CHEM 214 - Suggested Problems (9/21/04):

1. Calculate the percent conversion of acid at which gelation occurs in a mixture of 50 mol %
adipic acid, 40 mol % ethylene glycol and 10 mol % glycerol.
f avg = 2 ( 0.5 ) + 2 ( 0.4 ) + 3 ( 0.1) = 2.1

Carothers Approach:

pc =

f avg

2
2.1

0.952

pc = r 1 + ( f 2 )

Florys Approach:

We know:

and

r=

pc =

Finally:

1/ 2

[ f = 3]

3 ( 0.1)
= 0.272
3 ( 0.1) + 2 ( 0.4 )

1 mol COOH
= 0.909
1.1 mol OH

{( 0.909 ) 1 + 0.272 ( 3 2 )}

1/ 2

0.930

2. Poly(vinyl acetate) with an Mn = 100,000 g/mol is hydrolyzed to poly(vinyl alcohol).

Oxidation of the latter with periodic acid to cleave 1,2-diol linkages yields a poly(vinyl
alcohol) with DPn = 200. Calculate the fraction of head/tail and head/head linkages in the
poly(vinyl acetate).
C
H2

H
C

n
O
O
CH3

CHEM 214

Repeat unit = 86.09 g/mol

Initial DPn = 1162
DPn drops to 200 with addition of acid. On average, the parent
molecule is cleaved to form 5.81 smaller molecules, so it is
cleaved at 4.81 diol linkages.
So, H/H = (4.81/1162)*100% = 0.4 %

HW 1

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3. The benzoyl peroxide initiation of styrene follows the simplest kinetic scheme:
1/ 2

fk [ I ]
Rp = k p [M ] d
kt

with all rate constants and f being independent of conversion.

Derive an expression for the percent conversion p as a function of f , [ I ]o , rate constants
and time. Hint, you will have to determine the integrated rate laws for [M] and [I].
In the initiation step:
kd
I
2 Ri

d [I ]
= kd [ I ]
dt
[ I ] = [ I ]o e kd t

So,
Solving gives:

Now:

Rp =

Rearranging:

d [M ]
dt

d [M ]

[M ]
[M ]
ln
[ M ]o

Solving gives:

1/ 2

fk [ I ]
= k p [M ] d o
kt

e kd t / 2

1/ 2

fk [ I ]
= kp d o
kt

1/ 2

f [ I ]o
= 2k p

kt k d

e kd t / 2 dt

(1 e

kd t / 2

But, p is the percent conversion, and is defined as:

p=

[ M ]o [ M ]
[M ] ,
= 1
[ M ]o
[ M ]o

so
1/ 2

Finally:

CHEM 214

f [ I ]o
ln (1 p ) = 2k p

kt k d

HW 1

[M ]
[ M ]o

(1 e

= 1 p

kd t / 2

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4. The rate constant for benzoyl peroxide decomposition has a temperature dependence given
by kd = 3.0 1013 e Ea / RT where Ea = 123.8 kJ / mol and T is in Kelvin. Determine a useful
temperature range for benzoyl peroxide as a radical initiator (ie. 106 < kd < 105 M / s .)

We can rearrange the Arrhenius equation:

ln k = ln ( 3.0 1013 ) 123,800 J / ( 8.314 T )
T is in Kelvin, and we want ln k = 13.8 and ln k = 11.5 .

57.0o C < T < 74.8o C

This corresponds to

5. For the free-radical polymerization of 5 M styrene at 60 oC, k p = 74 and

kt = 3.3 106 1/ M i s . A typical initiation rate is 106 M / s . Assuming the rate of initiation
is constant:
(a) Calculate the steady-state concentration of free radicals

Rt = 2kt [ M i ] = Ri
2

Assume:
1/ 2

Now:

R
[ M i] = i
2 kt

1/ 2

106
=
6
2 3.3 10

3.89 107 M

Very SMALL!

(b) Calculate the time required to polymerize 20% of the monomer

d [M ]
= k p [ M ][ M i ]
dt
[ M ] = e k p [M i]t
[ M ] = k M i t
ln
]
p[
[ M ]o
[ M ]o
Rp =

We know
Integrating:

For 20% polymerization,

Finally: t =

CHEM 214

[ M ] / [ M ]o = 0.8

ln 0.8
ln 0.8
=
=
k p [ M i]
( 74 1/ M sec ) ( 3.89 107 M )

HW 1

7.8 103 sec = 2.15 hours

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6. Vinyl acetate at a concentration of 4 M in benzene is polymerized at 60 oC using benzoyl

peroxide (0.05 M) as the initiator. The rate constant kd is given above. You may assume an
initiation efficiency of 0.75, and that the termination mechanism is solely coupling. You
may also assume that chain transfer to initiator and polymer is negligible. The densities of
VA and benzene are 0.93 and 0.87 g/mL respectively.
Calculate:
(a) the rate of polymerization
1/ 2

R
R p = k p [ M ]o i
2 kt

We know:

But:

Ri = 2 fkd [ I ]o = 2 ( 0.75 ) 3.0 1013 e

123,800 / 8.314( 273.2 + 60 )

) ( 0.05)

Ri = 1.17 107 M / sec

k p2
1/ 2
R p = Ri [ M ]o
2k
t

Now:

k p2

2 kt

From Table 12.2 in CPC:

So:

R p = (1.17 107 )

1/ 2

1/ 2

1/ 2

= 0.13

( 4M )( 0.13)

1.78 104 M / sec

(b) the kinetic chain length

We know:

CHEM 214

= R p / Ri =

HW 1

1522

[unitless]

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(c) the DPn

We must consider all possible chain transfer reactions, except to initiator and polymer, which
we are told can be neglected.
So:
We know:

[ S ] , and R = R
1
R
= t + CM + CS
t
i
DPn 2 R p
[M ]
CM = 2.5 104 and CS = 1.2 104

Now we need [S]:

870 g Bz 1 mol

= 11.2 M
1L Bz
78 g Bz
This is not necessarily true, and to calculate a more accurate [Bz], we can use additive partial
molar volumes. Since this is not a PChem class, we will simply make the (poor) assumption
that the VA does not affect the concentration of solvent. Now:
1
1.17 107
11.2M
=
+ 2.5 104 + 1.2 104
4
4M
DPn 2 (1.78 10 )
Finally
This corresponds to

CHEM 214

1
= 3.36 10-4 , and DPn = 2976
DPn
M n = 310, 000 g / mol

HW 1

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