Determination of Intrinsic

Viscosity and MW OF Polystyrene

By/ Mohamed Ali Mohamed

ID/143445

Module leader: Prof Dr/ Mostafa Radwan

Teaching assistant: Esraa Darwish

Faculty of Chemical Engineering

Degree Year Three

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 Abstract
Molecular weight of most of polymers can be determined by different techniques such as Gel
Permeation Chromatography (GPC), Static Light Scattering (SLS) and intrinsic viscosity
measurement. Determination of molecular weight by intrinsic viscosity measurement is a simple
method for characterization of poly styrene. The aim of the experiment is to Determine the
intrinsic viscosity and MW of Polystyrene, by using different concentrations of polystyrene in
toluene were prepared and measurement was done at room temperature. The concentrations of
the polystyrene are 2.001,4.09, 6.09 and 8.06 (g/cm3). The flow time data was used to calculate
the intrinsic viscosity by extrapolating the reduced viscosity to zero concentration. The value of
intrinsic viscosity was then recalculated into the viscosity-average molecular weight using Mark-
Houwink equation to get the intrinsic viscosity equal to 51.78 (cm3/g) and the molecular weight
of the polystyrene equal to 131496 g/gmole.

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Contents
Abstract............................................................................................................................................2

1 Introduction..............................................................................................................................6

1.1 Molecular Weight.............................................................................................................6

1.2 Viscosity Average Molecular Weight...............................................................................7

1.3 How to calculate the molecular weight of the polymer....................................................7

1.4 Manual Constant Temperature Bath Systems.................................................................10

1.4.1 Advantages..............................................................................................................11

1.5 Cannon-Fenske Capillary Viscometers...........................................................................11

2 Experimental procedures, equipment and material used.......................................................12

2.1 Materials used.................................................................................................................12

2.2 Experimental procedures.................................................................................................12

3 Experimental results..............................................................................................................14

3.1 Data and chart.................................................................................................................14

3.2 Calculations steps............................................................................................................15

4 Discussion..............................................................................................................................16

5 Sources of error......................................................................................................................17

6 Conclusion.............................................................................................................................18

7 References..............................................................................................................................19

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 List of figures
Figure 1 Mwt Expression.................................................................................................................6
Figure 2 Bulb part from visco meter...............................................................................................7
Figure 3 Relative Viscosity equation...............................................................................................8
Figure 4 Specific viscosity equation................................................................................................8
Figure 5Reduced viscosity equation................................................................................................8
Figure 6Concn vs η..........................................................................................................................9
Figure 7 Inherent viscosity equation...............................................................................................9
Figure 8 Concentration vs η 2.........................................................................................................9
Figure 9 Final graph.....................................................................................................................10
Figure 10Mark Houwink equation................................................................................................10
Figure 11Cannon Instrument Company constant temperature bath..............................................10
Figure 12Cannon-Fenske Capillary Viscometers..........................................................................11
Figure 13Cannon-Fenske Capillary Viscometers..........................................................................12
Figure 14 Concentration vs Reduced viscosity.............................................................................14

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 List of tables
Table 1 Results table......................................................................................................................14

List of equations
Equation 1 Standard error.............................................................................................................17

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 1 Introduction
1.1 Molecular Weight
The molecular weight of a polymer molecule is the product of the degree of polymerization and
the molecular weight of the repeating unit. The polymer molecules are not identical but are a
mixture of many species with different degrees of polymerization, that is, with different
molecular weights. Therefore, in the case of polymers we talk about the average values of
molecular weights. Almost all properties of a polymer depend on the molecular weight and its
distribution, that is, low and high molecular weight polymers will have vastly different
mechanical and thermo-physical properties. For example, polymeric materials consisting of a
rather small number of repeat units (often called oligomers1) will be rather soft or even liquid
and will possess little or no strength whereas polymeric materials of high molecular weight will
be solid and have much improved mechanical properties. One usually observes a steep rise in the
mechanical and visco-elastic properties with increasing molecular weight until a certain
molecular weight is reached, beyond which the properties are nearly independent of the chain
length, that is, all properties will eventually reach an asymptotic value [ CITATION Shi07 \l
1033 ]. It was found, that the molecular weight dependence of many properties can be described
by an expression of the form as the following picture: -

Figure 1 Mwt Expression

Examples of properties that are very sensitive to the molecular weight are softening and melting
point, solution and melt viscosity, solubility, mechanical strength and moduli. Not only the
average molecular weight but also its distribution has a noticeable effect on the physical,
mechanical, and processing properties. In most cases, a narrow molecular weight distribution
will yield better mechanical and processing properties than a broad distribution because the low
molecular weight portion will act as a plasticizer and soften the polymeric material, whereas an
exceedingly high molecular weight portion will make processing of the polymer resin very

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difficult due to its disproportionately high contribution to the melt viscosity [ CITATION
Has93 \l 1033 ].

