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A Scientific Report
Submitted to Prof. Jacob Glenn Jansalin
In Partial Fulfilment
of the Requirements for
Chem 151 – Physical Chemistry I Laboratory
Molar mass determination is characterized into primary and secondary techniques based
on whether or not standards are needed to calibrate the analytic instrument. Primary or absolute
techniques are based on colligative properties of a compound, which depend only on the number
and not on the nature of the particles of a compound. Examples of this technique include melting
point depression, vapor pressure and osmotic pressure. Secondary or relative techniques are
much simpler and more reducible with the use instrumentation such as gel permeation
coefficients for the thermal and solvent conditions of measurement. Some handbooks, such as
The Polymer Handbook, 3rd edition by Brandrup and Immergut, provide useful reference for the
values for the Mark-Houwink equation as well as a concise description of intrinsic viscosity.
To describe the relationship between intrinsic viscosity and molecular weight, the Mark-
Houwink-Sakurada equation is used: [η] = K Ma, where a and K are constants for a specific
usually a capillary viscometer. The viscometer uses the Poiseuille equation for laminar pressure
flow in a capillary tube. The volumetric flow rate, Q = dV/dt, under gravity, following the
Poiseuille’s law is given by, Q = rgpR4/(8h). For constant volume, dV, the time for flow is
Since time is proportional to viscosity, the intrinsic velocity can be calculated from a
capillary viscometer substituting time for viscosity. Intrinsic viscosity method is usually applied
The very high molecular weight and a very high viscosity of chitosan precluded its use in several
biological applications. The efficacy of chitosan depends on its molar mass and polydispersion.
If the molar mass is known and there is good understanding of the conformation of the polymer
in the solvent medium, the rheological and mechanical properties can be estimated (Kassai,
2007).
polymer. The molecular weight of chitosan can be determined by various techniques. One of the
simplest and rapid methods for determining the polymer is through viscometry. It is the method
used to determine the viscosity of a given polymer solution by means of comparing the flow
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 intrinsic viscosity reflects the average interactions of
single polymer molecules with the solvent and, if the molecule is considered spherical, intrinsic
viscosity is proportional to the volume of the molecule (Neira-Velasquez, et. al., 2013). The
relationship between intrinsic viscosity and molar mass is given by the Mark-Houwink-Sakurada
equation. The intrinsic viscosity of a polymer in a given solvent increases with the polymer’s
molar mass. This relation is the base for the viscometric method to assess the molar mass of a
are determined by evaluating a plot of log [η] versus log molecular weight.
where in a Cannon-Fenske viscometer is used. This is an opportunity for the students to explore
other methods aside from the commonly known, Dumas method, in molar mass determination.
This study generally aimed to determine the molecular weight of chitosan by measuring
chitosan sample;
ii. apply Mark-Houwink-Sakurada equation to compute for the molecular weight
iii. show the relationship between intrinsic viscosity and molecular weight
through a plot.
The study was limited to the measurement of intrinsic viscosity to determine the
molecular weight of the low-molecular chitosan sample. A Cannon-Fenske viscometer was used
for the measurement and the Mark-Houwink-Sakurada equation was used for computing the
molecular weight.
This study was conducted on the 10th and 23rd of October 2017 in the analytical
laboratory of the Department of Pure and Applied Chemistry, Visayas State University, Baybay
City, Leyte.
II. MATERIALS AND METHOD
Materials
through the courtesy of Sir Candelario L. Calibo. The solvent used to dissolve chitosan was
prepared from Analytical Reagent (AR) grade chemicals - glacial acetic acid and ammonium
Sample Preparation
An acetic acid/sodium acetate buffer solvent was prepared by mixing equal volumes of
0.25 M acetic acid and 0.25 sodium acetate solutions. The pH of the buffer was measured then
readjusted to pH=4.0 using sodium hydroxide solution. One gram of chitosan sample was
dissolved in 125 mL of the buffer solvent system. The resulting solution (0.8g/dl) was
continuously stirred for 3-4 hours until the chitosan has completely dissolved. Two other
concentrations of the chitosan solution were prepared by serial dilution – 10 mL aliquot of the
higher concentration chitosan solution was diluted to 100 mL, making 0.08g/dl and 0.008g/dl
chitosan solutions.
The flow rate of the viscous chitosan solutions were measured using a Cannon-Fenske
viscometer (Figure 1). The experiment was initially performed at room temperature (36oC) but
due to the time-consuming preparation and measurements, a water bath was used to maintain the
temperature in the later parts of the experiment. The flow time of the solution at test was read
with the aid of a stopwatch. Three readings were made for each chitosan solution, starting with
For each chitosan concentration, the following viscosities were determined using the
equation given;
The reduced viscosity and inherent viscosity values were plotted against chitosan
concentration. The value of intrinsic viscosity was obtained by extrapolating the graph of
reduced viscosity and inherent viscosity to zero concentration. The average of the two obtained
The results of the flow time of each chitosan concentration are shown in Table 1. It is
observable that the flow tine of the chitosan solution decreases along with its concentration.
