝑃 𝜆 1 1
ln 𝑃2 = [𝑇 − ] ---- (1)
1 𝑅 1 𝑇2

526 𝜆 1 1
ln = [ − ]
61 𝑅 273 323
𝜆
=3799.695 substituting this value in eqn (1)
𝑅
𝑃2 1 1
ln = 3799.695 [ − ]
61 273 373
P2 = 2546.107 mm Hg

ii. Cox Chart

Robert H Perry Chemical Engineers’ Handbook.

 iii. Antoine equation
𝐵′
ln 𝑃𝐴 = 𝐴′ −
𝐶′ + 𝑇
where,
PA = vapour pressure of component A in mm Hg,
T = temperature in °C,
A′, B′, C′ = Antoine constants.
The values of the constants A′, B′, C′ for a few common substances are given in Table below
Constants for the Antoine Equation (vapour pressure relation with temperature)
(Mass Transfer: Principles and Operations by A P Sinha and P. De)
e.g. find the vapor pressure of water at 100 oC
3984.92
ln PA = 18.5882 – 233.43+100

PA = 762.73 mm Hg (actual is 760 mmHg)

e.g. find the vapor pressure of water at 70 oC
3984.92
ln PA = 18.5882 – 233.43+70

PA = 233.99 mm Hg (actual is 233.7 mm Hg)

Ideal Solutions
Raoult’s Law
For an ideal solution, the equilibrium partial pressure ̅̅̅
𝑝𝐴 of a constituent at a fixed temperature
equals the product of its vapor pressure P when pure at this temperature and its mole fraction
in the liquid. This is Raoult's law.

. . . . . A + B (components)
. . . . .
. . . . yA , yB (vapor compsn)
.
xA, xB (liquid composition)
𝑝𝐴 = 𝑃𝐴 𝑥𝐴
̅̅̅ 𝑃𝐴 = 𝑉𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝐴 at temperature T
̅̅̅
𝑝𝐵 = 𝑃𝐵 𝑥𝐵 𝑃𝐵 = 𝑉𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝐵 at temperature T
𝑥𝐴 + 𝑥𝐵 = 1 𝑥𝐴 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑃𝑇 = ̅̅̅
𝑝𝐴 + 𝑝̅𝐵 𝑥𝐵 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐵 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑃𝑇 = 𝑃𝐴 𝑥𝐴 + 𝑝𝐴 = equilibrium partial pressure of A in vapor mixture
̅̅̅
𝑃𝐵 (1 − 𝑥𝐴 )
̅̅̅
𝑝𝐵 = equilibrium partial pressure of B in vapor mixture
𝑃𝑇 − 𝑃𝐵
𝑥𝐴 = 𝑃𝑇 = total pressure
𝑃𝐴 − 𝑃𝐵
𝑝̅𝐴 𝑃𝐴 𝑥𝐴 𝑦𝐴 = mole fraction of A in vapor at eqbm
𝑦𝐴 = =
𝑃𝑇 𝑃𝑇 𝑦𝐵 = mole fraction of B in vapor at eqbm
𝑝̅𝐵 𝑃𝐵 𝑥𝐵
𝑦𝐵 = =
𝑃𝑇 𝑃𝑇
Or,
𝑦𝐵 = 1 − 𝑦𝐴

Constant Pressure Equilibria

 i. T-xy diagram
ii. X-y diagram

(From Robert E. Treybal, Mass Transfer Operations.)

