Polymer Molecular weight and its Measurement methods

Dr. Bapu R. Thorat

Assit. Professor of Chemistry
Government College of Arts and Science, Aurangabad,
Maharashtra 400060
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Cellulos
e

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 Molecular weight of Polymers
“Molecular weight of a polymer is defined as sum of the atomic weight of each of the atoms in the molecules, which is
present in the polymer”.

Simple chemical compounds contains If a polymer sample

molecules, each of which has the same of molecular weight
molecular weight (a monodispersed system), 40000 Mn.
whereas a polymer contains molecules, each Molecules with molecular weight ranging from 20000-80000, or 500-100000, the figure is
of which can have different molecular weights uncertain
(polydisperse system).
Methane (CH4) molecules have the same
molecular weight (16), but all polyethylene do
not have the same molecular weight because
the statistical distribution of molecular weight
Polydisperse nature of the polymer is the basis of the concept of average
may be different for the different grade of the molecular weight.
polyethylene and the degree of polymerization
may also be different. To know a polymer property, we must have a knowledge of the both the average
molecular weight and its dispersion pattern.
Molecular Weight:
Molecular weight of a chemical compound can be defined, simply, as the sum of the atomic weights of each of the
atoms in the molecule.
Examples:
Water (H2O) is 2 H (1g) and one O (16g) = 2*(1) + 1*(16)= 18 g/mol
Methane CH4 is 1 C (12g) and 4 H (1g)= 1*(12) + 4 *(1) = 16 g/mole
Polyethylene -(C2H4)-1000 = 2 C (12g) + 4H (1g) = 28g/mole * 1000 = 28,000 g/mole

Average Molecular Weight

Polymers are made up of many molecular weights or a distribution of chain lengths. In other other words, if one
takes polyethylene as an example, this polymer may have chains of ethylene (C2H4) with different lengths; some
longer than others.

Example:
Polyethylene -(C2H4)-1000 has some chains with 1001 repeating ethylene units, some with 1010 ethylene units, some
with 999 repeating units, and some with 990 repeating units. The average number of repeating units or chain
length is 1000 repeating ethylene units for a molecular weight of 28*1000 or 28,000 g/mole .

Therefore, polymers must be represented by the value of average molecular weight. 5

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There are four ways to represent the average molecular weight:
(1) Number-average molecular weight (Mn) for a discrete distribution of molecular weights is given as:

The number average molecular weight is not too difficult to understand. It

is just the total weight of all the polymer molecules in a sample, divided
by the total number of polymer molecules in a sample.

where Ni indicates the number of moles of molecules having a molecular weight of Mi and Wi, is the weight of molecules with
molecular weight Mi. Thus, Wi = Ni Mi.

The expression for the number-average molecular

weight of a continuous distribution function is:

In general,
Total number of molecules (n) id given by - n  n1  n2  n3  n4  ...........   ni
ni ni M i
Number fraction of each molecule is =
 ni Number average weight contribution of each entity is =
 ni
Number average weight molecular weight is =
n1M 2 n2 M 2 n3 M 3 n4 M 4
   ...... 
n M i i
 Mn
 ni  ni  ni  ni n i
Consider a polymer, which contains four molecular weight polymers in different numbers and weight.

Total number of polymer in containing each entity of poly-1, poly-2, poly-3 and poly-4 is = 15
Number of Poly-1 present in the polymer = 2
Number of fraction of poly - 1 = 2/15
Similarly, Number of fraction of poly - 2 = 4/15, Number of fraction of poly - 3 = 6/15, Number of fraction of
poly - 4 = 3/15

Contribution made by poly-1 towards the average weight of polymer =

number of fraction of each polymer x weight of each poly entity
Therefore, each poly contribution is =
(2/15) x 10 =1.33 g, (4/15) x 20 = 5.33 g, (6/15) x 100 =40 g, (3/15) x 250 = 50 g
Summing up the contribution to get Number Average Molecular Weight = 1.33 + 5.33 + 40 + 50 = 96.66 g
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(2) Weight-average molecular weight (Mw) for a discrete distribution of molecular weights is given as:

The expression for the weight-average molecular weight of a continuous distribution function is:

