Chapter 5: Homework Solutions

1.

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 Chapter 5: Homework Solutions

2. Given: 45 wt% PS 55 wt% PP

Assume Total Weight = 1 gram

WPS W PS
.45 PS  
WTotal 1gram

W PS  .45 gramsPS

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 Chapter 5: Homework Solutions

WTotal  WPS  WPP

W PP  1gram  .45 g  .55 g

grams grams grams

RMM PP  8 * (12.01 )  8 * (1.008 )  104.14
mol mol mol

grams grams grams

RMM PS  3 * (12.01 )  6 * (1.008 )  42.08
mol mol mol

1mol PS
.45 grams PS   .00432mol PS
104.14 grams PS

1mol PP
.55 grams PP   .013mol PP
42.08 grams PP

.0043mol PS
Mole Fraction PS   .25
.00432mol  .013mol

3. Nylon 6,6 forms through condensation polymerization. A Nylon 6,6 chain with a degree
of polymerization of three will have three repeating units. The first step is shown below:

Step 1: In this step, a Nylon 6,6 chain with a degree of polymerization of two is formed
along with a water molecule.

Step 2: In this step, a Nylon 6,6 chain with a degree of polymerization of three is formed,
along with another water molecule. This reaction occurs when a monomer reacts
with the Nylon 6,6 chain formed in Step 1.

The final product in Step 2 is Nylon 6,6 with a degree of polymerization of three.

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 Chapter 5: Homework Solutions

4. The structure for polymethylmethacrylate is:

The relative molecular mass, RMM, and the degree of polymerization, D Pn , are related
through the following equation:

RMM= D Pn * MW

The molecular weight of one monomer of PMMA can be calculated as follows:

g g g g
MW= 5(12.01 ) + 2(15.99 ) + 8(1.008 ) = 100
mol mol mol mol

Since RMM = 120,000

g
120,000
RMM mol  1,200
D Pn  
MW g
100
mol

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 Chapter 5: Homework Solutions

5. In order to calculate the number average molecular weight, the total number of moles
must be determined. Table H.4-5 shows all the values determined during this process.

Table H.4-5
Range RMM Range Average RMM Mass Fraction Mass (grams) Moles (n)
1 0 – 2500 1,250 .03 .03 2.4 x 10-5
2 2,500 – 5,000 3,750 .12 .12 3.2 x 10-5
3 5,000 – 7,500 6,250 .08 .08 1.28 x 10-5
4 7,500 – 10,000 8,750 .24 .24 2.74 x 10-5
5 10,000 – 12,500 11,250 .22 .22 1.96 x 10-5
6 12,500 – 15,000 13,750 .15 .15 1.09 x 10-5
7 15,000 – 17,500 16,250 .11 .11 6.77 x 10-6
8 17,500 – 20,000 18,750 .05 .05 2.67 x 10-6
Total: 1 1 1.36 x 10-4

First, a total mass of 1 gram was assumed. Then, the average RMM value for each range was
determined. These values are recorded in the table above. Next, the mass of each range was
determined using the mass fraction and the total mass. Example calculations are shown
below, and all values are shown in the table above.

m1  1gram * .03  .03 grams

m2  1gram * .12  .12 grams

m3  1gram * .08  .08 grams

Next, the number of moles in each range were determined and recorded in the table.
Example calculations are shown below:

mol
n1  .03grams   2.4  10 5 mol
1,250 grams

mol
n2  .12 grams   3.2  10 5 mol
3,750 grams

mol
n3  .08 grams   1.28  10 5 mol
6,250 grams

After the number of moles in each range was determined, the total number of moles was
determined by adding all these values. The total number of moles is also recorded in Table
H.4-5. Next the number average molecular weight was determined.

WTotal 1gram grams

M n   7,345
 ni 1.36  10 mol
4
mol

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 Chapter 5: Homework Solutions

Next, the weight average molecular weight was determined.

M W
W M i i

g g g g2
Wi M i  (.03g ) * (1,250
mol
)  (.12 g ) * (3,750
mol
)  (.08 g ) * (6,250
mol
)  ....  10,350
mol
2
g
10,350
M W
 i i
W M mol  10,350 g
W 1g mol

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 Chapter 5: Homework Solutions

6. In order to calculate the number average molecular weight, the total number of moles
must be determined. Table H.4-6 shows all the values determined during this process.

