E

FG M IJ kM
H M K
.
.
. .
.
.
.







CHAPTER ELEVEN


11.1


a.






b.


The peroxide mass fraction in the effluent liquid equals that in the tank contents, which is:
M p
x p =
M
Therefore, the leakage rate of hydrogen peroxide is m`1 M p / M
Balance on mass : Accumulation = input output


dM
= m` 0 m`1
dt
t = 0, M = M 0 (mass in tank when leakage begins)

Balance on H 2O 2: Accumulation = input output consumption
E
dM p
dt


= m` 0 x p 0 m`1



p



p
t = 0, M p = M p0


11.2


a.


Balance on H3PO4: Accumulation = input
Density of H3PO4: ) = 1834 g / ml .
Molecular weight of H3PO4: M = 9800 g / mol .

Accumulation =
dn p
dt

(kmol / min)

Input =
E
20.0 L 1000 ml 1.834 g
min L ml
mol 1 kmol
98.00 g 1000 mol
= 0.3743 kmol / min
dn p
dt
= 0.3743
t = 0, n p0 = 150 0.05 = 7.5 kmol



b.


np


t
dn p = 03743 dt n p = 75 + 0.3743t (kmol H3PO 4 in tank )
7.5 0
x p =
np
n
=
n p
n0 + n p n p0
=
7.5 + 0.3743t
150 + 0.3743t
kmol H 3PO4
kmol



c.



015 =


7.5 + 03743t
150 + 03743t



t = 471. min








11-1
` ` ` ` h
` `
b450g + 4b25gb750g t = 1.54 h, 19.54 h
b450g + 4b25gb750 2693g t = 719. h ,1081. h
R|750 + 450t - 25t b0 o t o 719. and 1081. o t o 1954. g (tank is filling or draining)
||T0
.
.








11.3








a.







mw = a + bt bt = 0, mw = 750g & bt = 5, mw = 1000g mwbkg hg = 750 + 50tbg
Balance on methanol: Accumulation = Input Output
M = kg CH3OH in tank
= m f mw = 1200 kg h b750 + 50tg kg h
-170dM
dt
E
dM
dt
= 450 50tbkg h g
t = 0, M = 750 kg


b.

M


dM =

t

b450 50tgdt
750
E
0
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;

(2)
dM
dt
= 450 50t reproduces the mass balance.


c.

dM
dt

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

M = 0 = 750 + 450t 25t 2

t =
450
2
2b25g


d.


3.40 m 3 103 liter 0.792 kg
1 m 3 1 liter



= 2693 kg (capacity of tank)
M = 2693 = 750 + 450t 25t 2

t =

450
2
2b25g
Expressions for M(t) are:
2
M(t) = S2693 (719 o t o 10.81) (tank is overflowing)
(19.54 o t o 2054) (tank is empty, draining
as fast as methanol is fed to it)




11-2







11.3 (contd)


3000
2500
2000
1500
1000
500
0
0 5 10 15 20
t(h)




11.4 a.




Air initially in tank: N 0 =



10.0 ft 3



492 R 1
lb - mole




532 R 359 ft 3bSTPg




= 0.0258 lb - mole
Air in tank after 15 s:

Pf V N f RT Pf 0.0258 lb - mole 114.7 psia
P0V N0 RT P0 14.7 psia
.
15 s


b.


Balance on air in tank: Accumulation = input

dN
dt

= 0.0117blb - moles sg ; t = 0 , N = 0.0258 lb - mole


c.


Integrate balance:

N

t
dN = n` dt N = 0.0258 + 0.0117t lb - mole air

g
0.0258 0
Check the solution in two ways :
(1) t = 0, N = 0.0258 lb - mole satisfies the initial condition

(2)
dN
dt
= 0.0117 lb - moleair / s reproduces the mass balance


d.



O 2
in
tan
k =
0.2
1
b
143
g = 030 lb - mole O 2

t = 120 s N = 0.0258 +b0.0117gb120g = 143 lb - moles air


M
(
k
g
)

= N f = N0 = = 0.2013 lb - mole
b02013 0.0258g lb - mole air = 0.0117 lb - mole air s
Rate of addition: n` =
b
. .
.
















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
dt

=

540 m
h
3

1h
60 min

w ( m3 min

)
t = 0, V = 3.00 103 m3 ( t = 0 corresponds to 8:00 AM)
V
+
3.0010 3
t t
dV = + (9.00 w ) dt V m3 = 3.00 103 + 9.00t + wdt t in minutes
0 0


b.




