Lecture 03

Another example of developing rate expression for a non-elementary reaction:

Ex. Free radical addition polymerization kinetics

⇒ In general, such reactions include

1) Monomer
2) Initiator
3) Catalyst

, and the mechanistic steps are initiation, propagation, and termination.

𝑘𝑖
a) Initiation: 𝑎𝑀1 + 𝑏𝐼 → 𝑃1
𝑎𝑐𝑡𝑖𝑣𝑒 𝑝𝑜𝑙𝑦𝑚𝑒𝑟 𝑟𝑎𝑑𝑖𝑐𝑎𝑙
𝑚𝑜𝑛𝑜𝑚𝑒𝑟 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑜𝑟

(𝑝𝑒𝑟𝑜𝑥𝑖𝑑𝑒, 𝑠𝑢𝑛𝑙𝑖𝑔ℎ𝑡, 𝑈𝑉 𝑠𝑜𝑢𝑟𝑐𝑒, 𝑒𝑡𝑐)

(𝑒𝑔. 𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒, 𝑠𝑡𝑦𝑟𝑒𝑛𝑒)

𝑘𝑝𝑟
b) Propagation: 𝑃1 + 𝑀1 → 𝑃2
⋮
𝑘𝑝𝑟
𝑃𝑛−1 + 𝑀1 → 𝑃𝑛
𝑘𝑡
c) Termination: 𝑃𝑛 + 𝑃𝑚 → 𝑀𝑛+𝑚 𝑜𝑟 𝑀𝑛 + 𝑀𝑚 ,
(𝑖𝑛𝑎𝑐𝑡𝑖𝑣𝑒⁄𝑠𝑡𝑎𝑏𝑙𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠)

The rates of the reactions are developed as

𝑑𝑀1
⇒ = −𝑎𝑟𝑖 − 𝑘𝑝𝑟 𝑀1 ∑ 𝑃𝑛 (𝑟𝑖 =
𝑑𝑡
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑖𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑓𝑜𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑟𝑎𝑑𝑖𝑐𝑎𝑙𝑠)
𝑑𝑃1
⇒ = 𝑟𝑖 − 𝑘𝑝𝑟 𝑀1 𝑃1 − 𝑘𝑡 𝑃1 ∑ 𝑃𝑛
𝑑𝑡

⋮ 𝑖𝑛𝑐𝑙𝑢𝑑𝑖𝑛𝑔 𝑖𝑡𝑠𝑒𝑙𝑓(𝑃1 )

𝑑𝑃𝑛
⇒ = 𝑘𝑝𝑟 𝑀1 𝑃𝑛−1 − 𝑘𝑝𝑟 𝑀1 𝑃𝑛 − 𝑘𝑡 𝑃𝑛 ∑ 𝑃𝑛 (𝒏 ≥ 𝟐)
𝑑𝑡
𝑓𝑟𝑜𝑚 𝑝𝑟𝑒𝑣𝑖𝑜𝑢𝑠 𝑡𝑜 𝑓𝑜𝑟𝑚
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑃𝑛+1
1
Make use of PSSA (pseudo steady state assumption) or QSSA:

𝑑𝑃𝑛
≈ 0 (true for all reactions involving the short-lived reactive radical species)
𝑑𝑡

Add ∑𝑛 ∶

0 = 𝑟𝑖 − 𝑘𝑡 (𝑃𝑛 )2
(Thus, under the PSSA, the initiation and termination rates are equal)

𝑑𝑀1 𝑟
Therefore, = −𝑎𝑟𝑖 − 𝑘𝑝𝑟 𝑀1 √( 𝑖 ) (substitute 𝑃𝑛 𝑖𝑛 𝑡ℎ𝑒 1𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
𝑑𝑡 𝑘 𝑡

( usually, the amounts of

𝑟𝑖
= −𝑘𝑝𝑟 𝑀1 √( ) monomer is small
𝑘 𝑡
a ≈ 0)

𝑑𝑀1 𝑘 ( assuming the rate of initiation

= −𝑘𝑝𝑟 √( 𝑖 ) 𝐼 1⁄2 𝑀1 is 1st order, i. e. k i I )
𝑑𝑡 𝑘

rate at which monomer is consumed

or the rate of overall polymerization reaction

See the book by Froment and Bischoff on examples of polyethylene synthesis or thermal cracking
of the long-chain hydrocarbons in sunlight.

