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Thermodynamics of Polymerization: G O, Then Depolymerization Will Be Favored
Thermodynamics of Polymerization: G O, Then Depolymerization Will Be Favored
Thermodynamics of Polymerization: G O, Then Depolymerization Will Be Favored
• 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
• In practice:
Polymerization is favored at low temperatures: TSp is small
Depolymerization is favored at high temperatures: TSp is large
• Therefore, thermal instability of polymers results when TSp overrides Hp and
thus Gp > O; this causes the system to spontaneously depolymerize (if kinetic
pathway exists).
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
[M]c H o So
ln
[M]o RTc R
or
H S Behavior
- - Ceiling temperature
- + Always spontaneous toward polymer
+ + Floor temperature
+ - Never spontaneous toward polymer
H3C
CH3
H3C O Si S S
Si O S S
H3C CH3
O Si S S
Si O CH3 S S
H3C CH3
k2
~~(A+M) P
-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),
such that [COOH] = [OH] at all times, and the rate equation
becomes
-d[COOH]
= kexp[COOH]3
dt
1 1
= + 2kexpt
[COOH]2 COOHo
2
-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
Mn
may be defined Nas:
xMx
X n M o 18
Mo
18
Nx 1 P
M 1 2[COOH] kt
12
Mn o
2
o 18 (uncatalyzed)
Mn M o 1 [COOH ]o kt 18 (catalyzed)
Mn M o [COOH]o kt (catalyzed)
• Thus, we have:
No
Mn xM
x 1
o Prob(x) (7)
No
M o (1 p) xp x 1
x 1 (8)
2
No
1
xp x 1
(9)
x 1 1 p
Mo
Mn (10)
1 p
1 p
x 2 p x1 1 p 3 (12)
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
X n max
1 r
1 r
and M n max
1 r
Mo
1 r
1 r
Xn
1 r 2rp
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