chemical reaction engineering asynchronous video series chapter 7, part 1: pssh enzyme kinetics h....

Chemical Reaction Engineering

Asynchronous Video Series

Chapter 7, Part 1:

PSSH

Enzyme Kinetics

H. Scott Fogler, Ph.D.

Active Intermediates/Free Radicals

Active Intermediates/Free Radicals

Active Intermediates/Free Radicals

Mechanism:

€

r1NO 3* = k1CNOCO2

Active Intermediates/Free Radicals

Mechanism:

€

r2NO 3* = −k 2CNO 3

*

€

r1NO 3* = k1CNOCO2

Active Intermediates/Free Radicals

Mechanism:

€

rNO2= k3CNO 3

* CNO

€

r2NO 3* = −k 2CNO 3

*

€

r1NO 3* = k1CNOCO2

Active Intermediates/Free Radicals

Mechanism:

€

r2NO 3* = −k 2CNO 3

*

€

r1NO 3* = k1CNOCO2

€

rNO2= k3CNO 3

* CNO

€

r3NO2

Pseudo Steady State Hypothesis (PSSH)A* is an active intermediate that is highly reactive. It disappears as fast as it is formed.

€

rA*net

=0

Pseudo Steady State Hypothesis (PSSH)A* is an active intermediate that is highly reactive. It disappears as fast as it is formed.

€

rNO3

* =r1NO3

* +r2NO3

* +r3 NO3

*

€

rA*net

=0

Pseudo Steady State Hypothesis (PSSH)A* is an active intermediate that is highly reactive. It disappears as fast as it is formed.

€

rNO3

* =r1NO3

* +r2NO3

* +r3 NO3

*

€

rA*net

=0

€

r1NO3

* =k1 NO( ) O 2( )

r2NO3

* = −k 2 NO 3*

( )

Pseudo Steady State Hypothesis (PSSH)A* is an active intermediate that is highly reactive. It disappears as fast as it is formed.

€

rNO3

* =r1NO3

* +r2NO3

* +r3 NO3

*

€

rA*net

=0

€

r3NO3

* = −r3 NO2

2= −

k 3

2NO 3

*( ) NO( )

€

r3NO 3

*

−1 =r3NO 2

2

€

r1NO3

* =k1 NO( ) O 2( )

r2NO3

* = −k 2 NO 3*

( )

Pseudo Steady State Hypothesis (PSSH)A* is an active intermediate that is highly reactive. It disappears as fast as it is formed.

€

rNO3

* =r1NO3

* +r2NO3

* +r3 NO3

*

€

rA*net

=0

€

r3NO3

* = −r3 NO2

2= −

k 3

2NO 3

*( ) NO( )

€

r3NO 3

*

−1 =r3NO 2

2

€

k1 NO[ ] O 2[ ]− k 2 NO3*

( ) −k 3

2NO 3( ) NO( ) = 0

€

r1NO3

* =k1 NO( ) O 2( )

r2NO3

* = −k 2 NO 3*

( )

Pseudo Steady State Hypothesis (PSSH)A* is an active intermediate that is highly reactive. It disappears as fast as it is formed.

€

rNO3

* =r1NO3

* +r2NO3

* +r3 NO3

*

€

rA*net

=0

€

r3NO3

* = −r3 NO2

2= −

k 3

2NO 3

*( ) NO( )

€

r3NO 3

*

−1 =r3NO 2

2

€

k1 NO[ ] O 2[ ]− k 2 NO3*

( ) −k 3

2NO 3( ) NO( ) = 0

€

r1NO3

* =k1 NO( ) O 2( )

r2NO3

* = −k 2 NO 3*

( )

Pseudo Steady State Hypothesis (PSSH)

Enzymes: Michaelis-Menten Kinetics

Enzymes: Michaelis-Menten Kinetics

Enzymes: Michaelis-Menten Kinetics

Urea DecompositionA given enzyme can only catalyze only one reaction.  Urea is decomposed by the enzyme urease, as shown below.