Generalization of Concept:
Total number of molecules (n) id given by = n  n1  n2  n3  n4  ...........   ni
Total weight of the polymer is = N Mi i =W
n1M 1 nM
Weight fraction of each molecule is =  1 1
W  n1M1
2
n1M 1M 1 ni M i
Weight average weight contribution of each entity is =
 ni M i  ni M i
 ni M i  M
2 2 2 2 2
n1M 1 n2 M 2 n3 M 3 n4 M 4
Weight average weight molecular weight is =    ...... 
i i i i i i i i i i
w
n M n M n M n M n M

For synthetic polymers Mw is greater than the Mn. If they are equal than they will consider as perfectly
homogeneous. (Each molecule has same molecular weight).
 Weight Average Molecular Weight (Mw )

Total weight of polymer sample (containing each polymer) = 1450 g

Weight of poly-1 present in polymer = 20 g
Weight fraction of poly-1 = 20/1450, Weight fraction of poly-2 = 80/1450,
Weight fraction of poly-3 = 600/1450, Weight fraction of poly-4 = 750/1450

Contribution made by each polymer towards average weight of polymer =

weight fraction of polymer x weight of each unit
For poly-1 (20/1450) x 10 = 0.14 g
For poly-2 (80/1450) x 20 = 1.10 g
For poly-3 (600/1450) x 100 = 41.38 g
For poly-4 (750/1450) x 250 = 129.31 g
Summing up the contribution made by each poly to get weight average molecular weight is =
0.14 + 1.10 + 41.38 + 129.31 = 171.93 g
(3) Z-average molecular weight (Mz) for a discrete distribution of molecular weights is given as:
(4) Viscosity-average molecular weight (Mv) can be obtained, experimentally, from dilute-solution viscometer
using Mark-Howink equation. The viscosity-average molecular weight falls between Mn and Mw
depending upon whether the solvent is a good or poor solvent for the polymer. In the case of a good
solvent, Mv = Mw .

- Mark-Howink-Sakurada equation:

When α = 1 then Mv = Mn; Generally the value of α is 0.5 < α < 1, The value of α varies with polymer, solvent and
temperature systems.

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 Molecular weight and degree of polymerisation

Number of repeating unit in a polymer called as degree of polymerisation (DP). DP provides the
indirect method of expressing the molecular weight and the relation is as follows;
M = DP x m
Where, M is the molecular weight of polymer, DP is the degree of polymerisation and m is the molecular weight
of the monomer.

 n i (DP)i  n i (DP)i
2

(DP) n = and( DP ) w =
n i  n (DP)
i i

Each of these averages can be related to the corresponding molecular weight average by the
following two equations;
Mn = (DP)n. m
Mw = (DP)w. m

m is the molecular weight of the monomer.

 Lowers in:
The influence of molecular weight on the bulk Hardness
properties of polyolefin's, an increase in the Stiffness
molecular weight leads to:
Softening point
Brittle point
High molecular weight polymer does not crystallize so easily
as lower molecular weight material crystallizes.

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• A high molecular weight polymer increases the mechanical properties. Higher molecular weight implies
longer polymer chains and a longer polymer chain implies more entanglement thereby they resist sliding over
each other.
• Increasing the molecular weight and the chain length of the polymer increases impact strength.
• Thermal properties can also improved by increasing the molecular weight.

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A measure of the breadth of the molecular-weight distribution is given by the ratios of molecular-weight
averages. For this purpose, the most commonly used ratio is Mw/Mn ,called the polydispersity index or PDI.

PDI = > 1 ; polymers having PDI = 1 are called monodiseperse polymers

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Polydispersity is a very important parameter and it gives an idea of lowest and the highest molecular weight species as well
as the distribution pattern of the intermediate molecular weight species.

Figure in this slide shows molecular weight distribution in two

samples having same number average molecular weight but
different polydispersities. Sample 1 obviously has narrower
dispersion pattern and hence a lower polydispersity than sample 2.

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There are several reasons why we might want to measure polymer average molecular weight and its
distribution:
1. The molecular weight and its distribution determine the viscous and elastic properties of the molten
polymer. This affects the processibility of the melt and also the behavior of the resulting solid material.
For example, a resin suitable for extrusion must have a high viscosity at low shear rates so that the
extrudate maintains its integrity. To be suitable for injection molding, however, the same resin must
have a low viscosity at high shear rates so that the injection pressure not be excessive.
2. The molecular weight of a polymer can determine its applications.
For example, the resin used for making polycarbonate water bottles, for example, differs significantly in
molecular weight from the polycarbonate that goes into compact disks.
3. Differences in molecular weight distribution also influence the polymer properties.
As a consequence, two chemically similar polymers, processed identically, that have the same molecular
weight but different molecular-weight distributions may result in products that show significantly
different shrinkages, tensile properties, and failure properties.
For this very important reason, it is advantageous to know the molecular weight and molecular-weight
distribution of the polymers used.
4. Other situations where the molecular weight and its distribution directly influence results include phase
equilibrium and crystallization kinetics.
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Example 2.1:
A polydisperse sample of polystyrene is prepared by mixing three monodisperse samples in the following proportions:
1 g 10,000 molecular weight
2 g 50,000 molecular weight
2 g 100,000 molecular weight

