Exercise 2.

Subject: Minimum work for separating a hydrocarbon stream.

Given: Component flow rates, ni , of feed and product 1, in kmol/h. Phase condition;
temperature in K; enthalpy, h, in kJ/kmol; and entropy, s, in kJ/kmol-K for feed, product
1, and product 2. Infinite heat sink temperature = T0 = 298.15 K.

Find: Minimum work of separation, Wmin , in kJ/h

Analysis: From Eq. (4), Table 2.1,

Wmin = nb nb
out in

From Eq. 2-1,

b = h T0 s

For the feed stream (in), n = 30 + 200 + 370 + 350 + 50 = 1,000 kmol/h
b = 19,480 - (298.15)(36.64) = 8,556 kJ/kmol
For product 1 (out), n = 30 + 192 + 4 + 0 + 0 = 226 kmol/h
b = 25,040 - (298.15)(33.13) = 15,162 kJ/kmol
For product 2 (out), n = nfeed - nproduct 1 = 1,000 - 226 = 774 kmol/h
b = 25,640 - (298.15)(54.84) = 9,289 kJ/kmol

From Eq. (4), Table 2.1,

Wmin = 226(15,162) + 774(9,289) - 1,000(8,556) = 2,060 kJ/h

 Exercise 2.2

Subject: Minimum work for separating a mixture of ethylbenzene and xylene isomers.

Given: Component flow rates, ni , of feed ,in lbmol/h. Component split fractions for
three products, Phase condition; temperature in oF; enthalpy, h, in Btu/lbmol; and
entropy, s, in Btu/lbmol-oR for feed and three products. Infinite heat sink temperature =
T0 = 560oR.

Find: Minimum work of separation, Wmin , in kJ/h

Analysis: From Eq. (4), Table 2.1,

Wmin = nb nb
out in

From Eq. 2-1,

b = h T0 s

For the feed stream (in), n = 150 +190 + 430 + 230 = 1,000 lbmol/h
b = 29,290 - (560)(15.32) = 20,710 Btu/lbmol
For product 1 (out), using Eq. (1-2),
n = 150(0.96) + 190 (0.005) + 430(0.004) = 146.7 lbmol/h
b = 29,750 - (560)(12.47) = 22,767 Btu/lbmol
For product 2 (out), using Eq. (1-2),
n = 150(0.04) + 190(0.99) + 430(0.99) + 230(0.015) = 623.3
lbmol/h
b = 29,550 - (560)(13.60) = 21,934 Btu/lbmol
For product 3 (out), by total material balance,
n = 1,000 - 146.7 - 623.3 = 230 lbmol/h
b = 28,320 - (560)(14.68) = 20,099 Btu/lbmol
From Eq. (4), Table 2.1,

Wmin = 146.7(22,767) + 623.3(21,934) + 230(20,099) - 1,000(20,710) = 924,200 Btu/h

 Exercise 2.3

Subject: Second-law analysis of a distillation column

Given: Component flow rates, ni , from Table 1.5 for feed, distillate, and bottoms in
kmol/h for column C3 in Figure 1.9. Condenser duty, QC ,= 27,300,00 kJ/h. Phase
condition; temperature in K; enthalpy, h, in kJ/kmol; and entropy, s, in kJ/kmol-K for
feed, distillate and bottoms. Infinite heat sink temperature = T0 = 298.15 K. Condenser
cooling water at 25oC = 298.15 K and reboiler steam at 100oC = 373.15 K.

Assumptions: Neglect shaft work associated with column reflux pump.

Find: (a) Reboiler duty, QR , kJ/h

(b) Production of entropy, Sirr , kJ/h-K
(c) Lost work, LW, kJ/h
(d) Minimum work of separation, Wmin , kJ/h
(e) Second-law efficiency,

Analysis: (a) From Eq. (1), the energy balance for column C3,

QR = QC nh + nh
in out

= 27,300,000 - 445.5(17,000) + 175.5(13,420) + 270(15,840)

= 26,360,000 kJ/h
(b) From Eq. (2), the entropy balance for column C3,

Q Q
Sirr = ns + ns +
out Ts in Ts
27,300,000 26, 360, 000
= 175.5(5.87) + 270(21.22) + 445.5(25.05)
298.15 373.15
= 16,520 kJ/h-K
(c) From Eq. (2-2), LW = T0Sirr = 298.15(16,520) = 4,925,000 kJ/h
(d) Combining Eqs. (3) and (4) of Table 2.1,

T0 T
Wmin = QR 1 QC 1 0 LW
Tsteam Tcw
298.15 298.15
= 26,360, 000 1 27, 300, 000 1 4, 925, 000
373.15 298.15
= 373, 000 kJ/h
(e) From Eq. (5), Table 2.1, = 373,000/(4,925,000 + 373,000) = 0.0704
= 7.04%
 Exercise 2.4

Subject: Second-law analysis for a membrane separation of a gas mixture

Given: Component flow rates in lbmol/h for the feed. Permeate of 95 mol% H2 and 5
mol% CH4. Separation factor, SP, for H2 relative to CH4, of 47. Phase condition;
temperature in oF; enthalpy, h, in Btu/lbmol; and entropy, s, in Btu/lbmol-oR for the feed,
permeate, and retentate. Infinite heat sink temperature = T0 = 539.7oR.

Assumptions: Neglect heat transfer to or from the membrane.

Find: (a) Production of entropy, Sirr ,Btu/h-oR

(b) Lost work, LW, Btu/h
(c) Minimum work of separation, Wmin , Btu/h
(d) Second-law efficiency,
Suggest other separation methods.

