Power Law Kinetics Doesn’t WORK where ???

Biological Processes
(receptor:ligand binding; protein adsorption)

Reactions
(Enzyme-mediated)

Most biological processes exhibit kinetic expressions

that span multiple orders; depending on concentration.

Alcoholic fermentation First to crystalize an enzyme in Mathematically described

without cells pure form enzyme reaction
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 Rate Enhancements Created by Enzymes

How Does a Catalyst Work ??

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 Active sites: highly specific for their substrates…

determines specificity
where catalysis takes place
enzyme–substrate complex

A B +C
catalyzed B (enhanced selectivity) 7

Some Inorganic Elements that Serve as

Co-factors for Enzymes

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 Enzyme Kinetics

1902 thioglycolic acid could dissolve keratin

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 Vary Initial Substrate
ê

Enzyme is invertase, the Substrate sucrose, and the products glucose and
fructose.
L. Michaelis and M. L. Menten. Die kinetik der invertinwirkung. Biochem. Z.,
49:333–369, 1913.

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Substrate Depletion in Batch System

So
P (t)
S(t)

Concn.
dS/dt = rate of S
depletion

E:S (t)
Eo E (t)

Time
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 Derivation of Menten-Michaelis Equation
Assumed Mechanism
k1 k2
E+S ES P+E
k-1
Rate of Product
Formation
v=dP/dt=k2 [ES]
€

Net Accumulation of ES
d[ES]
=k1 [E][S]*k *1 [ES]*k2 [ES]
dt
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Derivation of Menten-Michaelis Equation

Assumes Equilibrium in Step 1:

k %1 [E][S]
Ks = =
k1 [ES]
Assumes Quasi-Steady State for ES complex:

d[ES]
≈0
dt
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 d[ES]
=k1 [E][S]*k *1 [ES]*k2 [ES]
dt
0≈k1 [E][S])k )1 [ES])k2 [ES]
Allows you to solve for [ES] in terms of [E] & [S]

& E0 = [E] + [ES]

vmax [S] where Vmax = k*E0

d[S]
rs =- = Km = (k-1 + k2) / k1
dt (Km +[S])
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Substrate Depletion in Batch System

So
P (t)
S(t)

Concn.
dS/dt = rate of S
depletion

E:S (t)
Eo E (t)

Time
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 rS

dS kmaxE0S vmaxS
! =&rs = =
dt (Km +S) (Km +S)

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dS kmaxE0S vmaxS
! =&rs = =
dt (Km +S) (Km +S)
rS

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 dS kmaxE0S vmaxS
! =&rs = =
dt (Km +S) (Km +S)

At S >>> Km ?? rs ≈ (Vmax S / S) ≈ Vmax

rs is ZERO-ORDER in S
rs ≈ (Vmax S / Km) ≈ K* S
At S <<<< Km ??
rs is FIRST-ORDER in S
To statistically determine best Vmax & Km , linearize …
! 1 $ ! (K +S) $ ' K * ' S * ' K * 1 ' 1 *
# &=## m &&=) m ,+) ,= ) m , + ) ,
" rs % " VmaxS % )( VmaxS ,+ )( VmaxS ,+ )( Vmax ,+ S )( Vmax ,+
y = m•X + b 20

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1/V

1/rs

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 Effect of Temperature on Reaction Rates
k
A + B ! C rate = r
Rate expression relates rate to experimental parameters effecting
reaction
r = ƒn(T, concentrations A,B,C, etc)
r = ƒ1(T) ƒ2(A) ƒ3(B) etc

ƒ(T) is Arrhenius Equation: k = Z•exp(-Eact/RgT)

Where Eact = activation energy [KJ/mole]
Rg = universal gas law constant (8.3 KJ/mole-oK)
T = temperature, oK
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Chemical reactions k = Z•exp(-Eact/RgT)

ln k To determine Z & Eact,
need data on K as fn(T)…
Linearize equation
yields..
1/T