Using this information, calculate the number-average molecular weight, weight- average molecular weight, and PDI of the
mixture.

Solution:

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Example 2.2:
A polymer is fractionated and is found to have the continuous molecular-weight distribution shown below as
a plot of the weight, W, of molecules having molecular weight, M, versus W. Given this molecular-weight
distribution, calculate Mn and Mw.

Solution:

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NOTE: The choice of method for polymer molecular weight determination is influenced by factors such as: (i) information required, (ii)
operative region, (iii) cost effectiveness, and (iv) experimental conditions and requirements.
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End-group Analysis
This method has presumed importance particularly in the determination of average molecular weight of step-
growth polymers (condensation). Consider the step-wise condensation polymerization of polyesters:

Under the assumption that each polymer chain contains one – OH and one – COOH groups, direct
measurement of the concentration of the groups can be done using chemical (titrimetric or pH measurement) or
spectroscopic (infrared or nuclear magnetic) techniques. This is also applicable to other step-growth polymers.

If functional groups present in a given weight of the sample and this is expressed
as a functional group equivalent/100 g. From knowledge of the functional Functionality
Mn 
group equivalent and the functionality, The molecular weight is calculated using Functionalgroupequivalent
the equation:

LIMITATIONS:
1. The major setback of this technique is the decrease in sensitivity with increasing polymer chain length. This
method is restricted to polymer with molecular weight 20,000 amu. Aside this, it requires high concentration
of polymer.
2. This method requires that the polymer be free of impurities and other groups present in the chain should not
interfere in the determination of end group of interest.
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The end group analysis is a chemical method used to determine the number average molecular weight of a polymer
sample through the analysis of reactive functional groups at one end or both end e.g. Carboxyl terminated polybutadiene,
hydroxyl terminated polybutadiene. Apart from hydroxyl and carboxyl groups, other end groups (aldehyde, amino, ester)
can possibly be present in various polymers. For detecting and analyzing quantitatively functional end-groups of linear
polymer (nylon), the amino end-groups of nylon dissolved in m-cresol are readily determined by titration with a
methanolic perchloric acid solution. Other titratable end groups are the hydroxyl and carboxyl groups in polyesters and
the epoxy end groups in epoxy resins. The sensitivity of this method decreases as the molecular weight increases.

Functionality

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End Group Analysis:
The carboxyl value of cabroxyl terminated polybutadiene (CTPB) can be determined by dissolving a known amount of
the polymer in a mixture of toluene and ethanol (1:3) and titrating against alcoholic KOH using phenolphthalein
indicator.
Let, the volume of KOH consumed= V ml; Normality of KOH= N; and Weight of the sample taken= w g.
Carboxyl value =

Carboxyl equivalent/100g =

In a particular measurement, if 0.8734 g of the sample has consumed 5.1 ml 0f 0.1242 (N) alcoholic KOH solution then:

Carboxyl equivalent/100g = = 0.0725

Assuming functionality of 2,

Number average Molecular weight =

The chemical analysis method is limited to the insolubility of the polymer in the solvent.

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Viscometry: The molecular weight obtained by this technique is the viscosity average molecular weight, M v.
A method that is widely use for routine molecular-weight determination is based on the determination of
intrinsic viscosity, η, of a polymer in solution through measurements of solution viscosity.
The viscosity of a polymer solution is considerable high as compared to that of pure solvent. The increase in viscosity by the
macromolecules in a solution is a direct function of the hydrodynamic volume and hence the molecular weight of the
macromolecules.

The fundamental relationship

between η and molecular-weight is
given in Mark-Howink equation:

It is clear in the above equation that the value of intrinsic viscosity of the diluted polymer is needed to
determine the molecular weight. To find the intrinsic viscosity, a series of experimental measurements and
calculations have to be made.
For unknown polymer systems, the K and a values are generated by fractionating the polymer sample into
several fractions and for each fraction the molecular weight is determined by Osmometry or light scattering
method and corresponding intrinsic viscosity is measured.

