Exercise 8

Viscosity of Pure Liquids and Solutions

CHEM 111.1 3L

Distor, Nedrick T.
Flores III, Deogracias C.
Requiso, Princess J.
Sison, Richard Dean B.
Somera, Erika A.

Date Performed: March 4 and 11, 2014

Date Submitted: March 18, 2014

Mr. Hervin Errol T. Mendoza

Laboratory Instructor

I. Introduction
Fluids flow in a manner in which its components, which can be atoms or molecules, slip past
each other and allow movement whenever an adequate shear force is applied to its total or
partial mass. Viscosity,
magnitude of

, is usually defined as the ease at which the fluid is flowing. As the

increases, the more difficult to flow it is for the fluid. It is also sometimes

termed as the thickness of the fluid (Roussel, 2012); the higher the viscosity, the more thick a
fluid is. For different fluids, however, the ease at which fluids flow is affected by certain factors
such as temperature, the intermolecular forces present on the fluid, the structure of the
components of the liquid, for example, the length of the molecules in solution, and the
concentration, in case the fluid is a solution (Garland, 2003). Viscosity is usually expressed in
poise or g/cm s in CGS system, or in N s/m2 or kg/m s in SI units.
Different methods and apparatuses have been developed for the quantification and
determination of the value of

for liquids and solutions. A method of measuring viscosity is

by using rheometers, which consist of rotating concentric cylinders, an inner and outer cylinder,
with the torque of the inner cylinder observed while the outer cylinder being rotated by a motor
(Atkins, 2006). It makes use of the concept of spring deflection, torque and angular velocities.
Other methods include the use of an ultrasonic probe, a method involving the measurement of
pressure drop through a friction tube, the use of a torque viscometer, and a procedure involving
a timed fall of piston on a cylinder. One of the most common procedures, on the other hand,
involves the measurement of the flow time of fluids in a viscometer, which is composed of
several capillary tubes where fluid flow is observed. Some viscometers that are usually used are
the Ostwald, Cannon-Fenske, and Ubbelohde viscometers. In using viscometers, the time of
downward flow of a volume of a fluid, which is caused mainly by gravitational pull is measured
and then calculated using the modified and corrected Hagen-Poiseuille equation:

B
t

= At

The value of the standard Gibbs free energy,

o
G

(8-1)

can be computed using a modified

Eyrings equation:

o =RT ln
G

M
hNA

(8-2)

The viscosity of polymer solutions can be determined using the Mark-Houwink equation:

[ ] =k M a
where

(8-3)

[ ] is the intrinsic viscosity of the solution, and k and a are empirical constants

for a given polymer-solvent system at a certain temperature.

The objectives of the exercise are to: (a) determine the viscosities of aqueous solutions of
methanol (CH3OH) and 2-propanol ((CH3)2CHOH) at various concentrations; (b) the
thermodynamic properties of the mentioned test liquids using Eyrings equation, and; (c)
calculate the molecular weight and root-mean-square end-to-end length of sodium
carboxymethylcellulose (NaCMC)
at different salt concentrations using Mark-Houwinks
equation.
II. Materials and Methods
A. Apparatus and Equipment
Cannon-Fenske and Ubbelohde viscometers
Thermostatted water bath
Aspirator
Timers
Thermometer

Top loading balance

Stirring rod
Volumetric flasks
Beakers
Pycnometer

B. Reagents
Calibration liquids: water, ethanol, ethyl acetate
Test liquids: methanol, 2-propanol
Solvent: 0.10 M and 0.001 M NaCl solutions
Polymeric salt: sodium carboxymethylcellulose (NaCMC)
C. Procedure
For the general procedure of the use of Cannon-Fenske (and Ostwald) viscometers, the
viscometers were initially washed with detergent and water, then rinsed with dH2O and acetone,
and finally rinsed with the sample liquid for analysis. 10 mL of the sample liquid was placed into
the viscometer, which was equilibrated afterwards in the thermostatted bath of recorded
temperature. Three consecutive flow times with 0.1-second difference were obtained, allowing
more trials whenever it was necessary.
With the general procedure, the viscometers were calibrated using the calibrating liquids as
sample liquids at constant bath and room temperature; measured flow times at 20, 25, 30, 35,
40, 45, and 50 C using pure test liquid; and measured flow times solutions of different
concentrations. Binary solutions of the test liquid and H2O were prepared at concentrations
0.10, 0.20, 0.40, 0.60, 0.80 and 0.95, using serial dilution to make the solutions of lower
concentrations. The density of H2O at the specified temperature and the bath temperature were
maintained.
For the general procedure of the use of the Ubbelohde viscometer, it was rinsed using
suitable solvents, making sure of absence of substance traces, impurities. Solvents placed
inside had its flow times measured (like the usage of the previous viscometers.
0.05, 0.10, 0.25, 0.50, 0,75, and 1.00 g/dL solutions were analyzed using flow time runs. These
solutions were not prepared by serial dilution but rather by direct dilution in the faculty, and the
solvent used were 0.100 M NaCl for the first trial and 0.001 M NaCl for the second. Foam
formation was avoided.