Table H.4-6
Range RMM Range Average RMM Mass Fraction Mass (grams) Moles (n)
1 0 – 5,000 2,500 .01 .01 4.0 x 10-6
2 5,000 – 10,000 7,500 .10 .10 1.3 x 10-5
3 10,000 – 15,000 12,500 .12 .12 9.6 x 10-6
4 15,000 – 20,000 17,500 .14 .14 8.0 x 10-6
5 20,000 – 25,000 22,500 .18 .18 8.0 x 10-6
6 25,000 – 30,000 27,500 .25 .25 9.1 x 10-6
7 30,000 – 35,000 32,500 .13 .13 4.0 x 10-6
8 35,000 – 40,000 37,500 .07 .07 1.9 x 10-6
Total: 1 1 5.79 x 10-5

First, a total mass of 1 gram was assumed. Then, the average RMM value for each range was
determined. These values are recorded in the table above. Next, the mass of each range was
determined using the mass fraction and the total mass. Example calculations are shown
below, and all values are shown in the table above.

m1  1gram * .01  .01grams

m2  1gram * .10  .10 grams

m3  1gram * .12  .12 grams

Next, the number of moles in each range were determined and recorded in the table.
Example calculations are shown below:

mol
n1  .01grams   4.0  10 6 mol
2,500 grams

mol
n 2  .10 grams   1.3  10 5 mol
7,500 grams

mol
n3  .12 grams   9.6  10  6 mol
12,500 grams

After the number of moles in each range was determined, the total number of moles was
determined by adding all these values. The total number of moles is also recorded in Table
H.4-6. Next the number average molecular weight was determined.

WTotal 1gram grams

M n   17,274
 ni 5.79  10 mol
5
mol

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 Chapter 5: Homework Solutions

Next, the weight average molecular weight was determined.

M W
W M i i

g g g g2
W M i i  (.01g ) * (2,500
mol
)  (.10g ) * (7,500
mol
)  (.12 g ) * (12,500
mol
)  ....  22,500
mol
2
g
22,500
M W
 Wi M i
 mol  22,500
g
W 1g mol

7. Above the glass transition temperature, a polymer becomes more rubbery and flexible.
Therefore, the stress-strain curve would look like the one shown in Figure H.4-7a, since the
polymer is more capable of flexing and stretching before breaking.

Figure H.4-7a: A Ductile Stress-Strain Tensile Plot

Below the glass transition temperature, a polymer becomes harder and acts like a glassy material.
Below the glass transition temperature, the only movement in the chain is at the molecular level,
therefore making the polymer more brittle. Thus, the stress-strain curve looks more like that of a
brittle material, as shown in Figure H.4-7b below.

Figure H.4-7b: A Brittle Stress-Strain Tensile Plot

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 Chapter 5: Homework Solutions

8. Four different types of polymers listed in Table 4-1 are capable of forming both
syndiotactic and isotactic dyads. These polymers are listed in Table H.4-8 along with the
structures of their isotactic and syndiotactic dyads.

Polymer Isotactic Dyad Structure Syndiotactic Dyad Structure

Polymethylmethacrylate

Polypropylene

Polystyrene

Polyvinylchloride

9. A degree of polymerization of four means the polymer chain will have four repeats of the
monomer unit. This polymer will form through addition polymerization.

Step1: Initiation

Step 2: Propagation – In this step the chain lengthens until it reaches a degree of
polymerization of four. In the following steps, C3H3O2 will be substituted with
X, for simplicity.

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 Chapter 5: Homework Solutions

Step 3: - Termination – In this step, the last repeat unit is added to the chain, and the final
polymer chain is formed.

10. Table H.4-10 shows these polymers in order of best crystallization to worst
crystallization:
Table H.4-10
Polymer Monomer Structure

Polyethylene

Polypropylene

Polyvinylchloride

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 Chapter 5: Homework Solutions

Polyvinyldiene Chloride

Polyethylene has the highest crystallization because it is the most regular. All of the
substituents in the monomer are hydrogen. Therefore, this polymer has the best ability for
the polymer chains to pack close to one another. Crystallization will occur when the polymer
chains are aligned in linear patterns throughout the polymer. Since polyethylene has the best
chance for close packing of strands, it is most likely that this polymer will be able to form
portions of crystallization throughout the polymer.