240 24 24

0







=
2
4
8
8
m
3








V =
300 1
03 +
9.00
b240
g
2488 =
2672
m3

Let wi = tabulated value of w at t = 10bi 1g

i = 1, 2, ., 25

10
. . .
3
c.



d.
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.

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
1
2
CONTINUE
FORMAT ('TIME (MIN) VOLUME (CUBIC METERS)')
FORMAT (F8.2, 7X, F6.0)
END
$DATA
11.4 11.9 12.1 11.8 11.5 11.3
.
Results :
TIME (MIN)
0.00
10.00
20.00
`
( )
` `
L
O
10
` wdt E ` w1 + ` w 25 + 4 ` w i + 2 ` w i =
M P i=2, 4,. i= 3, 5, .
3
b g b g 114 + 98 + 4 1246 + 2 113.4
.
` `
.
230.00
VOLUME (CUBIC M ETERS)
3000.
2974.
2944.
.
2683.
240.00 2674.
Vtrapezoid = 2674 m 3 ; VSimpson = 2672 m 3 ;

2674 2672
2672

100% = 0 .07%
Simpsons rule is more accurate .



11-4


V

` out = 0.200V ` out = 20.0 L min Vs = 100 L
` out= 60
` L
.
.
.
dV
F I = t
H K
1 20.0 0.200V
40.0
g = 26.5 min
b g
lnb1 200
.









11.6









a.








out bL ming = kV bg










V = 300


b.


Balance on water: Accumulation = input output (L/min).
(Balance volume directly since density is constant)
dV
dt

= 20.0 0200V
t = 0 , V = 300



c.


dV
dt



= 0 = 200 0200Vs Vs = 100 L
The plot of V vs. t begins at (t=0, V=300). When t=0, the slope (dV/dt) is
200 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.
















t




d.



V t
= dt
300 20.0 0.200V 0

ln
0.200
0.5 + 0.005V = expb 0.200tg V = 100.0 + 200.0 expb0.200t
V = 101b100g = 101 L b1% from steady stateg
101 = 100 + 200 exp 0.200t t =














0.200












11-5








g
l n D2D1 l nb755 2385 g
t 2 t1
6 1
b = 3000 e 0.230t kg week
.
3000 0.230t
b g = 45, 440 mol
b g = 28,920 mol min
x

n` = 28,920
`
15 mol SO 2
.
. . .









11.7









a.














b.









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 = = = 0230
ln a = ln D1 bt1 = lnb2385g + b0.230gb1g = 8.007 a = e 8.007 = 3000
E
D = 3000e 0.230t


Inventory balance: Accumulation = output
g
-170dI
dt
t = 0, I = 18,000 kg





c.
I t
dI = 3000e 0.230 t dt I 18,000 =
18, 000 0

t = I = 4957 kg


0.230

e

t
0

I = 4957 + 13,043e 0.230 t




11.8




a.



Total moles in room: N =



1100 m3



273 K 103 mol
295 K 22.4 m 3 STP

Molar throughput rate: n` =
700 m 3
min
273 K 103 mol
295 K 22.4 m3 STP
SO 2 balance ( t = 0 is the instant after the SO 2 is released into the room):
Nbmolgbmol SO2 molg = mol SO2 in room
Accumulation = output.
d
d t
bNxg = nx
dx
N =45,440 dt

= 0.6364x

t = 0, x =

.
45,440 mol

= 330 105 mol SO2 mol



b.



The plot of x vs. t begins at (t=0, x=3.30 10-5). When t=0, the slope (dx/dt) is
06364 330 10 5 = 210 10 5. As t increases, x decreases.
dx dt = 0.6364x becomes less negative, approaches zero as t . The curve
is therefore concave up.







11-6
x

.
.
. .
.
. .
.







11.8 (contd)















0
t




c.




Separate variables and integrate the balance equation:
x

3.30105
dx
x
t
= 06364dt ln
0
x
330 10

5

= 06364t x = 330 105 e 0.6364t

Check the solution in two ways :
(1) t = 0, x = 3.30 10-5 mol SO2 / mol satisfies the initial condition;

(2)
dx
dt
= 0.6364 330 105 e 0.6364 t = 0.6364x reproduces the mass balance.


d.

