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Chap. 7'

Questions and Problems

413 P7-8*
Consider the application of the PSSH to epidemiology. We shall treat each of
the following steps as elementary in that the rate will be proportional to the
number of people in a particular state of health. A healthy person, H, can
become ill, I, spontaneously,
H
k')I
(E'-8.1)
or he may become ill through contact with another ill person:
I+"
' ) 21
(P7'-8.2)
The ill person may become healthy:
I
">H
(W-8.3)
or he may expire:
I
k4>D
(P7-8.4)
The reaction given in Equation (P7-8.4) is normally considered completely
irreversible, although the reverse reaction has been reported to occur.
(a)
Derive an equation for the death rate.
(b)
At what concentration of healthy people does the death rate become crit-
ical? [Ans.: When [HI = (k3 + k4)/k2.]
(c)
Comment on the validity of the PSSH under the conditions of part (b).
(d)
If
k, =
h-*, k2 = IO-'
(peopleah)-', k3 = 5 X
h, k4 =
lo-'
P7-9c
h, and H, = lo9 people, plot H, I, and D versus time. Vary k, and describe
what you find. Check with your local disease control center or search the
WrW to modify the model and/or substitute appropriate values of k,.
(Postacidijication in yogurt) Yogurt is produced by adding two strains of bac-

teria (Lactobacillus bulgaricus and Streptococcus thermophilus) to pasteur-

ized milk. At temperatures of llO"F, the bacteria grow and produce lactic acid. The acid contributes flavor and causes the proteins to coagulate, giving the characteristic properties of yogurt. When sufficient acid has been pro- duced (about 0.90%), the yogurt is cooled and stored until eaten by consum- ers. A lactic acid level of 1.10% is the limit of acceptability. One limit 0111the shelf life of yogurt is "postacidification," or continued production of acid by the yogurt cultures during storage. The table that follows shows acid produc- tion (% lactic acid) in yogurt versus time at four different temperatures. YO@d

ChemicalEngineering

in the Food Industry

 Time (days) 35°F 40°F 45°F 50°F 1 1.02 1.02 1.02 1.02 14 1.03 1.05 1.14 1.19 28 1.05 1.06 1.15 1.24 35 1.09 1.10 1.22 1.26 42 1.09 1.12 1.22 1.31 49 1.10 1.12 1.22 1.32 56 1.09 1.13 1.24 1.32 63 1.10 1.14 1.25 1.32 - 70 1.10 1.16 1.26 1.34

Acid production by yogurt cultures is a complex biochemical process. For the purpose of this problem, assume that acid production folllows first-order kinetics with respect to the consumption of lactose in the yogurt to produce lactic acid. At the start of acid production the lactose concentration is  414

Nonelementary Reaction Kinetics

Chap. 7

about 1.5%, the bacteria concentration is 10" cells/dm3, and the acid concen- tration at which all metabolic activity ceases is 1.4% lactic acid.

(a) Determine the activation energy for the reaction.

(b) How long would it take to reach 1.10% acid at 38"F?

(c) If you left yogurt out at room temperature, 77"F, how long would it take to reach 1.10% lactic acid? (d) Assuming that the lactic acid is produced in the stationary state, do the data fit any of the modules developed in this chapter? [Problem developed by General Mills, Minneapolis, Minnesota] P7-10, The enzymatic hydrolization of fish oil extracted from crude eel oil has been carried out using lipase L (Proc. 2nd Joint ChindUSA Chemical Engineering. Conference, Vol. 111, p. 1082, 1997). One of the desired products is docosa- hexaenic acid, which is used as a medicine in China. For 40 mg of enzyme the Michaelis constant is 6.2 X (mLlmL) and V,, is 5.6 pmol/mL. min. Calculate the time necessary to reduce the concentration of fish oil from 1.4% to 0.2 vol %. Note: There may be an inconsistency in the article. The half life for an initial volume of 25% fish oil is stated to be 4.5 days. However, this yields a different initial fish oil concentration one finds from looking in the lit- erature. Search the web forjsh oil. Suggest a way to resolve this controversy. P7-llB Beef catalase has been used to accelerate the decomposition of hydrogen per- oxide to yield water and oxygen [Chem. Eng. Educ., 5, 141 (1971)l. The con- centration of hydrogen peroxide is given as a function of time for a reaction mixture with a pH of 6.76 maintained at 30°C.    t (min) Io 10 20 50 100 CHZo2(mol/L) I 0.02 0.01775 0.0158 0.0106 0.005

(a) Determine the Michaelis- Menten parameters V,, and K,. (b) If the total enzyme concentration is tripled, what will the substrate con- centration be after 20 min?

