14-1

CHAPTER 14

POLYMER STRUCTURES

PROBLEM SOLUTIONS

Hydrocarbon Molecules
Polymer Molecules
The Chemistry of Polymer Molecules

14.1 The repeat unit structures called for are sketched below.
(a) Polychlorotrifluoroethylene

(b) Poly(vinyl alcohol)

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 14-2

Molecular Weight

14.2 Repeat unit weights for several polymers are asked for in this problem.
(a) For polytetrafluoroethylene, each repeat unit consists of two carbons and four fluorines (Table 14.3).
If AC and AF represent the atomic weights of carbon and fluorine, respectively, then

m = 2(AC) + 4(AF)

= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol

(b) For poly(methyl methacrylate), from Table 14.3, each repeat unit has five carbons, eight hydrogens,
and two oxygens. Thus,

m = 5(AC) + 8(AH) + 2(AO)

= (5)(12.01 g/mol) + (8)(1.008 g/mol) + (2)(16.00 g/mol) = 100.11 g/mol

(c) For nylon 6,6, from Table 14.3, each repeat unit has twelve carbons, twenty-two hydrogens, two
nitrogens, and two oxygens. Thus,

m = 12(AC) + 22(AH) + 2(AN) + 2(AO)

= (12)(12.01 g/mol) + (22)(1.008 g/mol) + (2)(14.01 g/mol) + (2)(16.00 g/mol)

= 226.32 g/mol

(d) For poly(ethylene terephthalate), from Table 14.3, each repeat unit has ten carbons, eight hydrogens,
and four oxygens. Thus,

m = 10(AC) + 8(AH) + 4(AO)

= (10)(12.01 g/mol) + (8)(1.008 g/mol) + (4)(16.00 g/mol) = 192.16 g/mol

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 14-3

14.3 We are asked to compute the degree of polymerization for polystyrene, given that the number-
average molecular weight is 500,000 g/mol. The repeat unit molecular weight of polystyrene is just

m = 8(AC) + 8(AH)

= (8)(12.01 g/mol) + (8)(1.008 g/mol) = 104.14 g/mol

Now it is possible to compute the degree of polymerization using Equation 14.6 as

Mn 500, 000 g/mol

DP = = = 4800
m 104.14 g/mol

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 14-4

14.4 (a) The repeat unit molecular weight of polypropylene is called for in this portion of the problem.
For polypropylene, from Table 14.3, each repeat unit has three carbons and six hydrogens. Thus,

m = 3(AC) + 6(AH)

= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol

(b) We are now asked to compute the number-average molecular weight. Since the degree of
polymerization is 15,000, using Equation 14.6

M n = (DP)m = (15, 000)(42.08 g/mol) = 631, 000 g/mol

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 14-5

14.5 (a) From the tabulated data, we are asked to compute M n , the number-average molecular weight.

This is carried out below.

Molecular wt
Range Mean Mi xi xiMi

10,000-20,000 15,000 0.03 450

20,000-30,000 25,000 0.09 2250
30,000-40,000 35,000 0.15 5250
40,000-50,000 45,000 0.25 11,250
50,000-60,000 55,000 0.22 12,100
60,000-70,000 65,000 0.14 9100
70,000-80,000 75,000 0.08 6000
80,000-90,000 85,000 0.04 3400
____________________________
M n = xi M i = 49,800 g/mol

(b) From the tabulated data, we are asked to compute M w , the weight-average molecular weight.

Molecular wt.
Range Mean Mi wi wiMi

10,000-20,000 15,000 0.01 150

20,000-30,000 25,000 0.04 1000
30,000-40,000 35,000 0.11 3850
40,000-50,000 45,000 0.23 10,350
50,000-60,000 55,000 0.24 13,200
60,000-70,000 65,000 0.18 11,700
70,000-80,000 75,000 0.12 9000
80,000-90,000 85,000 0.07 5950
___________________________
Mw = wi M i = 55,200 g/mol

(c) Now we are asked to compute the degree of polymerization, which is possible using Equation 14.6.
For polytetrafluoroethylene, the repeat unit molecular weight is just

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 14-6

m = 2(AC) + 4(AF)

= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol

And
Mn 49,800 g/mol
DP = = = 498
m 100.02 g/mol

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 14-7

14.6 (a) From the tabulated data, we are asked to compute M n , the number-average molecular weight.

