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SOLUTIONS MANUAL

Bioprocess Engineering Principles


Pauline M. Doran
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E-mail: Ico.tnha.ao.ki. -~ --
SOLUTIONS MANUAL
Bioprocess Engineering Principles
Pauline M. Doran
University of New South Wales, Sydney, Australia
ISBN 0 7334 15474
Pauline M. Doran 1997
Table of Contents
Solutions
Page
Chapter 2 Introduction to Engineering Calculations 1
Chapter 3 Presentation and Analysis ofData 9
Chapter 4 Material Balances 17
ChapterS Energy Balances 41
Chapter 6 Unsteady-State Material and Energy Balances 54
Chapter 7 Fluid Flow and Mixing 76
Chapter 8 Heat Transfer 86
Chapter 9 Mass Transfer '98
Chapter 10 Unit Operations 106
Chapter 11 Homogeneous Reactions 122
Chapter 12 Heterogeneous Reactions 139
Chapter 13 Reactor Engineering 151
NOTE
All equations, tables, figures, page numbers, etc., mentioned in this manual refer to the textbook,
Bioprocess Engineering Principles.
Introduction to Engineering Calculations
2.1 Unit conversion
(a)
From Table A.9 (Appendix A): 1cP::::: kg m-
I
k
1
1 m= lOOcrn
Therefore:
1.5 x10-6 cP ::::: 1.5 x 10-6 cP ,1
10
-
3
k
t
g
;-1 I= 1.5 x 10-
11
kg s-1 cm-
1
Answer: 1.5 x 10-
11
kg s-1 em-
t
(b)
From Table A.S (Appendix A): 1 bp (British)::::: 42.41 Btu min-I
Therefore:
Answer: 5.17 Btu min-
1
(e)
From Table A.S (Appendix. A): 1mmHg:= 1.316 x 10-
3
attn
From Table A.I (Appendix A): 1 ft = 0.3048 m
From Table A.7 (Appendix A): 11 atm =9.604 x 10-
2
Btu
From Table A8 (Appendix A): 1Btu min-I::::: 2.391 x to-
2
metric horsepower
Im=lOOcm
11= lOOOcm
3
Ih=60min
Therefore:
670mmHgft
3
=670 mmHg ft3 .11.316X 10-
3
atml.19.604X 1O-2Btul.I.3048m1
3
1 100 em 1
3
1 11 I.
1 mmHg llatm 1 it 1 m lOOOcm3
1
2
.391 x 10-
2
metric horsepowerI I I h I 956 10-4 . h h
1
. -60. = , x metric orsepower
1Btu min- mm
Answer: 9.56 x 10-4 metric horsepower h
(d)
From Table A.7 (Appendix A): 1 Btu =0.2520 kcal
From Table A.3 (Appendix A): Ilb = 453.6 g
Therefore:
345 Btu Ib-
1
= 345 Btulb-
1
.1 g I= O.192kcal g-l
Answer: 0.192 kcal g-1
2.2 Unit conversion
Case 1
Convert to units of kg, m, s.
FromTable AJ (Appendix A), lIb = 0.4536 kg
2 Solutions: Chapter 2
From Table A.2 (Appendix A): 1 tt3 =: 2.832 x 10-
2
m
3
FromTable A.9 (Appendix A): 1 cP::: 10-
3
kg m-
l
sl
1 rn= tOOcm= lOOOmm
Therefore, using Eq. (2.1):
(
2mm.1 1m Ift
3

Dup l000mmU l00cmU lIb 2.832 x 10 2


m
3U _ 7
Re::: -p- = I -3 1 -11 - 2.4 x 10
10
-6 P 10 kgm s
c . 1cP
Answer: 2.4 x 10
7
ease 2
Convert to units of kg, m, s.
From Table Al (Appendix A): 1 in.::: 2.54 x 10-
2
m
From Table A.9 (Appendix A): 1 Ibm ft-I h-
1
::: 4.134 x 10-4 kg m-t st
Ih=3600s
Therefore, usingEq. (2.1):
= 1.5 x 10
4

Answer: 1.5 x 104
2.3 Dimensionless groups and property data
From the Chemical Engineers' Handbook, the diffusivity of oxygen in water at 2S"C is 2.5 x 10-
5
cm
2
sl. Assuming
this is the same at 28"C, !lJ= 2.5 x 10-
5
cm
1
st, Also, from the Chemical Engineers' Handbook, the density of water
at 28"e is PL ::: 0.9962652 g cm-
3
, and the viscosity of water at 28"C is JlL::: 0.87 cPo The density of oxygen at 28C
and 1 atm pressure can be calculated using the ideal gas law. As molar density is the same as n,V, from Eq. (2.32):
Temperature in the ideal gas equation is absolute temperature; therefore, from Eq. (2.24):
T = (28 + 273.15) K = 301.15 K
From Table 2.5, R "" 82.057 cm
3
atm K-I Substituting parameter values into the density equation gives:
Pa "" L "" latm "" 4.05 x 10-
5
gmolcm-
3
RT (82.057cm
3
almK:""1 gmol 1)(301.15K)
From the atomie weights in Table B.l (Appendix B), the molecular weight of oxygen is 32.0. Converting the result
for Pa to mass tenns:
Pa "" 4.05
x
lO-
5gm
olem-
3
1 "" l.30XlO-
3
gcm-
3
From Table A.9 (Appendix A): 1 eP "" 10-
2
g s-l; from Table A.l (Appendix A): 1 ft "" 0.3048 m "" 30.48 cm.
The parameter values and conversion factors, together with Db "" 2 mm "" 0.2 em, can now be used to calculate the
dimensionless groups in the equation for the Sherwood number.
Solutions,' Chapter 2
1'0
-2 -1 -11
0,87eP. gem s
S_J1.L_ leP -349
c - PrJ) - (0.9962652g cn,-3)(2.5 x 10 5em
2
s I) -
Therefore:
From the equation for Sh:
k
_Sh:lJ_(ll.21(2.5xl0-5cm2s-I)_IA 10-3 -I
L---- 02 -,<tUX ems
D1J . em
Answer: lAO x em s1
2.4 Mass and weight
From the definition of density on p 16, mass is equal to volume multiplied by density, Therefore:
3
From p 16, weight is-the force with wrncha body is attracted to the centre of the earth by gravity. According to
Newton's law(p 15), this force is equal to the mass of the body multiplied by the gravitational acceleration.
(a)
From pIS, at sea level and 45 latitude. gravitational acceleration g = 32.174 it s-2. Therefore:
Weight:::: 624 Ibm (32.174 ft s-2) = 2.008x 104 Ibm it sZ
Converting these units to lbj' from Eq. (2.16), 1lbf= 32,174 Ibm it s2; therefore:
4 2 llbf
Weight = 2.008 x 10 lbmfts- , 2 .= 6241b
f
32.174Ib
m
ft s
Answer: 624lbI When g :::: 32.174ft s2, the number of lb mass is equal to the number of lb force,
(b)
From Table A.I (Appendix A): 1 m= 3.281 ft. Using the same procedure as in (a):
Weight = 624 Ibm(9.76 m s-Z = 1.998 x 10
4
Ibmfts-
Z
Converting to Ibf
4 2 llbf
Weight = 1.998 x 10 lbmfts- . = 6211bf
32.1741b
m
ft s-2
Answer: 621lbf
2.5 Dimensionless numbers
First, evaluate the units of the groups cCP J.ll
k
) and (D G1p):
. (ep ") (Bmlb-
I
'1'1) Ibh-
I
ft-
I
Umtsof -- :::: = 1
k BIUh-1 ft-2('Pft-1tl
UnilsOf(DG) = (ftllbh-
1
ft-
2
= 1
J1. Ibh1ft1
4 Solutions: Chapter 2
Therefore, these groups are dimensionless. For the equation to be dimensionally homogeneous, (hIC
p
G) must also be
dimensionless; the units of h must therefore cancel the units of C
p
G.
Unitsofh "'" unitsofCpG "'" (Btulb-
1
"p-l)(1bh-
1
fr
2
) "'" Btu "F-l h-
1
ft-
2
The dimensions of h can be deduced from its units. From Table A.7 (Appendix A), Btu is a unit of energy with
dimensions "'" L2Ml2. OF is a unit of temperature which, from Table 2.1, has the dimensional symbol E>. h is a unit
of time with dimension"'" T; ft is a unit of length with dimension"'" L. Therefore:
Dimensions of h = L2M'l2 a-I 1'"1 L-2 = MT"
3
e-
1
Answer: Units = Btu opi h-
1
ft-2; dimensions =Ml
3
e-
1
2.6 Dimensional homogeneity and Cc
FromTable A8 (Appendix A), dimensions of P = L2MT"3
Dimensions of g = LT-z
Dimensions of p =ML3
Dimensions of Di "'" L
From p 11, the dimensions oirotational speed, Nj =T-!; from p 15, the dimensions of gc= 1. Therefore:
As Np is a dimensionless number, equation (i) is not dimensionally homogeneous and therefore cannot be correct.
Equation (ii) is dimensionally homogeneous and therefore likely to be correct
Answer: (li)
2.7 Molar units
From the atomic weights in Table Rl (Appendix B), the molecular weight of NaOH is 40.0.
(a)
FromEq. (2.19):
lb moles NaOH = 20.0 lb = 050 lbmol
4O.0lblbmol 1
Answer: 050 lbmol
(b)
FromTable A.3 (Appendix A): lIb =453.6 g. Therefore:
1
453.6gl
20.01b =20.0Ib. -lib =9072 g
From Eq. (2.18):
9072g
grammoles NaOH = I =227 grool
4O.0g gmol-
Answer: 227 gmol
(c)
From p 16, 1 kgmol::::: 1000 gmot. Therefore, from (b):
.-----
Solutions: Chapter 2
Answer: 0.227 kgmol
1
1kgmol I
kg molesNaOR =227 gmol. 1000 gmol =0.227 kgmol
5
2.8 Density and specific gravity
(a)
From p 16, the density of water at 4C can be taken as exactly 1 g cm-
3
. Therefore, for a substance with specific
gravity the density at 20C is 1.5129 g cm*3,
(I)
lkg=l000g
1 m: 100cm
Therefore:
Answer: 1512.9 kg m-
3
(il)
From the atomic weights in Table 8.1 (Appendix B), the molecular weight of nitric acid (RN03) is 63.0. In 1 cm
3
RNO" from Eq. (2.18)0
LS129g
grammoles : 1 : 0.0240 gmot
63.0ggmor
Therefore, the molar density is 0.0240 gmol cm-
3
. From the definition of specific volume on p 16:
Molar specific volume : 1 d
1
. : .,-__,,-1-:--:::;- : 41.67cm
3
gmor
1
mo ar enslty 0.0240 gmol em 3
Answer: 41.67 cm
3
gmol-l
(b)
(I)
From p 16, as density is defined as the mass per unit volume, the mass flow rate is equal to the volumetric flow rate
multiplied by the density:
Answer: 80 g min-
l
(ii)
From the atomic weights in Table B.l (Appendix B), the molecular weight of carbon tetrachloride, CC14, is 153.8.
Using the mass flow rate from (a):
Molar flow rate : 80 g min-
l
.l =0.52gmolmin-
1
Answer: 0.52 grool min-
I
2.9 Molecular weight
From p 17, the composition of air is close to 21% oxygen and 79% nitrogen. For gases at low pressures, this means
21 mol% 02 and 79 mol% NZ. Therefore, in 1 gmol air, there are 0.21 gmot Oz and 0.79 gmol NZ From the atomic
weights in Table B.l (Appendix B), the molecular weights of Oz and NZ are 3Z.0 and 28.0, respectively. The
molecular weight of air is equal to the number of grams in 1 gmol:
1gmolair =0.21 gmOlOz1 + 0.79 gmol NZ 1 =28.8g
Answer. 28.8
6 Solutions.' Chapter 2
2.10 Mole fraction
The molecular weights can be obtained from Table B.7 (Appendix B): water 18.0; ethanol 46.1; methanol 32.0;
glycerol 92.1; acetic acid 60.1; benzaldehyde 106.1. In 100 g solution, there are 30 g water, 25 g ethanol. 15 g
methanol, 12 g glycerol, 10 g acetic acid, 8 g benzaldehyde, and no other components. Therefore:
Moles water = 30 g _I ~ r : ; ~ l l =1.67 gruol
Moles ethanol:: 25 g.1 ~ ~ ~ l l :: 054 gmol
Molesmethanol:: 15 g _I ; ~ ~ l l =0.47 gmol
. IIgmaII
Molesglycerol =12g. 92.1g = O.13gmol
Moles acetic acid =10g.1 ~ ~ ~ I I = 0.17 gmol
Moles benzaldehyde: 8 g _I : ~ o ~ I =0.08 gmal
The total number of moles is 1.67 +0.54 +0.47 +0.13 + 0.17 +0.08:: 3.06 gmal. From Eq. (2.20):
Mole fraction water = ; : ~ ~ = 0.55
Mole fraction ethanol =~ : ~ =0.18
Mole fraction methanol = ~ : ~ ~ = 0.15
Mole fraction glycerol = ~ : ~ = 0.04
Mole fraction acetic acid =~ : ~ ::::: 0.06
Mole fraction benzaldehyde ::::: ~ : : ::::: 0.03
Answer: 0.55 water; 0.18 ethanol; 0.15 methanol; 0.04 glycerol; 0.06 acetic acid; 0.03 benzaldehyde
2.11 Temperature scales
From Eq. (2.27\
-40 ::::: 1.8 T(0C) + 32
Tee) = -40
From Eq. (2.25),
T (OR) ::::: -40 + 459.67
T(R) = 420
From Eq. (2.24) and the result for T ("C);
T(K) = -40+273.15
T(K) = 233
2.12 Pressure scales
(a)
Assume that the atmospheric pressure is 14.7 psi. From Eq. (2.28):
Absolute pressure ::::: 15 psi +14.7 psi::::: 29,7 psi
Solutions: Chapter 2
From Table A.5 (Appendix A): 1 psi = 6.805 x Hy2 atm. Therefore:
. 16.805 x 10-
2
atm1
Absolutepressure = 29.7psl. 1 psi = 2.02atm
Answer: 29.7 psi; 2.02 atm
(b)
From p 19, vacuum pressure is the pressure below atmospheric. If the atmospheric pressure is 14.7 psi:
Absolutepressure = 14.7psi-3psi = IL7psi
Answer: 11.7 psi
7
2.13 Stoichiometry and incomplete reaction
(a)
The molecular weights are calculated from TableB.l (Appendix B): penicillin =334.;4; glucose =180.2. The
maximum theoretical yield from the stoichiometric equation is 1 gruol of penicillin for every 1.67 gruol of glucose.
'This is equivalent to 334.4 g penicillin per 1.67 x 180.2 = 300.9 g glucose. or 1.1 g g-l.
Answer: 1.1 g
(b)
The maximum theoretical yield in (a) is obtained when all the glucose consumed is directed into penicillin production
according to the stoichiometric equation. If only 6% of the glucose is used in this way, the actual yield of penicillin
from glucose is much lower, at 334.4 g penicillin per (300.9 x 100/
6
) g glucose, or 0.067 g
Answer: 0.067 g g-1
(c)
From the atomic weights in Table B.I (Appendix B), the molecular weight of phenylacetic acid is 136.2.
(I)
The only possible limiting substrates are glucose and phenylacetic acid. Using a basis of II medium, if (50 - 5.5) =
44.5 g glucose are consumed but only 6% is available for penicillin synthesis, the mass of glucose used in the
penicillin reaction is 44.5 x 6/
100
=2.67 g. 'This is equivalent to 2.67 g/180.2 g gmol-1 =1.48 K 10-
2
gmol glucose
available for penicillin synthesis. At the same time, 4 g or 4 g/136.2 g gmol-1 =2.94 x gruol phenylacetic acid is
available which, according to the stoichiometric equation, requires 1.67 x 2.94 x 10-
2
=4.91 x 10-
2
gruol glucose for
complete reaction. As the gmol glucose required is greater than the gmol glucose available after growth and
maintenance activities, glucose is the limiting substrate.
Answer: Glucose
(il)
Of the 44.5 g I-I glucose consumed, 24% or 10.7 g I-I is used for growth. In a tank. the total mass of glucose
consumed for growth is therefore 1070 g or 1.07 kg.
Answer: 1.07 kg
(iii)
From (i), 1.48 x 10-
2
gmol glucose is used in the penicillin reaction per litre. According to the stoichiometry, this
produces 1.48 x 10-
2
/1.67 = 8.86 x gmol penicillin per litre. Therefore, in a l00-litre tank, 0.886 gmol or 0.886
gmol x 334.4 g gmol-1 =296 g penicillin are formed.
Answer: 296 g
(iv)
IT, from (i), 1.48 x 10-
2
gmol [1 glucose is used in the penicillin reaction, 1.48 x 10-
2
/1.67 = 8.86 x 10-
3
gmoll-l
phenylacetic acid must also be used. This is equivalent to 8.86 x 10-
3
gmoll-l x 136.2 g gmol-1 = 1.21 g t
I
phenylacetic acid. As 4 g I-I are provided, (4 - 1.21) = 2.79 g phenylacetic acid must remain.
Answer: 2.79 g I-I
8 Solutions: Chapter 2
2.14 Stoichiometry, yield and the ideal gas law
(a)
Adding up the numbers of C, H, 0 and Natoms on both sides of the equation shows that the equation is balanced.
Answer: Yes
(b)
The molecular weights are calculated from Table B.I (Appendix B).
Cells: 91.5
Hexadecane: 226.4
Fromthe stoichiometry, as 1 gmol of hexadecane is required to produce 1.65 gmol of cells, the maximum yield is 1.65
gmol x 91.5 g gmol-l =: 151 g cells per 226A g hexadecane, or 0.67 g g-I,
Answer: 0.67 g g-1
(e)
From the atomic weights in Table RI (Appendix B), the molecular weight of oxygen is 32.0. From the
stoichiometry, 16.28 gmol of oxygen is required to produce 1.65 gmal of cells which, from (b), is equal to 151 g cells.
The maximum yield is therefore 151 g cells per (16.28 groal x 32.0 g groot-I) =: 521 g oxygen, or 0.29 g g-1.
Answer: 0.29 g g-1
(d)
Production of 2.5 kg cells is equivalent to 2500 g =: 2500 g/91.5 g gmoI-l = 27.3 gmol cells. The minimum amounts
of substrates are required when 100% of the hexadecane is converted according to the stoichiometric equation.
(I)
From the stoichiometry, production of 27.3 gmol cells requires 27.3/1.65 =16.5 gmol =16.5 gmol x 226.4 g gmol-I =
3736 g = 3.74 kg hexadecane.
Answer: 3.74 kg
(il)
From the answer in (d)(i), the concentration ofhexadecane required is 3.74 kg in 3 m
3
, or 1.25 kg m-
3
.
Answer: 1.25 kg m-
3
(ill)
According to the stoichiometric equation, production of 27.3 gmol cells requires 27.3 x 16.28/1.65 =269.4 gmol
oxygen. As air at low pressure contains close to 21 mol% oxygen (p 11), the total moles of air required is 269.410.21
= 1282.9 gmot The volume of air required can be calculated using the ideal gas law. From Eq. (2.32):
V = nRT
p
Temperature in the ideal gas equation is absolute temperature; from Eq. (2.24):
T = (20 +273.15) K = 293.15K
From Table 2.5, R "" 82.057 cm
3
atm K-I gmol-I. Substituting these values into the equation for V gives:
v= (1282.9gmolj(82.057cm
3
atmK-
1
gmol-l)(293.15Kj 1-.!.."'...1
3
= 31 3
1atm . l00cm m
Answer: 31 m
3
Presentation and Analysis of Data
3.1 Combination of errors
"" 0.25 mol m-
3
4%"= 0.25 O.OlOmol m-
3
CAL =0.183 mol m-
3
4% =: O.183O.OO73molm-
3
OTR =O.Qll mol m-
3
s-1 5%
For subtraction, absolute errors are added. TherefOre:
-CAL"'" (O.25-0.183){O.OlO+0.0073)molm-
3
"'" O.067O.0173molm-
3
=: 0.067 molm-
3
25.8%
For division, relative errors are added. Therefore:
kLa =: {25.8 +5)% =O.16s-
1
31% = O.16 0.05 s-l
O.Q67molm
31%. This example illustrates how a combination of small measurement errors can result in a relatively
large uncertainty in the final result.
3.2 Mean and standard deviation
(a)
The best estimate is the mean, X. FromEq. (3.1):
x =5.15+5.45+5.50+5.35 = 5.36
Answer: 5.36
(b)
Calculate the standard deviation from Eq. (3.2):
(5.15 - 5.36)' +(5.45 - 5.36)' +(5.50- 5.36)' +(5.35 - 5.36)'
4-1
= 0.15
Answer. The standard deviation is 0.15. Note that standard error, which can be calculated from the standard
deviation, is a more direct indication of the precision ofa mean.
(c)
x =5.15 +5.45 =5.30
2
Standard deviation is not appropriate for expressing the accuracy of a mean evaluated using only two samples. In this
case the maximum error, Le. the difference between the mean and either of the two measured values, might be used
instead. The maximum error in this example is (5.30 - 5.15) =0.15.
Answer. 5.30; an indication of the accuracy is 0.15
(d)
x= 5.15+5.45+5.50+5.35+5.15+5.45+5.50+5.35 = 5.36
10 Solutions: Chapter 3
2 (S.lS -S.36f + + (S.50-S.36f +2(S.3S -S.36)2 = 0.14
Answer: The best estimate of optimal pH is unchanged at 5.36, but the standard deviation is slightly lower at 0.14.
This example illustrates that although the standard deviation decreases as the number ofmeasurements is increased,
(j is not strongly dependent on n. The best way to improve the reliability of the mean is to ensure that the individual
measurements are as intrinsically accurate as possible, rather thanrepeat the measurement many times.
3.3 Linear and non-linear models
(a)
Xl =1; Yl =10
X2=8;Y2=0.5
A straight line plot of y versus x on linear coordinates means that the data can be represented using Eq. (3.6). From
Eqs (3.7) and (3.8),
A = (Yz-Y1) = 0.5-10 =-136
(x2 Xl) 8-1 .
B = YI-Axi = 10-(-1.36)1 = 11.4
Answer: y =-1.36 x + 11.4
(h)
Xl = 3.2; Yl =14.5
);2 = 8.9; Y2 = 38.5
A straight line plot of y versus xIh on linear coordinates means that the data can be represented using the equation:
Y=Axlh+B
with A and B given by the equations:
A = YrY1 = 38.5-14.S = 201
112_ 112 89Ih_32'k .
x2 Xl . ,
B = YI-Axi
h
= 14.5-20.1(3.2
112
) = -21.5
'k
Answer:y=20.1x -21.5
(0)
Xl=5;Yl=6
X2= l;Y2=3
A straight line plot of Ity versus xl on linear coordinates means that the data can be represented using the equation:
lly = Ax
2
+B
with A and B given by the equations:
A =
lin- Ity} 1/3 -lI6 -3
2 2 = 2 2 =-6.9xlO
x2-xl 1 -5
B = 1/
y1
-Ax; = 1/6-(-Mx 1O-
3
)<S2) = 0.34
Answer: l/y = -6.9 x 10-
3
xl + 0.34
(d)
Xl=0.5;Yl=25
x2 =550; Y2 =2600
A straight line plot of y versus x on log-log coordinates means that the data can be represented using Eq, (3.10).
From Eqs (3.13) and (3.14),
Solutions: Chapter 3
Answer: Y= 39.6 x
O
.
663
A =(lnY2-
ln
Yl) =ln2600-ln25 =0.663
(lnx2-lnxI) ln550-1nO.5
lnB =InYI-Alnxl =ln25-(0.663}ln0.5 =3.678
B = e
3
.
678
= 39.6
11
(eJ
Xl = 1.5; YI = 2.5
X2 = 10; Y2 = 0.036
A straight line' plot of y,versus X on semilog coordinates means that the data can be represented using Eq. (3.15).
From Eqs (3.17) and (3.18):
A =(lnY2-
ln
YI) =lnO.036-ln2.5 =-0.50
(x2 - xl) 10- 1.5
In B = In Y1 - A Xl = In 2.5 - (-o.50J 1.5 = 1.666
B = el.
666
= 5.29
Answer: Y= 5.29 e-o.s
Ox
3.4 Linear curve fitting
(aJ
The results determined using Eqs (3.1) and (3.2) are listed below.
Sucrose concentration (g l ~ l )
6.0
12.0
18.0
24.0
30.0
(bJ
Mean peak area
56.84
112.82
170.63
232.74
302.04
Standard deviation
1.21
2.06
2.54
1.80
2.21
35
30
-
-
.
.9
25
0

~
20

g
15
8
~
10
g
"'
5
0
0 50 100 150 200 250 300 350
Peak area
12 Solutions: Chapter 3
(e)
The linear least squares fit of the data is:
y ::: 0,098 x +0,83
Answer: y "'" 0.098 x + 0.83, where y is sucrose concentration in g 1-1 and x is peak area.
(d)
For x::: 209,86, the equation in (c) gives a sucrose concentration oi2IA g I-I.
Answer: 21.4 g I-I
3.5 Non-linear model: calcnlation of parameters
(a)
The proposed model equation has the general form of Eq. (3.15); therefore, if the model is suitable, a plot of a versus
lIT on semi-logarithmic coordinates will give a straight line. As T in the equation is absolute temperature, "'c must
first be converted to degrees Kelvin using Eq. (2.24). The data are listed and plotted below.
Temperature (0C) Temperature (K) IIT(K-l) Relative mutation frequency. a
15 288.15 3.47 x 10-
3
4.4 x 10-
15
20 293.15 3.41 x lO
w3
2.0x 10-
14
25 298.15 3.35 x leT
3
8.6x 10..
14
30 303.15 3.30 x lfr3 3.5 x Jer
I3
35 308.15 3.25 x 10-
3
lAx }0"'12
10-
11

"
[
10-12

"
f
c
10-
13
.Q
lii
"E

=
10. 14
-ll
lJ:
3.5 x 10-3 3.3x 10-3 3.4x 10-
3
1ITemperature (K-1)
10-'5 __ __....l.__ __....J
3,2 x 10-3
As the data give a straight line on coordinates, the model can be considered to fit the data well.
(b)
The equation for the straight line in (a) is:
y =: 9.66 x 10
24
e-
26
,12lx
where y is relative mutation frequency and x is reciprocal temperature in units of For dimensional homogeneity
the exponent must be dimensionless (p 12), so that -26,121 has units of K, and EIR in the model equation is equal to
26,121 K From Table 2.5, R =: 8.3144 J gmol-l K1; therefore:
E =: (26,121 K) (8.3144 J K*l) =: 217,180.4 J gmol-1 =: 217.2 kJ gmot
1
Solutions: Chapter 3
Answer: 217.2 kJ gmol-l
(c)
From the equation in (b) for the straight line, ao is equal to 9.66 x 10Z4.
Answer: 9.66 X 1024
3.6 Linear regression: distribution of residuals
(aJ
13
12345 6
Decrease in medium conductivity (mS cm-
1
)
16
-
-
,
14
!'!l
c

12
i'!
C
10

g
0
0
8
~
6
~

4
m

~ 2
.i1
0
0


The linear least squares fit of the data is:
y =: 1.58 + 2.10x
where yis increase in biomass concentration in g r
1
and xis decrease in medium conductivity in mS c m ~ l .
(b)
The residuals are calculated as the difference between the measured values for increase in biomass concentration and
the values for y obtained from the equation in (a).
Decrease in medium conductivity (mS
o
0.12
0.31
0.41
0.82
1.03
lAO
1.91
2.11
2.42
2.44
2.74
2.91
3.53
4.39
5.21
5.24
5.55
Residual
-1.58
0.57
-!l.23
0.36
1.20
1.36
1.28
0041
0.19
-0.46
-!l.50
-!l.73
-1.69
-1.99
-1.00
1.48
0.02
1.37
14 Solutions: Chapter 3
These results are plotted below.
3.-_-,.__.,-_-,__.,...__,-_-,
2
1
2
6 1 2 3 4 5
Decrease in medium conductivity (mS em-
1
)
3 '-_-'-__-'-_---'__......__'-_-'
o
The residuals are not randomly distributed: they are mainly positive at low values of decrease in medium
conductivity, then negative, then positive again. Therefore, the straight line fit of the data cannot be considered a very
good one.
3.7 Discriminating between rival models
(aJ
The results are plotted using linear coordinates below.

