CHAPTER ELEVEN

11.1 a. The peroxide mass fraction in the effluent liquid equals that in the tank contents, which is:
Mp
xp =
M
Therefore, the leakage rate of hydrogen peroxide is m1 M p / M
b. Balance on mass: Accumulation = input output
E
dM
= m0 m1
dt
t = 0, M = M 0 (mass in tank when leakage begins)

Balance on H 2 O 2 : Accumulation = input output consumption

E
dM p
= m0 x p 0 m1
FG M IJ kM
p
dt HMK p

t = 0, M p = M p 0

11.2 a. Balance on H3PO4: Accumulation = input

Density of H3PO4: = 1834
. g / ml .
Molecular weight of H3PO4: M = 98.00 g / mol .
dn p
Accumulation = (kmol / min)
dt
20.0 L 1000 ml 1.834 g mol 1 kmol
Input = = 0.3743 kmol / min
min L ml 98.00 g 1000 mol
E
dn p
= 0.3743
dt
t = 0, n p0 = 150 0.05 = 7.5 kmol

z z
np t
b. dn p = 0.3743 dt n p = 7.5 + 0.3743t (kmol H 3PO 4 in tank )
7.5 0
np np 7.5 + 0.3743t kmol H 3PO 4
xp = = =
n n0 + n p n p 0 150 + 0.3743t kmol

7.5 + 0.3743t
c. . =
015 t = 471
. min
150 + 0.3743t

11-1
11.3 a. b g b g b
mw = a + bt t = 0, mw = 750 & t = 5, mw = 1000 mw kg h = 750 + 50t hg bg
Balance on methanol: Accumulation = Input Output
M = kg CH 3OH in tank
dM
dt
b
= m f mw = 1200 kg h 750 + 50t kg h g
E
dM
dt
= 450 50t kg hb g
t = 0, M = 750 kg

z zb
M t
b. dM = 450 50t dt g
750 0

E
M 750 = 450t 25t 2
E
M = 750 + 450t 25t 2

Check the solution in two ways:

(1) t = 0, M = 750 kg satisfies the initial condition;
dM
(2) = 450 50t reproduces the mass balance.
dt

dM
c. = 0 t = 450 50 = 9 h M = 750 + 450(9) 25(9)2 = 2775 kg (maximum)
dt

M = 0 = 750 + 450t 25t 2

t=
450 b450g + 4b25gb750g t = 1.54 h, 19.54 h
2

2b 25g

3.40 m 3 103 liter 0.792 kg

d. = 2693 kg (capacity of tank)
1 m3 1 liter

M = 2693 = 750 + 450t 25t 2

t=
450 b450g + 4b25gb750 2693g t = 719
2

2b 25g
. h,10.81 h

Expressions for M(t) are:

R|750 + 450t - 25t b0 t 719
. and 10.81 t 19.54g (tank is filling or draining)
2

M(t) = S2693 . t 10.81)

( 719 (tank is overflowing)
||T0 (19.54 t 20.54) (tank is empty, draining
as fast as methanol is fed to it)

11-2
11.3 (contd)

3000

2500
2000
M(kg)

1500

1000
500

0
0 5 10 15 20
t(h)

10.0 ft 3 492 R 1 lb - mole

Air initially in tank: N 0 =
11.4 a.
b g = 0.0258 lb - mole
532 R 359 ft 3 STP

Air in tank after 15 s:

Pf V N f RT Pf 0.0258 lb - mole 114.7 psia

= N f = N0 = = 0.2013 lb - mole
P0V N 0 RT P0 14.7 psia

Rate of addition: n =
b0.2013 0.0258g lb - mole air = 0.0117 lb - mole air s
15 s

b. Balance on air in tank: Accumulation = input

dN
dt
b g
= 0.0117 lb - moles s ; t = 0, N = 0.0258 lb - mole

z z
N t
c. Integrate balance: dN = n dt N = 0.0258 + 0.0117t lb - mole air b g
0.0258 0

Check the solution in two ways:

(1) t = 0, N = 0.0258 lb - mole satisfies the initial condition
dN
( 2) = 0.0117 lb - mole air / s reproduces the mass balance
dt

d. b
t = 120 s N = 0.0258 + 0.0117 120 = 143 gb g
. lb - moles air

O 2 in tank = 0.21 143 b g

. = 0.30 lb - mole O 2

11-3
11.5 a. Since the temperature and pressure of the gas are constant, a volume balance on the gas
is equivalent to a mole balance (conversion factors cancel).
Accumulation = Input Output
dV 540 m 3
dt
=
h
1h
60 min
w m 3 min e j
b
t = 0, V = 3.00 103 m 3 t = 0 corresponds to 8:00 AM g
z zb z
V t t
dV = g e j
9.00 w dt V m 3 = 3.00 103 + 9.00t w dt t in minutes
3.00103 0 0

b. Let w i = tabulated value of w at t = 10 i 1 b g i = 1, 2, , 25

LM OP
z
240
b g b g
24 24
10 10
w dt w1 + w 25 + 4 w i + 2 w i = . + 9.8 + 4 124.6 + 2 113.4
0
3 MN i = 2, 4, i = 3, 5, 3 PQ
114

= 2488 m 3
b g
V = 3.00 103 + 9.00 240 2488 = 2672 m 3

c. Measure the height of the float roof (proportional to volume).