This is carried out below.

Molecular wt.
Range Mean Mi xi xiMi

8,000-20,000 14,000 0.05 700

20,000-32,000 26,000 0.15 3900
32,000-44,000 38,000 0.21 7980
44,000-56,000 50,000 0.28 14,000
56,000-68,000 62,000 0.18 11,160
68,000-80,000 74,000 0.10 7400
80,000-92,000 86,000 0.03 2580
_________________________
Mn = xi M i = 47,720 g/mol

(b) From the tabulated data, we are asked to compute M w , the weight-average molecular weight. This

determination is performed as follows:

Molecular wt.
Range Mean Mi wi wiMi

8,000-20,000 14,000 0.02 280

20,000-32,000 26,000 0.08 2080
32,000-44,000 38,000 0.17 6460
44,000-56,000 50,000 0.29 14,500
56,000-68,000 62,000 0.23 14,260
68,000-80,000 74,000 0.16 11,840
80,000-92,000 86,000 0.05 4300
_________________________
Mw = wi M i = 53,720 g/mol

(c) We are now asked if the degree of polymerization is 477, which of the polymers in Table 14.3 is this
material? It is necessary to compute m in Equation 14.6 as

Mn 47,720 g/mol
m = = = 100.04 g/mol
DP 477

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 14-8

The repeat unit molecular weights of the polymers listed in Table 14.3 are as follows:

Polyethylene--28.05 g/mol
Poly(vinyl chloride)--62.49 g/mol
Polytetrafluoroethylene--100.02 g/mol
Polypropylene--42.08 g/mol
Polystyrene--104.14 g/mol
Poly(methyl methacrylate)--100.11 g/mol
Phenol-formaldehyde--133.16 g/mol
Nylon 6,6--226.32 g/mol
PET--192.16 g/mol
Polycarbonate--254.27 g/mol

Therefore, polytetrafluoroethylene is the material since its repeat unit molecular weight is closest to that calculated
above.

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 14-9

14.7 This problem asks if it is possible to have a poly(vinyl chloride) homopolymer with the given
molecular weight data and a degree of polymerization of 1120. The appropriate data are given below along with a
computation of the number-average molecular weight.

Molecular wt.
Range Mean Mi xi xiMi

8,000-20,000 14,000 0.05 700

20,000-32,000 26,000 0.15 3900
32,000-44,000 38,000 0.21 7980
44,000-56,000 50,000 0.28 14,000
56,000-68,000 62,000 0.18 11,160
68,000-80,000 74,000 0.10 7440
80,000-92,000 86,000 0.03 2580
_________________________
Mw = xi M i = 47, 720 g/mol

For PVC, from Table 14.3, each repeat unit has two carbons, three hydrogens, and one chlorine. Thus,

m = 2(AC) + 3(AH) + (ACl)

= (2)(12.01 g/mol) + (3)(1.008 g/mol) + (35.45 g/mol) = 62.49 g/mol

Now, we will compute the degree of polymerization using Equation 14.6 as

Mn 47,720 g/mol
DP = = = 764
m 62.49 g/mol

Thus, such a homopolymer is not possible since the calculated degree of polymerization is 764 not 1120.

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 14-10

14.8 (a) For chlorinated polyethylene, we are asked to determine the weight percent of chlorine added for
8% Cl substitution of all original hydrogen atoms. Consider 50 carbon atoms; there are 100 possible side-bonding
sites. Ninety-two are occupied by hydrogen and eight are occupied by Cl. Thus, the mass of these 50 carbon atoms,
mC, is just

mC = 50(AC) = (50)(12.01 g/mol) = 600.5 g

Likewise, for hydrogen and chlorine,

mH = 92(AH) = (92)(1.008 g/mol) = 92.74 g

mCl = 8(ACl) = (8)(35.45 g/mol) = 283.60 g

Thus, the concentration of chlorine, CCl, is determined using a modified form of Equation 4.3 as

mCl
CCl = x 100
mC + mH + mCl

283.60 g
= x 100 = 29.0 wt%
600.5 g + 92.74 g + 283.60 g

(b) Chlorinated polyethylene differs from poly(vinyl chloride), in that, for PVC, (1) 25% of the side-
bonding sites are substituted with Cl, and (2) the substitution is probably much less random.

