A Review of Methods of Molecular Weight

Determination of Polymers
Dr. Aniruddh Singh
Department of Applied Sciences and Humanities, Ajay Kumar Garg Engineering College, 27 Kmstone,
NH-24, Ghaziabad 201009 UP India
[email protected]

Abstract – A polymer sample is an aggregate of a large number The distribution can be unimodal or bimodal and can be skewed
of macromolecules with different molecular weights. The which means that the peak and the entire distribution is not
macromolecule is constructed by repeated bonding of monomer symmetric about the mean. Such a distribution of molecular
units where the repetition can extend to the order of 105 to 106.
weights can be described by statistics in terms of moments.
The average molecular weight and its distribution are important
parameters which determine critically the end use properties of
the polymer. Therefore several methods are employed to make The simplest description of a unimodal (one peak) symmetric
a reasonable estimate of these quantities. These methods come distribution (same on both sides of the peak) will involve two
under the category of physical characterization of polymers. parameters, the mean, μ and the standard deviation, σ. More
In this article, an overview of these methods is given which are complicated continuous distribution functions will involve
extensively engaged in industrial environment. higher moments of the distribution. The k’th moment of a
distribution about a value, xo, is given by:
I. INTRODUCTION
THE average molecular weight is an important characteristic
of a polymer sample. Almost the entire range of mechanical
properties like thermal properties, stress-strain properties, where fi is the fraction of molecules, Ni/N having the molecular
impact, fracture, fatigue, creep, stress relaxation and cracking mass xi. Using different moments, one can define different
are influenced by average molecular weight and molecular average molecular weights. If the sample contains Ni molecules
weight distribution. Electrical properties like conductivity, of the ith kind, for a total no. of molecules , and each of
dielectric constant, dielectric loss and breakdown are also the i-th kind of molecule has a mass mi, then the total mass of
significantly dependent on molecular weight. all the molecules is . The number average molecular
mass is :
Molecular weight and its distribution have dramatic effect on
the physical properties like melting and boiling point, osmotic
pressure, viscosity, light scattering and transport through porous
materials. All these methods are employed for the measurement On the other hand, the weight-average molecular weight is
of average molecular weight . For a typical industrial synthesis defined as:
a wide molecular weight distribution results. Different possible
MWD are shown in Fig. 1.

Figure 1. Different MWD of polymers.

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A typical distribution of molecular weights in a polymer is insensitive at high molecular weight as the fraction of end
shown in fig.2. The relative position of Mn and Mw is also shown. groups becomes too small to be measured with precision [3].

Osmotic Pressure: The relation between osmotic pressure

and molecular weight dilute solutions rests on the fact that
the activity of a solute in a solution becomes equal to its
molefraction as the solute concentration becomes sufficiently
small. Since the osmotic pressure of a solution depends on
molecular weight and concentration c, the following equation
can be used to determine the number average of the molecular
weight:

where П is the osmotic pressure, c is the solute concentration,

Figure 2. Relative position of Mn and Mw. R is the ideal gas constant, T the temperature, Mn is the
number average, and A2 and A3 are the second and third
For a non uniform sample, the following relation holds true: virial coefficients. The most common method of osmometry
is membrane osmometry. In membrane osmometry, the
osmotic pressure is measured directly using a semi-permeable
The dispersity is given by the ratio of the mass average molar membrane [1].
mass to the number average molar mass.
In experiments, the osmotic pressure must be measured at
several different concentrations. By extrapolating the П/c
versus c plot to zero, the intercept gives the molecular weight,
The DM is a general measure of the heterogeneity with regard to whereas slope yields A2. It represents the interaction of a single
chain length. A DM of 1.000 refers to a single molecular mass, molecule with the solvent. For the theory of osmometry and its
a ĐM close to 1 refers to a very narrow distribution. different applications, see Hunt and James [4].