CS O2 =

45,440 moles
1100 m 3

x mol SO2
mol

1 m 3
103 L

= 4131102 x = 13632 106 e 0.6364t mol SO2 / L

i) t = 2 min CSO2
= 382 107
mol SO2
liter



ii)


x = 10 6 t =

lne10 6 3.30 105



0.6364

j = 55. min


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
kmol P p
Molar flow rate of entering and leaving gas: n ( ) =
FG IJ
Rate at which CO leaves: n` (
H K
F I
` p x
d( Nx ) P p dx P
H K
dx p
`
` p r
e j
ln 100 35 10 6 = 283 hrs tr =
` `
b g = xm`bkg ming
E
dx m
m








11.9








a.








Balance on CO : Accumulation=-output

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


h RT
kmol kmol CO P p
) x = x
h kmol RT
CO balance: Accumulation = -output

= x =
dt RT dt NRT
E PV = NRT
= x
dt V
kmol CO
t = 0, x = 0.01
kmol


b.

x

0. 01


dx
x


=

t

V 0


dt tr =


V
` p

lnb100 xg


c.




d.











11.10 a.

V = 350 m3
350
.
700


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.


Total mass balance: Accumulation = input output
dM
dt
= m mbkg ming = 0 4 M is a constant = 200 kg

b.

Sodium nitrate balance: Accumulation = - output
x = mass fraction of NaNO3
d xM
dt


= x = x
dt M 200
t = 0, x = 90 200 = 0.45



11-8




x

x

FG
H
IJ
`
dx m m t m
`
.






11.10 (contd)
c.

0.45













0


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








t(min)

dx
dt


=

m`
200


x < 0 , x decreases when t increases
dx
dt

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

d.
x

0.45

dx
x

=
t

0
m`
M

dt ln

x
0.45

=
m`
200

t x = 0.45 exp

mt
200

K
Check the solution :
(1) t = 0, x = 0.45 satisfies the initial condition;
(2) = 0.45 exp( ) = x satisfies the mass balance.
dt 200 200 200

0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0

m` = 50 kg / min
m` = 100 kg / min
m` = 200 kg / min
0 5 10 15 20 25
t(min)

e.

m = 100 kg min t = 2 lndx f 0.45i
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: Vem3 jekg m3







j
Tracer balance : Accumulation = output. If perfectly mixed, C out = C tank = C


d VC
dt


V is constant

=
dt V
t = 0, C =


C

m0
V


b.


C

m0 V


dC
C


=


t
0 V


dt ln

F

C
m0 V

I

=

`t
V


C =


m0
V


exp



V

c.











11.12 a.

Plot C (log scale) vs t (rect. scale) on semilog paper: Data lie on straight line (verifying assumption
of perfect mixing) through et = 1, C = 0223 10 3 j & et = 2, C = 0.050 10 3 j .

V 2 1


min


In tent at any time, P=14.7 psia, V=40.0 ft 3, T=68F=528 R

N =

PV
RT

= m(liquid) =
14.7 psia
ft 3 psia
10.73
lb - mole o R
40.0 ft 3
528 o R

= 01038 lb - mole

b.

Molar throughout rate:
60 ft 3 492 R 16.0 psia 1 lb - mole




2

min 528 R 14.7 psia 359 ft 3bSTPg
= 01695 lb - mole min

Balance on O2: Accumulation = input output

d Nx
dt dt



c.


x
0.21 0.35 x


t

0



.



b
0
.
3
5

0
21g


b0.35 xg
C
b g = ` C bkg ming
dC
z z
`
FG IJ
`t
H K GH JK
l nb0. 050 0. 223g
= = 1.495 min 1
E
V = e30 m j e1.495 min j = 201 m
3 1 3
.
.
n`in = n`out = n` =
Moles of O2 in tank= N (lb - mole) F lb - mole O I
H lb - mole K
.
b g = 0.35n` xn` 0.1038 dx = 0.1695b0.35 xg dxdt = 1.63b0.35 xg
t = 0, x = 0.21
z
dx
z
= 163dt ln
.
.
= e 1.63t x = 0.35 014e 1.63t
LM FG IJOP x = 0.27 t = ln = 0.343 min (or 20.6 s)
N H KQ
.
.


= 163t
035 x
.
014
1 0.35 0.27
1.63 0.35 0.21








11-10
C
FG IJ b g
H K
L s
= kC
z z FC I = kt t = lnbC C g
dC
= kdt ln
0
t 1 2 = 2.6 hr k =
C = 0.01C0
b g = 17.2 hr
.
b g = kC V
dt
z z
dC A
= kdt ln
C A 0 C A
FG C IJ = kt C
H C K
b g b g . .
l n b0. 0 1 85 00 26 2
120.0 213
.
b g = kC V bV constant; cancelsg
dt
z z
dC A
= kdt
CA 0 CA
LM OP







11.13 a.






