Molecular Weight Concepts

Average molecular weight

• The molecular weight can vary from a single-digit figure for a simple chemical entity to a
number in millions for a complex polymer, e.g. the molecular weight of hydrogen is just
two, while that of circular DNA in Escherichia coli is around 2 billion.

• A simple compound has a fixed molecular weight. In contrast, a polymer comprises

molecules of different molecular weight and, hence, its molecular weight is express in
terms of an ‘average value’.

• Ethylene gas is a low molecular weight simple chemical compound; each of its molecules
has the same chemical structure (CH2=CH2) and hence, a fixed molecular weight of 28. But
we polymerize ethylene to make polyethylene and we encounter an indefinite chemical
structure of
[-CH2-CH2-]n
• Wherein n can change its value from one polyethylene molecule to another present in the
same polymer sample. Dr. H. M. Parekh 2
• This is so because when ethylene is polymerize to form polyethylene, a number
of polymer chains start growing at instant, but all of them do not get terminated
after growing to the same size. The chain termination is a random process and,
hence, each polymer molecule formed can have a different number of monomer
units and thus different molecular weights.

Dr. H. M. Parekh 3
• The three molecules have different sizes, their molecular weights are
different, and yet, they are all very much ‘polyethylenes’. A polymer
sample can, therefore, be thought of as a mixture of molecules of the
same chemical type, but of different molecular weights.

• The molecular weight of the polymer sample can only be viewed

satisfactory and expressed as some average of the molecular weights
contributed by the individual molecules that make the sample.

Dr. H. M. Parekh 4
 Number-average and weight-average molecular
weights
Number-Average concept
Consider a basket containing 4 vegetables: tomatoes, brinjals, cabbages and
cauliflowers. Just for ease of understanding, let each tomato of the tomato
lot weigh the same and so also each of the other vegetables. Assume that
the number of each vegetable and its weight are as tabulated.

Vegetable Number of Weight of each Total weight of each

entity units in each unit, M(g) entity W = nM(g)
entity, n
Tomatoes 2 10 20
Brinjals 4 20 80
Cabbages 6 100 600
Cauliflowers 3 250 750
15 -------
Dr. H. M. Parekh
1450 5
• Now, we have to find out the average weight of the vegetable present in the
basket.
• To work this out, one might assume that the individual vegetable entity
contributes to the average weight in the proportion of its numbers. What we
then get in the number-average weight, arrived at as follow:

Total number of vegetables contained in the basket = 15

Number of tomatoes present in the basket = 2

Therefore, number fraction of tomatoes (to the total number of

vegetables) = 2/15

Similarly,
Number fraction of brinjals = 4/15
Number fraction of cabbages = 6/15
Number fraction of cauliflowers = 3/15
Dr. H. M. Parekh 6
 Contribution made by two tomatoes towards average weight of vegetables in the
basket:

Number fraction of tomatoes x weight of each tomato = 2/15 X 10 = 1.33 gram

Similarly,
Contribution made by 4 brinjals to the average weight of the vegetables in the
basket = 4/15 X 20 = 5.33 gram

Similarly,
Contribution made by 6 cabbages to the average weight of vegetables in the basket
= 6/15 X 100 = 40.00 gram

Similarly,
Contribution made by 3 cauliflowers to the average weight of the vegetables in the
basket = 3/15 X 250 = 50.00 gram

Summing up the contributions made by each vegetable variety, we get the ‘number-
average weight of the total vegetable as

1.33 + 5.33 + 40 + 50 = 96.66 gram

7
Dr. H. M. Parekh
Weight-Average concept

• The other method of calculating the average weight is based on the assumption
that the individual vegetable variety contributes to the total weight in the
proportion not of its number but its weight. What we then get is the ‘weight-
average’, arrived at as follow:

Total weight of all vegetables in the basket = 1450 grams

Weight of tomatoes present in the basket = 20 grams
Therefore, weight fraction of tomatoes = 20/1450

Similarly, weight fractions of brinjals cabbages and cauliflowers are 80/1450,

600/1450 and 750/1450, respectively.

• Next, contribution made by tomatoes towards average weight of vegetables in

the basket = Weight fraction of the tomatoes x Average weight of the tomatoes
= (20/1450) X 10 = 0.14 gram
Dr. H. M. Parekh 8
Similarly,

Corresponding contribution by brinjals = (80/1450) X 20 =1.10 gram

Corresponding contribution by cabbages = (600/1450) X 100 = 41.38 gram

Corresponding contribution by cauliflowers = (750/1450) X 250 = 129.31 gram

Summing of the contributions made by each vegetable variety, we get the weight-
average molecular weight of the total vegetables as

0.14 + 1.10 + 41.38 + 129.31 = 171.93 gram.

Dr. H. M. Parekh 9
 Generalization of the foregoing concepts
• In computing the molecular weight of the polymer we can also use either the
number fraction or the weight fraction of the molecules present in the polymer
to get either the number-average (Mn) or the weight-average molecular weight
(Mw), respectively.

• The method of working out Mn and Mw can now be easily generalized using
simple mathematics.

• Assume that there are n numbers of molecules in a polymer sample and n1 of

them have M1 molecular weight; n2 have M2 molecular weight and so on till we
get ni having Mi molecular weight.