II. METHODS OF MEASUREMENT OF Ultracentrifugation: Ultracentrifugation technique is the

MOLECULAR WEIGHT most intricate of the existing methods for determination of
There are several methods available that give an estimate of molecular weights of high polymers. They are more suitable
the average molecular weight of a polymer. They include for compact proteins than random coil polymers and are used
the end group analysis, osmotic pressure measurement, overwhelmingly for biological materials.
ultracentrifugation, viscosity measurements, light scattering
methods and size exclusion chromatography. In this article The ultracentrifuge consists of an aluminum rotor several
these methods are described briefly to give an overview of inches in diameter that is rotated at high speed in an evacuated
the available methods which are employed to determine the chamber. The solution being centrifuged is held in a small cell
molecular weight of a polymer. within the rotor near its periphery. The cell is equipped with
windows and the concentration of the polymer along its length is
End Group Analysis: The molecular weight of polymers which determined by optical methods based upon the measurement of
have an end group amenable to analysis could be principally refractive index or absorption. Solvents for ultracentrifugation
analyzed by an end-group assay [1]. The biggest drawback experiments must be chosen for difference from the polymer in
of this method is the decrease in sensitivity with an increased both density and refractive index. When polymer chemistry was
chain length. The first measurements with this method were in its early stages in the 1920s, analytical ultracentrifugation
performed by Staudinger and Eder and gave determination experiments played an important role. Svedberg introduced
limits of about 15,000 g·mol−1 [2]. two analytical ultracentrifugation methods: the sedimentation
velocity method and the sedimentation equilibrium method [5].
The end group analysis requires that the polymer contains a
known number of determinable group per molecule. The long The sedimentation velocity method (performed at, for
chain nature of the polymer limits such group to end group. example, 70,000 RPM) provides information on the physical
Since the method counts the number of molecules in a given homogeneity of a sample, its conformation, interaction or co-
weight of a sample, it yields the number average molecular sedimentation, and flexibility information. The sedimentation
weight for polydisperse materials. The method becomes equilibrium, which is carried out at lower rotor speeds such

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as 15,000 RPM, yields information on absolute weight measurements, a minimum requirement is the knowledge of
averages (Mw, and Mz) and molecular weight distributions. the dependence of [η] on (M).
Ultracentrifugation is also capable of measuring the molecular
charge in polysaccharides. Diffusion parameters can also be
obtained by ultracentrifugation experiments; however, strictly
speaking, diffusion has nothing to do with ultracentrifugation,
though it is very closely connected to the theoretical and
practical background.

Viscosity Methods: The solution viscosity as a measure of

polymer molecular weight was recognized as early as 1930
by Staudinger [3]. Solution viscosity is the measure of size
or extension in space of a polymer molecule. Viscosity
measurements are simple and they are extremely useful in
correlating molecular weights that they have become a valuable
tool for molecular characterization of polymers.
Figure 3. Hydrostatic head (‘U’ tube) viscometers: (a) Ostwald; (b)
When the determination of molecular weight is required, Ubbelohde; and (c) reverse flow.
another related quantity called the intrinsic viscosity is brought Light Scattering: Light scattering occurs whenever a beam
into picture. The intrinsic viscosity is a quantity which is of light encounters matter. The nuclei and electrons undergo
independent of concentration of the solution but is the function induced vibrations in phase with the incident light wave and act
of the solvent used. The intrinsic viscosity is defined as: as sources of light that is propagated in all directions. According
to Rayleigh’s law of scattering for particles comparable to
the wavelength of light, the amount of scattering is inversely
proportional to the number of scattering particles per unit
where η/ηo is the viscosity ratio and c is the concentration. volume and to the fourth power of the wavelength.

The Mark–Houwink equation, also known as the Mark– In the static light scattering experiment (SLS), a vertically
Houwink–Sakurada equation  or the  Kuhn–Mark–Houwink– polarized (laser) light is scattered by the macromolecules
Sakurada equation  gives a relation between  intrinsic of a polymer in solution. The scattered light is detected by a
viscosity [η] and viscosity averaged molecular weight Mv: photometer or a photodiode: either one photometer is used to
encircle the sample in a horizontal plane or several photodiodes
are placed around the measurement cell, which detects the
scattered light from several positions and angles. The ratio:
From this equation, the molecular weight of a polymer can be
determined from data on the intrinsic viscosity and vice versa.
The values of the Mark–Houwink parameters, a and  K, depend
on the particular polymer-solvent system. For solvents, a value
of a = 0.5  is indicative of a theta solvent. A value of a = 0.8 is depends on: a) the concentration of solution c; b) the specific
typical for good solvents. refractive increment obtained at chemical equilibrium dn/dc or,
more accurately, (dn/dc)µ; c) the molecular weight of dissolved
The Mark Houwink equation relates the intrinsic viscosity of particles (M); d)Scattering angle θ. The scattering intensity is
a polymer solution with its viscosity averaged molecular mass dependent on the angle . For light scattering experiments, the
through a set of parameters (a and K) which are dependent Zimm equation [6] forms the basis for calculating the molecular
on the nature of the polymer and the solvent. The simplest weight (Fig. 4):
method for determining the viscosity of a polymer solution is by
capillary viscometry, using the Ubbelohde U-tube viscometer
(Fig. 3). Here, the flow time t of the polymer solution and of
pure solvent to are recorded. The ratio of the flow time of a
polymer solution t to that of pure solvent is equal to the ratio of where K* is the optical constant, R(θ, c) is the excess Rayleigh
their viscosities (η/ηo) if their densities are equal. This is only ratio of the solution as a function of scattering angle θ and
feasible for dilute solutions (in which density differences level concentration c, Mw is the molar mass weight average, P(θ) is
out). In industrial applications, the measurement of [η] provides the angular dependence of the scattered light, A2 is the second
a quick and easy route to the molecular weight. For viscosity virial coefficient, and c is the concentration of the solute.