(c) How could you make this problem more difficult?

P7-12B In this problem three different types of reaction inhibition are explored:

(a) In competitive inhibition, an inhibitor adsorbs on the same type of site as the substrate. The resulting inhibitor-enzyme complex is inactive. Show that the rate law for competitive inhibition

is

E+S

E+I

E.S <IE.1 <eE*S E+P (b) In uncompetitiveinhibition the inhibitor attachesitself to enzyme- substrate complex, rendering it inactive. Show that for uncompetitive inhibition,

E+S e E*S
IES
P+E

I+E-S e

E -S

Chap. 7

Questions and Problems

415

the rate law is (c) In

noncompetitive inhibition, the inhibitor adsorbs itself to a different type

of site than the substrate to render the enzyme- substrate complex inactive.

Assuming that all concentrations of a species can be expressed by their equilibrium concentrations, show that for noncompetitive inhibition 1

P+E

the rate law is (d) Sketch three different inhibitions on a Lineweaver- Burk plot. W-13B It has been observed that substrate inhibition occurs in the following enzy-

matic reaction:

(a)

 E+S Show that the rate law for the sequence above is consistent with the plot in Figure P7-13 of -r, (mmol/L.min) versus the substrate concentration S (mmoi/L). (Refer to Problem P7-12.)   o

4

o

12

16

20

24

26 S (rnrnol/litsr)

32

36 40

44

Figure W-13

40

52

416

Nonelementary Reaction Kinetics

Chap. 7 W-14,

(b) (e)

If this reaction is carried out in a CSTR that has a volume of loo0 dm3, to which the volumetric flow rate is 3.2 dm3/min, determine the threepossible steady states, noting, if possible, which are stable. The entrance concentra- tion of the substrate is 50 mm0i/dm3. What is the highest conversion? What would be the effluent substrate concentration if the total enzyme

concentration is reduced by 33%? The following data on bakers' yeast in a particular medium at 23.4"C and var-

ious oxygen partial pressures were obtained:  Po*

Q,,

(no sulfanilamide) Q,,

(20 mg sulfanilamide/mL added to medium)

 0.0 0 0 0.5 23.5 17.4 1.o 33 25.6 1.5 37.5 30.8 2.5 42 36.4 3.5 43 39.6 5.0 43 40

P

= oxygen partial pressure, mmHg; eo,= oxygen uptake rate, pL02 of O2 per hour per mg of cells.

(a)

Caalate the Qo, maximum (Vmax),and the Michaelis-Menten constant K,. (Am: V,,

= 52.63 pL O,/h.mg cells.)

W-15

(b) By use of the Lineweaver- Burk plot, determine whether sulfanilamide is

a competitive or noncompetitive inhibitor to 0, uptake. (Refer to Prob-

lem

W-12). (University of Pennsylvania)

(a) Use the supplementary reading to give three examples each of polymers formed by step polymerization and by chain polymerization. Describe the monomers, structural unit@)and repeating unit in each case.

Plot yj, wj as a function of j for degrees of polymerization of 5, 10, and

function of conversion of functional groups, p, for M, =

(b)

(c) Plot

20.Plot Pto as a 1 mol/dm3. fi and wj as

termination by combina -

tion for p = 0.8, p = 0.9 and p = 0.95. Determine the molecular weight distribution for the formation of polysty- rene for an initiator concentration 0f_'0-' molar and a: monomer concen- tration of 3 molar. What are an,M,, and the polydispersity, D, after 40 hrs? How would the anchange if chain transfer were neglected?

(e) The polymerization of styrene is carried out in a batch reactor. Plot the

(d) mole fraction of polystyrene of chain length 10 as a function of time for an initial concentration of 3M and 0.01M of monomer and initiator respectively. The solvent concentration is 10 molar. W-lh The instantaneous number-average degree of polymerization, X,, can be expressed as  zhl=

moles monomer consumed/dm3.s -
-rM
c r,

(P7-16.1)

(a) Consider an additional termination step resulting from the combination of the initiator molecule and a free radical R,:

 Chap. 7 Questions and Problems 417 Rj + 1  > kn Pj (P7- 16.2)

(b) Show that where

k, = k,+ k,+ k,,

(c) Neglecting solvent transfer, show that (d) Explain how you can determine rate law parameters from expenmental data obtained in a CSTR. Use sketches to elucidate your explanation.