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 14-11

Molecular Shape

14.9 This problem first of all asks for us to calculate, using Equation 14.11, the average total chain length,
L, for a linear polyethylene polymer having a number-average molecular weight of 300,000 g/mol. It is necessary
to calculate the number-average degree of polymerization, DP, using Equation 14.6. For polyethylene, from Table
14.3, each repeat unit has two carbons and four hydrogens. Thus,

m = 2(AC) + 4(AH)

= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol

and
Mn 300,000 g/mol
DP = = = 10, 695
m 28.05 g/mol

which is the number of repeat units along an average chain. Since there are two carbon atoms per repeat unit, there
are two CC chain bonds per repeat unit, which means that the total number of chain bonds in the molecule, N, is
just (2)(10,695) = 21,390 bonds. Furthermore, assume that for single carbon-carbon bonds, d = 0.154 nm and =
109 (Section 14.4); therefore, from Equation 14.11

L = Nd sin
2

109
= (21,390)(0.154 nm) sin = 2682 nm
2

It is now possible to calculate the average chain end-to-end distance, r, using Equation 14.12 as

r = d N = (0.154 nm) 21, 390 = 22.5 nm

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 14-12

14.10 (a) This portion of the problem asks for us to calculate the number-average molecular weight for a
linear polytetrafluoroethylene for which L in Equation 14.11 is 2000 nm. It is first necessary to compute the value
of N using this equation, where, for the CC chain bond, d = 0.154 nm, and = 109. Thus

L
N =

d sin
2

2000 nm
= = 15, 900
109
(0.154 nm) sin
2

Since there are two CC bonds per PTFE repeat unit, there is an average of N/2 or 15,900/2 = 7950 repeat units
per chain, which is also the degree of polymerization, DP. In order to compute the value of M n using Equation

14.6, we must first determine m for PTFE. Each PTFE repeat unit consists of two carbon and four fluorine atoms,
thus

m = 2(AC) + 4(AF)

= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol

Therefore
M n = (DP)m = (7950)(100.02 g/mol) = 795,000 g/mol

(b) Next, we are to determine the number-average molecular weight for r = 15 nm. Solving for N from
Equation 14.12 leads to

r2 (15 nm) 2
N = = = 9490
d2 (0.154 nm) 2

which is the total number of bonds per average molecule. Since there are two CC bonds per repeat unit, then DP
= N/2 = 9490/2 = 4745. Now, from Equation 14.6

M n = (DP)m = (4745)(100.02 g/mol) = 474,600 g/mol

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 14-13

Molecular Configurations

14.11 We are asked to sketch portions of a linear polypropylene molecule for different configurations
(using two-dimensional schematic sketches).
(a) Syndiotactic polypropylene

(b) Atactic polypropylene

(c) Isotactic polypropylene

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 14-14

14.12 This problem asks for us to sketch cis and trans structures for butadiene and chloroprene.
(a) The structure for cis polybutadiene (Table 14.5) is

The structure of trans butadiene is

(b) The structure of cis chloroprene (Table 14.5) is

The structure of trans chloroprene is

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 14-15

Thermoplastic and Thermosetting Polymers

14.13 This question asks for comparisons of thermoplastic and thermosetting polymers.
(a) Thermoplastic polymers soften when heated and harden when cooled, whereas thermosetting polymers,
harden upon heating, while further heating will not lead to softening.
(b) Thermoplastic polymers have linear and branched structures, while for thermosetting polymers, the
structures will normally be network or crosslinked.

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 14-16

14.14 (a) It is not possible to grind up and reuse phenol-formaldehyde because it is a network thermoset
polymer and, therefore, is not amenable to remolding.
(b) Yes, it is possible to grind up and reuse polypropylene since it is a thermoplastic polymer, will soften
when reheated, and, thus, may be remolded.

