ATENEO

DE MANILA UNIVERSITY
Ch 46.5 Applied Physical Chemistry Laboratory
1st Sem. 2014-15

Viscosity of Solutions: Molecular Weight of Dextrans

Experiment No. 5


INTRODUCTION

Fluids exhibit viscosity. Viscosity is a measure of resistance to flow. What causes this
resistance to flow? Imagine a sack of sand that you want to pour unto a bucket.
Would all the sand grans move at the same velocity as you pour it out? You would
expect that there will be resistance for some grains to flow since there are frictional
forces between the grains.

For a fluid at a molecular level, atoms or molecules may be driven to flow into a
certain direction by an external force (in the sands case, its weight). The following
molecules will experience friction that is influenced by the type of intermolecular
forces between them and factors such as their average kinetic energy (thermal
energy), density, molecular size, mass and shape.

Experimentally, we can quantify viscosity by the coefficient of viscosity, , or simply
termed as viscosity. This coefficient is the proportionality constant between the
driving force per unit area for the flow f/A (known as shear stress, ) and the rate of
!
the strain of the fluid, ! ;

= (1)

If we imagine again the sand, the grains on the top layer will flow faster than those
below it or those near the wall of the sack. Schematically, we can imagine layers of
rice grains moving in a fashion shown in Figure 1.

Figure 1. Schematic of a fluid flow. In a cylinder the plates are concentric circles.
The vectors show the velocity gradient perpendicular to the direction of the flow.

The top layer of a given area A moves fater than the layer below it, an so on and so
forth, as shown by the velocity vectors. The top layer drags along with it the lower
layers. The strain in this diagram is defines as (x/r); the rate strain is (x/r)/t.
We may arrange equation 1 to:

( )
(2)
=
= ( )

Which shows that the force is proportional to the velocity gradient perpendicular to
the direction of flow. A fluid that behaves as predicted by Equation 1 (or 2) is
termed as Newtonian fluid, and the flow behavior is decribed as laminar flow. For
Newtonian fluids, the applied shear stress is directly proportional to the strain rate
as shown in Figure 2; non-Newtonian flow behavior is exhibited by deviations from
this line. Shear thickening occurs when the fluid increases viscosity with increased
shear stress (e.g., when mixing ube) and shear thinning occurs when the fluid
becomes less viscous with increased shear stress (when beating egg).

In this experiment, you shall measure the viscosity coefficient of a liquid solution of
dextran. To measure the viscosity, you shall use an Ostwald viscometer (Figure 3)
wherein the efflux time for the liquid to move from point a to b will be measured.
Poiseuilles equation applies:

!
=

(3)

Where V is the volume of the liquid, t is the time, P is the hydrostatic pressure of
the flowing liquid, l is the length of the capillary, and R is the radius of the capillary.
The hydrostatic pressure is fixed by measuring the time across the same marks a
and b and keeping the volume of the liquid constant.


Figure 3. An Ostwald Capillary
Viscometer. The efflux time is
measured across flow from fiducial
mark A to B.

The hydrostatic pressure will change with the density of the liquid, (recall that this
pressure is equal to ) . Note that many of the parameters in Poiseuilles equation
are dependent on the geometry of the viscometer.

To facilitate the measurements we shall calibrate the viscometer against a liquid
with a known viscosity. In this case we have the following relation which can be
derived by taking the ratio of Equation 3 for the two liquids; the constant
parameters for the viscometer will cancel leaving:

! ! !
=

! ! !

(4)

Where the subscript 1 is the liquid with the known density and viscosity (water in
our case) and subscript 2 is the test liquid (the polymer solution). You will need to
measure the density of your test liquid using a pycnometer or if the liquid is dilute
enough, assume its density to be close to that of the solvent. Note that the relation
above assumes constant temperature and constant volume of the liquid.

You will use dextran, a polysaccharide that is made of glucose units linked together
via a -1,6- glycosidic bonds. Dextran is soluble in water. When dissolved, we can
model the dextran molecules to be coiled chains that resemble long spaghetti
noodles. These chains affect the viscosity of the solution. Imagine the sand mixed
with large gravel. As most polymers, dextran does not have uniform molecular
weight, that is, all chains are not of the same weight. The molecular weight is
therefore reported as average weight.



Modeling the polymer as randomly coiled chain means the end-to-end distance of
the chain is going to vary with the molecular weight s follows

(5)
! !