The feed rate decreased, or the withdrawal rate increased between data points,
or the storage tank has a leak, or Simpsons rule introduced an error.

d. REAL VW(25), T, V, V0, H

INTEGER I
DATA V0, H/3.0E3, 10./
READ (5, *) (VW(I), I = 1, 25)
V= V0
T=0.
WRITE (6, 1)
WRITE (6, 2) T, V
DO 10 I = 2, 25
T = H * (I 1)
V = V + 9.00 * H 0.5 * H * (VW(I 1) + VW(I))
WRITE (6, 2) T, V
10 CONTINUE
1 FORMAT ('TIME (MIN) VOLUME (CUBIC METERS)')
2 FORMAT (F8.2, 7X, F6.0)
END
$DATA
11.4 11.9 12.1 11.8 11.5 11.3

Results:
TIME (MIN) VOLUME (CUBIC METERS)
0.00 3000.
10.00 2974.
20.00 2944.

230.00 2683.
240.00 2674.
2674 2672
Vtrapezoid = 2674 m3 ; VSimpson = 2672 m 3 ; 100% = 0.07%
2672
Simpsons rule is more accurate.

11-4
11.6 a. b g
out L min = kV L bg out = 0.200V out = 20.0 L min Vs = 100 L
V = 300
out = 60

b. Balance on water: Accumulation = input output (L/min).

(Balance volume directly since density is constant)
dV
= 20.0 0.200V
dt
t = 0, V = 300

dV
c. = 0 = 200 0.200Vs Vs = 100 L
dt
The plot of V vs. t begins at (t=0, V=300). When t=0, the slope (dV/dt) is
20.0 0.200(300) = 40.0. As t increases, V decreases. dV / dt = 20.0 0.200V
becomes less negative, approaches zero as t . The curve is therefore concave up.
V

z z
V t
dV
d. = dt
300
20.0 0.200V 0

1 FG
20.0 0.200V
=t
IJ
0.200
ln
H 40.0 K
b g
0.5 + 0.005V = exp 0.200t V = 100.0 + 200.0 exp 0.200t b g
V = 101 b g b
. 100 = 101 L 1% from steady state g
b
101 = 100 + 200 exp 0.200t t = g b
ln 1 200 g = 26.5 min
0.200

11-5
11.7 a. A plot of D (log scale) vs. t (rectangular scale) yields a straight line through the points ( t = 1 week,
D = 2385 kg week ) and ( t = 6 weeks, D = 755 kg week ).
ln D = bt + ln a D = ae bt

b= =
b
ln D2 D1 ln 755 2385
= 0.230
g
t 2 t1 61
b g b gb g
ln a = ln D1 bt1 = ln 2385 + 0.230 1 = 8.007 a = e 8.007 = 3000
E
D = 3000e 0.230t

b. Inventory balance: Accumulation = output

dI
dt
b
= 3000e 0.230t kg week g
t = 0, I = 18,000 kg

z z
I t
3000 0.230t t
dI = 3000e 0.230t dt I 18,000 = e I = 4957 + 13,043e 0.230t
18,000 0
0.230 0

c. t = I = 4957 kg

1100 m 3 273 K 103 mol

Total moles in room: N =
11.8 a.
b g = 45,440 mol
295 K 22.4 m 3 STP

700 m 3 273 K 103 mol

Molar throughput rate: n =
min b g = 28,920 mol min
295 K 22.4 m 3 STP
SO 2 balance ( t = 0 is the instant after the SO 2 is released into the room):

b gb g
N mol x mol SO 2 mol = mol SO 2 in room
Accumulation = output.
d
dt
b g
Nx = nx
dx
N = 45, 440 dt
= 0.6364 x
n = 28,920

15
. mol SO 2
t = 0, x = . 10 5 mol SO 2 mol
= 330
45,440 mol

b. The plot of x vs. t begins at (t=0, x=3.3010-5). When t=0, the slope (dx/dt) is
. 10 5 = 210
0.6364 330 . 10 5 . As t increases, x decreases.
dx dt = 0.6364 x becomes less negative, approaches zero as t . The curve
is therefore concave up.

11-6
11.8 (contd)

0
t

c. Separate variables and integrate the balance equation:

z z
x t
dx x
= 0.6364dt ln . 10 5 e 0.6364t
= 0.6364t x = 330
3.3010 5
x 0 . 10 5
330

Check the solution in two ways:

(1) t = 0, x = 3.30 10-5 mol SO 2 / mol satisfies the initial condition;
dx
(2) . 10 5 e 0.6364t = 0.6364 x reproduces the mass balance.
= 0.6364 330
dt

45,440 moles x mol SO 2 1 m3

d. CSO 2 = . 10 2 x = 13632
= 4131 . 10 6 e 0.6364t mol SO 2 / L
1100 m 3 mol 103 L
mol SO 2
i) . 10 7
t = 2 min CSO 2 = 382
liter

ii) x = 10 6 t =
e
ln 10 6 3.30 10 5 j = 55. min
0.6364

e. The room air composition may not be uniform, so the actual concentration of the SO2
in parts of the room may still be higher than the safe level. Also, safe is on the average;
someone would be particularly sensitive to SO2.

