Thermodynamics of Polymerization

• Thermodynamics of polymerization determines the position of the equilibrium

between polymer and monomer(s). Thus, it impacts both polymerization,
depolymerization, and degradation. The thermodynamics of polymerization of
most olefins is favorable due to the exothermic nature of converting  bonds into 
bonds. For cyclic compounds, the driving force for polymerization can vary over a
much wider range, and one observes a variety of behaviors ranging from
completely unreactive to spontaneously polymerizable under all conditions.

• The well known thermodynamic expression:

G = H - TS
yields the basis for understanding polymerization/depolymerization behavior.
• For polymerization to occur (i.e., to be thermodynamically feasible), the Gibbs free
energy of polymerization Gp < O.
• If Gp > O, then depolymerization will be favored.
 Thus: Any factor that lowers the enthalpy, H (i.e., makes Hp more negative), or raises
the entropy, S (i.e., makes S more positive), will shift the equilibrium towards
polymerization.

• Standard enthalpy and entropy changes, Hop and Sop are reported for reactants
and products in their appropriate standard states. Generally:
 Temperature = 25oC = 298K
 Monomer – pure, bulk monomer or 1 M solution
 Polymer – solid amorphous or slightly crystalline

• Polymerization is an association reaction such that many monomers associate to

form the polymer
 Regardless of mechanism, there is a large loss in the total number of rotational and
translation degrees of freedom in the total system as the monomers associate.
 This occurrence thus yields a major loss in entropy upon polymerization.
 Thus: Sp < O for nearly all polymerization processes.
• Since depolymerization is almost always entropically favored, the Hp must then
be sufficiently negative to composite for the unfavorable entropic term. Only then
will polymerization be thermodynamically favored by the resulting negative Gp.

• In practice:
 Polymerization is favored at low temperatures: TSp is small
 Depolymerization is favored at high temperatures: TSp is large

• Therefore, thermal instability of polymers results when TSp overrides Hp and
thus Gp > O; this causes the system to spontaneously depolymerize (if kinetic
pathway exists).

PSC 480/740 Kinetics

1
 Thermodynamics of Polymerization
(continued)
• Since most polymerizations are characterized by an exothermic propagation
reaction and an endothermic depropagation reaction, the activation energy for the
depropagation reaction is higher, and its rate increases more with increasing
temperature compared to the propagation reaction. As shown below, this results in
a ceiling temperature, defined as the temperature at which the propagation and
depropagation reaction rates are exactly equal at a given monomer concentration.
6

5
kdp
4
-1

3
k, sec

kp[M]
2
kp[M] - kdp
1
Tc
0
300 350 400 450 500 550 600
o
Temperature, K

• At long chain lengths, the chain propagation reaction

kp
Pn* + M *
Pn+1
kdp
• is characterized by the following equilibrium expression:
kp [  Pn*1 ] 1
 
kdp [  Pn* ][M] [ M ]c
• The standard-state enthalpy and entropy of polymerization are related to the
standard-state monomer concentration, [M]o (usually neat liquid or 1 M solution) as
follows: [ M]
G  H o  TSo  RT ln o
[ M]

PSC 480/740 Kinetics

2
 Thermodynamics of Polymerization
(continued)
• At equilibrium, G = 0, and T = Tc (assuming that Hpo and Spo are
independent of temperature).
[M]o
H o  Tc So   RTc ln
[M]c
• Or: H o
Tc 
[M]c
So  Rln
[M]o
• Or:

[M]c H o So
ln  
[M]o RTc R

• At [M]c = [M]o, Tc = Hpo/Spo

Specific Examples of Monomer - Polymer Equilibrium

kcal/mol cal/mol-deg (H/S)

Monomer Hp Sp Tc(oC)
Ethylene -21.2 -24 610
Isobutylene -12.9 -28 175
Styrene -16.7 -25.0 395
-methyl styrene -8.4 -24 66
2,4,6-trimethyl styrene -16.7 --- ---
TFE -37 -26.8 1100

• Notice the large variation in the -H values.

 ethylene > isobutylene - attributed to steric hinderance along the polymer
chain, which decreases the exothermicity of the polymerization reaction.
 ethylene > styrene > -metylstyrene - also due to increasing steric
hinderance along the polymer chain.
 Note, however, that 2,4,6-trimethylstyrene has the same -H value as
styrene. Clearly, the major effect occurs for substituents directly attached to
the polymer backbone.