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 14-17

Copolymers

14.15 This problem asks for sketches of the repeat unit structures for several alternating copolymers.
(a) For poly(ethylene-propylene)

(b) For poly(butadiene-styrene)

(c) For poly(isobutylene-isoprene)

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 14-18

14.16 For a poly(acrylonitrile-butadiene) alternating copolymer with a number-average molecular weight

of 1,000,000 g/mol, we are asked to determine the average number of acrylonitrile and butadiene repeat units per
molecule.
Since it is an alternating copolymer, the number of both types of repeat units will be the same. Therefore,
consider them as a single repeat unit, and determine the number-average degree of polymerization. For the
acrylonitrile repeat unit, there are three carbon atoms, three hydrogen atoms, and one nitrogen atom, while the
butadiene repeat consists of four carbon atoms and six hydrogen atoms. Therefore, the acrylonitrile-butadiene
combined repeat unit weight is just

m = 7(AC) + 9(AH) + 1(AN)

= (7)(12.01 g/mol) + (9)(1.008 g/mol) + (14.01 g/mol) = 107.15 g/mol

From Equation 14.6, the degree of polymerization is just

Mn 1,000, 000 g/mol

DP = = = 9333
m 107.15 g/mol

Thus, there is an average of 9333 of both repeat unit types per molecule.

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 14-19

14.17 This problem asks for us to calculate the number-average molecular weight of a random
poly(isobutylene-isoprene) copolymer. For the isobutylene repeat unit there are four carbon and eight hydrogen
atoms. Thus, its repeat unit molecular weight is

mIb = 4(AC) + 8(AH)

= (4)(12.01 g/mol) + (8)(1.008 g/mol) = 56.10 g/mol

The isoprene repeat unit is composed of five carbon and eight hydrogen atoms. Thus, its repeat unit molecular
weight is

mIp = 5(AC) + 8(AH)

= (5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol

From Equation 14.7, the average repeat unit molecular weight is just

m = f Ib mIb + f Ip mIp

= (0.25)(56.10 g/mol) + (0.75)(68.11 g/mol) = 65.11 g/mol

Since DP = 1500 (as stated in the problem), M n may be computed using Equation 14.6 as

M n = m (DP) = (65.11 g/mol)(1500) = 97, 700 g/mol

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 14-20

14.18 For an alternating copolymer that has a number-average molecular weight of 100,000 g/mol and a
degree of polymerization of 2210, we are to determine one of the repeat unit types if the other type is ethylene. It is
first necessary to calculate m using Equation 14.6 as

Mn 100,000 g/mol
m = = = 42.25 g/mol
DP 2210

Since this is an alternating copolymer we know that chain fraction of each repeat unit type is 0.5; that is fe = fx =
0.5, fe and fx being, respectively, the chain fractions of the ethylene and unknown repeat units. Also, the repeat unit

molecular weight for ethylene is

ms = 2(AC) + 4(AH)

= 2(12.01 g/mol) + 4(1.008 g/mol) = 28.05 g/mol

Now, using Equation 14.7, it is possible to calculate the repeat unit weight of the unknown repeat unit type, mx.

Thus

m f e me
mx =
fx

45.25 g/mol - (0.5)(28.05 g/mol)

= = 62.45 g/mol
0.5

Finally, it is necessary to calculate the repeat unit molecular weights for each of the possible other repeat
unit types. These are calculated below:

mstyrene = 8(AC) + 8(AH) = 8(12.01 g/mol) + 8(1.008 g/mol) = 104.16 g/mol

mpropylene = 3(AC) + 6(AH) = 3(12.01 g/mol) + 6(1.008 g/mol) = 42.08 g/mol
mTFE = 2(AC) + 4(AF) = 2(12.01 g/mol) + 4(19.00 g/mol) = 100.02 g/mol
mVC = 2(AC) + 3(AH) + (ACl) = 2(12.01 g/mol) + 3(1.008 g/mol) + 35.45 g/mol = 62.49 g/mol

Therefore, vinyl chloride is the other repeat unit type since its m value is almost the same as the calculated mx.