0.11
~
'"
0.10
..
os'
0.09
. ~
~
0.08
"
0.07
."
'E
1l.
0.06
,

~
~
0.05
::J
0.04
0.00 0.02 0.04 0.06 0.08 0.10
Gas superficial velocity, uG (m s-1)
The data are reasonably well fitted using a linear model. The linear least squares equation for the straight line fit is:
y =0.054 +0.466 x
where y is liquid superficial velocity in m s-l andx is gas superficial velocity in m sl. The sum of the squares of the
residuals between the measured values for liquid superficial velocity and the values for y obtained from the above
equation is 8.4 x 10-
5
,
Solutions: Chapter 3 15
(b)
The proposed power law equation has the same form as Eq. (3.10). Therefore, if the power law model is suitable. the
data should give a straight line when plotted on log-log coordinates.
0.01
om
Gas superficial velocity, u
G
(m s1)
0.1
The data are reasonably well fitted using a power law- modeL The equation for the straight line in the plot is:
y = 0.199 x
O
.
309
where y is liquid superficial velocity in m sl andx is gas superficial velocity in m sl. The sum of the squares of the
residuals between the measured values for liquid superficial velocity and the values obtained from the above equation
is 4.2 x 10-
5
.
)
The nonlinear model is better because the sum of squares of the residuals is smaller.
3.8 Non-linear model: calculation of parameters
(a), (b)
The proposed model equation has the same form as Eq; (3.15). Therefore, if the model is suitable, the data should
give a straight line when plotted on semi-logarithmic coordinates.
10' .,.--.,...-....,--,----,----,,--...---.
10
3
10
1
35 30 25 15 20
Time (min)
100 '--_.1-_-'-_-'-_-'-_-L_----'-_---'
o 5 10
16
(c), (d)
The equation for the straight line in the figure is:
y =. 2.13 x 104 e-O.353x
Solutions: Chapter 3
where y is the number of viable cells and x is time in min. As the exponent must be dimensionless to preserve
dimensional homogeneity (p 12), the dimensions of kd are T-t; therefore k(! =. 0353 min-I, The dimensions of No are
the same as N, i.e, No is dimensionless and equal to 2.13 x 104.
Answer: kd =. 0.353 min-I. No =. 2.13 x 104; the dimensions of ka. are T"l, No is dimensionless
Material Balances
4.1 Cell concentration using membranes
L Assemble
(i) Flow sheet
Buffer solution in
80 kg min-
1
Cell concentrate
6% bacteria
I I
I I
I
Hollow-fibre membranes
I
I I
I I
Buffer solution out
Fennentation broth
350 kg min-
1
1% bacteria
99% water
(li) System boundary
The system boundary is shown on the flow sheet.
(iii) Reaction equation
No reaction occurs.
2. Analyse
(i) Assumptions
- steady state
-no leaks
- only water passes across the membrane
(ii) Extra data
No extra data are required.
(ill) Basis
1 min, or 350 kg fennentation broth
(iv) Compounds involved in reaction
No compounds are involved in reaction.
(v) Mass-balance equation
As there is no reaction, the appropriate mass-balance equation is Eq. (4.3):
mass in = mass out
3. Calculate
(i) Calculation table
The calculation table below shows all given quantities in kg. The total mass of cell concentrate is denoted c; the total
mass of buffer out is denoted B. The columns for water refer to water originating in the fermentation broth.
18 Solutions: Chapter 4
In Out
Stream
Water Bacteria Buffer Total Water Bacteria Buffer Total
Fermentation 346.5 3.5 0 350
broth
Buffer solution in 0 0 80 80
Cell concentrate ? O.06C 0 C
Buffer solution ? 0 80 B
out
Total 346.5 3.5 80 430 ? 0.06C 80 C+B
(li) Mass-balance calculations
Bacteria balance
3.5 kg bacteria in "'" 0.06 Ckg bacteria out
C =58.3 kg
Total mass balance
430 kg total mass in = (C+B) kg total mass out
Using the result for C:
B "'" 371.7 kg
Water balance
346.5 kg water in = water out
Water out = 346.5 kg
These calculations allow completion of the table with all quantities in kg.
Stream In Out
Water Bacteria 814fer Total Water Bacteria Buffer Total
Fennentation 346.5 3.5 0 350
broth
Buffer solution in 0 0 80 80
Cell concentrate 54.8 3.50 0 58.3
Buffer solution 291.7 0 80 371.7
out
Total 346.5 3.5 80 430 346.5 3.50 80 430
(iii) Check the results
All columns and rows of the completed table add up correctly.
4. Finalise
(a)
After rounding to three significant figures, the total flow rate of buffer solution out of the annulus is 372 kg min-I.
Answer: 372 kg min,t
(b)
The total flow rate of cell concentrate from the membrane tubes is 58.3 kg min-I.
Answer. 58.3 kg min I
Solutions: Chapter 4 19
4.2 Membrane reactor
t. Assemble
(i) Flow sheet
Product
Aqueous residue
0.2% glucose
0.5% ethanol
ystem boundary
- -- - --
- 1
I I
I I
I
Membrane system
I
I I
I I
s
Solvent
40 kg h-
1
Feed
40 kg h-
1
10% glucose
90% water
(li) System boundary
The system boundary is shown on the flow sheet.
(iii) Reaction equation
2. Analyse
(i) Assumptions
- steady state
-no leaks
- yeast cells do not grow or dislodge from the membrane
- no evaporation
- all C02 produced leaves in the
- no side reactions
(li) Extra data
Molecular weights (Table B.t, Appendix B): glucose = 180.2
ethanol =. 46.1
CO, =44.0
(iii) Basis
1 h, or 40 kg feed solution
(iv) Compounds involved in reaction
Glucose, ethanol and carbon dioxide are involved in the reaction.
(v) equations
For glucose, ethanol and carbon dioxide, the appropriate mass-balance equation is Eq. (4.2):
mass in + mass generated =. mass out +mass consumed
For water, solvent and total mass, the appropriate mass-balance equation is Eq. (4.3):
mass in =. mass out
3. Calculate
(i) Calculation table
The calculation table below shows all given quantities in kg. The total mass of aqueous residue is denoted R; the total
mass of product out is denoted p; the total mass of carbon dioxide out is denoted G.
20 Solutions: Chapter 4
Stream In Out
Glucose Ethanol CO, Solvent H,O Total Glucose Ethotwl CO, Solvent H2O Total
-------
Feed 4 0 0 0 36 40
Solvent 0 0 0 40 0 40
Aqueous 0_002R 0.005 R 0 0 ? R
residue
Product 0 ? 0 ? 0 P
Off-gas 0 0 ? 0 0 G
Total 4 0 0 40 36 80 0.002 R ? ? ? ? R+P
(ii) Mass-balance calculations
Solvent balance
Solvent is a tie component.
40 kg solvent in ::::: solvent out
Solvent out ::::: 40 kg
Water balance
Water is a tie component.
36 kg water in ::::: water out
Water out::::: 36 kg
As water appears on the Out side of the table only in the aqueous residue stream:
0.002 R + 0.005 R + 36 kg ::::: R
R = 36.254 kg
Therefore, the residual glucose in the aqueous residue stream.::::: 0.002 R ::::: 0.073 kg; the ethanol in the aqueous residue
stream::::: 0.005 R::::: 0.181 kg.
Glucose balance
4 kg glucose in +0 kg glucose generated ::::: 0.073 kg glucose out +glucose consumed
Glucose consumed ::::: 3.927 kg
Converting the glucose consumed to molar terms:
1
1 kgmOll
3.927 kg glucose ::::: 3.927kg. 180.2kg ::::: O.0218kgmol
From the reaction stoichiometry, conversion of this amount of glucose generates 2 X0.0218 = 0.0436 kgmol ethanol
and 2 x 0.0218 = 0.0436 kgmol COZ. Converting these molar quantities to mass:
0.0436kgmolethanol =0.0436kgmOI1 i Z : ~ ~ 1 1 = 2.010kg
0.0436kgm
o1CO
z = OJM36kgmOLI ~ : ~ l l = 1.92kg
C02 balance
okg COZ in + 1.92 kg C02 generated =C02 out +0 kg C02 consumed
C02 out = 1.92 kg = G
Ethanol balance
okg ethanol in + 2.010 kg ethanol generated = ethanol out +0 kg ethanol consumed
Ethanol out =2.010 kg
Ethanol leaves the system only in the product and aqueous residue streams. Therefore:
Solutions: Chapter 4 21
Ethanol out in the product stream = (2.010 - 0.181) kg = 1.829 kg
As the product stream consists of ethanol and solvent only:
P = (1.829 + 40) kg = 41.829 kg
These calculations allow completion of the table with all quantities in kg.
Stream In Out
Glucose Ethanol CO, Solvent H,O Total Glucose Ethanol CO2 Solvent H,O Total
Feed 4 0 0 0 36 40
Solvent 0 0 0 40 0 40
Aqueous - 0.073 0.181 0 0 36 36.254
residue
Product 0 1.829 0 40 0 41.829
Off-gas 0 0 1.92 0 0 1.92
Total 4 0 0 40 36 80 0.073 2.010 1.92 40 36 80.00
(iii) Check the results
All columns and rows of the completed table add up correctly.
4. Finalise
(0)
1.829 kg ethanol are contained in 41.829 kg of product stream. The ethanol concentration is therefore 1.829/41.829 x
100%:::: 4.4%.
Answer: 4.4%
(h)
The mass flow rate ofCOz is 1.92 kg b-
1
.
Answer: 1.92 kg
4.3 Ethanol distillation
1. Assemble
(i) Flow sheet
Bottoms
Distillate
5,000 kg h-
1
45% ethanol
55% water
System boUnda'l'\.
r
-t---,
I I
I I
I I
I
Distillation
I
I
column
I
kg h-l
thanal I I
atar
I I
I I
I I
-
-
-+-
-
-
Feed
50,000
10%e
90%w
22
(li) System boundary
The system boundary is shown on the flow sheet.
(ill) Reaction equation
No reaction occurs.
2. Analyse
(i) Assumptions
- steady state
-no leaks
(ll) Extra data
No extra data are required.
(ill) Basis
1 h, or 50,000 kg feed
(Iv) Compounds involved in reaction
No compounds are involved in reaction.
(v) Massbalance equation
As there is no reaction, the appropriate mass-balance equation is Eq. (4.3):
mass in ::::: mass out
3. Calculate
(i) Calculation table
The calculation table shows all given quantities in kg.
SolutilJns: Chapter 4
Stream
Feed
Distillate
Bottoms
Total
Ethanol
5,000
5,000
Water
45,000
45,000
In
Total
50,000
50,000
Out
Ethanol Water Total
2,250 2,750 5,000
? ? ?
? ? ?
(li) Mass-balance calculations
Total mass balance
50,000 kg total mass in ::::: total mass out
Total mass out ::::: 50,000 kg
Therefore, from the total column on the Out side of the table:
Bottoms out::::: (50,000 - 5,000) kg ::::: 45,000 kg
Ethanol balance
5,000 kg ethanol in ::::: ethanol out
Ethanol out ::::: 5,000 kg
From the ethanol column of the Out side of the table:
Ethanol out in the bottoms := (5,000..,... 2,250) kg := 2,750 kg
Water balance
45,000 kg water in := water out
Water out := 45,000 kg
From the water column of the Out side of the table:
Water out in the bottoms == (45,000 - 2,750) kg == 42,250 kg
These calculations allow completion of the table with all quantities in kg.
Solutions: Chapter4 23
Stream
Feed
Distillate
Bottoms
Total
Ethanol
5,000
5,000
Water
45,000
45,000
In Out
Total Ethanol Water Total
50,000
2,250 2,750 5,000
2,750 42,250 45,000
50,000 5,000 45,000 50,000
(ill) Check the results
All columns and rows of the completed table add up correctly.
4. Finalise
(a)
The bottoms contains 2,750 kg ctha,")l and 42,250 kg water in a total of 45,000 kg. Therefore, the composition is
2,750/45,000 x 100% = 6.1% ethanol. and 42,250/45,000 x 100% = 93.9% water.
Answer: 6.1% ethanol, 93.9% water
(b)
Directly from the table, the rate of alcohol loss in the bottoms is 2,750 kg h-
I
.
Answer: 2,750 kg h-
I
4.4 Removal of glucose from dried egg
1. Assemble
(i) Flow sheet
Off-gas
Enzyme reactor
--t- -
System boundary
r\.
I
I
1
Egg slurry -----L.o-l
3000 kg h
1
I
2% glucose
20% water I
78% egg solids I
-------,
1
I
I--.L 1---_- Product
I 0.2% glucose
1
I
Inlet air
18 kg h-
1
02
(n) System boundary
The system boundary is shown on the flow sheet
(ill) Reaction equation
2. Analyse
(i) Assumptions
- steady state
-no leaks
- air and off-gas are dry
- gases are at low pressure so vol% = mol%
- H202 remains in the liquid phase
24 Solutions: Chapter 4
(ti) Extra data
Molecular weights (Table B.I, A.ppendix B): glucose::::: 180.2
02=32.0
NZ::::: 28.0
H20 =IS.0
gluconic acid::::: 196.2
HZOz::::: 34.0
Composition of air (p 17): 21% 02, 79% Nz by volume
(ill) Basis
1 h, or 3000 kg egg slurry
(iv) Compounds involved in reaction
Glucose, 02, water, gluconic acid and HzOz are involved in the reaction.
(v) Mass-balance equations
For glucose, 02, water, gluconic acid and HZOz,the appropriate equation is Eq. (4.2):
mass in +mass generated ::::: mass out +mass consumed
For egg solids. Nz and total mass, the appropriate mass-balance equation is Eq, (4.3):
mass in = mass out
3. Calculate
(i) Calculation table
The mass of NZ accompanying 18 kg 02 in air can be calculated from the known composition of air. Converting 18
kg 02 to molar units:
1
1 kgmOll
ISkg02 =ISkg0
2
32.0kg =0.563kgm
o10
2
Therefore, 79/21 x 0563 kgmol = 2.118 kgmol NZ enter in the air stream. Converting this to mass units:
1
2S.0kg I
2,118kgmo1N2 = 2.118kgmoIN2 lkgmol =59.30kg N2
The calculation tables below show all known quantities in kg. The total mass of off-gas is denoted G; the total mass
of product is denoted P. The In side of the mass-balance table is complete,
Solutions: Chapter 4
59.30 kg NZ in ::::: NZ out
NZ out::::: 59,30 kg
Glucose balance
60 kg glucose in + 0 kg glucose generated ::::: 0.002 P kg glucose out + glucose consumed
Glucose consumed ::::: (60 - 0.002 P) kg
Converting the glucose consumed to molar tenus:
25
1
1kgmOll (60 -0.002 P)
Glucoseconsumed ::::: (60 - 0.002 P) kg. 180.2 kg::::: 180.2 kgmol
Glucoseconsumed ::::: (0.333-1.11 x 10-
5
p) kgmol
From the reaction stoichiometry, conversion of this amount of glucose requires the same number of kgmol OZ.
Converting this molar quantity to mass of Oz:
(0.333 -1.11 x 10-
5
p) kgmo102 = (0.333-1.11 x 10-
5
p) kgm01.1 = (10.656- 3.552x 10-4 p) kg 02
02 balam.:e
18 kg Oz in +0 kg Ozgenerated :::::{)Z out + (10.656 - 3.552 x 10-4 P) kg Oz consumed
02 out =(18 - (10.656 - 3.552 x 10"" P) kg
02; out::::: (7.344 +3.552 x 10-4 P) kg
Adding this mass of Oz to the mass of NZ in the
G ::::: 59.30 + (7.344 +3.55Z x 10-4 P) kg
G =(66.64 +3.552 x 10
4
P) kg
Total mass balance
3077.3 kg total mass in ::::: (G + P) kg total mass out
Substituting the expression for G into the total mass balance:
3077.3 kg ::::: (66.64 +3552 x 10-4P + P) kg
301O.7kg = I.0004Pkg
P =3009.6kg
Therefore, from the oxygen balance:
G ::::: (66.64 + 3.552 x 10-4 x 3009.6) kg
G = 67.71 kg
and:
Oz out::::: (7.344 + 3.552 x 10,4 x 3009.6) kg
Oz out::::: 8.41 kg
The mass of glucose out is 0.002 x 3009.6::::: 6.02 kg. The moles of glucose consumed is:
Glucose consumed::::: (0.333 - 1.11 x 10-
5
x 3009.6) kgmol ::::: 0.300 kgmol
Therefore, from stoichiometry and the molecular weights:
Water consumed ::::: 0.300kgm01.1 5.40kg
26
Water balance
Solutions: Chapter 4
Gluconic acid generated = 0.300 kgmOI.! I= 58.86 kg
HZOz generated = 0.300 kgmOl.ll = 10.20kg
600 kg water in +0 kg water generated = water out +5.40 kg water consumed
Water out =594.6 kg
Gluconic add balance
okg gluconic add in + 58.86kgglllcomc acid generated ::: gluconic acid out +0 kg gluconic acid consumed
Gluconic acid out ::: 58.86 kg
o kg HZOZ in + 10.20 kg HZOZ generated = HzOZ out + 0 kg HZOZ consumed
HZOZ out = 10.20 kg
These calculations allow completion of the Out side of tab1e.withall,quantities-mJcg.. _
Stream Out
Glucose Water Egg solids 02 N2 Gluconic acid H2O, Total
Egg slurry -
All-
Off-gas 0 0 0 8.41 59.30 0 0 67.71
Product 6.02 594.6 2340 0 0 58.86 10.20 3009.6
Total 6.02 594.6 2340 8.41 59.30 58.86 10.20 3077.3
(iii) Check the results
All columns and rows of the completed table add up correctly to within round-off error.
4. Finalise
(a)
To determine which is the limiting substrate, the number ofmoles available of each substrate involved in the reaction
must be determined. From the mass-balance table for streams in:
I
1 kg mOll
Moles glucose = 60 kg. 180.2 kg = 0.333 kgmol
1
1kgmOIl
Moleswater = 600 kg . 18.0kg = 33.3kgmol
1
1kgmOIl
Moles 02 = 18 kg. 32.0kg = 0.563 kgmol
As the substrates are required in the molar stoichiometric ratio of 1: 1: 1 and glucose is available in the smallest molar
quantity, the extent of the reaction must be limited by glucose.
Answer: Glucose
(b)
Water and 02 are available in excess. As only 0.333 kgmol of each will be used if the reaction proceeds to
completion, from Eq, (2.34);
(33.3 - 0.333) kgmol
% excess water = 0.333 kgmol x 100% = 9900%
% 0
- (0.563 - 0.333) kgmol 100m _ 69%
excess 2 - 0.333 kgmol x "10 -
Answer: 9900% excess water; 69% excess 02
Solutions: Chapter 4 27
(c)
From the completed table. the reactor off-gas contains 8.41 kg Oz and 59.30 kg N2. As gas
compositions are normally expressed in molar or volumetric terms (p 17), these mass values must be converted to
moles:
1
1kgmOll
8.41 kg 02 = 8.4lkg0
2
32.0kg =0.263kgmo102
As the number of kgmol N2 was determined in the preliminary calculations to be 2.118, the total number of moles of
off-gas is (0.263 + 2.118) =2.381 kgmoJ. Therefore, the composition of the off-gas is 0.263/2.381 =0.11 02, and
2.118/2.381 = 0.89 N,.
Answer: 0.11 Oz, 0.89 Nz
(d)
From the completed mass-balance table, the product stream has a total mass of 3009.6 kg and contains 6.02 kg
glucose, 594.6 kg water, 2340 kg egg solids, 58.86 kg gluconic acid and 10.20 kg H202. Therefore, the composition
is:
6.02 0002 1
3009,6 =. g ucose
594.6
3009.6 =0.198 water
2340 .
3009.6 = 0.778 egg solids
58.86 0020 I . d
3009.6 =. g UCONC act
10.20
3009.6 =0.003 H2
0
,
Answer. 0.002 glucose. 0.198 water. 0.778 egg solids. 0.020 gluconic acid, 0.003 H202
4.5 Azeotropic distillation
1. Assemble
(0 Flow sheet
,...-----------------..,
--1---
--j-
System boundary"r-
1
1
Feed
95% ethanol I
5% water I
1
Benzene feed ------'-1-ol
1
1
1
(ii) System boundary
The system boundary is shown on the flow sheet
Distillation
tower
.,
1
1
1
1
1
1
1
1
1
Overhead
74.1% benzene
18.5% ethanol
7.4"1" H20
Product
100% ethanol
28
(iii) Reaction equation
No reaction occurs.
2. Analyse
(i) Assumptions
- steady state
-no leaks
(li) Extra data
lOOOcm
3
=11
l000g=lkg
(iii) Basis
2501 ethanol product
(iv) Compounds involved in reaction
No compounds are involved in reaction.
(v) equation
As there is no reaction, the appropriate mass-balance equation is Eq. (4.3):
mass in "'" mass out
Solutions: Chapter 4
3. Calculate
(i) Calculation table
As all quantities in mass-balance calculations must be masses (rather-than vo!umes), 250 l-absolute ethanol must first
be converted to mass. From the deflnition of density on p 16, mass is equal to volume multiplied by density:
2501absoluteethanol ::::: 2501 x 0.785 gcm-
3
"'" 196.25kg
The calculation table shows all given quantities in kg. The total mass of feed in is denoted F; the total mass of
benzene feed in is denoted B; the total mass of overhead out is denoted v.
Stream
Feed
Benzene feed
Product
Overhead
Total
Ethanol
0.95 F
o
0.95F
Water
0.05F
o
0.05F
In
Benzene
o
B
B
Total
F
B
F+B
Out
Ethanol Water Benzene Total
196.25 0 0 196.25
0.185 V 0.074 V 0.741 V V
196.25 + 0.074 V 0.741 V 196.25 +
0.185 V V
(ii) Mass-balance calculations
Ethanol balance
0.95 F kg ethanol in =. (196.25 + 0.185 V) kg ethanol out
F =(206.58 +0.195 V) kg
Benzene balance
B kg benzene in =. 0.741 Vkg benzene out
B =. 0.741 V
Total mass balance
(F +B) kg total mass in =. (196.25 + V) kg total mass out
Substituting for F and B from the ethanol and benzene balances:
(206.58 + 0.195 V + 0.741 V) kg =(196.25 +V) kg
10.33 =. 0.064 V
V=. 161.4kg
Using this result in the ethanol and benzene balances gives:
F = 238.1 kg
Solutions: Chapter 4 29
B = 119.6kg
These calculations allow completion of the mass-balance table with all quantities in kg.
Stream In Out
Ethanol Water Benzene Total Ethanol Water Benzene Total
F,ed 226.2 11.9 0 238.1
Benzene feed 0 0 119.6 119.6
Product 196.25 0 0 196.25
Overhead 29.9 11.9 119.6 161.4
Total 226.2 11.9 119.6 357.7 226.2 11.9 119.6 357.7
(ill) Check the results
All columns audrows of the completed table add up correctly to within round-off error.
4. Finalise
Prom the completed mass-balance table, the mass of benzene required is 119.6 kg. Using the definition of density on
p 16, volume is equal to mass divided by density:
119.6 kg 1
1000g
li 11 1
Volumeofbenzene"'" -3' lk . 3 "'" 1371
O.872gcm g l000cm
Answer: 137 titres
4.6 Culture of plant roots
1. Assemble
(i) Flow sheet
Off-gas
47 1m-as 02
15 litres CO2
Drained liquid
1110g
0.063% glucose
1.7% ammonia
1
J
Air-driven
reactor
----l
1
1
I
1
I
1
1
System boundary )..
Medium -----'-1_-I
1425 9 1
3% glucose
1.75% ammonia I
95.25% water I
1
1
I
1
L _
Air
22 cm
3
milr
1
10r 10 d
25C, 1 atm
(n) System boundary
The system boundary is shown on the flow sheet.
Moles of air in = n = p V =
RT
30 Solutions: Chapter 4
(iii) Reaction equation
From Table B.2 (Appendix B), the molecular formula for glucose is C6H1206. The reaction equation is based on the
general stoichiometric equation for aerobic growth, Eq. (4.4):
C6H1206+aOZ+bNH3 cCHaOpNo+dCOz+eHzO
2. Analyse
(i) Assumptions
- steady state
-no leaks
- air and are dry
- all the COz produced leaves in the
- gases are at low pressure so vol% = mol%
(li) Extra data
11= lOOOcm
3
Molecular weights (Table B.1, Appendix B): glucose = 180.2
02 = 32.0
NZ = 28.0
NH3 = 17.0
cOz =44.0
HzO= 18.0
Composition of air (p 17): 21% OZ, 79% NZ by volume
Ideal gas constant (Table 2.5): R = 82.057 cm
3
atm I
(iii) Basis
10 d. or 1425 g nutrient medium
(iv) Compounds involved in reaction
Glucose, OZ' NH3. biomass, COZ and HZO are involved in the reaction.
(v) Mass-balance equations
For glucose. 02, NH3, biomass, C02 and HzO, the appropriate mass-balance equation is Eq. (4.2):
mass in + mass generated = mass out + mass consumed
For NZ and total mass, the appropriate mass-balance equation is Eq. (4.3):
mass in = mass out
3. Calculate
(i) Calculation table
Over 10 d. the volume of air sparged into the fennenter is:
Volumeofairin = = 3.168x10
5
cm
3
Converting tbis gas volume to moles using the ideal gas law, Eq. (2.32), with the temperature converted from <>C to
degrees Kelvin using Eq. (2.24):
1 atm.(3.168 x 10
5
cm
3
) = 12.95gmol
82.057cm
3
atmK-
1
gmor
1
(25 +273.15) K
From the known composition of air, the moles ofOZ in the incoming air is 0.21 X 12.95 = 2.72 gmol, and the moles of
NZ is 0.79 x 12.95 = 10.23 gmo!. Converting these values to masses:
MassofOZin = 2.72gmOI.I = 87.04g
MassofNZin = = 286.4g
The total mass of air in is therefore (87.04 + 286.4) g = 373.44 g.
The gas volumes in the off-gas must also be converted to masses. First, convert the volumes of 02 and COZ to moles
using the ideal gas law. Eq. (2.32), with the temperature converted from c to degrees Kelvin using Eq. (2.24):
Solutions: Chapter 4
. 11000em31
V 1atm(47litres). 11
Mo1esofO
z
out::: n::: L::: ::: 1.92gmol
R T 82.057cm
3
atmK-
1
gmor
1
(25+273.15) K
(
. )I1000em' I
V 1atm 15litres. 11
Moles ofCOZ out =n =L = =O.613gmol
RT 82.057em'.tmK Igmoll(25+273.15)K
Calculate the corresponding masses:
MassofOz out =1.92
g
mOl.! =61.44g
MassofCOzout::: = 26.97g
31
The calculation tables below show all known quantities in g. The In side of the table is complete. The
total mass of out is denoted G; the total biomassbarvested is denoted R As the ratio of biomass fresh weight
to dry weight is 14:1, dry biomass comprises l!IS ::: 0.0667 of the total biomass. Because this problem requires an
integral mass balance, the biomass remaining in the fermenter after 10 d culture must also be included in the table
even though it is not contained in any of the streams flowing into or out of the vesseL
Using this result and adding up the row for the off*gas in the out table:
G =61.44 + 286.4 + 26.97 =374.81 g
Total mass balance
1798.44gtotalmassin::: (1110+G+B)gtotalmassout
Using the result for G:
32
B =: 313.63 g
Solutions: Chapter 4
Therefore, the dry biomass produced is 0.0667 x 313.63 =20.92 g; the mass of water in the biomass is 0.9333 X
313.63 = 292.71 g.
These calculations allow completion of the Out side of the massbalance table with all quantities in g.
Further mass-balance calculations allow evaluation of the masses of components consumed 'or generated in the
reaction.
Glucose balance
42.75 g glucose in +0 g glucose generated = 0.699 g glucose out + glucose consumed
Glucose consumed = 42.05 g
02 balance
87.04 g 02 in +0 g 02 generated = 61.44 g 02 out + 02 consumed
02; consumed =25.60 g
NH3 balance
24.94 g NH3 in +0 g NH3 generated =18,87 g NH3 out +NH3 consumed
NH3 consumed = 6.07 g
C02 balance
og C02 in + C02 generated = 26.97 g C02 out +0 g C02 consumed
C02 generated =26.97 g
H20 balance
1357.31 g H20 in +H20 generated = (1090.43 +0.9333 B) g H20 out +0 g H20 consumed
Substituting the value for B from the total mass balance:
H20 generated = 25.83 g
(iii) Check the results
All columns and of the completed mass-balance table add up correctly.
4. Finalise
(a)
Rounding to three significant figures from the completed table, the mass of dry roots produced is 20.9 g.
Answer: 20.9 g
(b)
To determine the stoichiometry, the calculated masses of components consumed or generated in the reaction must be
converted to molar quantities:
Solutions: Chapter 4
Moles of glucose consumed =42.05 g.1 =0.233 gmol
Moles of oz consumed =25.60 g .1 =0.800 gmol
MolesofNH3consumed = 6.07 g .1 = 0.357gmol
MolesofCOzgenerated= = 0.6l3gmol
MolesofHzO generated = 25.83 g = 1.435 gmol
Moles ofbiomass generated = g
10mass
33
The moles of biomass generated is not yet known explicitly because the molecular formula for the dry biomass is
unknown. The above molar quantities can be used as coefficients in the reaction equation:
20.92
0.233 Coli1206 +0.800 0, +0.357 NH3 -+ MWb' CH"OoN
S
+0.613 CO, + 1.435 H,O
lomass P'"
Dividing each coefficient by 0.233 to obtain the stoichiometry per gmol glucose:
89.79
CoH1206+3.430,+1.53NH3 -+ MWb' CH"OoNS+2.63CO,+6.16H,O
lOmass fJ
The values of a, /3 and 8 and the molecular formula for the biomass can obtained using elemental balances.
89.79
Cbalance:6 =MWb' +2.63
lomass
Therefore:
89:79 = 3.37
MWblomass
This result can be used in the remaining elemental balances for completion of the stoichiometric equation.
Hbalance: 12 + 3 x 1.53 = 3.37 a+ 2 x 6.16 --) a = 1.27
Obalance:6+2x3.43 =3.37/3+2x2.63+6.l6 --) /3 = 0.43
N balance: 1.53 =3.37 8 --) 8 =0.45
A11SWer: 1he complete stoichiometric equation is:
The chemical formula for the dry roots is CHI .Z700.43N0,4S.
(cj
Converting to moles the mass quantities of glucose, 0z and NH3 available for reaction on the In side of the mass-
balance table:
Moles of glucosein = =O.24gmol
Moles of 0z in = 8704g.1 =2.72gmol
MoiesofNH3in = = 1.47gmol
From the stoichiometric equation, reaction of 0.24 gmol glucose requires 0.24 x 3.43 = 0.82 gmol 0z and 0.24 x 1.53
=0.37 gmol NH3' As the molar quantities of Oz and NH3 available for reaction are in excess of these values, glucose
must be the limiting substrate.
Answer: Glucose
34 Solutions: Chapter 4
(d)
The mass of glucose consumed is 42.05 g; the mass of dry biomass produced is 20.92 g. Therefore, the biomass yield
from glucose is 20.92/42.05 = 0.50 g g-1 dry weight.
Answer: 0.50 g g-1 dry weight
4.7 Oxygen requirement for growth on glycerol
From TableB.2 (Appendix B), the molecular formula for glycerol is C3Hg03. From Table 4.3, the chemical formula
for Klebsiella aerogenes can be taken as CH1. 7S00.43NO.22. Substituting these formulae into the general
stoichiometric equation for growth. Eq. (4.4), gives:
C
3
Hg03 +a02 +b NH3 --t cCHI.7.s00:4JNO.22+dCOZ +eHZO
From Table B:8 (Appendix B), the molecular weight of glycerol is"92.1. The biomass formula weight calculated from
the atomic weights in Table B.l (Appendix B) is 23.74. Taking into account the 8% ash:
Biomassmolecularweight = zg;: = 25.8
The value of the stoichiometric coefficient ccan be detennined from:the yield Yxs =0.4 g g-1 and Eq. (4.12):
c = Yxs(MWsubstrate) = 0.40 g g-l (92.lggmOr
l
) = 1.43gmolgmol-1
MWcells 25.8 g grool 1
From Table B.2 (Appendix B), the degree of reduction of glycerol relative to NH3 is rs = 4.67. The degree of
reduction of the biomass relative to NH3 is:
1B = 1x4+1.75xl-0.43x2-0.22x3 = 4.23
which is also listed in Table 4.3. The theoretical oxygen demand can be determined from Eq. (4.16) with/= 0; from
Eq. (4.13). w = 3 for glycerol:
a = 1/
4
(w - c 1B) = 1/
4
(3 x 4.67 - 1.43 x 4.23) = 1.99
Therefore. 1.99 gmo! oxygen are required per grool glycerol. From the atomic weights in Table B.l (Appendix B),
the molecular weight of oxygen is 32.0. Converting a to mass terms:
a = 1.99gmolgmol-1 = = 0.69gg-
1
Answer: 0.69 g oxygen is required per g glycerol conswned
4.8 Product yield In anaerobic digestion
From Eq. (4.13), the stoichiometric equation for anaerobic growth and product fonnation by methane bacteria can be
written as:
0I
3
COOH+ bNH3 --j. c CH1.400.4ONo.20+ deo2 + eH
2
0 +/0I
4
From Table B.8 (Appendix B), the molecular weight of acetic acid is 60.1. From Table B.l (Appendix B), the
molecular weight of CO2 is 44.0. The value of the stoichiometric coefficient d can be determined based on Eq. (4.14)
with carbon dioxide as the product and the yield YpS = 0.67 kg kg-
1
= 0.67 g g-l:
d = = 0.67gg-
I
(60.1ggmor
1
j = 0.915 gmol gmol-l
MWC02 44.0ggmol I
The other coefficients can be determined using this result and elemental balances.
Cbalance:2 = c+d+/= c+0.915+f--j.f= L085-c
Hbalance:4+3b = 1.4c+2e+4f
balance: 2 = 0.40c+2d+e = OAOc+2xO.915+e = OAOc+L83+e --j. e = O.17-0.40c
N balance: b = 0.20 c
Solutions: Chapter 4
Substituting the expressions fort, e and b from the C, 0 and N balances, respectively, into the H balance:
4+3x0.20c = l.4c+2x(0.17-0.40c)+4x(l.085-c)
4 c = 0.680
C : 0.170
35
Substituting this value for c into the expressions for the other coefficients gives b = 0,034, e = 0.102 and/: 0.915.
The yield of methane is therefore 0.915 gmol per gmol acetic acid
The maximum possible methane yield can be calculated using Eq. (4.20). From Eq. (4.13), w=2 for acetic acid and)
=1 for methane. From TableB.2 (Appendix B); the degree of reduction of acetic acid relative to NH3 is it =4.00,
and the degree of reduction of methane relative to NH3 is lP = 8.00. Substituting these values into Eq. (4.20) gives:
. WYs :i 1.00) -1
fmax = )IP = 1(8.00) = 1.0gmolgmol
The actual methane yield of 0.915 gmol gmol-l therefore represents 91:S%of the theoretical maximum.
Answer: 91.5% of the theoretical maximum
4.9 Stoichiometry of single-cell protein synthesis
(aJ
From Table B.2 (Appendix B), the .molecular formula for glucose isC6H1206. If all carbon in the substrate is
converted into biomass, production of carbon dioxide is zero. Therefore, from Eq. (4.4), the stoichiometric equation
for anaerobic growth of Cellulomonas is:
+b NH3 -+ c +e H
2
0
The stoichiometric coefficients can be determined using elemental balances.
Cbalance: 6 = c
Hbalance:12+3b: 1.56c+2e
obalance: 6 =0.54 c + e
N balance: b : 0.16 c
Substituting the value for c from the C balance ,into the and N balances gives e = 2.76 and b = 0.96. respectively.
The yield of biomass from substrate in molar terms is therefore 6 gmol gmol-l.
Using the atomic weights in Table B.l (Appendix B), the molecular weight of glucose is 180.2. The biomass formula
weight calculated from Table B.l (Appendix B) is 24.46. Taking into account the 5% ash:
Biomass molecularweight = = 25.75
Therefore, in mass terms, the molar biomass yield of 6 gmol gmol-l= (6 x 25.75) g biomass per 180.2 g substrate:
0.86 g g-l.
The maximum possible biomass yield is calculated using Eq. (4.19). From Eq. (4.13), W = 6 for glucose. From Table
B.2 (Appendix B). the degree ofreduclion of glucose relative to NH3 isrs = 4.00. The degree of reduction of the
biomass relative to NH3 is:
I x4+ 1.56 x 1-0.54x2-0.16x3 00
JB = = 4.
Substituting these values into Eq. (4.19):
wYs 6(4.00) -1
croax = 1i3 = 4.00 = 6.0 gmol gmol
The theoretical maximum biomass yield is therefore the same as the actual biomass yield.
36 Solutions: Chapter 4
Answer: The biomass yield from substrate of 0.86 g g-t is 100% of the theoretical maximum. When there is no
product formo.tion and no oxygen for electron transfer, all the available electrons from the substrate must go to the
biomass.
(b)
(I)
From Table B.2 (Appendix B), the molecular formula for methanol is CH40 and the degree of reduction relative to
NH3 is 1S =6.00. The degree ofreduction of Methylophilus methylotrophus biomass relative to NH3 is:
_ lx4+1.68xl-0.36x2-0.22x3 -430
JB- 1 -.
From Eq. (4.13), W "" 1 for methanol. Substituting'values into Eq. (4.19);
W JS 1(6.00) 140 1 1-1
emu"" Jh" "" 4.30 "" . gIno gmo
From Table B.g (Appendix B). the molecular weight of methanol is 32.0. The biomass formula weight calculated
from the atomic weights in Table B.I (Appendix B) is 22.55. With 6% ash:
Biomassmolecularweight = ~ : : =23.99
In mass terms, the maximum possible molar biomass yield of lAO gmol gmoll is equal to (1.40 x 23.99) g biomass
per 32,0 g substrate = 1.05 g g-l,
Answer: 1he maximum possible biomass yield from methanol is 1.05 g g-}, In terms of Catoms,.the biomass yield is
1.40 grool grool-l as both biomass and substrate have 1 C atom each. In comparison, the C*atQm biomass yield from
glucose in (a) is 1 grool grool}. The main reason for the increased yield in (b) is the high degree of reduction of
methanol compared with glucose.
(il)
The actual yield of biomass from methanol is c = OA2 x lAO gmol gmol} = 0.59. The ox.ygen demand can be
determined from Eq. (4.16) if biomass remains the only major product so thatf= O. Using the parameter values
determined in (b) (i):
Therefore, 0.87 gruol ox.ygen is requiredr:.r gmol methanol. As the molecular weights of methanol and oxygen are
the same, the oxygen demand is 0.87 g g. methanol.
Answer. 0.87 g oxygen is required per g methanol consumed
4.10 Ethanol production by yeast and bacteria
(a)
From Table B.2 (Appendix B), the molecular formula for glucose is C6H1206 and the molecular formula for ethanol
is C2H60. From Eq> (4.13), the stoichiometric equation for anaerobic growth and product formation is:
CJI}P6+bNH3 -+ cCHl.sO05NO.2+dC02+eH20+fC2H60
From Table B.8 (Appendix B), the molecular weight of ethanol is 46.1. Using the atomic weights in Table B.l
(Appendix B), the molecular weight of glucose is 180.2 and the biomass molecular weight is 24.6. The values of the
stoichiometric coefficients c can be determined from Eq. (4.12) and the yields Yxs -= O.ll g g.1 for yeast and Yxs =
0.05 g g.1 for bacteria.
F t. - Yxs(MWsubstrare) _ O.ll gg-' (180.2 g gmOr') - 081 1 1-'
oryeas c - MW II - 1 -. gmo gmo
ce s 24.6 g gmol
F b
. Yxs(MWsubstrate) 0.05 g g-' (I80.2ggmor
1
) 037 1 1-'
or actena, c = MW II = ,= . gmo gmo
ce s 24.6 g gmol-
The other coefficients can be determined using elemental balances.
Solutions: Chapter 4
Yeast
Cbalance:6 = c+d+2j= d = 5.19-2j
Hbalance: l2+3b = 1.8c+2e+6j= 1O.54+3b = 2e+6j
obalance: 6 = 0.sc+2d+e+f= 5.595 = 2d+e+j
Nbalance:b = 0.2e = O.2xO.81 = 0.16
Substituting the expression for b from the N balance into the H balances gives:
10.54+3xO.16 = 2e+6f
e=5.51-3f
Substituting this and the expressionfor d from the C balance into the 0 balance gives:
\ ...... "
5.595 =2x(5.19-2j)+(5.51-3j)+f
6f =10.295
f= 1.72
Therefore, for yeast, the yield of ethanol from glucose is 1.72 grool grool,l.
37
Bacteria
C balance: 6 = c+d+2f= d = 5.63-2f
Hbalance:12+3b = 1.8c+2e+6f= 11.33+3b = 2e+6f
obalance: 6 = 0.5c+2d+e+f= 5.815 = 2d+e+!
N balance: b = 0.2 c = 0.2 x 0.37 = 0.074
Using the same solution procedure as for yeast, substituting the expression for b from the N balance into the H
balances gives:
11.33 +3xO.074 = 2e+6j
e=5.78-3f
Substituting this and the expression for d from the C balance into the 0 balance gives:
5.815 = 2x(5.63-2j)+(5.78-3j)+f
6f= 11.225
f =1.87
Therefore, for bacteria. the yield of ethanol from glucose is 1.87 grool grool'}.
1.72 grool grool"} for yeast; 1.87 grool grool,l for bacteria
(b)
The maximum possible ethanol yield can be calculated using Eq. (4.20). From Eq. (4.13), w =6 for glucose andj =2
for ethanol. From Table B.2(Appendix B), the degree of reduction of glucose relative toNH3 is rs =4.00, and the
degree of reduction of ethanol relative to NH3 is =6.00. Using these values in Eq. (4.20) gives:
WJS 6 (4.00) 1
fmax = 1P = 2(6.00) = 2.0gmolgmor
There:ore, the ethanol yield of 1.72 gmol'} for yeast represe.nts 86%. of the theoretical maximum; for
bactena, the actual yield of 1.87 grool grool' represents 94% of the theoretical maxunum.
Answer: 86% of the theoretical maximum for yeast; 94% of the theoretical maximum for bacteria
4.11 Detecting unknown prodncts
From Table B.2 (Appendix B), the molecular formula for glucose is C6H1206. Assuming that no products other than
biomass are formed, from Eq. (4.4), the stoichiometric equation for growth
38 Solutions: Chapter 4

Using the atomic weights in Table B.l (Appendix B), the molecular weight of glucose is 180.2. the molecular weight
of oxygen is 32.0, and the biomass molecular weight is 25.16. The value of the stoichiometric coefficient c can be
determined from the yield Yxs =0.37 g g-l andEq. (4.12):
0.37gg-
1
(180.2ggmor
'
j -1
c = MW II = 1 = 2.65gmolgmol
ce s 25.16ggmor
Therefore, 2.65 groat cells are produced per gmol glucose consumed. Converting the oxygen demand to a molar
basis:
O.88g02125.16gcellslllgmOlOZI -1
0.88 g 02 per gcells 1gce!J.s . 19mol cells . 32.0 g 02 =0.69 gmol 02 groot cells
Combining this with the result for c, the observed oxygen demand a is:
0.69 gmol O2 (2.65 gmat cens)
a= =183
1gIno! cells 1gmol glucose .
From Table B.2 (Appendix B), the degree of reduction of glucose relative to NH31srS'='4;00. The degree of
reduction of the biomass relative to NH3 is:
_ lx4+1.79xl-0.56x2-0.17x3 -416
- .
If no products are formed other than biomass, the theoretical oxygen demand can be determined from Eq. (4.16) with!
=0; from Eq. (4.13), w = 6 for glucose:
a = 1/4(w1!l-clll) = 1/
4
(6x 4.00-2.65 x 4.16) = 3.24
As the theoretical oxygen demand is significantly higher than that observed, formation of other products acting as
electron acceptors is likely to have occurred in the culture.
Answer: Yes
4.12 Medium formulation
Using the atomic weights'in Table B.l (Appendix B), the molecular weight of (N14)zS04 is 132,1 and the biomass
molecular weight is 26.16. Using a basis of 1 litre, production of 25 g cells corresponds to 25/26,16 = 0.956 grool
cells. As each gmolcells contains O.25gmol N, (0.956x0.25) = 0.239gmol Nare-neededfrom the'medium for
biomass synthesis, As (NH4)zS04 is the sole N source and each gmol (Nl4)zS04contains 2gmol N, 0.239/2= 0.120
gmol (N14)zS04 is required. Multiplying this by the molecular weight, 0.120 x 132.-1 = 15.9 g (N14)zS04 are
required. The minimum concentration of (N}4)zS04 is therefore 15.9 g 1*1.
Answer: 15.9 g I-I
4.13 Oxygen demand for production of recombinant protein
(a)
Recombinant protein can be considered as a product of cell cuItureeven though it is not excreted from the cells;
assume that recombinant protein is synthesised in addition to the normal E.- coli biomass composition. From Table
4.3, the chemical formula for E. coli can be taken as CH1.7700.49N0.24; from Table B.2 (Appendix B), the molecular
formula for glucose is C6H1206' Substituting these formulae into the general stoichiometric equation for growth and
product formation, Eq. (4.13), gives:
+a02 +bNH3 -lo +dC02 +e H20+fCHl.s.sO0.3INO,2S
Using the atomic weights in Table B.l (Appendix B), the molecular weight of glucose is 180.2, the biomass molecular
weight is 25.00, and the recombinant protein molecular weight is 22.03.
Solutions: Chapter 4 39
Assume that the biomass yield refers to the cell mass without recombinant protein. The value of the stoichiometric
coefficient c can be determined from the yield Yxs =0.48 g g-l and Eq, (4,12):
Yxs(MWsubs"ate) 0.48gg-
1
(180.2g gmol-l) 346 I I-I
c= = =. gmogmo
MWcells 25,OOggmoll
The value of the stoichiometric coefficientfcan be determined from the yield Yps =0.20 x 0.48 =0.096 g g-l and Eq,
(4.14)'
f
- Yps(MWsubstrate) _ 0.096gg-
1
(180.2ggmol-l) _ 079 I I-I
_ _ -,gmogmo
MWproduct 22.03 g gmol 1
The ammonia requirement can be, detemPneq. using an elemental balance for N.
N balance: b = 0.24 c + 0,25f .'
Substituting the above valoesforc and/into the N balance gives b = 0,24 x 3.46 + 0.25 x 0,79 = 1.03,
Answer: 1.03 gmol grool-l glucose
(h)
The oxygen demand can be determined using an .electron balance. From Table B,2 (Appendix B), the degree of
reduction of glucose relative to NH3 is -ns =4.00; from Table 4.3," the degree of reduction 'Of E. coli relative to NH3 is
JB =4.07. The degree of reduction of the recombinant protein relative to NH3 is:
_ lx4+1.55xl-0.31x2-0.25x3 _ 418
- .
From Eq. (4.13), w =6 for glucose andj =1 for recombinant protein. Substituting these values into Eq. (4.16) for the
theoretical oxygen demand gives:
a = = 1/4 (6 x 4.00-3.46x 4.07- 0.79 x 1 x4.18) = 1.65
Answer: 1.65 gmol per gmol glucose
(e)
Iff in the stoichiometric equation is zero but c remains equal to 3.46, the ammonia requirement can be determined
using an elemental balance for N as follows:
N balance: b = 0.24 c = 0.24 x 3.46 = 0.83
Therefore, in wild-type E. coli the ammonia requirement is reduced from 1.03 to 0.83 grool gmol-1 glucose, a
decrease of 19%, Eq. (4.16) for the oxygen requirement becomes:
Therefore, the oxygen demand is increased from 1.65 to 2.48 gmol gmol-l glucose, a rise of 50%.
Answer. The ammonia and oxygen requirements for wild-type E. coli are 0.83 grool and 2.48 gmol per gmol glucose,
respectively. These values represent a 19% reduction and a 50% increase, respectively, compared with the genetically
engineered strain.
4.14 Effect of growth on oxygen demand
The stoichiometric equation for acetic acid production using cell culture must include terms for growth. Based on Eq.
(4.13), the stoichiometric equation for growth and product formation is:
C2H4>+a02+bNH3 cCHLSOo.sNo.2+dC02+eH20+jC2f402
From Table 8.8 (Appendix B), the molecular weights of ethanol and acetic acid are 46.1 and 60.1, respectively. From
the atomic weights in Table B.1 (Appendix B), the biomass molecular weight is 24.63. The value of the
stoichiometric coefficient c can be determined from the yield Yxs =0.14 g and Eq. (4.12):
_
Yx",s"(MW"","S::U,,bs::"_at-,-e) 0.14 gg-1 (46.1 g gmol-
1
) -1
c = = "'" 0.26groolgmol
MW cells 24.63 g gmol 1
40 Solutions: Chapter 4
The value of the stoichiometric coefficient!can be determined from the yield Yps = 0,92 gg-1 and Eq. (4.14):
Yps(MWsubstrate) O.92gg-
t
(46.1ggmol-l) -I
f = MW odu =. 1 =. 0.71 gmol gmol
pr ct 6O.1ggmor
From Table B.2 (Appendix B), the degree of reduction of ethanol relative to NH3 is rs =. 6.00, and the degree of
reduction of acetic acid relative to NH3 is 'no =. 4.00. The degree of reduction of the biomass relative to NH3 is :
_ lx4+1.8xl-0.5x2-0.2x3 _ 420
1ll- 1 -.
From Eq. (4.13), W = 2 for ethanol and j =. 2 for acetic acid. Substituting these values into Eq. (4.16) for the
theoretical oxygen demand gives:
a=. 1/4(w/S-C1B-fj1P) =1/4(2x6.00-0.26x4.20-0.71x2x4.00) =. 1.31
Therefore, with growth, 1.31 groat oxygen are required per gmol glucose consumed, compared with 1 gmoloxygen
per gmol glucose without groWth. Therefore, with growth, the oxygen demand for acetic acid production is increased
by31%.
Answer. The oxygen demand is increased by 31%.
Energy Balances
5.1 Sensible energy cbange
(a)
From Table B.5 (Appendix B), C
p
for between 25"'C andlOO"C is 0.551 calg-
I
oC-t.Thespecific enthalpy
change calculated using Eq. (SIB) is:
M =C
p
aT =0.551 cal g-IoC
l
(100 - 25)OC
!ill :::::: 41.3 cal g-t
Answer. 41.3 cal g-1
(b)
From Table B.5 (Appendix B). C
p
for ethylene glycol betweenlO"C and 20"C can be taken as 0.569 cal g-1 "C-
1
.
The specific enthalpy change calculated using Eq. (5,13) is:
M = C
p
aT = 0.569 cal g-l Cl (10- 20)OC
!ih :::: -5.69 cal g-1
Answer: -5.69 cal
(c)
Prom Table B.6(Appendix B), C
p
for succinic acid between 15"C-and 120Cis given by the expression 0.248 +
0.00153 T. where Tis in "c and C
p
is in cal got The sensible energy change is best determined from the integral
of this equation between the limits T:::: 15"C and T:::: 1200C:
J.
'''''' J,,,,,"c
6h = CpdT = (0.248+ 0.(01531) dT calg-
l
lS"C 1S"C
6h = calg-
l
M =36.9 cal g.l
(d)
From Table B3 (Appendix B), the heat capacity of air between 65"C and 150"C is given by the equation:
C
p
:::::: 28.94 + 0.4147 x W
2
T + 0.3191 x lOw
5
y'2 _ 1.965 x lO
w9
T3
where C
p
is heat capacity in J gmol-l C
l
and Tis temperature in C. The sensible energy change can be determined
by evaluating the integral of this expression between the limits T =150C and T =65C:


M = C
p
dT = (28.94 +0.4147x 10-
2
T+ 0.3191 x 10-
5
f2 - 1.965 x 10-
9
rJ) dT J gmor
1
15O"C l5O"C
42 Souaions: Chapter 5
t:.h = -2500.9 J "" -2.50 kJ gmat-
l
Answer: -2.50kJ gmal-]
5.2 Heat of vaporisation
-The latent heat of vaporisation of water at BOC is obtained from Table C.l (Appendix C). Taking the average of the
values at nee and Ah
v
=2423.55 kJ at 33C From Eq. (5.16);
Mf = M!>h
v
= 20 gb-
I
(2423.55 kJ kg-Ij
Mf = 48.5 kJ h-
I
Answer: 48.5 kJ h-
l
5.3 Steam tables
(aJ
The heat of vaporisation of water at 85"C is obtained from Table C.I (Appendix C). Taking the average of the values
at 84"C and 86"C, !:J.hy = 2296.05 kJ kg-! at 85C.
Answer: 2296.05 kJ kg-
l
(bJ
From Table C.l (Appendix C), the enthalpy of liquid water at IOce relative to the triple point is 42.0 kJ kg-
t
, The
enthalpy of liquid water at 3S"C relative to the triple point can be estimated as the average of the values in Table Col
for 34<>C and 36C = 146.55 k:J kg-t. Using the relationship on p 89, the enthalpy of water at 35C relative to 1000e is
therefore (146.55 - 42.0) kJ kg-I"" 104.55 kJ kg-I.
Answer: 104.55 kJ kg-I
(cJ
-The enthalpy of saturated water vapour at 40C relative to the triple point can be read directly from Table C.I
(Appendix C) as 2574.4 kJ kg-I.
Answer: 2574.4 kJ kg-
l
(dJ
The enthalpy of superheated steam at 2.5 atm and 275C relative to the triple point can be obtained from Table C.3
(Appendix C). To convert the pressure to kPa, from Table A.S (Appendix A), 1 atm "" 1.013 x lOS Pa. Therefore:
2.5 atm =2.5 atm =253.3kPa
From Table C.3, the enthalpy at 100 kPa and 275C is 3024 kJ kg-I; the enthalpy at 500 kPa and 275"'C is 3013 kJ
kif 1. Interpolating between these values gives an enthalpy of 3019.8 kJ kg-
l
at 253.3 kPa.
Answer: 3019.8 kJkg-
1
5.4 Pre-heating nutrient medium
1. Assemble
(i) Units
kg, h, kJ, C
(ii) FkJw sheet
Solutions: Chapter 5 43
System boundar; \.
r
Q (loss) =0.22 kW
1
I
I
Medium in . . l . - _ ~
3250 kg h-
1
15C
Heating vessel 1--'----_Medium out
3250 kg h-
1
44C
-Q(from condensing steam)
(ill) System boundary
The system boundary is shown on the flow sbeet.
2. Analyse
(i) Assumptions
- steady state
-no leaks
- system is homogenous
- condensate temperature is 150C
- no shaft work
(li) Basis
1 h, or 3250 kg medium in
(ill) Reference state
H = 0 for water (steam) at its triple point
H =0 for medium at 15C
(iv) Extra data
C medium=0.9 cal g-l 0(;-1 =0.9 kca1 kg-I C-
1
6h
v
waterat 150C= 2113.1 kJ kg-
1
(fable C.2, Appendix C)
1 kcal = 4.187 x 103 J (fable A.7, Appendix A)
1 W = 1 J s-1 (fable A.S, Appendix A); therefore, 1 kW =1 kJ s ~ l
(v) Mass balance
The mass balance is already complete.
(vi) Energy-balance equation
At steady state, Eq. (5.9) applies:
:E(Mh) - :E(Mh)- Q+ W, = 0
input output
""""" """""
3. Calculate
(i) ldmtify ta"" in the 'nagy-balan" ,quatian
W
s
=O. There are two components for the beat term, Q: Qross and Q from the condensing steam. With symbol MD =
medium. the energy-balance equation becomes:
(Mh)MD in - (M h)MD out - Q- Qloss =0
(Mh)MD in = 0 (reference state)
(M h)MD out at 44C is calculated as a sensible energy change from H = 0 at 15C using Eq. (5.13):
(Mh)MDuut =M C
p
aT =3250 kg (0.9 keal kg-
l
0c-
l
)(44 -15loe =8.483 x 10
4
keal
Converting to kJ:
44
4 14.187X103J111kJ I 5
(Mh)MDout = 8.483 x 10 kcaL 1kcal '10001 "" 3.55 x 10 kJ
The rate of heat loss is 0.22 kW. Converting to k:J hoi:
[
lkJ,-1113600'1 -1
O.22kW =O.22kW. 1kW lh =792kJh
Solutions: Chapter 5
Therefore, on the basis of 1 h, {hess "" 792 kJ. Substituting values into the equation gives:
0-3.55 x 10
5
kJ-Q-792kJ "" 0
Q = -3.56 x 105 kJ
Q has a negative value which is consistent with the sign conventions outlined on pp 87-88: heat must be supplied to
the system from the surroundings. This heat is provided as the latent heat of vaporisation as saturated steam at 150<>C
condenses. The enthalpy change from this change ofphase is calculated using Eq. (5.16) and must be equal to -Q.
3.56xloSkJ "" Msteam!JJl
v
=M
s
team(21l3,lkJkg-
1
)
M
stearn
"" 168 kg
4. Finalise
Answer: 168 kg
5.5 Production of glutamic acid
(a)
L Assemble
(i) Units
kg, b, kJ; C
(ii) Flow sheet
Off-gas
System boundary

- -- - - --
1
I I
I I
Feed
I
Reactor I
(25,000 lltres)
Product
2000 kg h-
1
I I
0.5% glucose
4% glucose
I
/ I 96% water
25C
r--t-
I
- --
.
Q (cooling)
Inlet gas
100,000 litres min-
1
1 atm, 15"C
88% air
12%NHs
(ill) System boundary
The system boundary is shown on the flow sheet.
Solutions: Chapter 5
(iv) Reaction equation
2. Analyse
(i) Assumptions
- steady state
-no leaks
- system is homogenous
- solutions are ideal
- inlet air and off-gas are dry
- all excess NH3 is dissolved in the aqueous phase
- all COz produced leaves in the off-gas
- negligible sensible heat change
- no evaporation
- no shaft work
(ii) Basis
I h, or 2000 kg feed
(ill) Reference state
H = 0 for water at its triple point
H = 0 for feed at 25C
(iv) Extra data
Molecular'weights (Table B.t, Appendix B): glucose = 180.2
NH3 = 17.0
02=32.0
Nz = 28.0
glutamic acid = 147.1
C02 =44.0
H20 = 18.0
air = 28.8 (see Problem 2.9, Chapter 2)
Ideal gas constant (fable 2.5): R = 0.0820571 atm K-l gmol-l
Composition of air (p 17): 21% Oz, 79% Nz by volume
Heats of combustion (Table B.8, Appendix B):
glucose = -2805.0kJ gmol-l
=-382.6kJ gmol-
1
glutamicacid =-2244.1 kJ gmor
1
45
(v) Compounds involved in reaction
Glucose, ,ammonia, oxygen, glutamic acid, carbon dioxide and water are involved in the reaction.
(vi) Mass-balance equations
For,glucose, ammonia, oxygen; glutamic acid. carbon dioxide and water, the appropriate Eq.
(4.2),
mass in + mass generated = mass out +.mass consumed
For Nz and total mass, the appropriate mass-balance equation is Eq. (4.3):
mass in = mass out
(vii) Energy-balance equation
The modified energy-balance equation, Eq. (526), applies:
-MIrxn-MyAhv-Q+ W
s
= 0
3. Calculate
(i) Mass balance
As gas compositions are normally given in Yol%, 88,000 litres air and 12,000 litres NH3 enter the reactor every min.
On a basis ofl h, the volume of air in is 88,000 x 60 = 5.28 x 10
6
litres; the volume ofNE3 in is 12,000 x 60 = 7.20
x 10
5
litres. Using the known composition of air, the volume of Oz in = 0.21 x 5.28 x 10
6
= 1.11 x 10
6
Utres; the
volume ofNZ in = 0.79 x 5.28 x 10
6
= 4.17 x l06litres. Converting these gas volumes to moles using the ideal gas
law, Eq. (2.32), with the temperature converted from C to degrees Kelvin using Eq. (2.24):
46 Solutions: Chapter 5
Moles of 02 in = pV = 1atm(l.l1 x 1Q6t) = 4.69xI04gmol
RT 0.0820571almr' gmor
1
(15 + 273.15) K
MI fN
_pV _ laJln(4.17XI0'1) -176 10' I
o eso 2m - - - - . x gmo
RT 0.0820'71aJlnK 19moll(I'+273.I5)K
MolesofNH in=pV = latm(7.20xt051) =3.05x10
4
g.mol
3 RT 0.0820571aJlnK 'gmol-'(15+273.I5)K .
These molar quantities can now be converted to masses using the molecular weights:
Mass of02 in = 4.69 x 10
4
= 1500.8kg
Mass ofN2 in = L76x 10
5
= 4928.0kg
MassofNH3 in = 3.05 x 10
4
gmol.! = 5185 kg
Therefore, the total mass of inlet gas is 1500.8 + 4928.0 +518.5 =6947.3 kg.
The calculation tables below show all known quantities in kg. The total mass of is denoted G; the total mass
of product is denoted P.
2000
6947.3
Total
1920
o
HZO
In
Gluconic acid C02
o 0
o 0
o
4928.0
o
1500.8
02
o
518.5
80
o
80 518.5 1500.8 4928.0 0 0 1920 8947.3
Out
Glucose NHS
z
NZ
Gluconic acid COz HZO Total
0 0 ? ? 0 ? 0 G
0.005P ? 0 0 ? 0 ? P
0.005P ? ? ? ? ? ? G+P
Glucose
Stream
Peed
Inlet gas
Off-gas
Product
Total __-=__ -,,,-__--,,=__-==,-_
Stream
Peed
Inlet gas

Product
Total
N2 balance
N2 is a tie component.
4928.0 kg N2 in = N2 out
N2 out = 4928.0 kg
Glucose balance
80 kg glucose in + 0 kg glucose generated = 0.005 P kg glucose out + glucose consumed
Glucose consumed :::: (80 - 0.005 P) kg
Converting the glucose consumed to molar terms:
Olucoseconsumed = (80-0.005 P) kg 1 1= (0.444-2.775x 10-' P)kgmol
From the reaction stoichiometry, conversion of this number of kgmol glucose requires the same number of kgmol
NH3 and 1.5 x the number of kgmo1 02. Converting these molar quantities to masses:
Solutions: Chapter 5
NH, consumed =(0.444-2.775 x 10-
5
P)kgmol =(0.444-2.775 x 10-
5
p) kgm01.1 ; ~ ~ ~ l l
NH3 consumed = (7.548-4.718 x 10-4 P) kg
02 consumed =1.5 x (0.444-2.775 x 10-
5
P)kgmol =1.5X(0.444-2.775X 10-
5
p)kgm01.j ; ~ : ~ 1 1
02 consumed =(21.312-1.332 x 10-
3
P) kg
47
Similarly, expressions for the masses of glutamic acid, C02 and water generated can be determined ,from the
stoichiometry:
Glutamicacidgenerated = (0.444-2.775 x 10-
5
P)kgmol = (0.444-2.775X W-
5
p)kgm01.1 ~ 4 : ~ ~ ~ I
Glutamic acid generated =(65.312 -4.082 x 10-
3
P) kg
CO2 generated = (0.444-2.775 x 10-
5
P)kgmol = (0.444-2.775 x 10-
5
p)kgm01.1 ~ : ~ l l
C02 generated = (19.536 - 1.221 x 10-
3
P) kg
Water generated =3 x (0.444-2.775 x 10-
5
P)kgmol =3 x (0.444-2.775 x 10-
5
p)kgm01.1 ; ~ : ~ 1 1
Water generated =(23.976 - 1.499 x 10-
3
P) kg
02 balance
1500.8 kg02 in + 0 kg 02 generated =02 out + (21.312 - 1.332 x 10-
3
P) kg 02 consumed
02 out = (1500.8 - (21.312 - 1.332 x 10-' P)) kg
02 out =(1479.5 + 1.332 x 10-
3
P) kg
C02 balance
okg C02 in + (19.536 - 1.221 x 10-
3
P) kg C02 generated = C02 out + 0 kg C02 consumed
C02 out = (19.536 - 1.221 x 10-
3
P) kg
Adding together ,the masses ofN2, 02 and C02 out gives the total mass of off-gas,O:
a = 4928.0 kg N2 + (1479.5 + 1.332 x 10-
3
P) kg 02 + (19.536 - 1.221 x 10-
3
P) kg C02
G = (6427.0+ 1.11 x 10-
4
P) kg
Total mass balance
8947.3 kg total mass in =(0 + P) kg total mass out
Substituting the above expression for a into the total mass balance:
8947.3kg = (6427.0+ 1.11 x 10-
4
P+ P)kg
2520.3 kg = 1.000 P kg
P = 2520.3 kg
Therefore, from the total mass balance:
G =(8947.3 - 2520.3) kg
G =6427.0kg
Substituting the result for P into the glucose, 02 and C02 balances gives:
48
Glucose consumed = (80 - 0.005 P) kg = 67.40 kg
Glucose out =0.005 P kg = 12.60 kg
Ozconsumed = (2L312-1.332xlO*3p) kg = 17.95kg
02 out = (14795 + 1.332 x 10-
3
P) kg = 1482.9 kg
C02 out =C02 generated =(19.536 - 1.221 x 10-
3
P) kg =: 16.46 kg
Solutions: Chapter 5
Using the result for P to evaluate the masses of the other reactants and products involved in the reaction:
NH3consumed = (7.548-4.718 x 104 P) kg =6.36 kg
Glutamic acid generated = (65.312..;,. 4.082 x 10.
3
P) kg :::: 55.02 kg
Water generated = (23.976 - 1.499 x 10*3 P) kg = 20.20 kg
These results can be used directly in the energy balance for evaluation of the cooling requirements. However,
completion of the mass balance allows the calculations to be checked.
NH3 balance
518.5 kg NH3 in + 0 kg NB3 generated =NH3 out + 6.36 kg NB3 consumed
NH3 out =512.14kg
Water balance
1920 kg water in +20.20 kg water generated = water out +0 kg water consumed
Water out::: 1940.20 kg
Glutamic acid balance
okg glutamic acid in +55.02 kg glutamic acid generated ::: glutamic acid out +0 kg glutamic acid consumed
Glutamic acid out::: 55.02 kg
The Out side of the mass-balance table can now be completed with all quantities in kg.
Stream Out
Glucose NHl
z
NZ Gluconic acid CO2 HZO Total
Feed
Inlet gas
Off-gas 0 0 1482.9 4928.0 0 16.46 0 6427.4
Product 12.60 512.14 0 0 55.02 0 1940.20 2520
Total 12.60 512.14 1482.9 4928.0 55.02 16.46 1940.20 8947.3
All columns and rows of the completed table add up correctly to within round-off error.
(ii) Energy balance
W
s
=0; M
v
=O. Therefore, the energy*balance equation becomes:
-AHrxn-Q::: 0
The heat of reaction is evaluated using Eq. (5.20). As the heat of combustion ofCOZ and H20 is zero:
Mfrxn =
where G ::: glucose, A ::: NH3 and GA = glutamic add. The nin this equation are the moles of reactant or product
involved in the reaction. Converting the masses of reactants and products consumed or generated to moles:
Glucoseconsumed::: 67.40kg ::: 67AOkg I::: 374gmol
Solutions: Chapter 5 49
: 1.25kgOZh-
1
As NH3 and glutamic acid are involved in the reaction in stoichiometric quantities. 374 gmol NH3 are consumed and
374 gmol glutamic acid are produced. Substituting these quantities into the heat of reaction equation gives:
MI"" : 374 gmol (-2805.0kJ gmol-lj + 374 gmol(-382.6kJ gmOl-lj_ 374 gmol(-2244.1 kJ gmol-lj
M:l
rxn
=-353 x lOS kJ
Substituting this result into the equation:
3.53 x loS kJ -Q : 0
Q : 3.53 x loS kJ
From the sign conventions outlined on W 87-88. Qpositive indicates that,heat must be removed from the system.
Answer: 353 x 10
5
kJ h-
1
(b)
If cooling were not provided, the heat of reaction would be absorbed as sensible heat by the streams passing through
the reactor. For a rough calculation of the effect of this heat on the temperature of the reactor, assume that the 353 x
10
5
kJ h-
1
is absorbed by 2000 kg h-
1
aqueous medium and 6947-3 kg l:r1 gas. ,Assume that the heat capacity of the
aqueous medium is close to that of water:: 75.4 J gmol-l C-l (Table B-3, Appendix B) =75.4 kJ kgmol-l C-l, and
that the heat capacity of the gas stream is equal to that of air :: approx. 29 J gmol-l 0C-
1
(Table B.3, Appendix B):: 29
kJ kgmol-l C-l. From Eq. (5.12):
6T: MI
(M Cplliquid +(M Cpl..,
T :: 353 x 10
5
kJ h-
1
:: 23"C
(2000 kg h-
1
)(75.4kJ kgmor
1
oc-1j.1 +(6947.3 kg h-
1
)(29 kJkgmor
1
oc-1j .1
As a temperature rise of 23C in the reactor would not be well tolerated by most commercial organisms, provision of
adequate cooling for this reaction is an important consideration. Assuming that the usual temperature for the reaction
is 25C, the temperature without cooling woulJ,i increase to (25 +23)OC =48C.
5.6 Bacterial production of alginate
Alginate production at a rate of 5 kg
1
requires:
5 kgh-
1
4kgkg 1
Converting this quantity to gInol using the molecular weight of 02 =32.0 (Table B.I, Appendix B):
0zrequired:: 1.25kgh-
1
.1
1
0:
g
1.1 :: 39.06gmolh-
1
The heat of reaction for aerobic metabolism is approximately -460 kJ gmol-
1
Oz (p 100). Therefore, the heat of
reaction for alginate production is:
'This result can be used in the modified energy-balance equation, Eq. (5.26):
-6H
rxn
-M
v
tih
v
-Q+ W
s
:: 0
with W
s
:: 1.5 kW andM
v
:= 0 (no evaporation). From Table A.8 (Appendix A), 1 W:: 1 J s-1; therefore 1 kW:: 1 kJ
s1 and:
50
1.80x 10
4
kJh-1_O_ Q+ 1.5 kJ 8-
1
1:: 0
Q = 2.3 x 10" kJ h-
I
Solutions: Chapter 5
From the sign conventions outlined on pp 87-88, Qpositive indicates that heat must be removed from the system.
Answer: 2.3 x 104kJh
1
5.7 Acid fermentation
From Tables B.S andB,l(Appendix B), the molecular fannulae and molecular weights are:
sucrose = C12H2Z011: MW:: 342.3
propionicacid=C3H60 Z: MW=74.1" -
acetic acid = Czf40Z: MW=60.1
butyric acid=C4HgOZ: MW = 88.1
lactic acid =C3H603: MW =90.1
Fromp 75. the biomass molecular formula can be taken..asthe,average, CH1.80o.sNo.z'. From the end of Table E.8
(Appendix B). the molecular weight of the biomass is 25.9.
The reaction equation can be obtained by modifying Eq. (4.13) for anaerobic growth andproo.uct-fonnation:
C
12
HZZ0
11
+bNH3 -+ cCHl.gOo.sNo.2 +dCOZ +eHZO+!I
+h C2
H
4
0
2+Jj C4
H
,02 +14 C,H6
0
3
The biomass yield from substrate Yxs = 0.12 g gol, This value can be used to determine the stoichiometric coefficient
c using Eq. (4.l2):
_ Yxs (MWsubstraJe)) _ 0.12 gg-l (342.3) _
c - MWcells - 25.9 - 1.59
The coefficientsh,/2./3 and/4 can be determined similarly using the product yields and Eq. (4.14):
Yps (MW substrate)) 0040 g g-I (342.3)
11 = MWpropionicacid = 74.1 = 1.85
= Yps(MWsubstrate)) = 0.20gg-
1
(342.3) = 114
h MWacetic acid 60.1 .
Yps (MWsubstrate)) 0.05 g g-I (342.3)
Jj = = = 0 19
MWbutyric acid 88.1 .
_ Yps (MWsubstrate)) _ 0.034 g g-l (342.3) _
/4 - MWI . d - 90 I - 0.13
achC acl ..
Of the remaining coefficients b, d and e, because CO2 and H20 do not figure in heat of reaction calculations as their
heat of combustion = 0, only b need be determined. nus can be done using an elemental balance on N.
N balance: b = 0.2 c = 0.2 x 1.59 = 0.32.
To calculate the heat of reaction, the heats of combustion of the reactants and.products are required from Table E.8
(Appendix B):
sucrose=-5644.9kJ gulOr
l
=-382.6kJ gmol-l
-552kJ gmor
1
propionicacid = -l527.3kJ gmol-l
acetic acid=-874.2kJ gulOr
l
butyric acid =-2183.6kJ gmor
1
lactic acid = -1368.3 kJ gmol-l
Solutions.' Chapter 5 51
The heat of reaction is determined using Eq. (5.20). As the heat of combustion of C02 and H20 is zero:
Mlrxn = (n -(n -(n
where S =sucrose, A = NH3, B = biomass, PA =propionic acid, AA =acetic acid, BA =butyric acid, and LA = lactic
acid. Using a basis of I gmol sucrose, the n in this equation are the stoichiometric coefficients, Substituting values:
Iili"" =1gmol(-5644.9kJ gmol-l) +0.32gmol (-382.6kJ gmol-l)_ 1.59 gmol(-552kJ gmol-l)
- 1.85 gmol(-1527.3 kJ gmol-1)-1.l4 gmol (-874.2 kJ gmol-l) -0.19 gmol(-2183.6kJ gmol-l)
-0.13 gmol(-1368.3 kJ gmol-l)
t:Ji
rxn
=-474.8 kJ
This M
rxn
was determined on the basis of I gmol sucrose. For 30 kg sucrose consumed over a period of 10 d:
l
IOOOgll,gmOll( -I) 4
M
rxn
=30kg. lkg . 342.3g -474.8 kJ gmol =-4.16x 10 kJ
The cooling requirements are determined using the modified (5.26). For no evaporation
and no shaft work, M
v
= W
s
=0, so that:
Q = -Mf
rxn
=4.16 x 104 kJ
From the sign conventions outlined on pp 87-88. Qpositive means that heat must be removed from the system.
Answer:4.16x 10
4
kJ
5.8 Ethanol fermentation
From Table B2 (Appendix B), the molecular formula for glucose is C6H1206 and the molecular fonnula for ethanol
is C2H60. FromEq. (4.13), the stoichiometric equation under anaerobic conditions is:
C6H1206+bNH3 CCH1.7.s00.5SNO.lS+dC02+eH20+fC2H60
From Table B.8 (Appendix B), the molecular weight of ethanol is 46,1. From the atomic weights in Table B.I
(Appendix B), the molecular weight of glucose is 180.2 and the biomass fonnula weight is 25.58. Taking into
account the 8% ash:
Biomassmolecularweight = 2;'::: =27.80
The value of the stoichiometric coefficient/can be determined fromthe yield Yps= 0.45-g g-1 and Eq. (4.14):
Yps(MWsubstrate) 0.45gg-
1
(180.2ggmol-l) -1
f = = - = 1.76gmolgmol
MWproduct 46.1 g gmol I
The other coefficients can be determined using elemental balances.
Cbalance:6 =c+d+2f= e+d+2x1.76 -+ c =2.48-d
Hbalance: 12+3b =1.75c+2e+6f= 1.75c+2e+6x1.76 1.44+3b =1.75c+2e
o balance: 6 = 0.58c+2d+e+f= 0.58c+2d+e+1x1.76 4.24 = 0.58c+2d+e
Nbalance: b = 0.18e
Substituting the expression for c from the C balance into the N balance:
b =0.18 (2.48-d) =0.45-0.18d
Substituting this and the results from the C and N balances ioto the H balance:
L44+ 3 (0.45-0.18d) = 1.75 (2.48-d) + 2e
1.21d-L55 =2e
e = 0.61 d-0.78
52
Substituting the expressions for c, b and e into the 0 balance:
4.24 =0.58 (2.48 - d) + 2 d + (0.61 d - 0.78)
3.58 =2.03 d
d =1.76
Solutions: Chapter 5
Substituting this value for d into the expressions for the other coefficients gives c "" 0.72, b = 0.13 and e "" 0.29. The
completed stoichiometric equation is therefore:
C6H1206+0.13NH3 O.72CH
u
sOO.SSNO.
1
8+ 1.76 CO2 + O.29HZO+ 1.76CZH60
Using a basis of 1 h, 0.4 kg ethanol are produced. Converting this to moles:
Molesethanolproduced= OAkg "" 8.68gmol
From stoichiometry:
1
Moles glucose consumed "" 8.68gmolx 1.76 =4.93gmol
Moles NH3 consumed "" 8.68 gmol x "" 0.64 gmal
Moles biomass produced "" 8.68 gmol x "" 3.55 gmat
The heats of combustion from Table B.8 (Appendix B) are:
glucose: -Z805.0kJ gmor
1
=-382.6kJ gmol-l
ethanol"" -1366.8 k:J gmar
l
From p 101, the heat of combustion of yeast can be taken as -21.2 kJ g-1. The heat of reaction is determined using
Eq. (5.20). As the heat of combustion of C02 and H20 is zero:
Ml
rxn
=
where G =glucose, A = NH3' B =biomass and E = ethanol. The n in this equation are the actual moles of reactants
and products consumed or produced. Substituting values gives:
/lH= = 4.93 gmol (-2805.0kJgmor1) +O.64gmol (-382.6kJ gmol-1)_3.55 gmol(c21.2kJ g-l)1 I
- 8.68 gmol (-1366.8 kJ gmol-l)
Mlrx,n =-1175 kJ
Using the modified equation, Eq. (5.26), with M
v
=0 and W
s
=0:
Q=-Mlrx,n= 117.5kJ
From the sign conventions outlined on ,pp87-88, Qpositive means that heat must be removed from the system; in this
case, 117.5 kJ h-
I
is used to raise the temperature' of 25 I h-
I
water from lOoC. The sensible heat change of the water
can be calculated from Eq. (5.12). Using a value of 1 kg I-I for the density of water, C
p
for water = 75.4 J gmol-I
C*I (Table B-3, Appendix B), and the molecular weight of water =18.0 (Table B.l, Appendix B):
lJ.T = = 117.5 kJ h-
1
_ 112"<:
Me
p
(25Ih-1 1-
1o
C-
1
- .
. . 11 U . gmo . 18.0g lkg . lOOOJU
The final temperature of the water is therefore lOoe + ll.2C = 2L2C
Answer: 21.2C
Solutions: Chapter 5 53
5.9 Production of bakers' yeast
From Table B,8 (Appendix B), the molecular formula for sucrose is C12HZ2011' Therefore, from Eq. (4.4), the
stoichiometric equation for aerobic cell growth is:
CIZH22011 +a02+bNH3 -? cCHl.8300.5sNo.17+dCOZ+eHZO
Using the atomic weights in Table R1 (Appendix B), the molecular weight of sucrose is 342.3 and the biomass
formula weight is 25.04. Taking into account the 5% ash:
Biomass molecularweight = : 26.36
The degree of reduction of the biomass relative to NH3 is:
ni:::h 4.22
. .... 1 ..
The degree of reduction of sucrose relative to NH3 is:
_ 12x4+22x1-11x2 _ 400
rs - - .
The value of the stoichiometric coefficient c can be determined from the yield Yxs: 0.5 g and Eq. (4.12):
C =Yxs(MWsubstrate) =0.5gg-
1
(342.3ggmol-
1
) =6.49gmolgmol-l
MWcells 26.36 g gmol 1
The oxygen requirements can be determined from Eq. (4.16) with/: 0; from Eq (4.13), w: 12 for sucrose:
a =1/
4
(w)S-cJ1!) =1/
4
(12x 4.00-6.49 x 4.22) =5.15
Therefore, 5.15 gmol Oz are required for each 6.49 gmol biomass produced; this corresponds to 0.79 gmol Oz per
gmol biomass. Converting this oxygen demand to mass terms using the molecular weight of oxygen: 32.0 from
Table B.I (Appendix B):
. _ 0.79 gmolOz 132.0 g Ozlll gmol biomass 1_ -1
0.79 gmol 0Zper gmol blOmasS - 1gmol biomass' 1 gmol0
z
. 26.36 g biomass - 0.96 g g
The specific growth rate represents a rate of growth of 0.45 g biomass produced per g biomass per h. As 0.96 g 02
are required per g biomass produced, the specific rate of Oz consumption is 0.45 x 0.96: 0.43 g Oz.r,r g biomass per
h. When the biomass concentration is 10 g in a 50,000 litre fermenter, the mass of cells is 10 g 1- x 50/}00 1: 5 x
10
5
g. Therefore, the total rate of 02 consumption is 0.43 g g-1 h-
1
x 5 x 10
5
g: 2.15 x loS g Oz h
1
. Converting
this to moles:
Rate of 0
1
consumption : 2.15x 10
5
gh-
1
.l : 6.72x 10
3
gmolh-
1
From p 100, the heat of reaction for aerobic growth is approximately -460 kJ gmol-l 02 consumed. Therefore:
The rate of heat removal from the fermenter is determined using the modified energybalance equation, Eq. (5.26),
withWs:Mv:O:
From the sign conventions outlined on pp 87-88, Qpositive confrrms that heat is removed from the system.
Answer: 3.09 X10
6
kJ h-
1
Unsteady-State Material and Energy Balances
6.1 Dilution of sewage
(i) Flew sheet and system boundary
These are shown in the figure below,
Water
F::::: 40,000 I h
1
System boUndary\
,
"
- - 1---
- 1 r
I I
I
-
I
I I
I I
I I
I V
I
I
C
A
I
Outlet stream
F=40,OOO I h-
1
CA
(Ii) Define variables
V =volume of material in the tank; F ::::: volumetric flow rate into and out of the vessel::::: 40,000 1 h
I
; CA :::::
concentration of suspended solids
(ill) Assumptions
-no leaks
-tank is well mixed; therefore CA in the outlet stream::::: CA inside the tank
- density of the solids is the same as that of water"'" 1 kg I-I
(iv) Boundary conditions
At t =0, V::::: Vo ::: 440,000 litres + the volume of the solids. The initial mass of solids in the tank is 10,000 kg;
therefore. if the density is 1 kg I-I, Vo::::: (440,000 + 10,000) 1=450,000 L Att::::: 0, CA::::: CAO:
C
10,000kg 0022k 1-1
AO::::: 450,ooof:::::' g
(v) Total mass balance
As the volumetric flow rates of material in and out are the same and the density of the inlet and outlet streams are
assumed to be equal, the volume of material in the tank is constant (see Example 6.2) so that V = Vo at all times.
(vi) Solids mass balance
The general unsteady-state mass-balance equation is Eq. (6.5). As there is no reaction, RO =RC = 0; in this problem,
Mi =0, M
o
=F CA and M= V CA. Substituting into Eq. (6.5) gives:
d(VCA)
dt = -FCA
As V is constant, it can be taken outside of the differential:
Solutions: Chapter 6
As Fis also constant, the differential equation contains only two variables, CA and t. Separating variables gives:
dCA -F
-=-dt
CA V
Integrating:
f
dCA = J-Fdt
C
A
V
Using integration rules (D'.27) td(D.24) from Appendix D and combining the constants of integration:
-F
InCA = -yl+K
From the initial condition for CA, at t = 0, In CAO = K, Substituting this value of Kinto the equation gives:
-F
InCA = -yt+InCAO
CA -F
In- =-1
CAO V
C C
(-FIV; t
~ = AOe
Substituting the known values for CAo. F and V:
CA = 0.022 e-O089 t
where CA has units of kg I-I and t has units of b. From this equation, at t= 5h, CA =0,014 kg I-I,
Answer: 0.014 kg I-I
55
6.2 Production of fish-protein concentrate
(i) System
The system is the whole gutted fish placed in the batch drier at time zero. During drying, the mass of the system
decreases as water is removed.
(li) Assumptions
No additional assumptions are required,
(iii) Boundary conditions
At t = 0, the mass of water in the fish in the drier is equal to M()
(iv) Water mass balance
The general unsteady-state mass-balance equation is Eq. (6.5), As there is no reaction, RO = RC = O. No water is
added during drying; t h e ~ f o r e Mi =0, At any time during drying, as the rate of water removal Me is proportional to
the moisture contentM, M
e
=k M where k is a constant, Substituting into Eq, (6.5) gives:
dM
Cit =-kM
where M and t are the only variables. Separating variables and integrating:
Using integration rules (D.27) and (0,24) from Appendix. D and combining the constants of integration:
lnM=-kt+K
At I"'" 0, M = Mo; therefore. K"'" In Mo- Substituting this value of K into the equation gives:
56
InM = -kt+1nMo
M
In M
o
=-let
At t= 20 min, M =0.5 MO. Substituting these values into the equation:
O.5M
o
In -:MO =-k(20 min)
In 0.5 = -k (20 min)
k = 0.0347
Therefore:
M
In Mo =-0.0347t
where t has units of min. When 95% of the water has been removed, M=0.05 Mo_ Therefore:
O.05M
O
In M
o
= -0.0347 t
In 0.05 := -0.0347 t
t =86.3 min =: = l.44h
Answer. 1.44 h
6.3 Contamination of vegetable oil
(i) Flow sheet and system boundary
These are shown in the figure below.
Solutions: Chapter 6
System boUndary\ \.
;
- - -
- -
1 r
I I
I I
Inlet stream I I
Outlet stream
Cod-liver oil drum F;
I I F
o
P
I I
p
V
</
I
p
I
I
</
I
L
Oil tank
J
- - - - - -
-
(li) Define variables
V = volume of oil in the tank; Fi "'" volumetric flow rate of oil into the oil tank; F0 =volumetric flow rate of
mixed oil out of the oil tank; = mass fraction of vegetable oil; p"'" density of vegetable and cod-liver oils
(ill) Assumptions
- no leaks
- oil tank: is well mixed; therefore in the outlet stream= inside the tank
- densities of each oil and the oil mixture are the same
Solutions: Chapter 6
(iv) Boundary conditions
At t= 0 when cod-liver oil first enters the oil tank, V = Vo = 60 litres. At t= 0,4>= o = 1.
57
(a)
Total mass balance
The general mass--balance equation is Eq. (6.5). As there is no reaction, RO = RC = O. The t2.ta1 mass
flow rate into the oil tank is equal to the volumetric flow rate multiplied by the density of the cod-liver oil: Mi =Fi p.
Similarly, M
o
=F
o
p. The total mass of oil in the tank is equal to the volume of oil multiplied by its density: M = V p.
Substituting these expressions into Eq. (6.5) gives:
d(VP)=Fp_Fp
dt ' 0
As Pis constant it can be taken outside of the differential and cancelled:
dV
Pdt =(Fi-FdJp
dV
dt = (Fi-FdJ
The differential equation contains only two variables, Vand t. Separating variables and integrating:
I dV =I (Fi-FdJdt
Using integration rule (0.24) from Appendix D and combining the constants of integration:
From the initial condition for V, at t =0, K = Vo. Substituting this value of K into the equation gives:
V= (i-Fo)t+ Vo
The time between 8 p.m. and 9 a.m. the next morning is 13 h. From the above equation for V,- for t =13 h, Fi =7.5 1
h-
1
,F
o
=4.81h-
1
and Vo=60l,V""'95.11. As this volume is less than the tank capacity of 1001, the tank will not
overflow. '
Answer: No
(b)
Total mass balance
As the volumetric flow rates of oils into and out of the tank are the same and the density of the inlet and outlet streams
are assumed to be equal, the volume of oil in the tank is constant (see Example 6.2)-s0 that V= Vo;:::; 60 1at all times.
Vegetable oil mass balance
The general mass-balance equation is Eq. (6.5). As there is no reaction, RG "'" RC =O. No vegetable oil
enters the tank; therefore Mi "'" O. The mass flow rate of vegetable oil out is M
o
"'" F
o
P4>. The mass of vegetable oil
in the tank at any time is M"", V p 4>. Substituting these expressions into Eq. (6.5) gives:
d(V;:) =-Fop
As both V and p are constants, they can be taken outside of the differential and p can be cancelled:
= -Fop
= -F
o

As F0 is also constant, the differential equation contains only two variables, 4> and t. Separating variables and
integrating:
58 Solutions: Chapter 6
Using integration rules (D.27) and (D.24) from Appendix D and combining the constants of integration:
-F
o
In::::: yt+K
From the initial condition for 41, at t =0, In <Po::::: K.. Substituting this value of K into the equation gives:
-F
o
l n ~ = y'+lnib
~ -Fo
lnib=y'
~ = ib e(-F,II'J'
In this problem. F0 ::::: 4.8 I h-l. Substituting the known values for </Jo and V:
II ::::: 1 e....(l080 t
where <P is dimensionless and t has units of h. The time between 8 p.m. and midnight is 4 h. From the above
equation, at t= 4 h, 4'= 0.73. Therefore, at midnight, the composition of oil in the tank is 73% vegetable oil and 27%
cod-liver oil.
Answer. 73% vegetable oil, 27% cod-liver oil
6.4 Batch growth of bacteria
The general unsteady-state mass-balance equation is Eq. (6.5). For a batch culture, M
j
::::: M
o
::::: O. For a mass balance
on cells. assuming there is no loss of cells from the system, e.g. by lysis, RC::::: O. The rate of generation of cells RG is
proportional to the concentration of cells present: RO = J.t xV where jJ is a constant, xis the cell concentration and V
is the culture volume. The total mass of cells M is equal to the culture volume V multiplied by the cell concentration
x: M = Vx, Substituting these results into Eq. (6.5) gives:
d(Vx) = J.txV
dt
Assuming that V is constant throughout the batch culture, it can be taken outside of the differential:
dx
V dt = J.tx V
dx
dt =J.tx
The differential equation contains only two variables, x and t. Separating variables and integrating:
dx
- =I'dt
x
Using integration rules (0.27) and (0.24) from Appendix. D and combining the constants of integration:
lnx = j1.t+K
Assume an initial condition: at t =0 at the beginning of ex.ponential growth, x =xo. Therefore, at t =0, In Xo =K.
Substituting this value of K into the equation gives:
Solutions: Chapter 6
lnx = j.tt+lnxo
x
In- = j1,t
XO
When t =45 min, x = 2 xo. Substituting these values into the equation:
2XO
In- = ,u(45 min)
XO
ln2 = j.t (45 min)
j.t = 0.0154 min'l
Therefore:
In''::' = 0.0154t
XO
x = XQ eO.Ol54 t
where thas units of min. For t= 12h = 12 x 60= nomin:
x=6.54x 104 XQ
59
After 12 h, the cell concentration is 6.54 x 104 times the cell concentration at the beginning of exponential growth. If
there is a lag phase, the cell concentration at the beginning of exponential growth is usually very close to that at
inoculation; therefore, the cell concentration is about 6.54 x 104 times the inoculum level.
Answer: 6.54 X104 times the inoculum level
6.S Radioactive decay
The general equation is Eq. (6.5). In this problem, M
j
=M
o
=O. For a mass balance on
isotope, RO =O. The rate of isotope decay RC is proportional to the concentration of isotope present: RC =-/q C V,
where kl is a constant, C is the isotope concentration and V is the solution volume. The total mass of isotope M is
equal to the solution volume V multiplied by the isotope concentration C: M =V C. Substituting these results into Eq.
(6.5) gives:
d(:CJ =-k,CV
If we assume that the density of the solution is constant during isotope decay, V is constant and can be taken outside
of the differential and cancelled:
dC
V(if =-k
1
CV
dC
(if =-k1 C
The differential equation contains only two variables, C and t, Separating variables and integrating:
dC
C = -k
1
dt
Jdg =f-k) dt
Using integration rules (D27) and (D.24) from Appendix D and combining the constants of integration:
lnC=-k1 t +K
60 Solutions: Chapter 6
Assume an initial condition: at t "'" 0, C "'" CO, Therefore, at t "'" 0, In Co = K, Substituting this value of K into the
equation:
InC = -ktt+lnCo
C
In-=-k
i
t
Co
(a)
When t= !h, the half-life of the isotope; C= 0.5 Co. Substituting these values into the equation:
0.5 Co
In-- = -kIth
Co
In 0.5 = -ki !h
t
_ -tn0.5
h---
k,
Using mathematical rule (D. 10) in Appendix D, -In 0.5 =In 1/
0
.5 =In 2. Therefore:
In2
th =kl
Answer. Q.E.D.
(b)
From the equation derived in (a):
For t:h =14.3 days:
kl =4.85 x 10-
2
d-
I
Substituting this value of kl into the general equation for isotope concentration:
In go =-4.85 x 10-
2
t
where thas units of days. ForC=O.Ol CO:
0.01 Co -2
In Co = -4.85 x 10 t
In 0.01 =-4.85 x 10.
2
t
t = 95 days
Answer. 95 days
Solutions: Chapter 6
6.6 Continuous fermentation
(i) Flow sheet and system boundary
'These are shown for a continuous fermenter in the figure below,
61
Sy
Feed
F
xI =0
"
stem boUndary\ ....
"
- - r- - - - 1 r
I I
I I
I I
I I
I
V
I
I x I
I