III. Results and Discussion

Viscosity,

is a measure of a resistance to flow of fluid; more specifically it quantifies the

resistance that a portion of the fluid extends to the other portions of the same fluid. If two solid
plates are separated by a thin film of fluid, as shown by the figure below, and the upper plate is
moved steadily in the x-direction with a given velocity,

V o , a force will be needed to

overcome the friction present due to the fluid between the plates. This required force varies for
different fluids, velocities, plate sizes, and the distances between the plates. By measuring the
force per unit area of the plate defined as the shear stress,

, however, the effect of different

plate sizes considered is eliminated.

Figure 8.1. The sliding plate experiment.

At low values of

V o , the velocity profile in the fluid between the plates is linear. If a plot of

versus the differential change in the velocity with respect to the vertical distance of the

parallel plates,

dV
dy , commonly called as the shear rate or velocity gradient, is constructed

for different fluids at constant temperature and pressure, the following figure would be observed:

Figure 8.2. Plot of

versus

dV
dy

for different fluids at constant temperature and pressure.

The behavior that is mostly exhibited by many fluids in nature is that represented by the straight
line passing through the origin. These fluids are called newtonian fluids, which obeys the
Newtons law of viscosity, expressed mathematically as (De Nevers, 1991):

dV
dy

(8-4)

which implies that the shear stress experienced by the liquid is directly proportional to the
velocity gradient, where the proportionality constant is the absolute viscosity of the fluid,

Newtons law of viscosity conceptualizes a fluid as being arranged into layers of planes of
molecules wherein a plate is kept static while the other parallel plate is moving steadily at a
certain velocity, as exhibited by the sliding plate experiment. A moving plate pulls a layer of
liquid as it moves at a certain length, creating a transfer of momentum to the other layers. The
same is also exhibited by the other layers located above the other layers. Because of the
frictional forces due to the inherent characteristics of the fluid, the magnitude of the velocity of
each layer will be less than the speed of the layer above it. The layers of the fluid offer frictional
forces of resistance that gives rise to the viscosity of the fluid, generally symbolized as

However, this is only valid for laminar flows characterized by smooth streamlines and highly
ordered motion, which occurs as a series of thin plates of liquid smoothly sliding past each other
at different velocities. Laminar flow is in contrast with a turbulent flow, which exhibits eddy
formation and is characterized by velocity fluctuations and highly disordered motion. Turbulence
is determined by different models and equations, since it does not obey the Newtons law of
viscosity (Foust, Wenzel, Clump, Maus & Andersen, 1960).

Figure 8.3. (a) Laminar and turbulent flow.

Fluids can be generally classified as either newtonian or non-newtonian fluids. Newtonian
fluids usually exhibit laminar flow at low velocities. The values of

is constant at certain

temperatures and pressures and is independent of the velocity gradient. Some examples of
newtonian fluids include all gases, all liquids with simple chemical formulas, and most solutions
of simple molecules. On the other hand, non-newtonian fluids have
dependent on the values of

values, which are

, which is defined as the force parallel to the area being

considered, as opposed to normal forces and stresses that acts perpendicularly to an area.
Common types of non-newtonian fluids are Bingham fluids, which can resist small shear forces
infinitely but flow easily under large shear stresses. Examples are slurries, jellies and
toothpaste. Pseudoplastics like blood and other polymer solutions exhibit viscosities that
decrease with increasing velocity gradient. Those considered uncommon are dilatants fluids like
starch solutions, which have values of viscosity that increases as the velocity gradient increase.
The method used in the experiment is the capillary rise method, where the viscosity of fluids
are determined by measuring the time of flow of a given volume,

V , of a liquid through a

vertical capillary tube under the influence of gravity. Capillary viscometers consist of a U-shaped
glass tube held vertically; in one arm of the U is a vertical section of precise narrow bore, the
capillary. Above this is a bulb; with it is another bulb lower down on the other arm. The liquid is
drawn into the upper bulb by suction, and then allowed to flow down through the capillary into
the lower bulb. Two marks, one above and one below the upper bulb, indicate a known volume.
Ostwald and Cannon-Fenske viscometers are some apparatuses that make use of this idea. An
Ostwald viscometer has a straight tube curved at the bottom part and two bulbs, which are
located at the upper and lower ends of the tube as shown in the following figure:

Figure 8.4. An Ostwald viscometer.

Because the tube is straight, the flow time of a given liquid is longer compared to that of the
Cannon-Fenske viscometer, which is also composed of two bulbs, but exhibits a slanted part of
the tube, as shown by the figure below.

Figure 8.5. A Cannon-Fenske viscometer.