Dr. H. M. Parekh 10
Now, we have a total number of molecules (n) in given by

n = n1 + n2 + n3 + ------- + ni = Ʃni

Number of molecules in fraction 1 = n1

Number fraction of fraction 1 = n1/n = n1/Ʃni

Molecular weight contribution by fraction 1 = n1M1/Ʃni

Similarly molecular weight contribution by other fractions will be as follows.

n2M2/Ʃni, n3M3/Ʃni, n4M4/Ʃni, ………… niMi/Ʃni

Number-average molecular weight of the whole polymer will then be given by

(n1M1/Ʃni) + (n2M2/Ʃni) +………+ (niMi/Ʃni) = ƩniMi/Ʃni = Mn

Similarly, total weight of the polymer = W = ƩniMi

Dr. H. M. Parekh 11
 Weight of fraction 1 = W1 = n1M1

Weight fraction of fraction 1 = n1M1/W = n1M1/ƩniMi

Molecular weight contribution by fraction 1 is given by

n1M1M1/ƩniMi = n1M12/ƩniMi

Similarly, the molecular weight contribution by the other fractions will be

n2M22/ƩniMi, n3M32/ƩniMi ……….. niMi2/ƩniMi

The weight-average molecular weight of the whole polymer will then be

(n1M12/ƩniMi) + (n2M22/ƩniMi) + ……….. + (niMi2/ƩniMi) = ƩniMi2/ƩniMi = Mw

• For all synthetic polymers, Mw is greater than Mn. If they were to be equal, the
polymer sample may be considered as perfectly homogeneous but this does not
happen. Dr. H. M. Parekh 12
 Sedimentation and viscosity-average molecular weights

• Apart from Mn and Mw there are two other ways of accessing the molecular
weight based on the sedimentation and flow behavior of the polymer in
solution. They are: z-average molecular weight Mz and viscosity-average
molecular weight Mv, express as

Mz = ƩniMi3/ƩniMi2

and
Mv = (ƩniMi1+a/ƩniMi)1/a

• In this two equations ni is the number of molecules having the molecular weight
of Mi present in the sample and α is a variable (its value ranging from 0.5 to 1.0)
in the Mark-Houwink equation which relates intrinsic viscosity [η] with the
viscosity-average molecular weight Mv.

Dr. H. M. Parekh 13
 Molecular weight and Degree of Polymerization
• The size of polymer molecule depends on the number of repeat units it
contains and this number represents the ‘degree of polymerization’.
• If there are 1000 repeat units in a polymer molecule, the degree of
polymerization (DP) is 1000. DP provides another way of expressing the
molecular weight a follows:
M = Dp x m

• Where, M is the molecular weight of the polymer, Dp its degree of

polymerization and m the molecular weight of the monomer or the repeat unit.

• Both DP and molecular weight are related to the molecular size. Hence, like
molecular weight, DP can also be averaged over the size of the sample. The
‘number-average’ and ‘weight-average’ degree of polymerization can then be
defined in a manner similar to that in which Mn, Mw are defined earlier, viz.,
(Dp)n = Ʃni(Dp)i/Ʃni
and
(Dp)w = Ʃni(Dp)i2/Ʃni(Dp)i
Dr. H. M. Parekh 14
• Each of these averages can be related to the corresponding molecular weight
averages by the following two equations:

Mn = (Dp)n x m

Mw = (Dp)w x m

Dr. H. M. Parekh 15
 Polydispersity and Molecular Weight Distribution in Polymers
• A simple chemical compound contains molecules, each of which has the same
molecular weight, where as a polymer contains molecules, each of which can
have different molecular weights.
• Monodispersity and polydispersity can be represented as below.

Dr. H. M. Parekh 16
• While the polydisperse nature of the polymer is the basis of the concept of
‘average’ molecular weight, this ‘average’ by itself conveys nothing on the
dispersity pattern in a given polymer sample.

• Take a polymer sample of, say, 40,000 average molecular weight. Now, this may
mean that the molecules have molecular weights ranging from 20,000 to 80,000
or from 500 to 100,000- the figure is uncertain.

• This is the reason why two polymer samples of the same 40,000 Mn can display
similar properties in some respects but not in some others.

• To know a polymer properly, we must have a knowledge of both the average

molecular weight as well as its dispersion pattern. This dispersity with respect to
the lowest to the highest molecular weight homologues is expressed by a simple
molecular weight distribution curve.

• Such a curve for a polymer sample is computed by plotting the number fraction
(ni) of molecules having a particular molecular weight (Mi) against the
corresponding molecular weight.
Dr. H. M. Parekh 17
• The curve shown in above figure brings out the relative positions of various
average molecular weights in a polydispersed polymer sample. It may be noted
that Mw is greater than Mn and that
Dr. H.M is closer to Mw than to Mn.
M.vParekh 18
• Figure shows molecular weight distribution in two samples having the same
number-average molecular weight but different polydispersities. Sample 1
obviously has a narrower dispersion pattern and, hence, a lower polydispersity
than sample 2.
• Polydispersity is a very important parameter. It gives an idea of the lowest and
the highest molecular weight species as well as the distribution pattern of the
intermediate molecular weight species.
• To quickly ascertain the degree of polydispersity, we can determine Mw and Mn
by two different experimental methods and then compute Mw/Mn. This ratio is
indicative of the extent of polydispersity.
Dr. H. M. Parekh 19
• For all synthetic polymers, this ratio is higher than 1. As the molecular weight
distribution becomes broader (as the dispersity increases), the value of Mw/Mn
is increases.

• The three curves in figure show the dispersity ratio increasing for the three
samples with the same Mn, but a different molecular weight distribution.

Dr. H. M. Parekh 20