Homework (Froment & Bischoff, 2nd ed): 1.11, 1.12, 1.14 (development of rate
expression for the non- elementary reactions)

One more example of developing rate expression for a non-elementary reaction

(All catalytic reactions are non-elementary!)

𝑇=450𝑜 𝐶
𝑒𝑔. 𝐶𝑂 + 𝐻2 𝑂 → 𝐶𝑂2 + 𝐻2 (𝑤𝑎𝑡𝑒𝑟 − 𝑔𝑎𝑠 𝑠ℎ𝑖𝑓𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
(𝐹𝑒 − 𝑜𝑥𝑖𝑑𝑒𝑠)

- It is a non-elementary reaction (not exact path of the reaction)

Some introduction to catalyst:

′𝑋′ 𝑎𝑐𝑡𝑖𝑣𝑒 𝑠𝑖𝑡𝑒𝑠 (′𝑋 ′ )

(𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑖𝑐𝑎𝑙𝑙𝑦 𝑎𝑐𝑡𝑖𝑣𝑒)
2
Mechanistic steps (or elementary steps) are as follows:
𝑘1
𝐻2 𝑂 + 𝑋 → 𝐻2 + 𝑋𝑂
𝑘2 } 𝑒𝑙𝑒𝑚𝑒𝑛𝑡𝑎𝑟𝑦 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠/𝑠𝑡𝑒𝑝𝑠
𝑋𝑂 + 𝐶𝑂 → 𝐶𝑂2 + 𝑋

𝑑(𝐶𝑂) 𝑑(𝐻2 𝑂) 𝑑(𝐶𝑂2 ) 𝑑(𝐻2 )

1) 𝑟 = − =− = =
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑(𝐶𝑂)
2) = −𝑘2 [𝑋𝑂][𝐶𝑂]
𝑑𝑡
𝑑(𝑋𝑂)
3) = 𝑘1 [𝑋][𝐻2 𝑂] − 𝑘2 [𝑋𝑂][𝐶𝑂]
𝑑𝑡

𝑑(𝑋)
= −𝑘1 [𝑋][𝐻2 𝑂] + 𝑘2 [𝑋𝑂][𝐶𝑂]
𝑑𝑡

𝑑(𝑋𝑂) 𝑑(𝑋)
4) PSSA: = ≈0
𝑑𝑡 𝑑𝑡
𝑘1 [𝑋][𝐻2 𝑂]
[𝑋𝑂] =
𝑘2 [𝐶𝑂]
𝑘2 [𝑋𝑂][𝐶𝑂]
} identical expressions
[𝑋] =
𝑘1 [𝐻2 𝑂]

⇒ All it means is that we need one more independent equation.

Site conservation/balance:

[𝑋] + [𝑋𝑂] = [𝑋𝑜 ]

𝑡𝑜𝑡𝑎𝑙 𝑠𝑖𝑡𝑒𝑠 (𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦 𝑜𝑓
𝑓𝑟𝑒𝑒 𝑠𝑖𝑡𝑒𝑠 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑠𝑖𝑡𝑒𝑠 𝑡ℎ𝑒 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙)

(At any time, site is either ′𝑋′ or ′𝑋𝑂′)

[𝑋𝑜 ]𝑘1 𝑘2 [𝐶𝑂][𝐻2 𝑂] 𝑓(𝑇)𝜙(𝐶)

𝑟= ≠
𝑘1 [𝐻2 𝑂]+𝑘2 [𝐶𝑂]
(which is the feature of
an elementary reaction)
Note:

⇒ order of the reaction cannot be not defined here

(𝑒𝑔. 𝑟 ≠ 𝑘1 (𝐶1 )𝛼 (𝐶2 )𝛽 ⋯ )

3
 ⇒ Activation energy is also not defined here (there is no energy barrier or energy barrier diagram
per say)

However if k1 ≫ k 2 or k 2 ≫ k1 , the order of the reacton or E(apparent)can be calculated.

or r ≈ k 2 [𝑋𝑜 ][CO] or k1 [𝑋𝑜 ][H2 O]

Possibilities:

linear with the slope − E⁄R (always true for elementary reaction)
E is always + ve and unique.
ln(𝑘)
𝐸1
𝐸2 non − linear over the
entire temperature range
1⁄𝑇

𝐁𝐞 𝐜𝐚𝐫𝐞𝐟𝐮𝐥: there are two Es, but these are not true activation energies; these should be

termed as apparent activation energies.