Lecture 20

Chemical Reaction Engineering (CRE) is the field that studies the rates and mechanisms of chemical reactions and the design of the reactors in which they take place.

Todays lecture
Pseudo Steady State Hypothesis (PSSH) Net Rate of Reaction of Active Intermediates is Zero

Reactive intermediate as shown (b); they cause noninteger reaction order or conteration in both numerator and denominator

An active intermediate is a molecule that is in a highly energetic and reactive state It is short lived as it disappears virtually as fast as it is formed. That is, the net rate of reaction of an active intermediate, A*, is zero. The assumption that the net rate of reactive intermediate is zero is called the Pseudo Steady State Hypothesis (PSSH)

rA* = riA* = 0
i =1
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Example The rate law for the reaction

A B+C
is found from experiment to be

rA =

kC2 A 1+ k C A

How did this rate law come about? Suggest a mechanism consistent with the rate law.
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Solution

(1)
(2)

A+A A * + A
k1
Activation

r1 A* = k1C

2 A

A * +A A + A
k2
Deactivation

r2A* = k 2 C A*C A

(3)
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A* B + C
k3

r3A* = k 3C A*

Pseudo Steady State Hypothesis r*A = 0

rA* = rA* = r1 A* + r2 A* + r3 A*
= k1C2 k 2 C AC A* k 3C A* = 0 A
Solving for

C A*
C A* =

2 k1C A

k 3 + k 2C A

Net Rates: Rate of Formation of Product

rB = r3B = r3A* = k 3C A*

Substituting for C A* in Equation for the rate of formation of B is k1 k 3C 2 A rB = k 3 + k 2C A Relative rates overall

A B+C
rA 1 = rB 1

2 k1k3C A rA = rB = k3 + k 2C A

For high concentrations of A, we can neglect k 3 with regard to k 2 C A , i.e.,

k 2 C A >> k 3

and the rate law becomes

rA =
Apparent first order.

k1k 3 k2

C A = kC A

(10)

For low concentrations of A, we can neglect k 2 C A with regard to k3, i.e.,

k 3 >> k 2 C A

and the rate law becomes

k 3 k1 2 rA = C A = 2k1C 2 A k3

(11)

Apparent second order. Dividing by k3 and letting k=k2/k3 and k=k1 we have the rate law we were asked to derive

kC 2 A rA = 1 + k C A

(12)
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Active Intermediates
What about

Why so many Reactions Follow Elementary Rate Laws

rA = kC A

(1)

A + I k1 A * + I

(2) A * + I k2 A + I (3) A k3 B + C

k1k3C AC I rA = rB = = kC A k3 + k 2C I
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I0 = A + BC X I Let X = C X I 1 = I 0 A + BX
X concentration in denominator indicates X deactivates

Proposed mechanism : * Activation : M + CS 2 k1 CS 2 + M

* Deactivation : M + CS 2 k 2 CS 2 + M * X + CS 2 k3 CS 2 + X * Luminescence : CS 2 k 4 CS 2 + hv

* I = k 4 (CS 2 )

I ~ (CS 2 )
So the activated intermediate is from CS2
* M + CS 2 CS 2 + M

Use PSSH
* * * rCS * = 0 = k1 (CS 2 )( M ) k 2 (CS 2 )( M ) k3 ( X )(CS 2 ) k 4 (CS 2 )
2

I=

k 4 k1 (CS 2 )( M ) k 2 M + k3 X + k 4
Without alcohol X = 0 k k (CS 2 )( M ) I0 = 4 1 k 2M + k 4

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I0 = 1+ k ' X I