David R.

Smith1 Polymer Molecular Weight Distribution

and John W. Raymonda2
University of Arizona An undergraduate physical
Tucson, 85721

chemistry experiment

flflany undergraduate physical chemistry
laboratory texts contain an experiment on the deter-
mination of the molecular weight of a high polymer
either by osmotic pressure or intrinsic viscosity mea-
surements (1). However, to these authors’ knowledge,
none of the presently available experiments makes clear
the relationships between the average molecular weights
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PVOH should be dissolved slowly with stirring and
gentle heating. The PVOH is added to somewhat less
than I 1 of distilled water; the solution is transferred
quantitatively to a volumetric flask and the volume is
carefully brought up to 11.
P’or the viscosity determinations, we employ the
dilution type viscometer divised by Ubbelohde (5).

determined by different methods. We have devel- We did not obtain these commercially; rather, we had
oped an experiment in which the viscosity average standard Ostwald-Fenske type viscometers altered in
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(M„) and number average (Mn) molecular weights arc the departmental glass shop. A scale drawing of a
determined for samples of a given polymer; the factor typical instrument is shown in Figure 1. This viscom-
relating these may then be calculated and compared eter has the advantage that the pressure head driving
with theory. We feel that the student obtains a better the flow is independent of the total amount of solution
feeling for molecular weight distributions in polymers being used, as long as the solution does not rest above
by being required to consider explicitly the influence of the bottom of the capillary at quiescence. To make a
the distribution upon the magnitudes of the average run, the operator closes tube A and sucks solution into
molecular weights than is possible from a determination B with an aspirator bulb until it has risen above the
of just a single kind of average weight. It would, of upper fiduciary mark F\. Then B is held closed and A
course, be even better if we could have the students is opened. Now the solution below the capillary can
determine the weight average (Mw) molecular weight return to the ballast bulb E. The pressure head now is
also, but the necessary light scattering measurements always measured from the bottom of the capillary.
are beyond the scope of the usual undergraduate’s
abilities and require apparatus not generally available
as well.
The theory of polymer molecular weight statistics
has been treated by Flory (2) and need not be repeated
here. We have found the presentation in reference
(lb) excellent for our purposes. Supplementary refer-
ence material for undergraduates can be found in this
Journal (3, 4).
Materials, Apparatus, and Procedures
All measurements are done on polyvinyl alcohol
(PVOH). This polymer lias the advantage of being
readily soluble in water; thus the need for handling
large quantities of organic solvents such as toluene,
used as solvent in work on polystyrene (la), is elimi-
nated. It has the disadvantage that concentrated
solutions are prone to form, rendering quantitative
transfers difficult. Wc have used Elvanol® 71-30,3 a
completely hydrolyzed preparation with Mv of about
60,000. The apparatus and procedures employed are
those described in reference (lb) except for certain
modifications which wc now describe.
A stock solution of concentration no greater than 16
g/1 is made by the student. It is best to prepare this
well in advance of the planned working days since the
1
Present address: Department of Chemistry, University of
Oregon, Eugene, Ore. 97405.
2
To whom inquiries should be directed. Present address: Di- Figure 1, Scale drawing of Ubbelohde viscometer. All distances in cm.
vision of Physics, Rm 1057, National Research Council of Canada, dA = 0.6, djj = 0-8/ dc = 1.8, dE = 5.0. Fi and Ft are the fiduciary
marks. To operate, A is closed and solution is drawn by suction into B
100 Sussex Dr., Ottawa, Ontario KIA OR6, Canada. until it is above Fi. Then B is closed and A is opened. The solution below
s
We thank Dr. A. Beresniewiez of E. I. Du Pont de Nemours the bulb D drops back into reservoir E. Total volume of solution must be
and Co. for providing generous samples of several PVOH samples, such that level in tube B is below D at the end of a run. E holds about 50

including the Elvanol® 71-30. ml in this model.