PSC 480/740 Kinetics

3
 Thermodynamics of Polymerization
(continued)
• Other possible effects on Hp
 loss of resonance stabilization upon polymerization
 changes in bond hybridization
 changes in H-bonding between M and P states
 Notice the small changes in the Sp values. This small
variation is attributed to the loss of translational entropy
which is about constant from system to system.
• For the systems in the table above, the equilibrium at 25
oC (i.e., at the standard state condition) favors the

formation of polymer. This may be verified using the

equation we examined previously.
Go = -RT lnKeq
• As the temperature increases, the equilibrium constant
decreases (characteristic of an exothermic reaction).
When Tc is exceeded, Keq becomes less than 1, and
thus, depolymerization becomes the dominant process.
• It is very important to note that the Tc concept applies
only to closed systems at equilibrium. For open systems,
monomer may volatilize away, and thus,
depolymerization may occur well below the predicted Tc.
In fact, few polymers actually match their thermal stability
as predicted from the Tc approach.

PSC 480/740 Kinetics

4
 Experimental Determination of
Hop and Sop

• Hop - by direct calorimetric measurement of amount of heat

evolved when known amount of the monomer is converted to a
known amount of polymer.

or

• by heats of combustion of M and P which yields Hof (enthalpy

of formation) of M and P. The Hop is thus obtained by the
relationship:
1
ΔHop  ΔHof (Pn )  ΔHof (M)
n

• Sop - from the absolute entropies of M and P, such that:

1 o
ΔS o
p  ΔS (Pn )  ΔSo (M)
n

• The absolute entropies may be obtained from calorimetric

measurements of heat capacities of M and P over a wide T
range, as given by:
T
Cp
S (T)  
o
dT
0
T

PSC 480/740 Kinetics

5
 Floor Temperature Behavior
• Although the vast majority of all polymerizations possess negative H
and S, and hence display ceiling temperature behavior, four distinct
possibilities exist as outlined in the table:
• As stated earlier, -S for polymerization is almost universal.
 Therefore, for olefins and small cyclics, polymerization is possible at low
temperatures.
 However, many compounds are never spontaneous toward polymer due to
+H (e.g. cyclohexane, tetrasubstituted olefins)
• +S for polymerization is rare, but known examples exist (see below).
 This rare behavior leads to floor temperature behavior or entropy-driven
polymerizations.
 Floor temperature monomers are invariably large cyclics containing large
atoms from the third row and below of the periodic table, that yield polymers
with highly flexible chains.

H S Behavior
- - Ceiling temperature
- + Always spontaneous toward polymer
+ + Floor temperature
+ - Never spontaneous toward polymer

 Examples of monomers possessing a floor temperature:

H3C
CH3
H3C O Si S S
Si O S S
H3C CH3
O Si S S
Si O CH3 S S
H3C CH3

octamethylcyclotetrasiloxane (OMCTS) elemental sulfur

Hp ~ 0 Hp = 13.5 kJ/mole
o
Sp = 6.7 J/mole K Sp = 31 J/mole K
o

PSC 480/740 Kinetics

6
 The Reactivity of Large Molecules

• In general, when considering growing polymer chains (i.e.,

regardless of the type of polymerization mechanism), the
reactivity of the chain ends will be the primary focus in studying
the kinetics of the polymerization reaction.
 Thus, investigations of the kinetics of polymerization may be
simplified by assuming that the rate constant of the chain growth
reaction is independent of the size of the molecule to which the
reactive functional group is attached.
 The validity of the assumption that the rate of polymerization is
independent of changes in molecular size of the reactants may be
rationalized by observing the behavior of several small molecule
reactions.
• For reactions involving homologous series of reactants, the rate
constant levels off and becomes independent of molecular size
when n > 2.
• Note that this behavior is quite analogous to step-wise
polymerization.
• Further physical rationalizations for the underlying assumption
include:
1. The larger and heavier the molecule, the greater the distance
between the center of mass of the molecule and the reactive chain
end. Thus, the mobility of the reactive end group in solution is
much greater than the mobility of the molecular center of mass
(i.e., the average mobility of the total chain). This enhanced
mobility of the reactive sites yields an "encounter rate" which is
much greater than that predicted by the total molecular mass and
is approximately independent of the molecular size.
2. In most polymerization reactions, the diffusion rate of reactants
(i.e., the reactive chain ends and monomers) is much more rapid
than the chemical reaction.
PSC 480/740 Kinetics
7
 Dependence of kp on Molecular Size