(Eact 1 ln k
lnk=lnz+( )
Rg T

y = b + mX
1/T

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 rS

dS kmaxE0S vmaxS
! =&rs = =
dt (Km +S) (Km +S)

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Heterogenous vs. Homogeneous Reactions

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 How to operate an Enzymatic Reaction in Continuous Flow ??
F (L3/t) Whazzz Wrong with this Picture ??
F (L3/t)
Sin (M s/L3) S (M s/L3)
P (M P/L3) How to operate CSTR with
V Enzymatic Reaction without
continuously feeding SOLUBLE
Enzyme??

F (L3/t) Immobilize E on a solid that

F (L3/t) stays in Reactor for ∞
Sin (M s/L3) S (M s/L3)

--E
P (M P/L3)
E -- --E

--E
V
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How to operate an Enzymatic Reaction in Continuous Flow ??

--E

F (L3/t)
F (L3/t) E -- --E
Sin (M s/L3) S (M s/L3)
--E

P (M P/L3)

E concn. = (ME/Area) = (ME/L2 )

V

Mass Balance on S: VdS/dt = F(Sin – S) – kmax E S/ (Km + S) V

But now E = (ME/L2) thus, M s/t = M s/t - (M s/M E-t)(M E/L2) L3

NOT CORRECT !!
Should be M s/t = M /t - (M /M -t)(M /L2) L2
s s E E 27

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 Immobilized Enzymes
Economic purpose
Enzymes can be reused
Recovery of product is easier
Choice of immobilization A. Adsorption
E
B. Covalent
Coupling
E
+
+ +
+ +
+
E + + E
E
C. Entrapment in
E
Polymer Matrix
D. Encapsulation
E E
E E

E E E
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Heterogenous vs. Homogeneous Reactions

F (L3/t) Heterogenous Rxns = occur at the interface between two phases

F (L3/t)
Sin (M s/L3) S (M s/L3) Homogeneous rates r = mass or moles/L3-t
P (M P/L3)
Heterogenous Rxns, r = mass or moles/L2-t
V
Thus would like to maximize surface area A per reactor volume, V.

Reactor Schemes to use for continuous operation: CSTR and PFR

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Reactor Schemes to use for continuous operation: CSTR F (L3/t)
S (M s/L3)
Fluidized-Bed P (M P/L3)
V

F (L3/t) Eim
Sin (M s/L3)

F (L3/t)
Packed or Stationary-Bed S (M s/L3)
P (M P/L3)
V

F (L3/t) Eim
Sin (M s/L3)
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Packed bed of SOLID Support Particles –

Catalyst only on outer particle surface area,
A= 4πr2
Atotal = Np 4πr2 where
Np = # particles in bed

Only way here to increase r (Ms /L2-t) is to shrink

particle radius; that approach has limits ….

>2000 m 2/gram
tennis court =~300m2
US football = 5400 m2
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soccer= 7500 m2

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 Steps in a Heterogeous Reaction within a Porous Carrier
reactant

Concn.

1. Reactants diffuse through external boundary layer

2. Reactants diffuse into pores
3. Reactants adsorb to surface catalysts/enzymes
4. Reactants “react”
5. Product desorbs from surface
6. Product diffuses out of pores
7. Product diffuses away from sphere product

Distance from center

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Concepts:

• Simultaneous Diffusion + Reactions

(in series)

• The “rate – limiting” step

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 Steps in a Heterogeous Reaction within a Porous Carrier
reactant

Concn.

1. Reactants diffuse through external boundary layer

2. Reactants diffuse into pores
3. Reactants adsorb to surface catalysts/enzymes
4. Reactants “react”
5. Product desorbs from surface
6. Product diffuses out of pores
7. Product diffuses away from sphere product

Distance from center

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Simulataneous
Diffusion and Reaction

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 Desilu Productions

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Fox 43

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