Because virtually all polymers are mixtures of many large molecules, one must

resort to averages to describe molecular weight. Among many possible ways of

reporting averages, three are commonly used: the number average, weight average,
and z-average molecular weights. The weight average is probably the most useful
of the three, because it fairly accounts for the contributions of different sized
chains to the overall behavior of the polymer, and correlates best with most of the
physical properties of interest.

The ratio of Mw to Mn is known as the polydispersity index (PDI), and provides a

rough indication of the breadth of the distribution. The PDI approaches 1.0 (the
lower limit) for special polymers with very narrow MW distributions, but, for
typical commercial polymers, is typically greater than 2 (occasionally much
greater). Here is a typical MW distribution curve, measured by Size Exclusion
Chromatography (SEC):
Dependance of Polymer Properties on MW

Many polymer properties of interest (T g, modulus, tensile strength, etc.) follow a

peculiar pattern with increasing MW. Small molecules have small values, then
there is a sharp rise in properties as the chains grow to intermediate size
(oligomers), and then the properties level off as the chains become long enough to
be true polymers.

However, a few properties important for polymer processing, like melt viscosity
and solution viscosity, increase monotonically with MW. This means that the goal
of polymer synthesis is not to make the largest possible molecules, but rather, to
make molecules large enough to get onto the plateau region. Increasing the MW
beyond this does not improve the physical properties much, but makes processing
more difficult.

A few properties are dictated by the repeat units alone, and therefore these are not
changed much by MW. Examples: color, dielectric constant, and refractive index.
Definition of molar mass averages
Different average values can be defined depending on the statistical method that is applied.
The weighted mean can be taken with the weight fraction, the mole fraction or the volume fraction:

 Number average molar mass or Mn

 Weight average molar mass or Mw
 Viscosity average molar mass or Mv
 Z average molar mass or Mz

 [1]

Here a is the exponent in the Mark-Houwink equation which relates the intrinsic viscosity to molar

mass.

[edit]Measurement

These different definitions have true physical meaning because different techniques in physical
polymer chemistry often measure just one of them. For instance osmometry measures number
average molar mass and small angle laser light scattering measures weight average molar mass.
Mv is obtained from viscosimetry and Mz by sedimentation in an analytical ultracentrifuge. The quantity
a in the expression for the viscosity average molar mass varies from 0.5 to 0.8 and depends on the
interaction between solvent and polymer in a dilute solution. In a typical distribution curve the average
values are related to each other as follows Mn < Mv < Mw < Mz. Polydispersity of a sample is defined
as Mw divided by Mn and gives an indication just how narrow a distribution is. [1]

The most common technique for measuring molecular weight used in modern times is a variant of
high pressure liquid chromatography (HPLC) known by the interchangeable terms of size exclusion
chromatography (SEC) and gel permeation chromatography or (GPC). These techniques involve
forcing a polymer solution through a matrix of cross-linked polymer particles at a pressure of up to
several thousand psi. The limited accessibility of stationary phase pore volume for the polymer
molecules results in shorter elution times for high molecular weight species. The use of low
polydispersity standards allows the user to correlate retention time with molecular weight although the
actual correlation is with the Hydrodynamic volume. If the relationship between molar mass and the
hydrodynamic volume changes (i.e., the polymer is not exactly the same shape as the standard) then
the calibration for mass is in error.

The most common detectors used for size exclusion chromatography include online methods similar
to the bench methods used above. By far the most common is the differential refractive index detector
which measures the change in refractive index of the solvent. This detector is concentration sensitive
and very molecular weight insensitive so it is ideal for a single detector GPC system as it allows the
generation of mass v's molecular weight curves. Less common but more accurate and reliable is a
molecular weight sensitive detector using multi-angle laser light scattering - see Static Light
Scattering. These detectors directly measure the molecular weight of the polymer and are most often
used in conjunction with differental refractive index detectors. A further alternative is either low angle
light scattering, which uses a single low angle to determine the molar mass or Right Angle Light Laser
scattering in combination with a viscometer, although this last technique does not actually give an
absolute measure of molar mass but one relative to the structural model used.

The molar mass distribution of a polymer sample depends on factors such as chemical kinetics and
work-up procedure. Ideal step-growth polymerization gives a polymer with polydispersity of 2.
Idealliving polymerization results in a polydispersity of 1. By dissolving a polymer an insoluble high
molar mass fraction may be filtered off resulting in a large reduction in M w and a small reduction in
Mnthus reducing polydispersity.

[edit]Number average molecular weight

The number average molecular weight is a way of determining the molecular weight of a polymer.
Polymer molecules, even ones of the same type, come in different sizes (chain lengths, for linear
polymers), so the average molecular weight will depend on the method of averaging. The number
average molecular weight is the ordinary arithmetic mean or average of the molecular weights of the
individual macromolecules. It is determined by measuring the molecular weight of n polymer
molecules, summing the weights, and dividing by n [2].

The number average molecular weight of a polymer can be determined by gel permeation
chromatography, viscometry (Mark-Houwink equation), and all colligative methods like vapor pressure
osmometry or end-group determination.

An alternative measure of the molecular weight of a polymer is the weight average molecular weight.
The ratio of the weight average to the number average is called the polydispersity index.

High Number-Average Molecular Weight Polymers may be obtained only with a high fractional

monomer conversion in the case of step-growth polymerization, as per the Carothers' equation.

[edit]Weight average molecular weight

The weight average molecular weight is a way of describing the molecular weight of a polymer.
Polymer molecules, even if of the same type, come in different sizes (chain lengths, for linear
polymers), so we have to take an average of some kind. For the weight average molecular weight,
this is calculated by
where Ni is the number of molecules of molecular weight Mi.

Intuitively, if the weight average molecular weight is w, and you pick a random monomer, then the
polymer it belongs to will have a weight of w on average (for a homopolymer).

The weight average molecular weight can be determined by light scattering, small angle neutron
scattering (SANS), X-ray scattering, and sedimentation velocity.

An alternative measure of molecular weight for a polymer is the number average molecular weight;
the ratio of the weight average to the number average is called the polydispersity index.

The weight-average molecular weight, Mw, is also related to the fractional monomer conversion, p,

in step-growth polymerization as per Carothers' equation:

, where Mo is the molecular weight of the

repeating unit.