PSC 480/740 Kinetics

8
 The Reactivity of Large Molecules
(continued)
• Consider the following kinetic scheme:
k
~~A + M k-1 ~~(A+M)

k2
~~(A+M) P

 where A is the reactive site, M is a monomer, (A+M) represents the

pair of reactants trapped in the "liquid cage", and P is the product
polymer.
• The rate constants k1 and k-1 represent diffusion rate constants
into and out of the liquid cage, while k2 is the rate constant for
the chemical reaction.
• Assuming a steady-state concentration of the trapped
reactants, the rate of polymer formation is given by:
d [P] k1k2
 [A][M]
dt k1  k2

• If the diffusion is much more rapid than the chemical reaction,

such that k-1>>k2, then:
d [P] k1
 k2 [A][M]
dt k1

• Since diffusion into the cage is affected by molecular size in the

same way as diffusion out of the cage, the effect of molecular
size cancels out of the rate expression.

PSC 480/740 Kinetics

9
 Kinetics of Condensation (Step-
Growth) Polymerization

• Step-Growth polymerization occurs by consecutive reactions in

which the degree of polymerization and average molecular
weight of the polymer increase as the reaction proceeds.
Usually (although not always), the reactions involve the
elimination of a small molecule (e.g., water). Condensation
polymerization may be represented by the following reactions:

Monomer + Monomer Dimer + H2O

Monomer + Dimer Trimer + H2O
Monomer + Trimer Tetramer + H2O
Dimer + Dimer Tetramer + H2O
Dimer + Trimer Pentamer + H2O
Trimer + Trimer Hexamer + H2O