Polypropylene is the polymer with the next smallest substituent: a methyl group. Therefore,
this polymer has the second best ability to form sections of crystallization because it has the
second best ability to pack its strands close together.

Finally, polyvinyldiene chloride will be less likely to form sections of crystallization than
polyvinylchloride because PVDC has two chlorine substituents instead of one, as in PVC.
Therefore, PVC will be able to pack its chains more tightly, since only one of its substituents
is large.

11.
g W
M n  4,000 
mol  ni

1 mol
1,000 chains   1.66  10  21 mol
6.02  10 chains
23

W    ni   M n   (1.66  10  21 mol )(4,000

g
)  6.6  10 18 grams
mol

g2
1.96  1011
Mw 
n M i i
2

 mol  2.95  10 28 g / mol

18
W 6.6  10 grams

12. A blend is a mechanical mixture of two or more polymers, each with their own chains. A
copolymer is made up of two different monomers that are repeated in the polymer backbone,
as shown in the Figure below.

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 Chapter 5: Homework Solutions

13. a) Primary bonding in a PMMA chain occurs between the carbons in the
backbone of the chain. Secondary bonding occurs between molecules in adjacent
chains. Although the primary bonds in the backbone of the PMMA chain are
stronger than the secondary bonds formed between chains, the secondary bonds
govern the arrangement of the chains. In order to move the chains, a large
number of the secondary bonds must be broken. Although the individual strength
of these bonds is less than the strength of the primary bonds, the combined
number of secondary bonds that must be broken in order to move the chains is so
high that these bonds restrict the movement of the chains.

a. PMMA can form both isotactic and syndiotactic dyads. These isomers are
shown below in Table H.4-13.

Table H.4-13: Isomers of PMMA

Isotactic Syndiotactic

b. For simplicity, the CO2CH3 substituent is denoted in this portion as X.

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 Chapter 5: Homework Solutions

14. Two different combinations of functional groups in Figure 4-27 will undergo
condensation reactions with one another.

Acids and Alcohols:

Acids and Amines:

15. The melting temperature is the point at which a polymer changes from a hard, glassy,
rigid material into a flowing, liquid material. The glass transition temperature is the
temperature at which large scale segmental motion occurs. Below Tg, the polymer becomes
more flexible and rubbery, but not liquid.

16. The student’s statement is not correct because there is no one single definition of
crystallinity in a polymer. Many different methods including x-ray diffraction, relative
densities, and thermodynamic measurements can be used to measure the crystallinity of a
polymer. Each of these methods utilizes a different standard by which local order is counted
as crystalline. Therefore, the exact crystallinity of the sample will depend on the standard set
and the method used to conduct the measurement.

17. Table H.4-17 shows ten examples of household items that are made from polymers, as
well as the structure of each of these polymers. Obviously, many more examples are possible.

Item Polymer Structure

PVC Pipe PVC

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 Chapter 5: Homework Solutions

Water Bottle PET

Hard Contact
PMMA
Lenses

Nylon
Nylon
Stockings

Carpet Fibers PET

Car Tires Polybutadiene

Dishwasher-
Polypropylene
safe Plates

Saran Wrap PVDC

Garbage Bag HDPE

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 Chapter 5: Homework Solutions

Styrofoam Cup PS

18. Aramids are stronger than other polyamides because of a blend of in-chain and inter-
chain properties. Aramids have more than 85% of their amide groups bonded to two
aromatic rings. Polyamides are polymers in which less than 85% of their amide groups are
bonded to two aromatic rings. Aromatic rings are resonance stabilized and connect adjoining
carbons with more than one bond. Therefore, aramids are stronger than other polyamides
because of the presence of more aromatic rings. Most aramids are formed through a dry-jet
wet spinning process that results in near perfect alignment of the polymer chains, leading to
significant improvement in unidirectional strength.