I
Product
F
x

(li) Define variables


V=volume of broth in the fennenter; F = volumetric flow rate into and out of the vessel; x = concentration of cells; s
= concentration of substrate; Xi. =concentration of cells in the feed; Si =concentration of substrate in the feed
(iii) Assumptions
-no leaks
- fermenter is well mixed; therefore x and s in the outlet stream=x and s, respectively, inside the fermenter
- density of the fermentation broth is the same as that of the feed
(iv) Boundary condition
Att=O,x=XO
(v) Total mass balance
As the volumetric flow rates into and out of the fermenter are the same and the density of the inlet and outlet streams
are assumed equal, the volume of broth in the fermenter is constant (see Example 6.2) 8..Iid equal to Vat all times.
(aj
Cell mass balance
The general unsteady-state mass-balance equation is Eq, (6.5). As no cells enter in the feed stream, Mi =O. The mass
flow rate of cells out M
o
= F x. The rate of cell generation RG =rx V = kl x V. Assuming that cell lysis is negligible,
RC = O. The mass of cells in the fermenter M is equal to Vx. Substituting these terms into Eq. (6.5) gives:
d(Vx)
-_.- =-Fx+k1xV
d'
As Vis constant, it can be taken outside of the differential.
dx
V dt = -Fx+k1xV
Dividing through by V and grouping terms:
dx F
- = x(kt--)
d' V
dx F
Answer: dt = x (k I - V)
(b)
At steady state, dxl
dt
= O. Therefore, from the equation derived in (a), at steady state kl must be equal to FIV.
Answer: kl =f.<iv
62 Solutions: Chapter 6
(e)
As F, Vand kl are constants, the differential equation derived in (a) contains only two variables, x and t. Separating
variables and integrating:
<Ix F
-;- = (k'-l1)dt
=
Using integration rules (D.27) and (D.24) from Appendix D and combining the constants of integration:
F
lux:::: (k1-V)t+K
From the initial condition for x,at t= 0, In Xo = K. Substituting this value of K into the equation gives:
F
Inx:::: (k1-y)t+1nXO
F
10- :::: (kl--)t
'0 V
F
(kl--)t
x=.xoe ,v
F
(k
1
--) ,
Answer: x:::: XOe V
(d)
Substituting the parameter values into the equation derived in (c}
-1 22001h-
1
x:::: (0.5gl-
1
)e(0.33h - 10,0001)/
x :::: 0.5 e
O
.
IlI
where x has units of g 1-1 and thas units ofh. For x:::: 4.0 g I-I;
4 = 0.5 eO.II t
inS = 0.11 t
t:::: 18,9h
Answer: 18.9 h
(e)
Substrate mass balance
The general unsteady-state mass-balance equation is Eq. (6.5). For substrate, the mass flow rates in and out are
M
j
=F si and M
o
= Fs. The rate of substrate generation RG =0; the rate of substrate consumption RC =IS V = k2 x
V.The mass of substrate in the fermenter M is equal to Vs. Substituting these terms into Eq. (6.5) gives:
d(Vs)
(it = Fs
i
-Fs-k
2
xV
As V is constant, it can be taken outside of the differential:
Dividing through by V and grouping tenus:
Substituting the expression for x from (c):
Solutions: Chapter 6 63
In this equation, F, V, kl and X{) are constants and there are only two variables, s and t. However, the variables cannot
be easily separated as in the previous problems, making algebraic solution difficult.
& F ~ l - ~ t
Answer. dt =V (si -s)-k1X{)e V
(f)
An equation for &/dt in terms of x was dt;:rived in (e) as:
,
At steady state, &/dt =O. Therefore:
F
V(si -s) =k
2
x
Vk
Z
si-
s
= F'x
Vk
Z
Answer. s =si -Tx
6.7 Fed-batch fermentation
(i) Flow sheet and system boundary
These are shown for a fed-batch fermenter in the figure below.
1
I
I
I
I
1
I
I
L J
stem bOUndary\ \.
'"
- - - -
r
I
I
-
I
I
I
V
x
I
s
I
p
s;
p
Sy
Feed
F
(ll) Define variables
V = volume of broth in the fermenter; F = volumetric flow rate into the fermenter; x = concentration of cells in the
fermenter; s = concentration of substrate in the fermenter; Si = concentration of substrate in the feed; p = density of the
feed and fermentation broth
(iii) Assumptions
-no leaks
- fermenter is well mixed
- density of the fermentation broth is the same as that of the feed
64
(iv) Boundary condition
Att=O, V=Vo.
Solutions: Chapter 6
(a)
Total mass balance
The general unsteady-state mass-balance equation is Eq. (6.5). As total mass cannot be generated or consumed, RO=
RC =O. No mass leaves the fennenter; therefore M
o
=O. The mass flow rate in Mj = p F. The total mass in the
fermenter M is equal to V p. Substituting these terms into Eq. (6.5) gives:
d(VP)=pF
dt
As Pis constant, it can be taken outside of the differential and cancelled:
dV
Pdi =pF
dV =F
dt
As F is constant, the differential equation contains only two variables, V and t. Separating variables and integrating:
dV = Fdt
Using integration rule (D.24) from Appendix D and combining the constants of integration:
v = Ft+K
From the initial condition for V, at t =0, Vo =K. Substituting this value of K into the equation gives:
v= Ft+Vo
Answer: V=Ft+Vo
(b)
Substrate mass balance
The general unsteady-state mass-balance equation is Eq. (6.5). The mass flow rates of substrate in and out are
Mj =F si and M
o
=o. The rate of substrate generation RO =0; the rate of substrate consumption RC =rs V =kl S V.
The mass of substrate in the fermenter M is equal to Vs. Substituting these terms into Eq. (6.5) gives:
d(V,)
-at =Fsi-klsV
As neither V nor S is constant, both must be kept in the differential as a product. Expanding the differential using the
product rule (D.22) from Appendix D:
Using the equation dV1dt =F derived in (a) :
Grouping terms gives:
<is F
Answer: dt =V(Si-S)-kt s
Solutions: Chapter 6
6.8 Plug-flow reactor
(i) Flow sheet and system boundary
These are shown for a plug-flow reactor in the figure below.
System bOUndary, ...
__!..I ---"'---__
: -=-.,.....,.:.. S-....... -
I z
L J
65
(ii) Define variables
u := fluid linear velocity; z =distance along the reactor; CA := concentration of reactant; CAi =concentration of
reactant in the feed stream; A =reactor cross-sectional area
(iii) Assumptions
-no leaks
-plug flow
(a)
Reactant balance
Consider the system to be a small section of the reactor located between z and z +&. The general unsteady-state
mass-balance equation is Eq. (6.5). The rate ofentry of reactant into the system is:
Mj = CAuAl
z
where kmeans that the parameter values are those at distance z from the front of the reactor. Similarly, the rate at
which reactant leaves the system is:
M
o
= CAuAI
,+<\,
Reactant is not generated; therefore RO = O. The rate of consumption of reactant is given by the equation:
Rc=rcV:=rc A &
where A ilz is the volume of the system and rc is the volumetric rate of reaction. At steady state there is no
accumulation in the system and dM/
dt
= O. Substituting these expressions into Eq. (6.5) gives:
0= CAuAlz-CAuAlz+hz-rcA&;
As A is constant and does notdepend on z, it can be cancelled from each of the terms:
0= CAulz-CAulz+&-rcAz
Dividing through by A.<;:
Taking the limit as Llz approaches zero and applying the definition of the derivative (0.13) in Appendix D:
-d(eA u)
0= '"--az--rC
or
d(C
A
u)
dz =-rC
As the fluid velocity is constant throughout the reactor, u can be taken outside of the differential:
66
dCA
Answer: uliZ "" -rC
(b)
Answer: at Z"" O. CA =CAi
Solutions: Chapter 6
(e)
Ifthe reaction is first-order, rc =: kl CA where kt is the first-order rate constant. The differential equation becomes:
As uand kl are constants, the differential equation contains only two variables, CA and z. Separating variables and
integrating:
dCA = -k) dz
CA U
f
dCA "" f-k) dz
CA U
Using integration rules (D.2?) and (D.24) from Appendix D and combining the constants of integration:
-k)
InCA =-z+K
U
From the initial condition in (b), at z= 0, In CAi =: K. Substituting this value of Kinto the equation gives:
C
A
-kl
1n-=-z
CN U
CA =: CAi e(-k,lu) z
(d)
The equation derived in (c) is directly analogous to the equation for change. in reactant concentration in a batch
reactor. As z"" ut where t is the time taken for the fluid to travel distance z. the above equation can be written as:
C
A
"" CAie""*lt
which is the same as the equation for reactant concentration in a batch reactor where CAi is the concentration at time
zero.
Answer: Essentially identical
6.9 Boiling water
The system is the beaker containing water.
(i) Assumptions
- no evaporation
- water is well mixed
- no shaft work
- heat capacity is independent of temperature
- beat losses are negligible
- the density of water is constant between 18"C and lOO"C
Solutions: Chapter 6
(ii) Extra data
Density of water = 1 kg I-I
C
p
water = 75.4 J gmol-1 "'C-l (fable B.3, Appendix B) = 75.4 kJ kgmol-l "'C-l
Molecular weight of water (fable B.l, Appendix B) =18.0
1 W = 1 J s-l (fable A.8, Appendix A); therefore, 1 kW = 1 kJ sl
(iii) Boundary conditions
Att=O,T=TO=18C
67
(a)
The general unsteady-state energy-balance equation is Eq. (6.10). For a batch system, Mi = M
o
=0; also W
s
=O.
Energy is accumulated by the system in the fonn of sensible beat only; therefore:
dE <IT
(jJ=MC
pdt
where M is the mass of water in the beaker and T is its temperature. Substituting these expressions into Eq. (6.10)
gives:
dT -
MC
Pdt
=-Q
dT -
Answer: M C
p
dt = -Q
(b)
If Q, C
p
and M are constant, T and t are the only variables in the differential equation. Separating variables and
integrating:
Using integration rule (D,24) from Appendix D and combining the constants of integration:
T= -Q t+K
MC
p
From the initial condition for T, at t= 0, To =K. Substituting this value of K into the equation gives:
-12
T= MC t+To
p
Using the density of water = 1 kg t-
1
, the mass of 2 litres of water M= 2 kg. Converting the C
p
for water to mass
terms:
C
p
= 75.4kJ kgmor
1
"'C-
1
.1 = 4.189 kJ kg-
1
"'e-
I
T =the boiling temperature of water =100C; t =11 min. Substituting the parameter values into the equation for T:
lOO"C = ( -Q 1 I) (11 min) + 18C
2kg 4.189kJkg "'e-
Q =-62.45kJmin-
1
=-62.45kJmin-
1
=-L04kW
From the sign conventions outlined on pp 87-88, the negative value for Qconfirms that heat is added to the system.
Answer: L04 kW
68
6.10 Healing glycerol solution
The system is the stirred tank containing the solution of glycerol in water.
(i) Assumptions
-no leaks
- no evaporation
- tank is well mixed
- no shaft work
- heat capacities are independent of temperature between 15<>C and 90"C
- ideal solution
- system is adiabatic; therefore heat losses are negligible
(ii) Extra data
C
p
glycerol =0.576 cal g-t C-
l
(Table B.s, Appendix B) = 0.576 keal kg-I "C-
1
C
p
water = 75.4 J gmol-l C-
l
(Table B.3, Appendix B) = 75.4 kJ kgmol-l C-
1
Molecular weight of water (Table B.I, Appendix B) "" 18.0
1kcal "" 4.187 x 10
3
J (Table A.7, Appendix A) = 4.187 k1
1W=1J s-1 (Table A.S, Appendix A); therefore, 1kW = 1kJ 5-
1
(iii) Boundary conditions
Att=O,T=To=15"C
Solutions: Chapter 6
(a)
The general unsteady-state energy-balance equation is Eq. (6.10). For a batch system, Mj =M
o
=0; also W
s
=O.
Energy is accumulated by the system in the form of sensible heat only; therefore:
dE=MC
dT
dt Pdt
where M is the mass of glycerol solution in the tank and T is its temperature, Substituting these expressions into Eq,
(6.10) gives:
M has two components, glycerol and water, which have different heat capacities. Therefore, this equation can be
written:
where Mw is the mass of water in the tank, MO is the mass of glycerol, CpW is the heat capacity of water, and CpO is
the heat capacity of glyceroL
<IT -
Answero(MWCpW+MOCpG)"dI =-Q
(b)
If ii, Cpw, CpO, MW and Mo are constant, T and t are the only variables in the differential equation. Separating
variables and integrating:
Using integration rule (0.24) from Appendix D and combining the constants of integration:
T= -0. t+K
(MwCpW+MGCpG)
From the initial condition for T, at t= 0, To:: K. Substituting this value of K into the equation gives:
Solutions: Chapter 6 69
-12
Answer: T =(MwCpw+MOCpG) t+ To
(c)
The mass of glycerol in the tank MO = 4S kg; the mass of water Mw =55 kg. Converting the C
p
for water to mass
terms:
C
pw
= 7SAkJkgmor
l
= 4.189 kJ kg-
1
<)C-
1
Converting the C
p
for glycerol to kJ:
CpO = =2.412kJkg-
l
oc-
l
The rate of heat input to the system is 0.88 x 2.5 kW "'" 2.2 kW "'" 2,2 kJ s-l.From the sign conventions outlined on pp
87-88, Qmust be negative as heat is added to the system; therefore, Q"'" -2.2 kJ s-l. Substituting the parameter
values into the equation for Twith To =15<)C and T= 90<)C:
9O"C "'" 2.2kJs-
1
t+ 15"C
55kg(4.189kJkg loC l)+45kg(2.412kJkg loe 1)
t =1.l6x10
4
s = "'" 3.2h
Answer: 3.2 h
6.11 Heating molasses
(i) Flow sheet and system boundary
These are shown in the figure below.
System boundary
- - - -- - -
1
I I
I I
Molasses solution in
I
Heating tank
I
Molasses solution out
1020 kg h-
1
I
M
I
1020 kg h-
1
20'C
/
T
I
T
I
I I
-
- --
- - -
- -
-Q (from steam)
(ii) Assumptions
- no leaks
- no evaporation
- tank is well mixed; therefore the temperature of the molasses solution out is the same as in the tank
- no shaft work
- beat capacity is independent of temperature
- negligible heat losses
70
- condensate from the steam leaves at saturation conditions
(iii) Reference state
Tref"" 20
o
e; H"" 0 for molasses solution at 20
0
e
(iv) Extra data
C
p
"" 0.85 kcal C-
1
1psi = 6.895 x 10
3
Pa (fable A.S, Appendix A) = 6.895 kPa
Converting 40 psi to kPa:
Solutions: Chapter 6
40psi = =275.8kPa
The temperature of saturated steam at 275.8 kPa interpolated from Table C.2 (Appendix C) "" l30.7e.
(v) Boundary conditions "
Att=O, T=To=20C
(vi) 'Total mass balance
As the mass flow rates into and out of the tank are the same, the mass of molasses solution in the tank M is constant
and equal to 5000 kg at all times.
(a)
The general unsteady-state energy-balance equation is (6.10). From the reference state, hi = 0; The value of h
o
relative to the reference state is equal to the sensible heat-absorbed by the molasses'solution between Tref and the exit
temperature T. From Eq. (5.13):
h
o
= =Cp(T-Tref)
W
s
= O. The rate at which the molasses solution is heated is given by the equation:
Q=-UA (T
steam
-1)
From the sign conventions outlined on pp 87-88, Q must be negative as heat is added to the system. Energy is
accumulated in the form of sensible heat only; therefore:
dE=MC
dT
<It P <It
Substituting these expressions into Eq. (6.10) gives:
dT -
M C
p
dt = -M
o
C
p
(T- Tref) +UA (Tsteam- n
After rearranging, the differential equation is:
dT = UATsteam+MoCpTref _(fJoCp+UA)T
dt MC
p
MC
p
dT
Answer: dt
(b)
As U, A, Tsteam, Mo. C
p
Tref and M are all constant, Tand t are the only variables in the differential equation derived
in (a). Substituting the known numerical values for the parameters:
dT _ 190kcal m-
2
.-1 0C-
'
(1.5 m
2
) (130.7'C) + 1020 kg .-1 (0.85 kCalkg-
1
oC-
'
) (20"C)
<It - 5000kg(0.85kcalkg lo
C
1)
_(1020 kg .-1 (0.85 kcal kg-
1
oC-
'
) + 190 kcalm-
2
.-1 oC' (l.5 m
2
)) T
5000kg(0.85kcalkg loC 1)
dT
dt =12.84-0.271 T
where T has units C and t has units h. Separating variables and integrating:
Solutions: Chapter 6 71
dT = eIt
12.84-0.271 T
f
dT -felt
12.84-0.271 T -
Using integration rules (D.28) and (D.24) from Appendix D and combining the constants of integration:
-1
0.271 In (12.84-0.2711) =t+ K
From the initial condition for T, at t = 0:
-I
K =0.271 In (12.84-0.271 To)
Applying the numerical value of To =20C, K =-7.395. Substituting this value for K into the equation gives:
-I
0.271In(l2.84-0.2711)+7.395 =t
-I
Answer: 0.271 In (12.84- 0.2711) +7.395 = t
(c)
Values of t corresponding to various temperatures in the tank can be calculated from the equation derived in (b).
Temperature, T
CC)
Time, t
(h)
20
25
30
35
40
45
46
47
47.3
0.00
0.74
1.68
2.93
4.84
9.01
11.0
15.8
21.5
The results are shown in the figure below.
50 r----,----,----,,----,-----,
25 20 10 15
Time (h)
5
20 ..-__-'-__..L__-'-__-'-__-'
o
72 Solutions: Chapter 6
(d)
From the equation derived in (b), as the logarithm of zero and negative numbers is not defined (p 413), the theoretical
maximum temperature that can be achieved in the tank occurs when 12.84 - 0.271 T= 0; Le. when T= 47.4C.
(e)
'The temperature cbanges constantly with time; therefore, strictly speaking, there is no steady state. For practical
purposes, however, the temperature approaches a constant value after about 16 h.
Answer. About 16 b
(f)
From the calculation table in (c), the temperature reaches 40C after 4.84 h.
Answer: 4.84 h-
6.12 Pre-heating culture medium
The system is the glass fermenter containing nutrient medium.
(i) Assumptions
- no evaporation
- fennenter is well mixed
- no shaft work
- heat capacities are independent of temperature between 15C and 36C
- beat losses are negligible
(li) Extra data
C
p
glass vessel"" 0.20 cal g-l 0C-
l
"" 0.20 keal kg-I oct
C
p
medium"" 0,92 cal g-l C
l
"" 0.92 keal kg-loCi
1W"'" 1.433 x 10-
2
keal min-I (Table A.S, Appendix A)
(ill) Boundary conditions
Att=O,T=To=15C
(iv) Energy balance
The general unsteady-state energybalance equation is Eq. (6.10). For a batch system., Mi =M
o
= 0; also W
s
=0.
Energy is accumulated by the system in the form of sensible heat only; therefore:
dE dT
dt =MC
pdt
M has two components, the glass vessel and the medium, which have different heat capacities. Therefore, this
equation can be written:
where My is the mass of the glass vessel, MM is the mass of the medium, Cpy is the heat capacity of the vessel, and
CpM is the heat capacity of the medium. Substituting into Eq. (6.10) gives:
( )
dT -
MyCpy+MMCpM dt =-Q
As (i, Cpy, CpM, My and MM are constant, T and t are the only variables in the differential equation. Separating
variables and integrating:
dT= -Q dt
(My Cpy + MM CpM)
f
dT-f -Q dt
- (My Cpy+MM C
pM
)
Using integration rule (D.24) from Appendix D and combining the constants of integration:
Solutions: Chapter 6
T= -Q t+K
(MV CpV +MM CpM)
From the initial condition for T, at t= 0, To =K. Substituting this value of K into the equation gives:
T= -Q t+T
o
(Mv CpV +MM CpM)
The rate of heat input to the system is 450 W. Converting this to kcaI min-l:
Q= -450W =-450W.!1.433X =-6A5kcalmin-t
Co
73
36'C =
From the sign conventions outlined on pp 87-88, Qmust be negative as heat is added to the system. Substituting this'
and the other parameter values into the equation for Twith To = 15C and T= 36C:
6.45 kcal min-
l
t+ 150C
12.75 kg (0.20 kcal kg-I 'C-
I
) +7.5 kg (O.92kcal kg-I 'C-
I
)
t =30.8 min
Answer: 30.8 min
6.13 Water heater
The system is the tank containing the water.
(i) Assumptions
- no leaks
- no evaporation
- tank is well mixed
- no shaft work
- heat capacity is independent of temperature
- condensate from the steam leaves at saturation conditions
(li) Extra data
C
p
water =75.4 J oC-L(Table B.3, Appendix B) =75.4 kJ kgmol-t 0C-
1
Molecular weight of water (Table R.l, Appendix B) =18.0
1 kcal = 4.187 x 103 J (fable A.7, Appendix A) =4.187 kJ
(iii) Boundary conditions
Att=O, T=T
o
=24"C
(iv) Energy balam:e
The general unsteady-state energy-balance equation is Bq. (6.10). For a batch system, Mi=M
o
=O;a1soW
s
=O.
Energy is accumulated by the system in the form of sensible heat only; therefore:
dE dT
dt =MC
Pdt
where Mis the mass of water in the tank and Tis its temperature. Substituting these expressions into Eq. (6.10) gives:
dT -
MCpdi=-Q
(aj
There are two components to Q: the rate of heating from the steam, and the rate of heat loss to the surrounding air:
Q =UtAt (T-Tair)-UZAz(T
steam
-1)
This equation reflects the sign conventions outlined on pp 87-88: the term for the heat loss to the atmosphere is
positive to indicate heat removal from the system, while the term for heat input from the steam is negative.
Substituting into Eq. (6.10) gives:
74
MC dT
Pdt
dT
Cit =
UZA2(Tsteam-1) - VtA
I
(T-Tair)
MC
p
Solutions: Chapter 6
As Vt. A 1> Uz. AZ, Tsteam, Yair, C
p
and M are all constant, T and t are the only variables in the differential equation.
Substituting the known parameter values:
dT 220 kcal m-
2
h-
I
0c-
l
(03 m
2
)(130-1)C _ 25 kcal m-
2
h-
I
0C-
l
(O.9m
2
) (T- 20Y'C
=
dt (-1 -1 11 kgmOllllkCai n
lOOOkg 75.4kJkgmol "'C . 18.0kg . 4.187k:JU
dT
dt = 9.026-0.088 T
where T has units of"C and t has units of h. Separating variables and integrating:
dT =dt
9.026 - 0.088 T
f = fdt
Using integration rules (0.28) and (D.24) from Appendix D and combining the constants of integration:
='+K
From the initial condition for T. at t= 0:
-I
K = 0.088 In (9.026-0.088 ToJ
Applying the numerical value of To =24"C, K = -21.97. Substituting this value for K into the equation gives:
-1
0.088 In (9.026-0.0881) +21.97 = ,
From this equation, for T = 80"C, t =14.2 h.
Answer: 14.2 h
(b)
If beat losses can be neglected, Qhas only one component and Eq. (6.10) becomes:
dT
MC
p
<It
dT UZAZ (T
steam
-1)
Cit = MC
p
Substituting the known numerical values:
dT 220kcalm-
2
h-
1
0C-
l
(0.3m
2
)(130-n"C
dt =-1-000-'k=g7(7'=S=.4"'kJ=-k-'gm=-OI--I"'o-c--"'1
dT
dt =8.576 - 0.066 T
where Thas units of "C and t has units ofh. Separating variables and integrating:
Solutions: Chapter 6
dT = <It
8.576- 0.066 T
f8.576 ~ . 0 6 6 T = f<It
Using integration rules (0.28) and (D.24) from Appendix D and combining the constants of integration:
-1
0.066 In (8.576-0.0661) =t+K
From the initial condition for T, at t= 0:
-1
K =0.066 In (8.576-0.066 ToJ
Applying the numerical value of To =24C, K =-29.47. Substituting this value for K into the equation gives:
-1
0.066 In(8.576-0.0661) +29.47 =t
75
From this equation, for T =80C, t "'" 11.4 h, Therefore, from (a), the time saved is (14,2..:,- 11.4) h"'" 2.& h, which
corresponds to 20% of the time required when heat losses occur.
Answer: 2.8 h, or 20% of the time required when heat losses occur
Fluid Flow and Mixing
7.1 Rheology of fermentation broth
(a)
The rheogram is obtained by plotting shear stress againSt shear rate.
700 ...---r---,---,,--,.----r---,
1200 1000 400 600 800
Shear rate (s1)
200
ol-_...L_......l._---''-_-'-_....L_--'
o
300
600
400
600
200
100
(b)
The rheogram in (a) is similar to those for pseudoplastic and Casson plastic fluids in Figure 7.7. It is not clear from
the rheogram whether the fluid exhibits a yield stress at r= 0 or not; therefore. both non-Newtonian models are worth
checking. From the equation in Figure 7.7 for pseudoplastic fluids, a plot of shear stress versus shear rate on log-log
coordinates would be expected to give a straight line. This plot is shown below.
100 1000
Shear rate (s-l)
10000
Solutions: Chapter 7 77
The equation for the straight line in the log-log plot is '1:= 11.43 ;-0587. Therefore, the flow behaviour index n =
0.587 and the consistency index K =. 11.43 dyn sit cm-
2
. The sum of squares of the residuals for this data fit is' 1137.
From the equation in Figure 7.7 for Casson plastic fluids, a plot of the square root of shear stress versus the square
root of shear rate on linear coordinates would be expected to give a straight line. This plot is shown below.
The equation for the straight line in the plot is liZ=. 5.93 +0.648 ytl2.. From the equation in Figure 7.7, this means that
K
p
=0.648 dyn
11z
Sllz cm-
l
and the yield stress 't{) = 35.2 dyn cm-
2
. The sum of squares of the residuals for this data
fit is 8986.
Comparison of the residuals from the two models suggests that the equation for a pseudoplastic fluid is the better fit
Answer. Pseudoplastic fluid: n = 0.587; K = 11.43 dyn sn cm-
2
(e)
The apparent viscosity for a pseudoplastic fluid is given by Eq. (7.8) and can be calculated using the parameter values
determined in (b).
(I)
Answer. 3.7 dyn s cm-
2
(Ii)
J1a =Kyn-l =11.43dynsO.587 cm-
2
(200 S_I)O.587-1 =1.3dynscm-
2
Answer: 1.3 dyn s cm-
2
7.2 Rheology of yeast suspensions
From Eq. (7.8), for pseudoplastic fluids, a plot of apparent viscosity versus shear rate on log-log coordinates can be
expected to give a straight line. Log-log plots for the different cell concentrations are shown below.
78 Solutions: Chapter 7
10
Cen concentrations:
.1.5%
03%
0::-
D 6%
L ..
t
10.5%

I
t3-
"
~
1
1 10 100
Shear rate (8-
1
)
100
Cell concentration: 12%
0::-
..
t

E
e
!l
~
10
1 10 100
Shear rate (sol)
1000
,
Cell concentration: 18%
0::-
..
~
....
8
. ~ 100 ~
E
I
...
10
1 10 100
Shear rate (sl)
Solutions: Chapter 7 79
Cell concentration: 21%

f
I
10
Shear rate (5-
1
)
100
The equations and parameter values for the straight lines in each plot are listed below.
Cell concentration (%) Equation Flow behaviour index, n Consistency index, K
(cp
s
n-l)
1.5
3
6
10.5
12
18
21
0
I', = 1.5 r = 1.5
0
1',=2.0r =2.0
Pa = 2.91 r-:O,050
I', =5.38 r..<>.07.
Jl.a =50.1 r-:0.395
J.la = 162 7-:0307
Jla =833 7-:0.251
1
1
0.95
0.92
0.61
0.69
0.75
1.5
2.0
2.9
5.4
50
K and n are plotted as a function of cell concentration below.
10
c
.
~ - "
1.0
0.6
5
!
! 0.8

1.4,--,.---..--....--"..---.....
1.2
Flow behaviour index, n
o Consistency, index, K
0.4 '--__..J.....__.....J..__-''-__-'-__.....Il
o 5 10 15 20 25
Cell concentration ('Yo)
80 Solutions: Chapter 7
The cell broth is Newtonian up to a cell concentration of about 2%, then becomes pseudoplastic. The flow behaviour
index continues to decrease until a cell concentration of about 12% is reached. The consistency index rises
!broughout the culture with increasing cell concentration.
7.3 Impeller viscometer
(a)
If the rheology can be described using a model, a plot of shear stress versus shear rate on log-log
coordinates can be expected to give a straight line. Values of shear stress and shear rate can be determined from
torque and stirrer speed data using Eqs (7.11) and (7.12) with k =10,1 and Dj, "'" 4 em "'" 4 x 1<r
2
m. The results are
listed below and plotted below.
Stirrer speed (sl) Torque (Nm) Shear stress (Nm-
2
) Shear rate (gw
1
)
0.185 3.57 x 0.0559 1.89
0.163
3.45 x 10-
6
0.0540 1.66
0.126
3.31 x 10-
6
0.0518 1.29
0.111
3.20 x 10.
6
0.0501 1.13
0.07
0.06
i
0.05
0

11-

e
"
"
0.04
m

<J)
2 1.5
Shear rate (s-1)
0.03'- ..L... -'
1
The equation for the straight line on the log-log plot is 1'=O,049jr20. From Eq. (7.7), this means that the flow
behaviour index n is 0.20 and the consistency index K is 0.049 N sn m-
2
.
Answer: Yes: n = 0.20; K= 0,049 N s1l m-
2
(b)
The impeller Reynolds number for pseudoplastic fluids is defined in Eq. (7.23). IfRei at the highest stirrer speed is in
the laminar range, conditions at the other stirrer speeds are also laminar. Therefore, for Ni = 0.185 s1 and using the
unit conversion factor 1 N =1 kg ms2 (Table A.4, Appendix A):
D' P (0.185,-1)2-0.20(O.04m)' l000kg m-
3
Rei = =-->=="(r'---"==-"IC"':""-"'-:"O,,, =10,0
10.20.20-1 0.049NsO.20m-2.
This value for Rei is at the upper limit of the laminar range (p 137); therefore, we can conclude that flow at this and
lower stirrer speeds is laminar.
Answer: Flow is laminar.
Solutions: Chapter 7 81
(oj
From Table 7.4, k = 30 for a helical-ribbon impeller. From Figure 7.25, flow with this type of impeller is laminar up
to about Rei = 10
3
. These conditions allow use of higher stirrer speeds within the laminar region than is possible
using a turbine impeller. Solving for Ni from Eq. (7.23) and substituting values of n and Kfor the fluid from (a), the
maximwn stirrer speed at Rej = 30 can be calculated as:
N?--n = Rei K
1 vf P
103 (30o.zo-1) (0.049 NsO.20
m
-21
1
kgms-
2

!if..".20 = 1N II
I (0.04m)21000kgm 3
Nl-
8
= 2.02s-1.8
Ni = 1.48 s-l
Therefore, from Eq. (7.11), as r= 30Ni for a helical-ribbon impeller, shear rates up to 30 x 1.48 = 44 s-1 can be used.
This is a considerable improvement on the restricted range-of.up to about 1.9 s-l as determined in (a) for the upper
limit of laminar flow with a Rushton turbine impeller.
Answer: The shear rate range can be extended from 1.9 s-1 with a Rushton turbine impeller to 44 s-1 with a helical-
ribbon impeller.
7.4 Particle suspension and gas dispersion
The Zwietering equation is an equation in numerics (p 12); therefore, the parameter values used in the equation must
have the units specified. V
p
=10 J.llll =10 xlo-
6
m; g =9.8 m (p 16); Vj =30 em =0.3 m; PL =density of water =
1000 kg m-
3
. The dynamic viscosity of water J4... at 20"C is about 1 cP (p 133); from Table A.9 (Appendix A), this is
the same as J4... = kg m-
I
Using the definition of .kinematic viscosity from p 133:
f.lL 10-
3
kgm-
1
8-
1
V
L
=-= =10-u m2 s-1
PI. lOOOkgm-
3
The density of the cells PP is 1.04 g cm-
3
. Converting to kg m-
3
;
_ 104 -3 Iloocml3 lO4Okg -3
Pp - . gcm. m . lOOOg - m
Substituting values in the correct units into the Zwietering equation:
This minimum stirrer speed for suspension of the cells can be compared with the minimum stirrer speed for dispersion
of air bubbles. Taking the average minimum tip speed of 2.0 m s-1 for bubble dispersion:
N =tipspeed =2.0ms-
I
=2.1 s-1
1 1t Vi 1t (0.3 m)
The stirrer speed for air dispersion is 3.7 times higher than for ceIl suspension. As power in the turbulent regime is
proportional to the stirrer speed cubed, about 50 times more power is required to disperse the air bubbles than to keep
the cells in suspension.
Answer: Bubble dispersion requires significantly more power than cell suspension.
82 Solutions: Chapter 7
7.s Scale-up of mixing system
(aJ
The Reynolds number for a Newtonian fluid in a stirred vessel is defined in Eq. (7.2). Using this equation to evaluate
the maximum viscosity jJ. under turbulent conditions with the density of water p= 1000kg m-
3
:
N P (SOOmin-
1
.1 160miDll(5 cm)2 .1100
1
m1
2
) 1000 kg m-
3
1 I S U em 33 10-3 k -1-1
I.t = = = . x gm s
Rei 10
4
From Table A.9 (Appendix A), 1.kg m-
I
s1 =103 cP; therefore:
3
33 10
-3k -1 -1 10 cP 33 P
J.l=.x gms. ll='c
1kgm- s-
Answer: 3.3 cP
(bJ
The tip speed in the laboratory equipment is:
Tipspeed = 7tNj Di =1 (800min-
1
-I 1
6
:
s
D1)(5 em = 2.1 m8-
1
In the large-scale vessel. Di =15 x 5 em=75 em. If the tip speed is kept the same after scale-up:
M. _ tip speed _ 2.1 ill s-1 _ 089 -1
'" _ _ ( ) _ . s
1tDj 1m
1t 75cm.l
lOocm
l
Using this value of Ni to calculate the maximum viscosity as in (a):
O.89S-I((75Cm)21100Im 1
2
)lOOOkg m-
3
JJ.= = .em =O,05kgm-
l
s-
1
Rei 10
Converting to cP:
= 50cP
Answer: Scale-up increases the maximum viscosity for turbulent conditions to 50 cP.
7.6 Effect of viscosity on power requirements
(aJ
Dj =1 m;p= 1 gcm-
3
=1000 kg m-
3
.
(1)
The viscosity Of water at 20"C is about 1 cP (p 133); from Table A.9 (Appendix A), this is the same as lO-3 kg m-
1
s-l. Substituting parameter values into Eq.(7.2):
NiDrp 6
Rei = = 3 11 =1.5 x 10
Ji lO kgm- C
From Figure 7.24 for a Rushton turbine, this value of Rei corresponds to turbulent flow and N
p
can be taken as 5.8,
The power required is evaluated using Eq. (720):
P = NppNf Dr =5.8 (lOOOkg m-
3
)(90 min-
I
(l m)5 =1.96x 10
4
kg m
2
s-3
Solutions: Chapter 7
From Table A8 (Appendix A), 1W=I kg m
2
s-3; therefore:
P = L96xl04w = 19.6kW
Answer: 19.6 kW
83
(ti)
For a viscosity of 100 x 10-
3
kg m-
1
s-1 =0.1 kg m-
1
s-l, Rei is:
NiDf p (90min-
1
m)21000kgm-3
Ret' = = 1 1 = 1.5 x 10
4
# 0.1 kgm- s-
From Figure 7.24 for a Rushton turbine, this value of Rei is still within theturbulent regime so that N
p
isagain5.8.
Therefore, the power required is the same as that calculated in (i): P =19.6 kW.
Answer: 19.6 kW
(iii)
For a viscosity of 104 x 10-
3
kg m-
1
s-l = 10 kg m-
1
s-l, RCi is:
NiD[ p (90 min-
1
m)2 1000kgm-3
=
J.l IOkgm1s1
From Figure 7.24 for a Rushton turbine, this value of Rei is within the transition regime. Np read from Figure 7,24 is,
about 3.5. The power required is evaluated using Eq. (7.18):
P = NppNf Dr = 3.5 {tOOOkg m-
3
) (90 min-
1
.! (l m)5 = 1.18x 10
4
kg m
2
s-
3
From Table A8 (Appendix A), 1 W= 1kg m
2
s-3; therefore:
P = L18xl04W = 11.8kW
Answer: 11.8 kW
(b)
From Figure 7.24 for a Rushton turbine, turbulence with N
p
=5.8 is achieved at a minimum Reynolds number of
about 10
4
. For a viscosity of 1000 x 10-
3
kg m-
1
s-1 = 1kg m-
1
s-l, the stirrer speed required can be detennined from
Eq. (7.2),
Using this result in Eq. (7.20):
P= NppNI D; = 5.8 (1000 kg m-
3
j(1Os-lj3 (I m)S =5.80x 10
6
kg m
2
s-3
From Table A8 (Appendix A), 1 W= 1kg m
2
s-3; therefore:
P = 5.80 x 10
6
W = 5.80 x 1()3 kW
Answer: 5.80 x 10
3
kW
84 Solutions: Chapter 7
7.7 Electrical power required for mixing
Di =- 7 em =- 0.07 m; p =- 1000 kg The viscosity of water at 20C is about I cP (p 133); from Table A.9
(Appendix A), this is the same as 10.
3
kg m-
1
8.
1
, Substituting parameter values into Eq. (7.2):
2 (900' -1 11minn(007 )2
1OOOk
-3
NiDi P nun. 60s U . m gm 4
Rei = --'-cC:-C- = 3 II=-7Ax 10
J.l. 10- kgm s
From Figure 7.24 for a Rushton turbine, this value of Rei corresponds to turbulent flow and can be taken as 5.8.
The power required is evaluated using Eq. (7.20):
p = NpPNf Dr = 5.8 (1000 kg m-
3
) (900min-
1
(O.07m)5 =32.9kgm
2
s-
3
From Table A,S (Appendix A), 1 W =- 1kg m
2
8-
3
; therefore:
P = 32.9W
This value is considerably lower that the electrical power consumed by the stirrer motor.' Much of the remainder of
the electrical power is converted into heat within the motor bousing.
Answer: 32.9 W; a significant fraction of the electrical power is dissipated as beat within the motor housing
7.8 Mixing time with aeradon
Di = 0,67 m; p = density of water = 1000 kg m-
3
. From TableA.9 (Appendix A). I cP = 10.
3
kg mol s-l; therefore. Jl
= 4 cP = 4 x 10,3 kg s'l. For a cylindrical tank of diameter Dr= 2 mand height H= 2m. the volume Vis:
V = 7t{;YH = 7t{2;t 2m = 6.28m
3
(aJ
If the maximum specific power consumption is 1.5 kW m'3. the maximum power Pis:
P = (L5kWm-3)6.28m
3
= 9.42kW
From Table A.8 (Appendix A), I W= I kg m
2
s'3; therefore 1 kW = 1000 kg m
2
s-3. ConvertingP to kg m
2
s3:
P = 9.42kW = = 9.42 x 10
3
kg m
2
C
3
Assume for now that the fluid flow is turbulent and N
p
= 5.8. The stirrer speed can be evaluated using Eq. (7.20):
N:= P =120s-3
, NppDi 5.S(1000kg m-
3
) (O.67m)5 .
Ni = 2.29 sol = 137 rpm
Check that this stirrer speed provides turbulent mixing conditions by evaluating the Reynolds number. Rei for
Newtonian fluids in a stirred vessel is defined in Eq. (7.2):
Rei = NiDf P = (2.29s-l)(O.67m)21000kgm-3 = 2.6x 105
j.l 4 x 10 3kg m-
I
s 1
From Figure 7.24 for a Rushton turbine. this value of Rei is well into the turbulent regime; therefore the value for
assumed above is valid.
For high Rei> the mixing time can be calculated using Eq. (7.16):
Solutions: Chapter 7
t = 1.54 V = 1.54(6.28m')
m D; Nj (O.67m)3
2
.
29S
-1
=14s
85
Answer: The maximum allowable stirrer speed is 2.29 s-1 or 137 rpm; the mixing time is 14 s.
(b)
The ungassed power number was 5.8; therefore, the power number with gassing (Np)g =0.5 x 5.8 = 2.9. The stirrer
speed which delivers the maximum power P= 9.42 x 103 kg m
2
s-3 can be evaluated using Eq. (7.18):
Nt = P 5 = 9,42x10
3
kgm
2
s-
3
- 241 -3
(Np) pD; 2.9(lOOOkgm-'j(O.67m)5 - . s
g
Nj = 2.89 s1 = 173 rpm
The mixing time evaluated using Eq. (7.16) is:
t =!541' = 1.54(6.28m')
m DfN
1
(O.67m)3
2
.
89s
-1
=II s
Answer: The maximum allowable stirrer speed is 2.89 s-1 or 173 rpm; the mixing time is 11 s.
Heat Transfer
8.1 Rate of condnction
(a)
B::::: 15 em "" 0.15 m; liT"", qoo-.80) ::::: 620"C. which is equal to 620 Kas temperature differences are the same on the
Celsius and Kelvin scales (p 18). The rate of heat conduction can be calculated using Eq. (8.10):
Q = kA !'J = (0.3 Wrn-
l
K-
1
) Urn
2
(620K) = 1860W = 1.86kW
B a.15m
Answer: 1.86 kW
(b)
In this case there are two thermal resistances in series. Their magnitudes are calculated using Eq. (8.15). For the
firebrick:
For the asbestos, B2 ::::: 4 em ::::: 0.04 m, so that:
RZ::::: 82::::: a.04m ::::: O.27KW-1
k2A (o,tWm lK 1)1.5m
2
Therefore, the total wall resistance RW=RI + RZ ::::: (0.33 + 0.27) K I ::::: 0.60 K For thennal resistances in
series, the rate of heat conduction is calculated using Eq. (8.14):
Q= I1T = 620K = 1033W= 1.03kW
Rw O.60KV
I
Answer: 1.03 kW
8.2 OveraU heat-transfer coefliclent
The overall heaNransfer coefficient is calculated using Eq. (8.24) with hfh::::: 830 W K-I, hh::::: 1.2 kW m
2
K-I, B
=6mm::::: 0.006 m, k= 19 Wm,l K-l, he"" 1.7 kWm
w2
K-l and hfc= O.
1 lIB 1 1
- = -+-+-+-+-
U hfh hh k he hfc
1. = 1 + 1 + O.OO6m + 1 +0
U 830Wm 2r-
1
19Wm IK-
1