• Generally, the reactions are reversible, thus the eliminated

water must be removed if a high molecular weight polymer is to
be formed.
• Based on the assumption that the polymerization kinetics are
independent of molecular size, the condensation reactions may
all be simplified to:

~~~~COOH + HO~~~~  ~~~~COO~~~~ + H2O

• Note that there are many types of step-growth polymerization

reactions which yield a wide variety of polymers including
proteins, nylons, and polyesters. Although similar treatments
apply to all step-growth polymerizations, this section will focus
on the kinetics of polyesterification.
PSC 480/740 Kinetics
10
 Kinetics of Condensation (Step-
Growth) Polymerization
• Polyesterification reactions are catalyzed by acid and the
mechanism is given by:
• Step 1: Fast Equilibrium
k1
R-(C=O)OH + H+ k-1
R-(C=OH)OH

• Step 2: Nucleophilic attack – slow, rate determining step

k2
R'-OH + R-(C=OH)OH R-C(OH)2-(OH )-R'
• Step 3: Loss of water
k3
R-C(OH)2-(OH )-R' R-(C=OH )-O-R' + H2O

• Step 4: Regeneration of catalyst

k4
R-(C=OH )-O-R' + H 2O R-(C=O)-O-R' + H+
• In this mechanism, step 1 is a fast equilibrium and step 2 is the
slow, rate-determining step, which follows the rate law:
-d [COOH]
= k2[R(C=OH )OH][R'-OH]
dt

By applying the fast equilibrium assumption, the rate law

becomes:
-d[COOH]
= k2Keq1[R-(C=O)OH][R'-OH][H+]
dt

PSC 480/740 Kinetics

11
 Polyesterification Without Acidic
Catalyst
• In this case, the carboxylic acid groups must themselves
function as the catalyst such that [H+]  [COOH] and thus,

-d[COOH]
= kexp[COOH]2[OH]
dt

where kexp includes k2, Keq1, and other constants of the acid-
base equilibrium of the carboxylic acid.
• For a stoichiometric feed ratio of the reactants at the
beginning of the reaction (t = 0),

[RCOOH]o = [R'OH]o = 2[HOOC-R-COOH]o = 2[HOR'OH]o

such that [COOH] = [OH] at all times, and the rate equation
becomes
-d[COOH]
= kexp[COOH]3
dt

which upon integration yields:

1 1
= + 2kexpt
[COOH]2 COOHo
2

PSC 480/740 Kinetics

12
 Polyesterification Without Acidic
Catalyst (continued)
• Consider the fractional conversion of the polymerization
reaction, P, expressed in terms of the fraction of COOH
groups (or OH groups) that have reacted:
[COOH]
XCOOH = p = 1 - or [COOH] = [COOH]o(1-p)
[COOH]o

Substitution into the integrated rate expression yields:

1
(1-p)2
= 1 + 2COOH 2
o k expt

 Note that experimental data for esterification reactions

show that plots of 1/(1-p)2 vs. time are linear only after ca.
80% conversion.
 This behavior has been attributed to the reaction medium
changing from one of pure reactants to one in which the
ester product is the solvent.
 Thus, the true rate constants for condensation
polymerizations should only be obtained from the linear
portions of the plots (i.e., the latter stages of
polymerization).

• For example, the kinetic plots for the polymerization of

adipic acid and 1,10-decamethylene glycol show that at
202oC, the third-order rate constant for the uncatalyzed
polyesterification is k = 1.75 x 10-2 (kg/equiv)2 min-1.
PSC 480/740 Kinetics
13
 Uncatalyzed Polyesterification

PSC 480/740 Kinetics

14
 Acid-Catalyzed Polyesterification

• Recall that the rate law from the acid catalyzed

polyesterification is given by:

-d[COOH]
= k2Keq1[R-(C=O)OH][R'-OH][H+]
dt
• If acid is added to the system, then by definition of a
catalyst, the acid concentraion remains constant.
• Furthermore, at the stoichiometric feed, [RCOOH] = [OH],
the rate expression becomes:
-d[COOH] = kexp[COOH]2
dt
and in terms of their fractional conversion of the reactive
groups,
1
= 1 + kexp[COOH]ot
1-p

 Thus a second-order plot of 1/(1-p) vs. time yields a linear

relationship.
 Note that experimental data are usually linear only beyond
ca. 80% conversion.
 The polyesterification of adipic acid catalyzed by p-toluene
sulfonic acid shows the the rate constant for reaction with
1,10-decamethylene glycol at 161 oC and 0.4% p-toluene
sulfonic acid is k = 9.7 x 10-2 (kg/equiv) min-1.
 Note that this rate constant is significantly larger than the
noncatalyzed rate constant.
PSC 480/740 Kinetics
15
 Catalyzed Polyesterification

PSC 480/740 Kinetics

16
 Time Dependence of the Degree of
Polymerization
• Consider a polyesterification of bifunctional monomers, at
a stoichiometric feed ratio.
• In general, a polymer of (AB)n may be formed in the
reaction:

HO-(C=O)-R-(C=O)-OH + HO-R'-OH  HO-(C=O)-R-(C=O)-O-R'-OH + H2O

or
HO-A-OH + H-B-H  HO-A-B-H + H2O

 where A and B are the structural units -(C=O)-R-(C=O)-

and -O-R-O-, respectively.
• If water is efficiently removed during the reaction (which
must be done to obtain high polymer), then the number of
COOH groups present is equal to the number of
 [COOH]o 1  p 
N
molecules present,  at all times.
[COOH]
V

 where N is the total number of molecules in the system and

V is the volume.
• Since the structural units A and B are never removed
during the reaction, the total number of structural units
present at all times is constant and equal to the number