Measurements obtained using an Ostwald viscometer is dependent on the volume of the liquid
used because the pressure head varies with different solutions. By using the Cannon-Fenske
viscometer, a modification of the Ostwald viscometer, minimum changes in the pressure head
since the lower bulb is located directly below the upper bulb is produced resulting to the vertical
alignment in the viscometer. The differences in pressure heads and other inherent errors, which
are mostly caused by the geometry of the tubes, are corrected by the Cannon-Fenske.
Another apparatus used in the experiment is the suspended level or Ubbelohde viscometer,
which is composed of three tubes, and bulbs located and designed in such a way that errors
due to certain conditions, such as the pressures acting above, and other inherent errors are
corrected. The liquid initially drawn into the small upper bulb is not connected to the reservoir as
it flows down the capillary during measurement. The capillary is rather suspended above the
reservoir. It has a third arm extending from the end of the capillary and open to the atmosphere,
which ensures that the only pressure difference between the top of the bulb and the bottom of
the capillary is that due to the hydrostatic pressure or the weight of the liquid. The pressure

head of the suspended liquid on the capillary tube is independent of the liquid originally placed
on the viscometer. This type of viscometer is usually used for viscous and polymer solutions
(Daniels, Matthews, Williams, Bender & Alberty, 1956).

Figure 8.6. An Ubbelohde viscometer.

The flow of the liquid in the capillary is governed by the Hagen-Poiseuille equation developed
by Jean Louis Poiseuille and Gotthilf Heinrich Hagen, expressed as (Bird, Stewart & Lightfoot,
2002):

V=

where

is the tube radius,

r4t P
8 l

is the tube length,

(8-5)

is the time of flow, and

is the

pressure difference at the tube ends. Since the two viscometers have tubes open at both ends,
the value of

can be calculated as:

P= gh
By substituting the equation for

(8-6)

P , the Hagen-Poiseuille equation could be written as:

V=

r 4 tgh
8 l

(8-7)

The Hagen-Poiseuille equation does not consider the pressure drop due to the motion of the
fluid itself; the kinetic energy correction are necessary for accuracy. The equation should be
corrected for tube-end effects because the liquid flow could not be considered entirely laminar,
because a layer of a liquid is sliding relative to one another both in the entrance and exit
regions, resulting to eddy formations, which implies turbulence. In the entrance region of the

tube, the acceleration of the fluid decreases the value of P ; in the exit region, the energy
due to the deceleration of the fluid is dissipated as heat. The value of the correction factor,

V
8 lt . To simplify calculations, constants

expressed as

and

are introduced in the

equation, reducing it into the following relation:

where
and

is defined as

r 4 gh
8Vl

and

= A t

B
t

V
8 lt . The values of the constants

as

(8-8)

can be calculated using the information of the dimensions of the viscometers used,

but some errors cannot be avoided due to some irregularities such as the non-uniformity of the
capillary tube. For further simplification of the calculations, the viscometers to be used should be
calibrated. Constants

for liquids with known

. By rearranging the equation above,

and

can be determined by the determination of

B
=A 2
t
t

By plotting
equal to

t
B

versus

and

(8-9)

1
t 2 , a straight line with a y-intercept equal to

and a slope

can be obtained, as suggested by the modified equation. Using the liquids

water, ethyl acetate and ethanol, different values were obtained which were used for the
calibration of the viscometers. The following data were obtained for the calibration of the
Cannon-Fenske viscometers, which were used in the experiment.
Table 8.1. Calibration of the Cannon-Fenske viscometer used for 1-propanol.
Average time of
Viscosity ( ),
Calibrating Liquid
Density ( ), kg/m3
flow ( t ), s
cP
Water
995.738539
10.75
0.88
Ethyl Acetate
889.123
7.5
0.43
Ethanol
782.2337
7.2
0.315
Slope from linear regression ( B ), m2

2.28624x10-6

y-intercept from linear regression ( A ), m2/s2

1.02384x10-7

Correlation coefficient ( r )

0.981446203

Table 8.2. Calibration of the Cannon-Fenske viscometer used for 2-propanol.

Average time of
Viscosity ( ),
Calibrating Liquid
Density ( ), g/cm3
t
flow (
), s
cP
Water
0.995738539
50.5712
0.88
Ethyl Acetate
0.889123
34.8965
0.43
Ethanol
0.7822337
29.2312
0.315
Slope from linear regression ( B ), cm2

4.886747023

y-intercept from linear regression ( A ), cm2/s2

0.01891778116

Correlation coefficient ( r )

0.902995

0
0
0

f(x) = - 0x + 0
R = 0.96

0
0

/t (m2/ s2)

0
0
0
0
0
0.01

0.01

0.01

0.01

0.02

0.02

0.02

1/t2 (1/s2)

Figure 8.7. Calibration data for the Cannon-Fenske viscometer for methanol and 0.1 M NaClpolymer solution.

/t (cm2/s2)

0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0
0
0

f(x)==0.82
R
- 4.89x + 0.02

1/t2 (1/s2)

Figure 8.8. Calibration data for the Cannon-Fenske viscometer for 2-propanol and 0.001 M
NaCl-polymer solution.
After the calibration of the viscometers, the values of

of the pure test liquids methanol

and 2-propanol at different temperatures were determined by measuring the corresponding flow
times for the particular temperature. Viscosities were computed using the modified HagenPoiseuille equation. Theoretically, as the temperature of the liquid increases, its viscosity
decreases. When the temperature is increased, the average kinetic energy and the random
motion of the molecules are also increased, thereby reducing the time of interaction and the
distance between them, reducing the shear stresses experienced by a stratified layer of
molecules and the bulk viscosity of the fluid (Garland, Nibler & Shoemaker, 2003). The following
data were gathered for the effect of temperature on the value of

Table 8.3. Viscosities of pure methanol at various temperatures.