1.2 Viscosity Average Molecular Weight

Molecular weight can also be calculated from the viscosity of a polymer solution. The principle
is a simple one: Bigger polymers molecules make a solution more viscous than small ones do.
The molecular weight obtained by measuring the viscosity is a different from either the number
average or the weight average molecular weight. But it's closer to the weight average than the
number average [ CITATION Mez11 \l 1033 ].

1.3 How to calculate the molecular weight of the polymer

To calculate the Mwt of the polymer, that looks like the one in the picture, and let measure how
long it takes for a given volume of the solution to flow through it.

Figure 2 Bulb part from visco meter

To make sure, by measuring the same volume each time, then measure the time the level the
solution takes to drop from the first line (marked a in the picture) to the second line (marked b).
The big bulge in the tube between the two lines is to increase the volume between the two lines.
Without it, the time for the solution level to drop would be too fast to measure with just a
stopwatch. The time it takes for the solution level to drop, called an efflux time, by measuring
efflux times for solutions of our polymer solution at varying concentrations. for comparison
measure the efflux time of the pure solvent, with no polymer dissolved in it. So, the first thing is
to give a name to one of them call it t0. Then by starting to do some number crunching. The first

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thing is the calculation of the viscosity of the polymer solutions to the viscosity of the pure
solvent by taking the efflux time of the polymer solution at a given concentration (call this t) and
dividing it by t0, the efflux time for the pure solvent. This gives us what we call the relative
viscosity. By using the Greek letter η to denote the relative viscosity.

Figure 3 Relative Viscosity equation

Then by using the relative viscosity in minute, but first thing I to do some more number
crunching with the efflux times. This is time to look at the difference in the efflux times of the
solution and the pure solvent, relative to the efflux time of the pure solvent. By taking subtract
the efflux time of the pure solvent, t0 from the efflux time of the solution, t. Then we take the
answer and divide it by t0. The answer is the specific viscosity. As the following equations: -

Figure 4 Specific viscosity equation

Then by crunching some more on the specific viscosity then divide it by the concentration of the
solution in question, and the result will be the reduced viscosity: -

Figure 5Reduced viscosity equation

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figured out that the different reduced viscosity at each concentration. (by measuring lots of
different concentrations in this kind of experiment.) plot reduced viscosity on the y-axis, and
concentration on the x-axis, to get a plot that looks something like this:

Figure 6Concn vs η

Take the natural logarithm of the relative viscosity, and let's divide that number by the
concentration of the solution we measured. This gives us a number we call the inherent viscosity.

Figure 7 Inherent viscosity equation

The last steps will be repeated here, but there's a different inherent viscosity for each
concentration which is measures. Make a plot of inherent viscosity on the y-axis, and
concentration on the x-axis. To get a plot that looks like this: -

Figure 8 Concentration vs η 2

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Put the plots from both methods together to get a plot that looks like this, with the two lines
meeting at their common intercept:

Figure 9 Final graph

By using the intrinsic viscosity [n] to calculate molecular weight. calculate it with a simple little
equation:

Figure 10Mark Houwink equation

This is called the Mark-Houwink equation. M is what we call the viscosity average molecular

weight (at last1) and K' and a are the Mark-Houwink constants. There is a specific set of Mark-
Houwink constants for every polymer-solvent combination [ CITATION Ian89 \l 1033 ].

1.4 Manual Constant Temperature Bath Systems

In these systems, the direct-flow capillaries are immersed in a

highly accurate temperature-controlled bath. A sample of oil,
usually 10 ml, is suctioned into the tube until it reaches the start
point. Then, the suction is released to make the oil flow by
Figure 11Cannon Instrument Company constant
gravity through the controlled capillary section of the tube. temperature bath

Two or three marks are visible on the tube. An operator

observes the oil meniscus as it passes the start point and then measures the time taken for the oil

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to pass the final mark. The tubes are chosen so that the test takes at least 200 seconds to
complete, making it easier for manual timekeeping. ASTM D 445 is the technique for kinematic
viscosity and was initially written for the manual method.

1.4.1 Advantages
 Easy tube replacement

 Inexpensive

 Accurate

1.4.1.1 Disadvantages
 Opaque/dark oils require additional steps

 At least 10 ml of oil required

 Manual cleaning is required for tubes

 Slow operation and requires operator to monitor time manually (typically 10 samples per
hour) [ CITATION Con14 \l 1033 ].