Mass of is otope at any time = Vblitersgbmg isotope liter
Balance on isotope: Accumulation = consumption






g

d
d t

bVCg = kC

mg


V L

Cancel V
dC
dt
t = 0, C = C0

Separate variables and integrate
C t
C0 C 0 H C0 K k

C = 0.5C0 t1 2

=
lnb0.5g
k

t


12

=

ln 2
k


b.


ln 2
2.6 hr


t=-ln(C/C0)/k


= 0267 hr 1

ln 0.01
t =
0.267


11.14 A products

a.

Mole balance on A: Accumulation = consumption
d C AV


A
bV constant; cancelsg
t = 0, C A = C A0
C A t




0



A
A0




A


= C A0 expbktg


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, C A = 00262 & t = 120.0, C A = 0.0185 .
ln C A = kt + ln C A0

k =
.

g = 353. 10


3


min 1 k = 35 10 3 min 1


11.15 2 A 2 B + C

a.

Mole balance on A: Accumulation = consumption
d C AV 2
A

t = 0, C A = C A0
CA t




0



1
C A



+



1
CA0



= kt C A =




N



1
C A0



+ kt




Q


1




11-11


; but C A0 = A0 =
.
. . .
.
= = 1432 s atm
1060 209
1 0135 1 0683
b1015 Kgb008206 L atm mol Kg = 0582 L mol s
k =
143.2 s atm
FG IJ
H K
GH JK
s K
.
FG
H
IJ
b0.08206 L atm mol Kgb980 Kg = 1045 10
. .
L O
C A = 0.10C A0 t = = LM OP






11.15 (contd)

b.

C A = 0.5C A0
1
0.5C A0

+
1
CA0

= kt1 2 t1 2 =
1
kC A0
n
V
P0
RT

t1 2 =

RT
kP0
n A = 0.5n A0
n B = b0.5n A0 mol A react.gb2 mol B 2 mol A react.g = 05n A0
nC = b0.5n A0 mol A react.gb1 mol C 2 mol A react.g = 0.25n A0
total moles = 125n A0 P1 2 = 125
n A0 RT
V
= 125P0

c.

Plot t1 2 vs. 1 P0 on rectangular paper. Data fall on straight line (verifying 2nd order
decomposition) through dt1 2 = 1060, 1 P0 = 1 0135i & dt1 2 = 209, 1 P0 = 1 0.683i

Slope:

RT
k


. .




.

.




.



d.


t 1 2 =


RT
k 0 P0



exp


E
RT


ln

F

t1 2 P0
RT

I

= ln


1
k 0


+


E 1
R T
Plot t1 2 P0 RT (log scale) vs. 1 T (rect. scale) on semilog paper.
t1 2bg, P0 = 1 atm, R = 0.08206 L atm / (mol K), Tbg
Data fall on straight line through dt1 2 P0 RT = 74.0, 1 T = 1 900i &
d
t
1 2 P0 RT = 0.6383, 1 T = 1 1050i

E
R

=
lnb0.6383 74 .0g
1 1050 1 900

= 29,940 K

R=8.314 J/ (mol K)

E = 2 .49 105 J mol

l n
1
k 0
= lnb06383g
29 ,940
1050

= 28.96 k 0 = 3.79 10

12

L (mol s)


e.

T = 980 K k = k 0 exp

E
RT

K
= 0.204 L (mol s)

C A0 =
070b120 atmg

.

2

mol L

90% conversion

1 1 1
k N C A C A0 Q
= 4222 s = 70.4 min

1 1

0.204 N1.045 10


3



1
1.045 10 2

Q









11-12
z
dC A =
z
dt b g b g + 2 C A C A0 = t t = 2 C A0 C A

b g
= +
FG IJ FG IJ
H K H K
k1 k
.
.
. . .
b g = 0.12035 mol gas
bC g = 0.60b012035 molg 3.00 L = 0.02407 mol L CO U|
dC i = 0.40b012035 molg 3.00 L = 0.01605 mol L Cl V|Winitial concentrations
.
Cl 2 i
.
btg = 0.02407 C btg U|
btg = 0.01605 C btg V|W Since 1 mol COCl formed requires 1 mol of each reactant
C
d i =
875CCO C Cl 2
2.92d0.02407 Cpi d0. 01605 Cp
d1941 24.3C i
=
.
.
z
d1941 24.3C i







11.16 A B

a.