Analysis: First compute the material balance to obtain the flow rates of the retentate
and permeate. From Eq. (1-4), for the separation factor, SP, using the subscript P for
permeate and R for retentate,
nH 2 / nH 2
47 = P R
(1)
nCH 4 / nCH 4
P R

For 95 mol% H2 and 5 mol% CH4 in the permeate,

nH 2
0.95 = P
(2)
nH 2 + nCH 4
P P

By component material balances for H2 and CH4 around the membrane separator.
nH 2 = 3,000 = nH 2 + nH 2
F P R
(3) and (4)
nCH 4 = 884 = nCH 4 + nCH 4
F P R

Solving Eqs. (1), (2), (3), and (4) for the 4 unknowns,
nH 2 = 2,699.9 lbmol / h, nH 2 = 3001
. lbmol / h, nCH 4 = 142.1 lbmol / h, nCH 4 = 741.9 lbmol / h
P R P R

Therefore, nP = 2,699.9 + 142.1 + 0 = 2,842 lbmol/h

nR = 300.1 + 741.9 + 120 = 1,162 lbmol/h
Also, nF = 2,842 +1,162 = 4,004 lbmol/h
 Exercise 2.4 (continued)
Analysis: (continued)

(a) From Eq. (2), the entropy balance for the membrane

Sirr = ( ns ) ( ns )
out in

= 1,162(2.742) + 2,842(4.222) 4, 004(1.520)

= 9,099 Btu/h- o R
(c) From Eq. (2-2), LW = T0Sirr = 536.7(9,099) = 4,883,000 Btu/h
(d) Combining Eqs. (3) and (4) of Table 2.1,

Wmin = LW
= 4,883, 000 Btu/h
Note the negative value. The energy of separation is supplied from the high pressure of
the feed.
(e) Because the minimum work of separation is equal to the negative of the lost
work, Eq. (5), Table 2.1 does not apply. The efficiency can not be computed unless heat
transfer is taken into account to give a permeate temperature of 80oF.

Gas adsorption could also be used to make the separation.

 Exercise 2.5

Subject: Expressions for computing K-values.

Given: Seven common thermodynamic expressions for estimating K-values.

Find: Expression assumptions if not rigorous

Analysis:

iL
(a) K i = is a rigorous expression.
iV

(b) K i = iL is not rigorous. It assumes ideal solutions so that iL and iV are 1.0.
iV
(c) K i = iL is not rigorous. It assumes ideal solutions and an ideal gas,
such that iV , iL , and iV are 1.0.

(d) K i = iL iL is a rigorous expression.
iV
Pi s
(e) K i = is not rigorous. It assumes ideal solutions and an ideal gas,
P
such that iV , iL , and iV are 1.0. It also assumes a low
pressure for the liquid phase, such that iL =1.0.
iLiL
(f) K i = is a rigorous expression
iV iV
iL Pi s
(g) K i = is not rigorous. It assumes low pressure for the liquid
P
Pi s
and the ideal gas law, such that iL = and iV =1.0.
P
 Exercise 2.6

Subject: Comparison of experimental K-values to Raoult's law predictions.

Given: For the propane-isopentane system at 167oF and 147 psia, propane mole fractions
of 0.2900 in the liquid phase and 0.6650 in the vapor phase. Vapor pressures at 167oF of
409.6 psia for propane and 58.6 psia for isopentane.

Find: (a) Experimental K-values.

(b) Raoult's law K-values.

Analysis: (a) Mole fraction of isopentane in the liquid phase = 1 - 0.2900 = 0.7100
Mole fraction of isopentane in the vapor phase = 1 - 0.6650 = 0.3350
From Eq. (2-9), Ki = yi /xi
= 0.6650/0.2900 = 2.293 for propane
= 0.3350/0.7100 = 0.472 for isopentane

(b) From Eq. (3), Table 2.3, K i = Pi s / P

= 409.6/147 = 2.786 for propane
= 58.6/147 = 0.399 for isopentane
This is rather poor agreement. Note that the experimental values give a
relative volatility of 2.293/0.472 = 4.86, while Raoult's law predicts 2.786/0.399 = 6.98.
A modified Raoults law should be used to incorporate a liquid-phase activity
coefficient. Also a fugacity correction for the gas phase might improve the agreement.
 Exercise 2.7

Subject: Liquid-liquid phase equilibrium data.

Given: Experimental solubility data at 25oC for the isooctane (1)-furfural (2) system.
In the furfural-rich liquid phase, I, x1 = 0.0431
In the isooctane-rich liquid phase, II, x1 = 0.9461

Assumptions: The furfural activity coefficient in phase I = 1.0

The isooctane activity coefficient in phase II = 1.0

Find: (a) The distribution coefficients for isooctane and furfural.

(b) The relative selectivity for isooctane relative to furfural.
(c) The activity coefficients.

Analysis: From summation of mole fractions in each liquid phase,

x2 in phase I = 1 - 0.0431 = 0.9569
x2 in phase II = 1 - 0.9461 = 0.0.0539

(a) From Eq. (2-20), K Di = xi( I ) / xi( II )

0.0431 0.9461
K D1 = = 0.456 and K D2 = = 17.75
0.9461 0.0539

(b) From Eq. (2-22), ij = K Di / K D j

K D1 0.0456
12 = = = 0.00257
K D2 17.75
Note that the I and II designations for the two liquid phases are arbitrary. If
they
were interchanged, the relative selectivity would be 1/0.00257 = 389.

(c) From rearrangements of Eq. (2-30),

x1(II) 0.9461
1( I) = 1(II) (I)
= 1.0 = 21.95
x1 0.0431
x2(I) 0.9569
(II)
2 = (I)
2 (II)
= 1.0 = 17.75
x2 0.0539
 Exercise 2.8

Subject: Activity coefficients of solids dissolved in solvents.