11-7
11.9 a. Balance on CO: Accumulation=-output

N ( mol ) x ( mol CO / mol) = total moles of CO in the laboratory

kmol P p
Molar flow rate of entering and leaving gas: n ( )=
h RT
kmol kmol COFG P p IJ
Rate at which CO leaves: n (
h
)x
kmol H =
RT
x
K
CO balance: Accumulation = -output
d ( Nx )
=
P p
x
dx
=
P
px
FG IJ
dt RT dt NRT H K
E PV = NRT
dx p
= x
dt V
kmol CO
t = 0, x = 0.01
kmol

z p r
z
x t
b.
dx
x
=
V 0
dt tr =
V
p
ln 100 xb g
0.01

c. V = 350 m 3
tr =
350
700
e j
ln 100 35 10 6 = 2.83 hrs

d. The room air composition may not be uniform, so the actual concentration of CO
in parts of the room may still be higher than the safe level. Also, safe is on the
average; someone could be particularly sensitive to CO.

Precautionary steps:
Purge the laboratory longer than the calculated purge time. Use a CO detector
to measure the real concentration of CO in the laboratory and make sure it is
lower than the safe level everywhere in the laboratory.

11.10 a. Total mass balance: Accumulation = input output

dM
dt
b g
= m m kg min = 0 M is a constant = 200 kg

b. Sodium nitrate balance: Accumulation = - output

x = mass fraction of NaNO 3

b g
d xM
= xm kg minb g
dt
E
dx m m
= x= x
dt M 200
t = 0, x = 90 200 = 0.45

11-8
11.10 (contd)
c. 0.45

m = 50 kg / min
m = 100 kg / min
m = 200 kg / min
x

0
t(min)

dx m
= x < 0 , x decreases when t increases
dt 200
dx
becomes less negative until x reaches 0;
dt
Each curve is concave up and approaches x = 0 as t ;
dx
m increases becomes more negative x decreases faster.
dt

z z FG IJ
x t
dx m x m mt
= dt ln = t x = 0.45 exp
d.
0.45
x 0
M 0.45 200 200 H K
Check the solution:
(1) t = 0, x = 0.45 satisfies the initial condition;
dx m mt m
(2) = 0.45 exp( )= x satisfies the mass balance.
dt 200 200 200

0.45

0.4

0.35 m = 50 kg / m in
0.3 m = 100 kg / m in
0.25 m = 200 kg / m in
x

0.2

0.15

0.1

0.05

0
0 5 10 15 20 25
t(m in)

e. m = 100 kg min t = 2 ln x f 0.45 d i

90% x f = 0.045 t = 4.6 min
99% x f = 0.0045 t = 9.2 min
99.9% x f = 0.00045 t = 138
. min

11-9
11.11 a. Mass of tracer in tank: V m 3 C kg m 3e je j
Tracer balance: Accumulation = output. If perfectly mixed, Cout = C tank = C

dC 
d VCb g =  C bkg ming V is constant
dt
= C
V
dt m
t = 0, C = 0
V

b. z C

m0 V
dC
C
= z0
t 
V
dt ln
FG C IJ = t C = m
Hm VK V
0 V
0 FG t IJ
exp
H VK
c. Plot C (log scale) vs t (rect. scale) on semilog paper: Data lie on straight line (verifying assumption
e
of perfect mixing) through t = 1, C = 0.223 10 3 & t = 2, C = 0.050 10 3 . j e j


=
b
ln 0.050 0.223 g = 1495
. min 1
V 2 1
E
V = e30 m 3
min j e1495
. min j = 201
. m 1 3

11.12 a. In tent at any time, P=14.7 psia, V=40.0 ft3, T=68F=528R

14.7 psia 40.0 ft 3
PV
N= = m(liquid) = ft psia
3 = 01038
. lb - mole
RT 10.73 528 o R
lb - mole R
o

b. Molar throughout rate:

60 ft 3 492 R 16.0 psia 1 lb - mole
n in = n out = n = = 01695
min 528 R 14.7 psia 359 ft 3 STP
. lb - mole min
b g
Moles of O2 in tank= N (lb - mole)
FG lb - mole O IJ
H lb - mole K
2

Balance on O2: Accumulation = input output

d Nxb g = 0.35n xn 01038

.
dx
= 01695
.
dx
. b0.35 x g
b0.35 xg dt = 163
dt dt
t = 0, x = 0.21

c. z x dx
0.21 0.35 x 0
t
= 163 z
. dt ln
0.35 x
0.35 0.21
= 163
. t
b
b g
g
0.35 x
= e 1.63t x = 0.35 014
. e 1.63t
014
.

x = 0.27 t =
1
ln
LM FG
0.35 0.27 IJ OP
= 0.343 min (or 20.6 s)
163
. N H
0.35 0.21 KQ

11-10
11.13 a. b gb
Mass of isotope at any time = V liters C mg isotope liter g
Balance on isotope: Accumulation = consumption

d
b g
VC = kC
mg FG IJ b g Cancel V
dC
= kC
dt Ls
V L
H K dt
t = 0, C = C0

Separate variables and integrate

z z
C

C0
dC
C
=
0
t
kdt ln
FG C IJ = kt t = lnbC C g
HC K0 k
0

lnb0.5g ln 2
C = 0.5C0 t 1 2 = t = 12
k k

ln 2
b. t 1 2 = 2.6 hr k = = 0.267 hr 1
2.6 hr

C = 0.01C0 t=
b g = 17.2 hr
ln 0.01
t=-ln(C/C0)/k 0.267

11.14 A products

a. Mole balance on A: Accumulation = consumption

b g = kC V
d C AV
A bV constant; cancelsg
dt
t = 0, C A = C A0

zCA0
CA dC A
CA
= z0
t
kdt ln
FG C IJ = kt C
HC K
A

A0
A b g
= C A0 exp kt

b. Plot C A (log scale) vs. t (rect. scale) on semilog paper. The data fall on a straight line (verifies
assumption of first-order) through t = 213 b
. , C A = 0.0262 & t = 120.0, C A = 0.0185 . g b g
ln C A = kt + ln C A0

k =
b
ln 0.0185 0.0262 g = 353
. 10 3
min 1 k = 35
. 10 3 min 1
120.0 213
.