1.5 Cannon-Fenske Capillary Viscometers

Cannon-Fenske Opaque Viscometers (reverse flow type) are
used for dark Newtonian liquids; especially suitable for liquids
so dark in colour that cannot be seen in a Cannon-Fenske
routine viscometer. Also used to study shearing stress and
shearing rate. Sample volume: approx. 12 ml. Precision: ±0.3%.
Value indicated at 40ºC and 100ºC in both bulbs. Cannon-
Fenske Routine Viscometers quickly and easily measure the
viscosities of transparent Newtonian liquids. Sample volume:
aprox. 7 ml. Precision: ±0.2%. With constant value indication at
+40 ºC and +100ºC [ CITATION Con14 \l 1033 ].

Figure 12Cannon-Fenske Capillary Viscometers

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 2 Experimental procedures, equipment and material used
2.1 Materials used
1- Standard polystyrene of known weight average molecular weight.
2- Toluene Annular.
3- Five 50 ml volumetric flask.
4- Shaker.
5- Cannon-Fenske Capillary Viscometers.
6- Manual Constant Temperature Bath Systems
7- Spatula.
8- Rubber pump.
9- Funnel.

2.2 Experimental procedures

1- Use the analytical balance to weigh five samples of dry standard polystyrene (PS). The weight
of the PS samples should be with range 0.1-0.4g.

2-Use the spatula to place each PS sample in a 50 ml volumetric flask and fill these flasks with
toluene using the glass funnel till their halves.

3-Cover the volumetric flasks by their ground joint caps and leave them for swelling about 1
hour.

4-Use the shaker for about 10 hours to accelerate the dissolving of PS in toluene until real
solutions are obtained.

5-Complete the flasks with toluene till the marks on their necks and shake two or three times for
good mixing.

6-The intrinsic viscosity, [η], is determined by measuring the flow times of PS solutions and
toluene in suspended level viscometer shown in figure.

7-The viscometer was held vertically in a thermostated bath at

suitable temperature by means of a brass plate which was

Figure 13Cannon-Fenske Capillary

Viscometers 12 | P age
cemented at right angles to the viscometer and bolted securely to a further plate attached
horizontally to the side of the bath.

8-A known volume of solution was pipetted into reservoir [D] through [A]. The liquid was
pumped into [C] by applying pressure to [A] with [B] closed off. When the bulb was full of
liquid the pressure was released. The times was noted for the liquid to flow between the two
fiducial marks X and Y with a stop-watch (accurate to within 0.1 seconds).

9-The intrinsic viscosity was obtained graphically by the extrapolation of linear plots of reduced
viscosity against concentration according to the Huggins equation.

10-Select the constants K,a of Mark-Houwink equation according to the experiment conditions
(Temperatures).

11-Apply Mark-Houwink equation to find the weight average molecular weight Mw for the PS
sample [ CITATION DrM19 \l 1033 ].

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 3 Experimental results
3.1 Data and chart
Table 1 Results table

Concentration Tim Relative Specific viscosity Reduced Intrinsic Viscosity

In e In viscosity ηsp = ηr -1 viscosity [η]= (ηsp /c) c=0
(g/cm3) Sec ηr = t/to ηr = ηsp / c (cm3/g)
C x 10-3 (cm3/g)
2.001 111 1.11 0.11 54.97
4.09 143 1.43 0.43 105.13
6.09 142 1.42 0.42 68.96 51.78
8.06 154 1.54 0.54 66.99

Reduced Viscosity Versus Concetration

120 105.13
eReduced Visocisty in (mL/g)

100

80 68.96 66.99
54.97
60

40 We must neglect
20 the point
0
1 2 3 4 5 6 7 8 9 (4.09,105.13) to get
Concentration in (g/mL more accurate trend
line between the
points. To get the following chart: -

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 Reduced Viscosity Versus Concetration
80
70
Reduced Visocisty in (mL/g)

f(x) = 4.43 x + 51.82

60
50
40
30
20
10
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5
Concentration in (g/mL)

Figure 14 Concentration vs Reduced viscosity

3.2 Calculations steps

By using Mark-Houwink equation to get the Mwt of the polystyrene as discussed in the
introduction: -

Equation 1 Mark Houwink equation

[η]=k M a

[η] = intrinsic viscosity = y- intercept from the graph.

k= 7.5 × 10-3 ml/g from the lab manual.

a= 0.75 from the lab manual.