Given: Solubility at 25oC of naphthalene in 5 solvents. Vapor pressure equations for

solid and liquid naphthalene

Find: Activity coefficient of naphthalene in each solvent.

Analysis: From a rearrangement of Eq. (2-34) for solid-liquid phase equilibrium of

naphthalene,

s
1 Psolid
L = s
(1)
x L Pliquid

From the given naphthalene vapor pressure equations at 25oC = 298.15 K,

8,712
s
Psolid = exp 26.708 = 0.080 torr
298.15
3992.01
s
Pliquid = exp 16.1426 = 0.234 torr
. 71.29
29815

From Eq. (1),

1 0.080 0.342
L = = (2)
x L 0.234 xL

Using the solubility data with Eq. (2),

Solvent Solubility, xL L
Benzene 0.2946 1.16
Cyclohexane 0.1487 2.30
Carbon tetrachloride 0.2591 1.32
n-Hexane 0.1168 2.93
Water 0.18 x 10-5 190,000
 Exercise 2.9

Subject: Minimum isothermal work of separation for a binary gas mixture.

Given: A feed gas mixture, F, of A and B to be separated at infinite surroundings

temperature, T0, into two products, P1 and P2.

Assumptions: Ideal gas law and ideal gas solution at temperature T0. Isobaric at P0.

Find: Derive an equation for the Wmin in terms of the mole fractions of the feed and
products.
Plot Wmin/RT0nF versus the mole fraction of A in the feed for:
(a) A perfect separation.
(b) A separation with SFA = 0.98 and SFB = 0.02.
(c) A separation with SRA = 9.0 and SRB = 1/9.
(d) A separation with SFA = 0.95 and SRB = 361
Determine the sensitivity of Wmin to product purities.
Does Wmin depend on the separation method?
Prove that the largest value of Wmin occurs for an equimolar feed.

Analysis: From Eq. (4), Table 2.1,

Wmin = nb nb
out in (1)

From Eq. 2-1,

b = h T0 s (2)

Combining Eqs. (1) and (2) for one feed, F, in and two products, P1 and P2, out:

Wmin = nP1 hP1 + nP2 hP2 T0 nP1 sP1 + nP2 hP2 nF hF + T0nF sF (3)

However, for isothermal separation of an ideal gas mixture, the change in enthalpy = 0.
Therefore, from Eq. (3),

Wmin = T0nF sF T0 nP1 sP1 + nP2 hP2 (4)

From Eq. (3), Table 2.4, for an ideal gas mixture at T0 and P0 ,

s = R yi ln yi (5)
i
 Exercise 2.9 (continued)

Analysis: (continued)

Substituting Eq. (5) into Eq. (4),

Wmin
= nF yA F ln yA F + 1 yA F ln 1 yA F
RT0
+ nP1 yA P ln yA P + 1 yA P ln 1 yA P (6)
1 1 1 1

+ nP2 yA P ln yA P + 1 yA P ln 1 yA P }
2 2 2 2

By combining a component material balance for A with a total material balance,

yA F yA P
nP1 = nF 2
(7)
yA P yA P
1 2

yA F yA P
nP2 = nF 1
(8)
yA P yA P
2 1

Equations (6), (7), and (8) give a relationship for Wmin/RT0 in terms of the molar feed rate
and the
mole fractions of A in the feed and two products.

(a) Let product P1 be pure A and product P2 be pure B. Then, from Eqs. (7) and
(8),

nP1 = yA F nF and nP2 = 1 yA F nF (9) and (10)

Combining Eqs. (6) through (10), noting that 1x ln(1) = 0 and 0x ln(0) = 0

Wmin
= yAF ln yA F + (1 yAF ) ln (1 yAF ) (11)
nF RT0

(b) From Eq. (1-2), letting 1 be P1,

nF
yA P nP1 = 0.98 yA F nF or yA P = 0.98 yA F (12)
1 1
nP1
 Exercise 2.9 (continued)

Analysis: (b) (continued)

and,

nF
yBP = 0.02 1 yA F (13)
1
nP1

Combining (12 and (13) to give yA P + yBP = 1, we obtain,

1 1

nP1 = nF 0.96 yA F + 0.02 (14)

By total material balance,

nP2 = nF nP1 or nP2 = nF 0.98 0.96 yA F (15)

Also, from the SFA = 0.98 for the split fraction of A to P1 , we can write for
the split fraction of A to P2 ,

nF
yA P nP2 = 0.02 yA F nF or yA P = 0.02 yA F (16)
2 2
nP2
The final equations are (6) combined with (12) and (14) through (16).

(c) From Eq. (1-3),

yA P nP1
1
=9 (17)
yA P nP2
2

and,

yBP nP1 1
1
= (18)
yBP nP2 9
2

Combining (17) and (18), with component and total material balances around
the separator gives the following equations that can be used with Eq. (6):

nF
yA P = 0.9 yA F (19)
1
nP1
 Exercise 2.9 (continued)

Analysis: (c) (continued)

nF
yA P = 01
. yA F (20)
2
nP2

nP1 = nF 0.8 yA F + 01
. (21)

nP2 = nF 0.9 0.8 yA F (22)

(d) From Eq. (1-5),

SFA / SFB
SPA,B = = 361 (23)
1 SFA / 1 SFB

SFA = 0.95 is given. Combining this with Eq. (23), gives SFB = 0.05.

This part then proceeds as in part (b) to give:

nP1 = nF 0.90 yA F + 0.05 (24)

nP2 = nF nP1 or nP2 = nF 0.95 0.90 yA F (25)

nF
yA P = 0.95 yA F (26)
1
nP1

nF
yA P = 0.05 yA F (27)
2
nP2

Equations (24) through (27) are combined with Eq. (6).