11.15 2 A 2 B + C

a. Mole balance on A: Accumulation = consumption

b g = kC V
d C AV 2
A bV constant; cancelsg
dt
t = 0, C A = C A0

z z LM OP 1
CA dC A t 1 1 1
= kdt + = kt C A = + kt
CA0 C A2 0 C A C A0 C A0 N Q

11-11
11.15 (contd)
1 1 1 n P RT
b. C A = 0.5C A0 + = kt 1 2 t 1 2 = ; but C A0 = A0 = 0 t 1 2 =
0.5C A0 C A0 kC A0 V RT kP0
n A = 0.5n A0
b gb
n B = 0.5n A0 mol A react. 2 mol B 2 mol A react. = 0.5n A0 g
nC = b0.5n A0 mol A react.gb1 mol C 2 mol A react.g = 0.25n A0
n A0 RT
total moles = 125
. n A0 P1 2 = 125
. = 125
. P0
V

c. Plot t 1 2 vs. 1 P0 on rectangular paper. Data fall on straight line (verifying 2nd order

d
decomposition) through t 1 2 = 1060, 1 P0 = 1 0135
. & t 1 2 = 209, 1 P0 = 1 0.683 i d i
RT 1060 209
Slope: = = 143.2 s atm
k 1 0135
. 1 0.683

k =
b1015 Kgb0.08206 L atm mol Kg = 0.582 L mol s
143.2 s atm

FG IJ
t 1 2 P0 F I
d. t1 2 =
RT
k 0 P0
exp
E
RT
ln
H K RT
= ln +GH
1 E 1
k0 R T JK
Plot t 1 2 P0 RT (log scale) vs. 1 T (rect. scale) on semilog paper.

bg
t 1 2 s , P0 = 1 atm, R = 0.08206 L atm / (mol K), T K bg
d
Data fall on straight line through t 1 2 P0 RT = 74.0, 1 T = 1 900 & i
dt 1 2 P0 RT = 0.6383, 1 T = 1 1050 i
=
b
E ln 0.6383 74.0
= 29,940 K
g R=8.314 J/ (mol K)
E = 2.49 10 5 J mol
R 1 1050 1 900

ln
1
k0
b
= ln 0.6383
1050
g
29,940
= 28.96 k 0 = 3.79 1012 L (mol s)

T = 980 K k = k 0 exp
FG E IJ
= 0.204 L (mol s)
e.
H RT K
C A0 =
0.70 120b
. atm g = 1045 10 2 mol L
b0.08206 L atm mol Kgb980 Kg .

90% conversion

C A = 010
. C A0 t =
1 1 LM
1
=
1 1 OP
LM
1 OP
N
k C A C A0 0.204 1045
. 10
Q
3
.
1045 N
10 2 Q
= 4222 s = 70.4 min

11-12
11.16 A B

a. Mole balance on A: Accumulation = consumption(V constant)

dC A k C
= 1 A
dt 1+ k2CA
t = 0, C A = C A0

z CA

C A0
1+ k2CA
k 1C A
dC A = z 0
t
dt
1 C k k
b
ln A + 2 C A C A0 = t t = 2 C A0 C A
k 1 C A0 k 1 k1
1 C
ln Ag
k 1 C A0
b g
b
b. Plot t C A C A0 vs. ln C A / C A0 g b g bC A0 g
C A on rectangular paper:

 y
   x 
t
=
1 ln C A C A0 k
+ 2
b g
b
C A0 C A k 1 C A0 C A g ;
k1 1
slope intercept

Data fall on straight line through 116.28, 0.2111 & 130.01, 0.2496
FG y1 x1 IJ FG y2 x2 IJ
H K H K
1 130.01 116.28
= = 356.62 k 1 = 2.80 10 3 L (mol s)
k 1 0.2496 0.2111 b g
k2
k1
= 130.01 + 356.62 0.2496 = 4100 b
. k 2 = 0115
. L mol g

11.17 CO + Cl 2 COCl 2

3.00 L 273 K 1 mol

a.
b g = 012035
.
303.8 K 22.4 L STP
mol gas

bC g = 0.60b012035 molg 3.00 L = 0.02407 mol L CO U

CO i .
|Vinitial concentrations
dC i = 0.40b012035
Cl 2 .
i
molg 3.00 L = 0.01605 mol L Cl |
W 2

C bt g = 0.02407 C bt g U
| Since 1 mol COCl formed requires 1 mol of each reactant
C bt g = 0.01605 C bt g V|
CO p
2
Cl 2
W p

b. Mole balance on Phosgene: Accumulation = generation

d i=
d VC p 8.75CCO CCl 2 V=3.00 L
dC p
=
d id
2.92 0.02407 C p 0.01605 C p i
dt
d1 + 58.6C + 34.3C p i 2
dt
d1941
. 24.3C i p
2

