MOLAR MASS AND DEGREE OF POLYMERIZATION

 Many properties of polymer show a strong dependence upon the size of the
polymer chains.
 So it is essential to characterize their dimensions.
 This is normally done by measuring the molar mass (M) of a polymer.
 Molar mass defined as the mass of 1 mole of the polymer it is quoted in gmol -1 or
kg mol-1.
 For network polymer we use the molar mass of chains existing between junction
points. The molar mass of the network is infinite .
 Usually the molar mass of a homopolymer is related to the degree of
polymerization ( X) which is the number of repeat units in the polymer chain by
the simple relation.
 M = XMo 1.1a
 where
 Mo  molar mass of the repeat unit
 example: (C2H4)1200 X= 1200

 For copolymer the sum of the products Mo for each type of R.U. is required to
define the molar mass.
 M = Xi Moi 1.1b
 Molar Mass Distribution
 A polymer sample is a mixture No. Mn = 100,000
of molecules with different 6000 of
mole
degree of polymerization. 5000
cules
of
mass
 In general a polymer contain a 4000 Mi

range of molar masses. Mw = 200,000

3000
 Fig. 1.1 shows a typical molar
mass distribution curve 2000

 A sample of polymer has 1000

Mz = 300,000

molecules of different
molar mass
 M1, M2, M3, M4 ........ Mi 1 2 3 4 5 6 7
Mi gmol (105)
-1

 N1, N2, N3, N4 ....... Ni

Figure 1.1
 Molar Mass Averages
 It is some times convenient to use a molar mass average in
place of a complete distribution.
 The number - average molar mass Mn
 Definition  the sum of the products of the molar mass of
each fraction multiplied by its mole fraction.
 Mn = XiMi
1.2
 where :
 Ni
Xi is the mole fraction of the molecules of molar mass Mi
Xi = _______
N = number of moles
Ni
NiMi Wi W
Mn = ___________
= ________
= _____

Ni Ni Ni 1.3

Sometimes weight fraction are used in place of mole fraction.

The weight fraction Wi is defined as the mass of molecules of molar mass Mi

divided by the total mass of all the molecules present.
NiMi
Wi = __________ 1.4
NiMi
Wi  Ni
 ______
= ________
1.5
Mi NiMi

Combining equations 1.3 & 1.5 gives Mn in terms of weight

fraction.

1 Wi 1
Mn = _____________
or  _______ = _______
1.6
Wi/Mi Mi Mn
The weight -average molar mass Mw

Definition  the sum of the products of the molar mass of each

fraction multiplied by its weight fraction.
WiMi
Mw = _________
1.7
W i

Combine equation 1.4 and 1.7

NiMi2 WiMi WiMi
Mw = ____________
= __________
= ___________

NiMi W i W 1.8
We use Mw rather than Mn for polymeric materials where some of
the physical properties the contribution of the high Mi species
dominates the behavior.

Because of the squared Mi term in the numerator, Mw is sensitive to

the presence of high Mi species.
 Example1.1
 Consider a blend of mass 2g formed from 1g of each of the two paraffin's:
one C95H192 and the other C105H212, What are Mn and Mw of the blend ?
 Solution
 The two molar masses are
 M95 = 95*12+192 = 1332 g/mol
 M105 = 105*12+212 = 1472 g/mol
 It then follows that in the 2g specimen the number of moles present is
 n95 = 1 / 1332 = 7.51*10-4 mol
 n105 = 1 / 1472 = 6.79*10-4 mol
 The average molar masses are then, From eqn. 1.3
 Mn = 1+1/ (7.51+6.79) *10-4 = 1399 g/ mol
 Mw = 1*1332 + 1*1472 / 2 = 1402 g/ mol
 In this case the two averages are almost the same.
 Example1.2
 Consider a blend of mass 2g formed from 1g of each of the two paraffin's:
on C10H22 and the other C190H382, What are Mn and Mw of the blend ?
 Solution
 The two molar masses are
 M10 = 10*12+22 = 142 g/mol
 M190 = 190*12+382 = 2662 g/mol
 It then follows that in the 2g specimen the number of moles present is
 n10 = 1 / 142 = 70.42*10-4 mol
 n190 = 1 / 2662 = 3.76*10-4 mol
 The average molar masses are then, From eqn. 1.3
 Mn = 1+1/ (70.42+3.76) *10-4 = 270 g/ mol
 Mw = 1*142 + 1*2662 / 2 = 1402 g/ mol
 In this case the two averages are not the same.
 Example1.3
 Consider a blend of mass 2g formed from 1g of each of the two paraffin's:
on C10H22 and the other C1000H2002, What are Mn and Mw of the blend ?
 Solution
 The two molar masses are
 M10 = 10*12+22 = 142 g/mol
 M1000 = 1000*12+2002 = 14002 g/mol
 It then follows that in the 2g specimen the number of moles present is
 n10 = 1 / 142 = 70.42*10-4 mol
 n1000 = 1 / 14002 = .71*10-4 mol
 The average molar masses are then, From eqn. 1.3
 Mn = 1+1/ (70.42+.71) *10-4 = 281 g/ mol
 Mw = 1*142 + 1*14002 / 2 = 7072 g/ mol
 In this case the two averages are not the same.
 Comments on Example 1.1, 1.2 and 1.3
The result of the example illustrate the following points.
 Mn is sensitive to the mixture of molecules of low molecular mass.
 Mn for 10/190 and 10/1000 are much lower than the 95/105 blend
 Mw is sensitive to the mixture of molecules of high molecular
mass.
 Mw for 10/1000 blend greatly exceeds that for the other two
(where they are equal 1402)
 Mw always higher than Mn
 The ratio Mw/Mn is a measure of the range of molecular sizes in
the specimen it is 1.00, 5.19 and 25.17 it is normally in the ranges
of 2 - 100 some polymer has very small or very high value of
polydispersity index.
 This ratio is known as polydispersity or heterogeneity index.
 Monodisperse polymer would have Mw/Mn = 1.00
 Z-average Molar Mass (Mz)
 quoted for higher molar mass averages.

NiMi3 WiMi2
Mz = _____________
= ____________
1.9
NiMi2 WiMi

The number average and weight average degree

of polymerization
For a homopolymer are given by
Xn = Mn/Mo 1-10
and Xw = Mw/Mo 1-11
 Homework
 Solve the last three example for the Z-average
molar mass ?
 Comment on the results ?
 Thank You

See You Next Lecture