A spreadsheet can be used to compute the dimensionless minimum work,

Wmin
RT0nF

with the following results for Parts (a) through (d):

 Exercise 2.9 (continued)

From the plot on the previous page, it is seen that the dimensionless minimum work is
very sensitive to the feed mole fraction and to the product purities.

From the derivation of the minimum work equations, it is seen that they are independent
of the separation method and only depend on thermodynamics.

To prove that the largest value of Wmin occurs for a feed with equimolar quantities of A
and B, consider the case of a perfect separation, part (a), as given by Eq. (11).
Let W = Wmin/nFRT0 and y = yA F . Then, the derivative of W with respect to y
is,

dW y 1
= ln y + ln(1 y ) + (1 y )
dy y 1 y
= [ ln y ln(1 y ) ]
For min/max, set the derivative to zero and solve for y.
Therefore,
dW
= 0 = [ ln y ln(1 y ) ]
dy
Solving, y = 1 y or y = 0.5. This is an equimolar feed.
Furthermore, it gives a maximum value of W .
 Exercise 2.10

Subject: Relative volatility of the isopentane-normal pentane system

Given: Experimental data for relative volatility 125-250oF. Vapor pressure constants.

Find: Relative volatilities from Raoult's law over the same temperature range and
compare them to the experimental values.

Analysis: Combining Eq. (5), Table 2.3, for Raoult's law, with Eq. (2-21) for .
PiCs
iC5 ,nC5 = s 5 (1)
PnC5
Only the first three constants of the extended Antoine equation are given. (T=K, P= kPa)
2345.09
PiCs 5 = exp 13.6106
T 40.2128
(2), (3)
2554.60
PnC5 = exp 13.9778
s

T 36.2529
Using a spreadsheet to calculate the relative volatility from Eqs. (1), (2), and (3):
T, F Expt. T, K PiCs 5 , kPa PnsC5 , kPa Raoult's law

125 1.26 325 214 167 1.28
150 1.23 339 314 251 1.25
175 1.21 352 446 364 1.22
200 1.18 366 614 512 1.20
225 1.16 380 823 700 1.18
250 1.14 394 1079 834 1.16
The Raoult's law values are within 2% of the experimental values.
 Exercise 2.11

Subject: Condenser duty of a vacuum distillation column separating ethyl benzene (EB)
and styrene (S).

Given: Phase condition, temperature, pressure, flow rate, and compositions for streams
entering and leaving a condenser, which produces subcooled reflux and distillate.
Property constants in Example 2.3.

Assumptions: Ideal gas and ideal gas and liquid solutions.

Find: Condenser duty in kJ/h.

Analysis: For the thermodynamic path, cool the overhead from 331 K to 325 K. Then
condense at 325 K. Because this temperature change is small, compute vapor specific
heats at the two temperatures and take the arithmetic average. From Eq. (2-35) and the
constants in Example 2.3, for vapor heat capacity in J/kmol-K and temperature in K,

CPoEB = 43098.9 + 707.151T 0.481063T 2 + 130084

. 10 4 T 3
CPoS = 28248.3 + 615.878T 0.40231T 2 + 0.993528 10 4 T 3

Solving,
Vapor heat capacity, J/kmol-K
Comp. kg/h MW kmol/h 331 K 325 K Avg.
EB 77,500 106.17 729.975 142,980 140,380 141,680
S 2,500 104.15 24.003 132,130 132,830 133,980

The sensible vapor enthalpy change, Qsensible from 331 K to 325 K is,

Qsensible = ni CPoi T = ni CPoi (331 325)

i i

= 729.975(141,680)(331 325) + 24.003(133,980)(331 325)

= 620,560,000 J / h = 620,560 kJ / h

For the latent heat of condensation, use Eq. (2-41) to estimate the molar heats of
vaporization of at 325 K for the two components, using the vapor pressure constants
given in Example 2.3.
 Exercise 2.11 (continued)

2 7440.61 9.87052 5
HEB
vap
= 8314 325 2
+ 0.00623121 + + 6(4.13065 1018 ) 325
325 325
= 40,740,000 J / kmol = 40,740 kJ / kmol
2 914107
. 17.0918 5
HSvap = 8314 325 2
+ 0.0143369 + + 6(18375
. 1018 ) 325
325 325
= 42,440,000 J / kmol = 42,440 kJ / kmol
The latent heat of condensation, Qlatent , in kJ/kmol is,

Qlatent = ni Hivap = 729.975(40,740) + 24.003(42,440)

i

= 30,760,000 kJ / h

The total condenser duty = Qsensible + Q latent = 620,000 + 30,760,000 = 31,380,000 kJ/h
 Exercise 2.12

Subject: Thermodynamic properties of a benzene (B) -toluene (T) feed to a distillation

column.

Given: Temperature, pressure, and component flow rates for the column feed. Property
constants, critical temperature

Assumptions: Phase condition is liquid (needs to be verified). Ideal gas and liquid
solution.

Find: Molar volume, density, enthalpy, and entropy of the liquid feed.

Analysis: The feed is at 100oF and 20 psia. From Fig. 2.4, since the vapor pressures of
benzene and toluene are 3.3 and 0.95 psia, respectively, the feed is a subcooled liquid. T
= 311 K.
From Eqs. (4) , Table 2.4 and (2-38),

Mi Mi
L = =
L
2/ 7
i T
i
1
Tc
AB
78.11
L =
B 311
2 /7 = 0.0905 m3 / kmol
1
562
304.1(0.269)
92.14
L =
T 311
2/ 7 = 01083
. m3 / kmol
1
593.1
290.6(0.265)

Total flow rate = 415 + 131 = 546 kmol/h

Benzene mole fraction = 415/546 = 0.760 Toluene mole fraction = 1-0.76 = 0.240

From Eq. (4), Table 2.4 for a mixture (additive volumes),

L = 0.76(0.0905) + 0.24(0.1083) = 0.0948 m3/kmol = 1.52 ft3/lbmol

Mixture molecular weight = M = 0.76(78.11) + 0.24(92.14) = 81.48

From Eq. (4), Table 2.4 for conversion to density,

L = M/L = 81.48/1.52 = 53.6 lb/ft3
 Exercise 2.13

Subject: Liquid density of the bottoms from a distillation column.

