Professional Documents
Culture Documents
Distor, Nedrick T.
Flores III, Deogracias C.
Requiso, Princess J.
Sison, Richard Dean B.
Somera, Erika A.
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
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
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
o
G
(8-1)
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
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
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.
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,
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,
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:
versus
dV
dy
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).
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
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:
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).
V=
where
r4t P
8 l
(8-5)
is the
pressure difference at the tube ends. Since the two viscometers have tubes open at both ends,
the value of
P= gh
By substituting the equation for
(8-6)
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
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
and
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
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
1.02384x10-7
Correlation coefficient ( r )
0.981446203
4.886747023
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
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
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)
o =RT ln M
G
h NA
where
o
G
(8-11)
o
H
NA
is the
can be expressed
as:
o = H
oT So
G
By plotting
o
G
versus
T , the values of
and
(8-12)
o
H
o
H
. The following
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)
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)
), 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
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
o
G
86000
85000
84000
83000
82000
G, J/mol
81000
80000
79000
78000
77000
76000
290
295
300
305
310
Temperature, K
315
320
325
o
G
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
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
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
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)
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)
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)
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
and extrapolating to
c 0 is taken.
A relationship between viscosity values and molecular weight of a polymer is found out to be:
sp
=kM
c
where
(8-20)
c=0 , the
[ ] =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
= []
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
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
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)
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)
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
9
8
7
6
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
log M
log [ ]
versus
(8-25)
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)
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
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 )
)
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.
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
= A t
B
t
kg
ms
o =RT ln M
G
hNA
= 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
soln =
m pyc+soln m pyc
mpyc + H Om pyc H
soln =
A =0.95 ,
24.291 g16.2521 g
g
995.738539 3
26.072 g16.2521 g
cm
soln =815.1450159
g
cm3
) (
sp =
tt o
to
sp =
3.65 s0.75 s
=3.866667
0.75 s
sp
c
3.866667
dL
=3.866667
g
g
1
dL
=3.866667
dL
g
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
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
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
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
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.