Mole balance on A: Accumulation = consumption(V constant)
dC A
dt

=
k1C A
1 + k 2 C A
t = 0, C A = C A0
CA 1 + k 2C A
CA0 k1C A

t

0

1
k 1


l n

C A
C A0

k k
k1 k1

1
k1


l n

C A
C A0


b.

Plot t bC A C A0 g vs. lnbC A / C A0

g bC


A 0

C A g on rectangular paper:
y
t 1 ln C A C A0 k 2
bC A0 C A g ; C A0 C A 1
slope intercept
y1 x1 y 2 x 2
Data fall on straight line through 116.28, 02111 & 130.01, 0.2496




1
k 1


=

13001 116.28
0.2496 b0.2111g


= 356.62 k1 = 2 .80 10 3 L (mol s)
k 2
k1
= 130.01 + 356.62b02496g = 4100 k 2 = 0115 L mol


11.17 CO + Cl 2 COCl 2


a.

3.00 L

273 K 1 mol
303.8 K 22.4 L STP

CO i

2

CCO p
2
Cl 2 p

b.

Mole balance on Phosgene: Accumulation = generation


d VC p
dt


.
d1 + 586CCl 2 + 34.3C p



i



2


V=3.00 L

dC p
dt



. p
t = 0, C p = 0


2
i


c.

Cl 2 limiting; 75% conversion C p = 075b0.01605g = 0.01204 mol L

t =

1
2.92

0.01204
0
2
. p
d0.02407 C p id0.01605 C p i

dC


p



11-13
.
FjG molsIJ dCdt = kSV eC
H s K t = 0, C = 0
*
z z e j
dC A
kS kS
= dt ln C *A C A =
C A CA C A = 0
kS expb g
*







11.17 (contd)
d.













20



30



40



10
1
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)
CONTINUE
SUM1 = 0.
DO 30 J = 2, NM1, 2
SUM = SUM1 + F(S)
CONTINUE
SUM2 = 0.
DO 40 J = 3, NM2, 2
SUM2 = SUM2 + F(J)
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
CONTINUE
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 = 904 minutes



11.18 a.


Moles of CO2 in liquid phase at any time = Vecm 3jC A emols cm 3
Balance on CO 2 in liquid phase: Accumulation = input


j


d
d t

bVC A g = kSeC A C A



|V

A




A

*
A

C A

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

CA t C A
t
0 0 V V


ln


C *A C A
C *A


=



V


t 1


CA
C*A


= e kSt V C A = C Ae1 e kSt V


j
1 CA C*A







11-14


lnL1 OP
a fa f d9230 atm cm moli = 0.65 10 mol cm
C *A = y A P H = 0.30 20 atm
.
F 0.62 10 I = 9800 s 2.7 hr
e5000 cm j
3
b002. cm sge785. cm j H 0.65 10 JK
= )v`
=
E
`
z z
vdt V = vt` `
dV =
z z
dN A
=
C A0 v` kN A
F I
1 C A0 v kN A
H K
C A0 v`
`







11.18 (contd)


b.


t =

V
kS


NM

C A
C *A


QP
V = 5 L = 5000 cm3 , k = 0.020 cm s , S = 785 cm 2 , C A = 0.62 10 3 mol / cm3
3 3 3


t =

3


2 lnG1 3

(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 )
dt dt

dV
dt

= v`
t = 0, V = 0

A Balance : Accumulation = input consumption
dN A
dt
= C A0v (kC A )V CA=NA/V
dN A
dt
= C Ao v` kN A
t = 0 , N A = 0


b.


Steady State:


dN A
dt


= 0 N A =

C A0 v`
k


c.


V t

0 0
NA t
0 0

ln










k





dt









= t








C A0 v` kN A
C A0 v`








= e kt

N A

=
C A0v
k
1 expbktg

t N A =
C A0 v`
k


C A =


N A
V


=

C A0[1 exp(kt )]
kt




11-15
(1) In our calculation, V = vt` t , V .
lim C A = lim
= Q` W`
. .
z z o
a f
z z
0 25 C
s.