Given: Temperature, pressure, component flow rates

Assumptions: Ideal liquid solution so that volume of mixing = 0

Find: Liquid density in various units using Fig. 2.3 for pure component densities.

Analysis: From Eq. (4), Table 2.4,

M
L = xi iL =
i L
M
iL =
iL

The calculations are summarized as follows using Fig. 2.3 for pure component densities,

Comp. MW Flow rate, Mole Density, Molar xi

lbmol/h fraction, Fig. 2.3, volume,
xi g/cm3 cm3/mol
C3 44.09 2.2 0.0049 0.2 220 1.1
iC4 58.12 171.1 0.3841 0.40 145 55.7
nC4 58.12 226.6 0.5086 0.43 135 68.7
iC5 72.15 28.1 0.0631 0.515 140 8.8
nC5 72.15 17.5 0.0393 0.525 130 5.1

L = xi iL = 139.4 cm3/mol MW = 59.5

i

MW 59.5
L = = = 0.427 g/cm 3
L 139.4

= 427 kg/m3
= 26.6 lb/ft3
= 3.56 lb/gal
= 149 lb/bbl
where 1 bbl = 42 gal
 Exercise 2.14

Subject: Condenser duty for a distillation column, where the overhead vapor condenses
into two liquid phases.

Given: Temperature, pressure, and component flow rates of overhead vapor and the two
liquid phases.

Assumptions: Ideal gas and ideal liquid solution for each liquid phase.

Find: Condenser duty in Btu/h and kJ/h

Analysis: Take a thermodynamic path of vapor from 76oC to 40oC and condensation at
40oC.
For water, use the steam tables. Change in enthalpy from vapor at 76oC to
40oC and 1.4 bar = 1133.8 - 71.96 = 1,062 Btu/lb = 2,467,000 J/kg = 2,467
kJ/kg.

For benzene, using data on p. 2-221 from Perry's 7th edition, change in
enthalpy from vapor at 76oC to 40oC and 1.4 bar = 874 - 411 = 463 kJ/kg

For isopropanol, using data on p. 2-179 from Perry's 7th edition,

Average CP over the temperature range = 1.569 kJ/kg-K
From data of p. 2-157 of Perry's 7th edition,
Heat of vaporization at 40OC = 313 K = 770.4 kJ/kg

Therefore, the enthalpy change of isopropanol = 1.569(76-40) +770.4 = 827

kJ/kg

Condenser duty, QC = 2,350(2,467) + 24,600(463) + 6,800(827)

= 22,810,000 kJ/h
= 21,640,000 Btu/h
 Exercise 2.15

Subject: K-values and vapor tendency of light gases and hydrocarbons

Given: Temperature of 250oF and pressure of 500 psia.

Find: K-values in Fig. 2.8 and vapor tendency.

Analysis: If the K-value is < 1.0, tendency is for liquid phase. If the K-value > 1.0,
tendency is for vapor phase. Using Fig. 2.8,

Component K-value Tendency

N2 17 vapor
H2S 3.1 vapor
CO2 5.5 vapor
C1 8 vapor
C2 3 vapor
C3 1.5 vapor
iC4 0.71 liquid
nC4 0.35 liquid
iC5 0.38 liquid
nC5 0.10 liquid
 Exercise 2.16

Subject: Recovery of acetone from air by absorption in water.

Given: Temperature, pressure, phase condition, and component flow rates of feeds to
and products from the absorber, except for exiting liquid temperature.

Assumptions: Ideal gas and zero heat of mixing.

Find: Temperature of exiting liquid phase. Potential for explosion hazard.

Analysis: From the given component flow rates, water evaporates at the rate of 22
lbmol/h, and 14.9 lbmol/h of acetone is condensed. Take a thermodynamic path that
evaporates water at 90oF and condenses acetone at 78oF.
Energy to heat air from 78oF to 80oF = nCPT = 687(7)(80-78)=9,620 Btu/h
Energy to heat unabsorbed acetone from 78oF to 80oF is negligible.
Energy to vaporize water at 90oF = nHvap = 22(1,043)(18) = 413,000 Btu/h
Total required energy = 9,620 + 413,000 = 423,000 Btu/h

Energy available from condensation of acetone with Hvap = 237 Btu/lb and a
molecular weight of 58.08 = 14.9(58.08)(237) = 205,000 Btu/h
Energy available from the cooling of evaporated water from 90oF to 80oF =
22(18)(0.44)(90-80) = 2,000 Btu/h
Total available energy = 205,000 + 2,000 = 207,000 Btu/h
Energy required - Energy available = 423,000 - 207,000 = 216,000 Btu/h
This energy must come from cooling of the water absorbent from 90oF to T , and
condensed acetone from 78oF to T.

Therefore, using a CP of 0.53 for liquid acetone,

216,000 = 14.9(58.08)(78-T) + 1,722(18)(1.0)(90-T)

Solving, T = temperature of exiting liquid = 83oF.

The mol% acetone in the entering gas = 15/702 x 100% = 2.14 %.

This is outside of the explosive limits range of 2.5 to 13 mol%.
 Exercise 2.17

Subject: Volumetric flow rates of entering and exiting streams of an adsorber for
removing nitrogen from subquality natural gas.