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These steps are as follows:
1. The relative viscosity can be measured
experimentally using a suitable viscometer:

2. The intrinsic viscosity can be calculated as shown below:

Intrinsic viscosity is also known as Staudinger index or limiting viscosity index

(dimension is reciprocal of concentration). For calculating the intrinsic viscosity
of a polymer sample in solution , we need not know the absolute viscosities of
solvent and solution, but only the flow time of constant volume of solvent and
the solution through a particular tube. This principle is used in the viscometric
technique of molecular weight determination. The term [η] has related to the
two viscosity functions through the following two equations by Huggins and
Kraemer equations.
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 Intrinsic Viscosity

Fig. 1 Reduced viscosity and inherent viscosity of nylon 66 in 90% formic acid (Adapted from Ph.D thesis of R Walia, P.
S., Chemical Engineering, West Virginia University, Morgantown, 1998). 27
Viscosity-Molecular Weight Constants
Problem: Calculate the relative viscosity, specific viscosity, and reduced viscosity of a 0.5% (made by dissolving 0.25 g of
polymer in 50 mL of solvent) solution where the time for solvent flow between the two appropriate marks was 60 s and the
time of flow for the solution was 80 s.
𝜂 𝑡 80
Solution: Using the relation of time of flow with relative viscosity, 𝜂𝑟 = = = =1.33
𝜂 0 𝑡 0 60

𝜂
The specific viscosity η𝑠𝑝 is determined by using the relation, Specific viscosity , 𝜂 𝑠𝑝= −1=1.33 −1= 0.33
𝜂0

𝜂 𝑠𝑝
The reduced viscosity is ηred is given by the relation, 𝜂 𝑟𝑒𝑑 =
𝐶

The most widely employed concentrations in viscosity determinations are g/mL (g/cc) and g/dL or %. The units g/cc are
recommended by IUPAC, while the units of % or g/dL are the most commonly used units.

𝜂 𝑠𝑝 0.3 −1
The reduced viscosity, ηred is: 𝜂 𝑟𝑒𝑑 = = =0.06 % =0.6 𝑑𝐿𝑝𝑒𝑟 𝑔 .
𝐶 0.5

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Problem 2: Determine the molecular weight of a polystyrene sample which has an α value of 0.60, a K value of 1.6 x104
dL/g, and a limiting viscosity number or intrinsic viscosity of 0.04 dL/g.

Solution: The molecular weight can be found by the relationship:

[ 𝜂 ] =𝐾 𝑀 𝛼
log [ 𝜂 ] =𝛼 log 𝑀 + log 𝐾

𝑀=1 𝑥 104
Hence, the molecular weight of the polymer is 1 x 104

Problem 3: If the value of K and α in the Mark-Houwink equation are 1x10-2 cm3 g-1 and 0.5, respectively, what is the
average molecular weight of a polymer whose solution has an intrinsic viscosity of 150 cc/g? (Try to solve the problem
and send it to me)

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Colligative properties:
The relations between the colligative properties and molecular weight for infinitely dilute solutions in a fact that the activity
of the solute in a solution becomes equal to its mole fraction as the solute concentration becomes sufficiently small.
This method is based on:
•Vapour-pressure lowering •Boiling-point elevation (ebulliometry),

•Freezing-point depression (cryoscopy)

•Osmotic pressure (osmometry)

Where,
∆Tb, ∆Tf, and π = the boiling-point elevation, freezing-point depression, and osmotic pressure, respectively.
ρ = the density of the solvent,
∆Hv and ∆Hf = the enthalpies of vaporization and fusion, respectively, of the solvent per gram,
c = the solute concentration (gr/cm3),
Mn = the number-average molecular weight.
A2 = a constant.
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 The suitability of methods based on Colligative properties Vs Molecular Weight

Lowering of Vapour Pressure

The partial vapor pressure PI of solvent 1 in a solution is lower than the vapor pressure
0
over the pure solvent p1 . This is expressed by Raoult's law: 1
0 p  X p
1 1

0
Where X1 is the mole fraction of the solvent. For a binary X  p1  p1  p1
2 0 0
solution containing a mole fraction X2 of solute then, p1 p1

n2 w2 M 1
For a dilute solution, X 2  
n1 M 2 w1
0
M p
Combining above two equation, M 2  w2 1 1
w1 p1
w2 M sVs
Assuming ideal solution behavior, the unknown molecular weight Mn 
is calculated from: V2 wn
 Ebulliometry (Elevation of boiling point):

