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Answers To Problem Set #2: F P P P
Answers To Problem Set #2: F P P P
1. (20)
a). fA is the number of amine hydrogens, so fA = 4+m
(2)
(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)
(2)
(2)
pc =
2
= 0.816
3
(4)
1
1
2
=
=
1 + ( f 2) 1 + 0.5 (3 2) 3
(4)
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
(1)
(POH)c = r (PCOOH)c
(2)
(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)
1
( p A )c = ( pB )c =
1 + ( f 2)
1/ 2
(2)
(1)
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)
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
(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] = (
fk
R p = k p ( d )1/ 2[ M ][ I ]1/ 2
kt
(1)
(2)
(2)
(1)
(2)
(2)