Cl 2
t = 0, C p = 0

c. Cl 2 limiting; 75% conversion C p = 0.75 0.01605 = 0.01204 mol L b g

z d1941 24.3C i
2
1 0.01204 . p
t= dC
2.92 0 d0.02407 C id0.01605 C i
p p
p

11-13
11.17 (contd)
d. REAL F(51), SUM1, SUM2, SIMP
INTEGER I, J, NPD(3), N, NM1, NM2
DATA NPD/5, 21, 51/
FN(C) = (1.441 24.3 * C) ** 2/(0.02407 C)/(0.01605 C)
DO 10 I = 1, 3
N = NPD(I)
NM1 = N 1
NM2 = N 2
DO 20 J = 1, N
C = 0.01204 * FLOAT(J 1)/FLOAT(NM1)
F(J) = FN(C)
20 CONTINUE
SUM1 = 0.
DO 30 J = 2, NM1, 2
SUM = SUM1 + F(S)
30 CONTINUE
SUM2 = 0.
DO 40 J = 3, NM2, 2
SUM2 = SUM2 + F(J)
40 CONTINUE
SIMP = 0.01204/FLOAT(NM1)/3.0 * (F(1) + F(N) + 4.0 * SUM1 + 2.0 * SUM2)
T = SIMP/2.92
WRITE (6, 1) N, T
10 CONTINUE
1 FORMAT (I4, 'POINTS ', 2X, F7.1, 'MINUTES')
END
RESULTS
5 POINTS 91.0 MINUTES
21 POINTS 90.4 MINUTES
51 POINTS 90.4 MINUTES
t = 90.4 minutes

11.18 a. Moles of CO 2 in liquid phase at any time = V cm 3 C A mols cm 3 e j e j

Balance on CO 2 in liquid phase: Accumulation = input

d
b g
VC A = kS C *A C A e FjG molsIJ dCdt = kSV eC
A *
CA j
H s K t = 0, C = 0
A
dt V
A

Separate variables and integrate. Since p A = y A P is constant, C *A = p A H is also a constant.

z0
CA dC A
C *A CA
= z
0
t kS
V
e
dt ln C *A C A j
CA

CA =0
=
kS
V
t

C *A C A kS expb g
ln
C *A
=
V
C
t 1 *A = e kSt V C A = C *A 1 e kSt V
CA
e j
1 C A C *A

11-14
11.18 (contd)

b. t=
V LM
C
ln 1 *A
OP
kS MN
CA PQ
3
V = 5 L = 5000 cm , k = 0.020 cm s , S = 78.5 cm , C A = 0.62 10
3 2 3
mol / cm

a fa f d9230 atm cm moli = 0.65 10 mol cm

C *A = y A P H = 0.30 20 atm 3 3 3

e5000 cm j lnF1 0.62 10 I = 9800 s 2.7 hr

3
3

b0.02 cm sge78.5 cm j GH 0.65 10 JK

t= 3
2

(We assume, in the absence of more information, that the gas-liquid interfacial surface area equals
the cross sectional area of the tank. If the liquid is well agitated, S may in fact be much greater than
this value, leading to a significantly lower t than that to be calculated)

11.19 A B

a. Total Mass Balance: Accumulation = input

dM d ( V )
= = v
dt dt
E
dV
= v
dt
t = 0, V = 0

A Balance: Accumulation = input consumption

dN A dN A
= C A0 v ( kC A )V C =N /V = C Ao v kN A
dt A A
dt
t = 0, N A = 0

dN A C v
b. Steady State: = 0 N A = A0
dt k

c. z z
V

0
dV =
t

0
 V = vt
vdt 

z0
NA dN A
C A0 v kN A
= z
0
t
dt

1 FG
C v kN A
ln A0
IJ C v kN A
= t A0 = e kt
k HC A0 v K C A0 v

C v C A0 v
NA = 1 expb kt g
A0
t NA =
k k

N A C A0 [1 exp( kt )]
CA = =
V kt

11-15
 11.19 (contd)

When the feed rate of A equals the rate at which A reacts, NA reaches a steady value.
NA would never reach the steady value in a real reactor. The reasons are:
(1) In our calculation, V = vt t , V .
But in a real reactor, the volume is limited by the reactor volume;
(2) The steady value can only be reached at t . In a real reactor, the reaction time is finite.

C A0 [1 exp( kt )] C
d. lim C A = lim = lim A0 = 0
t t kt t kt
NA
From part c, t , N A a finite number, V C A = 0
V
dT
11.20 a. MCv = Q W
dt
M = (3.00 L)(100
. kg / L) = 3.00 kg
Cv = C p = (0.0754 kJ / mol o C)(1 mol / 0.018 kg) = 4.184 kJ / kg o C
W = 0
dT
= 0.0797Q (kJ / s)
dt
t = 0, T = 18 o C

b. z z
100o C
dT
o
18 C
=
240 s

0
0.0797Q dt Q =
100 18
240 0.0797
= 4.287
kJ
s
= 4.29 kW

c. Stove output is much greater.

Only a small fraction of energy goes to heat the water.
Some energy heats the kettle.
Some energy is lost to the surroundings (air).

dT
11.21 a. Energy balance: MCv = Q W
dt
M = 20.0 kg
C v C p = ( 0.0754 kJ / mol C)(1 mol / 0.0180 kg) = 4.184 kJ / (kg C)
o o

a f
Q = 0.97 ( 2.50) = 2.425 kJ s
W = 0
dT
dt
b g
= 0.0290 C s , t = 0, T = 25 C

The other 3% of the energy is used to heat the vessel or is lost to the surroundings.

z z
T t
b. dT = 0.0290dt T = 25 C + 0.0290t s bg
o 0
25 C

c. b g
T = 100 C t = 100 25 0.0290 = 2585 s 43.1 min

No, since the vessel is closed, the pressure will be greater than 1 atm (the pressure at the normal
boiling point).