Urea DecompositionA given enzyme can only catalyze only one reaction.  Urea is decomposed by the enzyme urease, as shown below.

Urea DecompositionA given enzyme can only catalyze only one reaction.  Urea is decomposed by the enzyme urease, as shown below.

Rate Laws:

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( )

Urea DecompositionA given enzyme can only catalyze only one reaction.  Urea is decomposed by the enzyme urease, as shown below.

€

rE•S = r1E•S + r2E•S + r3E•S

Rate Laws:

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( )

Urea DecompositionA given enzyme can only catalyze only one reaction.  Urea is decomposed by the enzyme urease, as shown below.

€

rE•S = r1E•S + r2E•S + r3E•S

Rate Laws:

€

=k1 E( ) S( ) − k 2 E • S( ) − k 3 E • S( ) W( )If

€

E • S( ) =k1 E( ) S( )

k2

+ k3

€

rE•S ≈ 0

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( )

Urea Decomposition

€

E T( ) = E( ) + E • S( )

€

= E( ) +k1

k 2 + k 3

⎛

⎝ ⎜ ⎞

⎠ ⎟ E( ) S( )

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( ) =k1 k 3 E( ) S( )

k2

+ k3

Urea Decomposition

€

E T( ) = E( ) + E • S( )

€

= E( ) +k1

k 2 + k 3

⎛

⎝ ⎜ ⎞

⎠ ⎟ E( ) S( )

€

E( ) =k 2 + k 3

k1

⎛

⎝ ⎜ ⎞

⎠ ⎟E T

k 2 + k 3

k1

⎛

⎝ ⎜

⎞

⎠ ⎟ + S

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( ) =k1 k 3 E( ) S( )

k2

+ k3

Urea Decomposition

€

rP =k 3 E T

k 2 + k 3

k1

⎛

⎝ ⎜

⎞

⎠ ⎟ + S

€

E T( ) = E( ) + E • S( )

€

= E( ) +k1

k 2 + k 3

⎛

⎝ ⎜ ⎞

⎠ ⎟ E( ) S( )

€

E( ) =k 2 + k 3

k1

⎛

⎝ ⎜ ⎞

⎠ ⎟E T

k 2 + k 3

k1

⎛

⎝ ⎜

⎞

⎠ ⎟ + S

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( ) =k1 k 3 E( ) S( )

k2

+ k3

Urea Decomposition

€

rP =k 3E TS

k 2 + k 3

k1

⎛

⎝ ⎜

⎞

⎠ ⎟ + S

€

E T( ) = E( ) + E • S( )

€

= E( ) +k1

k 2 + k 3

⎛

⎝ ⎜ ⎞

⎠ ⎟ E( ) S( )

€

E( ) =k 2 + k 3

k1

⎛

⎝ ⎜ ⎞

⎠ ⎟E T

k 2 + k 3

k1

⎛

⎝ ⎜

⎞

⎠ ⎟ + S

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( ) =k1 k 3 E( ) S( )

k2

+ k3

Urea Decomposition

VMAX

rP

S

€

VMAX

2

Km

€

E T( ) = E( ) + E • S( )

€

= E( ) +k1

k 2 + k 3

⎛

⎝ ⎜ ⎞

⎠ ⎟ E( ) S( )

€

E( ) =k 2 + k 3

k1

⎛

⎝ ⎜ ⎞

⎠ ⎟E T

k 2 + k 3

k1

⎛

⎝ ⎜

⎞

⎠ ⎟ + S

€

rP = ′ k 3 E • S( ) W( ) = k 3 E • S( ) =k1 k 3 E( ) S( )

k2

+ k3

€

rP =k 3E TS

k 2 + k 3

k1

⎛

⎝ ⎜

⎞

⎠ ⎟ + S

Urea Decomposition

Types of Enzyme Inhibition

Types of Enzyme Inhibition

Types of Enzyme Inhibition

Types of Enzyme Inhibition

Types of Enzyme Inhibition