Given: Temperature and pressure of feed gas and two product gases. Composition of
the feed gas. Specification of 90% removal of nitrogen and a 97% methane natural gas
product.

Assumptions: Applicability of the Redlich-Kwong equation of state.

Find: Volumetric flow rates of the entering and exiting gas streams in actual ft3/h.

Analysis: Removal of nitrogen = 0.9(176) = 158.4 lbmol/h

Nitrogen left in natural gas = 176 - 158.4 = 17.6 lbmol/h
Methane in natural gas product = 17.6(97/3) = 569.1 lbmol/h
Material balance summary:

lbmol/h:
Component Feed gas Waste gas Natural gas
Nitrogen 176 158.4 17.6
Methane 704 134.9 569.1
Totals 880 293.3 586.7
Temperature, oF 70 70 100
Pressure, psia 800 280 790

Using the ChemCAD simulation program, the following volumetric flow rates are
computed using the Redlich-Kwong equation of state:

Stream Actual volumetric

flow rate, ft3/h
Feed gas 5,844
Waste gas 5,876
Natural gas 4,162
 Exercise 2.18

Subject: Estimation of partial fugacity coefficients of propane and benzene using the
R-K equation of state.

Given: From Example 2.5, a vapor mixture of 39.49 mol% propane and 60.51 mol%
benzene at 400oF and 410.3 psia.

Assumptions: Applicability of the Redlich-Kwong equation of state.

Find: Partial fugacity coefficients

Analysis: From Example 2.5, the following conditions and constants apply, where the
Redlich-Kwong constants, A and B, for each component are computed from Eqs. (2-47)
and (2-48) respectively.

T = 477.6 K ZV = 0.7314 A = 0.2724

P = 2829 kPa R = 8.314 kPa-m3/kmol-K B = 0.05326

From Eqs. (2-47) and (2-48),

aP ai (2819) a
Ai = 2i 2 = 2 2
= i
RT (8.314) (477.6) 5593
bP bi (2819)
Bi = i = = 0.7099bi
RT (8.314)(477.6)

Component, i a, kPa-m6/kmol2 b, m3/kmol Ai Bi

Propane 836.7 0.06268 0.1496 0.04450
Benzene 2,072 0.08263 0.3705 0.05866

The Redlich-Kwong equation for partial vapor fugacity coefficients is given by Eq. (2-
56). Applying it to propane (P) and benzene (B), using the above values for constants
and conditions,

0.04450 0.2724 0.1496 0.04450 0.05326

PV = exp (0.7314 1) ln ( 0.7314 0.05326 ) 2 ln 1 +
0.05326 0.05326 0.2724 0.05326 0.7314
= 0.934

0.05866 0.2724 0.3705 0.05866 0.05326

BV = exp (0.7314 1) ln ( 0.7314 0.05326 ) 2 ln 1 +
0.05326 0.05326 0.2724 0.05326 0.7314
= 0.705
 Exercise 2.19

Subject: Estimation of K-values by the P-R and S-R-K equations of state for a butanes-
butenes stream.

Given: Experimental K-values for an equimolar mixture of isobutane, isobutene, n-

butane, 1-butene, trans-2-butene, and cis-2-butene at 220oF and 276.5 psia.

Find: K-values by the P-R and S-R-K equations of state using a process simulator.

Analysis: Using the ChemCAD process simulation program, the following values
are obtained and compared to the experimental values:

Component Experimental K-value P-R K-value S-R-K K-value

Isobutane 1.067 1.088 1.095
Isobutene 1.024 1.029 1.036
n-butane 0.922 0.923 0.929
1-butene 1.024 1.015 1.022
Trans-2-butene 0.952 0.909 0.916
Cis-2-butene 0.876 0.882 0.889

The experimental and estimated K-values agree to within 3% for all components except
trans-2-butene. For that component, the P-R and S-R-K values are in close agreement,
but deviate from the experimental value by from 4 to 5%.
 Exercise 2.20

Subject: Cooling and partial condensation of the reactor effluent in a toluene

disproportionation process.

Given: Reactor effluent component flow rates, and temperature and pressure before and
after a cooling-water heat exchanger.

Find: Using the S-R-K and P-R equations of state with a process simulation program,
compute the component K-values, and flow rates in the vapor and liquid streams leaving
the cooling-water heat exchanger, and the rate of heat transfer in the cooling-water heat
exchanger.

Analysis: Using the ChemCAD simulation program, the following phase equilibrium
results are obtained for 100oF and 485 psia.
S-R-K Equation of State:
lbmol/h:
Component K-value Reactor effluent Equilib. Vapor Equilib. liquid
Hydrogen 85.2 1900 1873.79 26.21
Methane 10.12 215 192.35 22.65
Ethane 1.715 17 10.03 6.97
Benzene 0.00827 577 3.98 573.02
Toluene 0.00264 1349 2.98 1346.02
Paraxylene 0.000881 508 0.37 507.63
Total 4566 2083.51 2482.49

P-R Equation of State:

lbmol/h:
Component K-value Reactor effluent Equilib. Vapor Equilib. liquid
Hydrogen 34.4 1900 1834.46 65.54
Methane 11.27 215 193.85 21.15
Ethane 1.890 17 10.30 6.70
Benzene 0.0110 577 4.95 572.05
Toluene 0.00359 1349 3.93 1345.07
Paraxylene 0.001008 508 0.42 507.58
Total 4566 2047.91 2518.09

Except for hydrogen, the results are in good agreement.

