Determination Molecular weight of polymers

using intrinsic viscosity method

Prepared by: Mahmoud Mohamed

ID: 141761
ABSTRACT
The experiment was carried out in order to calculate the average molecular weight of polystyrene-
toluene solution. Four samples of the polystyrene were prepared by dissolving 0.2-0.8 grams of
polystyrene in 100 ml toluene. Viscometer of Cannon-Fenske type was use in order to determine
the flow time for polystyrene solution as well as for the toluene. All calculations depend on the
flow time which leads to Huggins plot. Finally, using Mark-Houwink-Sakurada equation the
average molecular weight of the polymer was calculated to be 131496 g/gmole.

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CONTENTS
Abstract ........................................................................................................................................... 2

1 introduction ............................................................................................................................. 5

1.1 Capillary rheometry.......................................................................................................... 5

1.1.1 How does it work? .................................................................................................... 5

1.1.2 What is it useful for? ................................................................................................. 5

1.2 Methods of determining molecular weight of polymers .................................................. 6

1.2.1 Intrinsic viscosity method ......................................................................................... 6

1.2.2 GPC method .............................................................................................................. 6

2 Procedures ............................................................................................................................... 7

2.1 Equipment used ................................................................................................................ 7

2.2 Material provided ............................................................................................................. 7

3 Results ..................................................................................................................................... 8

4 Discussion ............................................................................................................................. 10

4.1 Sources of error .............................................................................................................. 10

5 Conclusion ............................................................................................................................ 11

6 Bibliography ......................................................................................................................... 12

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List of figures
Figure 1 Cannon-Fenske viscometer ........................................................................................... 5
Figure 2 Huggins Plot ................................................................................................................... 8
List of tables

Table 1 Calculations data ............................................................................................................. 8

List of equations

Equation 1 Huggins equation....................................................................................................... 8

Equation 2 Mark-Houwink-Sakurada equation ........................................................................ 9

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1 INTRODUCTION

1.1 CAPILLARY RHEOMETRY

1.1.1 How does it work?

A sample is forced to extrude through a barrel or die of well-defined dimensions under high
pressure. The pressure drop across the barrel or die is measured to give pressure-flow rate data for
the fluid, from which viscosity is calculated. Temperature and shear rate can be closely controlled
to simulate the processing environment of interest. (Rheometry, n.d.)

1.1.2 What is it useful for?

Originating in the polymer industry, capillary rheometry is useful for measuring the viscosity
profiles of suspensions and slurries containing relatively large particles, at high particle loadings.
Industrial examples include polymer melts, ceramic slurries, foodstuffs, inks and coatings.
Capillary rheometers can apply very high force, which enables the exploration of behavior at far
higher shear rates than is possible with rotational rheometry. High shear rate performance is
pertinent in many industrial processes, such as extrusion and spraying. For certain applications the
sample size required for capillary rheometry, around a liter for the generation of a flow curve, is a
limitation. (Rheometry, n.d.)

Figure 1 Cannon-Fenske viscometer

(Desiderio, 2014)

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1.2 METHODS OF DETERMINING MOLECULAR WEIGHT OF POLYMERS

1.2.1 Intrinsic viscosity method

The measurement of intrinsic viscosity is simple and inexpensive when compared with other
measurements related to the polymer MW. However, it can be time consuming, even if modern
semiautomatic instruments are used for that purpose. Measurements of intrinsic viscosity were
historically important in establishing the concept of macromolecules. The determination of the
intrinsic viscosity of a polymer essentially requires the measurement of the flow time of a polymer
solution through a glass capillary at different solution concentrations. A polymer solution passing
through a capillary obeys the Poiseuille’s law for laminar flow through capillaries, which indicates
that the pressure drop ∆P is directly proportional to the viscosity η of the fluid. (SALD´ıVAR-
GUERRA, 2013)

1.2.2 GPC method

Gel permeation chromatography (GPC), also known as size-exclusion chromatography (SEC), is
a chromatographic technique that employs specialized columns to separate natural and synthetic
polymers, biopolymers, or proteins on the basis of their size. GPC is the most widely used
technique for the analysis of polymers, in relation to other techniques of molecular weight (MW)
measurement; the analysis is very fast (compared to older techniques) and can be carried out in a
couple of hours. It can be used for samples soluble in organic and aqueous eluents, and for MWs
from approximately 100 to several million daltons (Da). With GPC, it is also possible to obtain the
MW of polymers that are soluble only at high temperatures. Besides, in contrast to traditional
techniques, it yields all MW averages and the molecular weight distribution (MWD).
(SALD´ıVAR-GUERRA, 2013)

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2 PROCEDURES
1. Four masses of polystyrene from 0.2 – 0.8 grams are weighed using a sensitive balance.
2. By using spatula, transfer each of the weighed masses into a separate 100ml flask plus an
empty flask.
3. Fill each flask with toluene till reaching the mark of the flask.
4. Cover the flasks using ground joint caps, and leave them for about 1 hour for swelling.
5. For 10 hours leave flasks on a shaker in order to dissolve the polystyrene.
6. Adjust the temperature of the thermostated bath at 25⁰C.
7. Using a pipette take pump the polystyrene solution till it fills the bulb inside the
viscometer.
8. Place the viscometer vertically inside the bath and record the flow time of each sample
starting from the mark located at the end of the bulb till the meniscus of the fluid reaches
the other mark on the viscometer.
9. Recorded time is then used in the calculations and graphical plots to determine the
average molecular weight.