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:

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.


d.



t t

C A0 [1 exp(kt )]
kt


= lim
t

CA0
kt


= 0
From part c, t , N A a finite number, V C A =
N A
V
0
11.20 a.
MCv
dT
dt
M = (3.00 L)(100 kg / L) = 300 kg
Cv = C p = (0.0754 kJ / mol o C)(1 mol / 0.018 kg) = 4.184 kJ / kg o C
W` = 0
dT
dt
= 0.0797Q` (kJ / s)

t = 0, T = 18 o C


b.

100o C 240 s
dT =
18 C 0


0.0797 Q` 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).


11.21 a.


Energy balance: MCv

dT
dt

= Q` W`
M = 20.0 kg
C v H C p = ( 0.0754 kJ / mol o C)(1 mol / 0.0180 kg) = 4.184 kJ / (kg o C)
Q` = 0.97 (2.50) = 2.425 kJ s
W` = 0
dT
dt
= 0.0290 b C sg , t = 0 , T = 25 C

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

b.
T
t

o

dT =

00290dt T = 25 C + 0.0290tbg

c.
T = 100 C t = b100 25g 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


T
b
(
o
C
)

` `
B
e j e7. 7gcm j= 462g
M = 60 cm
U = 0.050 J (min cm C)
dTb
T 25
FG T 25IJ = 002635t
H 95 25K
ln .
.







11.22 a. Energy balance on the bar


MCv

dTb
dt

= Q W = UAbTb Tw

g
Table B.1
3 3
Cv = 0.46 kJ (kg C), Tw = 25 C
2
A = 2 a2fa 3f + a2fa10f + a3fa10f cm2 = 112 cm2

dTb
dt
= 0.02635bTb 25gbC min g
t = 0, Tb = 95 C


b.


dTb
dt

= 0 = 0.02635dTbf 25i Tbf = 25 C






9 5
8 5
7 5
6 5
5 5
4 5
3 5
2 5
1 5
5


















0



















t

c.
Tb t
= 0.02635dt
95 b 0
b

Tbbtg = 25 + 70 expb0.02635tg

Check the solution in three ways :
(1) t = 0, Tb = 25 + 70 = 95o C satisfies the initial condition;

(2)
dTb
dt
= 70 0.02635e 0.02635 t = 002635(Tb 25) reproduces the mass balance;
(3) t , Tb = 25o C confirms the steady state condition.
Tb = 30 C t = 100 min











11-17










T
(
o
C
)

`
.
.
FG IJ
. . .
. . .
.
z z
=
0.3947 + 0.096x ( 0.01579 + 5721 104 x)T
L 0.3947 + 0.096 x e 0.01579 + 5721 10 xj 55OP
lnM
4
1
MM 0.3947 + 0.096x e0.01579 + 5721 10 xj 25PP = 40
0.01579 + 5.721 104

N Q
4
. .
.
.







11.23
12.0 kg/min
25o C
12.0 kg/min
T (oC)


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


a.


Energy Balance : MCv


dT
dt

= mC pb25 Tg +UAbTsteam T

g
M = 760 kg
m` = 12.0 kg min
dT / dt = 150 0.0224T ( oC min), t = 0 , T = 25oC
Cv H Cp = 2.30 kJ (min C)
UA = 11.5 kJ (min C)
Tsteama sat'd; 7.5barsf = 167.8 C


b.


Steady State:

dT
dt

= 0 = 150 0.0224Ts Ts = 67 C



67







25
0
t

c.
T
f

2
5

dT
150 00224T
t
= dt t =
0

1
00224

l
n

H
150 0.0224T
0.94

K
T =
150 094 exp( 0.0224t )
0.0224
t = 40 min. T = 498 C

d.

U changed. Let x = (UA) new . The differential equation becomes:
dT
dt
55


25

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

dT
.



x
.
x = 14.27 kJ / (mino C)



4
0


0




dt







.

U
U initial

=

(UA)
(UA)initial

=

1427 115
115

100% = 241%



11-18
= Q` W`
b gU|V T = 20 + 0.0649tbsg
= 0.0649 C s
|W T = 40 C t = 308 s 51. min
b g
Time to reach Tb neglect evaporation : t = = 926 s
b g
.
.
`
/ .
.
b g
= Q` W`
b g b ` ` `
` `
`
`










11.24 a.









b.












c.









dT
Energy balance: MCv
dt
W` = 0, Cv = 1.77 J g C
M = 350 g, Q` = 40.2W = 40.2 J s
dT
dt
t = 0, T = 20C

The benzene temperature will continue to rise until it reaches Tb = 801 C ; thereafter the heat
input will serve to vaporize benzene isothermally.
801 20
0.0649
Time remaining: 40 minutes 60 s min 926 s = 1474 s
Evaporation: Hv = b30.765 kJ molgb1 mol 78.11 ggb1000 J kJg = 393 J g
Evaporation rate = b40.2 J sgb393 J gg = 0102 g s
Benzene remaining = 350 g b0102 g sgb1474 sg = 200 g

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.


