Initiation step: “slow” rate determining step

𝑘𝑑
𝐼 → 2𝑅 ∙ 𝑘𝑑 ~ 10−4 − 10−6 /𝑠𝑒𝑐

Propagation step:

𝑅∙ + 𝑀 → 𝑅𝑀∙
𝐿
𝑅𝑀∙ + 𝑀 → 𝑅𝑀𝑀∙ 𝑘𝑝 ~ 102 − 104
𝑔𝑚𝑜𝑙 ∙𝑠𝑒𝑐
𝑘𝑝
∙
𝑅𝑀𝑛∙ + 𝑀 → 𝑅𝑀𝑛+1

Termination step
𝑘𝑡𝑐
Combination: 𝑅𝑀𝑥∙ + 𝑅𝑀𝑦∙ → 𝑅𝑀𝑥+𝑦 𝑅
𝑘𝑡𝑑
Disproportionation: 𝑅𝑀𝑥∙ + 𝑅𝑀𝑦∙ → 𝑅𝑀𝑥 + 𝑅𝑀𝑦

ktc + ktd = kt
𝐿
where 𝑘𝑡 ~ 106 − 108
𝑔𝑚𝑜𝑙 ∙𝑠𝑒𝑐

𝑑[𝐼]
Initiation: = −𝑘𝑑 [𝐼] 1st order kinetics
𝑑𝑡

Where [I] = concentration of the initiator at any given time, gmol/L

Where [I]0 = initial concentration of the initiator, gmol/L

⇒ [𝐼] = [𝐼]𝑜 𝑒 −𝑘𝑑 𝑡 (1)

 𝑑[𝑅 ∙ ]
= 2𝑘𝑑 [𝐼] 𝑓 − 𝑘𝑝 [𝑅 ∙ ][𝑀] (2)
𝑑𝑡

f = efficiency factor (< 1)

Pseudo steady state Hypothesis ⇒ active intermediates reach
steady state rapidly, so rate of change of their concentration is
approximately zero.
𝑑[𝑅 ∙ ]
⇒ ≈0
𝑑𝑡
𝑑 [𝑅 ∙ ]
= 2𝑘𝑑 [𝐼] 𝑓 − 𝑘𝑝 [𝑅 ∙ ][𝑀] ≈ 0
𝑑𝑡

𝑑 [−𝑀∙ ]
= 𝑘𝑝 [𝑅 ∙ ][𝑀] − 2𝑘𝑡𝑐 [𝑀∙ ][𝑀∙ ] − 2𝑘𝑡𝑑 [𝑀∙ ][𝑀∙ ] ≈ 0
𝑑𝑡

= 𝑘𝑝 [𝑅 ∙ ][𝑀] − 2𝑘𝑡 [𝑀∙ ]2 ≈ 0 where 𝑘𝑡 = 𝑘𝑡𝑐 + 𝑘𝑡𝑑 (3)

𝑓𝑘𝑑 [𝐼]
(2) and (3) ⇒ 𝑓 2𝑘𝑑 [𝐼] = 2𝑘𝑡 [𝑀∙ ]2 ⇒ [𝑀∙ ] = √
𝑘𝑡

Polymer Production Rate

Molar rate of monomer consumption (gmol monomer/Liter.sec)

−𝑑[𝑀] 𝑓𝑘𝑑
𝑅𝑝 = = 𝑘𝑝 [𝑀][𝑀∙ ] = 𝑘𝑝 √ [𝑀][𝐼]0.5
𝑑𝑡 𝑘𝑡

𝑘𝑑 𝑡
𝑑[𝑀] 𝑓𝑘𝑑 −
− = 𝑘𝑝 √ [𝐼]0.5
0 𝑒 2 dt
[𝑀] 𝑘𝑡
 𝑘 𝑡
[𝑀] 𝑓[𝐼] − 2𝑑
𝑙𝑛 [𝑀] = −2𝑘𝑝 ( 0 )0.5(1- 𝑒 )
0 𝑘𝑡 𝑘𝑑

Total mass of monomer consumed = Reaction volume x ([M]0 –[M]) x

mol wt of monomer

Rate of formation of polymer by mass (grams/s) =

Rate of consumption of monomer by mass (grams/sec)