[η]= y-intercept = 51.79 cm3/g

By substituting in the Mark-Houwink equation: -

51.79=7.5 × 10−3 M 0.75

M =131496 g/ gmole

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 4 Discussion
Dilute solution viscometry is a well-known analytical technique in polymer chemistry for
characterizing polymers in solution. The technique is based on the fact that dissolving a polymer
in a solvent increases the viscosity of the final polymer solution. The increase of viscosity
depends on the temperature, the type of polymer and solvent, the concentration of the polymer,
and the molar mass of the polymer. Generally, it can be said that the higher the molar mass of a
polymer, the higher the viscosity of the polymer solution will be. The viscosity of the pure
solvent and the viscosity of the polymer solution (polymer dissolved in solvent) are set in
relation to each other, which leads to a relative viscosity value. The flow behaviour of the
polymer solution is highly dependent on the molecular structure of the polymer as well as on
interactions of the molecules with each other in solution. As the molecular interactions decrease
with decreasing concentrations, viscosity measurements are carried out with very dilute
solutions. A solution free of any interactions between the polymer molecules could only be
reached in the state of the “ideal dilute solution. In this “ideal dilute solution” the concentration
approaches zero meaning that the polymer molecules are isolated from each other and only
interact with the solvent molecules. However, this state can never be reached and therefore small
polymer interactions have to be considered. Both the calculation of the reduced and the inherent
viscosity require the concentration value and therefore the intrinsic viscosity is an important
parameter as it is an extrapolation to a theoretical zero concentration. The sources of error that
can be happen in the experiment will be discussed in the sources of error part.

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 5 Sources of error
Errors are classified into type one error which take place between the interface and the
equipment while the second type is called type two error which takes place within the instrument
itself. Errors can be found in the electricity by using insufficient source of electricity, and there
will be errors in the used pipette, burette and flasks for each of the mentioned apparatus there
will a maximum error.

Moreover, the standard error of burette is ± 0.2 %, standard error of the pipette is ± 1%, and the
standard error of the flask is ± 1% and standard errors can be calculated as in the following:

Equation 2 Standard error

Smallest measurement value

Standard error = ×100 %
Total measurement value

Moreover, in this this experiment the manual constant temperature Bath Systems, it has a
maximum error of ± 0.1o C .Other errors within the instrument itself. other errors can take place
which are:

1) Concentration of the mixed solution of polystyrene and toluene was not prepared
accurate.
2) The taken concentration of the samples that will be studied are not accurate.
3) The obtained toluene was not clear and contain water.
4) The sensitive balance was not clean, so it was not calibrated.
5) Errors in the calculations due to wrong measurement.
6) Wrong time in taken the samples that will studied from the Cannon-Fenske Capillary
Viscometers.
7) The taken samples was not enough.
8) Errors in the calculations due to wrong reading taken or not accurate reading.

There are many ways to reduce the errors in this experiment which are:

1- All devices and settings must be digital devices to take more accurate readings and it
should be freshly calibrated.
2- Let the taken samples to dissolve to take more accurate readings.

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 3- Take more readings and repeat the steps all over again to make sure that the obtained
results are reliable and correct.

6 Conclusion
Polymer molecular weight determination will play an important role in the development of new
polymer materials, ongoing processing / production over the polymer’s lifecycle and its
performance in the finished product. A polymer's properties and performance are influenced by
its molecular weight distribution. A high molecular weight, for example, can influence both a
polymer’s brittleness as well as tensile strength. A low molecular weight can have an influence
on a polymer’s melt processing abilities. The molecular weight of the polymer is measured by
using viscometer and the molecular weight obtained by this technique is called viscosity average
molecular weight. The molecular weight of the polymer solution is very high, so the viscosity of
polymer solution is very high compared to that of pure solvent. The measurement of the viscosity
of a solution is simple and inexpensive, although somewhat time consuming. By using Cannon-
Fenske Capillary Viscometers and Manual Constant Temperature Bath Systems in the
experiment with the different concentrations of the polystyrene in toluene as the following
(2.001,4.09,6.09 and 8.06 g/cm3). The polymer solution is introduced into the reservoir of the
viscometer and aspirated to the upper bulb. Air is then admitted which causes the solution to
flow down the capillary by gravity at 25 Celsius to get that the intrinsic viscosity equal to 51.78
(cm3/g) and the molecular weight of the polystyrene equal to 131496 g/gmole

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 7 References
Constitució. (2014, 10 1). Kinematic Viscosity. Retrieved from Fungilab:
http://www.reotrade.cz/data/fungilab/fungilab-katalog-kulickovy-viskozimetr-kapilarni-
viskozimetry.pdf

D.Robb, I. (1989). Comprehensive Polymer Science and Supplements. In I. D.Robb,

Comprehensive Polymer Science and Supplements (pp. 733-758). London: Elsevier Ltd.

Hasegawa. (1993). Polymer scince. In Hasegawa, Polymer scince (pp. 279-283). New York:
Rokita.

Mezger, T. (2011). The Rheology Handbook. 3rd revised ed. In T. Mezger, The Rheology
Handbook. 3rd revised ed (pp. 258-260). New York: Vincentz Network.

Radwan, D. (2019). Polymer engineering lab manual. Cairo: The British University In Egypt.

Shigemasa, Y. (2007). Carbohydrate Polymers. In Y. Shigemasa, Polymer scince (pp. 640-644).

Okamoto.

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