11.25 a.

Moles of air in room: n =

60 m3

273 K 1 kg - mole
283 K 22.4 m 3 STP

= 2.58 kg - moles

Energy balance on room air: nCv
dT
dt
Q = ms Hv H 2O, 3bars, sat'd 30.0 T T0
W` = 0


g
nCv
dT
dt
= msHv 30.0bT T0 g
N = 2.58 kg - moles
Cv = 20.8 kJ (kg- mole C)
H v = 2163 kJ kg bfrom Table B.6
T0 = 0 C

g
dT
dt
= 40.3ms 0.559T b C hr 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
.
= t
L gO = 4. 8 hr
1 13. 4 0 559 b23
b
gPQ MN
. .
250 kg 4.00 kJ b60 20g C
.
.
` t
dT = 0001 Q` dT T = 20o C + Qdt `
b
g
`
30
3
b g
Past 600s, Q= 100+ b g t 600 s = t 6
z z z
T = 20 + 0.001 Qdt =20 + 0001MM Qdt +
t P
6 P
MM_ PP
N Q
GH 6 6002 JK tbsg =
b
0001F t I
.
. .
M P






11.25 (contd)

b.




c.
At steady-state , dT dt = 0 40.3m` s 0.559T = 0 m` s =
T = 24 C m` s = 0.333 kg hr

Separate variables and integrate the balance equation:
0559T
40.3
Tf
10
dT
40.3m` s 0.559T

=
t
0

dt


m` s = 0.333
T f = 23C
23 dT
10 13.4 0.559T
E
t = ln
0559 134 0.559 10

11.26 a.




Q = U =
MCv T =
Integral energy balance bt = 0 to t = 20 ming


kg C




= 400 10




4




kJ

Required power input: Q` =
4.00 104 kJ 1 min
20 min 60 s

1 kW
1 kJ s

= 333 kW


b.


Differential energy balance: MCv

dT
dt

= Q`


M = 250 kg

dT
dt

= 0.001Qbg
Cv = 4.00 kJ kgC
t = 0, T = 20 C

Integrate:
T t
t

.
20oC 0 0

Evaluate the integral by Simpson's Rule (Appendix A.3)
600 s
Qdt = 33 + 4 33 + 35 + 39 + 44 + 50 + 58 + 66 + 75 + 85 + 95
0
+2 34 + 37 + 41 + 47 + 54 + 62 + 70 + 80 + 90 + 100 = 34830 kJ
Tb600 sg = 20o C +e 0.001 oC / kJjb34830 kJg = 54.8 C


c.












T = 548 + 12000 T 248






t
6
0
0
t


0
0
60
0







` . ` dt





6


10 kW
60 s







2 2




L

O










34830












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






11-20


V

C

= 4.00 L / s
.
dM KCl
= m` i,KCl m` o,KCl Accumulation=Input-Output
dC dV
=
. .
dV = 4 dt V = 400 + 4t







11.27 a. Total Mass Balance:
Accumulation=Input Output


dM tot
dt
E
= m` i m` o


d( )V)
dt


= 800) 4.00)


) =constant

dV
dt
t = 0 , V0 = 400 L

KCl Balance:



V + C = 8 4 C

dt dt


dt dt
d(CV )


dV dt = 4
= 100 8.00 400C
dC 8 8C
dt V
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







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










0
t


c.

dV
dt


= 4


V t
400 0



11-21


C

S
1
,

C

S
2
,

C

S
3

.
ln(1 C) 0 = 2 ln(50 + 0.5t ) 0
ln(1 - C)-1 = 2 ln = ln(1 + 0.01t )2
E
= CS1v`
E
= CS1v` CS 2v`
E
= CS 2v` CS 3v`