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Figure 4. A Zimm plot showing the light scattering for Figure 5. A typical SEC chromatogram.
a particular sample.
II. CONCLUSION
Size Exclusion Chromatography: This method is a separation Different methods of determination of molecular weight of
method for high polymers, similar to but advanced in practical polymers are described briefly to give an overview of the
usage over gel filtration as used by biochemists. It has become available methods to research scientists. As the time advances
a prominent and widely used method for determining the newer methods are discovered and major improvements are
molecular weight distribution in recent times. It consists of made over the older ones. It is hoped that with the knowledge
a chromatographic column filled with beads of rigid porous of these methods one can devise experiments to obtain the most
gel. The gel is usually made up of highly cross-linked porous optimal information regarding their samples.
polystyrene or porous glass as a packing material. The pores
of these materials are of the same size as the dimension of the REFERENCES
[1]. J.M.G. Cowie and V. Arrighi, Polymers: Chemistry and Physics
polymer material. of Modern Materials; CRC Press: Boca Raton, FL, USA, 2008.
[2]. H. Staudinger and K. Eder, “Über das Viskositätsgesetz für
A sample of dilute polymer solution is introduced into a solvent Fadenmoleküle”, Naturwissenschaften, Volume 29, 1941, pp.
stream flowing in the column. Molecules are only separated 221–221.
according to their hydrodynamic volume. In contrast to other [3]. Billmeyer, Textbook of Polymer Science, Wiley India, 2012,
chromatography techniques, large molecules (in terms of page 187.
hydrodynamic volume) are eluted first, whereas small molecules [4]. J. Hunt and M.I. James, Polymer Characterization; Springer:
will enter the pores of the solid porous phase and elute later. Dordrecht, The Netherlands, 1993.
[5]. C.S.W. Koehler, “Developing the Ultracentrifuge”, Today’s Chemist
This is because larger molecules can enter only a small fraction
at Work 2003, February 2003, pp. 63–66. 57. Vollmert, B.
of the internal portion of the gel, or are completely excluded, [6]. B.H. Zimm, J.Chem Phys. Volume 16, 1948, pp.1093-1099.
smaller polymer molecules penetrate a larger fraction of the [7]. H. Benoit, Z. Grubisic, P Rempp, D.Decker and J-G Zilliox,
interior of the gel. The large molecules thus spend less time J. Chem Phys. Volume 63, 1966, pp.1507-1514.
inside the gel and quickly flow out of the gel. The different
molecular species are eluted from the column in order of their Dr. Aniruddh Singh is Ph.D in Theoretical Nuclear
molecular size [7], the largest emerging first. A specific column Physics from Jamia Millia Islamia, New Delhi.
is calibrated empirically to give a relation between retention He obtained BSc Hons in Physics from Delhi
time or volume as a function of molecular size, with the help University and MSc Physics from IIT Kanpur. His
of which a chromatogram (Fig. 5) is converted into a molecular PhD thesis is in the field of Variational Monte Carlo
size distribution curve. methods as applied to light nuclei and hypernuclei.
He has eleven years of teaching experience at
various universities and about 1.5 years research
experience in industry.

Currently, working as Assistant Professor in Department of Applied Sciences

and Humanities, AK Garg Engineering College, Ghaziabad.

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