Ebulliometry is another technique for determining the depression of the solvent activity by the
solute. In this case the elevation of the boiling point is determined. The boiling-point elevation
Tb is measured with sensitive thermocouples or matched thermostats in a Wheatstone bridge.
The molecular weight Mn is calculated from:
Kb c
Mn 
Tb
Where, c is the concentration of solute in g/1000g of solvent and -
2
RTb M
Kb 
1000H v
is the molal ebullioscopic constant. M is the molecular weight of the solvent and Tb its boiling
point; Hv is the molar latent heat of vaporization of the solvent.

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 Cryoscopy (Depression in freezing point)

The freezing point of a solution is depressed below that of the pure solvent by an amount
proportional to the mole fraction of solute. The value for M n is obtained from:
Kfc
Mn 
T
Where c is the concentration of solute in g/1000 g of solvent and:
2
RTm M
Kf 
1000H fus
is the molal cryoscopy .constant; M is the molecular weight of the solvent and Tm its melting
point; Hfus is the molar latent heat of fusion of the solvent.

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 Osmometry
Membrane osmometry is absolute technique to determine Mn. The solvent is separated from the polymer
solution with semipermeable membrane that is strongly held between the two chambers.
One chamber is sealed by a valve with a transducer attached to a thin stainless steel diaphragm which
permits the measurement of pressure in the chamber continuously.
Membrane osmometry is useful to determine Mn about 20,000-30,000 g/mol and less than 500,000 g/mol.

When Mn of polymer sample more than 500,000 g/mol, the osmotic pressure of polymer solution becomes
very small to measure absolute number average of molecular weight.
In this technique, there are problems with membrane leakage and symmetry.
The advantages of this technique is that - it doesn’t require calibration and it gives an absolute value of M n for
polymer samples.
Since osmotic pressure is dependent on colligative properties, i.e., the number of particles present, the measurement of
this pressure (osmometry) may be applied to the determination of the osmotic pressure of solvents vs. polymer solutions.
𝑅𝑇 2
𝜋= 𝐶+𝐵 𝐶
𝑀𝑁 35
The difference in height (h) of the liquids in the columns may
be converted to osmotic pressure (π) by multiplying the gravity
(g) and the density of the solution (p), i.e., π = hpg.

In an automatic membrane osmometer, the unrestricted capillary rise in a dilute 𝑅𝑇 2

𝜋= 𝐶+𝐵 𝐶
solution is measured in accordance with the modified van’t Hoff equation: 𝑀𝑁

The reciprocal of the number

average molecular weight (Mn)
is the intercept when data for
π/RTC vs. C are extrapolated to
zero concentration.

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37
 Light Scattering
This method is presumed most popular for the determination of weight average molecular weight (M w). It allows polymer
molecular weight and structure to be assessed.
When a beam of light is passed through a colloidal solution, it is scattered. This is well-known Tyndall effect,
which results from the scattering of a part of the beam of light by the colloidal particles in all directions. Since
polymer solutions can be considered as colloidal (lyophilic) solutions and as the intensity of light scattered
depends on the size of colloidal particles (or polymer molecules)

This technique thus relies on the

measurement of light scattered at an angle to
the incident ray as it passes through the
target. The intensity of scattered light incident
on polymer sample is dependent of the
polarity, chain size, and concentration.
Consequent upon this, light technique
measures polymer molecular weight by
quantifying the Raleigh scattering (elastic
light scattering) from each polymer molecule.
The measurement approach is simple as
illustrated in the Figure.
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The famousness of this method stems from the fact that wide range of molecular weight (typically 10 4 to 6 x
105 g/mol) can be determined.

In the determination of the weight-average molecular weight of polymer molecules in dust-free solutions, one measures
the intensity of scattered light from a mercury arc lamp or laser at different concentrations and at different angles
(θ), typically 0, 90, 45, and 135. The incident light sends out a scattering envelope that has four equivalent quadrants. The
ratio of scattering at 450 compared with that for 1350 is called the dissymmetry factor or dissymmetry ratio Z. The
reduced dissymmetry factor Z0 is the intercept of the plot of Z as a function of concentration extrapolated to zero
concentration.