11-16
11.22 a. Energy balance on the bar

MCv
dTb  
dt
= Q W = UA Tb Tw b g
B
Table B.1

e
M = 60 cm
3
je7.7 g cm j = 462 g 3

Cv = 0.46 kJ (kg C), Tw = 25 C

2
U = 0.050 J (min cm C)
a fa f a fa f a fa f
A = 2 2 3 + 2 10 + 3 10 cm = 112 cm
2 2

dTb
dt
b
= 0.02635 Tb 25 C min gb g
t = 0, Tb = 95 C

b.
dTb
dt
d
= 0 = 0.02635 Tbf 25 Tbf = 25 C i
95
85
75
65
Tb( oC)

55
45
35
25
15
5
0
t

z z
Tb t
dTb
c. = 0.02635dt
T 25 0
95 b
FG T 25 IJ = 0.02635t
ln
H 95 25K
b

T bt g = 25 + 70 expb0.02635t g
b

Check the solution in three ways:

(1) t = 0, Tb = 25 + 70 = 95o C satisfies the initial condition;
dTb
(2) = 70 0.02635e 0.02635t = 0.02635(Tb 25) reproduces the mass balance;
dt
(3) t , Tb = 25o C confirms the steady state condition.
Tb = 30 C t = 100 min

11-17
11.23
12.0 kg/min 12.0 kg/min
25oC T (oC)

Q (kJ/min) = UA (Tsteam-T)

a. Energy Balance: MCv

dT
dt
= mC b g b
 p 25 T + UA Tsteam T g
M = 760 kg
m = 12.0 kg min
dT / dt = 150
. 0.0224T ( o C min), t = 0, T = 25o C
Cv C p = 2.30 kJ (min C)
UA = 115
. kJ (min C)
a f
Tsteam sat' d; 7.5bars = 167.8 C

dT
b. Steady State: = 0 = 150
. 0.0224Ts Ts = 67 C
dt

67
T(oC)

25
0
t

z
Tf
dT
= dt t =
1
z
t
. 0.0224T
150
T =
150 FG
. 0.94 exp( 0.0224t ) IJ
c.
25
. 0.0224T 0
150 0.0224
ln
0.94 H
0.0224 K
t = 40 min. T = 49.8 C

d. U changed. Let x = (UA) new . The differential equation becomes:

dT
= 0.3947 + 0.096 x ( 0.01579 + 5.721x )T
dt

z z
55 40
dT
= dt
0.3947 + 0.096 x (0.01579 + 5.721 104 x )T
25 0
L 0.3947 + 0.096x e0.01579 + 5.721 10 xj 55 OP
4
ln M
1
x M 0.3947 + 0.096 x e0.01579 + 5.721 10 x j 25 P
= 40
0.01579 + 5.721 104 4
NM PQ
x = 14.27 kJ / (mino C)

U (UA) 14.27 115

.
= = 100% = 241%
.
U initial (UA)initial 115
.

11-18
 dT
11.24 a. Energy balance: MCv = Q W
dt
W = 0, Cv = 177
. J g C
M = 350 g, Q = 40.2W = 40.2 J s
dT
= 0.0649 C s b gU|V T = 20 + 0.0649tbsg
dt
t = 0, T = 20 C |W T = 40 C t = 308 s 51. min
b. The benzene temperature will continue to rise until it reaches Tb = 801
. C ; thereafter the heat
input will serve to vaporize benzene isothermally.
. 20
b
Time to reach Tb neglect evaporation : t =
801
g
0.0649
= 926 s

b
Time remaining: 40 minutes 60 s min 926 s = 1474 s g
b gb
Evaporation: H = 30.765 kJ mol 1 mol 78.11 g 1000 J kJ = 393 J g
v gb g
b gb g
Evaporation rate = 40.2 J s / 393 J g = 0102
. g s
Benzene remaining = 350 g b0102
. g sgb1474 sg = 200 g

c. 1. Used a dirty flask. Chemicals remaining in the flask could react with benzene. Use a clean flask.
2. Put an open flask on the burner. Benzene vaporizes toxicity, fire hazard.
Use a covered container or work under a hood.
3. Left the burner unattended.
4. Looked down into the flask with the boiling chemicals. Damage eyes. Wear goggles.
5. Rubbed his eyes with his hand. Wash with water.
6. Picked up flask with bare hands. Use lab gloves.
7. Put hot flask on partners homework. Fire hazard.

60 m 3
273 K 1 kg - mole
Moles of air in room: n = = 2.58 kg - moles
11.25 a.
283 K 22.4 m 3 STP b g
dT
Energy balance on room air: nCv = Q W
dt
b
Q = m H H O, 3bars, sat' d 30.0 T T
s v 2 g b 0 g
W = 0
nCv
dT
dt
=m s H v 30.0 T T0 b g
N = 2.58 kg - moles
Cv = 20.8 kJ (kg - mole C)
H v = 2163 kJ kg from Table B.6 b g
T0 = 0 C
dT
dt
= 40.3m s 0.559T C hr b g
t = 0, T = 10 C
(Note: a real process of this type would involve air escaping from the room and a constant pressure
being maintained. We simplify the analysis by assuming n is constant.)

