FT-IR SAMPLING TECHNIQUES

Shorter Wavelengths Near-IR Mid-IR Far-IR Longer Wavelengths

 UV-Vis

Wavelength
Wavenumber
Frequency
Energy
0.7 μm
14000 cm -1
10 8 MHz
1.771 eV
X-H Overtones and
Combination Bands
2.5 μm
4000 cm -1
10 8 MHz
0.496 eV
Fundamental Vibrations, Overtone
and Combination Bands
25 μm
400 cm -1
10 7 MHz
0.050 eV
Fundamental and Heavy
Atom Vibration Bands
1000 μm
10 cm -1
10 6 MHz
0.001 eV
Microwave


Transmission/Absorption Attenuated Total Reflection (ATR) Diffuse Reflection Specular Reflection
(internal reflection) (scattered reflection) (mirror-like reflection)
Sample is positioned directly in the beam of the FT-IR spectrometer Sample is placed in intimate contact with the internal reflection element (IRE) Sample is diluted with KBr (or similar) and placed in a cup for analysis Sample is placed on top of the specular reflection accessory
b Evanescent Wave
Large surface areas can be analyzed directly IR I0
Beer-Lambert Law
A=a b c
Bulk Sample
ATR Crystal
Depth of Penetration
dp = λ
2π(n1 sin θ n2 )
2 2 2 1/2 Specular energy Diffuse energy ..
Reflection
Incident beam angle = reflected beam angle
Angle of incident beam transmitted into a sample is reflected by Snell’s Law
n1
θ1

A - Absorbance dp
a - absorptivity dp - depth of penetration IT θ2 n2
b - pathlength
c - concentration
θ λ - wavelength of light
θ - angle of incidence
n1 - refractive index of crystal
..
Reflection-Absorption at Near-Normal and Grazing Angle (< 65°)
Beam enters and exits sample deposited on reflective substrate
Equivalent to double-pass transmission measurement
IR I0
Absorbance is linearly proportional to sample Refracted Incoming θ1
n2 - refractive index of sample IA n1
concentration and pathlength. IR Beam IR Beam

..
Reflection in Free Standing Films IT n2
Integrating Sphere Beam enters sample and reflects from top and bottom surfaces of the film
Attributes θ2

. Attributes Constructive and destructive interference generate fringe pattern

.
High quality, representative spectral data, compatible with many digital libraries
Depth of penetration can be controlled by changing angle of incidence beam and/or use of crystals with different
refractive indices. . Simplified sample preparation
.
Spectra represent bulk sample composition . Direct measurement of large samples Kubelka-Munk Equation
I0 - Incident beam IA - Reflected beam (2) n1 - refr. index of air
θ1

. Representative sample spectra (not a f(R) = (1-R) = k

2
IT - Transmitted beam θ1 - angle of incidence n2 - refr. index of sample
Ability to control sample thickness – intensity of spectral features/sensitivity 2R S IR - Reflected beam (1) θ2 - angle of trans. light
Number of Reflections Refractive Index and Critical Angle IR I0
surface measurement) R - absolute reflectance of the layer
Special Considerations
.
L
n2 . Sensitivity and versatility k - molar absorption coeffecient
s - scattering coefficient Snell’s law indicates that the angle of the incident beam into the sample is equal to the
IA θ1
n1
Thick samples may absorb totally and need to be thinned-out or diluted IT
. n1 angle of reflection: n1 sin θ1 = n2 sin θ2 n2
T
Original material may be destroyed in sample preparation process
. Pellet making and other sample preparation methods require skill and time
45o 45o Special Considerations
. θ2

. Beer’s law is limited to simple, linearly absorbing samples rn = L/(2T tanθ) θc = sin-1 ( )
n2
.
Diffuse reflection spectra will appear different to their transmission equivalents
Kubelka-Munk conversion brings spectra to transmission-like format
Attributes
. Film Thickness (µm)