19. There are several specific barriers to commercial recycling of polymers. The first, and
often the largest, is the manpower needed to collect, clean, and sort recycled commercial
products. It is difficult to distinguish between most commercial polymers by sight alone,
making sorting errors common. The second barrier is the presence of polymer blends,
copolymers, additives, and dyes that make the recycling process far more complex. Most
blends and copolymers are landfilled or incinerated because of these difficulties. Finally,
used polymers have been exposed to stresses in the environment such as light, oxygen, and
heat. These variables damage the polymer, and reduce its mechanical properties, which can
never be fully restored. Therefore, recycled polymers do not possess the same properties as
fresh polymers, limiting their potential uses.

20. In a polyethylene chain, the substituents are uniform, whereas in a polystyrene chain one
of the substituents is very different from the other substituents:

In the polyethylene molecule, all the substituents are small hydrogen molecules. When the
small hydrogen molecule attempts to rotate, the energy barrier caused by the interaction of
the electron clouds of the substituent hydrogen atoms is relatively small and easy to
overcome.

In the polystyrene molecule, the second carbon has the benzene ring attached. The large
benzene rings of adjacent dyads interact and create a large energy barrier to rotate out of the
most stable trans-state.

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 Chapter 5: Homework Solutions

21. In addition polymerization, a free radical attacks a double bond, which results in a longer
chain containing a free radical at one end. Because a free radical is very unstable, the free
radical then seeks out another double bond, and continues the process until a termination step
occurs. Therefore, in addition polymerization, the lengthening of the chain depends on the
attraction of a free radical to a double bond. The driving force for chain lengthening is the
instability of the free radical on the chain. The chain will continue to grow until it becomes
stable and the free radical becomes stable through a termination step.

In condensation polymerization, the end groups of the polymer chains must collide to form a
bond and lengthen the chain. This collision is less likely to occur than the free radical
finding a double bond during addition polymerization for various reasons. First, the end
groups are small compared to the relative size of the polymer chain, making it less probable
that two end groups will randomly collide. Second, the end groups are not attracted to one
another as the free radical is attracted to the double bond. There is no driving force that
causes the end groups to search for one another because the end groups are already stable.
Therefore, the chain will not lengthen unless two end groups randomly collide. Because the
end groups are stable, chain lengthening through condensation polymerization is less likely
to occur than through addition polymerization.

22. The mechanical properties of a polymer vary dramatically with molecular weight. A
narrow molecular weight distribution ensures that the mechanical properties of the sample
will be more uniform throughout the sample.

23. For a crystalline region to form, a regular pattern must occur in the arrangement of the
polymer chains. An ordered region is less likely to occur if the polymer backbones contain
irregular patterns, as in a copolymer. This is especially true for random and block
copolymers, in which there is no uniform order to the AB patterns of the monomers.
Alternating copolymers have a regular structure and are more likely to be crystalline than the
other forms .

24. a) The key properties for a flyswatter would be cost, flexibility, and sufficient toughness
to withstand some impact (during the swatting process). Low density polyethylene
(LDPE) is flexible, inexpensive, readily available, and ideal for the product.

b) A children’s picnic table must be strong enough to hold the weight of several children and
withstand some abuse during play. In addition, the material should be resistant to
weather and scratching. Both PVC and PP would fit these characteristics. However, PP
is likely a better choice because of lower cost and the lingering concerns about the health
and environmental effects of PVC.

c) Padding should be made using a material that is a good insulator that is also flexible. The
polymer should also be able to regain its original shape after the stress has been released.
Polyurethanes are a good choice for material to be used as padding various applications,
such as seat cushions. Polyurethanes regain their shape after stretching. In addition,
polyurethanes are resistant to sweat and body oils. Although polyurethanes are a bit more

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 Chapter 5: Homework Solutions

expensive than many other polymers, most padding are made by injecting large quantities
of air into the polymer, reducing the total material demand.