Liquid and vapor mixtures at equilibrium are at the same temperature and pressure throughout,
so that horizontal tie lines such as line DF join equilibrium mixtures at D and F. There are an
infinite number of such tie lines for this diagram. A mixture on the lower curve as at point D is a
saturated liquid; a mixture on the upper curve, as at F is a saturated vapor.
Constant Temperature Equilibria
P-xy diagram
Q89. The vapour pressure of pure hexane and heptane are 141 and 56.8 kN/m2 respectively at
a temperature of 90 oC. Calculate the composition of the solution and the equilibrium vapour
at a total pressure of 101.3 kN/m2.
𝑃 −𝑃 101.3−56.8
𝑥𝐴 = 𝑃𝑇 −𝑃𝐵 = =0.5285 =52.85%
𝐴 𝐵 141−56.8

𝑥𝐵 = 1-0.5285 = 0.4715 = 47.15%

𝑃 𝐴 𝑥𝐴 141 𝑋 0.5285
𝑦𝐴 = = = 0.7356
𝑃𝑇 101.3

𝑦𝐵 = 1- 0.7356 = 0.2644
Liquid composition Vapor composition
moles % moles %
Hexane 0.5285 52.85 % 0.7356 73.56 %
Heptane 0.4715 47.15 % 0.2644 26.44 %
Q90 The following table gives the vapour pressure of pure hexane and heptane.
VP (in mm Hg)
Temp Hexane Heptane
o
C (A) (B)
69 760 295
75 915 348
80 1060 426
85 1225 498
90 1405 588
95 1577 675
99.2 1765 760
i. Calculate x-y data at a total pressure of 760 mm Hg
ii. Draw T-xy diagram and x-y diagram.
𝑃𝑇 − 𝑃𝐵 𝑃𝐴 𝑥𝐴
𝑥𝐴 = 𝑦𝐴 =
𝑃𝐴 − 𝑃𝐵 𝑃𝑇
760−295 760 𝑋 1
= 1.0 760
=1
760−295
760−348 915 𝑋 0.7266
= 0.7266 = 0.874
915−348 760
760−426 1060 𝑋 0.5268
1060−426
= 0.5268 = 0.735
760
760−498 1225 𝑋 0.3604
= 0.3604 = 0.581
1225−498 760
760−588 1405 𝑋 0.2105
= 0.2105 = 0.389
1405−588 760
760−675 1577𝑋 0.0942
= 0.0942 = 0.195
1577−675 760
760−760 0.0
=0
1765−760
Q 91. Calculate the total pressure and the composition of vapours in contact with the solution
at 100oC containing 35% Benzene, 40% Toluene and 25% Xylene by wt.
V.P. Data
Benzene = 1.763 bar
Toluene = 0.737 bar
Xylene = 0.275 bar
Ans:

Wt% MWt moles Mole frn

Benzene 35 78 35/78= 0.4487 0.4487/1.1193 = 0.4
Toluene 40 92 40/92= 0.4348 0.4348/1.1193 = 0.389
Xylene 25 106 25/106 = 0.2358 0.2358/1.1193 = 0.211
Σ = 1.1193 Σ = 1.00
̅̅̅
𝑝𝐵 = 𝑃𝐵 𝑥𝐵 = 1.763 x 0.4 = 0.7052 bar
𝑝𝑇 = 𝑃𝑇 𝑥𝑇 = 0.737 x 0.389 = 0.2867 bar
̅̅̅
𝑝𝑋 = 𝑃𝑋 𝑥𝑋 = 0.211 x 0.275 = 0.058 bar
̅̅̅
𝑃𝑇 = 𝑝̅𝐴 + 𝑝̅𝐵 + 𝑝̅𝐶
𝑃𝑇 = 0.7052 + 0.2867 + 0.058
= 1.05 bar
𝑝̅𝐵 𝑃 𝐵 𝑥𝐵
𝑦𝐵 = = = 0.7052 /1.05 = 0.6716
𝑃𝑇 𝑃𝑇
𝑝̅𝑇 𝑃 𝑇 𝑥𝑇
𝑦𝑇 = = = 0.2867/1.05 = 0.2730
𝑃𝑇 𝑃𝑇
𝑝̅𝑋 𝑃 𝐴 𝑥𝑋
𝑦𝑋 = = = 0.058/1.05 = 0.0553
𝑃𝑇 𝑃𝑇