Average time of flow
Density ( ),
Temperature, K
( t ), s
kg/m3
293.15
794.3460
9.85
298.15
789.5790
9.35
303.15
784.7567
9.1
308.15
779.8770
8.65
313.15
774.9376
8.35
318.15
769.9361
8.1
323.15
764.8697
7.9
Table 8.4. Viscosities of pure 2-propanol at various temperatures.
Average time of flow
Density ( ),
Temperature, K
( t ), s
g/cm3
293.15
0.7861917
176.5

Viscosity ( ),
kg/m s
0.000616715
0.000562793
0.000533998
0.000484553
0.000450323
0.000421202
0.000397303

Viscosity ( ),
g/cm s
678.0987868

298.15
303.15
308.15
313.15
318.15
323.15

0.781544
0.776906
0.772209
0.7675857
0.7629342
0.7582827

155.3
134.3
117.1
103.7
91.9
81.2

593.1228785
509.8756266
441.887268
388.9782628
342.6275279
300.8893244

The experimental data generally shows that as the temperature is increased, the viscosity of the
liquid decreases and agrees with the theoretical result as can be seen from the figures and
tables above.
Eyrings Theory, based on the Transition State Theory, which explains chemical reactions
and other molecular processes, provides an explanation on viscous flow, properties of liquids
and solutions, and a basis on correlation of viscosity data. For viscous flow, Eyrings equation is
expressed as:
o

h N A RTG
=
e
V

(8-10)

By rearranging the equation,

o =RT ln M
G
h NA
where

o
G

(8-11)

is the standard molar free energy for viscous flow,

which is equal to 6.626x10-34 J s,

is the Plancks constant

is the molar volume of the substance and

o
H

Avogadros number. Assuming the molar enthalpy change for flow,

entropy of activation,

are both independent of temperature,

NA

is the

and the molar

can be expressed

as:

o = H
oT So
G
By plotting

o
G

versus

T , the values of

linear regression, with slope equal to

and

(8-12)

o
H

can be calculated using

and y-intercept equal to

o
H
. The following

values were calculated on the experiment:

Table 8.5. Computed
Temperature, K

o
o
o
G
, H and S

of pure methanol.

Density ( ),

Viscosity ( ),

kg/m3

kg/m s

, J/mol

293.15
794.3460
298.15
789.5790
303.15
784.7567
308.15
779.8770
313.15
774.9376
318.15
769.9361
323.15
764.8697
Slope of the line, J/mol K
y-intercept (b), J/mol
Correlation coefficient (r)

Standard molar entropy, ( S

Standard molar enthalpy, ( H

Table 8.6. Computed

Temperature, K

g/cm3
293.15
0.7861917
298.15
0.781544
303.15
0.776906
308.15
0.772209
313.15
0.7675857
318.15
0.7629342
323.15
0.7582827
Slope of the line, J/mol K
y-intercept (b), J/mol
Correlation coefficient (r)

Standard molar enthalpy, ( H

), J/mol K
o

-0.060666

), J/mol

Density ( ),

28.440994
28.714210
29.078817
29.325476
29.627109
29.940458
30.271797

0.060666
10.65
0.999379467

), J/mol K

o
o
o
G
, H and S

Standard molar entropy, ( S

0.000616715
0.000562793
0.000533998
0.000484553
0.000450323
0.000421202
0.000397303

), J/mol

10.65

of pure 2-propanol.
Viscosity ( ),

o
G
, J/mol

g/cm s
678.0987868
593.1228785
509.8756266
441.887268
388.9782628
342.6275279
300.8893244

79205.16774
80238.90506
81218.34921
82206.81172
83224.29118
84233.58478
85224.816
200.39
20472
1.0000
-200.39
20472

30.500000
f(x) = 0.06x + 10.65
R = 1

30.000000

29.500000

G, J/mol

29.000000

28.500000

28.000000

27.500000
290

295

300

305

310

315

320

325

Temperature, K

Figure 8.9. Plot of

o
G

versus temperature for pure methanol.

86000
85000
84000

f(x) = 200.39x + 20472.3

R = 1

83000
82000
G, J/mol

81000
80000
79000
78000
77000
76000
290

295

300

305

310

Temperature, K

315

320

325

Figure 8.10. Plot of

o
G

versus temperature for pure 2-propanol.

Another condition that possibly affects the value of viscosity is the concentration. Its effect
was tested using binary solutions of the test liquids and water with different concentrations. The
volume of the pure test liquid needed to prepare a volume of the solution to be tested was
computed using the following formula:

VA
B A M A
=
V T A M B A A M B + B A M A
where

(8-13)

is the mole fraction of the test liquid, A is the pure test liquid and B is the solvent

which is water in this case.