Volume 49, Number 8, August 1972 / 577

The operator releases B and times the passage of the
solution from to F2 as in the usual viscosity mea-
surement.
Since flow times are independent of the volume of
solutions, measurements at a series of concentrations
can be made by successive dilutions right in the vis-
cometer. This has the advantages of speed and of
alleviating problems connected with cleaning the vis-
cometer when different solutions are introduced. As a
result, our students have been able to do measurements
of up to six concentrations in the time formerly required
for three. Concentrations approaching zero are espe-
cially easy to investigate simply by adding successive
pipets full of solvent. The student can collect enough
data that extrapolation of j?sp/c (lb) to its limit at
c =
0 can be made with confidence. Some sample data
collected by students is shown in Figure 2.
Figure 2. Some typical viscosity results found by students for uncleaved
Elvanol® 71-30. The upper line is r}$p/c versus c and the lower, flat line
is 1 /c In 7j/r]o* The lines are determined by least squares using only the
data of the authors (D. R. Smith). The lines extrapolate to [17]
[Mv = 60,000} and fo] = 0.848 [Mv = 60,000).
Viscometers having capillary sizes4 designated
50 and 100 were tried. The flow times vary from about
300 sec for water to 500 sec for polymer stock in the
size 50. This is well in excess of the recommended
100 sec (6) and is, in fact, so long as to be inconvenient.
Flow times for the size 100 were in the 60-100-sec range,
shorter than recommended. However, results obtained
\Vith both sizes agreed to within experimental error.
The osmometry was carried out using a Zimm-Myer-
son type osmometer similar to that shown in reference
(lb). It was found satisfactory to use retaining plates,
bolts, and nuts all of brass instead of the recommended
stainless steel, even though aqueous solutions were
being studied. Different metals cannot be used in the
same assembly because corrosion quickly occurs due to
electrolysis effects.
Cellulose membranes were employed. Fresh mem-
branes were conditioned by boiling in distilled water for
1 hr; membranes once conditioned were never allowed
to dry out.
Procedures followed reference (lb) exactly. Students
were given the choice of using the static method or the
half-sum method. Comparable results were obtained
by both methods.
Data and Calculations
The PVOH normally polymerizes in the so-called
"head-to-tail” fashion: —CH2—CHOH—CH2—
4
These sizes are those specified by Van Waters and Rogers for
their Cannon-Fenske viscometers. This vendor also can
an Ubbelohde-type viscometer in similar sizes.
578 / Journal of Chemical Education
CHOH—. However, a certain percentage of “head-
to-head” linkages are also present: —CH2—CHOH—
CHOH—CH2—. Following the procedures of refer-
ence (lb), these were cleaved with KI04, and Mn and
Mv were determined for both uncleaved and cleaved
polymer. The relationship between Mv and Mn for
PVOH having “the most probable distribution” of
molecular weights is (7)
M,/Mn 1.89 -
(1}
Values around 1.9 are typically found by the students
for the uncleaved polymer, in striking agreement with
the literature. However, for the cleaved polymer,
much smaller values are found, sometimes even less than
1. We attribute this to permeation of the membrane
by the lower molecular weight species. This problem
is nearly always present, even for heavy polymers, un-
less an extremely small-pore membrane is used. It
seems reasonable that the problem would be much more
severe for the degraded polymer. The expected result
is that osmotic pressures which are too low are observed,
leading one to calculate an M„ which is too high. We
are searching for a suitable membrane for use with low
molecular weight polymers in the hope that the student
can measure M,./Mn accurately for both uncleaved and
cleaved polymer. If the occurrence of “head-to-head”
linkages is random in the original polymer, the values
of Mt/Mn should be equal for cleaved and uncleaved
samples.
Suggested Research Project for Interested Students
Two partnerships have undertaken to fractionate the
uncleaved Elvanol® 71-30 in order: (1) to verify the
stated molecular weight distribution supplied with the
=
0.834
sample and (2) to observe the decrease of Mv/Mn to-
wards 1 that should occur as the molecular weight dis-
tribution is narrowed by measurement, of both M„ and
as
Mn for all the fractions. Fractionation was achieved
by adding isopropanol (iPOH) to an aqueous PVOH
solution causing precipitation of successively lower
molecular weight polymer as the iPOH content of the
solvent was increased. Fractions were separated by
decantation and washing. M, and Mn were measured
for each fraction as described above; the weight con-
centrations of the solutions were determined by weigh-
ing the polymer which remained after evaporating
aliquots to dryness.
The authors will be happy to provide further pro-
cedural details and sample data to interested persons.
Acknowledgment
The authors acknowledge fruitful conversations with
Professors James E. Mulvaney and Carl S. Marvel,
as well as the assistance of Professor Marvel in obtain-
ing PVOH samples from Du Pont. We thank
undergraduates Fern Wood, Julie Ramsey, Joseph
Tadano, and William Roberts for permission to repro-
duce their data.
Literature Cited
(1) For example see (a) Daniels, F. Williams, J. W., Bender, P., Alberty,
R. A., Cornwell, C. D,, and Harriman, J. E., “Experimental Physi-
cal Chemistry” (7th Ed.) McGraw-Hill Book Co., Inc., New York,
1970, pp. 329, 335; (5) Shoemaker, D., and Garland, C-, "Experi-
ments in Physical Chemistry’’ (2nd Ed.) McGraw-Hill Book Co., Inc.,
New York, 1967, pp. 272, 278.
(2) Flory, Paul J., "Principles of Polymer Chemistry," Cornell University
Press, Ithaca, New York, 1953, Chap. VII.
(3) Rudin, A., J. Chem. Educ., 46, 595 (1969).
(4) Palit, S. Rm J. Chem. Educ., 24, 199 (1947).
(5) See Billmeyer, F. W., "Textbook of Polymer Science,” John Wiley &
Sons, Inc., New York, 1962, p. 80.
(6) Billmeyer, op. cit., p. 81.
supply (7) Flory, P. S., and Leutner, F. S., J. Polymer Sci., 3, 880 (1948); 5, 267
(1950).