.
n1
No or limited sample preparation
rn - number of reflections θc - critical angle
.
If not eliminated, specular reflection component may distort spectra
. Measurement simplicity/versatility
T= 10,000 N
(2 ∆ν) (n2 -sin2θ) 1/2
Applications
.
L - crystal length
T - crystal thickness
n1 - refractive index of crystal
n2 - refractive index of sample
Spectra of samples with high refractive indices require higher dilution to reduce distortion
. Sensitivity/ability to look at very thin samples
.
T - thickness of film (µm)
Solids, gels, pastes, liquids and gases
.
θ - angle of incidence ∆ν - wavenumber range of fringes count (cm-1)
Non-destructive sampling
Film thickness and liquid cell pathlength N - number of fringes within ∆ν
. Qualitative and quantitative
n - refractive index of polymer

Attributes Special Considerations

.
Effects of number of

. Minimal sample preparation

reflections on peak
Specular reflection spectra of thick reflecting samples may be distorted due to anoma-
.
intensity
Transmission Ranges of
∆ν
Short sampling time and easy cleaning lous dispersion. Kramers-Kronig transform brings spectra to absorption-like format.
Popular IR Windows

NaCl 52600-455 cm-1

. High versatility, non destructive sampling
3 Reflections

%R
KBr 48000-345 cm-1
Special Considerations
1 2 3 4 5
.
%T

ABS

CaF2 79500-895 cm-1 1 Reflection

The angle of incidence must exceed the
BaF2 66600-690 cm -1

critical angle to produce good quality spectra Kramers-Kronig

.
I I I I I

3000 2500 2000 1500 1000 cm-1

ZnSe 15000-460 cm-1
I

2500
I

2000
I

1500 cm-1 ATR is not a bulk technique; it measures only the Diluted (red) and undiluted (blue)
spectra of caffeine
surface of a potentially inhomogeneous sample Applications
. Correction needs to be applied to spectra for . Measurements of powdered samples
%R

.
I I

3000 2800 cm -1
Free Standing Film Thickness (µ) Cell Pathlength (mm) direct comparison with transmission data
T = (N 10,000)/(2n ∆ν) P = (N 10)/(2 ∆ν)
. ATR crystals must be cleaned between samples to avoid contamination and carry-over .
Selected liquids/liquid residues

T - thickness of polymer film (µ) P - cell pathlength (mm) . Spectral ranges and properties of ATR crystals vary and need to be considered when .
Rough surface solids/coated surfaces
Abrasion measurements
I

1800
I

1600
I

1400
I

1200
I

1000
I

800
I

600 cm-1

∆ν - wavenumber range of fringes count (cm-1)

N - number of fringes within ∆ν
∆ν - wavenumber range of fringes count (cm-1)
N - number of fringes within ∆ν working with specific samples . Temperature and catalytic studies Applications
n - refractive index of polymer
. Measurements of thin and thick film composition and thin film thickness
Applications Transmission Ranges of Popular
Sample Handling . Analysis of monolayers on reflective substrates
Sample Handling . Solids, gels, pastes and liquids
ATR Crystals
. . Reflectance measurements – coatings, optical
. Films, thin materials – direct placement in the transmission sample holders . Qualitative and quantitative ZnSe 52600-650 cm-1 .
Powders – 1% to 3% dilution in KBr, KCl or similar matrix
Small particle size (50 µ or less) and homogeneous mixture components/glass, EPI, lubricants on hard drives
. Powder and solid samples: KBr pellets, (solid samples require processing), mulls Ge 5500-780 cm-1 . Maintain more than 2 mm sample depth, even and loose packing in the cup
. Gels/pastes: smears on IR transparent windows Sample Handling . Liquids – dispense small amount on top of KBr powder located in the sampling cup Sample Handling
. . . . Polarized light is recommended for
Diamond 30000-50 cm-1

Liquids: liquid cells Intimate contact between the sample Large samples placed directly on top of upward looking diffuse reflection accessory
.
Si 8900-1460 cm-1

Gases: short- and long-path gas cells and the ATR crystal is required or integrating sphere grazing angle measurements

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