The rate of heat transfer is computed by an energy balance, using an exchanger inlet
condition of 235oF and 490 psia. Stream enthalpies are obtained from the ChemCAD
program.
For S-R-K, QC = 25,452,000 - (-6,018,000) - 15,059,000 = 16,411,000 Btu/h
For P-R, QC = 26,001,000 - (-6,057,000) - 15,928,000 = 16,130,000 Btu/h
 Exercise 2.21

Subject: Minimum work for the separation of a nonideal liquid mixture.

Given: A 35 mol% acetone (1) and 65 mol% water (2) liquid mixture at 298 K and
101.3 kPa, to be separated into 99 mol% acetone and 98 mol% water. Van Laar
constants for the system.

Find: Minimum work for the separation in kJ/kmol of feed.

Analysis: Material balance for 1 kmol of feed.

Let the two products be R and S, where the former is acetone-rich.
Total mole balance: 1 = nR + nS
Acetone balance: 0.35 = 0.99 nR + 0.02 nS
Solving, nR = 0.3469 kmol and nS = 0.6531 kmol
From the problem statement,

Wmin
= nR xi ln i xi + nS xi ln i xi nF xi ln i xi (1)
RT0 iR iS iS

The activity coefficients are given by the van Laar equations, (3) in Table 2.9, which with
the given constants, A12 = 2.0 and A21 = 1.7, become,

2.0 .
17
ln 1 = 2
(2) ln 2 = 2
(3)
2.0 x1 1.7 x2
1+ 1+
1.7 x2 2.0 x1

Applying Eqs. (2) and (3) to the given mole-fraction compositions,

Feed Product R Product S_____

Component x x x
Acetone (1) 0.35 2.116 0.99 1.000 0.02 6.735
Water (2) 0.65 1.291 0.01 5.318 0.98 1.000

Substituting the above values into Eq. (1),

 Exercise 2.21 (continued)
Analysis: (continued)

Wmin
= 0.3469 {0.99 ln [ (0.99)(1.00)] + 0.01ln [ (0.01)(5.318) ]}
RT0
+0.6531{0.02 ln [ (0.02)(6.735) ] + 0.98ln [ (0.98)(1.00) ]}
1.0000 {0.35 ln [ (0.35)(2.116)] + 0.65 ln [ (0.65)(1.291)]}
= 0.1664 kmol
Wmin = 0.1664 RT0 = 0.1664(8.314)(298) = 412 kJ/kmol feed

For ideal liquid solutions, all values of are equal to 1.0. Therefore,

Wmin
= 0.3469 {0.99 ln [ (0.99)(1.00)] + 0.01ln [ (0.01)(1.00]}
RT0
+0.6531{0.02 ln [ (0.02)(1.00)] + 0.98 ln [ (0.98)(1.00) ]}
1.0000 {0.35 ln [ (0.35)(1.00)] + 0.65 ln [ (0.65)(1.00)]}
= 0.5639 kmol
Wmin = 0.5639 RT0 = 0.5639(8.314)(298) = 1,397 kJ/kmol feed

Thus, the minimum work of separation for the ideal solution is 3.4 times that of the
nonideal solution.
 Exercise 2.22

Subject: Relative volatility and activity coefficients of the benzene (B) - cyclohexane
(CH) azeotropic system at 1 atm

Given: Experimental vapor-liquid equilibrium data, including liquid-phase activity

coefficients, and Antoine vapor pressure constants.

Assumptions: Ideal gas and gas solutions

Find: (a) Relative volatility of benzene with respect to cyclohexane as a function of

benzene mole fraction in the liquid phase.
(b) Van Laar constants from the azeotropic point and comparison of van Laar
predictions with experimental data.

Analysis: (a) From Eqs. (2-21), (2-19), and (3) in Table 2.3,

KB y /x yB / xB Ps
B,CH = = B B = = B Bs
KCH yCH / xCH 1 yB / 1 xB CH PCH (1)

Using the y-x data for benzene, the following values of relative volatility are computed
from (1):

Temperature, oC xB yB B,CH
79.7 0.088 0.113 1.317
79.1 0.156 0.190 1.269
78.5 0.231 0.268 1.218
78.0 0.308 0.343 1.173
77.7 0.400 0.422 1.095
77.6 0.470 0.482 1.049
77.6 0.545 0.544 0.996
77.6 0.625 0.612 0.946
77.8 0.701 0.678 0.898
78.0 0.757 0.727 0.854
78.3 0.822 0.791 0.821
78.9 0.891 0.863 0.771
79.5 0.953 0.938 0.746
 Exercise 2.22 (continued)
Analysis: (a) (continued)

(b) From the data, take the azeotrope at xB = yB = 0.545 and xCH = yCH = 1 - 0.545 =
0.455, and with = 1.079 and CH = 1.102.
To determine the van Laar constants, use Eqs. (2-73) and (2-74) with 1= benzene
and 2 = cyclohexane:
2
0.455ln1.102
AB,CH = ln1.079 1 = 0.3247
0.545ln1.079
2
0.545 ln1.079
ACH,B = ln1.102 1 = 0.3247
0.455 ln1.102

Compute with a spreadsheet values of activity coefficients, using these values for the
binary interaction parameters with the van Laar equations, (3), Table 2.9:
1
ln B = 2
1 + 0.3247 xB / 0.3647 xCH
1
ln CH = 2
1 + 0.3647 xCH / 0.3247 xB
Note that because the activity coefficients are provided, the vapor pressure data are not
needed.
Exercise 2.22
Analysis: (b) (continued)
Experimental van Laar______
Temp., oC xB CH B CH
79.7 0.088 1.300 1.003 1.317 1.002
79.1 0.156 1.256 1.008 1.271 1.007
78.5 0.231 1.219 1.019 1.224 1.016
78.0 0.308 1.189 1.032 1.181 1.030
77.7 0.400 1.136 1.056 1.136 1.052
77.6 0.470 1.108 1.075 1.107 1.074
77.6 0.545 1.079 1.102 1.079 1.102
77.6 0.625 1.058 1.138 1.054 1.139
77.8 0.701 1.039 1.178 1.035 1.181
78.0 0.757 1.025 1.221 1.023 1.218
78.3 0.822 1.018 1.263 1.013 1.266
78.9 0.891 1.005 1.328 1.005 1.326
79.5 0.953 1.003 1.369 1.001 1.387

It is seen that the van Laar equation fits the experimental data quite well.
 Exercise 2.23

Subject: Activity coefficients from the Wilson equation for the ethanol-benzene system
at 45oC.