The densities of the solutions were calculated using the measurements obtained from a
pycnometer using the following equation:

soln =

m pyc+soln m pyc

mpyc+ H Om pyc H

(8-14)

Viscosity values, theoretically, are largely dependent on the nature of the binary solution
considered, the intermolecular forces of attraction, IMFA, present between the solute and
solvent particles, and the mole fraction of the solute in the solution, which implies its
concentration. Strong IMFA impedes flow and increases the viscosity of the liquid. If the solutesolute and solvent-solvent interactions are more occurring than the solute-solvent interactions,
as the mole fraction of the solute increases, the viscosity decreases. If solute-solvent
interactions are more occurring than the solute-solute or solvent-solute interactions, as the mole
fraction decreases, viscosity increases. It is also found out that as the viscosity increases, the
boiling point of the solution rises, together with the molar enthalpy of vaporization (Levine,
2009).
The following values were obtained for the effect of concentration on the viscosity of a liquid.
Table 8.7. Viscosities of methanol-water solutions at various concentrations.
Mole fraction of
Average time of
Viscosity ( ),
), kg/m3
Density
(

t
A
solute,
flow (
), s
kg/m s
0.95
815.14502
29.45
0.002394561
0.8
864.83105
31.35
0.002712823
0.6
900.90919
30.95
0.002788249
0.4
953.46485
23.8
0.002231764
0.2
980.84287
17.15
0.0015915
0.1
992.14898
13.15
0.001163291
Table 8.8. Viscosities of 2-propanol-water solutions at various concentrations.

Mole fraction of

Density ( ), g/cm3

solute,
0.95
0.8
0.6
0.4
0.2
0.1

Average time of

Viscosity ( ),

160
177
151
159
161
131

g/cm s
511.4865867
630.7118472
584.5573736
677.9027706
744.051723
601.3754448

flow ( t ), s

0.654175801
0.729185324
0.792191927
0.872469983
0.945708862
0.939408827
0
f(x) = 0x + 0
R = 0.69

0
0

(kg/m s)

0
0
0
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Mole fraction of solute

Figure 8.11. Plot of viscosity versus concentration of solute of 1-propanol.

0.9

800
700
f(x) = - 151.17x + 701.86
R = 0.4

600
500
( g/cm s)

400
300
200
100
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Mole fraction of solute

Figure 8.12. Plot of viscosity versus concentration of solute of 2-propanol.

Sodium carboxymethylcellulose, abbreviated NaCMC, a polymer with many uses in food
sciences, pharmaceuticals, oil-drilling industry, protein purification and many other industrial
applications, has the following structure:

Figure 8.13. A sodium carboxymethylcellulose molecule.

On the experiment, the polymer was dissolved using two different concentrations of the solvent
to investigate on the effect of the polymer concentration on the viscosity of liquids, particularly a
polymer solution; 0.1 and 0.001 M sodium chloride, NaCl solution were used.

Some derived viscosity measurements and functions presented below can be conveniently used
in the determination of the average molecular weight and molecular weight distribution of a
polymer (CHEM 111 Lecturers and Laboratory Instructors, 2012). Viscosity values give
information about the shape and size of the polymer molecules.

where

Relative viscosity

rel =

t
=
o t o

(8-15)

Specific viscosity

sp =

o tt o
=
o
to

(8-16)

Reduced viscosity

sp
c

(8-17)

Inherent viscosity

1
inh = ln
c o

(8-18)

Intrinsic viscosity

lim
1 c 0 sp
[ ] =lim ln =
o
c
c 0 c

(8-19)

is the concentration of the solution, while

o ,

t , and

to

are the

viscosities and flow times for polymer solution and pure solvent, respectively.
A polymer is coiled without a solvent. In a polymer solution, as the concentration increases,
the viscosity also increases because more polymer chains mean stronger attraction between
molecules. Generally, as the concentration of the solvent increases, the viscosity of the polymer
solution decreases because the solvent competes for interaction. At low concentrations of the
solvent, solvation or dissolution, which is the process of association and attraction between the
molecules of the solute and solvent, increases. This invokes uncoiling of the polymer, thereby
increasing the viscosity of the polymer solution. The following tabulated values were calculated
using 0.1 M and 0.001 M NaCl solvent.
Table 8.9. Specific viscosities of NaCMC solutions at various concentrations using 0.100 M
NaCl solution as solvent.
Concentration (g/dL)

Average flow time, s

1.00
0.75
0.50
0.25
0.10
0.05

3.65
2.45
1.85
1.25
1.05
1.05

Specific viscosity (
3.866667
2.266667
1.466667
0.666667
0.4
0.4

sp )

Table 8.10. Specific viscosities of NaCMC solutions at various concentrations using 0.001 M
NaCl solution as solvent.
Concentration (g/dL)

Average flow time, s

1.00
0.75
0.50
0.25
0.10
0.05

1.1
1.39
1.75
2.84
3.9
0.92

Specific viscosity (

sp )