Lower concentration of the polymer resulted to a less viscous solution; with lower viscosity, a
Using Equations 2-5 and the flow rates, the viscosity values were calculated. These
Both relative and specific viscosities depend on polymer concentration. The reduced
viscosity is a measure of the specific capacity of the polymer to increase the relative viscosity
(Flory, 1953). By extrapolating the reduced viscosity to zero concentration, the inherent
properties of the polymer are measured. The plot (Figure 2) shows the reduced viscosity and
From the equation of the curve of the inherent viscosity, ηinh = -0.0595x + 3.9961, the y-
intercept was known. The value of the reduced viscosity at zero concentration is 4.56 based from
the equation ηred = 27.21x + 4.56. The average of the two extrapolations, 4.56 and 3.9961, was
substituted to the MHS equation to obtain the molecular mass of the chitosan polymer. The
constants for the polymer-solvent system as determined by Kassai, et. al. (2000) system:
[𝜂]
[𝜂] = 𝐾𝑀𝛼 ⇒ log 𝑀 = 𝑙𝑜𝑔 ( )
𝐾
4.27805
𝑙𝑜𝑔 ( )
𝑀 = 𝑎𝑛𝑡𝑖𝑙𝑜𝑔 [ 1.4𝑥10−4 ] = 𝟐𝟓𝟑, 𝟑𝟕𝟎. 𝟕𝟏 𝒈/𝒎𝒐𝒍
0.83
The determined molecular weight of chitosan sample manufactured by Sigma-Aldrich is
calculated value from the experiment which is 253,370.71 g/mol, is off the given range. Thus,
there was an error in the experiment. Moreover, as can observed in Figure 2, the curves of the
plotted viscosities are not completely linear. One can expect that the experimental value will not
be accurate. The basis for the determination of intrinsic viscosity through extrapolation is the
Kraemer-Huggins plot. Figure 3 shows the expected plot which is different from result of this
experiment.
Based on the closeness of the flow rates of the chitosan concentrations, the experiment
gave quite precision. The errors that affected the results may be systematic or random.
Systematic error may come from the uncontrolled temperature throughout the experiment. The
water bath was only used in the later part of the experiment when the room temperature dropped
as the time of the day passed because the lengthy time for the experimentation was overlooked.
Since the viscosity of solutions depend on temperature, any slight change in the temperature of
the environment during the experiment will affect the flow rate measurement. It would have been
more appropriate to have used the water bath for all the measurements. The possible major
source of random error that affected the measurements may be the presence of impurities in the
solutions. Based on the literatures, before subjecting the chitosan solution to the viscometer, it
must be filtered using filters with pore size of 5 to 8 μm. However, this was not applied in the
experiment because of time constraint. The filtration of the viscous chitosan solution would take
a lot of time, even before the arduous flow rate reading. Any impurity in the solution will affect
the flow rate of the polymer solution in the viscometer, most especially within the smallest radius
of the capillary.
For future experiments using the intrinsic viscosity method where the experimenters have
a lot of time in their hands, more dilute solutions of the polymer should be prepared and more
measurements must be repeated to obtain a linear behavior in the plot. This will result a better
Conclusion
viscometer is feasible but laborious and time-consuming. It is not advised to use this method
especially when doing analytical measurements because the results are not accurate especially
when the system is not kept at uniform condition throughout. For this reason, the determination
of molecular weight of polymers using intrinsic viscosity method requires patience and time.
Instead, many other more advanced and more reliable methods can be used to determine
molecular weight of substances such as gel permeation chromatography (GPC) or high pressure
Recommendation
Better results and conclusion can be obtained from reconducting the experiment with the
following recommendations;
i.) Before testing a polymer, measure the viscosity of a solution, preferably with
ii.) Use other types of viscometers such as Ostwald and Ubbelohde viscometers;
iii.) Use a water bath all throughout the experiment to maintain the temperature of
the solutions and during the flow rate measurement and ensure the solutions come
in thermal equilibrium with the bath for a longer period of time; and
iv.) Filter the solution before subjecting to the viscometer to lessen impurities
FLORY, P.J. 1953. Principles of Polymer Chemistry. New York: Cornell Univesity Press, p. 309
KASSAI, M.R., ARUL, J., and CHARLET, G. 2000. Intrinsic viscosity-molecular weight
relationship for chitosan. Journal of Polymer Science Part B: Polymer Physics, 3, 19: 2591-
2598
PENICHE, C., ARGUELLES-MONAL, W., PENICHE, H., and ACOSTA, N. 2003. Chitosan:
An attractive biocompatible polymer for microencapsulation. Macromolecular Bioscience, 3,
511-520.