Viscosity Average Molecular Weight of Polystyrene

Polymers and Coatings Laboratory

California Polytechnic State University

Back in the early days of polymer chemistry at Cal Poly, a student was weighing out a sample of
expensive monodisperse (very narrow molecular weight distribution) polystyrene molecular
weight standard to use in calibrating a light-scattering instrument he had constructed. The student
weighed the sample out in a polystyrene weigh boat. Upon realizing it would be difficult to make
a quantitative transfer of the light, powdery solid, he added some of the solvent (p-xylene) to the
weigh boat to dissolve the sample for easier transfer. Can you guess what happened? Was his
advisor a happy camper?

This experiment makes use of the principle illustrated above to determine the viscosity average
molecular weight, Mv, of the polystyrene in an ordinary polystyrene cup. [Note: when synthetic
polymers are made, a distribution of molecular weights results; this distribution can be
characterized by several molecular weight averages, among them, Mn, the number average
molecular weight (from colligative properties), Mw, the weight average molecular weight
(obtained from light scattering), and Mv, the viscosity average molecular weight. The ratio of
Mw/Mn is called the polydispersity and is a measure of the width of this distribution]

A measured mass of cut-up cup pieces of weigh boat will be dissolved in p-xylene to make a
stock solution which will be diluted to make other solutions. The time required for a known
volume of these solutions (and the pure solvent) to flow through a viscometer will be measured.
The intrinsic viscosity will be determined for the polystyrene and using the Mark-Houwink
equation and constants for the p-xylene-polystyrene system, Mv of the polystyrene will be
determined.

Theory

Several viscosity expressions enter into this discussion.

η is the viscosity of the solution
ηo is the viscosity of the solvent
ηr = η/ηo is the relative viscosity
η - ηo
ηsp = = ηr - 1 is the specific viscosity
ηo
ηsp
[η] = lim c->o c is the intrinsic viscosity
This last equation comes from the Huggins equation:
ηsp
2
c = [η] + k'[η] c
and strictly applies only at very high dilution. A form of the above equation suitable for use at
higher concentrations is:
ηsp
log c = log [η] + K"[η]c
 ηsp ηsp
Thus, [η] is the intercept of a plot of c vs. c or log [η] is the intercept of a plot of log c vs.
c. Once [η] is obtained, Mv is obtained by using the Mark-Houwink equation:
[η] = K(Mv)a

where K and a are the empirical Mark-Houwink constants for the polymer-solvent pair chosen.

Capillary viscometers actually determine the kinematic viscosity which must be corrected for
solution density to obtain the true viscosity. These viscometers also must be calibrated using a
solvent of known viscosity. Since we are only interested in η/ηo and our solutions are fairly
dilute (so solvent and solution densities are approximately the same) we can assume
η/ηo = t/to
where t and to are the viscometer flow times for solution and solvent respectively.

Remember, viscosity is very temperature dependent, so all measurements must be performed in a

constant temperature bath at 25oC.

Experimental

Obtain a polystyrene (styrofoam) cup or polystyrene weigh boat and tear it into pieces small
enough to place in a 50 ml beaker. Weigh between 0.3-0.6 g of the polystyrene on an analytical
balance (not in a polystyrene weigh boat!). Place the polystyrene in a clean, dry 50 ml beaker.
Add about 25 ml (no need to measure exactly) of p-xylene (CAUTION! P-xylene is flammable
and somewhat toxic. Be sure no open flames are in use. Wearing of gloves when making
solutions is recommended. Place all p-xylene waste in the proper waste container. Do not pour
any p-xylene down the drain.) Stir until all of the polystyrene is dissolved (10-20 minutes).

Transfer the dissolved polystyrene to a clean, dry 50 ml volumetric flask (alternately, use a clean
flask which has been rinsed with p-xylene). Rinse the beaker with several small washings of p-
xylene and add to the flask. Carefully add p-xylene up to the calibration mark. Mix thoroughly.
Make up three additional solutions by successively diluting the original solution. In each case,
use a 25 ml volumetric pipet to obtain 25 ml of the solution to be diluted. Add this to a clean 50
ml volumetric flask. Add p-xylene to the flask up to the calibration mark. Mix thoroughly.

Using a 10 ml volumetric pipet, transfer 10 ml of p-xylene to a clean, dry viscometer. The

viscometer can be rinsed with acetone and dried with an aspirator. Place the viscometer in the
bath and allow to come to bath temperature (25oC). Using a pipet bulb, draw liquid up the
capillary, past the calibration mark. Release the bulb and start the stopwatch when the level
reaches the first calibration line. Stop the stopwatch when the level reaches the second
calibration line. The time should be measured to at least three significant figures. Repeat at least
twice more. Values should agree to within 1%. The average of these values is to. Remove the
viscometer from the bath, drain out the p-xylene, and rinse with a small sample of the most dilute
solution. Measure the time for this solution and use the same procedure for the other solutions.
Always obtain at least three time values for each solution. The average of these values is t.

Clean all glassware when done and place all solutions in the proper waste container.
Calculations

Determine the concentration, c, of each solution in g/ml. Obtain the relative and specific
ηsp
viscosity for each solution (remember, t/to = [η]/[ηo]). Using the Huggins equation, plot c vs.
ηsp
c . If this plot does not yield a satisfactory intercept, plot log c vs. c. Use Excel to fit your
data to a line or second order polynomial. Obtain the intrinsic viscosity, [η], from the intercept.

The Mark-Houwink constants for this polymer-solvent system are K = 0.0105 and a = 0.73 for
temperatures between 20-30oC and concentrations in g/ml. Using your [η] and these constants,
obtain Mv for this polymer.

Questions

1. Why do you suppose p-xylene was chosen as the solvent for this experiment? What shape do
you think the polymer molecules take when in solution? Does this differ from their shape in the
bulk or foam?

2. How would values of K and a be obtained for a "new" polymer?

References
1. Allcock, Lampe and Mark, Contemporary Polymer Chemistry, 3rd ed., pp. 451-467.
2. Painter and Coleman, Fundamentals of Polymer Science, pp. 343-353