0.195652174
0.510869565
0.902173913
2.086956522
3.239130435
0

Good solvents, when mixed with polymers, results in the uncoiling and extension of polymers
in solution because the strong polymer-solvent attraction predominates. This increases the
viscosity of the solution. The heat of reaction or mixing of a polymer with a good solvent is
negligible or zero since energy is not needed and the process is spontaneous. In contrast, bad
solvent results to more coiling of the polymer considered which reduces the viscosity of the
polymer solution. A positive value of heat of reaction or mixing is obtained when a bad solvent is
mixed with a polymer, because more energy is required to form the solution. Aqueous sodium
chloride is a good solvent for NaCMC at low concentrations; at high concentrations, the salting
out effect alters the polymer-solvent interactions since water solvates NaCl instead of the
polymer, which results to more polymer coiling (Andrady, 2008).
The equations for the intrinsic viscosity may be considered linear at low concentrations and
the value of
against

[ ] can be obtained as the y-intercept of a line by plotting the reduced viscosity

or the inherent viscosity against

considered valid since the limit as

and extrapolating to

c=0 . This may be

c 0 is taken.

A relationship between viscosity values and molecular weight of a polymer is found out to be:

sp
=kM
c
where

is a constant for class similar polymers. At infinite dilution, that is,

(8-20)

c=0 , the

value of the intrinsic viscosity may be obtained as:

[ ] =kM

(8-21)

A relationship that also relates viscosity and the molecular weight of a polymer is the MarkHouwink or Mark-Houwink-Staudinger-Sakurada (MHSS) equation, which is derived taking into
account the root-mean-square end-to-end distance of a linear molecule. For branched polymers
with complicated geometries, the Mark-Houwink equation should be corrected for bond angle
corrections, restriction to free rotation about bonds and for the finite volume of the chain
segments for accurate results (Andrady, 2008). In equation form,

a
[ ] =k M
By rearranging the equation, the value of

can be calculated as:

= []
M
k

( )

where

(8-22)

1
a

M
is the viscosity average molecular weight, and

(8-23)

and

are empirical

constants that can be determined experimentally for a given polymer-solvent system at a certain
temperature. Specifically, the constant
solution. The value of

is a function of the geometry of the polymer

is 0.5 for well-connected or tightly curled polymer, while for rigidly

extended polymers, its value is 1.7. The following table presents the literature values for
calculations, calculated values for the viscosity values together with other parameters and

.
M

Table 8.11. Literature values and constants used for calculations.

Solvent/Parameter
0.100 M
0.010 M
0.001 M
Florys constant ( )

Kx 10

dL/g

12.3
0.646
0.100

0.91
1.20
1.40
2.84x1021 dL/mol cm3

Table 8.12. Viscosity values of NaCMC solutions at various concentrations using 0.100 M NaCl
solution as solvent.
Viscosity Values
Concentration (g/dL)

Inherent viscosity ( inh )

Reduced viscosity ( )
1.00
0.75
0.50
0.25
0.10
0.05
Slope of the line (m)
y-intercept (b)
Correlation coefficient (r)

1.582409
1.57836
1.805735
2.043302
3.364722
6.729445
-3.7672584
4.51453486
0.708394

3.866666667
3.022222222
2.933333333
2.666666667
4
8
-2.43940861
5.15888695
0.463654

Intrinsic viscosity ( [ ]

4.51453486

5.15888695


Average molar mass ( M

120181.0941

), g/mol

103791.6765

Table 8.13. Viscosity values of NaCMC solutions at various concentrations using 0.001 M NaCl
solution as solvent.
Viscosity Values
Concentration (g/dL)

Inherent viscosity ( inh )

Reduced viscosity ( )
1.00
0.75
0.50
0.25
0.10
0.05
Slope of the line (m)
y-intercept (b)
Correlation coefficient (r)

3.573835775
4.126853561
2.571989587
2.254371322
1.925810883
0
-3.594322324
3.996302548
-0.944034093

3.913043478
5.108695652
3.608695652
4.173913043
4.31884058
0
-3.339396542
4.99543154
-0.703830482

Intrinsic viscosity ( [] )

3.996302548

4.99543154

51936.23756

60910.89884

Average molar mass ( M

), g/mol

9
8
7
6
5

f(x) = - 2.44x + 5.16

R = 0.21
f(x) = - 3.77x + 4.51
R = 0.5

4
3
2
1
0

0.2

0.4

0.6

0.8

1.2

Figure 8.14. Plot for the determination of the intrinsic viscosity of 1-propanol using inherent and
reduced viscosities.

5
f(x) = - 3.34x + 5
R = 0.5

f(x) = - 3.59x + 4
R = 0.89

Reduced viscosity
Linear (Reduced viscosity)
Inherent viscosity
Linear (Inherent viscosity)

0
0

0.2

0.4

0.6

0.8

1.2

Figure 8.15. Plot for the determination of the intrinsic viscosity of 2-propanol using inherent and
reduced viscosities.
The values of the empirical constants

and

can be determined experimentally by

modifying the Mark-Houwink equation:

log [ ] =log k + a log M

log M

By plotting the values of

log [ ]

value of a slope equal to

a and with y-intercept log k

versus

(8-25)

and through linear regression, a line with a

After the calculation of the intrinsic viscosity, the value of

is obtained.

