Answers to Problem Set #2

1. (20)
a). fA is the number of amine hydrogens, so fA = 4+m

(2)

b). This is a 4+m 2 system,

the critical value of probability of branching c=1/( fA -1) and p2= , so that
1
1
pc2 = (1 / 3)2 =
=
fA 1 3 + m
m
m= 6

(3)

c).
nAfA = nBfB
fA/fB = 10/2 =5
5 namine = nepoxy
Mamine = (60 + 6*57) g/mol = 402 g/mol
100 g (product) = 402 namine + 331 nepoxy = (402 + 5*331) namine
namine = 0.0486 mol
Wamine = 402*0.0486 = 19.543 g
Wepoxy = 100 19.543 = 80.457 g

(15)
(2)

2. (20)
total functional groups of dicarboxylic acid = 1.2x2=2.4 moles
total functional groups of alcohols = 0.4x3+0.6x2=2.4 moles
Thus, stoichiometric amounts of the reactants are used.
pA=pB, r = 1

(2)
(2)
(3)
(3)
(3)

(2)
(2)
(1)

favg = (2.4+2.4)/(1.2+0.4+0.6)= 2.18

(2)

Carothers Theory, Pc=2/ favg=0.917

(2)

Statistical Theory of Flory,

0.4 3
=
= 0.5
2.4
p A pB
p 2
p2
=
=
=
= 0.5
1 p A p B (1 ) 1 p 2 (1 ) 2 p 2
( p A p B ) c = pc2 =

pc =

2
= 0.816
3

(4)

1
1
2
=
=
1 + ( f 2) 1 + 0.5 (3 2) 3

(4)

Compared to the measured value of 0.866, the pc from Carothers Equation is

overestimated, and the pc from Statistics Equation is underestimated. Carothers Theory is

based on the Xn, tending to infinity. It neglects molecules with either higher or lower
Xn, and the largest molecules undergo gelation first. The simple statistical theory does
not take into account of possible intramolecular reactions between end-groups, which will
contribute to higher extend of reaction.
(3)
3. (25)
i) r = [COOH]/[OH] =1, = 0.194

# of functional groups from A f

= 0.194
total # of A groups

(1)

(POH)c = r (PCOOH)c

(2)

Carothers Eq. pc = 2/favg

(2)

Assume the total # of acid groups are 1 mol and total alcohol groups are 1 mol since r =1.
(1)
favg= Nifi/Ni
=(1+1)/(0.194/3+0.806/2+1/2)
=2.067
(2)

pc =

2
f avg

= 0.968

(2)

Statistic theory, since r =1,

1
( p A )c = ( pB )c =

1 + ( f 2)

1/ 2

Here, f=3, so (pA)c = (pB)c = 0.915

(2)
(1)

ii) r = [COOH]/[OH] =0.800, = 0.375

Carothers theory:
Assume the total acid groups are 0.8 mol and the total alcohol groups are 1 mol. (1)
Since r1, reaction proceeds until the deficient type of group, 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.
Here, we should calculate favg to obtain the critical extend of reaction, pc
favg= Nifi/Ni

favg =(0.8+1)/(0.375*0.8/3+0.625*0.8/2+1/2)
favg = 2.118

p=
pc =

2
favg

2
f avg

(2)

2
X n favg

= 0.944

(2)

Statistic theory, since r =0.8,

1
( pA )c =

r + r ( f 2)

r
( pB )c =

1 + ( f 2)

1/ 2

(2)

1/ 2

Here, f=3

( pCOOH )c = 0.953

(2)

( pOH )c = 0.763

(2)

4. (20)
Initiation:
kd

CN
N

CN
N2

N
NC

azobisisobutyronitrile (AIBN)
propagation:
CN

kp

CN

termination by combination
H2
C

H2
C
CH

CH

termination by disproportionation
H2
C

H
C

propagation:
CN

kp

CN

termination by combination
H2
C

H2
C
CH

CH

termination by disproportionation
H2
C

H
C
CH2

HC

(12)
14

C-AIBN will be the end group of polymer chains.

For combination, each chain has 2 14C-(CH3)2CN
For disproportionation, each chain has 1 14C-(CH3)2CN.

(4)

For polymer, Mn=1000kg/mol, radioactivity of 6x103 counts s-1 g-1= 6x109 counts s-1
mol-1
(2)
Each 14C-AIBN will generate two groups of 14C -(CH3)2CN. So the radioactivity of each
group is 3x109 counts s-1 mol-1.
Therefore, there are 2 14C-(CH3)2CN groups per PS molecule. So the termination is
100% combination.
(2)
5. (15)
(a) [M]0=4[M]0, [I]0= [I]0, (b) [M]0= [M]0, [I]0=4 [I]0,
(i) the total radical concentration at steady state,

fkd [I] 1/ 2
)
kt

(1)

(a) no change
(b) increasing by a factor of 2

(2)
(2)

[ M] = (

(ii) the rate of polymerization

fk
R p = k p ( d )1/ 2[ M ][ I ]1/ 2
kt

(1)

(a) increasing by a factor of 4

(2)

(b) increases by a factor of 2

(iii) the number-average degree of polymerization
k p [M ]
Xn =
q = ktd / kt (0 q 1)
(1 + q)(kt fkd [ I ])1/ 2
(a) increasing by a factor of 4
(b) decreasing by a factor of 2

(2)

(1)
(2)
(2)