Physical Properties of Polymers

Quantitative Analysis from

FTIR spectrometer

M. Zafar Iqbal
 Scheme
• Introduction to quantitative analysis and sources
• Sampling techniques for FTIR spectrometer
• Base Line correction: Problems and their solutions
• Curve fitting and its practical applications
• Absorpitivity Ratios and Quantitation
• References
 Introduction to Quantitative
•
Analysis
FTIR is commonly used for qualitative analysis
• You must be aware of this type of analysis before
going towards quantitative analysis
• The probe size of FTIR is ideal for the study of
phase behavior of polymers (i.e, Moleculer
vibrations and size scale is in angstrom)
• It can characterize the nature and strength of
strong interactions.
• It can determine the fraction of interacting groups
in a certainly H-bonded system.
 Cont’d
• Consider the following blend system:

• s

Two copolymers are mixed on molecular level to form a blend.

The fraction of carbonyl group H-bonded with phenolic group will
tell the blending extent. For a single phase blend, there will be some
Equilibrium conc. of H-bonded Carbonyl group present at a certain
Temperature. The distribution of free and H-bonded C-group can be
described by equilibrium constants from where free energy of
Formation can be calculated.
C-stretching= 1650-1800 cm-
Careful while selecting your
required peaks. The breadth
Strongly dictates the conc.of t
group.
 Some important points
• For quantitative measurements, Bee-Lambert law
is strongly recommended which is
A = log10 (I0/I) = abc

Where A= Absorbance (dimensionless)

I0 = Intensity of source radiation
I = Intensity of transmitted radiation
a = absorpitivity co-efficient
b = Thickness or path length
c = Conc. Of the absorber
The spectrum should be in Beer-Lambert law
absorbance units for quantitative measurements.
 Cont’d

• Select the peaks (bands) well defined

• Apply base line correction as recommended
• Apply least square curve fitting
• Determine the absorpitivities of free and H-
bonded Carbonyl groups in terms of ratio aR
• Determine the inter association fraction through
certain formulae
The most important point is the judgment where
your required groups lie and how much clear they
are.
 Experimental Necessities
Sample Preparation:
The samples for IR analysis can be in different form:
1- Solid
2- Liquid
3- Gas

Neat sample: If sample is a thin film then mount it as it is.

Solid: Mix with IR grade KBr in 1:100 ratio
Mull and salt window: fine powder of sample is mixed
with a hydrocarbon oil and it is placed between two salt
plates.
Typical salt windows: 1 inch diameter, 3-5 mm thickness
 Cont’d
Dissolution and liquid cell: sample is dissolved in
some solvent and place in the liquid cell. You
must consider the absorption ranges of solvents
to avoid from serious errors.
Conventional Liquid Cell

Gaskets help in making

Non-leak seals and spacer.
The sample is injected with
The help of a syringe. After
Usage, open the cell and rinse it.
 Cont’d
Gas samples: A gas sample cell is required which
is made of some standard salt like KBr or NaCl.
The gas in injected with the help of a small piston
system and kept at very low pressures. The main
precaution in this system is the partial pressure of
gas to be analyzed.
Films: less than 10 micron thickness, The
absorbance should not be greater than 0.6.
Baseline and playing with spectra
• Consider the following spectrum with sloping
baseline.
• 3 basic routes have been drawn here.
 Why sloping baseline?
• The most important factor for this sloping
baseline is the un-even film formation due to
which IR light is scattered and 2nd is the coloured
sample.
• Film cast method and KBr pellet method normally
strike with this type of problem.
• In Film cast method, certain factors must be
considered:
1- Evaporation rate of the solvent
2- Chemistry of the polymeric components
3- Surface tension of the solution
 Cont’d
• If the sample is non-uniform, then IR radiation will be
dispersed due to difference in refractive indices at the
curved surfaces and fraction of radiation will not reach the
detector.
• Scattering is inversely proportional to the fourth power of
wavelength. Therefore this effect is greatest in IR at higher
frequencies (high wave numbers).
• A good judgment of the sample is that the
absorbance should be with in 0.3-0.7 . Below 0.3,
poor signals are observed which if interpreted
would lead to serious errors. Modern FIR can go
up to 0.05 absorbance units. But if more than 0.7,
then bands are called over-absorbed and it goes
out of Beer law range. This can never give good
quantitative results.
• But if the following situation occurs:
 The art of Curve Fitting
• Sample baseline correction: First Step
 Understanding the Curve fitting mechanism
• First of all you have to assume a specific shape of the band.
This may be a Gaussian type or Lorenzian type or mixed.
Almost all the polymer sample bands resemble the
Gaussian Shape but not necessarily.
• Let us do some sample exercises to understand what curve
fitting is.

Consider five Gaussian curves named I-V, arbitrarily

Curve I Curve II Curve III Curve IV Curve V
synthesized as:
V= 1730 cm-1 V=1700 V= 1660 V= 1640 V=1620
FWHH = w1/2 = 15 cm-1 FWHH= 30 FWHH = 15 FWHH= 15 FWHH=15
A=0.15 A = 0.4 A = 0.3 A 0.2 A=0.5

Note: These all curves have Gaussian shape, Baseline at A=0 and are separated
By frequency at distances greater than w1/2 of the individual bands.
Curve fitting: cont’d
Again consider V1=1730: V2=1700: V3= 1670: V4= 1655:
V4= 1640

Curve fitting is the

knowledge of the
total no. of bands
That comprise an
Envelop.
 Second Derivative concept and its
application
• Sometimes, 2nd derivative of an IR-spectrum is
helpful to reveal unresolved bands like you have
seen in last picture.
If bands are spaced too close, then..
Least square curve fitting methodology