(e) Typical activation energies for the initiation, propagation, and termination

steps are: 20 kUmol, 20 kJ/mol, and 9 kT/mol. Discuss the effect of tem- perature on free-radical polymerization. W-17B The free-radical polymerization reaction discussed in Section 7.3.3 for a batch reactor is to be carried out in a CSTR and a PFR.

(a) Plot the effluent initiator and monomer concentrations as a function of the space-time T.

(b) Compare your results for two equal-sized CSTRs in series with one CSTR. The total volume is the same in both cases.

(c)

Vary the parameter values (Le., b,k,) and discuss your results.  Mo = 3 mol/dm3
b =
s-l

I20 = 0.01 mol/dm3

kp = 10 dm3/mol-s

kf = 5 X IO7dm3/mol.s

W-lfiA (Anionicpolymerization) (a) Determine the final number-average and weight-average chain lengths

and molecular weights along with the extent of polymerization and poly- dispersity in an anionic polymerization for an initial monomer concentra- tion of 2 M and for initiator concentrations of 1, 0.01, and 0.0001 Ai.

Calculate the radical concentration and polymer concentration as a func- tion of time for j = 3, 7, 10 for the same monomer and initiator concen- trations. k, = w, k, = 100 dm3/mol.s

(b) (c) Repeat (b) for the case

r, = k,[A-]M

and

W-19, with k, = 10 dm3/mol.s and K,= lo-* moi/dm3. An anionic polymerization is to be carried out in a CSTR. The reaction steps are k,
I+M
) R,
R,+M
kp > R,,,
 418 Nonelementary Reaction Kinetics Chap. 7 The entering concentration of monomer and initiator areMo and Io, respectively.  (a) Derive an equation involving the monomer concentration and only the variables kp, kl, Io, t (i.e., z = V/u),and MQ (b) Derive an equation of the radical concentration as a function of space time, z . (Ans. Rj =  (c) Choose representative values of k, (0.015 dm3/mol.s) and kp (lo3 W-20 dm3/mol-s) to plot I and M as a function of z . What if k, >> kp and R1= Io (dj Derive equations for the first and second moments and pn, pw,and D. Polyesters (shirts) can be formed by the reaction of diacids and diols   nHORIOH + nHOOCRzCOOH 4 HO(R,00CR2COO),, H + 2(n - 1)H20

Let [COOH] represent the concentration of carboxyl functional groups and [- OH] the concentration of hydroxyl groups. The feed is equimolar in [OH] and [COOH]. The combined mole balance and rate law is (a)

(b) - d[CooH1 dt

= k{COOH][OH][cat]

Assume that the polymerization is self catalyzed [cat] = [COOH], plot

the appropriate function of the

a function of time in order to obtain a linear plot. Plot the experimental data on the same plot. In what regions do the theory and experiment agree, and in which region do they disagree?

Assume that the reaction is catalyzed by the (H+) ion and that the (H+) ion is supplied by the dissociation of the weak acid [COOH]. Show that the overall rate of reaction is 5/2 order. Plot the appropriate function of p versus time so that the plot is linear. In which regions do the theory and experiment agree, and which regions do they disagree?

fraction of functional groups reacted, p, as (c) It is proposed that the mechanism for the polymerization is

H

I (1)
--
[COOH] + HA <I- -COH
+A-
+
OH
OH
I
I
- -
COH+ --OH
- - COH -
(2)
+
I

(3)

--OH +

OH

0 I
I1
A- +-
-COH
+ - -CO--

I

- - OH

+

+HA

Can this mechanism be made to be consistent with both rate laws?

Chap. 7'

Questions and Problems

Experimental Data

419

 t(min) 0 50 100 200 400 700 1200 1600 P 0 0.49 0.68 0.8 0.88 0.917 0.936 0.'944 Sketch the polymer concentration, P7,mole fraction of polymer with j mono- mer units, y,, and the corresponding weight fraction, w,,for j = 2, 10, 20 as a function of monomer conversion in Styrene polymerizatio-nfor

(a) Termination by means other than combination.

combination. The molecular weight of the monomer is 25

(b) Termination by   and its initial concentration is 3 M and the initiator concentration is 0.01M.