11-19
11.25 (contd)
0.559T
b. At steady-state, dT dt = 0 40.3m s 0.559T = 0 m s =
40.3
T = 24 C m s = 0.333 kg hr

c. Separate variables and integrate the balance equation:

z10
Tf dT
40.3m s 0.559T
= z
0
t
dt
m s = 0.333
z 23 dT
10 13.4 0.559T
=t

T f = 23C E
t=
1 LM
13.4 0.559 23 b g OP = 4.8 hr
ln
MN
0.559 13.4 0.559 10 b g PQ
11.26 a. Integral energy balance t = 0 to t = 20 min b g
Q = U = MCv T =
250 kg 4.00 kJ b60 20g C = 4.00 10 4
kJ
kg C

4.00 104 kJ 1 min 1 kW

Required power input: Q = = 333
. kW
20 min 60 s 1 kJ s

b. Differential energy balance: MCv

dT
dt
= Q M = 250 kg
dT
dt
= 0.001Q t bg
Cv = 4.00 kJ kgC
t = 0, T = 20 C

z z z
T t t
Integrate: dT = 0.001 Q dT T = 20 o C + Qdt

20o C 0 0

Evaluate the integral by Simpson's Rule (Appendix A.3)

z
600 s
b
 = 30 33 + 4 33 + 35 + 39 + 44 + 50 + 58 + 66 + 75 + 85 + 95
Qdt
3
g
0

b
+2 34 + 37 + 41 + 47 + 54 + 62 + 70 + 80 + 90 + 100 = 34830 kJ g
b g e
T 600 s = 20o C + 0.001 oC / kJ 34830 kJ = 54.8 C jb g

c. Past 600 s, Q = 100 +

10 kW
60 s
t 600 s = t 6 b g
LM OP
z
 = 20 + 0.001M Qdt
z z t P
t 600 t
T = 20 + 0.001 Qdt MM  + 6 P
dt
PP
0
MN
0
34830
600
Q
0.001 F t 600 I
t bsg = b g
2 2
T = 54.8 +
6 H6G
2 JK
12000 T 24.8

T = 85 C t = 850 s = 14 min, 10 s explosion at 10:14 + 10 s

11-20
11.27 a. Total Mass Balance:
Accumulation=Input Output
E dV
dM tot d( V) =constant = 4.00 L / s
=m
i m
o = 8.00 4.00 dt
dt dt t = 0, V0 = 400 L

KCl Balance:
dM KCl d( CV )
Accumulation=Input-Output =m
 i, KCl m
 o, KCl = 100
. 8.00 4.00C
dt dt
dC 8 8C
dC dV dV dt = 4 =
V +C = 8 4C dt V
dt dt t = 0, C 0 = 0 g / L

b. (i)The plot of V vs. t begins at (t=0, V=400). The slope (=dV/dt) is 4 (a positive constant).
V increases linearly with increasing t until V reaches 2000. Then the tank begins to overflow
and V stays constant at 2000.

2000
V

400

0
t

(ii) The plot of C vs. t begins at (t=0, C=0). When t=0, the slope (=dC/dt) is (8-0)/400=0.02.
As t increases, C increases and V increases (or stays constant) dC/dt=(8-8C)/V becomes
less positive, approaches zero as t . The curve is therefore concave down.

1
C

0
t

c.
dV
dt
=4 z
400
V
z t
dV = 4 dt V = 400 + 4t
0

11-21
11.27 (contd)
dC 8 8C dC 1 C
= =
dt V V = 400 + 4 t dt 50 + 0.5t

zC dC
0 1 C
=
t
z dt
0 50 + 0.5t
C t
ln(1 C ) 0 = 2 ln(50 + 0.5t ) 0

50 + 0.5t
ln(1- C)-1 = 2 ln = ln(1 + 0.01t )2
50
1 1
= (1 + 0.01t )2 C = 1
1- C (1 + 0.01t )2
When the tank overflows, V = 400 + 4t = 2000 t = 400 s
1
C = 1- = 0.96 g / L
1+ 0.01 400
2
b g
11.28 a. Salt Balance on the 1st tank:
Accumulation=-Output
E
d(CS1V1 ) dC v
= CS1v S1 = CS1 = 0.08CS1
dt dt V1
CS1 ( 0) = 1500 500 = 3 g / L

Salt Balance on the 2nd tank:

Accumulation=Input-Output
E
d(CS2V2 ) dC v
= CS1v CS 2 v S2 = ( CS1 CS 2 ) = 0.08( CS1 CS 2 )
dt dt V2
CS 2 ( 0) = 0 g / L

Salt Balance on the 3rd tank:

Accumulation=Input-Output
E
d(CS3V3 ) dC v
= CS 2 v CS 3v S3 = ( CS 2 CS 3 ) = 0.04( CS 2 CS 3 )
dt dt V3
CS 3 ( 0) = 0 g / L

b.

3
CS1, CS2, CS3

CS1

CS2

CS3

0
t

11-22
 11.28 (contd)

The plot of CS1 vs. t begins at (t=0, CS1=3). When t=0, the slope (=dCS1/dt) is 0.08 3 = 0.24 .
As t increases, CS1 decreases dCS1/dt=-0.08CS1 becomes less negative, approaches zero as
t . The curve is therefore concave up.

The plot of CS2 vs. t begins at (t=0, CS2=0). When t=0, the slope (=dCS2/dt) is 0.08(3 0) = 0.24 .
As t increases, CS2 increases, CS1 decreases (CS2 < CS1) dCS2/dt =0.08(CS1-CS2) becomes less
positive until dCS2/dt changes to negative (CS2 > CS1). Then CS2 decreases with increasing t as well
as CS1. Finally dCS2/dt approaches zero as t. Therefore, CS2 increases until it reaches a
maximum value, then it decreases.