25. There are many different stages in the life cycle analysis of a plastic grocery bag. Plastic
grocery bags are typically made of LDPE. First, the petroleum or natural gas must be
extracted from the ground. Next, the ethylene must be manufactured using the raw materials
acquired. The ethylene must then undergo a polymerization reaction to form polyethylene
from the ethylene monomers. The polymers generally are produced as pellets by major
manufacturers and shipped in quantity to smaller companies. Next, the bags must be
processed and manufactured. The pellets are shaped into bags, colored through the addition
of dyes, and have advertising or other printing added to them. The bags are then shipped and
distributed to various grocery stores. The bag is then used and (hopefully) reused by
customers. After the bags are reused a number of times, the bags are recycled (with the
removal of inks and coloring agents) and reformed with fresh polymer into new materials.
The bags that are not recycled are disposed of by landfilling or incinerating.

26. Thermosets are polymers that cannot be melted and reformed due to cross-linking among
polymer chains. Thus, polymerization of thermosets must occur while the thermosets are in
their final form. Injection molding involves melting polymer pellets before injecting the
melted polymer into a mold to be reformed into the desired shape. Because thermosets
cannot be melted in this manner, thermosets cannot be injection molded.

27. The main difference between extrusion and injection molding is that extrusion produces
polymer in a continuous form, while injection molding produces polymer in individually
molded parts. During extrusion through a die, the polymer is continually forced through the
die at the end of the barrel, producing long sections of formed polymer. As long as the screw
continues to turn and pellets continue to be added to the hopper, the extrusion process will
continually produce sections of polymer. During injection molding, the screw used to force
the molten polymer into the mold uses a reciprocating action to mechanically melt the
polymer pellets. The molten polymer is then forced forward into a reservoir. Once a certain
amount of polymer (the shot size) fills the reservoir, the polymer is forced into a detachable
mold. The polymer is then allowed time to cool in the mold. Once cool, the mold is opened
and the final product is removed.

28. During extrusion and injection molding, polymer pellets are melted and reshaped into a
desired form. If the barrel temperature gets too low, the polymer could begin to harden
before passing through the die or into the mold. If the temperature becomes too high, the
polymer will be begin to degrade and the mechanical properties of the product will suffer.

29. The structure of polyisoprene is shown below in Figure H.4-29:

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 Chapter 5: Homework Solutions

Figure H.4-29: Polyisoprene

Mass of one structural unit:

Mass Unit  (12.01g )(5 Carbons)  (1.008g )(8 Hydrogens )  68.114 g

In order to calculate the number of structural units present:

unit
100 g   1.47units
68.114 g

The maximum number of crosslinkages per structural unit possible is two. Because less than
two structural units are present in this sample, only two crosslinkages can be formed in this
case.

30. The key to this problem is the relevant functional groups. PET is formed through
condensation polymerization, which often involves the reaction of an alcohol and acid. The
terephthalate end of the PET is acidic while the ethylene glycol end of the chain is an
alcohol. During the reaction between the alcohol and the acid ends of the chain, the acidic
end of the chain forms a hydronium ion, which is attracted to the hydroxide ion formed from
the end of the alcohol. The hydroxide ion then forms a covalent bond with the hydronium,
which forms the water molecule. This reaction cannot occur between two alcohol ends or
between two acidic ends of the polymer chains. Therefore, terephthalic end of the chain will
always react with the ethylene glycol end of the chain.

31. Polymers with additional branching are less dense, less crystalline, and less strong than
polymers that do not have a lot of branching. Polymers with lots of branching also melt at
lower temperatures. In addition, low density polymers are dissolved more easily with
solvents. Therefore, low density polymers, or those with additional branching, are easier to
recycle than polymers with less branching.

32. Constitution includes all of the issues related to bonding, such as primary and secondary
bond, branching, formation of networks, and end groups. Configuration is the spatial
arrangement of substituents around the main chain carbon atom that can only be altered by
breaking bonds. Conformation refers to the spatial geometry of the main chain and its
substituents that can be changed by rotation and flexural motion.

In polystyrene, the carbon atoms are bonded through primary bonds in the back bone of the
chain. The hydrogen and benzene rings are also attached through primary bonding to these
carbons. Secondary bonding may occur between chains through van der Waals attractions.
In terms of configuration, polystyrene can form isotactic dyads, syndiotactic dyads, or atactic
dyads. In addition, the most stable conformation of the polystyrene is in the trans-state. The
large benzene ring will make rotation difficult and make the polymer more rigid.

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