M
, size, radius and length of the

polymer were calculated. Assuming the polymer shape is spherical, the radius,
polymer is expressed as:

r , of the

3 M V sp
r=
4

where

r
1
2

V sp

(8-26)

is the specific volume of the polymer. The root-mean-square end-to-end length,

, which came from the Kirkwood-Riseman theory, is calculated as:

r =( [ ] M )
1
2

where

1
3

1
3

(8-27)

is equal to 2.84x1021 dL/mol cm3, and is called the Florys constant. The following

were the calculated values for the mentioned parameters.

Table 8.14. Calculated parameters for NaCMC using 0.1 M NaCl as solvent.
Using inherent viscosity (
Using reduced viscosity (
Parameter
inh )
)

Average molar mass ( M ),

g/mol
Molecular radius ( r ), cm
Molecular radius ( r ),
cm/mol
Root-mean-square end to-end
length (

r
1
2

120181.0941

103791.6765

25.30843734

24.10131775

4.20266 x10-23

4.00221 x10-23

1.477497885x10-8

1.284484332x10-8

Table 8.15. Calculated parameters for NaCMC using 0.001 M NaCl as solvent.
Using inherent viscosity (
Using reduced viscosity (
Parameter
inh )
)

Average molar mass ( M ),

g/mol
Molecular radius ( r ), cm
Molecular radius ( r ),
cm/mol
Root-mean-square end to-end

51936.23756

60910.89884

21.95990236

22.20911201

3.647824312 x10-23

3.689221264 x10-23

4.180903736x10-6

4.749521886x10-6

length (

r
1
2

For accuracy of the measurements done on the experiment, certain conditions must be
satisfied. The flow of the fluid in the viscometer must follow that of the Newtonian fluid. The
liquid must be pure, free of certain impurities, which may affect the flow time that it would
exhibit. The temperature of the system must be maintained constant, since the viscosity values
of the liquid, or a fluid, in general, is affected by temperature, as suggested by the exercise.
Some sources of errors in the experiment can alter the results and reduce the accuracy of
the data obtained. The inherent assumption of the experiment that the flow of the liquid in the
capillary tube is completely laminar leads to some erroneous results. Temperature fluctuations,
which were minimized by the thermostatted water bath can produce in either increase or
decrease in the flow time of the fluid in the viscometer, depending on the fluctuations
experienced. When impurities are present in the tubes, drainage clogging occurs and the flow
time of the fluid is altered. Another error that affects flow time is the tilting of the viscometer as
the liquid flows; the viscometer should stand vertically for accurate results. The use of timers
can also be erroneous because every individual has different response times for different
instances. If there are occurrences of evaporation of solvent or increase in the concentration of
the solution, there are changes in the sample composition and the corresponding flow times and
densities measured are also altered. Other errors such as spillage of sample and not following
of procedures are other sources of errors.

IV. Summary and Conclusions

Viscosity is a property of a fluid that characterizes a fluids resistance to flow and is affected
by many conditions. Newtons law of viscosity conceptualizes a fluid as being arranged into
layers of planes of molecules wherein a plate is kept static while the other parallel plate is
moving steadily at a certain velocity. The method for viscosity determination used in the
experiment is the capillary rise method, where the viscosity of fluids are determined by
measuring the time of flow of a given volume,

V , of a liquid through a vertical capillary tube

under the influence of gravity. The flow of the liquid in the capillary is governed by the HagenPoiseuille equation, which was used entirely in the calculations of the viscosities and other
parameters used in the experiment. As the temperature of the liquid increases, its viscosity
decreases due to the addition of energy caused by the temperature rise, overcoming the
intermolecular forces of attraction, which hinders flow and increases viscosity. The effect of
concentration depends upon the solvation effect of the solvent in the solute. Derived viscosity
measurements and functions can be conveniently used in the determination of the average
molecular weight and molecular weight distribution of a polymer. Viscosity values give
information about the shape and size of the polymer molecules. Some sources of errors like

inherent assumptions, experimental conditions, and systematic and random in the experiment
can alter the results and reduce the accuracy of the data obtained.
For better understanding of the concepts, trends and effects of properties and conditions, it
is recommended that the experiment may use more compounds and solution-solvent pairs.

V. Sample Calculations
Calibration of Viscometer

B
=A 2
t
t

Calibrating Liquid

Density ( ), kg/m3

Water
Ethyl Acetate
Ethanol

995.738539
889.123
782.2337

By linear regression,

Average time of

Viscosity ( ),

10.75
7.5
7.2

g/cm s
0.88
0.43
0.315

flow ( t ), s

Slope = -2.28624x10-6 m2 [value for -B]

y-intercept = 1.02384x10-7 m2/s2 [value for A]
r = 0.981446203
Effect of Temperature on Viscosity

= A t

B
t

For pure methanol at 293.15 K,

= ( 1.02384 x 107 m2 )( 794.3460 kg / m3 ) ( 9.85 s )

=0.000616715

( 2.28624 x 106 m2 )( 794.3460 kg /m3 )