i, = 2.94 x 10-
3
W-
l
m
2
K
U= 340Wm
2
K-I
Solutions: Chapter 8
8.3 Effect of cooling-coH length on coolant requirements
(a)
The equation for the is Eq. (8.32):
Q= McC",(T",-Tct) = (0.5kgs-
I
)4.18kJkg-
l
oc-
l
(15-S)"C = 14.6kJs-
1
Answer. 14.6 kJ sol
87
(b)
The mean temperature difference between the fermentation fluid and the cooling water is calculated from Eq. (8.35):
2 Tp-(Tct+Tco) (2 x 35)OC-(S + 151'C
/iTA: 2 : 2 : 23.5OC
Answer. 23.5"C
(c)
UA is evaluated using Eq. (8.19) with /iT: /iTA:
UA = Q =
ATA
(d)
14.6 kJ s-l
23.5"<:
UA': 1.5UA: 1.5xO.62kJs-
I
"C-): 0.93kJs-
I0
C-
1
Answer: 0.93 kJ s'} Cl
(c)
Applying Eq. (8.19) to determine /iT: /iTA for the new coil:
- 1
!iTA : -iL : 14.6 kJ s-
UA' 0.93 kJ s-l C
1 =15.7"<:
The new cooling water outlet temperature T
co
is determined using Eq. (8.35):
Answer: 30.6"C
(f)
From Eq. (8.32), for the new coil with Q: 14.6kJ s-l, Tci = goC and Teo =30.6"C:
- -I
M - Q - 14.6kJ, _ 015k -I
c - C",(Tco-Tct) - 4.18kJkg-Io
C
I(30.6-
S
l'C -. gs
Therefore, installation of the new coil allows a 70% reduction in cooling-water requirements;
Answer: 70%
8.4 Calculation of area in fermenter design
Ni: 80 rpm =80'60 =1.33 sl. C
p
culture fluid =4.2 kJ kg
l
c
l
: 4.2 x 1()3 J kg'} "c
l
. C
pc
=C
p
water =75.4 J
gmol'} "C-
I
(Table B.3, Appendix B) =75.4 kJ kgmol-l "C-
l
. Converting C
pc
ta a mass basis using the molecular
weight af water =18.0 (Table B.I. Appendix B):
Cpc =75.4 kJ kgmol-l "C-
l
: 75.4kJkgmor
l
"c-I.1 ;:: 4.19kJkg-
1
"C-
l
,llb;:: 10.
3
N s m
2
; from Table A.9 (Appendix A), I N sm
2
=} kg m
l
s-l; therefore Jlb = 10-
3
kgm-
l
sl. ktb = 0.6
W mol "e
l
; from Table A.8 (Appendix A), 1 W=1 J sl; therefore k fb =0.6 J 8"1 m-
l
"C-l. B: 6 mm;:: 0.006 m.
88 Solutions: Chapter 8
From p 97, as the heat of reaction for an exothermic reaction is negative, Aii
rxn
=-2500kW. From the modified
energy-balance equation, Eq. (8.33), when evaporation and shaft work can be neglected. Q=-M
rxn
=2500 kW=2.5
x 106 W, According to the sign conventions on pp 88-89, Qpositive is consistent with heat being removed from the
system. From Table A.8 (Appendix A), 1 W =1 J 8.
1
; therefore Q= 2.5 x 10
6
J s1 =2500 kJ s-I,
(a)
The fermenter-side heat-transfer coefficient can be evaluated using the empirical correlation, Eq. (8A5). The
dimensionless nwnbers in this equation are Rei, Pr and Nu. Rei is given by Eq. (8.39):
Pr is given by Eq. (8AO):
From Eq. (8.45):
Nu =0.87Re?,62pr033(::fI4 =O.87(3.84X 10
6
).62 (7.0)0.33 (1)0.14= 2.0x 10
4
From the definition of Nu in Eq. (8.37):
Nukfb 2.0x 10
4
(0.6 Wm-
l
C-
1
) 3 2 I
h=--= =2.4 X 10 Wm- 0C;
D 5m
Therefore, as the fennenter fluid is the hot fluid, hh = 2.4 x 103 W m-2 e
1
.
Answer: 204 x 10
3
W m-Z oC-
1
(b)
The overall heat-transfer coefficient in the absence of fouling layers can be calculated using Eq. (8.23). Assuming
that the heat-transfer coefficient for the cooling water h
c
can be neglected (p 185):
1- =. ! . + ~ = 1 + O.OO6m =7.17xlO-4W-1mZoC
V hh k 2AxI03Wm 20(;"1 20Wm-1OC 1
U = L40x 103 wm-Zoe
1
= 1.40kWm-
20
e
l
From Eqs (8.21) and (8.22), the beat-transfer resistance due to the pipe wall is B/
k
A; from Eq. (8.20), the total
resistance to beat transfer is l/Vk Therefore, the proportion of tbetotalresistance,duetothe-pipe wallis:
BfkA = BU = O.OO6m (L40 x 10
3
Wm-2 oc-1j = 042
l/VA k 20Wm 10C-
1
.
Answer: lAO kW m-
2
C-
1
. The pipe wall contributes 42% of the total resistance to heat transfer.
(c)
The energy-balance equation for the cooling water, Eq. (8.32), relates the cooling water flow rate, the inlet and outlet
temperatures and the rate of heat transfer. From this equation, an expression for the outlet cooling-water temperature
is:
Solutions: Chapter8 89
where Tco has units of C and Me has units of kg b
1
. An expression for the mean temperature difference between the
fermentation fluid and the cooling water can be determined from Eq. (8.35);
_ 2 Tp-(Tci + Teo} _ (lx30)OC-(1O+T
co
}OC _ 6O"C-10"C-T
co
_ Teo
ATA - 2 - 2 - 2 - 25-
2
where !!TA and Teo have units of C. Substituting this expression into Eq. (8.19) for evaluation of A with AT= ATA
and the value of Ufrom (b);
A =~ = 2500kW =1.8x 10
3
U!1T
A
1.40kWm-Zoc-1(25_ T;'fe 25- T ~
where A has units of mZand .Teo has units of C. The above equations for Teo and A allow evaluation of these
parameters as a function of Me' The results for several values of Me between 1.2 x loS kg b
1
and 2 x 106 kg b
1
are
listed and plotted below.
M,(kgb-
I
) Tco (0C) A (m
2
)
1.2 x loS 27.9 163
2.0xloS 20.8 123
3.0x loS 17.2 1I0
4.0x loS 15.4 104
8.0x loS 12.7 97
1.0 x 106 12.2 95
2.0 x J(j6 ILl 93
30,.....---..,.,.....---.,..-----.,..-.----,200
41 Temperature
o Area
o'- J- -'- ...J''--__--' 50
o 5 10 15 20
Cooling-water flow rate, Me x 1Q-5 (kg h
1
)
(d)
From the,equations developed in (c), at a cooling.water flow rate of 5 x loS kg h*l, Teo =14.3C and A = 101 .tn.2.
The area A of a cylindrical coolingcoil is equal to 2 1t r L, where r is the cylinder radius and L is its length. For a
radius of 5 em=0.05 m:
A 101 m
2
L =21tr =21t(0.05m) = 321 m
Answer: 321 m. This is a long coolingcoil, representing a considerable expeme whenfabricatedfrom stainless steel.
90 Solutions: Chapter 8
8.5 Effect of fouling on heat-transfer resistance
(a)
C
pc
=C
p
water = 75.4 J groat-! 0C"l (Table B.3, Appendix B):o 75.4 kJ kgmo}l Converting to mass terms
using the molecular weight of water = 18.0 (Table B.I. Appendix B):
Cpc =75.4 kJ kgmor
l
'C-
l
=75,4 kJ kgmor
l
'c-ll =4,19kJ kg-
l
'C-
I
From Eq. (8.32), the rate of heat removal to the cooling water before cleaning is:
Q=McCpc(Tco-Tci) =20 kg s-I (4,19kJkg-
1
'C-
I
) (2S-12)'C =1340,SkJs-
1
The meantemperatute difference between the fennentation fluid and the cooling water can be calculated from Eq.
(835),
2 Tp-(Tci + Tco) (2 x 37)'C-(12 +2S)'C
LiTA = = =17'C
2 2
The area A ofthe cylindrical is equal to 2 1t r L, where r is the cylinder radius and L is its length, For r=
6cm =O.06mandL= 150m:
A =2 1t (0.06 m) (150 m) :0 56.5 m
2
Evaluating the overall heat-transfer coefficient U from Eq. (8.19) with aT=aTA:
- 1
U
- Q - 1340.8kJs- -140kJ -1 -Z'C-1
---- - sm
ALiTA (565m
2
)I7'C '
(b)
If the fermentation temperature is maintained the same after cleaning the cooling-coil, the rates of heat removal Q
before and after cleaning must be equal. The new outlet temperature can be calculated from Eq. (8.32):
1340.8kJ s-1 +120C = 36.6OC
13kgs-I(4,19kJkg-l,C I)
(e)
.The mean temperature difference between the fermentation fluid and the cooling water after cleaning is detennined
from Eq, (835),
2 TF-(Tci +Too) (2 x 37)'C-(12 +36,6)'C
1J.T
A
= 2 =_. 2 =12.7OC
The beat-transfer area is the same as before cleaning: A = 56.5 m
2
. Evaluating Ufrom Eq. (8.19) with AT=tiTA:
- ,
U = = 1340.8kJs- =1.87kJs-1m-20c-1
ALiTA (565 m
2
) 12,7'C
The overall beat-transfer resistance is given by Eq. (8.20):
RT = _1_ = I =9.46 X10..,3.k]""1 s 0C
UA L87kJs-'m 2'C-
l
(S65m
2
)
This is the beat-transfer resistance after cleaning the cooling coil. 'The resistance before cleaning is calculated from
Eg. (8.20) using the value of Ufrom (a):
Solutions: Chapter 8 91
The resistance due to the fouling deposits is equal to the difference between these two overall resistances =: (1.26 x
10-
2
_ 9.46 x 10"3) = 3.14 x 10-
3
kJ-
I
s 0c. Therefore, fouling contributes:
3.14x 1O-
3
kr
1
soC
=0.25
L26x 10 2
kr
i soC
of the total resistance before cleaning.
Answer. 0.25
8.6 Pre-beating of nutrient medium
Cph =: C
pc
=: C
p
water =: 75.4 J gmol"l C
l
(Table 8,3, Appendix B) =75.4 kJkgmot
l
C
l
. Converting to mass
terms using the molecular weight of water = IS.O(Table B.I, Appendix B):
Cph =Cpc =75.4kJkgmor
l
0c-
1
=: 75.4kJkgmor
l
OC-
1
.1 = 4.19kJkg-
1
C-
1
Pmedium =: p water =: 1000 kg m"3. The viscosity of water at 20C is about 1 cP (p 133); from Table A.9 (Appendix
A), this is the same as 10"3 kgm-
I
s-l; therefore,,u medium =:,u water =: H}"'"3 kg m-I s-l. kfb medium = 0.54 W m-
1
C-1; from Table A.S (Appendix A), this is the same as 0.541 5""1 0C-
1
.;tberefore, kfb medium =: 0.54 x 10-
3
kJ
s-l m-
1
C
l
. From Table S.l, kfb water at 303 K= 0.62 Wm-
1
C-l;from Table AS-{A-ppendix A), this is the same
as 0.62 J s-l mol C-1; therefore, ktb water =0.62 x 10-
3
kJ 5-
1
ar
1
0C-
I
. From Eq. (2.24), 303 K =: approx. 30C,
which is close enough to the conditions in the heat exchanger for evaluation of thermal conductivity. k pipe wall =50
W mol C-I; from Table A.8 (Appendix A), this is the same as 50 J s-l mol C-l; therefore, k =50 x 10..
3
kJ s-l m-
l
C
l
. B =: 5 mID =: 0.005 m.
(al
From the definition of density (P-16), the mass flow rate of the medium is equal to the volumetric flow rate multiplied
by the density:
The steady-state energy-balance equation for medium in the tubes of the heat exchanger is Eq. (8.32); therefore:
Q=M,Cpc(T,o-Td) =13.9kg,-1 (4.19kJkg-
1
'C
1
)(28-1O)OC =1048.3kJ,-1
Answer. 1048.3 kJ s-I
(b)
The heat-transfer coefficient for the mediumin the tubes of the heat exchanger can be calculated using the empirical
correlation, Eq. (8.42). The parameters in this equation are Re, Pr and Nu. Re is given by Eq. (8.38). The linear
velocity of the fluid u is equal to the volumetric fIowrate per tube divided bythecross.sectional area of the tube. The
cross-sectional area ofa cylindrical tube =: 1,.z where ris the tube radius = 25 cm =: 0.025m. Therefore:
50 3 h-1
u =: volumetricflowrate =: m . 3600s =: 0.236ms-1
numberoftube,(n?) (30) n (0.025 ml'
Substituting parameter values into Eq. (8.38) with the tube diameter D =5 cm=0.05 m:
Re =Dup =0.05m(0.236m,-I)IOOOkgm-
3
=1.18 x 104
JIb 1O-
3
kgm Is 1
This value of Re is within the range of validity of Eq. (8.42). Pr is given by Eq. (8.40):
_ Cpi'b _ 4.19kJkg-
1
"C
1
(10-
3
kgm-I ,-I)
Pr____ =78
k
tb
0.54x1O-3kJs-1m-1oC I .
This value of Pris also within the range of validity ofEq. (S.42). From Eq. (8.42):
92 Solutions: Chapter 8
Nu = 0.023 Re
O
.
S
Pr
OA
= 0.023 (1.18 X10
4
).8 (7.8)0,4 =94.6
From the definition of Nu in Eq. (8,37):
h
_ Nukfb _ 94.6{O.54xlO-
3
.kJs-
1
m-
1
oc-
1
) _ 102kJ -1 -2 "C-1
- D - O.05m -. s m
As the medium in the tubes is the cold fluid in this heat exchange system, he =1.02 kJ sl m-2 0C-
l
,
The heat-transfer coefficient for the water flowing in the shell of the heat exchanger can be calculated using the
empirical correlation, Eq. (8.44). The parameters in this equation are C, Remax, Prand Nu. As the tubes of the heat
exchanger are arranged in line, from p 183. C =0.26. Remax is given by Eq. (8.38) with D equal to the outer tube
diameterdetennined as the sum of the inner tube. diameter and the pipe wall thicknesses: D =0.05 m + 2 x 0.005 m =
0.06 m. Substituting parameter values into Eq. (8.38):
Re =Dup =0.06m{O.lSms-
1
)tOOOkgm-
3
=9.00 x 103
max fib 10-
3
kg m-
l
s-1
As this value is > 6 x UP, Remax is within the range of validity of Eq. (8.44). Prior theshellside water is given by
Eq. (8.40):
Therefore. from Eq. (8.44):
Nu = =O.26(9.00X 103}O.6 (6.8).33 = 115
From the definition of Nu in Eq. (8.37) with D the outside tube diameter:
Nukfb 115 (0.62 x 10-
3
kJ s-l m-
l
OC-
1
) 1 2 1
h =--= =1.19kJs- m- "C-
D O.06m
As water is the hot fluid in this heat exchange system, hb = 1.19 kJ 5-
1
m-
2
"C-l.
(e)
The overall heat-transfer coefficient without fouling factors is calculated using Eq. (8.23);
=1.92kJ
1
sm
2
C
U =0.52 kJ sl 0C-
1
(d)
The outlet temperature of the water from the shell is detennined from Eq. (8.31):
- I
- Q - 1048.3kJs-
.Lho - .Lbl - ..... - - =
MhCph 3x
The fluid flow directions and the inlet and outlet temperatures for a countercurrent shell-and-tube heat
exchanger are represented graphically below.
Solutions: Chapter 8
j60
0
C
Tei =- 10"C
/
Teo =- 28<>C
/'
Heat exchanger
Tho=-30"C
93
The temperature differences at the two ends of the exchanger are fl.Tl =- (30 - to) ::::: 20"C and /1T2 ::::: (60 - 28) ::::: 32"C.
Substituting these values into Eq. (8.34) for the log-mean temperature difference:
<IT. = LlTZ-LlTI = (32-
20
r
e
= 25.5OC
L In(LlT2I<lTd In (32120)
Answer: 25.5"C
(e)
The heat-transfer area is determined from Eq. (8.19) with AT::::: /1TV
- I
A ::::: ~ ::::: 1048.3k1s- ::::: 79m2
ULlTL 0.52kJ s-I m-
2
oc-
I
(25.5OC)
Answer: 79 m
2
(f)
The total area A of the tubes in a shall-and-tube heat exchanger is equal to 2 1t r L N, where r is the tube radius, L is
the length of the tubes and N is the number of tubes. For r::::: 2.5 cm::::: 0.025 m and N::::: 30:
A 79m
2
L::::: 21trN::::: 21t(0.025m)30 ::::: 16.8m
From these results, LID::::: 16.8/0.05 ::::: 336, where D is the tube diameter. As this value is > 60, application of Eq.
(8.42) used.to detennine the tube-side heat-transfer coefficient is valid.
Answer: 16.8 m
8.7 Suitability of an existing cooling-coil
Ni =- 50 rpm::::: 50/60::::: 0.83 s-l. Cph::::: Cpc::::: C
p
water::::: 75.4 J gmol-l C-l (Table B.3, Appendix B)::::: 75.4 k1
kgmoll C-
1
. Converting to mass tenns using the molecular weight of water::::: 18.0 (Table B.l, Appendix B);
Cph =- Cpc =-75.4kJkgmor
l
C-
1
=- 75.4kJkgmor
1
"'c-
l
.! ~ : : ~ 1 ! ::::: 4.19kJkg-
1
"'C-l
kfb fennentation fluid =-ktb water. From Table 8.1, kfb water at 303 K =- 0.62 W urI "'C-l; from Table A.8 (Appendix
A), this is the same as 0.62 J s-l m-
l
oCl; therefore, kfb::::: 0.62 x 10-
3
kJ sol m-
1
C
1
. From Eq. (2.24), 303 K =-
approx. 30C, which is close enough to the conditions in the fennentation system for evaluation of thennal
conductivity. p fennentation fluid::::: p water =- 103 kg m'3. # fennentation fluid =- # water. The viscosity of water at
20"'C is about 1 cP (p 133); from Table A.9 (Appendix A), this is the same as to-
3
kg m-
l
sol. Assume that this value
applies under the conditions in this system, and that the fluid viscosity at the wall J1w is equal to the bulk viscosity J.I.b.
The fennenter-side heat-transfer coefficient can be evaluated using the empirical correlation, Eq. (8.45). The
dimensionless numbers in this equation are Rei, Pr and Nu. Rei is given by Eq. (8.39):
94
Pr is given by Eq. (8.40):
Solutions: ChapterS
From Eq. (8.45):
Nu = 0.87 Re?,62Pr
0
.33 (::::)""14 = 0.87(8.3 x (6.8P33 (1)0,14 = 7,7 x 10
3
From the definition ofNu in Eg. (8.37) with D::::: the tank diameter:= 3 m:
Nu k 7.7 X10
3
(0.62 x 10-
3
kJ s-1 m-
I
oc-
l
)
h = = ,;", 1.59kJ 8-
1
m-
2
C-
1
D 3m
Therefore. as the fermentation fluid is the bot fluid, hh i:::: 1.59 .kJ sl m-
2
oe!. The overall heat-transfer coefficient in
the absence of fouling layers is .calculatedusing Eq. (8.23). Assuniingthat the beat-transfer coefficient for the cooling
water he and the tube wall resistance O'kean be neglected (p 185), from Eq. (8.23), U:= klJ = 1.59 kJ s-1 m-
2o
C-
I
.
To maintain thefennentation temperature constant, tbecooling-coil must be capable of removing heat from the
, fermenter attbe rate at which it isprodu.ced. From p100,the heatof reaction for aerobic cultures is -460 kJ pergmol
consumed, Therefore. if the maximum oxygen demand = 90 gmol m-
3
b-
l
and the fennenter volume = 20
From the modified energy-balance equation, Eq, (8.33), when evaporation and sbaft work can be neglected,
Q=-AH
rxn
= 230 kJ sl. According to the sign conventions on pp 88-89, Qpositive is consistent with beat being
removed from the system, From the definition of density(p 16), the mass flow rate of-the- cooling water is equal to
the volumetric flow rate multiplied by the density:
Xl, = = 5.56kgs-
1
From Eq. (8.32), the outlet cooling-water temperature is:
Q 230kJs-
I
Tco = ---- + Tei = ( )- + 12"C = 21.9"C
Mc Cpc 5.56 kg s-1 4.19 kJ kg-I oc;l
The mean temperature difference between the fermentation fluid and the cooling water can be determined from Eq.
(8.35):
2 Tp-(Tci + T,o) (2 x 28)'C-(12 +21.9)"C
tli'A = 2 = 2 = 11.1"C
Substituting the results into Eq. (8.19) for evaluation ofA with aT= !lTA:
The area A of a cylindrical cooling-coil is equal to 2 1t r L, where r is the cylinder radius and L is its length. For r =
7.5/
2
= 3.75 em = 0.0375 m:
A 13m
2
L=--= _ =55m
21tr 21t(0.0375m)
Solutions: Chapter 8 95
As the required length of cooling-coil is considerably longer than the 45 m available in the offered fermenter, the
secondhand fermenter without modification is unsuitable for the proposed culture.
Answer: No
8.8 Optimumstirring speed for removal of heat from viscous broth
J.tb = 10,000 cPo From Table A.9 (Appendix A), 1 cP = 10-
3
kg m-
I
s-l; therefore, JJb = 10,000 x .kg m-
I
= 10
kgm-
I
sol. kfu = 2 W m-
l
C-
l
. From Table A.8 (Appendix A), this is the same as 2 J gol mol C-
l
; therefore,ktb =
2 J s-1 m-
1
C = 2 x kJ s-l mol C-
1
.
(a). (b) and (e)
The fermenter-side beat-transfer coefficient can be evaluated using the empirical correlation, Eq. (8.45). The
dimensionless numbers in this equation are Rei, Pr and Nu. The dependence of Rejon stirrer speed is given by Eq.
(8.39),
where Ni has units s-l. Pr is given by Eq. (8.40):
C.LIb 2kJkg-Ioc-l(lOkgm-ls-I) 4
Pr=-P-= =10
ktb 2 x 10 3 k1 C
l
m-
l
0C-
l
From Eq. (8.45), assuming that the viscosity at the wall is equal to the viscosity of the bulk-fluid:
Nu = 0.87 Rep62 p,O.33(:::t 14 = 0.87 (60.8 N;)0.62 (10
4
)".33 (1)0.14 = 232AP,62
From the definition of Nu in Eq. (8.37) with D = the tank diameter = 2.3 m:
Nukfb 232NP62(2XlO-3kJs-lm-loc-l) .11.62 -1 -2
0
-1
h =-V= 203m =0.20Ni kJs m C
Therefore, as the fermentation broth is the bot fluid:
hh = 0.20N?62
kJs
-l
m
-2o
C
-1
Assuming that the coefficient for the cooling water he and he tube wall resistance Blk can be neglected
(p 185), from Eq. (8.23),
U = hh = 0.20N?62
kJs
-I m-
2
C-
1
Substituting the known parameters into Eq. (8.19) with liT=liTA = WOC:
Q= UA6T
A
= 0,20AP,62 kJ ,-l
m
-2'C
1
(14m
2
jzO"C = 56.0AP,62
kJ
,-1
The power dissipated from the stirrer, W
s
' is equal to the power P calculated using Eq. (7.18), In this system, the
value of Np with gassing (Npg) is 40% lower or 0.6 x the value of Np read from Figure 7.24. Therefore:
W, = P = NpgPN; Dr = 0.6Np(103 kgm-
3
1N; (0.78m)' = 173NpN; kgm
2
,-3
where the value of Np depends onRej, and Nj has units of From Table A.8 (Appendix A), 1J sl = I kg m
2
s3;
therefore, 1 kJ = 103 kg m
2
s3 and:
W
s
= 173NpN[ kgm
2
s-
3
.1 1 -31 = 0.173NpNf kJ s-l
lOOOkgm s
From the modified steady-state energy-balance equation, Eq. (8.33), assuming evaporation is negligible:
96 Solutions: Chapter 8
Therefore:
-M
rxn
= Q- W
S
= (S6.0,vp62_0.173NPNf)kJS-l
Values of Q, W
S
and -tJi
rxn
calculated using the equations derived above are listed below as a function of Ni.
Values of Np as a function of Rei were obtained from the original reference (I.H. Rushton, E.W. Costich and H.I.
Everett, 1950, Power characteristics of mixing impellers. Chern. Eng. Prog.46. 467-476) for more accurate
interpolation of the power curve in Figure 7.24,
Nj ( s ~ l )
Rei
Q(1<1 ,.1) Np Ws (kJ s-l) -Mi
rxn
(kJ sl)
0.5 30.4 36.4 4.5 0.10 36.3
0.8 48.6 48.8 4.1 0.36 48.4
l.0 60.8 56.0 4.0 0.69 55.3
2.0 122 86.1 3.7 5.12 80.9
3.0 182 111 3.7 17.3 93.4
4.0 243 132 3.6 39.9 92.4
5.0 304 152 3.6 77.9 74.0
6.0 365 170 3.8 142 28.1
7.0 426 187 3.8 225 -38
8.0 486 203 4.0 354 -151
10.0 608 233 4.0 692 -459
The values of ii, W
s
and -tili
rxn
are plotted as a function of Nj below.
10 5
00
a Ws
-AHrxn
Stirrerspeed, Nj (s1)
(d)
The rate of removal of metabolic heat (the -Aii
rxn
component of 'hreaches atnaltimurn at aroundNj =3 8.
1
,
Answer: About 3 s1
(e)
From p 100, the heat of reaction for aerobic cultures is -460.kJ per groal oxygen consumed. Therefore, if the rate of
oxygen consumption per g cells is 6 rnmol g.I h
I
= 6 x I O ~ 3 gmol g.I h
I
, when the stirrer speed is 3 sl and 6H
rxn
=-93AkJs
I
:
Solutions: Chdpter 8 97
Biomass = -93.4k:Js-
1
=L22XIIYg
6 x10-' gmolg-I h-
I
. I ' 6 ~ s l (-460kJ gmol-I)
The cell concentration is equal to the biomass divided by the fermenter volume:
5
II
. L22xl0 g 22 I-I
Ce concentration = 3 1
1000
11 = 1 . g
10m . --,-
1m
Answer: 12.2 g l ~ l
(I)
From the graph, as the stirrer speed is raised, the overall heat-transfer coefficient increases as beat transfer through the
boundary layer in the fermentation broth is improved. Therefore, the rate at which heat can be removed from the
system Qis increased. However, the rate at which heat is dissipated by the stirrer W
s
also increases with stirrer
speed.. When the curves for Qand W
s
intersect, the entire heat-transfer capacity of the fennenter cooling system is
being used just to remove the heat from stirring; the system in unable to remove any of the heat generated from
reaction. Accordingly, at high stirrer speeds, the system bas limited capacity to handle exothermic reactions.
Mass Transfer
9.1 Rate-controlling processes in fennentation
Converting the units of the maximum specific ox.ygen uptake rate using the molecular weigbt of oxygen =32.0 (Table
B.I, Appendix B):
= 5 1 -I b-
I
1 I gmol 1132.0g = 444 10-5 -1-1
qo mmo g . lOOOmmol . 1gmol . 3600s ' x g g s
At a cell density of 40 g the maximum oxygen requirement is:
qox = = 1.78 x 10-
3
kg m-
3
,-I
The rate of oxygen transfer is given by Eq. (9.37); NAis maximum when CAL "" 0:
"" O.15s-
1
(ax 1O-3 kgm-3) "" 1.20 x 10-
3
kg m-
3
s-l
As the maximum oxygen demand of the culture is greater than the maximum oxygen transfer rate in the fennenter, the
system will be limited by mass transfer.
Answer: Limited by mass transfer.
9.2 leLa required to maintain critical oxygen concentration
Converting the units of the oxygen uptake rate using the molecular weight of oxygen"" 32.0 (Table B.I. Appendix B):
= 80 11-
1
h-
I
1 1gmol 1132.0g = 711 10-4 k -3-1
qox mmo . lOOOmmol . 19mol . l000g' 1m
3
' 36008 . x gm s
Converting the units of the critical oxygen concentration:
C = 0004mM= 0004 11-
1
IlgmOI I1-,2.0
g
lI...'!LI 1100011-128 10-4 k -3
ent' ,mmo, l000mmol ' 19mol . l000g' 1m
3
- . x gm
(aJ
From Table 9.2. the solubility of oxygen in water at 30"C under 1 atm air pressure is 8,05 x 10-
3
kg m
3
. If the
solubility in medium is 10% lower;
= 0.9 x (8.05 x 10-
3
) kg m-
3
= 7.25x 10-
3
kgm-
3
To maintain the oxygen concentration in the medium at the critical level, from Eq. (9.41):
(kLa). = qox = 7.11XlO-4
kgm
-3
s
-1 =O.10 s-1
ent -Cerit) (7.25X 1O-3kgm-
3
_1.28X 10-4 kg m-
3
)
Answer: 0.10 s-1
(bJ
From Table 9.1, the solubility of oxygen in water at 30"C under 1 atln oxygen pressure is 3.84 x 10"2 kg m-
3
.
Therefore:
Solutions: Chapter 9
From Eq. (9.41),
(kLa) . = ... qox = 7.llxlO-4
kgm
-3
s
-1 = 0.021s-1
ent (CAL-Cerlt) (0.0346kgm-3-1.28XI0-4kgm-3)
Answer: 0.021 s-l
99
9.3 Single-point !<La determination using tbe oxygen-balance metbod
(a)
The oxygen transfer rate for kLa determination by the method is given as Eq. (9.48). From p 17, the
partial pressure of oxygen in the inlet air at 1 atm is (0.21 x 1 atm) = 0.21 atm; assuming that the exit gas leaves the
fermenter at the fermentation conditions (l atm pressure and 28C), the partial pressure of oxygen in the exit gas is
(0.201 x 1 atm) =0.201 atm. Using R =0.000082057 m
3
atm K-1 gmol-
1
from Table 2.5 and converting the
temperatures to degrees Kelvin using Eq. (2.24):
N =_I [(FgPAG) _(FgPAG) 1
A RVL TiT 0
1
NA = 0.OOOO82057m3 attn K-1 gmol 1(200 I) (20+ 273.15) K - (28 +273.15)K
NA =0.0174gmolm-
3
s
1
Answer: 0,0174 gmol
(b)
From Eq. (9,37) with the units of NA from (a) converted to mass terms using the molecular weight of oxygen = 32.0
(Table B.t, Appendix B):
Answer: 0.15 s-l
(e)
If the measured exit gas composition of 20.1% 02 is an overestimation, the actual value is (l/Ll x 20,1)% =18.3%
02. Therefore, the partial pressure of oxygen in the exit gas is (0.183 x 1 atm) = 0.183 atm. From Eq, (9.48):
N = _I [(FgPAG) _(FgPAG) 1
A RVL TiT 0
_ 1
NA - 0.OOOO82057m3 atmK-1 gmorl (2001) (20+273.15)K - (28 +273.15)K
NA =0,0289 gmol m-
3
s-1
Therefore, from Eq. (9.37) with NA converted to mass units:
0.0289 1 -3 -I 132.08 II...I.!>LI
N
A
groom s . 1 01'1000 _
kLa =... = gIn g =0,25s 1
(CAL- CAL) (7.8 x 10-
3
kg m-
3
-0.52x 7.8 x 10-
3
kg m-
3
)
The kr.,a value obtained in (b) using the incorrectly calibrated oxygen analyser is 60% of the actual leLa value; the
error is therefore 40%.
100 Solutions: Chapter 9
Answer: 40%. This calculation illustrates the sensitivity of the oxygen balance method to the accuracy ofall of the
measured parameters used in Eq. (9.48). This sensitivity arises from the subtraction of two similar numbers for the
moles of oxygen in and out of the system. When similar errors in both F
g
terms are taken into consideration. the
error in the final kIft value can be very large,
9.4 leLa measurement
(a)
From p 16, g "" 9.8 m 8.
2
. Assuming the density of the culture broth to be the same as warer, p "" 1000 kg m-
3
. The
static pressure at the sparger is:
Ps = Pg h "" 1000 kg m-
3
(9.8 m s2) (3.5 m) "" 3.43 x t()4 kg mwl sl
,From Table A.S (Appendix A), 1 kg m-
l
s2 = 9.869 x 10"6 aim; therefore:
_ 343 10
4
kg -1 -1 _ 343 10
4
k -1 -1 19.869Xlo-6atml_ 034
Ps - . x m 8 - . x gm s . 1 I -. atm
1kgm- s-
Ps is the pressure due to_the head of liquid above the sparger; oThctotal pressure at the'llparger iSh+atmospheric
pressure "" 1.34 atm.
Answer: 1.34 aim
(b)
From Tables B.8 and B.l (Appendix B), the molecular formulae for glucose and sucrose and the molecular weights of
the medium components are: glucose (C6H1206) = 180.2, sucrose (C12H22011) = 342.3, CaC03 = 100.1,
(NH4)2S04 = 132.1, Na2HP04 = 142.0 and KH2P04 = 136.1.
The parameter values for application in Eq. (9.45) are listed below. Values of Hi and Kj are taken from Table 95.
Medium component Hi or Kj(m
3
mo1l)
Zi GiL or CJL (mol m
3
)
Glucose 0.119 x 10.
3
20g1-111mOllfoooll = 11l
180.2g 1m3
Sucrose 0.149 x 10.
3
-I I1mol 11100011
8.5g1 . 342.3g 1m
3
=24.8
Ca
2
+ -0.303 x 10.
3
2
= 13.0
C032- 0.485 x 1<r
3
2
= 13.0
NR,+ -0.720 x 1<r
3
1
2x13 r
1
I 1mol I 1
10001
1 = 197
. g . 132.1 g' 1m
3
.
S04
2
- 0.453 x 10.
3
2
-I lImo] 11
10001
1
1.3g1 . 132.1g 1m
3
= 9.8
Na+ -0.550 x 10-
3
1 -I I 1mol 11100011
2xO.09g1 . 142.0g 1m
3
= 1.3
HP042- 0.485 x 10.
3
2
= 0.63
K+ -0596 x 10-
3
1
-I 11mol I1
10001
1
0,12g1 . 136.1g' 1m
3
= 0.88
H2P04- 1.037x 10-
3
1
-I 11mol 11
10001
1
0.12 g1 , 136.1 g' 1 m
3
= 0.88
Substituting these values into Eq. (9.45) gives:
Solutions: Chapter 9 101
= +
CAL t j
_ 05 [(-0.303 x 10-') (2)213.0+(0.485 x 10-') (2)2 13.0 + (-o.720x 10-') (1)2 19.7 +(0.453 x 10-') (2)2 9.8 +]
-. (-o.550X 10-') (1)2 1.3 + (0.485 X10-') (2)2 0.63 + (-0.596 x 1O-')cl)20.88 + (1.037 x 10-') (1)2 0.88
+[(0.119X 10-') 111 + (0.149 x 10-') 24.8J

CAL = 0.95CAIJ)
Solutes in the medium reduce the oxygen solubility by about 5%. From Table 9.2, the solubility of oxygen in water at
35C and 1 attn air pressure is 7.52 x 10-
3
kg Using this value for = 0,95 x 7,52 x 10-
3
kg m*3 =
7,14x
Answer:. 7,14 x 10-
3
kg m-
3
(e)
From Henry's law, Eq, (9.43), the solubility of a gas is directly proportional to the total pressure. From (a), the total
pressure at the bottom of the tank is 1.34 attn rather than 1 attn; therefore:
=L34(7.14xlO-
3
kgm-
3
} =957xlO-
3
kgm-
3
Answer: 957 x 10-
3
kg m-
3
(d)
The concentration difference is given by Eq. (9.53). From (b), the solubility of oxygen at the top or
outlet end of the vessel is 7.14 x 10-
3
kg the dissolved oxygen concentration at this location is 50% air saturation
or 0.50 x 7.14 x 10-
3
= 3.57 x 10-
3
kg m-
3
. From (c), the solubility of oxygen at the bottom or inlet end of the vessel
is 9.57 x 10-
3
kg the dissolved oxygen concentration at this location is 65% air saturation or 0.65 x 9.57 x =
6.22 x 10*3 kg Substituting these values into Eq. (9.53):
(c'" -CAL) = = {7.14-3.57)XIO-
3
kgm-
3
-(9.57-6.22)xlO-
3
kgm-
3
AL L [(c:u.-CALlo 10[(7.14-3.57) X10 'kgm-'j
In -CALli {9.57-6.22)xIO 3
kgm
3
-CALt = 3A6x 10-
3
kgm-
3
Answer: 3.46 x 10-
3
kg m-
3
(e)
The oxygen transfer rate for !La determination by the oxygen-balance method is given in Eq. (9A8). Assume that the
volumetric flow rates of gas into and out of the fermenter are measured under ambient pressure, Le. at I attn. From p
17, the partial pressure of oxygen in the inlet air at 1 attn is (0.21 x I attn) = 0.21 attn; the partial pressure of oxygen
in the outlet gas is (0.2015 x 1 aim) =0.2015 atm. Assuming that the exit gas leaves the fermenter at the fermentation
temperature (35C), using R = 0.000082057 m
3
attn K-l gmol-l from Table 2.5 and converting the temperatures to
degrees Kelvin using Eq. (2.24):
102 Solutions: Chapter 9
_ I [(25 m
3
min-
1