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 14-21

14.19 (a) This portion of the problem asks us to determine the ratio of butadiene to acrylonitrile repeat
units in a copolymer having a weight-average molecular weight of 250,000 g/mol and a degree of polymerization of
4640. It first becomes necessary to calculate the average repeat unit molecular weight of the copolymer, m , using
Equation 14.6 as

Mn 250, 000 g/mol

m = = = 53.88 g/mol
DP 4640

If we designate fb as the chain fraction of butadiene repeat units, since the copolymer consists of only two repeat
unit types, the chain fraction of acrylontrile repeat units fa is just 1 fb. Now, Equation 14.7 for this copolymer

may be written in the form

m = f b mb + f a ma = f b mb + (1 f b )ma

in which mb and ma are the repeat unit molecular weights for butadiene and acrylontrile, respectively. These values

are calculated as follows:

mb = 4(AC) + 6(AH) = 4(12.01 g/mol) + 6(1.008 g/mol) = 54.09 g/mol

ma = 3(AC) + 3(AH) + (AN) = 3(12.01 g/mol) + 3(1.008 g/mol) + (14.01 g/mol)

= 53.06 g/mol.

Solving for fb in the above expression yields

m ma 53.88 g/mol 53.06 g/mol

fb = = = 0.80
mb ma 54.09 g/mol 53.06 g/mol

Furthermore, fa = 1 fb = 1 0.80 = 0.20; or the ratio is just

fb 0.80
= = 4.0
fa 0.20

(b) Of the possible copolymers, the only one for which there is a restriction on the ratio of repeat unit
types is alternating; the ratio must be 1:1. Therefore, on the basis of the result in part (a), the possibilities for this
copolymer are random, graft, and block.

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 14-22

14.20 For a copolymer consisting of 35 wt% ethylene and 65 wt% propylene, we are asked to determine
the fraction of both repeat unit types.
In 100 g of this material, there are 35 g of ethylene and 65 g of propylene. The ethylene (C2H4) molecular

weight is

m(ethylene) = 2(AC) + 4(AH)

= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol

The propylene (C3H6) molecular weight is

m(propylene) = 3(AC) + 6(AH)

= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol

Therefore, in 100 g of this material, there are

35 g
= 1.25 mol of ethylene
28.05 g / mol

and
65 g
= 1.54 mol of propylene
42.08 g / mol

Thus, the fraction of the ethylene repeat unit, f(ethylene), is just

1.25 mol
f (ethylene) = = 0.45
1.25 mol + 1.54 mol

Likewise,

1.54 mol
f (propylene) = = 0.55
1.25 mol + 1.54 mol

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 14-23

14.21 For a random poly(styrene-butadiene) copolymer in which M n = 350,000 g/mol and DP = 5000, we

are asked to compute the fractions of styrene and butadiene repeat units.
From Table 14.5, the styrene repeat unit has eight carbon and eight hydrogen atoms. Thus,

mst = (8)(12.01 g/mol) + (8)(1.008 g/mol) = 104.14 g/mol

Also, from Table 14.5, the butadiene repeat unit has four carbon and six hydrogen atoms, and

mbu = (4)(12.01 g/mol) + (6)(1.008 g/mol) = 54.09 g/mol

From Equation 14.7

m = f st mst + f bu mbu

Now, let x = fst, such that

m = 104.14x + (54.09)(1 x)

since fst + fbu = 1. Also, from Equation 14.6

Mn
DP =
m
Or

350,000 g / mol
5000 =
[104.14 x + 54.09(1 x)] g / mol

Solving for x leads to x = fst = f(styrene) = 0.32. Also,

f(butadiene) = 1 x = 1 0.32 = 0.68

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 14-24

Polymer Crystallinity

14.22 The tendency of a polymer to crystallize decreases with increasing molecular weight because as the
chains become longer it is more difficult for all regions along adjacent chains to align so as to produce the ordered
atomic array.

