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CHE 3164 Chemical Reaction Engineering (Tutorial Problems)

Set 6

1. In many reactions the enzyme and product complex (E.P) is formed directly from the enzyme
substrate complex (E.S) according to the sequence
E + S !"E.S"!"P + E
Show that the rate laws for the above reaction can be simplified to
V (C − C P / K C )
− rS = max S
C S + K max + K P C P

Vmax [ S ]
2. Show that the rate law for the following reactions is rP =
E + S !"E.S""  [I ]
[ S ] + K m 1 + 
 Ki 
E + I !"E.I

E.S ! E + P

3. Beef catalase has been used to accelerate the decomposition of hydrogen peroxide to yield
water and oxygen. The concentration of hydrogen peroxide is given as a function of time for
a reaction mixture with a pH of 6.76 maintained at 30oC.

t (min) 0 10 20 50 100

CH2O2 (mol/L) 0.02 0.01775 0.0158 0.0106 0.005

(a) Determine the Michaelis-Menten parameters Vmax and Km.


(b) If the total enzyme concentration is tripled, what will the substrate concentration be after 20
min?
Q1 E YS n E S n Et p
a Propose reaction withintermediate

E t S k's E S I
E S k's E 15 2
E s k3 E YP 3
E yp H E S 4
Iii Write rate offormation ofintermediate
re s RE.si
rE.sztrE.s3trE.s
kiEEJ S
rE.si
rE.s2 kzEEoS
RES3 Ks E S
RES4 kaEETEP
teas kiEETES K2 Eos Ks Eos t Ky E P
Ciii Apply Psst

re s O

kitEIES t kaTETEP kz Eos 1 k3EE.SI


E s kitEIES t kaTEIEP
K2 k3
Civ write rate law
rs i rs t Rsz t rsz rsu
rs ki EEIES
Ps2 KalEos
Ps3 O
rs4 O

rs kEET18 t kz LE.SI
rs e
k EE S ka KilEIES t kaTEIEP
K2 Ks
KiLEI S kikz EI sltkzk4
EIEP .kz
1kg
KikaEETES kik3 EJESJ kikz EI.SI
kzk4
kik3 EIlsT kzk4EEI P
LEIEP kztk
K2 tk3
Totalenzyme concentration

Et E t Eos
EE t kitEIES t kaIETEP
K2 k3
kits 1 KyEP
E i x K2 1kg
E Et
ka t Ks kits 1 KyLP
ka t k3

rs
E kik 18 kokuEP
K21kg
e Ee kik 18 kzkyEP
ka t Ks kits t k4lP Kz1kg
ka t k3
kik3 SIEE 3 kzc4EPILE I
ka t k3 t kits 1 Kalp
Michaelis Menten equation

lil Divide numeratoranddenominator by ki


rs KzIS Et KIk4 IP Et
K2 3 t s t kk4 IP

Iii et Ks Keat
rs Kz SITE k YIK MEET
K2 3 t s t kk4 IP

Rs
Keat ESTEE11 Keat
k 4
MEET
Kz k3 y
t s t kk4 P

k2k4 l
et
Kiko ko
kcai E.cl KP
rs Es
K2 3 t s t kk4 TP
tin let kztk3 Kmax
ki
rs kcai E.cl Es LP
Kmax t Est t kk4 IP

let k4
ki Kp
rs kcai E.cl Es LP
Kmax t IS t KpEP
iv let kcat feel a Vmax
Kmax Michaelisconstant
rs Vmax Cs Ef Vmax maximumspecificrate
Cs t Kmax KpCp Kca1 i turnovernumber

Q2 Ci Propose reaction withintermediate

EtS k's E S I
E S ka E tS 2
E t I 13 E I 3
Ea I ka E 11 4
E S Ks Et P 5

Iii Write rate offormation ofintermediate


re s RE.si
rE.sztrE.s3trE.s4trE.s
kiEEJ S
rE.si
rE.s2 kzEEoS
RES3 0
RES4 O
re S5 Ks IE S
te s kiEETES K2 Eos kyEE.SI
re RE 2 RE za t RE 13 1 RE24

RE12
t.reoz rE.at
0
0
RE13 Kz E I
RE.z4 Ky E I
RE15
reo
Kz E EI ke EE I
iii Apply PSSH

E s e O
k E IS kz Eos tks E.SI
Eas KEE 15
K2 tk5

RE I e O
kzLET.CI a k4EEo1
EE I kzLET.CI
k4
Civ write rate law
1 t
rp rp rpa t
rp3 rp4 rp5
O
rp 0
rpa
rps O
rpu a O
rp5 KsIE SI
e Ks KilE IS
K2 tk5

rp Ksla tells
K2 tk5

total enzyme concentration


Et EE t E ST t E I
kit E IS kzLEJ.LI
Ey K2 tk5 k4
CEI it K7 Kk
E l KAEST t KB EI 1
where KA a ki KB k3
kztk5 k4
E Et
I KATS t KB EI

rp Kiska E ES
Kiska 5 Et
I KATS t KB EI
Michaelis Menten equation

lil Divide numerator and denominator


by KA
r
p Ks ESTEEt
In it Is t
E III
Iii let Ks Keat

rp Keat ESTEEt

In it Is t
E III
Iiii let Ka km

rp Keat ESTEEt
s t ka l Krs111
a kcat ESTEEc
s t km I 1 KB113

let KB ki
rp Keat Is Ite
Is km it

livl let Keat Et Vmax

rp Vmax Es
Is km it

03 a rs max Cs
Kmt Cs
Design equation for constantvolume reactor
rs a
des
dt
des e VmaxCs
dt Kmt Cs
Kmt Cs
VmaxCs des
e
dy
Is Hmmm
I v'ma des f de

1 Cso Cs
Ymha en fY Max

Emma en 14 1 imacs
tvma orx
Im
Vimamx
ten 14 form
c

Vmax Cso Cs 1
f en Yg km t km
m
Y e c t n

ten
Cso c
ten Esg
t Yi 28.19N10.018
0.01193 0.000225
0.01179 0.000210
0.01270 O000188 Cso Cs
O 01386 0.000150 t

Vma 0.018
Km
a
28.19 km
km i
0.0354 mall Max 6.385 104molllomin

b Vmax 3 x 6.385 x 10 41
1.9155 10 3 MOI l LoMin
Kim
t vmm.in Y tcsfmaEs
20 O 0354 0.02 Cs
10 3 ln
Oc
I 9155 I 9155 10 3
s 0.0092 MollL

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