Polymer “Quality”
Kinetic Chain length = average number of monomer units on a growing
polymer chain

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛

𝛾=
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑝𝑟𝑖𝑚𝑎𝑟𝑦 𝑟𝑎𝑑𝑖𝑐𝑎𝑙𝑠 𝑠𝑡𝑎𝑟𝑡𝑖𝑛𝑔 𝑎 𝑐ℎ𝑎𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑓𝑘
𝑘𝑝 √ 𝑘 𝑑 [𝐼]0.5 [𝑀] 𝑘𝑝 [𝑀]
𝑡
𝛾= =
2𝑓𝑘𝑑 [𝐼] 2√𝑓𝑘𝑑 𝑘𝑡 [𝐼]

Degree of Polymerization 𝐷𝑃)𝑛 = 2𝛾 if termination is by combination

𝐷𝑃)𝑛 = 𝛾 if termination is by disproportionation

𝟏
Summary: 𝜸 ∝ [𝑴], [𝑰]𝟎.𝟓
BUT 𝑹𝒑 ∝ [𝑴], [𝑰]𝟎.𝟓
Step-Growth Reactions
A – A + B – B → AABB
Reaction of end-group A with end-group B can be represented as
k=rate constant
~~~A + B~~~ → ~~~AB~~~

[𝐴]0 − [𝐴] = moles of A consumed = moles of B consumed =

[𝐵 ]0 − [𝐵 ]
⇒ [𝐵 ] = [𝐵 ]0 − [𝐴 ]0 + [𝐴 ] = [𝐴 ]
if [𝐴]0 = [𝐵]0 stoichiometric balance

Molar rate of consumption of A & B end groups

𝑑[𝐴] 𝑑[𝐵]
− = 𝑘 [𝐴][𝐵] ≡ −
𝑑𝑡 𝑑𝑡

(Multiply by molecular weight to get mass rate)

𝑑[𝐴]
− = 𝑘 [𝐴][𝐴] = 𝑘 [𝐴]2
𝑑𝑡

1 1
⇒ [𝐴] − [𝐴 =𝑘 𝑡
0]
[𝐴]0 −[𝐴]
Define extent of conversion of “A” end-groups 𝑃𝐴 = [𝐴]0

[𝐴] = [𝐴]0 (1 − 𝑃𝐴 ) = [𝐴]0 − 𝑃𝐴 [𝐴]0

1
(1−𝑃𝐴 )
− 1 = 𝑘 [𝐴 ]0 𝑡
In reality, stoichiometric imbalance is always present due to impurities:
[𝐴]0
[𝐵]0
=𝑅

If A is the limiting reactant, R < 1

[𝐴 ]0 − [𝐴 ] = [𝐵 ]0 − [𝐵 ] is still correct
[𝐴]0 1
[𝐵 ] = [𝐵 ]0 − [𝐴 ]0 + [𝐴 ] = − [𝐴]0 + [𝐴]0 − 𝑃𝐴 [𝐴]0 = 𝐴0 [ − 𝑃𝐴 ]
𝑅 𝑅

Molecular weight
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 𝑚𝑎𝑠𝑠
Average molecular weight = ≡ 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒𝑛𝑑−𝑔𝑟𝑜𝑢𝑝
𝑚𝑜𝑙𝑒𝑠
2

Average degree of polymerization of reaction mixture 𝑋̅𝑛 =

𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟
𝑚𝑜𝑙𝑒𝑠 𝑒𝑛𝑑−𝑔𝑟𝑜𝑢𝑝
𝑓𝑖𝑛𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑟 2

[𝐴]0 [𝐵]0
+ 2 [𝐴]0 +[𝐵]0
= 2
[𝐴]+[𝐵] = 1
[𝐴]0 −𝑃𝐴 [𝐴]0 +[𝐴]0 ( −𝑃𝐴 )
2 𝑅

1
[𝐴]0 (1+ ) 𝑅+1
𝑅
= 1 =
[𝐴]0 [1−𝑃𝐴 +( −𝑃𝐴 )] 𝑅+1−2𝑅𝑃𝐴
𝑅

2 1
= = for R = 1
2−2𝑃𝐴 1−𝑃𝐴

𝑋̅𝑛
Degree of polymerization of polymer D𝑃𝑛 = for AA and BB type
2
monomers