Given: Wilson constants and experimental activity coefficient data.

Find: Wilson activity coefficients and comparison with experimental data.

Analysis: Let: 1 = ethanol and 2 = benzene

The Wilson constants are 12 = 0.124 and 21 = 0.523
From Eqs. (4), Table 2.9,

0.124 0.523
ln 1 = ln ( x1 + 0.124 x2 ) + x2
x1 + 0.124 x2 x2 + 0.523 x1

0.124 0.523
ln 2 = ln ( x2 + 0.523 x1 ) x1
x1 + 0.124 x2 x2 + 0.523 x1

Using a spreadsheet and noting that = exp(ln ), the following values are obtained,

Experimental Wilson_______
x1 1 2 1 2
0.0374 8.142 1.022 8.182 1.008
0.0972 5.029 1.053 4.977 1.044
0.3141 2.032 1.297 2.033 1.294
0.5199 1.368 1.715 1.370 1.708
0.7087 1.140 2.374 1.120 2.350
0.9193 1.000 3.735 1.009 3.709
0.9591 0.992 4.055 1.002 4.108

It is seen that the Wilson equation fits the data very well.
Exercise 2.23 (continued)
 Exercise 2.24

Subject: Activity coefficients for the ethanol (1) - isooctane (2) system at 50oC.

Given: Infinite-dilution activity coefficients for the liquid phase.

Find: (a) van Laar constants

(b) Wilson constants
(c) Activity coefficients from van Laar and Wilson equations
(d) Comparison to azeotropic point
(e) y-x curve from van Laar equation to show erroneous prediction of phase
splitting

Analysis: (a) From van Laar Eqs. (2-72) for infinite dilution,

A12 = ln 1 = ln(21.17) = 3.053

A21 = ln 2 = ln(9.84) = 2.286

(b) From Wilson Eqs. (2-80) and (2-81) for infinite dilution,

ln 1 = 3.053 = 1 ln 12 21 (1)
ln 2 = 2.286 = 1 ln 21 12 (2)

Solving simultaneous, nonlinear Eqs. (1) and (2) using Newton's method,
12 =0.1004 and 21 = 0.2493

(c) Activity coefficients can be calculated with the above constants, using Eqs.
(3), Table 2.9 for the van Laar equations and Eqs. (4), Table 2.9 for the Wilson equations.
Results from a spreadsheet are as follows:

van Laar Wilson______

x1 1 2 1 2
0.0 21.17 1.000 21.17 1.000
0.1 10.13 1.039 6.63 1.054
0.2 5.56 1.154 3.76 1.162
0.3 3.44 1.354 2.61 1.310
0.4 2.35 1.661 2.00 1.510
0.5 1.75 2.11 1.631 1.784
0.6 1.40 2.77 1.387 2.174
0.7 1.198 3.71 1.219 2.77
0.8 1.079 5.06 1.103 3.74
0.9 1.018 7.02 1.029 5.58
1.0 1.000 9.84 1.000 9.84
 Exercise 2.24 (continued)

Analysis: (c) (continued)

Note that the Wilson activity coefficients vary more steeply at the infinite-
dilution ends.
(d) At the azeotropic point, x1 = 0.5941 and x2 = 0.4059. Using the van Laar
constants from part (a) with Eqs. (3), Table 2.9,
van Laar gives 1 = 1.419, compared to 1.44 experimental
van Laar gives 2 = 2.72, compared to 2.18 experimental
Using the Wilson constants from part (b) with Eqs. (4), Table 2.9,
Wilson gives 1 = 1.400, compared to 1.44 experimental
Wilson gives 2 = 2.147, compared to 2.18 experimental
The Wilson equation is acceptable for both components. The van Laar equation
gives poor agreement for isooctane.

(e) At 50oC, the vapor pressures are 221 torr for ethanol and 146 torr for
isooctane. Thus, system pressure will be low over the entire range of composition.
Therefore, the modified Raoult's law K-value expression, given by Eq. (4), Table 2.3
applies. When combined with Eq. (2-19), we obtain the following expression for
predicting the y - x curve:
x1 1 P1s
y1 = (3)
P
 Exercise 2.24 (continued)

Analysis: (e) (continued)

By Raoult's law, partial pressure is given by pi = xiPis

Therefore, the modified Raoult's law gives pi = xi i Pis
By Dalton's law, the sum of the partial pressures equals total pressure. Thus,

P= pi = xi i Pi s (4)
i i
Using a spreadsheet with Eqs. (3) and (4) and the van Laar activity coefficients
from the table above in part (c), values of y1 are computed for values of x1:
x1 P, torr y1
0.0 146 0.000
0.1 361 0.620
0.2 381 0.645
0.3 367 0.622
0.4 356 0.587
0.5 348 0.556
0.6 349 0.553
0.7 348 0.532
0.8 339 0.563
0.9 305 0.663
1.0 221 1.000
The y-x plot exhibits the same characteristics as the system in Fig. 2.20. Therefore, the
van Laar equation erroneously predicts phase splitting.