N structural units
of initial molecules.  [COOH]o
V

PSC 480/740 Kinetics

17
 The Number Average Molecular
Weight in Polycondensation
• By defining the average degree of polymerization of the
system, Xn, as the average number of structural units per
molecule, the relationship becomes:
[COOH]o 1
Xn  
[COOH] 1 p
• This relationship is a special case of the Carother's
Equation.
 Note that for condensation polymers prepared from two
reactants, the average number of repeating units per
molecule is one-half the average degree of polymerization.
• If Mo is the average molecular weight of the structural
units, then the number average molecular weight, Mn

Mn 

may be defined Nas:
xMx
 X n  M o  18 
Mo
 18
 Nx 1 P

 where Nx is the moles of x-mer of mass Mx, and 18 is

added to account for the unreacted (HOH) groups at the
ends of each polyester chain.

• The following figure demonstrates the dependence of the

number average molecular weight on the fractional
conversion.
• Clearly, very high conversions are required in order to
obtain useful polymers of molecular weights greater than
10,000.
PSC 480/740 Kinetics
18
 Mn as a Function of Conversion

PSC 480/740 Kinetics

19
 The Number Average Molecular
Weight (continued)
• Using the kinetic relationships derived earlier, a
dependence of the molecular weight on reaction time
may be given by:

M 1  2[COOH] kt 
12
Mn  o
2
o  18 (uncatalyzed)

Mn  M o 1  [COOH ]o kt   18 (catalyzed)

• For large reactions times (i.e., for conversions greater

than 80%) the following approximations are reasonable.

Mn  M o [COOH]o 2kt (uncatalyzed)

Mn  M o [COOH]o kt (catalyzed)

PSC 480/740 Kinetics

20
 Molecular Weight Distributions of
Linear Condensation Polymers
• While the average degree of polymerization may be determined
at any time t using the above relationships, it is equally
important to know the distribution of molecular weights and the
dependence of this distribution on reaction time.
• Given a reacting system composed of an A-B type monomer,
we wish to define the number fraction of molecules, at a given
conversion, p, which contain exactly x structural units. A key
question becomes:
• What is the probability that a molecule selected randomly from
the polymerization mixture willO contain exactly
O x structural units?
H NH R C NH R C OH (1)
x-1

• p = conversion = fraction of COOH groups that have reacted at

time = t, and
• (1-p) = fraction of COOH groups remaining at time = t
• Thus, the probability of obtaining the molecule shown above is
given by (2)
x-1
Prob(x) = p (1-p)

• The chance that a randomly selected molecule contains exactly

x structural units is equal to the fraction of molecules composed
of x-mers, such that
Nx
 Prob(x)
N

PSC 480/740 Kinetics

21
 Molecular Weight Distributions of
(continued)
• where Nx is the number of x-mers in a system of N
molecules. Thus, the relationship becomes:
Nx  Npx 1 (1  p) (3)

• Therefore, we can see that Prob(x) is the mole fraction of

molecules containing x structural units
• If the evolved water is completely removed during the
polymerization, then
NCOOH = N = No(1-p) (4)

• where No is the initial number of molecules. Combining

eqs. (3) and (4) yields:

Nx = No (1-p)2 px-1 (5)

• As shown in the following Figure, for any given

conversion, p, low molecular weight polymers (i.e., the
low values of x) have the highest probability of being
formed in the total distribution.
• However, the distribution becomes broader and the
average molecular weight increases as the conversion
increases.

PSC 480/740 Kinetics

22
 Effect of Conversion on the Number
Distribution of Structural Units

Numerical distribution of the number of structural units in a condensation

polymer for various conversions.

PSC 480/740 Kinetics

23
 Molecular Weight Distributions of
(continued)
• The number average molecular weight is obtained from Prob(x)
and the definition of an average. Neglecting the weight of water
on the terminal groups of the condensation polymer, the
molecular weight of an x-mer is given by:
Mx-mer = xMo
(6)
where Mo is the average molecular weight of the structural units.

• Thus, we have:
No
Mn   xM
x 1
o Prob(x) (7)
No
 M o (1  p) xp x 1
x 1 (8)

• Now, it can be shown that for p ≤ 1,

2
No
 1 
 xp x 1
   (9)
x 1 1 p 

• Combining eqs. (8) and (9) yields:

Mo
Mn  (10)
1 p

PSC 480/740 Kinetics

24
 Molecular Weight Distributions of
(continued)
• The weight fraction of x-mers, Wx, may be defined as the total
weight of molecules containing exactly x structural units divided
by the total weight of polymer:
NxMx x(1  p) 2 p x 1
Wx  N o  No (11)
 N x M x (1  p) 2  xp x1
x 1 x 1

• The following is true for p ≤ 1:

1 p
 x 2 p x1  1  p 3 (12)

• Combination of eqs. (11) and (12) yields the simplification:

Wx  x(1  p)2 p x 1 (13)

• Again, the following Figure shows that this distribution of Wx

favors low molecular weight polymer at low conversions.
• In addition, the weight average molecular weight, Mw , may be
defined as:
No No No
M w   Wx M x  M o  xWx  (1  p) M o  x 2 p x 1