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 14-25

14.23 For each of four pairs of polymers, we are asked to (1) state whether it is possible to decide which is
more likely to crystallize; (2) if so, which is more likely and why; and (3) it is not possible to decide then why.
(a) No, it is not possible to decide for these two polymers. On the basis of tacticity, the isotactic PP is more
likely to crystallize than the atactic PVC. On the other hand, with regard to side-group bulkiness, the PVC is more
likely to crystallize.
(b) Yes, it is possible to decide for these two copolymers. The linear and syndiotactic polypropylene is
more likely to crystallize than crosslinked cis-isoprene since linear polymers are more likely to crystallize than
crosslinked ones.
(c) Yes, it is possible to decide for these two polymers. The linear and isotactic polystyrene is more likely
to crystallize than network phenol-formaldehyde; network polymers rarely crystallize, whereas isotactic ones
crystallize relatively easily.
(d) Yes, it is possible to decide for these two copolymers. The block poly(acrylonitrile-isoprene)
copolymer is more likely to crystallize than the graft poly(chloroprene-isobutylene) copolymer. Block copolymers
crystallize more easily than graft ones.

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 14-26

14.24 For this problem we are given the density of nylon 6,6 (1.213 g/cm3), an expression for the volume
of its unit cell, and the lattice parameters, and are asked to determine the number of repeat units per unit cell. This
computation necessitates the use of Equation 3.5, in which we solve for n. Before this can be carried out we must
first calculate VC, the unit cell volume, and A the repeat unit molecular weight. For VC

VC = abc 1 cos 2 cos 2 cos 2 + 2 cos cos cos

= (0.497)(0.547)(1.729) 1 0.441 0.054 0.213 + 2 (0.664)(0.232)(0.462)

= 0.3098 nm3 = 3.098 x 10-22 cm3

The repeat unit for nylon 6,6 is shown in Table 14.3, from which the value of A may be determined as follows:

A = 12(AC) + 22(AH) + 2(AO) + 2(AN)

= 12(12.01 g/mol) + 22(1.008 g/mol) + 2(16.00 g/mol) + 2(14.01 g/mol)

= 226.32 g/mol

Finally, solving for n from Equation 3.5 leads to

VC N A
n =
A

=
(1.213 g/cm3 )( 3.098 x 10 -22 cm3/unit cell)( 6.023 x 10 23 repeat units/mol)
226.32 g/mol

= 1 repeat unit/unit cell

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 14-27

14.25 (a) We are asked to compute the densities of totally crystalline and totally amorphous poly(ethylene
% crystallinity
terephthalate) (c and a from Equation 14.8). From Equation 14.8 let C = , such that
100

c ( s a )
C =
s (c a )

Rearrangement of this expression leads to

c (C s s ) + ca C s a = 0

in which c and a are the variables for which solutions are to be found. Since two values of s and C are specified

in the problem statement, two equations may be constructed as follows:

c (C1 s1 s1 ) + ca C1 s1 a = 0

c (C2 s2 s2 ) + ca C 2 s2 a = 0

In which s1 = 1.408 g/cm3, s2 = 1.343 g/cm3, C1 = 0.743, and C2 = 0.312. Solving the above two equations for
a and c leads to

s1 s2 (C1 C 2 )
a =
C1 s1 C 2 s2

(1.408 g/cm3)( 1.343 g/cm3)(0.743 0.312)

= = 1.300 g/cm3
(0.743) (1.408 g/cm3 ) (0.312) (1.343 g/cm3)

And

s1 s2 (C 2 C1)
c =
s2 (C 2 1) s1 (C1 1)

(1.408 g/cm3)( 1.343 g/cm3)(0.312 0.743)

= = 1.450 g/cm3
3 3
(1.343 g/cm )(0.312 1.0) (1.408 g/cm )(0.743 1.0)

(b) Now we are to determine the % crystallinity for s = 1.382 g/cm3. Again, using Equation 14.8

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 14-28

c ( s a )
% crystallinity = 100
s (c a )

=
(1.450 g/cm3)(1.382 g/cm3 1.300 g/cm3 )
100
(1.382 g/cm3)(1.450 g/cm3 1.300 g/cm3)

= 57.4%

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 14-29

14.26 (a)
We are asked to compute the densities of totally crystalline and totally amorphous
% crystallinity
polypropylene (c and a from Equation 14.8). From Equation 14.8 let C = , such that
100

c ( s a )
C =
s (c a )