9.85 s

kg
ms

Calculation of Thermodynamic Data

o =RT ln M
G
hNA

( 0.000616715 mkgs )(60.096 x 10

= 8.314
G

kg
mol

J
( 293.15 K ) ln
mol K
( 6.626 x 1034 J s ) ( 6.023 x 10 23) ( 794.3460 kg /m3 )

o =28.440994 J
G
mol

o = H
oT So
G

Temperature, K
293.15
298.15
303.15
308.15
313.15

o
G
, J/mol
28.440994
28.714210
29.078817
29.325476
29.627109

318.15
323.15

29.940458
30.271797

By linear regression,
Slope = 0.060666 J/mol K [value for
y-intercept = 10.65 J/mol [value for

So ]
o
H
]

r = 0.981446203
Preparation of Solutions for Effect of Concentration

VA
B A M A
=
V T A M B A A M B + B A M A
For 1-propanol solution with

V A=

g
g
( 0.95 ) 0.995738539 3 ( 50 mL )
3
cm
cm
g
18.016
[ 10.95 ] + 0.995738539 g 3 ( 0.95 ) 60.096 g
mol
mol
cm

(0.8053 cmg )(
3

A =0.95 ,

) (

0.8053

V A =31.80437147 mL

Calculation of Densities of Solutions

soln =

m pyc+soln m pyc

mpyc + H Om pyc H

For 1-propanol solution with

soln =

A =0.95 ,

24.291 g16.2521 g
g
995.738539 3
26.072 g16.2521 g
cm

soln =815.1450159

g
cm3

) (

Calculation of Specific Viscosity

sp =

tt o
to

For 0.100 M and NaCMC 1.00 g/dL solution,

sp =

3.65 s0.75 s
=3.866667
0.75 s

Calculation of Reduced Viscosity

sp
c

For 0.100 M and NaCMC 1.00 g/dL solution,

3.866667
dL
=3.866667
g
g
1
dL

=3.866667

dL
g

Calculation of Inherent Viscosity

1
inh = ln
c o
For 0.100 M and NaCMC 1.00 g/dL solution,

inh =

1
3.65 s
ln
g
0.75 s
1
dL

inh =1.582409

dL
g

Calculation of Intrinsic Viscosity

Using the values for reduced viscosities of 0.100 M and NaCMC solution,
Concentration (g/dL)

Reduced viscosity ( )

1.00
0.75
0.50
0.25
0.10
0.05

3.866666667
3.022222222
2.933333333
2.666666667
4
8

By linear regression,
Slope = -2.43940861
y-intercept = 5.15888695 [value for intrinsic viscosity]
r = 0.463654
Calculation of Average Molecular Mass

= []
M
k

( )

1
a

Using the value of the intrinsic viscosity from reduced viscosities of 0.100 M and NaCMC
solution,

 = 5.15888695
M
5
12.3 x 10

1
0.91

=103791.6765 g
M
mol

Calculation of Molecular Radius

r=

3 M V sp
4

1
3

((

g
cm3
3 103791.6765
0.565
mol
g
r=
4

)(

1
3

1
3

r=24.10131775 cm

((

g
cm3
3 103791.6765
0.565
mol
g
r=
4

r=4.00221 x 1023

)(

1
( 6.02 x 1023 )

cm
mol

Calculation of Root-Mean-Square End-to-End Length of NaCMC

g
5.15888695 103791.6765
1
mol
r2 =
dL
2.84 x 10 21
3
mol cm

r =1.284484332 x 10
1
2

cm

1
3

VI. Literature Cited

Andrady, A.L. (2008). Science and Technology of Polymer Nanofibers. USA: John Wiley and
Sons.
Atkins, P.W. (2006). Physical Chemistry, 8th edition. Oxford, England: Oxford University Press.
Bird, R.B., Stewart, W.E. & Lightfoot, E.N. (2002). Transport Phenomena. USA: John Wiley and
Sons, Inc.
CHEM 111 Lecturers and Laboratory Instructors. (2012). Exercise 8: Viscosity of pure liquids
and solutions. Physical Chemistry I Laboratory Manual. Laguna: UPLB.
Daniels, F., Matthews, J.H., Williams, J.W., Bender, P. & Alberty, R.A. (1956). Experimental
Physical Chemistry, 5th edition. USA: McGraw-Hill Book Company, Inc.
De Nevers, N.D. (1991). Fluid Mechanics for Chemical Engineers, 2nd edition. Singapore:
McGraw Hill, Inc.

Foust, A.S., Wenzel, L.A., Clump, C.W., Maus, L.M. & Andersen, L.B. (1980). Principles of Unit
Operations, 2nd edition. Singapore: John Wiley and Sons, Inc.
Garland, C.W., Nibler, J.W. & Shoemaker, D.P. (2003). Experiments in Physical Chemistry, 8th
edition. New York: McGraw-Hill.
Levine, I.N. (2009). Physical Chemistry, 6th edition. Boston: McGraw-Hill Higher Education.
Rogers, D.W. 2011. Concise Physical Chemistry. New Jersey: John Wiley and Sons.
Roussel, R.M. (2012). A Life Scientists Guide to Physical Chemistry. London: Cambridge
University Press.