N
A
- 0.OOOO8Z057m3atmK 1gmor1(ZOm3) (25+273.15)K - (35 +273.I5)K
NA =- 0.0167 gInol m
3

Answer: 0.0167 gmol m-
3
sl
(f) ..
From Eq. (9.37) with (CAL - CAL) = (CAL - CAL)L from (d) and units of NA converted to mass terms using the
molecular weight of oxygen = 32.0 (fable B.t, Appendix B):
00167 1 -3 -1 1
3Z
.
0g
Illkg I
NA . gIno m s - lOf . 1000 _
kLa =- '" =- gIll g =- 0.15 s 1
(CAL-CALt 3.46 x 10 3kgm 3
Answer: 0.15 s-1
(g)
The maximum cell concentration supported by the fennenter can be calculated using Eq. (9.40) with to the
average solubility of oxygen between the top and bottom of the fermenter:
_ _ _ -1
x
max
- qo -74
. mmo g . lOOOmmol . 1gmol . looog . 36008
Answer: 19 g I-I
9.5 Dynamic kLa measurement
kLa is determined using Eq. (9.52) and the method described in Section 9.10.2. Take!} =- 10 s and CALI =- 43.5% air
saturation. The steady-state dissolved oxygen tension CAL = 73.5%. Calculated values of
In )
and (12 - (1) are listed and plotted below.
0.00
OAI
0.80
1.6
2.3
3.0
4.1
o
5
10
20
30
40
60
Solutions: Chapter 9 103
4
1

fq,a is equal to the slope of the straight line in the plot"'" 0.069 s-l.
Answer: 0.069
9.6 Measurement of kLa as a function of stirrer speed: the oxygen-balance metbod of
Mukhopadhyay and Ghose
From p 17, the mole fraction of oxygen in the inlet air CYAoh "'" 0210. Convert the data for CAL to units of gmol m-
3
using the molecular weight of oxygen"'" 32 (Table B.l, Appendix B) and assuming that the density of the fermentation
broth is the same as that of water = 1000 kg
1ppm = 1: (lOookgm-J) = 3.125x 10-
2
gmol m-
J
109 g.g
Values of CAL and fCYAO)i - CYAO)oJ for each stirrer speed are listed below.
Fermentation time Agitator speed
(h)
300 rpm 500 rpm 700 rpm
CAL [(YAGJi - (YAG)o] CAL [(YAG); -(YAG)o) CAL [(YAG); - (YAG)o]
(gmol m
3
) (gmol m-
3
) (gmol m-
3
)
0 0.184 0 0.184 0 0.184 0
4 0.175 0.001 0.178 0.001
5 0.166 0.001
6 0.163 0.002 0.169 0.002
7 0.147 0.002 0.153 0.003 0.159 0.003
8 0.128 0.003 0.138 0.004 0.147 0.004
9 0.106 0.004 0.125 0.005 0.128 0.006
10 0.106 0.004 0.125 0.005 0.128 0.006
11 0.109 0.003 0.131 0.004 0.131 0.005
The tabulated values of CAL and [(yAO)i - (yAO)oJ for 0-10 b are plotted below. As CAL increases at 11 b after
being constant at 9 and 10 b, the final values in the table for each stirrer speed most likely reflect the decline phase of
culture growth and are therefore not included in the lqp analysis.
104 Soluticns: Chapter 9
0.20.---,,.---,,.----,----,---,-----.
300 rpm
o 500 rpm
700 rpm
f
i 0.15

0.006 0.005 0.004 0.003 0.002 0.001
0.10 L-_.....L__....J..__.l-_-''-_.....L__...J
0,000
(a)
The slopes of the straight lines in the plot for 300, 500 and 700 rpm are -19.58, -12.04 and -9.68 groot m-
3
,
respectively. These values can be used to determine,qa using R= 0.000082057 m
3
atm gmol-l from Table 2.5
and converting the temperature to degrees Kelvin using Eg. (224):
3
(31
' -1 liminfi
-J1TF. - atm nun . 66SV _-2.02 gmol m-
3
8-1
kLa = = O,OOOO82057m3atmgmor1r1(29+273.15)K{31)xs}ope - stope
For 300 rpm:
For SOOrpm:
At 700 rpm'
k
-2.02gmolm-3s-1 1
La = = 0.21 s-
-9.68 gmol m-
3
Answer: 0.10 sl at 300 rpm; 0.17 sl at 500 rpm; 0.21 s1 at 700 rpm
(b)
The intercepts of the straight lines in the plot for 300, 500 and 700 rpm are 0.185, 0.186 and 0.187 gmat m-
3
,
respectively. Taking the average, is 0.186 gmol m-
3
. Converting to mass terms using the molecular weight of
oxygen = 32.0 (Table B.t, Appendix B):
= 0.l86gmolm-
3
= 0.186 gmol m-
3
.1 = 5.95 x 10-
3
kgm-
3
Answer. 5.95 x 1<r
3
kg
(c)
Equating Eqs (9.39) and (9P6.2),
Solutions: Chapter 9 105
PTF
g
qo x =R T II. [(YAG)i - (YAGlo]
__
qox = =2.02[(YAG)-(YAG) jgmolm 3, I
O'{)OOO82057m3atmgmolIrI(29+273.15)K(31) I 0
The maximum rate of oxygen uptake occurs when [(yAO:>i - (yAO)oJ is maximum. At 300 rpm. the maximum value
of [(YAo)i - (YAeVo] is 0.004; therefore, .(qO x)max = 2.02 x 0.004 = 8.1 x 10-
3
gmol nr
3
s-l. At 500 rpm, the
maximum value of [(YAo)i - (YAO)o] is 0.005; therefore, (qoxhnax = 2.02x 0.005 = 1.0 x gmol m-
3
s-l. At 700
rpm, the maximum value of [(YAo)i - (YAo)oJ is 0.006; therefore. (qO x)max = 2.02 x 0.006=1.2 x 10-
2
gmoJ m-
3
s-1.
Answer: 8.1 x 10-
3
gmoJ m-
3
sl at 300 rpm; 1.0 x 10-
2
gmol m-
3
8-
1
at 500 rpm; 1.2 x 10-
2
grool m
3
sl at 700 rpm
Unit Operations
10.1 Bacterial filtration
(aJ
According to Eqs (10.12)-(10.14), a plot of fl
Vf
versus Vf should yield a straight,line for determination of the
filtration parameters. The data after converting the units to s and m
3
are listed and plotted below.
Time, t (8) Filtrate volume, Vf(m
3
) tlVr(s rn*3)
120 0.0108 1.11 x 104
180 0.0l2l 1.49 x 104
360 0.0180 2.00 x 104
600 0.0218 2.75 x 104
900 0.0284 3.17x 104
1200 0.0320 3.75 x 104
4.0
1

.!!.
3.0
.,
0
-
x
....1:::.-
2.0

1.0

Il:
0.0
0.00 0.01 0.02 0.03 0.04
Filtrate volume, (m
3
)
The slope of the 'Straight line in the plot KI =1.18 x 10
6
s m-
6
; the intercept K2 = -363 s m
o3
. From Eq. (10.13),
using the conversion factors 1 mmHg = 1.333 x 102 kg m-
I
s2 (Table AS, Appendix A) and 1 cP = 10-
3
kg m-I g-l
(Table A.9, Appendix A), the specific cake resistance a is:
s-'j(1.l8x 10
6
sm-6)
=
4.00p.110 3kgm Is
lcP 1m3 lOOOglJ
a =8.0 x lO
lO
mkg-!
The intercept K2 is a relatively small negative number, which may practically be taken as zero. Therefore, from
Solutions: Chapter 10
Eq. (10.14), the filter medium resistance rm is zero.
Answer. a = 8.0 x 1010 mkg-I; rm is effectively zero.
(h)
tl
yr
= 7.5 x 10-
3
min From(a), K2 =0; therefore, from Eq. (10.12):
K
_ t/Vr = 7.5xl0-
3
minl-
1
1100011'160' 1 = 113 10' -6
1- Vf 40001' 1m
3
'lmin . x sm
The filter area is obtained fromEq. (10.13) using the result for a from (a):
, I'tac 4.0cP .1
10
-
3
\g:;:-I '-'I&ox 10
1O
mkg-
1
(22
g
l-
1

A = 2Kt6p = I I = 649m
4
2(1.13X 10' 'm-6) 360mmHg. ,-'
A = 25.5m
2
107
10.2 FUlratlon ofmyceUaI suspensions
(a)
After converting units using the conversion factor 1m
3
= 10
6
mI, the data for tlyfand Yr are listed and plotted below.
Pressure drop (mmHg)
100 250 350
Vf(m
3
) pelleted IfYr(S m
3
)
1.0 x 10.
5
2.2 x 10
6
12 x 1()6 9.0 x lOS
1.5 x 10.
5
3.5 x 10
6
1.7 x 1()6 1.3 x 1()6
2.0 x 10.
5
4.5 x 10
6
2.5 x 10
6
1.& x 1()6
2.5 x 10-
5
5.8 x 10
6
3.0x 10
6
2.4 x 1()6
3.0x 6.7 x 10
6
3.7 x 1()6 2.9 x 10
6
3.5 x 10.
5
8.1 x 10
6
4.3 x 10
6
3.4 x 1()6
4.0x 10.
5
9.2 x 10
6
4.& x 1()6 3.9 x 10
6
4.5 x 10.
5
l.0 x 10
7
5.3 x 1()6 4.3 x 10
6
5.0 x H,.5 6.0 x 1()6 4.8 x 10
6
550
7.0 x lOS
9.3x1OS
1.4 x 1()6
1.7 x 1()6
2.1 x 1()6
2.4 x 1()6
2.& x 1()6
3.1 x 1()6
3.5 x 10
6
750
5.0 x lOS
&.0 x lOS
1.1 x 10
6
1.4 x 1()6
1.7xl()6
2.0 x 1()6
2.3 x 1()6
25 x 1()6
2.& x 1()6
Pressure drop (mmHg)
100 250 350 550 750
Vf filamentous t/Vr(s m
3
)
1.0 x 1(T5 3.6 x 1()6 2.2 x 1()6 1.7 x 1()6 1.3 x 10
6
1.1 x 10
6
1.5 x 1(T5 55 x 1()6 3.1 x 1()6 2.7 x 1()6 2.1 x 10
6
1.7 x 1()6
2.0 x 10".5
72x10
6
4.3 x 1()6 3.6 x 1()6 2.7 x 10
6
2.3 x 1()6
2.5 x 1(T5 9.0 x 10
6
5.3 x 1()6 4.4 x 1()6 3.4 x 10
6
2.& x 1()6
3.0 x 1(T5 1J x 10
7
65 x I1J6 52 x I1J6 4.0 x 10
6
3.3 x I1J6
3.5 x 10-
5
1.3 x 10
7
7.5 x 10
6
6.IXI1J6 4.7 x 10
6
4.0 x 10
6
4.0 x 10"5 8.5 x 10
6
7.1 x I1J6 5.6x 10
6
45 x 1()6
4.5 x 10"5 9.6 x 10
6
7.& x 11J6 6.2 x 1()6 5.1 x 10
6
5.0x lOwS
&.& X11J6 6.& x 1()6 5.7 x 10
6
108 Solutions: Chapter 10
12
Pressure drops:
PaUeted
f
10
100mmHg
o 250mmHg
$ .350mmHg
~
8
o 550mmHg
6
~
.. 750mmHg
x
-1"'- 6
~
~
~ g
~ I
2
0
0 2 3

5 6
Filtrate volume, V; x 105 (m
3
)
,.
Pressure drops: Filamentous
f
12 100mmHg
o 250mmHg
$
10
.350mmHg
..
o 550mmHg
0
x
8
.. 750mmHg
_1:::.,-
0
6
E
~
~ g
F
i 2
0
0 1 2 3

6 6
Filtrate volume, V; x 105 (m
3
)
From Eq. (10.12), the slopes of the straight lines in the plots are equal to Kl for each pressure drop. 'These values are
listed below.
Pressure drop (romHg)
100 250 350 550 750
Pelleted
Slope::: Kl (s m
6
) 2.26 x 1011 L20x lOll 9.93 x lO
lD
7.07 x 1010 5.77 x 10
10
Filamentous
Slope:::: KI (8 rn
6
) 3.73 x lOll 2.13 X1011 1.75 x 1011 1.38 X lOll Ll4 x 10
11
From Eq. (10.13), using the conversion factors 1 mmHg =1.333 x 10
2
kg m-
I
8.
2
(Table A.S, Appendix A) and 1 cP
::::: 1 O ~ 3 kg m-
I
s1 (Table A.9, Appendix A), the specific cake resistance aofthe pelleted cells is:
Solutions: Chapter 10 109
o Pelfeted
Filamentous
2AZ.6pK
I
2(1.8Cm2 /;p.1 s-ZjKI
a = = -"-,--0'='-.::;,"-\,,-'---+'7',",--'--, = 2.47 x 1O-
5
/;pKI mkg-
I
Jl{c 1.4cP .1
1
0-
3
k;;-l s-
I
I(0.25 gml-
l
.
where tip has units ofmmHg andKl has units of s m-
6
. Similarly for the filamentous cells:
2A2 K /;p11.333xlOZkgm-ls-ZjKl
_ /;p 1_ loocml ImmHg -617 k-l
a - - I 3 1 lit I 6 I )- . x v Im g
Jl{c 1.4cP. 10- kf; s- 0.lgml-
1
. .ll::gl
The results for specific cake resistance obtained after substituting the values for tJ.p and K1 into the equations are
listed below.
Pressure drop (mmHg)
100 250 350 550 750
Pelleted
558 x 10
8
7.41 x loB 8.58 x 10
8
9.60 x 10
8
1.07 x 10
9
Filamentous
a(mkg-
I
) 2.30 x 10
9
3.29 x 10' 3.78 x 10
9
4.68 xla' 5.28 X10
9
(b)
From Eq. (10.2), the compressibility can be obtained by plotting the specific cake resistance a versus lip on log-log
coordinates. Using the conversion factor 1 mmHg:::: 1.333 x 102 kg m-
1
sZ (Table A.5, Appendix A) to convert the
units of lip, the data are listed and plotted below.
Pressure drop (kg m-
l
s-Z)
1.33 x 1()4 3.33 x 1()4 4.67 x 1()4 7.33 x 1()4 1.00 x lOS
Pelleted
arm kg-I) 5.58 x loB 7.41 x 10
8
8.58 X 10
8
9.60 x 10
8
l.07 X 10
9
Filamentous
a(mkg-
I
) 2.30x10
9
3.29 X 10
9
3.78 X 10
9
4.68 x 10' 5.28 x 10
9
_ 100 .-
,,-
!if
S
6
-
x
"
Pressure drop, Apx 10'4 (kg m1 s2)
10
110 Solutions: Chapter 10
10
6
m]
1m
3
Iooog
From Eq. (ID.2), the equations for the two lines in tJ:e figure have the form, a= a' 1,s. For the pelleted suspension.
a= 2.60 x 10
7
ApO.323; for the filamentous suspenSIon, a= 4.42 x 10
7
Ap0.415, where lip has umts kg m
l
s2, a has
units m kg-I, and a' bas units kg-(l +s) m1+3 sZs. Therefore. the compressibility is 0.323 for the pelleted suspension
and 0.415 for the fIlamentous suspension.
Answer: 0.323 for the pelleted suspension; OA15 for the filamentous suspension
(0)
The filtration equation for a compressible filter cake is Eq. (10.11) with a= a' ti[l. Assuming that the filter medium
resistance rm is negligible:
Solving for (61')$-1:
2
(Ap)J'-l :: _I
v3 I'f a' c
f
Substituting the parameter values for the filamentous suspension using consistent units, including the results ex':: 4.42
x 10
7
kg..(l+s) m
1
+
s
s2f and s= 0.415 from (b):
Ih
1
3600'1
. I h
(Ap)0.415-1 :: 2 x
(20m
3
)
IAcP .1
10
-
3
,-114.42X 10
7
kg-{I+O.415)m
l
+O.
415
,2x 0.415 ( 0.1 g ml-
1
.
{1ip)-O.585 :: 6.54 x 10-4 kg-o.585 mO.585 s1.170
Ap =2.78 x loS kg mol s2
Converting units using the conversion factor I mmHg =1.333 x 102 kg mol s2 (fable A.5, Appendix A):
!J =2.78 x 10
5
kgm-
1
8-
2
=2.78x 10
5
kg m-
l
8-
2
.1 I mmHg I= 2086mmHg
1.333 x 102 kg m I s-2
Answer: 2086 mmHg. An assumption associated with this answer is that the filter cake characteristics measured at
pressures between 100 and 750 mmHg apply at the much higher pressure of2086 mmHg.
10.3 Rotary-drum vacuum mtration
(a)
For negligible filter medium resistance, the filtration equation for a compressible fdter cake is Eq. (lO.lI) with rm =0
and a= c !Js:
t
=
Vf
Solving for fJf a' c:
t 2A
2
J1{a'c =----
Vi t>p>-1
Substituting the parameter values for the laboratory filter and using the conversion factor I psi =6.895 x 103 kg mol
s2 (fable A.5, Appendix A):
Solutions: Chapter 10
( )
2
. 60s 21
1m
1
2
23.5mm. -1-' 2 Scm. lOOcm
lI..,tXc "" 1 nun I "" 367x 105 kg0.43 m-2.43 s0.l4
r, ( )2 ( .
Sooml. 12 e21
10
6
m1 P 1pst
Answer: 3.67 x 105 kg0.43 m-2.43 sO. 14
(h)
The cycle time is lIN hours per revolution.
111
(el
As 30% of the rotating filter cloth is submerged at any time, each cm
2
of cloth is submerged for 0.3 x the cycle time ""
O.3/
N
h.
(d)
The volume filtered per revolution is 20 m
3
x liN h "" 20INm3.
(el
Eq. (10.11) with r
m
"" 0 and a",, !J.ps is:
lit a' c ;ips-I
2 V,
2A
Applying this equation to a single revolution of the filter, t "" O.3IN h and Vf"" 20lN m
3
. Substituting the filter cake
parameter values from (a), evaluating the filter area A "" 2 1t r Wwhere r is the drum radius"" 0.75 m and W is the
drumwidth "" 1.2 m, and using the conversion factor 1 psi = 6.89S-x 103 kg m-
I
s-2 (Table AS, Appendix A);
I I
(
168
5
3kg -1
0.3
h
3600s 367 105kg0.43 -2.430.14
45
.. 9 xlO m s
N'lh .x m s . pSt. Ii (20)
- ps m
3
20 m3 - 2(2n(0:75m)(1.2ml)' N
N
where N is the number of revolutions per hour. Calculating both sides of the equation gives:
54sm-3 "" sm-3
N = 24.9rph
Answer: 24.9 revolutions per hour
(I)
The ftltration time is increased from O.3IN h to O,SIN h. Substituting this value for t into the left-hand-side of the
equation in (e):
O.5
h
1
3600
'1
N . Ih _ 1343.9 -3
20 - -,;;-sm
_m
3
N
112
Answer; 14.9 revolutions per hour
10.4 Centrifugation of yeast
(a)
Convert the parameter values to units of kg, m, s:
N = 14.9 rph
Solutio1lS: Chapter 10
P
p
=: 1.06gcm-
3
= L06gcm-
3
=l060kgm-
3
Pr =: 0.997 gene
3
:= O.997gcm-
3
.Ili.:g 1
3
=997kgm-
3
Q = SOOlh-
1
= = l.39xlO-4
m
3
s
-1
From Table A.9 (Appendix A), INs m-
2
= 1 kg mol g-1; 'therefore J.I. =1.36 x 10-
3
kgm-
I
8-
1
. D
p
= 5 MlD= 5 x
10-
6
m. FromEq. (10.15) with g =: 9.8 ms-2 (p 16), the sedimentation velocity is:
u =P
p
-Pf
D
2
g
= (l060-997)kgm-
3
(SXI0-6m)29.8ms-Z_=6.31XIO-7ms-l
g 18p P 18 (1.36 x 10 3
kgm
1s-l)
Substituting this result into Eq. (10.18):
I: = JL =: 1.39x W..
4
m
3
s-1 = 110m2
lUg 2 (6.31 x 10 7
ms
-l)
Answer: 110 m2
(b)
From the relationship between specific gravity and density (p 16), as the density of water is close to 1.0000 g em-
3
(p
16),
20 -3 20 -31
1kg
1 1100em1
3
2000k -3
P
p
= . gem = . gem . l000g . 1m =: gm
D
p
=0.1 nun = 0.1 x 10-
3
m. From Eq. (10.15), the sedimentation velocity for the quartz particles is:
_ Pp-Pf
D
2 _ (2000-997) kg m-
3
(01 10-3 )2
98
-2 _ 402 10-3 -1
u
g
_ -- g _ ( ) . x m. ms - . x ms
18,u p 18 1.36x 10-
3
kgm 1s:-1
From Eq. (10.18), the sigma factor is:
r = -lL = L39x 1O-4
m
3
s
-1 = 0.017m2
lUg Z(4.02xlo-3ms-l)
From the result in (a), r for the yeast cells is 110/0.017 =6470 times that for the quartz particles.
Answer: By a factor of 6470.
10.5 Centrifugation offood particles
Convert the parameter values to units of kg, m, s:
Solutions: Chapter 10 113
Pr = 1.00gcm-
3
= 1.00gcm-
3
= l000kgm-
3
From Table A.9 (Appendix A), I Pa s = I kg therefore /.l = 1.25 x 10"3 kg 8"1. D
p
= 10--
2
mm = 10--
5
m;
b = 70 cm = 0.70 m; r= 11.5 cm = 0.115 m. As one revolution = 2ft radians where radians in a unit
(p 11), converting the centrifuge speed to radians
(J) = IO,OOOrpm = 2ft (lO,OOO) min-I .! 1::-1 = 1.047 x 10
3
s-l
From Eq. (10.22) withg =9.8 m (p 16), the sigma factor for the centrifuge is:
" ( 3 _1)2 2
1: = = 21t 1.047x1O s 0.70m(0.115m) = 6.506 x 103m2
g 9.8ms 2
From Eq. (10.15),
_ Pp -P'D2 _ (l030-1000)1Qlm-
3
(10-5 )2
98
-2 _ 1307 10-6 -1
u
g
_ -- g _ ( ) m. ms -. x ms
18,u p 18 1.25 x Io-
3
kgm-
1
s-1
From Eq. (10.18),
Answer. 0.017 m
3

10.6 Scale-up of disc-stack ceutrifuge
The sigma factor for the bowl centrifuge 1:1 is calculated using Eq. (10.20) withg =9.8 m s2 (p
16), and (J) converted to rad sl using the conversion factor I revolution = 2 1t radians where radians is a
dimensional unit (p 11). For the pilot-scale device, '2 = 5 cm = 0.05 m and rl = I cm = om m:
(
1
1 .
21t 21tx3000min-
l
. (25-1)
:!: = 2noJ-(N-ll(,3_,1j = 60s (0.05m)3_(0.0Im)3) = 89.6m2
1 3gIanO 2 1 3(9.8ms 2)clan35')
From Eq. (10.19), the sigma factor:rz for the bigger centrifuge is therefore:
:!: = Q2:!:I = 801min-
I
(89.6m
2
) = 200m
2
2 Q1 3.5 1OOn-
1
From Eq. (10.20), for the bigger centrifuge with 1"2 = 75 cm = 0.075 m and rt = 2.35 cm = 0.0235 m:
oJ- = 3glanO:!:, = 3(9.8 ms-2)clan 45') 2048m
2
= 4 34x 10' s-2
2n(N- IlH- ,1) 2 n (55 -1) (0.075 m)3 - (0.0235m)3) .
_ 659 ad -1 II revolutionII 60 s 1- 6290
(J)- r s . 21trad . lmin - rpm
Answer. 6290 rpm
10.7 CeutrifUgatiou of yeast and ceO debris
Combining Eqs (10.15) and (10.18),
and
114 Solutions: Chapter 10
where subscript 1 refers to the centrifugation conditions for the yeast suspension, and subscript 2 refers to the
centrifugation conditions for the cell debris. As the same centrifuge operated at the same speed is used in both
applications, ,1;1 =1:2 and:
Assuming that the particle and fluid densities are the same in both applications, cancelling terms gives:
~ 1 Ql !'2 Q2
-2- =-2-
D
pl
D
p2
or
Answer. 0.0671 min-I
10.8 Cen disruption
The relationship between pressure and protein release for a Manton-Gaulin homogeniser is given by Eq. (10.23). At
constant pressure, a semi-lagplat ofRm/(RnrR) versusN should yield a straight line, so thatthe value of k pa can be
determined from the slope.
The data for % protein release represent values of RIR
m
x 100. These data can be converted to Rm/(Rm_R) as
follows:
R
m
100
Rm-R =loo-RIR x 100 =
m
The results are listed and plotted below.
100
100-%protein release
Pressure drop (kgjcm-
2
)
200 300 400
N
R
m
Rm-R
1 1.05 1.16 1.30
2 1.10 1.31 1.67
3 1.16 1.50 2.11
4 1.22 1.75 2.99
5 1.28 1.90 3.70
6 1.35 2.22 4.88
500
1.56
2.41
4.00
5.71
8.70
11.5
550
1.72
2.94
6.13
8.70
18.2
Solutions: Chapter 10 liS
30...--,---,----,---,--,--....---,
200 kg
f
an-2
o 300kg
f
an"2
400 kg
f
an"2
o 500 kg,an'
2
.. 550 kg,an'
2
7 6 2 3 4 5
Number of passes, N
1
10
The values of k pa obtained from the slopes of the straight lines for each pressure are listed below.
200 300 500 550
0.050 0.129 0.267 0.406 0.580
A log-logplot of these values versus p can be expected to give a straight line with the value of a obtained from the
slope.
'l,. 0.1
'"
0.01 L- ---.__~ _ ~ ~ _ ~ ~ ~ _ '
100 1000
Pressure, p (kgfcm-
2
)
As the equation to the straight line in the plot is k pa = 1.71 x 10-
7
p2.37, a = 2.37. Therefore, for this system, Eq.
(10.23) becomes:
where p bas units ofkgjcm-
2
.
116 Solutions: Chapter 10
ln5.0 = 4.6
1.71 x 10-
7
(460)2.37
(a)
For 80% protein release, Rm/(Rm_R) "" 5.0. Rearranging the above empirical equation for the homogeniser and
substituting p "" 460 kgfcnc
2
gives:

N= =
1.71 x 10-
7
p2.37
Therefore, 80% protein release is achieved within 5 passes through the homogeniser.
Answer: 5
(b)
For 70% protein release, Rm/(Rm_R) "" 3.33. Rearranging the empirical equation for the homogeniser and substituting
N=2 gives:
_
p2.37 = -"-'''--,f- ln3.33 "" 3.S2x 10
6
L71xlO-
7
N-1.71xlO-
7
(2)
p := 578 kgjcm
2
Answer: 578 kgjcm
2
.An assumption associated with this answer is that the homogenisation characteristics
measured at pressures between 200 and 550 kgfcm
2
apply at the higher pressure of578 klJfcm2,
10.9 Enzyme purification using two-phase aqueous partitioning
(a)
From Eq. (10.24), for K"", 3.5, the product partitions into the upper phase. Eq. (10.27) withK:= 3.5 and Y
u
"" 0.8 is:
V
u
0.8 = v.
I
Vu +3.5
Rearranging gives:
0,8 V
u
+ 0,23 VI = V
u
0,23 VI = 0,2 V
u
v,
YJ = LI5
Answer: US
(b)
The mass of enzyme in the two phases must be equal to the mass of enzyme in the original homogenate, The
balance equation is:
From Eq. (10,24), for K = 3.5, CAu = 3.5 CAl. If VJ = 100 I, from (a) for 80% recovery, V
u
= 115 l. Substituting
these values into the equation with Vo = 150 I and CAD = 3.2 u ml-
J
= 3.2 x 103 u 1-1:
where CAl has units ofu Solving the equation fOTCM
502.5 CAl = 4.8 x loS
CAl = 955 u
Solutions: Chapter 10 117
As CAu =3.5 CAl> CAn = 3.34 x 10
3
u I ~ I . From Eq. (10.29), the concentration factor for product partitioning into
the upper phase is:
Answer: 1.04
10.10 Recovery of viral particles
From Eq. (10.24), for K,= 10..
2
CAn =m
2
CAl and the product partitions into the lower phase. If51 culture volume
is added to 2 I polymer solution and, after phase separation, the volume of the lower phase is 1 1, the volume of the
upper phase must be (5 + 2) - 1 =6 L
(a)
The yield of virus in the lower phase is given by Eq. (10.28) with VI =11, V
u
=61 and K = 10-
2
:
Vr 11
Y, = VuK + V, = 61(10-2)+ 11 = 0.94
Answer: 0.94
(b)
The mass of viral particles in the two phases must be equal to the mass of viral particles in the original culture broth.
The mass..balance equation is:
(e)
From Eq. (10.24):
Rearranging the mass-balance equation in (b) and substituting for CAI gives:
CAu
CAuVu+CAIVi CAuVu+KVI
CAO = Vo =
The concentration factor for product partitioning into the lower phase is given by Eq. (10.29). Substituting for CAl
and CAO in this equation gives:
(d)
Using the equation for 4: derived in (c) with Vo = 51, VI = I 1, V
u
= 61 and K = 10,2:
51
Answer: 4.7
118 Solutions: Chapter 10
10.11 Gel chromatography scale-up
(a)
The elution volume for the toxoid is lower than for the impurity. Therefore, as the toxoid stays in the column for the
shorter time. it must be the larger molecule.
Answer: Toxoid
(b)
The internal pore volume in the gel in the laboratory reactor can be calculated using Eq. (10,42):
!'i =aW, = =3Sml
As V0= 23 ml, the partition coefficients for the toxoid and impurity can be detennined using the measured elution
volumes and Eq. (10,41);
T idK
=(V,- Vol =(29-23)m! =171
axo p V; 35ml .
,
I
tyK =(V,-V
o
) = (45-23)m! =0629
mpun p Vi 35m1 .
,
Answer: Toxoid =- 0.171; impurity =- 0.629
(c)
Let subscripts 1 and 2 denote the small and large columns, respectively. The total volume of the laboratory columnaf
inner diameter Del =15 em=0.015 mand height HI::::' 0.4 mis:
(
DCI)2 (OoOISm)2 -5 3
V
Tl
::::. 1t 2 HI::::' 1& 2 OAm::::. 7.07 x 10 m
The total volume oitbe column of diameter D
c
2::::' 0.5 m and height HZ =- 0.6 m is:
(
D02)2 (osm)2 3
V
TI
=- 1t T HZ =- 1t O.6m =- 0.118m
If the void fraction in the large column is the same as in the small column, V
o
2 in the large column is:
3
23m!.
Vol 10
6
m! (3) 3
V
02
=r VTI = 5 3 0.118m = 0.0384m
TI 7.07 x 10 m
Ifthe pore volume fraction is also the same:
35m!. 1:
3
!'it 10 m! (3) 3
ViZ =r VTI = 5 3 0.118m =0.0584m
T1 7.07 x 10- m
If the largescale column is operated with the same packing and flow conditions, the partition coefficients can be
assumed to be the same-as those in the laboratory column. Therefore, from Eq. (10.41), for toxoid in the large column
with the value of K
p
from (b):
V
e
2 = K
p
Va + V
o
2 = 0.171 (0.0584 m
3
) +0.0384 m
3
= 0.0484 m
3
Similarly for the impurity:
V
e
2 = K
p
Vi2 + V
o
2 = 0.629 (0.0584 m
3
) +0.0384 m
3
= 0.0751 m
3
Answer: Toxoid =0.0484 m
3
; impurity =0.0751 m
3
Solutions: Chapter 10 119
(d)
The liquid flow rate is scaled up in proportion to the column cross-sectional area. As the cross-sectional area ""
1& (DC/2)2, the volumetric flow rate v2 in the large column is:
(
D02)2
n- (D)2 131 2
2 c2 . -1 1m 0.5 m 3 ,-1
v2 "" VI 2 "" VI -D "" 14mlmm . -6-' (0015 ) "" 0.0156m IDlD
n(D;I) cl 10 ml . m ,
Answer: 0.0156 m
3
min-I
(e)
The retention time t'R is equal to the elution volume divided by the volumetric flow rate. For the toxoid in the large
column, using the results from (c) and (d):
Ve2 0.0484m
3
IR=-= = 3.1 min
v2 0.0156m
3
min 1
Answer: 3.1 min
10.12 Protein separation nsing chromatography
(a)
Selected values of u and H are listed and plotted below.
Linear liquid velocity, u
(m s-l)
HETP,H
(m)
0,1 x 10
4
0.2 x 10
4
0.3 x 10-4
0.5 x 10-4
0,8 x 10-4
1.0 x 10-4
1.2 x 10-4
1.5 x 10
4
1.8 x 10.
4
2.0 x 10.
4
2.72 x 10.
4
1.87 x 10-4
1.69 x 10-4
1.72 x 10-4
2.02 x 10-4
2.27 x 10-4
2.54 x 10-4
2,95 x 10-4
3.38 x 10.
4
3.67 x 10-4
4,----,--...,---,---,----,
2.5 0.5 1.0 1.5 2.0
Unear rrquid velcoity, u x 1()4 (m $"1)
1 '--_---'__-'-__-'-__.L._--'
0.0
120 Solutions: Chapter 10
(h)
From the graph in (a), the minimum HETP is around 1.7 X H;4 m. This can be confirmed by differentiating the
equation for H and solving for dH/du = 0:
dB --A
- = -+8 = 0
du .2
Therefore:
The value of H corresponding to this u is:
A 2xlO"""m
2
,-1 ( )
H=-+Bu+C= 5 1 +1.5s 3.65x1O-
5
ms-
1
+5,7x1O-
5
m= 1.67xl0-4m
u 3.65x1O ms
Answer: The minimum HETP is 1.67 X 10-
4
m, obtained at a liquid velocity of 3.65 X 10-
5
m
(c)
The column diameter Dc = 25 em = 0.25 The --volumetric flow,.rate v is 0.311 min"1, ,The-linear ,flow-rate u is
obtained by dividing the volumetric flow rate by the column cross-sectional area:
0311 . -I II mini 1
'm3
I
v . mm. 60s . 10001 _
u = = = L05x 1O-4 ms 1
K(02gmr
Substituting this result into the equation for H:
A 2x 1O"""m
2
,-1 ( )
H=-+Bu+C= -4 1+1.5s 1.05xl0-4 ms-l +5.7xlO-
5
m= 2.34xlO-4 m
u 1.05xlO ms
The capacity factors for the A and B chains are kA= 0.85 andkn = 1.05, respectively. From Eq. (l0.38):
o= kB = 1.05 = 1.235
k
A
0.85
Substituting these parameter values into Eq. (10.51) with L = 1 m for the larger column and k2 = k]J:
R=! 1m (1.235-1)( 1.05 )=159
N, 4Vli 0 kB+l 4 2.34xI0-4
m
1.235 1.05+1 .
From p 248, as RN> 1.5. the two peaks are completely separated.
Answer: Yes
(d)
'.Por L = 0.7 m for the smaller column, the value of H corresponding to RN= 1.5 or virtual complete separation can be
detennined using Eq. 00.51):
.fIl =! =! .fiifID(1.235-1)( 1.05 ) = 0.0136Jiil
4RN 8 kB+I 41.5 1.235 1.05+1
H= 1.85xlO-4 m
The linear liquid velocity at which this value of H is obtained can be determined by rearranging the expression for H
as a function of u and solving for u:
Solutions: Chapter 10 121
The solution to this quadratic equation is:
-{C-H) \!<C_H)' -4BA
u = 2B
H-C,!<C-H)2_4BA
= 2B
Substituting the parameter values:
u =(1.85X 10
4
-5.7 x 1O-
5
)m V(5.7 x 10-
5
m-1.85x 10
4
m)' -4(1.5 s)(2X 10-
9
m
2
s-l)
2 (1.5 s)
u =4.27 x 1O,S ms-
l
2.21 x 10-
5
ms-
I
Therefore:
u =6.48 x 10-
5
m sl or u =2.06xlO-
S
ms
1
1be maximum flow rate for complete separation-is-u =6.48wlO-
5
ms-l. 'Betweenu = 2.06 x IO-
S
m sl and u = 6.48
x Io-S m sI,H< 1.85 x 10
4
m SO tbatRN> 1.5 and-eomplete:separationismaintained. The volumetric flow rate v is
equal to u multiplied by the column cross--sectional area:
v =U 1 t ( ~ c r ={6.48XlO-
S
ms-
1
}1t(o.2gmt = 3.18xW"
Q
m
3
s-
1
Converting units:
_ 3 18 10-6 3 -I 1
10001
1 1 60s 1= 0191 -1
v - . x m s . 1m
3
' lmin . nun
Answer: 0.191 min-I
Homogeneous Reactions
11.1 Reaction eqnilibrium
From p 258. take the standard conditions to be 25C and 1 attn pressure. The temperature is converted to degrees
Kelvin using Eq. (224); from Table 2.5, R =8.3144 J K-l gmol-l =8.3144x 10-
3
kJ K-I gmol-l.
(a)
FromEq. (11.3):
-t1GO 1
inK = = 14.1klmol- = 5.69
RT 8.3144xlO-3kJr1gmoll(25+273.15K)
K = 295
The large magnitude of K indicates that the reaction can be considered .irreversible.
Answer: 295; irreversible
(b)
FromEq. (11.3):
_AGO 1
In K = = -32kJ mor = -1.29
RT 8.3144xlO 3 kJK Igmoll(25+273.15K)
K =0.275
The relatively small magnitude of K indicates that the reaction is reversible.
Answer: 0.275; reversible
11.2 Eqnilibrium yicld
(a)
From Eq. (11.2) with G6P and GIP representing glucose 6-phosphate and glucose I-phosphate, respectively:
CGtiP at equilibrium 0,038 M
K = = = 19
C01patequilibrium O.OO2M
Answer: 19
(b)
FromEq. (11.9) and the reaction stoichiometry:
.. molesG6Pfonned 1mol -1
Theorettcal yIeld = 1 GlP ed G6P = -1-1 = I mol mol
mo es us to orm mo
Answer:: I mol
(c)
Fromp 260 and using a basis of I litre:
Gross ield = = 0,038m?1 = 0.95 mol mol-
1
Y moles GIP supplied 0.04 mol
Answer: 0.95 mol
Solutions: Chapter 11
11.3 Reaction rate
(a)
Tenns used to express reaction rate are outlined on p 261.
(I)
Answer: The volumetric productivity is unaffected by change in volume.
(ij)
Answer: The specific productivity is unaffected by change in volume.
(iii)
Answer. The total productivity is doubled if the fermenter volume is doubled,
123
(b)
Answer. The volumetric productivity is doubled, the specific productivity is unaffected. and the total productivity is
doubled.
(e)
(I)
RA =100 kg rA =0.8 g I-I h-
I
, From Eq. (1 1.16):
V =RA = lookgd-
I
=52081
rA
Answer: 5208 I
(ij)
FromEq, (11.67):
11.4 Enzyme kinetics
Evaluate the enzyme kinetic parameters by plotting sl
v
versus s as a Langmuir plot(p 272), The values are listed and
plotted below,
s(moll-
1
)
0.0250
0.0227
0.0184
0.0135
0.0125
0.00730
0.00460
0.00204
Slv (min)
12.89
11.88
9.95
750
7.02
5.00
3.93
2.62
124 Solutions: Chapter 11
15,----,-----,.----...,
10
!
-I>
5
0.03 0.02 0.Q1
0'------.......------'-------'
0.00
s (mol 1-
1
)
The equation for the straight line in the plot is slv = 1.70 +445 s,wheres has units ofmoll-} and Slv bas units aiulin,
Therefore, from Eq. (11.39), I/vmax = 445 mOlll min, so that Vmax = 2.25 x 10"3 moII-} min-I. Also from Eq.
(11.39), Ktn/
vmax
=1.70. Multiplying this value by the result for Vmax. K
m
= 3.83 x 10-
3
moll-
t
,
Answer: Vmax =2.25 X10-
3
mol 1-1 min'I; K
m
= 3.83 x 10-
3
mol 1-1
11.5 Effect of temperature on hydrolysis of starch
(a)
The activation energy is determined from the Arrhenius equation, Eq. (11.21), with k equal to the initial fate of
glucose production. According to the Arrhenius equation, a plot of k versus liT on semi-logarithmic coordinates
should give a straight line.. 'The parameter values are listed and plotted below; Tis converted to degrees Kelvin using
Eq. (2.24).
T('C) T(K) liT (K'I) Rate, k (mmel ro
w3
s' I)
20 293.15 3,41 x 10.
3
0.31
30 303.15 3.30 x 10-
3
0.66
40 313.15 3.19 x Icy3 1.20
60 333.15 3.00 x Icy3 6.33
Solutions: Chapter II
-
10
"
1
."
E
.
"
g