(c) How would your answers to parts (a) and (b) change if the initiator con- centration were (4.0001M?

(d) What are the corresponding average molecular weights at X = 0.2, 0.8,

and 0.999?

Rework Example 7-5 for the case when the initiator does not react immedi- ately with monomer to form the radical R; (i.e., R1), but instead reacts at a finite rate with a specific reaction rate ko: The rate law is

I+M

ko R, - r, = k, IM

The initiator concentration at time at t = 0 is Io. (a)

Derive an equation for Rl as a function of 0. mol/dm3, I, = Plot R8 and Ps as

(b) For M, = 3 dm3/mol.s.

mol/dm3, k, = 0.1 dm3/mol.s, a function of real time t.

kp =

10

W-23, Rework Problem P7-22 for the case in which the reaction is carried out in a CSTR. Derive an 6quation for R, as a function of the space-time, 7.

W-2% The growth of a bacteria Stepinpoopi can be described by the logistic growth law with ,p,   = 0.5 h-l and C, = 20 g/dm3. The substrate is in excess. (a) The cell growth is to be carried out in a 2-dm3 batch reactor. Plot the growth rate and cell concentration (g/dm3) as functions of time after inoculation of 0.4 g of cells into the reactor (ignore the lag period). (b) The batch vessel in part (a) is to be turned into a CSTR. Derive an equa-

tion for the wash-out rate. Choose values for the volumetric flow rate of the entering substrate and plot the cell concentration as a function of time afterinoculation. W-2SB The following data were obtained for Pyrodictium occulturn at 98°C. Run 1 was carried out in the absence of yeast extract and run 2 with yeast extra& Both runs initially contained Na,S. The vol % of the growth product H,S col- lected above the broth was reported as 8 functioh of time. [Ann. N. E ,A.cad.    Sci., 506, 51 (1987)l.

Nonelementary Reaction Kinetics

Chap. 7

Run 1:

rime (h)

Cell Density

(cells/mL) X

Run 2:

Time (h)

Cell density

(~elIs11nL)X lob4

% H2S

0

/ 2.7

I

0

2.7

0.1

 10 15 20 30 40 50 60 70 2.8 15 70 400 600 775 600 525 5 10 15 20 30 40 50 60 7 11 80 250 350 350 250 - 0.7 0.7 0.8 1.2 4.3 7.5 11.0 12.3
 (a) What is the lag time with and without the yeast extract? (b) What is the difference in the specific growth rates, kmax,of the bacteria with and without the yeast extract? (c) How long is the stationary phase? (d) During which phase does the majority production of H2S occur? (e) The liquid reactor volume in which these batch experiments were carried

out was 0.2 dm3. If this reactor were converted to a continuous-flow reac- tor, what would be the corresponding wash-out rate? W-2& Cell growth with uncompetitive substrate inhibition is taking place in a CSTR. The cell growth rate law for this system is

with kmax= 1.5 h-l, Ks = 1

g/dm3, KI = 50 g/dm3, Cd = 30 g/dm3,

Y,,, = 0.08, Cd = 0.5 g/dm3, and D = 0.75 h-l.

 (a) Make a plot of the steady-state cell concentration C, as a function of D. (b) Make a plot of the substrate concentration Csas a function of D on the same graph as that used for part (a). (c) Initially, 0.5 g/dm3 of bacteria was placed in the tank containing the sub-

strate and the flow to the tank started. Plot the concentrations of bacteria and substrate as functions of time. W-27B A solution containing bacteria at a concentration of 0.001 g/dm3 was fed to a semibatch reactor. The nutrient was in excess and the growth rate law is first order in the cell concentration. The reactor was empty at the start of the experiment. If the concentration of bacteria in the reactor at the end of 2 h is 0.025 g/dm3, what is the specific growth rate k in min-I? W-28*An understanding of bacteria transport in porous media is vital to the efficient operation of the water flooding of petroleum reservoirs. Bacteria can have both beneficial and harmful effects on the reservoir. In enhanced microbial oil recovery, EMOR, bacteria are injected to secrete surfactantsto reduce the inter- facial tension at the oil-water interface so that the oil will flow out more easily. However, under some circumstances the bacteria can be harmful, by plugging the pore space and thereby block the flow of water and oil. One bacteria that has been studied, Leuconostoc mesenteroides, has the unusual behavior that when it is injected into a porous medium and fed sucrose, it greatly