11.27 (contd)

dC
dt

=
8 8C
V


V = 400+ 4t

dC
dt

=
1 C
50 + 05t
C dC
0 1 C
=
t dt
0 50 + 0.5t
C t

50 + 0 .5t
50

1
1- C
= (1+ 0.01t )2 C = 1
1
(1+ 0.01t )2
When the tank overflows, V = 400 + 4t = 2000 t = 400 s
C = 1-

b1+ 0.01 400g
1

2
= 0.96 g / L


11.28 a. Salt Balance on the 1st tank:
Accumulation=-Output

d(CS1V1 ) dCS1
dt dt



= CS1


v`
V1



= 0.08CS1
CS1( 0 ) = 1500 500 = 3 g / L

Salt Balance on the 2nd tank:
Accumulation=Input-Output

d(CS2V2 ) dCS2
dt dt



= (CS1 CS 2 )


v`
V2



= 0.08(CS1 CS 2 )
CS 2( 0 ) = 0 g / L

Salt Balance on the 3rd tank:
Accumulation=Input-Output

d(CS3V3 ) dCS3
dt dt



= (CS 2 CS 3 )


v`
V3



= 0.04(CS 2 CS 3 )
CS3 ( 0 ) = 0 g / L


b.


3


CS1


CS2
CS3


0
t

11-22


C
S
1
,

C
S
2
,

C
S
3

(
g
/
L
)

E
.
E
.







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 ) d CS2 /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 ) d CS3 /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

2
CS1
1.5

1

0.5

0

CS2


CS3
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 = 0.2CA
(ii) Rate of consumption of B in the 2nd reaction : rB2 = r2 = 0.2CB2

b. Mole Balance on A:
Accumulation=-Consumption

d(C AV )
dt


= 01C AV

dCA
dt


= 01. CA
t = 0, C A0 = 100 mol / L

Mole Balance on B:
Accumulation= Generation-Consumption

d(CBV )
dt


= 0.2CAV 0.2CB2V

dCB
dt


= 0.2CA 0.2CB2
t = 0, CB0 = 0 mol / L




11-23




C

A
,

C
B
,

C
C

C
A
,

C
B

,

C
C

(
m
o
l
/
L
)

. .







11.29 (contd)
c.

2

CC


1

CB

C A

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 2B < CA) d CB/dt =0.2(CA- C 2B ) becomes less positive
until dCB/dt changes to negative ( C 2B > 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 2B becomes positive also increases with increasing t
CC increases faster until CB decreases with increasing t dCc/dt =0.2 C 2B 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
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0






CB
CA
CC
0 10 20 30 40 50
t (s)






11-24









11.30 a. When x =1, y =1 .

y =
ax x =1, y=1
x + b
a
1+ b

a = 1 + b


b. Raoults Law:

pC5 H12 = yP = xp *C5 H12 (46o C) y =

xp *C5 H12 (46o C )
P

Antoine Equation: p *C5 H12 (46o C ) = 10
(6.85221
1064 .63
46+ 232. 00
)
= 1053 mm Hg
y =
xp *C5 H12 (46o C )
P
=
0.7 1053
760
= 0.970

0.70a
.
TFrom part (a), a = 1+ b(2) |Tb = 0.078



c. Mole Balance on Residual Liquid :
Accumulation=-Output

dNL
dt


= n`V
t = 0, N L = 100 mol

Balance on Pentane:
Accumu lation=-Output

d( N L x)
dt







d
t

d
N

L
d
x
a
x



=

x



dt dt x + b
dN L / dt = n`V
t = 0, x = 0.70



1 =
R y = ax x=0.70, y=0.970 Ra = 1078
(1)
0970 =
.
S| x + b
S 0.70 + b
E
E
= n`V y x = n`V + N L
E
F I
H K
d x n a x
N L x + b
E
Q`


n`V H vap = Q` n`V =
`
dN L
t = 0, NL = 100 mol
= n`V N L = 100 n`V t = 100
Q` 27.0
n`V
`
NL Qt
.
d. Energy Balance : Consumption=Input

H vap =27.0 kJ/mol
b270 kJ / molg
Qt
From part (c),
dt 27.0
=
100 -
27.0
Substitute this expression into the equation for dx/dt from part (c):



11-25


x
,

y

FG
H
n ax
JK
` .
`
GH JK







11.30 (contd)

dx
dt


= V
N L x + b
xI =

Q 270
Qt
100 -
27.0
F
ax
x + b
xI
x(0) = 0.70

e.


1
0.9
0.8
0.7
0.6
0.5


x (Q=1.5 kJ/s)
y (Q=1.5 kJ/s)
0.4
0.3
0.2
0.1
0

x (Q=3 kJ/s)

y (Q=3 kJ/s)
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