'g 1
I
~
~
'5
~
0.1
2.9 3.0 3.1 3.2 3.3 3.4 3.5
1/Temperature X 103 (K
o
1)
125
The equation for the straight line in the plot is k =1.87 x lO
lD
c
73OO
/
T
, where k has units ofmmol m-
3
5"1 and T has
units ofK. Therefore, from Eq. (11.21), EIR = 7300K From Table 2.5,R = 8.3144 J K ~ 1 gmol-
l
= 8.3144 x 10-
3
kJ
Kw
l
gmol-l; therefore, E= 7300 K x 8.3144 x 10-
3
kJ K-I gmol-l =60.7 kJ grool-l.
Answer: 60.7 kJ gmol-
l
.
(b)
Converting 55<>C to degrees Kelvin using Eq. (2.24), T= 55 + 273.15 =328.15 K. Substituting this value into the
equation for k obtained in (a):
k = 1.87 x 1010 e-
73001T
= 1.87 x 1010 e-73001328.15 =4.08 romol m-
3
s1
Similarly, for T= 25"C =25 +273.15 = 298.15 K:
k = 1.87 x 1010 e-73OO/T = 1.87 x WiD e-73001298.15 = 0.43 mmol m
w3
s1
Therefore, the rate at 55"C is 4.08/0.43 = 9.5 times faster than at 25"C.
Answer: The reaction rateat55"C is 4.08 mmol m-
3
st or 9.5 times faster than the rate of 0.43 rnmol ro
3
sl at25"C.
(e)
From Table 2.5, the value of R in the appropriate units.is 1.9872 cal K-l gmol-
1
, At 55"C = 328.15 K:
k
d
=2.25 x 102
7
e-4I,
630
IRT =2.25x 10
27
e-4l,630/(1.9872
x
328.15) =0.42h-
l
Therefore, from Eq. (11.45), the half-life of the enzyme at 55"C is:
t = In2 = In2 = 1.65h
h k
d
0.42b 1
At 25"C =298.15 K:
kd = 2.25x 10
27
e-41,63O!RT = 2.25x 10
27
e-4I,630;(1.9872 x298. 15) =6.87x lO-4
h
-1
and the enzyme half-life is:
th - In2 _ In2 =l009h
- kd - 6.87x lO-4
h
-l
126 Solutions: Chapter II
Although the reaction rate is 9.5 times faster at 55
Q
C than at 25C, the rate of deactivation is 0.42/(6.87 x 104) =: 611
times greater. Therefore, unless there are other considerations. 25C would probably be the more practical
temperature for processing operations.
Answer: The enzyme halflife at 25C is 1009 h or 611 times longer than the of 1.65 h at 55C. The more
practical operating temperature is probably 2jl'C.
n.6 Enzyme reaction and deactivation
K
m
= 5 roM = 5 x 10-
3
gmol t
1
= 5 x Hy6 gmol m-
3
. The concentration offat is reduced from 45 gmol to 0.2 x
45 gmol m-
3
= 9,0 groat m-
3
: As this concentration range is well above the value of .&tn. s K
m
and. from p 269. v
"" v
max
' As v= -ds1dt. combining Eqs (11.35) and (11.44) gives:
-::: =VrnaxQ e-k
d
t
In this equation. s and t are the only variables. Separating variables and integrating:
J--<Is =fvmaxOe-kdtdt
Applying calculus rules (D.24) and (0.17) from AppendixD and combining the oonstants-ofintegration:
-v"""" -" = e-kdt+
K
kd
The initial condition is: at t =0, s= sO. Therefore:
-Vmaxfl
-$0= id+
K
Substituting this expression for K into the equation for -s gives:
-vmaxO -k t VmaxO
-" =---e ' +---'0
kd k
d
vmoxO ( -< I)
S = $0--- 1-e d
kd
At the beginning of the reaction, SO =45 gmol m-
3
. Converting the units of VrnaxO:
007 11-1 -1 007 11-1 -1 1 1 gmol 11
10001
11
60
'1 42 1 -3 -1
vmaxO = . nuno s = . mmo s. lOOOnunol' 1 m
3
. min = . gmo m nun
From Eq. (11.45):
k
_ln2 _ In2 -0087 -1
d-----.--. mm
th 8nun
Substituting parameter values into the equation for $, when 80% of the fat is hydrolysed:
0.2 x 45 gmolm-3 =45 gmol m-3 _ 4.2 gmol m-
3
(1_e-(l087 t)
0.087 min
where t has units of min. Grouping tenus:
12.276 =48.276 e-O087 t
e-o087 t =0.254
-0.087 t =-1.369
Solutions: Chapter 11 127
t =- 15.7 min
Answer:: 15.7 min
11.7 Growth parameters for recombinant E. coli
(a)
The average rate-equal area construction is used to determine growth rates from the concentration data. The data and
calculations are tabulated below.
Time, t(h) x (kg m-
3
) <!.x (kg m-
3
) <it (h) <!.xl<it (kg m-
3
h-
I
)
0.0 0.20
0.01 0.33 0.03
0.33 0.21
om 0.17 0.06
0.5 0.22
0.10 0.25 0.40
0.75 0.32
0.15 0.25 0.60
1.0 0.47
0.53 0.50 1.06
1.5 1.00
1.10 0.50 2.20
2.0 2.10
2.32 0.50 4.64
2.5 4.42
2.48 0.30 8.27
2.8 6.9
2.50 0.20 12.50
3.0 9.4
1.50 0.10 15.00
3.1 10.9
0.70 0.10 7.00
3.2 11.6
0.10 0.30 0.33
3.5 11.7
-0.10 0.20 -0.50
3.7 11.6
The values of luIfit are plotted as afunction of time below according to the method described on p 263.
4.0 3.5 3.0 1.5 2.0 2.5
Time (h)
1.0 0.5
, , , , , ,
-
rf
if -
/
1/
/
.--r-
I:".
, , , , , ,
:l
-2
0.0
o
2
4
6
8
12
14
10
16
128 Solutions: Chapter 11
Results for <ix/
dt
read from the average rate-equal area curve and the calculated specific growth rates are listed below.
Time, t(h)
0.0
0.33
0.5
0.75
1.0
1.5
2.0
2.5
2.8
3.0
3.1
32
3.5
3.7
o
0.05
0.20
0.45
0.70
1.5
3.3
6.5
10.4
14.5
11.0
3.5
-0.3
-0.8
o
024
0.91
1.41
1.49
1.50
1.57
1.47
1.51
1.54
1.01
0.30
-0.03
-0.07
Values of the-specific growth rate,u are plotted as a function of time below.
2.0
1.5
-
i:.
..
~
1.0
1
0.5
'"
t
/
'"
0.0
-0.5

0 1 2 3 4
TIme (h)
(b)
As expected for most batch cell cultures, growth occurs at around the maximum specific growth rate for most of the
culture period. Taking the average of the values of J1. between times 0,75 hand 3 h .Ltmax = 1.50 0.05 h-
l
, where
0.05 is the standard deviation.
Answer: 1.50 h-
I
(c)
,
From Eq. (11.49), the observed biomass yield Y
xs
at any point in time is equal to the ratio of the observed growth and
substrate consumption rates. The average rate-equal area construction is used to determine the substrate consumption
rates rs = -ds'dt from the concentration data, as shown below.
Solutions: Chapter 11
Time, t(h) ,(kg m-
3
) LI.Y (kg m-
3
) Lv (h)
0.0 25.0
-0.2 0.33
0.33 24.8
0.0 0.17
0.5 24.8
-0.2 0.25
0.75 24.6
-0.3 0.25
1.0 24.3
-1.0 0.50
1.5 23.3
-2.6 0.50
2.0 20.7
-5.0 0.50
2.5 15.7
-5.5 0.30
2.8 10.2
-5.0 0.20
3.0 5.2
-3.55 0.10
3.1 1.65
-1.45 0.10
3.2 0.2
-0.2 0.30
3.5 0.0
0.0 0.20
3.7 0.0
129
0.61
0.0
0.80
1.20
2.00
5.20
10.0
18.3
25.0
35.5
14.5
0.67
0.0
The values of-As/tit are plotted as a function of time below according to the method described on p 263.
4.0 3.5 3.0 1.5 2.0 2.5
Time (h)
1.0 0.5
,

l-

J
I-
rf

l-
I

1/
/
Y

.t>..
o
0.0
5
30
40
10
35
_ 25
1,
1
20
~
1 1 ~ 15
Results for -<is/
dt
read from the average rate-equal area curve are listed below, together with the instantaneous
biomass yield coefficients calculated using Eq. (11.49) and the values of rx from (a).
130
Time. t(h)
0.0
0.33
0.5
0.75
1.0
1.5
2.0
2.5
2.8
3.0
3.1
3.2
3.5
3.7
0.'
0.5
0.6
1.0
1.6
3.0
7.'
13.9
22.2
33.0
27.5
7.0
0.4
o
Solutions: Chapter 11
o
0.10
0.33
0.45
0.44
0.50
0.45
0.47
0.47
0."
0.40
0.50
-{J.75
,
Values of the observed biomass yield from substrate Y
xs
are plotted as a function oftime below.
0
D.
"x
~
D.
;;
~
,
0
0.4
-
E
e-
- ~
' l l ~
0.3
.'" '"
0"
~
E 0.2
~
~
0.1
J
.il
0
0.0
0
,
1
,
2
Time (h)
,
3
-

,
During the exponential growth phase between 0.75 b and 3 h when /.l = ,umax, Y
xs
is approximately constant with an
average value of 0.46 0.02 kg kg-I, where 0.02 is the standard deviation.
Answer:OA6 kg kg-I; ~ s is approximately constant during exponential growth
U.S Growth parameters for hairy roots
(a)
The mid-point slope method is used to determine rates from the concentration data. The growth data are listed and
plotted below according to the method described on pp 264-265. Values of [(x)t+e- (x)t_el are read from the graph.
Time, ted) Biomass concentration, x (g 1-1) e [(X),+e- (x),-e1 (g 1,1)
0 0.64 5
5 1.95 5 3.0
10 4.21 5 3.6
15 5.5. 5 3.8
Solutions: Chapter 11 131
20 6.98 5 3.7
25 9.50 5 3.4
30 10.3 5 2.6
35 12.0 5 1.9
40 12.7 5 1.2
45 13.1 5 0.8
50 13.5 5 0.6
55 13.7 5
16
1.
f
12
'" "
10 ~
~
~
j
8
6
0
0
~

~
2
0
0

10 20 30
Time (d)
40 50 60
The growth rate dxl
dt
is determined using the central-difference formula. Eq. (11.23). These results and values of the
specific growth rate J.I. are listed and plotted below as a function of time.
Time, tId)
o
5
10
15
20
25
30
35
40
45
50
55
0.30
0.36
0.38
0.37
0.34
0.26
0.19
0.12
O.os
0.06
0.154
0.086
0.069
0.053
0.036
0.025
0.016
0.009
0.006
0.004
Values of the specific growth rate J.I. are plotted below,
132
-

0.15
:!?-
"-
{

0,10 ,
e
'"
"
;e
"
l'l
0.05
'"
0.00
o 10 ro M W 00
Time (d)
-Answer: Near the beginning of the culture.
Solutions: Chapter 11
(bl
The slope method is used to determine the rate of substrate uptake as a function of time, The sugar
concentration data are plotted below according tathe method described onpp 264-265.
35
30
-
25

.$
c
0
20

c
15
8
,
"
I
il,
,
I
'"
10
<I I
I
I
I
I
5 I
I
I
I
I
I
0
0 10 20 30 40 50 60
Time (d)
Values of[(s)t+e- (s}t-el read from the graph are listed in the table below.
Solutions: Chapter 11
Time, t (d)
o
5
10
15
20
25
30
35
40
45
50
55
Sugar concentration, s (g 1-
1
)
30.0
27.4
23.6
21.0
18.4
14.8
13.3
9.7
8.0
6.8
5.7
5.1
e
5
5
5
5
5
5
5
5
5
5
5
5
133
-6.2
-6.1
-5.7
-5.4
-5.2
-4.6
-4.4
-3.9
-2.7
-1.9
The rate of substrate uptake -ds1dt is determined using the central-difference formula, Eq. (l1.23). These results and
values of the specific rate of substrate uptake qs are listed and plotted as a function of time below.
Time, t (d)
o
5
10
15
20
25
30
35
40
45
50
55
0.62
0.61
0.57
0.54
0.52
0.46
0.44
0.39
0.27
0.19
0.318
0.145
0.103
0.077
0.055
0.045
0.037
0.031
0.021
0.014
0.35
-
~
0.30
8'
i
0.25
!
"

0.20
l\!
Jl
0.15
"
0
7;
2 0.10
e
t
0.05
'"
0.00
0 10 20 30 40 50 60
TIme (d)
(c)
The instantaneous biomass yield coefficient is calculated using Eq. (11.49) and the values of rx and rs from (a) and
(b). The results are listed and plotted below.
134 Solutions: Chapter 11
Time, t(h)
o
5
10
15
20
25
30
35
40
45
50
55
0.48
0.59
0.67
0.69
0.65
0.57
0.43
0.31
0.30
0.32
_ 0
0.8
"x
1!i
0.7
e
jg
0.6

E
0.5
,g

0.4
'"
.S- '"
m-
0.3

E
.Q
'"
0.2

0.1

<3
0.0
0 10 20 30 40 50 60
Time (d)
Answer: Y
xs
varies during the culture period within the range 0.30-0.69 g dry weight.
11.9 Ethanol fennentation by yeast and bacteria
(al
From Table B.8 (Appendix B), the molecular formulae for glucose and ethanol are C6H1206 and C2H{jO,
respectively. The reaction equation for fermentation of glucose to ethanol without cell growth is:
From the stoichiometry, the maximum theoretical yield of ethanol from glucose is 2 gmol From Table B.1
(Appendix B) the mol,ecular weights are: glucose:: 180.2; ethanol:: 46,1, Therefore:
2 gmolethanol ,I _
Maximumtheoreticalyield = = gm =0.51gg 1
gmogucose 11802g1
1gmol glucose. 1
Answer: 0.51 g g-1
(h)
In the absence of growth. fJ. in Eq. (11.83) is zero and the equation reduces to:
Solutions: Chapter 11
, mp
Y
pS
=-
ms
Therefore, for Yr.s equal to the maximum theoretical yield:
135
mp = 051 ms
Foi S, cerevisiae, ms =0,18 kg kg-I h-
I
; for Z mobiUs, mS =22 kg kg-I h-
l
. Applying these parameter values in the
above equation gives mp =0.092 h-
l
for S. cerevisiae and mp =1.12 h-
l
for Z rrwbilis.
Answer: 0.092 h-
I
for S. cerevisiae; 1.12 h-
l
forZ mobilis
(cJ
During batch culture at usual glucose concentrations, J1. = J1.rnax for most of the culture period (p 279). Eq. (11.83) can
therefore be written as:
,
Y
ps
= Jlmax
--+ms
Y
xs
Substituting the parameter values for S. cerevisiae, including the result for mp from (b):
Yo
, _ 3.9kgkg-
I
(0.4h-
I
)+0.092h-
I
_ 043k k-
I
ps- 1 -.gg
0.4 h +0.18kg kg-I h-I
O.llkgkg 1
Similarly for Z 11Wbilis:
i - 7.7 kg kg-
I
(O.3h-
I
) +1.12h-
I
_ 048k kg-I
ps- 1 -. g
O.3h- +2.2 kg kg-
I
h-
I
O.06kgkg 1
Answer: 0.43 kg k:g"l for S. cerevisiae; 0.48 kg k:g"l for Z mobilis
(dj
Using the results from (8) and (c), for S. cerevisiae:
,
Efficiency = Y
ps
=0.43 kg kg-I =084
maximumtheoretical yield 0.51 g g-1 .
For Z mobilis:
,
Efficiency = Y
ps
=0.48kgkg-l =094
maximumtheoretical yield 0.51 g g-1 .
Answer: 0.84 for S. cerevisiae; 0.94 for Z mobilis
(ej
From Eq. (11.70) withf.l =J.!max, for S. cerevisiae:
For Z. mobilis:
Answer: 1.65 h-
1
forS. cerevisiae; 3.43 h-
l
forZ mobilis
136 Solutions: Chapter 11
(f)
In Eq (11.70), the term is Ypx ,umax, the nonwgrowthwassociated term is mp_ Therefore, using the
result from (e), the proportion of ethanol production from growth for S, cerevisiae is:
Ypxl'max _ 3.9 kg kg-I (0.4h-
l
)
Ypxl'max+mp - 3.9kgkg(OAh-
1
)+0.092h 1 = 0.94
so that the proportion from metabolism is 0.06. For Z mobilis:
Ypxl'max = 7.7 kg kg-I (0.3 b-
I
) =0.67
Ypxl'max+mp 7.7kgkg-I(0.3h-I)+L12h 1
and the proportion from metabolism is 0.33. ethanol production is more
substantial for Z. mobilis.
Answer: For S. cerevisiae, 0.94 of the ethanol production is and 0.06 is non-growthassociated. For
Z mobilis, 0.67 is and 0.33 is Z. mobilis produces a more substantial
proportion of its ethanol in metabolism.
(g)
Fromp261;volumetric productivity is equal to specific productivity multiplied byceU concentration. From (e), as
the specific ethanol productivity qp for Z mobilis is 3.43/1.65 = 2.1 times that of S. cerevisiae, to achieve the same
volumetric productivity, the concentration of yeast must be 2.1 times that of bacteria.
Answer: 2.1 times the concentration of bacteria
(h)
Fromp 261, total productivity is equal to specific productivity multiplied by cell concentration and fermenter volume.
At zero growth. ,u in Eq. (11.70) is zero and = mp, Therefore, from (b), the productivity qp for S.
cerevisiae is 0.092 h
l
, and for Z. mobilis, LI2 h' , As the value for Z. mobilis is LI /0.092 = 12.2 times that of S.
cerevisiae, to achieve the same total productivity at the same cell concentration, the fermenter volume for the yeast
culture must be 12.2 times that for the bacteria.
Answer: 12.2 times the volume for the bacterial culture
(0
From Eq. (11.81) with,u= #max, for S. cerevisiae:
-J- = _1_ + _m_,_ = 1 +0.18 kg kg-
l
h-
l
= 9.54 kg kg-l
Y
xs
YXS Pmax 0.11 kg kg-l O.4h-
l
, -I
Y
xs
= 0.105 kg kg
For Z mobilis:
I + 2.2 kg kg-
1
h-
l
=24.0 kg kg-l
Y
xs
Yxs J4nax 0.06 kg kg-
l
O.3h 1
, -I
Y
x
, =0.042 kg kg
Answer: 0.105 kg kg.l for S. cerevisiae; 0.042 kg kg-
l
for2. mobilis. As Z mobilis produces less biomass per mass
of substrate consumed and per mass of ethanol produced than S, cerevisiae. biomass disposal is less of a problem with
the bacteria.
OJ
The ethanol yield from substrate is 12% higher using Z mobilis than S. cerevisiae. the specific productivity is 2.1
times higher so that a smaller and cheaper fermentation vessel is required to achieve the same rate of ethanol
production. and Z mobilis produces less than half the amount of biomass generated by S. cerevisiae per mass of
glucose consumed. All of these factors mean that Z. mobilis perfonns better than S. cerevisiae for ethanol production.
Solutions: Chapter 11 137
However, other aspects of the cultures and the ethanol production industry also need to be considered. Z mobilis
requires a higher pH (5.0) for growth than S. cerevisiae (3.5-4.0), and is therefore more susceptible to contamination.
Z mobilis also does not grow well on molasses, a common substrate material for fermentations, because of the high
salt content. The biomass produced in ethanol fermentation by yeast is often sold for use in animal feeds, whereas
application of bacteria for this purpose is not as well accepted in the industry. These are some of the reasons why Z
mobilis has not been widely adopted for industrial ethanol production, despite its superior ethanol production
characteristics.
11.10 Plasmid loss during culture maintenance
FromEq. (11.65),
a = f.r = 0.033h-
1
= 1.32
J.l+ O.025h 1
The number of generations of plasmid-containing cells over the 28..day period is, from Eq. (11.66):
_ ,,", _ (0.025h-
I
)28d12::I_
n-
ln2
- ln2 _24.2
Ifthe fraction of cells containing plasmid is F= 0.66, fromEq. (11.64):
066 = l-a-p = l-L32-p = 0.32+p = 0.32+p
. l_a_2
n
(a+p-lJ
p
1_1.32_(224.2(1.32+p Il)p 0.32+ (2
24
.
2
(0.32+Pl)p 0.32+214.38p(224.2")
Multiplying through by the denominator:
0.211 + 141.49p(2
24
.2") =0.32+p
141.49p(2
24
.
2
p)-0.109_p = 0
1bis equation can be solved for p by trial and error.
listed below, starting withp =0.001 as the first guess.
p
0.001
0.002
0.0007
0.00076
0.00077
0.000766
Values of the left-band-side of the equation for various pare
141.49 p (2
24
.
2
p) -O.I09-p
0.0339
0.1816
-0.0095
-0.0008
0.0006
0.000017
As the value of the expression wben p = 0.000766 is sufficiently close to zero, the solution can be taken as p =
0.000766.
Answer: 0.000766
11.11 Medinm sterilisation
(a), (h) aad (c)
The specific death constant kd is evaluated using Eq. (11.46) with A = 10
36
.
2
s-1 and Ed = 283 k:J gmolw1. From Table
2.5, R =8.3144 J K-l grool-1 =8.3144 x 10-
3
kJ K-l gmol-1, Converting the temperatures to degrees Kelvin using
Eq. (2.24), 80"C =(80 + 273.15) =353.15 K, 121"C =(121 + 273.15) =394.15 K, and 140"C =(140 + 273.15) =
413.15 K. Therefore, at 8()'>C:
kd = A e--EalR T = 10
362
s-l e-
283
kJ gmor
1
/(8.3144x 10-
3
kJK""1 gmo1-
1
x 353.15K) = 2.20x 10--6 s-1
138 Solutions: Chapter 11
At 121C:
k
d
=. A e-ErJ/RT = 1036.2s-1e-283 kJ gmor
l
/(8.3144x 10-3 gmor
1
x 394.l5K) =. 0.04978-1
At 141C:
The relationship between the number of viable cells and time is given by Eq. (11.87). Converting the units of the
initial concentration of contaminants xo:
XC) =10
8
cells 1-1 =. =. 10
11
cellsm-
3
Therefore. per m
3
, No =. 1011; N =. 10.
3
. Substituting values into Eq. (11.87) gives:
10-
3
=. 1011 e-/cd t
10-
14
=. e-kdt
-32.24 =. -kd t
32.24
t=--
k
d
Therefore, at 8We:
t =. 32.24 =. 3224 =4070h
k
d
2.20 x 10-6
8
-1 3600s
t =. 32.24 = 32.24 _II min I =10.8min
k
d
0.04978-1 60s
t = 32.24 =. 32.24 =12.3 s
kd 2.638-
1
Answer: 4070 b at 80
o
e; 10.8 min at 121C; 12.3 s at 140C
Heterogeneous Reactious
12.1 Diffusion and reaction in a waste treatment lagoon
(a)
A substrate shell is perfonned around a thin slice of sludge of area A and thickness Llz locateddistance z
from the bottom of the lagoon, as shown in the diagram below.
Wastewater
Siudga Iu
---------------------- -------
--1-------
z
Bottom of lagoon
////
Substrate diffuses into the shell across the upper boundary at z+.dz. and diffuses out across the lower boundary at z.
Substrate consumption within the shell follows firstMorder kinetics. Following the procedure on p 301, from Pick's
law, the rate of substrate input by diffusion is:
where Vse is the effective diffusivity of substrate in the sludge. Similarly, the rate of substrate output by diffusion is:
The rate of substrate consumption in the shell is kl sA Az.Substituting these expressions into the mass-balance
equation, Eq. (4.1), with the rate of substrate generation =0, at steady state:
Assuming that the substrate diffusivity and sludge area do not vary with distance ;::::
!t'soA(:!,.", -:l)-k1SA'" =0
Cancelling A and dividing through by tlz" gives:
Taking the limit as A;::: --+ 0 and invoking the definition of the derivative as in Eq. (D. 12) in Appendix D:
=0
140
or
d
2
s
Answer: 2J
Se
d? -k
1
S ::::: 0
Solutions: Chapter 12
(b)
At z::::: L, s::::: Sb. At Z"" O. we assume that the substrate concentration profile reaches a minimum so that ds/dz =O.
Answer: At z::::: L, s::::: Jb; at z:::: O. cIs/dz::::: O.
(c)
(I)
Ifs:::: N efJz, using differentiation rule Eq. (0.17) in Appendix D:
: = pNeP'
Wld
Substituting the expressions for s and d
2
s/dz2 into the differential equation in (a):
!D"p2NeP
Z
-k
j
NeI" = 0
Dividing through by N eP
z
and solving for p2;
or
(H)
Ifs::::: N eP
Z
+M e-Pz, substituting the values for p from (I) above:
s;:; NezVk,/!Dse +Me-1:Jk,/Vse
Differentiating this equation using differentiation rule Eq. (D.17) in Appendix D:
: = NJkll!lJs. ezJk11flJ" - MJk
1
1
!D" e-zJk11flJ"
Applying the boundary condition at z::::: 0:
Cancelling the square root terms gives:
N=M
Answer.N=M
(iii)
Substituting N for M in the equation for $ in (6):
Solutions: Chapter 12
, = N(ezJk,l"s. +e-<Jk""s.)
Applying the boundary condition at z=L:
'b = N(,LJk,
12
lo, +e-LJk,l"s.)
Solving for N:
141
(Iv)
From the definition of cosh x, the numerator in the equation for s in (iii) is equal to 2 cosh (z Jkl/.27s )- Similarly,
the denominator is equal to2 cosh (L Jkl/psc)' Therefore: e
, _ 2cosh (Z Jk1/.q.)
- 'b2Cosh(LJkl/.q.)
or
, _ cosh(zJk11.q.)
'b - cosh(LJk1/.q,l
Answer: QE.D.
(d)
Taking the derivative of s using the equation for s in (c) (iv);
Evaluating the derivative at z =L:
Substituting this result into the expression for rA,obs:
sinh (L Jk]I:lJ, )
r - ~ A - ~ Jk I Se
A,obs - Se ~ o 1 !OSe COSh(L Jk I )
1 !OSe
142 Solutions.' Chapter 12
(e)
The internal effectiveness factor is defined in Eq. (12.26). For first-order reaction kinetics at substrate concentration
Sb everywhere in the sludge, the rate of reaction within the entire sludge volume is:
Substituting this and the expression for rA,obs from (d) into Eq. (12.26) for fIrSt-order kinetics:
rA,obs
1]il = -.- =
'A'
17i1 =
Cancelling and grouping terms and applying the definition of tanh x gives:
tanh(L JkIffD,,)
LJk1ffDs,
Therefore, applying the definition of 1'1;
tanhj
~ i l =-j-
Answer: Q.E.D,
(f)
From the definition of tanh x;
For L = 2 em, the values of I. tanh <ftI and Tlil evaluatedfor the three sets of conditions are listed below.
Condition
(1)
(2)
(3)
I
0.50
2.0
10
0.46
0.96
1.0
1]il
0.92
0.48
0.10
The substrate concentration profiles are calculated using the equation for s as a ,function of z from (c) (iii) and
applying the definition of 1'1:
The results for Sb =10-
5
grool em-] at various values of zare listed and plotted below.
Distance, z(em)
0.0
0.3
0.7
1.0
1.2
I.S
1.8
2.0
Condition (1)
8.87 x 10-<'
8.89x 10-
6
9.00 x 10-
6
9.15 x 10--6
9.27 x 10-
6
9.50 x 10-
6
9.78 x 10-
6
1.00 x 10-
5
Substrate concentration, S (gmo1 em-
3
)
Condition (2)
2.66 x 10-
6
2.78 x 10--6
3.34 x 10-
6
4.10 x 10--6
4.81 x 10-
6
6.25 x 10-
6
8.26 x 10-
6
1.00 x 10-
5
Condition (3)
9.08 x 10-
10
2.14x 10-
9
1.50 x 10-
8
6.74 x 10-
8
1.83 x 10-
7
8.21 x 10-
7
3.68 x 10-<'
1.00 x 10-
5
143
Condition(3) ;1=10;1111=0.10
4; =0.50; 1111 =0.92
Condition (1)
Condition (2)
Solutions: Chapter 12
.,
1.2
E
0
"
1.0
~
'&
0.8
-
x

f
0.6
0.4
g
~
0.2
I!
,
'"
0.0
0.0 0.5 1.0 1.5 2.0
Distance from the bottom of the lagoon, z (cm)
As tPi increases, 1Jil decreases. the concentration profile becomes steeper, and the minimum suhstrateconcentl'ation in
the sludge is reduced.
12.2 Oxygen prome in immobilised-enzyme catalyst
(aJ
From p 269, as CAs is O.5mM/0.015:tnM= 33 times the value of K
m
as a:frrst approximation we can consider the
kinetics to be effectively zero order with ko =vmax. Converting the units of ~ to a per volume of gel basis:
k
o
= V
max
=0.12 mol s-1 kg-
l
(0.012kgm-
3
) . 1 1 3 ; ~ 1 1 . 1 1 ~ g l =4.61 x to-
5
kgs-
l
m-
3
Converting CAs to units ofkg m-
3
:
-3 -1 11000III 32 g IIIkg I -3
CAs =0.5mM =05x to gmoH. 1m
3
. 1 gmol . looog = 0.Ol6kgm
For zero-order reaction. the equation used to determine the substrate concentration inside the beads depends on
whether CA remains > 0 throughout the particle. The maximum particle radius for which this occurs can be
calculated using Eq. (12.17);
=
Therefore. the maximum particle diameter for CA >0 everywhere is 4.2 nun. Because the immobilised-enzyme beads
are smaller than this, CA > 0 and the oxygen concentration profile can be calculated using the equation for zero-order
reaction and spherical geometry in Table 12.1. Values for CA asa function of r areJisted and plotted below.
Radius, r (m) Oxygen concentration, CA (kg m-
3
)
2.0x
1.7 x 10-
3
1.5 x 10-
3
1.2 x 1(J3
1.0 x 1(J3
0.8 x 10-
3
05 x 10-
3
0.2 x 10-
3
0.0
l.60x
1.19 x 10-
2
9.60 x 10-
3
6.63 x 10-
3
5.02 x 10-
3
3.71 x 10-
3
2.28 x 10-
3
L51 x 10-
3
1.37 x 10-
3
144 Solutions: Chapter 12
20
f
0>
"-
M 15
0
-
x
<J
"
10
~
~

5 0
c
~
0
2.0 1.5 0.5
O'-__--''--__-l. --'- -'
0.0
As the minimum value ofCA atthe centre, of the bead is still about 2.9 timesK
m
the assumption of zeroorder
kinetics is reasonable.
(b)
As CA > 0 everywhere within the bead. for zero-order reaction tbismeans that the entire bead volume is active.
Answer: 1.0
(0)
FOf zeroorder reaction, the maximum conversion rate occurs when the oxygen concentration is greater than zero
everywhere in the particle. The largest bead size for this to occur was calculated in (a) is 4.2 rom.
Answer: 4.2 rom
12.3 Effect of oxygen transfer on recombinant cells
(a)
Converting the units of ko to mass:
k
o
= 10-3 mols-
l
m-
3
. 1 1 3 ~ ~ I I . l l ~ g l = 3.2x 10-
5
kg s-l m-
3
The maximum particle radius for which oxygen concentration inside the beads remains greater than zero is calculated
usingEq. (12,17):
=
Therefore, the maximum particle diameter for aerobic conditions is 2 x 1A5 = 2.9 mm.
Answer: 2.9 rom
(b)
The particle radius is 1.45/
2
"'" 0.725 rom "'" 7.25 x 10-
4
m. As this radius is less than R
max
determined in (a), oxygen
is present everywhere in the particle. Therefore, as the kinetics are zero-order, T1i "'" 1. From Eq. (12.26) with 1Ji "'" I:
rA,obs = r~ s "'" k
o
"'" 3.2 x 10-
5
kg s-1 m-
3
Substituting parameter values into the equation for the observable Thiele modulus tP in Table 12.4 for spherical
geometry:
Solutions: Chapter /2 145
Using this value, the minimum intraparticle oxygen concentration can be calculated from the equation in Table 12.5
for spherical geometry and f/) < 0.667:
CA,min = = = 6.0xlO-
3
kgm-
3
Answer: 6.0 X 10-
3
kg m-
3
(c)
If the cell density is reduced bya factor of 5, ko is reduced to 1/
5
its previous value, Therefore, k
o
= 115 (3.2 x 10-
5
kg
s-1 m-
3
) = 6.4 x 10-
6
kg s-l m-
3
. From Eq, (12,17):
6 4 0
9 2 1) 3 3
LxI m s8xlO kgm =3,24xlO-
3
m=3.24mm
6.4 x 10-6 kg s 1
m
3
Therefore, the maximum particle diameter for aerobic conditions is 2 x 3.24 = 6.5 mm.
Answer: 6.5 rom diameter
12.4 Ammonia oxidation by Immobillsed ceUs
(a)
R = 1.5 mm = 1.5 x 10-
3
m. Calculating the observable modulus Dfor spherical geometry from Table 12.6:
l2=!i rA,obs = 1.5xlO-
3
m 2.2 x 1O-5
kgs
-l m-
3
= 0.031
3 kSCAb 3 6xlO-
S
ms 1(6xIO-3kgm-3}
From Eqs (12.43) and (12.44),
As CAs"'" CAb, external mass-transfer effects are insignificant.
Answer: Insignificant; the surface oxygen concentration is only 3% lower than in the bulk medium.
(b)
From Table 12,7 for zero-order oxygen uptake kinetics, 1Jeo =1. The internal effectiveness factor l1io can be
determined from Figure 12.11 as a function of the observable Thiele modulus CPo Evaluating tP from the equation in
Table 12.4 for spherical geometry using the result for CAJ> from (a):
(
R)2 rA,obs (I.5XlO-
3
m)2 2.2XlO-
5
kgs-
1
m-
3
fJ)='3 'vAe
CAs
= 3 1.9XlO-9m2s-1(0.97X6xI03kgm3)=0.s0
From Figure 12.11, attP=0.50,1Jio= I. Using Eq,(12.46), 11T= 1Jio l1eo= I X I = I.
Answer: 1
(c)
Using the results from (a) and (b), the minimum intraparticle oxygen concentration can be calculated from the
equation in Table 12.5 for spherical geometry and tJ) <0.667:
CA,min = CAS(l-itP) = = 1.5 x 10-
3
kg m-
3
This oxygen concentration is greater than the critical level.
Answer: Yes
146 Solutions: Chapter 12
12.5 Microcarrier culture and external mass transfer
D
p
"'" 120 JUD "'" 120 x 10.
6
m. The external mass-transfer coefficient can be determined using the equations on p 322
for The Grashof number is calculated from Eq. (12.51) with g "'" 9.8 m s2 from p 16 and the
uni{conversion factor 1 N s m-
2
= 1kg m-
l
sl from Table A.9. Appendix A:
Gr= =9.8 ms-2 (I20X lO-6 mj' 10
3
kg m-
3
(1.2 x Io'kgm-
3
_1o'kgm-
3
) =3.39
K (10-3 Nsm-2 .11 kg m-
I
,-I h
2
1Nsm 2 U
Therefore, from Eq. (l2.S2).Rep =Gr/18:= 3.39'18 =0.188. The Schmidt number from Eq. (12.49) is:
10-3 Nsm-
2
_II kgm-
1
8;11
$c = IlL = IN.sm = 435
PL.v
AL
103kgm-3(2.3xlO-9m2s I)
Therefore, Rep Sc = 0.188 x 435 = 81.8. As this value is less than 104. the Sherwood number can be evaluated using
Eq. (12.55):
Sh = J4 + 1.21(Re
p
Sc)"67 = v' 4 +1.21 (81.8P67 = 5.21
From the definition of the Sherwood number in Eq. (12.50):
k
_ Sh.vAL _ 5.21 (2.3 x 10-
9
m
2
,-1) _ 999 10-5 -I
S - - - . x ros
D
p
120xl0--6
m
Using this value of ks to determine nfrom the equation in Table 12.6 for spherical geometry:
D = R TA,obs =
3 k
s
CAb
From Eqs (12.43) and (12.44);
120xlO-6m
2 0.015 mol s-1 m-
3
::::: 0.015
3 9.99 x 10 'ms I (0.2molm-3j
CA, = CAb(l-D) = CAbO-0.QJ5) = 0.985 CAb
External mass*transfer effects are insignificant as CAs ,., CAb. Because respiration is zero-order and the cells are
present only-on the surface of the beads. CAs> 0 is all that is required to ensure maximum reaction rate.
Answer: Negligible
12.6 Immobllised.enzyme reaction kinetics
(3)
R=0.8 nun =0.8 x 10-
3
m. As external have been eliminated. CAs::::: CAb =0.85 kg m-
3
and fie =1.
The value of Pas defined on p 313 is:
jJ::::: K
m
::::: 35kgm-
3
::::: 4.12
CAs 0.85kgm 3
From Figures 12.10-12.12, this value of pmeans that the reaction kinetics can be considered effectively f:trst-order.
Evaluating the observable Thiele modulus tP from the equation in Table 12.4 for spherical geometry:
4> =(li)2 rA,obs = (0.8 x 10-
3
m)2 1.25 x 10-
3
kg 5-
1
m-3 ::::: 8 0
3 .P
Ae
CAs 3 1.3 x 1O-1l m
2
s-1 (0.85 kg m-
3
) .
From Figure 12.11. at <1>= 8.0. flil =0.12. Therefore. from Eq. (12.46). TJT =11i 11e::::: 0.12 x I ::::: 0.12.
Answer: 0.12
Solutions: Chapter 12 147
(b)
From the definition of the effectiveness factor. Eq. (12.26):
L25xtO-
3
.kgs-I m-3 =OOlO4k -I -3
0.12 . gs m
Por kinetics. r =kl CAs; therefore:

k
l
= rAJ; = O.OI04kg s-1 m-
3
=0.0122s-1
CAs 0.85kgm-
3
Answer: 0.0122 s-I
(e)
The value of 0.0122 s1 for kt corresponds to an enzyme loading of 0.1 Ilmol got. The Thiele modulus 4't can be
evaluated as a function of enzyme loading usingothe equation for first-order reaction and spherical geometry from
Table 12.2. with ktdirectly proportional to the' enzyme 10ad.ing,Por>I < 1O,.the-intemal effectiveness factor l1il is
determined using the equation in Table 12.3 and the' definitionof coth x; for tf1I > 10. from Eq. (12.30) 1]u =II!. For
each value of kJ, r =kt CAs. and rA,obs can be determined from these results and the,definition of the effectiveness
factor in Eq. (12.26); Calculated values of these'parameters for several different enzymeloadings are listed below.
Enzyme loading (llJllol
1
) kl (,-I)
I 'lit
r'" (kg s-t m-
3
) rA,obs (kg s-t m-
3
)
A,
0.01 0.0012 2.6 0.34 0.0010 3.40x lO4
0.05 0.0061 5.8 0.16 0.0052 8.32 x lO4
0.10 0.0122 8.2 0.12 0.0104 1.25 x Ily3
0.20 0.0244 11.6 0.086 0.021 1.81 X lO-3
050 0.0610 18.3 0.055 0.052 2.86 x
0.80 0.0976 23.1 0.043 0.083 3.57 x
1.0 0.122 25.8 0.039 0.104 4.06 x
1.3 0.159 295 0.034 0.135 4.59 X 10-
3
1.5 0.183 31.6 0.032 0.156 4,99 x lO-3
1.8 0.220 34.7 0.029 0.187 5.42 x lO-3
2.0 0.244 365 0.027 0.207 5.59 x to-
3
The resultsfor 11i1 and rA.obs are plotted below as a function of enzyme loading.
6
5
1"
"
4

