Determination of Polymer Molecular Mass Using
the Viscometry Method
VIRTUAL LAB 2(a) – UNIT 2
Determination of the molecular mass of polymer from
viscosity measurements using organic solvents
Background: Viscosity is a measure of a fluid's resistance to flow. For
polymer solutions, the viscosity depends on the size and shape of the polymer
molecules, as well as the interaction between the polymer and the solvent. By
measuring the viscosity of a polymer solution, we can infer the molecular
mass of the polymer, because larger polymer molecules (i.e., those with higher
molecular mass) contribute more to the solution’s viscosity.
The greater the molecular mass of the polymer, the larger the individual
polymer molecules, leading to higher viscosity. Polymers in solution do not
behave like small, simple molecules. Instead, they form large, flexible, and
extended chains. These chains can occupy significant volumes in the solvent,
and as the polymer concentration increases, the solution viscosity increases in
a nonlinear fashion due to interactions between the polymer chains.
Types of Viscosity in Polymer Solutions
• Relative Viscosity (ηr): This is the ratio of the viscosity of the polymer solution
(η) to that of the pure solvent (η0).
ηr or ηr =
Where ts = Time flow for polymer solution
t0 = Time flow for pure organic solvent
• Specific viscosity(ηsp) : The specific viscosity ηsp of the solution at a
different concentration(C) is
ηsp= ηr -1 = - 1 =
• Intrinsic Viscosity[η] : The viscosity of the solution at infinite dilution
(i.e., when the concentration approaches zero)
•
• The molecular mass of a polymer can be determined from its intrinsic viscosity
using the Mark-Houwink equation and is given by
[η] = K Mva
Where,
[η] is the intrinsic viscosity, a measure of the polymer’s contribution to the
solution’s viscosity.
Mv is the weight-average molecular mass of the polymer.
K and a are constants specific to the polymer-solvent system and temperature.
Materials Required
Procedure: Weigh approximately 1 g of polymer into a beaker and add 50
mL of organic solvent. Stir the mixture and allow it to stand until the
polymer is completely dissolved. Transfer the solution to a 50 mL
volumetric flask and top it up to the mark with organic solvent. Pipette 15
mL of pure solvent into a viscometer and measure the flow time. Prepare a
series of dilutions from the stock polymer solution and measure the flow
time of each. Use the data to determine the Intrinsic viscosity and calculate
the molecular mass of Polymer.
Note: The viscosity of the polymer solution and pure solvent depends
on the time flow of the liquid.
Intercept = Intrinsic viscosity
Viscometry
Aim of the
experiment:
To determine
the coefficient
of viscosity of a
given organic
liquid using
Ostwald
viscometer
The intrinsic viscosity [η] of a Polystyrene solution is found to be 0.55 dL/g at 25˚C
in benzene. Calculate its viscosity average molecular weight. Standard polystyrene
solution of molecular weight 39000 g/mol prepared under same condition exhibited
intrinsic viscosity of 0.40 dL/g and K value is found to be K=1.5×10−4 dL/g at 25˚ C
in benzene.
Solution
log[η] = log K + a logM
log0.40 = log(1.5*10-4)+a log39000
a=0.75
[η] = log K + a logM
log0.55 = log(1.5*10-4)+0.92 logM
M = 59979 g/mol
A polymer solution’s flow times are measured in a viscometer
with solvent flow time t0=100 s. The following data are obtained:
Concentration, c (g/dL) Flow time, t (s)
0.2 104
0.4 110
0.6 118
Given:
•Mark-Houwink constants: K=1.5×10−4 dL/g, a=0.7
Calculate:
[Link] intrinsic viscosity [η] by extrapolation.
[Link] molecular weight M of the polymer.
Solution
Calculate relative viscosities and specific viscosities for each concentration c
ηr = ηsp= ηr -1 /c
c ttt ηr = ηsp= ηr -1
0.04 / 0.2 =
0.2 104 1.04 0.04
0.20
0.10 / 0.4 =
0.4 110 1.10 0.10
0.25
0.18 / 0.6 =
0.6 118 1.18 0.18
0.30
Calculation of extrapolation of ηsp/cvs. c
Equation of line:
ηsp/c=[η]+k⋅c
Use two points (0.2,0.20) and (0.6,0.30) to find the slope k and
intercept [η]:
Slope:
k=(0.30−0.20)/ (0.6−0.2)=0.25
Intercept:
[η] = ηsp/c−k⋅c = 0.20−0.25×0.2= 0.15 dL/g
Mark-Houwink to find M:
[η]=KMa
M = 1.93 × 104 g/mol