Light-scattering envelopes. Distance from the scattering particle to the boundaries of the envelope represents the
magnitude of scattered light as a function of angle.

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 The scattered light and the average molecular weight is related according to the following equation:

KC / R90  HC /   1/ M w  2 BC Where, H is constant, B is the second

 KC  1 virial coefficient, C is the concentration of

    2 BC
the solution, and R90 is the Rayleigh ratio
 R  0 Mw
at 900 to observation angle. This ratio in
 KC  1
   a generalized case is represented as R
 R  0 Mw i.e. the Rayleigh ratio is determined at an
observation angle of 900, R = R90
Limitations:
However, the light scattering technique is deemed time consuming because it requires that the sample
solution is completely free of dust and other impurities as these are capable of influencing the light scattering
pattern.
Also, as could be deduced from the above equation, change in Raleigh scattering is proportional to the
sample concentration and molecular weight, hence this method requires high sample concentration to
produce a detectable signal.
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 Ultracentrifugation (Sedimentation) Method
It is the most common method used for determining the molecular-weights of high polymers. This method is useful for
biological materials, such as protein molecules.
An ultracentrifuge consists of an AL rotor (ø ∼1-2 inch) that is rotated
at high speed in an evacuated chamber. The solution being
centrifuged is held in a small cell within the rotor near its periphery.
The rotor is driven electrically or by oil or air turbine.
Polymer solutions are lyophilic colloids arid these can be
made to settle down on the application of centrifugal force.
The ultracentrifuge is used to determine molecular weights.
The rate of the settling (sedimentation rate) of polymer
molecules depends on the size of the molecules:
SRT
MolecularWeight
D(1  dVsp )
Where, R and T are the gas constant and temperature in Kelvin scale.
The above equation is known as Svedberg equation. For a
polydisperse solute the correct averages for S and D are combined in
https://www.britannica.com/technology/ultracentrifugation
the Svedberg equation.

The concentration of polymer is determined by optical methods based on measurements of refractive index
or absorption. The solvents must have difference both density and refractive index from the polymer. The
density differences allow the sedimentation and the refractive index differences allow the measurement.
The force on a particle (F):

F = ω2r (1− υρ) m

where:
ω- the angular velocity of rotation,
r- the distance of the particle from the axis of rotation,
υ- the partial specific volume of the polymer,
ρ- the density of the solution,
m- the mass of the particle.

For an ideal solution in the equilibrium condition:

where: c1 and c2 are the concentrations at 2 points r1 and r2 in the cell.

Limitations:
The disadvantage of sedimentation equilibrium experiment is taking quite long time (1-2 weeks) to reach
equilibrium.
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Example 01: At rotation rate 400 rpm (41.8 m/s) and 20oC, the concentration ratio (C2/C1) is 1000. If the r2
and r1 are 5 cm and 10 cm, respectively, the density is 1 gm/cm3 and the partial specific volume of the
polymer is 0.0077 cm3/gm, what is the molecular weight.
Solution:

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 Gel Permeation Chromatography (GPC)
One of the most widely used methods for routine determination of molecular weight and molecular-weight distribution is
GPC. This method based on the principle of size-exclusion chromatography to separate samples of polydisperse polymers
into fractions of narrower molecular-weight distribution.
The equipment:
Several small-diameter columns (L = 30 – 50 cm) are packed with
small highly porous beads (∅ = 10 – 107 Â). Pure pre-filtered solvent
is continuously pumped through the columns at a constant flow rate
(1 – 2 mL/min). Then, a small amount (1 – 5 mL) of a dilute polymer
solution is injected by syringe into the solvent stream and carried
through the columns. The smallest polymer molecules are able to
penetrate deeply into the bead pores but the largest may be
completely excluded.

The process is repeated until all polymer molecules have been eluted out of the column in descending order of
molecular weight. The concentration of polymer molecules in each eluting fraction can be monitored by means
of a polymer-sensitive detector, such as IR or UV device. The detector is usually a differential refractometer
(differ the refractive index between the pure solvent and polymer solution).
For a given polymer, solvent, temperature, pumping rate, and column packing size, elution volume (V r) is
related to molecular weight.
 Working Principle of GPC

Large molecules would have less

residence time and would emerge first.
GPC Curve for
standard polystyrene
sample showing
elution volumes
corresponding to
different molecular
weight
 Summary of the Measurements Method of M.wt

47
A = Absolute E = Equivalent R = Relative