The plot of CS3 vs. t begins at (t=0, CS3=0). When t=0, the slope (=dCS3/dt) is 0.04(0 0) = 0 .
As t increases, CS2 increases (CS3 < CS2) dCS3/dt =0.04(CS2-CS3) becomes positive CS2
increases with increasing t until dCS3/dt changes to negative (CS3 > CS1). Finally dCS3/dt
approaches zero as t. Therefore, CS3 increases until it reaches a maximum value then it
decreases.

c.
3

2.5
CS1, CS2, CS3 (g/L)

2
CS1
1.5

1 CS2

CS3
0.5

0
0 20 40 60 80 100 120 140 160
t (s)

11.29 a. (i) Rate of generation of B in the 1st reaction: rB1 = 2r1 = 0.2C A

(ii) Rate of consumption of B in the 2nd reaction: rB 2 = r2 = 0.2CB2

b. Mole Balance on A:
Accumulation=-Consumption
E
d ( C AV ) dC A
= 01
. C AV = 01. CA
dt dt
t = 0, C A0 = 100
. mol / L

Mole Balance on B:
Accumulation= Generation-Consumption
E
d ( CBV ) dCB
= 0.2C AV 0.2CB2V = 0.2C A 0.2CB2
dt dt
t = 0, CB 0 = 0 mol / L

11-23
11.29 (contd)
c.

CC

CA, CB, CC
1

CB

CA

0
t

The plot of CA vs. t begins at (t=0, CA=1). When t=0, the slope (=dCA/dt) is 01
. 1 = 01
. .
As t increases, CA decreases dCA/dt=-0.1CA becomes less negative, approaches zero as
t. CA0 as t. The curve is therefore concave up.

The plot of CB vs. t begins at (t=0, CB=0). When t=0, the slope (=dCB/dt) is 0.2(1 0) = 0.2 .
As t increases, CB increases, CA decreases ( C B2 < CA) dCB/dt =0.2(CA- C B2 ) becomes less positive
until dCB/dt changes to negative ( CB2 > CA). Then CB decreases with increasing t as well as CA.
Finally dCB/dt approaches zero as t. Therefore, CB increases first until it reaches a maximum
value, then it decreases. CB0 as t.

The plot of CC vs. t begins at (t=0, CC=0). When t=0, the slope (=dCC/dt) is 0.2(0) = 0 . As t
increases, CB increases dCc/dt =0.2 C B2 becomes positive also increases with increasing t
CC increases faster until CB decreases with increasing t dCc/dt =0.2 CB2 becomes less positive,
approaches zero as t so CC increases more slowly. Finally CC2 as t. The curve is therefore
S-shaped.

d.
2.2
2
1.8
CC
CA, CB, CC (mol/L)

1.6
1.4
1.2
1
0.8
0.6 CB
0.4 CA
0.2
0
0 10 20 30 40 50
t (s)

11-24
11.30 a. When x = 1, y = 1 .
ax x =1, y =1 a
y= 1= a = 1+ b
x+b 1+ b

xp *C5 H12 ( 46o C )

b. Raoults Law: pC5 H12 = yP = xp *C5 H12 ( 46o C ) y =
P
1060.793
(6.84471 )
Antoine Equation: p *C5 H12 (46o C) = 10 46 + 231.541
= 1053 mm Hg
o
xp *C5 H12 ( 46 C ) 0.7 1053
y= = = 0.970
P 760

R| y = ax x=0.70, y=0.970
0.970 =
0.70a
""(1) |Ra = 1078
.
S| x + b 0.70 + b S
TFrom part (a), a = 1+ b"""""""""""(2) |Tb = 0.078

c. Mole Balance on Residual Liquid:

Accumulation=-Output
E
dN L
= nV
dt
t = 0, N L = 100 mol

Balance on Pentane:
Accumulation=-Output
E
d(NLx) dN L dx ax
= nV y x + NL = nV
dt dt dt x+b
E
dN L / dt = nV
dx
= V
n ax FG
x
IJ
dt NL x + b H K
t = 0, x = 0.70

d. Energy Balance: Consumption=Input

E 
 H vap =27.0 kJ/ mol
Q
nV H vap = Q nV =
b 27.0 kJ / mol g
dN L t = 0, N L = 100 mol 
Qt
From part (c), = nV N L = 100 nV t = 100
dt 27.0
nV Q 27.0
= 
NL Qt
100 -
27.0
Substitute this expression into the equation for dx/dt from part (c):

11-25
11.30 (contd)

dx
= V
n FG
ax
x =
IJ
Q 27.0 ax
x
FG IJ
dt H
NL x + b
100 -
K

Qt x+b H K
27.0
x(0) = 0.70

e.

1
0.9
0.8
y (Q=1.5 kJ/s)
0.7
0.6
x (Q=1.5 kJ/s)
x, y

0.5
0.4
x (Q=3 kJ/s)
0.3 y (Q=3 kJ/s)
0.2
0.1
0
0 200 400 600 800 1000 1200 1400 1600 1800
t(s)

f. The mole fractions of pentane in the vapor product and residual liquid continuously decrease over a
run. The initial and final mole fraction of pentane in the vapor are 0.970 and 0, respectively. The
higher the heating rate, the faster x and y decrease.

11-26