IV.

MOLECULAR WEIGHT DEFINITIONS

& DISTRIBUTION
 MOLECULAR WEIGHT
• Molecular weight, M: Mass of a mole of chains.

Low M

high M

• Polymers can have various lengths depending on the number of repeat units.
• During the polymerization process not all chains in a polymer grow to the same length, so there is a
distribution of molecular weights. There are several ways of defining an average molecular weight.
• The molecular weight distribution in a polymer describes the relationship between the number of moles of
each polymer species and the molar mass of that species.

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MOLECULAR WEIGHT DISTRIBUTION

M n  x i M i
M w  w i M i

__
Mn = the number average molecular weight (mass)

Mi = mean (middle) molecular weight of size range i

xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i 3
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5
 Degree of Polymerization, DP
DP = average number of repeat units per chain

Mn
DP 
m
where m  repeat unit molecular weight

Ex. problem 4.1b,

for PVC: m = 2(carbon) + 3(hydrogen) + 1(Clorine)
(from front of book) = 2(12.011) + 3(1.008) + 1(35.45)
= 62.496 g/mol
DP = 21,150 / 62.496 = 338.42
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Molecular weight
•Large macromolecules synthesized from molecules
•Not all polymer chains grow to the same length
•Average molecular weight is determined by measuring
viscosity and osmotic pressure
•The chain is divided into size ranges
•No. of moles (or fraction) of each size range is
determined

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Longer chains make stronger polymers.

• There is a critical length

needed before strength
increases.
• An average No. of 100
repeating units is necessary
for HC polymers but only 40
for nylons.
A Typical Molecular Weight Distribution
Curve
104 wi

n = 100 000 g mol-1

4.0

w = 199 900 g mol-1

3.0

2.0 z = 299 850 g mol-1

1.0

200 000 400 000 600 000 800 000 1 000 000
Mi (g mol-1)
 Molecular Weight Distribution
The simplest, most common molecular weight is the
number-average molecular weight (n)
• end-group analysis or colligative properties (b.p. elevation,
osmotic pressure, etc)
others commonly used are weight-average molecular
weight (w), z-average molecular weight (z) and
viscosity-average molecular weight (u)
• light scattering (w), sedimentation equilibrium (z) and
solution viscosity (u)
Number-average molecular weight (n)
• based on methods of counting the number of molecules in a
given weight of polymer
• the total weight of a polymer sample, w, is the sum of the weights
of each molecular species present

 
w   wi  N i M i
N = number of molecules
M = molecular weight
i 1 i 1


w M N i i
Mn  
 i 1


N
i 1
i N i 1
i
Number-average molecular weight (n)
Example - a polymer sample consists of 9 molecules of
mw 30,000 and 5 molecules of mw 50,000


M N i i
(9  30,000)  (5  50,000)
Mn  i 1

  37,000
(9  5)
N i 1
i
Weight-average molecular weight (w)
determination of molecular weight based on size rather
than the number of molecules
• the greater the mass, the greater the contribution to the
measurement

 

 wi M i  Ni M i
2
w = weight fraction
M = molecular weight
Mw  i 1

 i 1
 N = number of molecules

w i 1
i N M
i 1
i i
Weight-average molecular weight (w)
Consider the previous example - 9 molecules of molecular
weight 30,000 and 5 molecules of molecular weight 50,000

9(30,000) 2  5(50,000) 2
Mw   40,000
9(30,000)  5(50,000)
Z-average molecular weight (z)
some molecular weight determination methods (e.g.
sedimentation equilibrium) yield higher molecular
weight averages - z

 

 i i
N M 3
 wi M i 2
w = weight fraction
M = molecular weight
Mz  i 1

 i 1
 N = number of molecules

 i i
N M
i 1
2
w M
i 1
i i
Z-average molecular weight (z)
Consider the previous example - 9 molecules of molecular
weight 30,000 and 5 molecules of molecular weight 50,000

9(30,000)3  5(50,000)3
Mz   42,136
9(30,000)  5(50,000)
2 2
Molecular Weight Determination
In measurements of colligative properties, each
molecule contributes regardless of weight, whereas in
light scattering, the larger molecules contribute more
because they scatter light more effectively.

For this reason, w are greater than n , except when

all molecules are of the same weight and w = n
Molecular Weight Distribution
The narrower the molecular weight range, the closer
are the values of w and n , and the ratio w / n
may thus be used as an indication of the breadth of
the molecular weight range in a polymer sample.

The ratio is called the polydispersity index, and any

system having a range of molecular weights is said to
be polydispersed
 Molecular weight distribution

The degree of polymerization (DP) = no. of monomers per polymer. It is

determined from the ratio of the average molecular weight Mw of the polymer to
the molecular weight of the repeat unit (MRP).
DP = Mw / MRP
where
Mw =  fi Mi : Mw = weight average molecular weight
Mn =  xi Mi : Mn = number average molecular weight
Mi = mean molecular weight of each range
fi = weight fraction of polymer having chains within that range
xi = fraction of total number of chains within each range
 MOLECULAR WEIGHT DISTRIBUTION Adapted from Fig. 14.4, Callister & Rethwisch 8e.

total wt of polymer
Mn 
total # of molecules

M n  xi Mi
M w  wi Mi

Mi = mean (middle) molecular weight of size range i

 xi = number fraction of chains in size range i

wi = weight fraction of chains in size range i

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Molecular Weight Distributions
Mn  x M i i
i

Mw  w M   x M i i i
2
i
i i
ni
xi   number fraction
n i
i


Degreeof Polymerization
M M
nn  n ; n w  w
m m
m  "mer" molecular weight


Example SOLUTION (Continued)

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