2
(14)
x 1 x 1 x 1

• In view of eq. (11) we have:

1 p 
M w  M o   (15)
1 p 

PSC 480/740 Kinetics

25
 Effect of Conversion on the Weight
Distribution of Structural Units

PSC 480/740 Kinetics

26
 Molecular Weight Distributions of
(continued)
• Combination of eqs. (10) and (15) shows that the
polydispersity is given by:
Mw
 1 p
Mn

PSC 480/740 Kinetics

27
 Effect of Non-Stoichiometric
Reactant Ratios
• The highest possible molecular weight is achieved in
polycondensation reactions using equal concentrations of
reacting groups.
• However, it is often desirable to produce a specific molecular
weight in polymerization. This is accomplished by designing
the system so that unreacted or unreactive end groups are
incorporated into the polymer. Since molecular weight is
inversely proportional to the number of end groups, this offers a
means for molecular weight control. We will consider three
types of systems.
• Type 1 – A system of A-A and B-B monomers in which the total
number of A functional groups, NA, is less than (or equal to) the
total number of B functional groups, NB. We define a
N
stoichiometric imbalance parameter,
r  A  1.0r, where,
NB

In this situation, reaction proceeds until the A groups are

completely consumed and all the chain ends possess
unreacted B groups. It is obvious that the greater the
stoichiometric imbalance, the more leftover B groups there will
be, and the lower the molecular weight.
• Type 2 – A system of A-A and B-B monomers in which
molecular weight control is achieved by the addition of small
amounts of a monofunctional monomer containing either a
single A or B group.
• Type 3 – A system of A-B monomers in which molecular weight
control is achieved by addition of small amounts of mono-
and/or polyfunctional monomers containing only A or only B
groups.

PSC 480/740 Kinetics

28
 Effect of Non-Stoichiometric
Reactant Ratios (continued)
• For all types of systems, the polymerization can be
designed to yield the desired through the use of the
Carother’s Equation. The key to this method is the
concept of number average functionality, favg. To
compute favg, one must first identify which is the minority
or deficient type of group, A or B. Thus for the case in
which the A groups are deficient in number,
2 N i (A)fi (A)
f avg 
N i

where,
N(A)’s = the number of moles of each type of monomer
carrying an A group
f(A)’s= functionality of each type of monomer carrying an
A group
N’s= the number of moles of each type of monomer present (A
and B)
2 2
• 
The Carother’s Equation fis:
p 
avg X n favg

• or Xn 
2
2  pfavg

Xn
• where,
p = the fractional conversion of the deficient groups
= the number average degree of polymerization
PSC 480/740 Kinetics
29
 Effect of Non-Stoichiometric
Reactant Ratios (continued)
• For Type 1 systems, the total number of molecules at
any time is given by:
 1 r 
N  N Ao 1  p  
 2r 
• With the degree of polymerization defined as the average
number of structural units per molecule, the average
degree of polymerization in terms of conversion and feed
ratio is now given by:
1 r
Xn 
1  r   2rp

• Note that at a stoichiometric ratio r = 1 the above

relationship reduces to the previous form:
1
Xn 
1 p

• In addition, the maximum average degree of

polymerization possible corresponds to a complete
conversion of the A groups (i.e., p = 1), such that:

X n max 
1 r
1 r
and M n max
1 r 
 Mo  
 1 r 

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 Effect of Non-Stoichiometric
Reactant Ratios (continued)
• For Type 2 systems (with NA ≤ NB + NB’)
NA
r
N B  2N B'
• where, NB’ = number of B groups contributed by a
monofunctional monomer, and

1 r
Xn 
1  r  2rp

• For Type 3 systems (with NA = NB)

NA
r
2N Bf
NB 
f
• where, NBf = number of B groups contributed by a
polyfunctional monomer, and f = functionality of
polyfunctional monomer, and,
1 r
Xn 
1  r  2rp

• All other cases should be treated using favg and the

general Carother’s Equation.

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 Branched and Cross-Linked
Condensation Polymers
• Mono and bifunctional monomers yield linear polymers;
however, if one of the reactants is a tri- or multifunctional
monomer, then a branched or crosslinked polymer will result.
• The general form of the Carothers equation allows the
possibility of calculating the conditions needed to avoid or
ensure the reaching of the gel point (i.e., the point of extensive
crosslinking).
• Since gelation is presumed to occur when the average degree
of polymerization becomes infinitely large, the Carothers
equation reduces to: 2
pc 
f avg

• where pc is the critical conversion.

• In practice, it is important to note that this approach often

overestimates the reaction point at which gelation occurs.
• This overestimation is attributed to the broad molecular weight
distribution in which the high molecular weight molecules reach
the gelation point before those which have the average value of
the molecular weight.

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