Rearrangement of this expression leads to

c (C s s ) + ca C sa = 0

in which c and a are the variables for which solutions are to be found. Since two values of s and C are specified

in the problem, two equations may be constructed as follows:

c (C1 s1 s1) + ca C1 s1a = 0

c (C 2 s2 s 2 ) + ca C 2 s 2a = 0

In which s1 = 0.904 g/cm3, s2 = 0.895 g/cm3, C1 = 0.628, and C2 = 0.544. Solving the above two equations for
a and c leads to

s1 s2 (C1 C 2 )
a =
C1 s1 C 2 s 2

(0.904 g /cm3)( 0.895 g /cm3) (0.628 0.544)

= = 0.841 g/cm3
(0.628) (0.904 g /cm3) (0.544) (0.895 g /cm3 )

And

s1 s2 (C 2 C1 )
c =
s2 (C 2 1) s1(C1 1)

(0.904 g /cm3)( 0.895 g /cm3) (0.544 0.628)

= = 0.946 g/cm3
(0.895 g /cm3) (0.544 1.0) (0.904 g /cm3) (0.628 1.0)

(b) Now we are asked to determine the density of a specimen having 74.6% crystallinity. Solving for s
from Equation 14.8 and substitution for a and c which were computed in part (a) yields

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 14-30

c a
s =
C (c a ) c

(0.946 g /cm3)( 0.841 g /cm3 )

=
(0.746) (0.946 g /cm3 0.841 g /cm3) 0.946 g /cm3

= 0.917 g/cm3

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 14-31

Diffusion in Polymeric Materials

14.27 This is a permeability problem in which we are asked to compute the diffusion flux of oxygen
through a 15-mm thick sheet of low density polyethylene. In order to solve this problem it is necessary to employ
Equation 14.9. The permeability coefficient of O2 through LDPE is given in Table 14.6 as 2.2 x 10-13 (cm3 STP)-

cm/cm2-s-Pa. Thus, from Equation 14.9

P P P
J = PM = PM 2 1
x x

and taking P1 = 150 kPa (150,000 Pa) and P2 = 2000 kPa (2,000,000 Pa) we get

(cm3 STP)(cm) 2,000,000 Pa - 150, 000 Pa

= 2.2 x 10-13
cm2 - s - Pa 1.5 cm

(cm3 STP)
= 2.7 x 10-6
cm2 - s

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 14-32

14.28 This problem asks us to compute the permeability coefficient for carbon dioxide through high
density polyethylene at 325 K given a steady-state permeability situation. It is necessary for us to Equation 14.9 in
order to solve this problem. Rearranging this expression and solving for the permeability coefficient gives

J x J x
PM = =
P P2 P1

Taking P1 = 2500 kPa (2,500,000 Pa) and P1 = 4000 kPa (4,000,000 Pa), the permeability coefficient of CO2

through HDPE is equal to

(cm 3 STP)
2.2 x 10-8 (5 cm)
cm2 - s
PM =
(4,000,000 Pa - 2,500, 000 Pa)

(cm3 STP)(cm)
= 0.73 x 10-13
cm2 - s - Pa

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 14-33

14.29 This problem asks that we compute the diffusion flux at 350 K for water in polystyrene. It is first
necessary to compute the value of the permeability coefficient at 350 K. The temperature dependence of PM is

given in the problem statement, as follows:

Q
p
PM = PM exp

0 RT

And, incorporating values provided for the constants PM and Qp, we get
0

(cm 3 STP)(cm) 42,300 J/mol

PM = 9.0 x 10-5 exp
cm - s - Pa
2 (8.314 J/mol - K)(350 K)

(cm3 STP)(cm)
= 4.4 x 1011
cm 2 - s - Pa

And, using Equation 14.9, the diffusion flux is equal to

P P P
J = PM = PM 2 1
x x

(cm3 STP)(cm) 20,000 Pa - 1,000 Pa

= 4.4 x 10-11
cm2 - s - Pa 3.0 cm

(cm3 STP)
= 2.8 x 10-7
cm2 - s

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