2.1 EQUIPMENT USED

- Sensitive balance.
- Spatula.
- 100ml flask.
- Pipette.

2.2 MATERIAL PROVIDED

- Standard polystyrene of known molecular weight.
- Toluene.

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3 RESULTS

Table 1 Calculations data

Concentration (C) of Time (s) tps ᶯr= t/t0 ᶯsp = ᶯr − 1 ᶯred= ᶯsp/C
PS (g/dl)
2.001× 𝟏𝟎−𝟑 111 1.11 0.1 54.97
4.09× 𝟏𝟎−𝟑 142 1.43 0.43 105.13
6.09× 𝟏𝟎−𝟑 143 1.43 0.42 68.69
8.09× 𝟏𝟎−𝟑 154 1.54 0.54 66.74

As per Huggins equation the y intercept is the intrinsic viscosity = 51.907 cm3/g

ᶯSP
ᶯred= C
= [ᶯ] + k 2 [ᶯ]2 C
Equation 1 Huggins equation

Huggins Plot y = 2.1432x 51.907

80
70
60
50
nr/C

40
30
20
10
0
0 1 2 3 4 5 6 7 8 9
C (g/dl) x10-3

Figure 2 Huggins Plot

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In order to determine the molecular weight Mark-Houwink-Sakurada equation is used.

ᶯ = 𝐾𝑀𝑣𝑎
Equation 2 Mark-Houwink-Sakurada equation

K and a are MHS constants of toluene at 25⁰C

𝐾 = 7.5 × 10−3

𝑎 = 0.75

Then,

𝑀𝑣 = 131496 g/gmole

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4 DISCUSSION
The experiment is based on using the intrinsic viscosity method in order to calculate the molecular
weight of polystyrene. The calculations mainly depended on measuring the time of flow of both
solvent (toluene) and polymer solution (polystyrene-toluene solution). The flow time is equal to
the viscosity divided by the density the fluid. Relative viscosity or the viscosity ratio is determined,
which is a ratio between viscosity of the solution to the viscosity of the solvent. Calculation of the
relative viscosity in the experiment was carried out by getting the ratio between the flow time of
polystyrene solution to the flow time of toluene. The intrinsic viscosity is determined graphically
using Huggins plot which is the reduced viscosity (specific viscosity/ concentration of solution)
vs the concentration of solution. The y intercept is the intrinsic viscosity required. The plot showed
a direct proportionality trend between the concentration and the reduced viscosity. Finally, using
Mark-Houwink-Sakurada equation the molecular weight of the polymer was determined to be
131496 g/gmole. The determined value of the molecular weight was just 13% from the expected
value and this shows that the application of the intrinsic method was not accurate enough to get
the correct value of the molecular weight or even an acceptable value.

4.1 SOURCES OF ERROR

- Concentrations were not 100% accurate which could alter the viscosity of the samples.
- Recorded time was not accurate enough which affect the calculations that are mainly
based on the time of flow.
- Masses weighed were not accurate as desired.
- Polystyrene was no completely dissolved in the toluene which affect the viscosity of the
solution.
- The polystyrene itself was not well prepared.

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5 CONCLUSION
It was required to determine the average molecular weight of the polystyrene in toluene solution
and this was achieved by using the intrinsic viscosity method. The determination of the flow time
of the polystyrene solution and toluene was an important step in the calculations starting from the
relative viscosity then specific viscosity, and finally the reduced viscosity. Reduced viscosity is
plotted against the concentrations of the prepared polystyrene solutions constructing Huggins plot.
The y axis intercept was the required intrinsic viscosity that the left-hand side of Mark-Houwink-
Sakurada equation to calculate the average molecular weight. 131496 g/gmole was the value of
the determined average molecular weight of the polystyrene in toluene solution which was by far
smaller than the given value. The large gap between the two values was resulted form the errors
concerning preparation of the samples as well as errors from the viscometer itself.

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6 BIBLIOGRAPHY
Desiderio, N. (2014). Determination of Saybolt, Kinematic, and Shear Viscosity.

Rheometry. (n.d.). Retrieved from Malvern Panalytical :

https://www.malvernpanalytical.com/en/products/technology/rheometry

SALD´ıVAR-GUERRA, E. (2013). Handbook of Polymer Synthesis, Characterization, and

Processing. John Wiley sons .

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