Rudin & Choi: The Elements of Polymer Science & Engineering, 3rd Edition

Chapter 3

Solutions Manual

3-1

̅ (∑ ) ( ) .
[ ] ̅ ( )
alternatively: [ ] ∑( ) .

3-2
h/c
h (cm
c (g/100ml) (cm
HCCl3)
HCCl3)(100ml)/g
0.57 2.829 4.96
0.28 1.008 3.60
0.17 0.521 3.06
0.10 0.260 2.60

plot (h/c) against c. The intercept at c = 0 = (h/c)0 = 2.30 (cm HCCl3)(100 cm3)/g

Pressure exerted by a column of HCCl3 2.30 cm long:

- -

Dimensions of
Dimensions of

( ) -

If π/c is in cm2/s2, R should be in ergs/(mol K) to yield ̅ in g/mol.

( )
( ) ̅ -

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Solutions Manual 3-2

3-3
(a)
22.0
21.0
20.0
19.0
π/c
18.0
(J/kg)
17.0 y = 0.35x + 16.03
16.0
15.0
14.0
0 1 2 3 4 5 6 7 8 9 10 11 12
c (kg/m3)

(b) Range: 0 – 8 or 9 kg/m3

(c)

(d)

3-4
(a)
Also,

( )

[ ( ) ]

[ ( ) ( ) ]

(b) [ ( ) ]

[ ( ) ]

[ ( ) ]

At low c,

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Solutions Manual 3-3

( )

( )

( )

( )

(c) [ ( ) ]
When ,
( )[ ]

Since , is negative when .

3-5
c (dl/g) ηr ηsp ηinh
0.20 1.290 0.270 1.27
0.40 1.632 0.632 1.22
0.60 2.026 1.026 1.18

plot data as in Figure 3-8 to obtain [η] = 1.32 dl/g.

̅
̅ .

3-6
See the discussion connected with equation (3-97) in the text.

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Solutions Manual 3-4

3-7
̅ ∑ ( ) ( )
̅ ( )
∑

Light scattering measures ̅ . The results of such determinations will not be affected to
within experimental uncertainty. Membrane osmometry measures ̅ . These results will
be significantly affected.

3-8
for ̅ : sample A - vapor phase osmometry
sample B - membrane osmometry.
for ̅ : use light scattering in both cases.

Gel permeation chromatography could be used for ̅ and ̅ for both samples with a
suitable calibration.

3-9
No. See Section 3.3.2.

3-10
(a) vapor phase osmometry
(b) light scattering or gel permeation chromatography (with calibration)
(c) membrane osmometry.

3-11
(a) No. Osmometry yields ̅ (eq. (3-29)) and light scattering gives ̅ (eq. (3-56)).
The two averages are the same within experimental error only for polymers with very
narrow molecular weight distributions.

(b) No. The slope of the light scattering zero concentration line will be ideally twice that
in the osmometry plot (compare equations (3-24) and (3-53)).

3-12
(a) If each polymer molecule contained 2 terminal –COOH groups there are
moles in the sample. ̅ is then given by .

(b) It is assumed that there are 2 carboxylic acid groups per molecule.

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Solutions Manual 3-5

3-13

( )
R is defined per unit volume (see text in connection with eq. (3-47)).
( )

3-14
( ) [ ] [ ]
[ ]
[ ]

Huggins’ constant is dimensionless.

3-15
Standard deviation of the weight distribution,
√̅ ̅ ̅
By extension from equation (2-39) measure of skewness of the weight distribution is:

̅ ̅ ̅ ̅ ̅ ̅
(̅ ̅ ̅ )

3-16

( ) (c = concentration in g/dl = g/100cm3).

c grams solute has volume = c/ρ cm3
(ρ = apparent density of solute).
∴ volume fraction solute at concentration of
c g/100 ml solution .

( ) ( ) (v = specific volume)

( )

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