Øvelser i Grænseflade- og Kolloidkemi, 28316

Laboratory Exercises in Colloid and Surface Chemistry

Exercise8

Properties of aqueous polymer solutions.

Dec. 2004. Institut for Kemiteknik, DTU

Room 237/bldg 229

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Øvelser i Grænseflade- og Kolloidkemi, 28316
Øvelse 8

Properties of aqueous polymer solutions.

This exercise will demonstrate some important features of aqueous polymer

solutions:
1. Viscosity of dilute polyelectrolyte solutions and effects of pH and
salinity.
2. Complex formation between a polymer and a surfactant.

Only few experiments are performed to demonstrate the phenomena studied.

The exercise also demonstrates the use of viscometry as a tool to monitor
changes in the interaction between molecules in solution.

1. Theory
The present exercise deals with the water solutions of low amounts of
polymers, modified by surfactants and electrolytes. Such solutions possess
rather nontrivial properties, since the molecules in them exhibit complex
interactions. Due to electrical and chemical forces, the molecules may exhibit
dissociation, change their shapes and form complexes. Correspondingly, the
properties of the solutions may vary depending on concentrations of different
compounds. In order to study the processes occurring in the solution, it is
necessary to select characteristic measurable properties, which strongly vary,
in spite of the insignificant variation of the concentrations. One such property
is viscosity of the mixture.

Viscosity is the property determining resistance of the mixture to the flux. This
resistance arises due to internal friction forces in the mixtures. The forces are
due to interactions between the molecules. If such interactions are strong, or
change strongly with the concentration(s), variation of viscosity is observed.

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More detail is given in Chapter 9 of the book of Shaw, “Colloid and Surface
Chemistry”, attached to the present exercise. Please notice the definitions of
relative and reduced viscosity on p. 249.

The viscosity of water is around 1cP = 10-3 Pa.s under normal conditions. It
decreases rapidly with the temperature, since the molecules become more
mobile and the interactions between them less significant. Addition of low
amounts of relatively small molecules does not modify viscosity very much,
even if these molecules dissociate and form ions. However, addition of the
polymer molecules to the solution, even in low molar amounts, may result in
significant increase of viscosity. The reason is that the polymer molecules are
large and difficult to move. Moreover, they organize the small molecules of the
solution causing their cooperative motion. Such an organization makes the
whole solution less mobile and leads to increase of the viscosity.

An extreme case of such organization is complexation, arising in the solutions

containing the polymer and the surfactant. The polymer molecules attract the
molecules of the surfactant. If the concentration of the surfactant exceeds
some limiting value, the critical aggregation concentration (CAC), the
molecules of surfactant form a sort of “necklace”: the surfactant molecules
“hang” on each segment of the polymer molecules (see introduction to the
paper of Nikas Blankschtein, surf. Sci. series 64. 1996 Marcel Dekker p.
193.). Such complexes strongly interact with each other (although micelles
are not formed, CAC << CMC), and are rather difficult to move. Viscosity of
the solution increases. Again, this effect may disappear with the temperature,
since the molecules become more mobile and do not stick to each other
anymore.

Another reason for variation of viscosities may be the shape of the molecules.
If the polymer is poly-acid, it may dissociate in a solution (or not). The
molecules of non-dissociated polymer are normally coiled. In spite the fact
that the molecules are rather large, in the coiled state they do not occupy a
large volume. Moreover, most of the interaction forces are “hidden” inside the
coiled molecules. The effect on viscosity is relatively small.

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When acidity of the solution changes the molecules of the polymeric acid may
dissociate. The segments of such molecules become negatively charged and
repel from each other. As a result, the molecules stretch. In the flow, the
negatively charged stretched molecules occupy a larger volume and interact
stronger with each other. This is likely to increase the viscosity of the solution
(although there may be other considerations).

Addition of some salts into the solution may result in the fact that the salt ions
neutralize the negatively charged segments, and the polymer molecules
become coiled again. The viscosity decreases.

Heating the solution normally reduces its viscosity: the molecules become
faster and more independent. However, the effect normally is not extreme. If a
drastic change of viscosity is observed, this normally indicates qualitative
changes in the solution. For example, in the complex-forming solutions, the
complexes may be destroyed with heating, since more mobile surfactant
molecules do not form complexes anymore.

Of course, dilution of the solution will normally lead to decrease of its

viscosity.

2. Effect of conformational changes

This section will demonstrate how the conformational changes of the polymer
caused by molecular change density and electrolyte content in the solution
affect the viscosity of a dilute solution.

We will investigate poly acrylic acid with an apparent molecular weight of

230,000 g/mol.

The viscosity measurements are performed in a capillary viscometer of the

Ostwald type. Other types of viscometers such as controlled shear

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viscometers could also be used as could our automatic miniviscometer based
on the falling ball principles. However in the present case it is desirable to be
able to also make visual observations of the state of the solutions (turbidity,
particles present etc.).

The following premixed solutions are available:

1 0.4 g/100 ml polyacrylacid in water. Adjusted with NaOH (1
M) to pH 4.0 (approximately 5-10 % dissociated carboxylic
acids)
2 0.4 g/100 ml polyacrylacid in water. Adjusted with NaOH to
pH 8.0 (approximately 100 % dissociated carboxylic acids)
3 0.4 g/100 ml polyacrylacid in 0.5 M NaCl. Adjusted with
NaOH to pH 8.0 (approximately 100 % dissociated carboxylic
acids)

Fill the viscometer with a given solution such that the liquid reaches the neck
of the lower bulb (approx. 7 ml). Measure the time t that it takes the upper
meniscus to pass between the marks on the bulb above the capillary. The
assistant will demonstrate the right use of the viscometer. Measure the run
time for:
A: solution 1
B: Solution 2
C: solution 2 diluted 1:3 with water
D. Solution 3
E solutions 3 diluted 1:3 with 0.5 M NaCl.

Also the runtime of the pure solvent liquids (to), respectively distilled water and
0.5 M NaCl should be determined.

Using the relation rel  (t  to ) / to calculate the relative viscosity. Calculate

rel /c where c is the polymer concentration. Plot the values of rel and rel /c
versus c and explain the variations observed based on conformational

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changes and charge density. Refer to Shaw chapter 9 on rheology and to
explanation given above.
Hint: As explained above, the viscosity of a diluted solution is more or less a
linear function of concentration. Hence, if the polymer solution would be
“normal”, the plot of its relative viscosity would be a straight line passing
through zero, while the reduced viscosity would be constant. The fact that this
is not observed indicates that some qualitative changes have occurred with
the solution.

3. Complex formation between polymers and surfactants .

If an ionic surfactant bond to a non-ionic polymer the polymer-surfactant

complex will attain polyelectrolyte properties. Hence complex formations can
therefore be observed by viscometry. The polymer used is poly vinylic alcohol
(MW 125,000) and the surfactant is SDS.

Procedure:

Available: polyvinylic alcohol solution 0.2 g/100 ml water. SDS solid.

Make a solution of 1.2 g SDS in 0.2 g polymer/100 ml water as well as a

solution of 1.2 g SDS/100 ml and the solution of 0.2 g polymer/100 ml water.
The solutions will probably foam.

Now measure the viscosity of the solutions and for pure water. Compare the
viscosity: Is it possible that poly vinylic alcohol and SDS forms a complex?
You will also need the solvent phase viscosities in order to be able to
calculate the relative viscosity.

Try to heat the solutions to a higher temperature and observe changes.

Report: describe all observations and analyse data in connection with

literature on the subject. In this also effects of added salt etc should of course
be included.

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