'0
-
x
3

<!-
2

l!
c
0
1 II

0:
0
2.0
'A,obs
0.5 1.0 1.5
Enzyme loading (1lffi01 g1)
0.0 '-__-..J'-__-l. -'- ...J
0.0
r- 0.3
I
! 02

0.1
0.4,----,,----,----,-----,
148 Solutions: Chapter 12
As the enzyme loading is increased from 0.01 got, the effectiveness factor drops significantly. Although the
reaction rate continues to rise with increasing enzyme loading, at loadings above about 0.5 !J.mol g-t, less than 5% of
the potential activity of the enzyme is being utilised. Further increases in enzyme loading therefore represent an
effective waste of more than 95% of that enzyme,
12.7 Mass-transfer effects in plant cell culture
(a)
D
p
::::: 1.5 nun =: 1.5 x 10-
3
m. The particle Reynolds number is evaluated using Eq. (12.48) withPL=: density afwater
::::: 103 kg m-
3
, andJiL =: viscosity afwater::::: 1 cP (p 133) = 10-
3
kg mol 5.
1
(Table A.9. Appendix A):
Re = DpUpLPL = 1.5 x 10-
3
m(0.83 x 1O-2 ms-l)(lO'kgm-
3
j = 12.5
p PL 10 3
kgm
1
8
-1
As this value is within the range 10 < Rep < 104, the external mass-transfer coefficient can be determined using Eq.
(12.57) for spberical particles in a packed bed. Converting the diffusivity units to m
2
8.
1
:
!lJ. ::::: 9x 1O-Qcm
2
s-
1
= 9x 10-6 cm
2
s-
1
=9x 1O-10
m
2
s
-1
Ae 100cml
iJ)AL =2 x iJ)Ae =2 x 9 x 10-
10
m
2
s1 =1.8 x 10-
9
m
2
s-l. The Schmidt number from Eq; (12.49) is:
From Eq. (12.57), the Sherwood number can be evaluated as:
Sh = 0.95 ReO.
5
Se
O
.
33
= 0.95 (12.51"5 (556)33 = 27.0
p
From the definition of the Sherwood number in Eq. (1250):
k
s
=Sha/AL = 27.0(1.8
X
1O-
9
m
2
s-
1
) = 3.24xlO-5 ms-I
Dp 1.5 x 10
3
m
'This value of ks can be used to-determine the observable modulus for external mass-transfer D from the equation in
Table 12.6 for spherical geometry. As the specific gravity of the wet cells is 1. from p 16, 1 g wet cells occupies a
volume of 1 cm
3
and rA,obs = 0.28 mg cm-
3
hoi. Converting these units to kg m-
3
:
rA,obs =0.28mgcm-3.
h
-I = 0.28 mg cm-
3
h-
I
j3 = 7.78 X10-
5
kg s-I m-3
Substituting this and the other parameter values into the equation for D:
1.5 X10-
3
m
2 7.78x 10-
5
kg s-l m-
3
_ 0075
3.24XlO-5ms-I(8mgl-I)I...!!'LjjlOOO11- .
1Q6
mg
1 m
3
From Eqs (12.43) and (12.44):
As CAs is close to CAb. external mass-transfer effects are present but small.
Answer: The effect is small; the surface oxygen concentration is 7.5% lower than in the bulk medium.
(b)
Evaluating the observable Thiele modulus tP from the equation in Table 12.4 for spherical geometry Using the result
for CAs from (a):
Solutions: Chapter 12 149
(
1.5X to-3m)2
<1>=(li)2 rA,obs = 2 7.78XlO'.."skgs-
1
m-
3
-073
3 aJAeCAs 3 9X10-lOm2s-1(o.925X8mgl-I).!16kg .
10 mg 1m
From Figure 12.11 for zero-order reaction, at t1J = 0.73, 17io is very close to but slightly less than 1.0. Therefore,
internal mass-transfer effects can be considered negligible.
Answer: Negligible
(cJ
CAs = 0.925 x 8 mg 1" I = 7.4 mg I-I. As 1Jia is only very slightly less than 1.0, it is likely that oxygen is exhausted
just close to the centre of the clumps. Taking rA,obs to be essentially equal to the intrinsic zero-order rate constantko,
the maximum particle radius for the oxygen concentration to remain greater than zero throughout the clump can be
evaluated using Eq. (12.17):


_ 1Omgl' 1m
- 7.78 x 10-
5
kg s-1 m 3
R
max
=7.2 x 10
4
m =0.72 mm
Therefore, the maximum particle diameter for oxygen through to the centre of the clump is 2 x 0.72 = 1.4 mm, which
is only slightly less than the plant cell clump diameter of 1.5 mm.
Answer. The oxygen concentration falls from 7.4 mg I-I at the external surface to zero just near the centre of the
clumps.
12.8 Respiration in mycelial pellets
(aJ
R = 2.5 mm= 2.5 x 10-
3
m. The presence of external boundary-layers can be checked by calculating the observable
modulus for external mass-transfer, D. From Table 12.6 for spherical goomelry:
,Q=!!.. rA,obs =2.5x10-
3
m 8.7XlO-
5
kgs-
1
m-
3
=024
3 kSCAb 3.8x10 5
ms
1(8XlO-
3
kgm-
3
) .
From Eqs (12.43) and (12.44):
CAs = CAb(1-D) = CAb(1-0.24) = 0.76 CAb = O.76(8Xl(r
3
kgm-
3
) = 6.1xlO-
3
kgm-
3
As. CAs is significantly less than CAb, external mass-transfer effects are present.
Answer: Yes
(bJ
As oxygen uptake is considered a zero-order reaction, for CAs> 0, l1eo = 1.
Answer: 1
(c)
In the absence of internal an;! external mass-transfer resistances, reaction rate is r corresponding to CA = CAb
throughout the pellets. As rAb is related to rA,obs by Eq. (12.45), r b can be determined if we know 1JTo. Evaluating
the observable Thiele modulus <P using the equation in Table 12.4 tor spherical geometry and the result for CAs from
(a):
150 Solutions: Chapter 12
From Figure 12.11 for zero-order reaction. at <P = 5,66,1'/io = 0.30. Therefore, from Eq. (12.46), as TJeo "'" 1 from (b),
l7To "'" TJio TJeo "'" 0.30 x 1 = 0.30. Using Eq. (12.45):
r 87 10-'k -1 -3
'* A,obs ,x gs m 29 10'""k -1 -3
rAb""'--"'" = ,x gs 00
~ r o 0.30
Answer. 2,9 x 10'4 kg lSI 00,3, or more than three times the rate actually observed
(d)
If external mass-transfer effects were eliminated, CAs = CAb = 8 x 10-
3
kg 00,3, and the observed reaction rate would
be greater than 8,7 x-1O-
5
kg g-l.m-
3
, Under these conditions. an-expression for the observable Thiele modulus ep
from the equation in Table 12.4 for spherical geometry is:
~ _(R)2 r A,obs _ (2.5 x 10-
3
00)2 r A,obs 4
.... - - - ()= 4.96x 10 rA,obs
3 :tJAeCAs 3 1.75xI0-9m2
s
1 8xlO-3kgm 3
where.rAObs has units of kgs-
1
00-
3
.- Because the reaction is zero--order, r ~ s = r ~ b ; therefore, from the result in (c),
r ~ s = 2,9'x 10-
4
kg g-1 00,3, Using Eq. (12.26):
r A,obs r A,obs
'ho =-.- =2.9 x 10-4 kg C 100-3
rAs
tP and TJio are related by the curve in Figure 12.11 for spheres and zero-order reaction. The value of rA,obs can be
determined bl trial-and-error using Figure 12.11, and the equations derived above, As a ftrst guess, take r A,obs = 2.0
x 10-4 kg S' 00,3. Depending on the difference between the values of 1]io obtained from the figure and from the
equation with r ~ s ' adjust rA,obs as shown in the table below.
rA.obs (kg s-I 00-
3
)
11iO = r ~ O b s
<1> 1Ji.o (from Figure 12.11)
rA,
2.0 x 10-4 0.69 9.92 0.19
1.0 x 10-4 0.34 4.96 0.34
Since the values for 11io in the last row are as close as practical, rA,obs "" 1.0 x 10-4 kg s-I 00-
3
. Therefore, compared
with the observed reaction rate of'8.7 x 10-
5
kg Sol 00-
3
in the presence of both 'internal and external mass-transfer
resistances, eliminating the external boundary layers increases the reaction rate by about 15%.
Answer. 1.0 x 10-4 kg lSI 00-
3
Reactor Engineering
13.1 Economics of batch enzyme conversion
For 75% conversion, sf = 0.25 so- TIle batch reaction time for enzyme processes is evaluated using Eq, (13.10):
Km I So sO-sf 1.5 g1-1 In 3g1-
1
+3gt-
1
-O.25X3g1-
1
__ 4.81h
tb = -- n-+-- =
Vmax sf vmax O.9gI
1
h
1
O.25X3g1
1
O.9gI
1
h
1
The operating cost is therefore:
Operatingcost = 4,81 h -I $4800 day-l = $962
The cost of downstream processing per kg product is:
C =155 -0.33 X =155 -0.33 (75) =$130.25 t<g-I
The mass of product formed is detennined from the mass of substrate consumed. which is equal to the change in
substrate concentration multiplied by the volume of the reactor V:
Mass of substrate consumed = (so-sf) V = (3-0.25x3)gl-1 (16001) = 3600g
As 1.2 g product are fonned per g substrate consumed:
Mass of product fonned = 1.2 x 3600 g "'" 4320 g "'" 4.32 kg
Therefore:
Downstream processing cost = $130.25 kg-I (4.32 kg) = $563
The revenue from sale of the product is:
Revenue"", $750 kg-
1
(4.32 kg) = $3240
Therefore the cost benefit at 75% substrate conversion is:
Cost benefit = revenue - operating cost-downstream processing cost = $3240- $962 - $563 = $1715
Carrying out the calculations for 90% conversion. the batch reaction time for Sf = 0.10 So is:
= 6.84h
At 90% conversion, the operating cost is increased due to the longer reaction
Operatingcost = 6.84h.j = $1368
The cost of downstream processing per kg product
C = 155 - 0.33 X = 155 - 0.33 (90) = $125.30 t<g-I
The mass of substrate consumed is:
152 Solutions: Chapter 13
Mass of substrate consumed =: ($0- Sf) V =: (3 - 0.10 x 3) g I-I (1600 1) =: 4320 g
and the mass of product formed is:
Mass of product formed = 1.2 x 4320g "'" 5184g =: 5.18 kg
Therefore, the downstream processing cost is:
Downstream processing cost =: Sl2S.30kg-l (5.18 kg) =: $649
The sales revenue is:
Revenue =: $750 kg-! (5.18 kg) = $3885
Therefore, the cost benefit at 90% substrate conversion is:
Cost benefit =: revenue - operating cost- downstream processing cost "'" $3885 -$1368 - $649 =: $1868
The gain per batch from increasing the conversion from 75%:to90% is therefore $1868 -" $1715 =: $153.
Answer: There is a gain of $153 per batch; representing a 9% increase in the cost benefit at 75% conversion.
13.2 Batch production of aspartic acid using cell-hound~ n z y m e
(0)
The initial concentration of substrate So =: 15% (w/v) =: 15 g per 100 ml =: 150 g 11. The final substrate concentration
Sf = 0.15 So = 0.15 x 150 g 1-1 = 22.5 g 1-1, Calculating the deactivation rate constant at 32"C using Eq, (11,45):
k = In2 = ~ I ~ I = 275 IO-3 h-1
d th 1O,5d'24h . x
For enzyme subject to deactivation, the batch reaction time is evaluated using Eq. (13.13);
tb =-lln[l-k
d
( K
m
In So + SO-S,)]
k
d
vmaxo Sf Vmaxo
= -I In 1_2.75XIO-3h-l( 4.0gl-
1
10 lSOgl-
1
+(150-22.5Jgr
l
) = 23.6h
2.75 x 10-
3
h-
1
5.9 gl 1h-
1
22.5 gI-I 5.9 gI-I h-
1
At 37"C, the deactivation rate constant is;
k = In2 = In2 I ~ I = 126 1O-2
h
-l
d t
h
2.3d 24h . x
The batch reaction time is;
tb = -lln[l-k
d
( K
m
In So + so-S,)]
k
d
vmaxo Sf Vmaxo
= -I In l-l.26XIO-Zh-l( 4.0gl-
1
In 150gl-
1
+ (150-22.5j gl-I) = 17.7h
L26xlO 2 h-l 8.5gl-
1
h-
1
22.5g1
1
8.5g11h 1
As the batch reaction time is lower at 37"C, 37"C is the recommended operating temperature.
Answer: 37"C
(h)
From Eq. (13.33), the total batch reaction time at 37"C is:
Solutions: Chapter 13
tT =- 1b+tdn =- 17.7h+28h =- 45.7h
153
Therefore. in one year. the number of batches carried out is:
365d!W!
Numberofbatches =- 45.7 h per batch =- 192
In each batch, the mass of ammonium fumarate converted is 0.85 x 150 g r
1
=- 127.5 g 1-1 multiplied by the reactor
volume V. Therefore. the mass of substrates converted is 1275 V g =- 0.1275 V kg, where V has units of litres. From
the reaction stoichiometry, as the molecular weights of ammonium fumarate and aspartic acid are approximately
equal, the mass of aspartic acid produced is also 0.1275 Vkg. After one year or 192 batches. the mass of aspartic acid
produced is 0.1275 V x 192 =- 24.5 Vkg. Using the conversion factor 1 tonne =- 103 kg (Table A.3, Appendix A), the
target level of aspartic acid production each year is 5000 x 103 =- 5 x 1()6 kg. To teach this target level:
24.5 Vkg = 5 x 10
6
kg
V= 2.04 x 1051 =204m
3
Answer: 204 m
3
13.3 Prediction of batch cnllnre time
(aJ
The initial cell concentration Xo =- 12 g/loo I =- 0.12 g 1-1. Assume that stationary phase is reached when Sf =- O. The
batch culture time can be determined using Eq. (l3.27):
I [Y
XS
] I [0.575
gg
-
I
( -I l]
tb =- --In l+-(so-sr) =- --lIn 1+ I lOgl -0 =- 4.3h
Pmax Xo 0.9 h- 0.12 g I
Answer: 4.3 h
(bJ
If only 70% of the substrate is consumed, Sf =- 0.3 So =- 0.3 x 10 g I-I =- 3 g I-I. From Eq. (13.27):
tb = _1_ln[1 + Y
XS
('o-'d] = _1_
1
1n[1 + 0.575 g g ~ I flO g I-I _ 3grIl] = 3.9 h
Pmax Xo 0.9h- 0.12g'-
The biomass density at this time can be calculated from Eq. (13.19):
xf =- Xo ePmax iI =- 0.12 g.-I e(O.9h-
1
x 3.9 h) =- 4.0 g I-I
Answer: 4.0 g 1-1
13.4 Fed-batch schednling
(aJ
The initial substrate concentration So =- 3% (w/v) =-3 g per looml =- 30 g I-I. The batch culture time to achieveS{=- 0
. is determined using Eq. (13.27):
tb = _1_ln[l+ YXS(so-'d] = I 11n[1+ 0.5 gg-I(30gl-I-Ol] = 13.3d
Jlmax Xo 0.18d- 1.5g1-
1
The biomass density at this time can be calculated using Eq. (13.19):
xf =- xoePmuft. =- 1.5 g 1-1 i0.18a' x13.3 d) =- 16.4g1-
1
Answer: The batch culture time is 13.3 days; the final biomass concentration is 16.4 g 1.
1
.
154 Solutions: Chapter 13
(b)
The mass of cells at the start of fed-batch operation is equal to the fmal batch cell concentration multiplied by the
initial medium volume:
Xo = xf V = 16.4 g 1,1 (100 I) = 1640 g
The fmal mass of cells after 40 d fed-batch culture can be determined using Eq. (13.50):
Answer, 4.04 kg
(c)
The mass of cells produced in each reactor run is equal to the final biomass minus the biomass used for inoculation:
Biomass produced per run := 4040 g - 1.5 g j-l (100 I) = 3890 g = 3.89 kg
By analogy with Eq. (13.33), the total reaction time is:
where lb is the batcbreaction time and lfb is the fed-batch operation time. Substituting parameter values using the
result for 1b from (a):
IT = !b+tfb+tdn:= 133d+40d+ld = 54.3d
In one year, the number of runs carried out is:
275d
Numberofruns = 54.3dperrun :: 5.06
The total biomass produced annually is equal to the biomass produced per run multiplied by the number of runs per
year:
Biomass produced per year = 3.89 kg x 5.06 := 19.7 kg
Answer: 19.7 kg
13.5 Fed-batch production of cheese starter cultnre
(a)
An expression for the liquid volume as a function of time during fedbatch reactor operation can be derived from an
unsteady-state total mass balance as shown in the solution to Problem 6.7afrom Chapter 6. Using this expression:
Vo =: V-Ft =: 40m
3
_4m
3
h
l
(6 h) = 16m
3
Answer: 16 m
3
(b)
From the definition of the dilution rate in Eq. (13.39), after 6 h cffed-batch operation when V"" 40 m
3
;
D =!:.. = 4m
3
b-
1
=: O,lOh-
1
V 40m3
Substituting this value into Eq. (13.45) for the substrate concentration at quasi*steady state:
s = DKS = O. 10 h-
I
(0.I5kgm-
3
) = 0.06kgm-3
Iimax-D 0.35h I_
O
.
lOb
1
Answer: 0.06 kg ro
3
(c)
Taking maintenance substrate requirements into account, for qp:: 0, Eq. (13.43) becomes:
Solutions: Chapter 13
Is = D(S.-S)-(.J!....+ms)x
dt 1 Y
xs
At state, dsld! '" 0, J1 '" D, ands Sj. Therefore, the equation reduces to:
o= +ms)x
Solving for r.
155
Ds, O.10h-
1
(SOkgm-
3
)
x =,,-'- =__
_D_+
ms
O.lOh I +0.135kgkg-I h-1
Yxs 0.23 kg kg 1
Answer: 14.0 kg m-
3
(d)
After 6 h operation, the mass of cells is:
=14.0kgm-
3
x = xV = 14.0 kg m-
3
(40 m
3
) = 560kg
At the start of fed-batch 0r.:ration when the liquid volume is 16 m
3
, if operation is at state, the cell
concentration", 14.0 kg m- and:
x = x V = 14.0 kgm-
3
(16 m
3
) = 224 kg
Therefore, the mass of cells produced during operation is (560 kg - 224 kg) = 336 kg.
Answer: 336 kg
13.6 Continuous enzyme conversion in a fIXed-bed reactor
Convert the parameter values to units of kg, m, s. Km. =0.54 g =0.54 kg m-
3
. During the reactor operation, s =
0.02 g = 0.02 kg = 0.42 g = 0.42 kg R= 1 mm = 10-
3
m. The active enzyme concentration per
unit volume of catalyst ea is:
e
a
= lO-4
g
= lO-4
g
=4xlO-4
kgm
-3
250cm
3
250cm3 looog 1m
The effective diffusivity of urea in the gel VAe is:
Ij) = 7xlO-6 cm2s-1 = = 7xlO-
lO
m
2
s-
1
Ae l00cm
From Table B.l (Appendix B), the molecular weight of urea is 60.1 and the molecular weight of NH4+ is 18.0.
Therefore, from the stoichiometry, reaction of 60.1 g urea produces 2 x 18.0 =36.0 g Nf4+. Expressing the turnover
number k2 in terms of urea:
k2 = l1,OOOg NH1 (g enzyme)-l s-l =11,000 g NH1 (g enzyme)-l s-l .1
60
.
1
ore: 1
36.0gNH
4
k2 = 1.84 x 104 g urea (g enzyme)"l = 1.84x 10
4
kg kg-I
From Eq. (11.33), Vmax expressed on a'per volume gel basis is:
Vmax = k2 ea = 1.84 x 104 kg sl (4 x 10-4 kg = 7.36 kg s-l
As there are 250 em
3
gel per litre of liquid in the reactor, Vrnax expressed on a per volume liquid basis is:
156 Solutions: Chapter 13
=736k -3 _1(2S0Cm
3
) 184k -3-1
vrnax . gm s 11 . lOOcm . 1m
3
. gm s
The rate of reaction can be determined after evaluating the effectiveness factor in the absence of external boundary
layers. From the definition of f30n p 313 with CAs = s:
p = K
m
= O.54kgm-
3
"'" 27
s O.02kgm-3
From Figure 12.10, for this value of pthe reaction kinetics can be considered first-order. Based on Eq. (11.36), the
effective first-order rate constant kl is:
I 84k
-3-1
. gills "'" 3.418-
1
0.54kgm-
3
_Calculating the Thiele modulus from the equation in Table 12.2 for first-order kinetics and spherical geometry:
As lPI > 10. fromEq. (12,30):
1 I
= <Pi / 23.3 = 0.043
From Eq. (12.46), as TIe = 1, 1]T= 0.043. The flow rate of urea solution iDto and out of the reactor can be detennined
by evaluating the dilution rate D in the mass-balance equation, Eq. (13.54):
D = = -,0",.04=3"(I".8"4",k
g
"m"-,3-:o,-_IL)0",.0,,,2:.okg=mc.-_
3
,, = 7.06 x 10-3s-I
(Km+$) (si $) (0,54+ 0.02) kg m-
3
(0.42-0.02) kg m-
3
From the definition of the dilution rate, Eq. (13.39):
F = D V = 7.06 x 10-
3
s-l (11) = 7.06 x 10-
3
1S'"l
In 30 min. the volume of urea solution treated is:
Volume treated = 7.06 x10-
3
I s-I (30 min) I= 12.71
Answer: 12.7litres
13.7 Balch and conllnuous hiomass production
SO= Si = 4% (w/v) = 4 gper 100ml =40 g 1-1 =40 kgm-
3
. Sf = s=0.02x40kg m-
3
=0.8 kg m-
3
. For the batch
reactor. X() = 0.01% (w/v) = 0.01 g per 100 ml = 0.1 g I-I = 0.1 kg m-
3
.
The batch culture time can be determined from Eq. (13.27):
1 [Y
xs
1 1 [04I
gg
-
1
' 3]
tb = " In I +-('O-Sf) = lin 1+. 3 (40-0.8) kg m- = 11.6h
r-max XO O.44h O.lkgm
The biomass density at this time is obtained fromEq. (13.19):
Xf = Xoe"mu;, = 0.1 kgm-3 i0.44h-1 x I 1.6 h) = 16.5kgm-
3
Calculating the mass of cells produced per batch:
x = (xf-x,,) V = (16.5 - 0.1) kg m-
3
(1000 m
3
) = 1.64 x 104 kg
Solutions: Chapter 13
If the downtime between batches tdn is 20 h, from Eq. (13.33):
IT = 1b+tdn = 11.6h+20h = 31.6h
Therefore. in one year, the number of batches carried out is:
_365dl*1 _
Numberofbatches - 31.6bperbatcb - 277
The total annual.biomass.productionfrom batch culture is therefore 1.64 x 104 kg x 277 = 4.54 x 106 kg.
For continuous reactor operation, the steady'-state cell concentration is given by Eq. (13.62):
x = (Si-S)Yxs = (40-0.8)kgm-
3
(0.41gg-
l
) = 16.1kgm-
3
The dilution rate D corresponding to S= 0.8 kg m-
3
can be detennined using Eqs (13.57) and (lL6O):
D = p = I'm",,' = M4h-
1
{O.8kgm-
3
j = O.44h-1
Ks+s 07 r
1
08k -3
. mg . 3' 6 +. gm
1m 10 mg
157
From the definition of the dilution rate. Eq. (13.39):
F = D V = O.44h-
l
(1000m
3
) = 440m
3
h-
l
The rate of biomaSs production F x= 440 m
3
h-
I
x 16.1 = 7084 kg b-
1
. The number of days per year available
for continuous reactor operation is (365 - 25) = 340 d; this corresponds to340 d x 24 h d-} = 8160 h. Therefore. the
total biomass produced per year is 7084 kgh-} x 8160 h =5.78 x 10
7
kg. This production level is 5.78 x 10
7
/4.54 x
10
6
= 12.7 times the amount produced using batch culture.
Answer: The annual biomass production using continuous operation is 5.78 X 10
7
kg, which is 12.7 times the
production of 4.54 x 10
6
kg from batch culture.
13.8 Reactor design for immobilised enzymes
So = Si = 10% (w/v) = 10 g per 100 ml = 100 g 1.
1
= 100 kg m-
3
. Sf = S = 0.01 x 100 kg m-
3
= 1 kg m-
3
. Based on the
-unsteadystate mass-balance equation derived in Example 6.1 in Chapter 6 for reaction, the equation for the
rate of change of substrate concentration in a batch reactor is:
d(V,) _ -Ie V
(it- IS
where V is the reaction volume and k} is the reaction rate constant. As V can be considered constant in a batch
reactor, this term can be taken outside of the differential and cancelled from both sides of the equation:
ds
dt =-k
1
s
The differential equation contains only two variables, sand t. Separating variables and integrating:
ds
- = -kl dt
,
Using integration rules (D.27) and (D.24) from Appendix D and combining the constants of integration:
Ins=-klt+K
The initial condition is: at t = 0, S = so. From the equation, therefore, In So = K. Substituting this value of K into the
equation gives:
158
lns = -kl t+lnsQ
,
In-=-kt f
'0
The batch culture time 1b is the time requited for the substrate concentration to reach Sf.
sf -l 1kgm-
3
-10- n 3
So lOOkgm
tb = -- = =16.0h
k
1

If the downtime between batches too is 20 b, from Eq. (13.33):
tT = tb+tdn =16.0h+20h =36h
Therefore, in one year, the number of batches carried out is:
l
24h
l
365d'
IT
Numberofbatches = 36hperbatcb = 243
Solutions: Chapter 13
Reactor volume =
To treat 400 tonues penicillin G annually, using the unit conversion factor 1 tonne:= 103 kg (Table A.3, Appendix A):
400tonnes 1_l0_
3
_k_
g
I
Mass of penicillin G treated per batch = her
400
fh,onn
h
" = o.ci--'-l"to"n"ne", =1.65 x 10
3
kg
num 0 ate esperyear 243
As the concentration of penicillin G added to the reactor is tOO kg m-
3
:
I.65xl0
3
k:g =165m3
100 kg m-
3
The batch reactor volume required is 16.5 m
3
.
For a CSTR operated under steady state conditions, Fi ::::: F
o
= F, V is constant, and ds/dt = O. Therefore,
balance equation for frrstoro.er reaction derived in Example 6.1 in Chapter 6 becomes:
0:= FSi-Fs-1q sV
0:= FIV(Si-S)-kl sV
Solving for Fly.
F; _ kt
s
_ O.8
X
lO-4 s-1(1kgm-
3
) _ 808 10-
7
-
1
V---- _.X s
si -s (100-1) kg m 3
The flow rate of penicillin G into the CSTR is 400 tonnes per year. Using the unit conversion factor 1 tonne:= 103 kg
(Table A.3, Appendix A) and the concentration of substrate in the feed stream Si := 100 kg m-
3
, the total volumetric
flow rate of the feed stream F is:
-1 I10
3
kg I1
1Yeai
i lId Illh I
400 tonnes year . 1 tonne . 365 d . 24 h . 3600 s
F:= := 1.27x 10-4
m
3 s-1
100kg m-
3
Applying this with the above result for Fly:
SolutWns: Chapter 13
F
v=-=
FIV
1.27 x 1O-4
m
3 s-I
8.08xlO 7
8
-1
=157m
3
159
The CSTR reactor volume required is 157 m
3
.
For the PFTR, if the density of enzyme beads is four times greater than in the other reactors. kl = 4 x 0.8 x 10
4
sl =
3.2 x 10-
4
sl. By analogy with Eq. (13.83), the differential equation for change in substrate concentration with
position in the reactor for firstorder kinetics is:
<Is
Uctz=-k1s
The differential equation contains only two variables, s and z. Separating variables and integrating:
<Is -k,
-=-dz
S u
Using integration rules (D.27) and (0.24) from AppendixD and combining the<;onstants"of integration:
-k,
Ins = -z+K
u
The boundary condition is: atz= 0, S = si. From the equation, therefore, In sf= K. Substituting this value of Kinto
the equation gives:
-k,
Ins = -z+lns
j
u
At the end of the PFIR, z=L and S = Sf, therefore:
Applying the defInition of the reactor residence time .. from Eq. (13.85):
sf
In- =-kl't'
si
Rearranging and solving for 't':
Note that this is 1/
4
the value obtained for the batch reaction time th. as expected from the analogous kinetic
characteristics ofbatch and PFTR reactors and the 4 x higher value ofk] in the PFTR.
As calculated for the CSTR, F = 1.27 X10-4 m
3
8.
1
. Therefore. from the definition of .. in Eq. (13.51):
V =-rF =4.0 h.! 3 ~ ~ 8 j1.27X 10-4 m
3
s-I =1.83 m
3
The PFrR reactor volume required is 1.83 m
3
.
Answer. The smallest reactor volume is 1.83 m
3
for a PFrR.
160 Solutions: Chapter 13
13.9 Two-stage cbemostat for secondary metabolite production
(a)
Sj::::: 10 g ::::: 10 kg m-
3
, The dilution rate, which is the same for both reactors, is calculated using Eq. (13.39):
501h-1 1
1m3
I
D =f. = . 10001 =O.lOh-'
V a.5m3
The cell and substrate concentrations entering the second reactor are the same as those leaving the first reactor. The
substrate concentration can be determined using Eq. (1358):
s = =O.lOb-' (l.Okgm-
3
) =S.Okgm-3
JJmax-
D
O.12h-
1
-O,lOh-
1
When maintenance requirements are significant, the cell concentration is calculated using Eq. (13.61):
x:::: D(sj -s) = _O"'c.
lO
"b"-.'",(l
co
O.-.c
S
".O",),,k
g
,.m=. -3_ = 2.2 kgm-3
.D. +ms O.lOh-
1
+0.025 kg kg-1 h-1
Y
xs
O.5kgkg I
Answer: The cell concentration is 2,2 kg m-
3
; the substrate concentration is 5,0 kg ro-
3
.
(b)
As growth is negligible in the second reactor,-x ::::; Xi ::::: 2.2 kg m-
3
. The substrate concentration is determined by
rearranging Eq. (13.59)and solvingfor s with fJ::::: 0:
(
qp ) V
s::::: $i- Y
ps
+mS x
p
Substituting the parameter values with Si ::= 5.0 kg m-
3
;
For the two reactors together:
(Si-
S
) (lO-O.3l)kgm-
3
Overallsubstrateconversion::= _-x100%::= 3 x 100% = 97%
si lOkgm
Answer: 97%
(cj
As product is not formed in the first reactor, Pi = 0 for the second reactor. The product concentration is determined by
rearranging Eq. (13.64) and solving for p:
p =qpxV = =3.Skgm-
3

Answer: 3.5 kg m-
3
13.10 Kinetic analysis of bioremediatlng bacteria uslug a cbemostat
(a)
From Eq. (13.92), Jlmax and Ks can be detennined from the slope and intercept of a plot of SID versus s. From the
definition of the dilution rate in Eq. (13.39), values of D are evaluated from the experimental flow rates using V= 11
= 1000 ml. The measured substrate concentration at 50 ml h-
l
indicates that washout occurs at this flow rate;
therefore, this result is not included in the kinetic analysis. The data are listed and plotted below.
Solutions: Chapter 13 161
Flow rate, F (ml h"l) Dilution rate, D (h"l) Substrate concentration, S (J,lM) SID OtM h)
10
15
20
25
30
35
50
0.010
0.015
0.020
0.025
0.030
0.035
O.OSO
17.4
25.1
39.8
46.8
69.4
80.1
100
1740
1673
1990
1872
2313
2289
2000
2500


2000

:2


ore,

1500
100 20 40 60 80
Substrate concentration, S (p.M)
1000
o
The slope of the straight line in the plot is 10.48 h; the intercept is 1493 liM h. From Eq. (13.92), the slope = llPmax;
therefore, J.tmax =1/10.48 h = 0.095 h"l. The intercept = KS/p:max;thereforeKg = 1493 J.l,M hx 0.095 h"l = 142 J.l,M.
Answer: Pmax =0.095 h"l; Kg = 142 liM
(b)
The critical dilution rate Dcrit is determined using Eq. (13.66):
tlmaxSj 0.095h-
1
(100/lM) -1
Derit = KS+sj = 142Jl,M+lOOliM = 0.039h
Calculating the flow rate from Eq. (13.39) with V = 1000 mI, F =D V"", 0.039 h"l x 1000 ml = 39 ml
Answer: 39 ml h"l
13.11 Kinetic and yield parameters of an auxotropWc mutant
From Eq. (13.92), Jlmax and Ks can be determined from the slope and intercept of a plot of SID versus s. From the
definition of dilution rate in Eq. (13.39), values of D are evaluated from the experimental flow rates using V"", 2 l.
The relevant data are listed and plotted below.
Flow rate. F (I hoI) Dilution rate, D (h-
1
) Substrate concentration, S (g 1"1) SID (g I-I h)
1.0
1.4
1.6
1.7
1.8
1.9
o.so
0.70
0.80
0.85
0.90
0.95
0.010
0.038
0.071
0.066
0.095
0.477
0.020
0.054
0.089
0.078
0.106
0.502
162
0.6
0.6
0.4
:2
-
0.3
.$

0.2
0.1
0.0
0.0 0.1 0.2 0.3 0.4 0.5
Substrate concentration, S (g 1-
1
)
Solutions: Chapter 13
'The slope of the straight line in the plot is 1.027 h;the intercept is 0.0119 g I-I h. From Eq. (13.92), the slope:
Iftlmax; therefore, J.Lmax:::: 1/1.027 h "'" 0.97 hoi. The intercept:::: KS/J.I.max; therefore Ks =0.0119 g I-I h x 0.97 h-
t
=
0.012 g l-t,
From Eq. (13.93), Yxs and ms can be determined from the slope and intercept of a plot of versus lID, where
is calculated using Eq. {13.94) '\II(ith Sj "" 10 g The relevantdata are listed and plotted beISt,
Flow rate, F(l h-
1
) Dilution rate, D (hw
l
) liD (h) g-l) Ill" (g g-l)
XS
1.0 050 2.00 0.315 3.175
1.4 0.70 1.43 0.323 3.096
1.6 0.80 1.25 0.329 3.040
1.7 0.85 1.18 0.328 3.049
1.8 0.90 1.11 0.324 3.086
1.9 0.95 LOS 0.326 3.067
3.20,---,---,-.,--,,--,---r--,

3.15
-
-
b
.$
3.10
_ m
'?:-X

-

3.05

3.00
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
YOilution rate (h)
Solutions: Chapter 13 163
= O.107h
The scatter in the plot is typical for measured values of The slope of the straight line in the plot is 0.12 g g.l
h-
I
; the intercept is 2.93 g g-1. From Eq. (13.93), the slope =- ms; therefore ms =- 0.12 g g.l h-
1
. The intercept =-
I/
yxs
; therefore Yxs =- 1/
2
.
93
h-I =- 0.34 g g-l.
Answer:,umax =- 0.97 h
1
; Ks =- 0,012 g 1.
1
; rns =- 0.12 g g-1 h
l
; Yxs =- 0.34 g g.1
13.12 Continuous sterilisation
From the definition of dilution rate in Eq. (13.39), the medium volumetric flow rate F =- D V =- 0.1 h-
1
x 15 m
3
=- 1,5
m
3
h
1
. The linear velocity u in the holding section of the steriliser is determined by dividing F by the pipe cross
sectional area A =- n: ,.z, where r is the pipe radius. For r =- 6 cm =- 0.06 m:
U =- f. =- 1.5m
3
h-
1
=- 132.6mh-
1
A 1t (0.06 m)Z
The value ofthe specific death constant is evaluated using Eq. (11.46) with R =- 8.3144 1. gruoll fromTable 2.5,
Ed =- 288.5 kJgmol-l =- 2.885 x loS J gruolI, A =- 7.5x 10
39
h
l
, and the temperature convertedfromoC to degrees
Kelvin using Eq. (2.24):
kd =A e-EdiR T == 7.5 x 103
9
h-
1
e-Z.885 xlOS J gmorlt[(8.3144J gmor
1
K"1)(130+ Z73.15H(] =313.1 h-
1
Within a period of 3 months "" 90 d, the number of cells Nl entering the steriliser is equal to the medium volumetric
flow rate Fmultiplied by the cell concentration and the time:
Nj =1.5 m
3
h-
I
(
10
5
ml
-1 =3.24 x 10
14
Within the same 3-month period, the acCeptable number of cells remaining at the end of the sterilisation treatment is
NZ =- L Therefore:
N
Z
1 =- 3.09 x 10-15
Nt =- 3.24x 10
14
(a)
For perfect plug flow.withno:axial dispersion, the sterilisation time can be determined using Eq. (13,97):
N
1
14
In- 1n
3
.
24XlO
N
2
1
thd =- kd = 313.1h 1
To allow the medium to remain for this period. of time in the.holding ,section,of:the steriliserpipe,.the length of pipe
required is equal to the linear velocity of the medium u multiplied by t'hd:
L = u!hd =- 132.6mh-
1
xOJ07h =- 14.2m
Answer: 14.2 m
(h)
Calculating the Reynolds number for pipe flow using Eq, (7.1) with pipe diameter D =- 12 cm =- 0,12 m:
Dup 0,12 m(132.6m h-
1
) lOOOkgm-
3
Re=---= =-3978
,u 4kgm-1 h 1
The value of !J)vu Dcorresponding to this Re is found from Figure 13.40. Using the experimental curve as this gives
a higher 2i than the theoretical curve and thus a more conservative design, 1Jzlu D "" 1.5. Therefore:
From Eq. (13.101), an expression for the Peelet number Pe is:
164 Solutions: Chapter 13
where L has units of m. Similarly, an expression for the Damkohler number Da from Eq. (13.102) is:
k
d
L (313.1 h-
1
) L
Da =- "'" "'" 2.36
u 132.6mb-1
The design problem can be solved from this point using methods and Figure 13.41. As a first guess, try
L =20 ID. The values for Pe and Da are evaluated using the equations determined above, and the corresponding value
for N2/Nl read from Figure 13.41. Depending on how this value compares with the target of 3.09 x 10-
15
, the value
of L is adjusted until the results for
N
2/N} coincide. The calculations are shown in the table below.
L(m)
20
18
19
Pe
110
99
105
Da
47
42
45
(from Figure 13.41)
4x
1 x 10-
14
1.5 x to-
15
The last value of N2/NI is as close as practicable to 3.09 x 10-
15
considering the resolution of Figure 13.4l.
Therefore. the required length of pipe in the holding section is about 19 m. or 34% longer than that detennined for
ideal plug flow.
Answer: About 19 m
(e)
For L =- 14,2 m, from the equations developed in (b), Pe :::: 78 and Va:::: 34, From Figure 13.41, N2/Nl is about 5 x
10-
12
; therefore, NI/N2 :::: 2 X 1011. As N2 :::: 1, N} :::: 2 x 1011, i.e. one contaminant enters the fermentetfor every 2 x
lOll that enter the steriliser, For F:::: 1.5 m
3
h-
l
and an input contaminant concentration of lOS ml-
l
, the time
required for 2 x 1011 contaminants to enter the steriliser is:
2 x 1011
Therefore, contaminants enter the fermenter at a rate of one every 80 min.
Answer: One contaminant enters the fermenter every 80 min.