And assuming the chains behave as spheres (or marbles) in solution, the viscosity
can be shown to be directly proportional to the square root of the molecular weight.

(6)
= ! !

Where K is a constant. However, we know that both polymer chains are nor really
hard spheres. They can expand or contract depending on how well they like to
imbibe solvent within them, or how well the solvent can swell the chain. A solvent
that swells the dimension of the chain by solvation is termed as a good solvent,
otherwise it is called a poor solvent. In the case when the chain behaves like an
unperturbed coil, we have a so-called theta solvent. Thus relation 6 can be modified
into a Mark-Houwink relation:

= !
(7)

Where is the instrinsic viscosity that vary from 0.5 for a random coil and 1.7 for a
chain that behaves a rod-like. The intrinsic viscosity is defined as the value of the
!" / when c approaches zero; c is the concentration of the polymer solution in
gram per 100 mL solution and !" is the specific viscosity of the solution:

!" =
1
1
(8)
!
!

Assuming that the density of solution is approximately equal to that of pure solvent
(see equation 4 above). Thus, is the value of the y-intercept of a linear plot of the
(!" /) .

EXPERIMENTAL:

Clean the viscometer thoroughly with cleaning solution (chromic acid or other
suitable acid-washing reagents) and rinse thoroughly with distilled water. You can
draw liquid into the bulbs using a rubber aspirator. You can quickly dry the
viscometer by rinsing with acetone.
Determine the volume needed to fill your viscometer. You should fill it up to the
upper fiducial mark above the small bulb and at the same time have the volume of
the liquid in the large bulb to about half. Note down this volume as you will use the
same volume every time for the rest of your measurements.

Fill your viscometer with distilled water with the volume you measured above, and
let it equilibrate for about 10 minutes in a constant temperature bath. Record the
temperature of the bath. The viscometer should be immersed in the bath up to the
first fiducial mark. After equilibration, bu suction, draw water above the first fiducial
mark. Let it flow naturally and record the time it takes for the liquid to flow from
mark A to B (Figure 3). Do the measurement of the efflux time a second time.

Prepare the polymer solution while waiting for the viscometer to equilibrate.
Prepare 100.00 mL stock solution of concentration about 1.0 g / 100 mL. Weigh out
exactly 1.00 g of the polymer in a small clean beaker. Dissolve the polymer by adding
a small volume of hot water (not boiling). Transfer the solution quantitatively from
the beaker to a 100-mL volumetric flask. Allow the solution and the flask to
equilibrate to room temperature before diluting to mark. Now prepare a two-fold
dilution of this stock solution to prepare a polymer solution that is 0.5 g/100 mL in
concentration. Prepare successively other solutions with the following
concentrations: 0.25, 0.125, and 0.0625 g/ 100 mL. Let your solutions equilibrate in
a water bath of the same temperature as your viscometer water bath. The
temperature should be keptwithin 0.05! throughout the entire experiment.

Measure the efflux times of your polymer solutions in your viscometer. To facilitate
filling and cleaning of the viscometer, do not let it dry with the polymer solution, but
rather, rinse it copiously with water, then acetone, air dry then fill with the new
solution. Note that polymers do not dissolve quickly, and if residues were left to dry
on the walls of the container, it will take time to remove them by simple rinsing.

Each one will use different dextran with different average molecular weight to be
assigned by your instructor.



DATA AND ANALYSIS:

Calculate the viscosities of your solutions using Equation 4 assuming the density of
water and the solutions are the same. Use the density value for water at the
temperature of your experiment as listed in a Physical Chemistry Handbook.

Calculate the specific viscosity !" for each of your solutions according to equation
8. Calculate the ratio (!" ). Plot this ratio versus c and obtain the intrinsic
viscosity of your polymer solution, [] (the y-intercept), by linear regression.

Collect the other intrinsic viscosities measured by your classmates and plot the
log . log . Obtain the slope and the y-intercept of this
plot by linear regression. What are these values?


QUESTIONS:

Briefly discuss the nature of dissolved dextran in solution and how it affects
viscosity. Why is dextran soluble in water? Is water a good or poor solvent for
dextran?

What is your K and a value for dextran? Compare this value from what is obtained in
literature sources (cite your reference). What can you say about the chain
characteristic of dextran in aqueous solution?

Explain how you use your plot of intrinsic viscosity and molecular weight to obtain
molecular weight of an unknown dextran sample.