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# The Science Behind What We Do

## What we can learn

Using the Qualitative properties of the spectral data
Structural conformation of new materials can be determined
Contaminants can be identified
Competitive products can be determined chemically

## Using the Quantitative properties of the spectral data

Concentration of critical additives can be determined
Consistency of product mixtures can be monitored
Quality of starting materials can be determined

FTIR Basics
With FTIR we measure light energy at many different frequencies
FTIR generates energy using a light bulb
That light travels trough space to a detector that measures the energy
present at some of the different frequencies available.
The interesting part is how the light energy changes between the light
bulb and the detector.

Light Source
Sample

Detector

## FTIR Basics - Samples

In order for FTIR to work, the light has to get past the sample to the
detector.

Light In

## Sample too thick.

No light comes through

## FTIR Basics - Samples

You can bounce the light off of a brick

Light In

Light Out

You can grind the brick up into powder and try to pass light through.

Light
In

Light
Out

## FTIR Basics Rules for Sampling

In order for FTIR to work the sample must change the energy of the
light. The light must interact with the sample.
The Energy going into the sample must be different than the energy
coming out of the sample.

Energy Out

Energy In

Liquid Cell

## Energy In = Energy Out

FTIR Result
To get an answer we divide Energy Out by Energy In.
Multiplying the ratio by 100 gives us a percentage.

Energy Out=50

Energy In = 100

Compression Cell

## 50/100 * 100 = 50%

50% of our light was used up by interacting with the sample.
We use this information for qualitative or quantitative purposes.

## Molecular Vibrations Provide Information

Deformation

Stretching
100
90
80

%T

70
60
50
40
30
20
4000

3500

3000

2500
2000
Wavenumbers (cm-1)

1500

1000

## The Source Making sure you have frequencies to measure

The Source is a light bulb that produces energy at different frequencies
We must select a source that produces light frequencies that we wish to
measure
99% of the time we want to see frequencies of light that interact with
our sample. Sometimes we want to make sure that certain frequencies
do not interact with our sample.
We have a source for producing Mid-IR frequencies (4000-400 cm-1)
We have a source for producing NIR frequencies(12,000-4000 cm-1)
When designing a spectrometer we have to match the hardware so we
can measure the desired frequencies.

## The Detector Making sure you can measure those frequencies

The detector must be able to measure the intensities of the frequencies
of interest.
There are many choices of detectors offering many different

## Speed Collect data faster

Sensitivity Collect data from small amounts of sample
Frequency range Collect the frequency range with relevant data
Linearity Collect data accurately over broader quantities of interaction

## In some systems, having multiple detectors is possible.

Detectors can overfill. Be careful! Too much energy is bad.

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## The heart of the FT-IR spectrometer.

Mirrors move to modulate the light.
The beamsplitter reflects 50% and transmits 50% of the available light.
Beamsplitter material determines frequencies measured (to name a
few)

KBr 7400-350cm-1
XT-KBr 11,000-375cm-1
CaF2 14,500-1,200cm-1
CsI 6,400-200cm-1

## Beamsplitters are interchangeable on the 6700 and 8700 systems.

Energy In
Interferogram Out
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The Interferogram

## Every datapoint in the interferogram contains the energy reading of

every frequency of light available.
The interferogram is collected over time while the mirror moves.
The larger the Interferogram peak to peak height, the more energy is
reaching the detector. (Useful for positioning and alignment)
The longer the interferogram, the higher the resolution.
Higher resolution defines more of the frequencies measured
Higher resolution takes more time to collect
Higher resolution has more noise

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The Background

Background

Single Beam

Volts

## To collect a finished spectrum there must be a background.

The background is the energy available to analyze the sample
The background energy is used to determine the amount of energy that
the sample interacted with. We measure the relative change in energy.
If possible, the hardware configuration should match the configuration
when collecting the sample data, less the sample itself.

2200215021002050200019501900
Data points

Volts

Sample
2400230022002100200019001800
Data points

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3000
2000
1000
Wavenumbers (cm-1)

Single Beams

Spectrum
Ratio

%T

Interferograms

Single Beam

4000

3000
2000
1000
Wavenumbers (cm-1)

4000

## 3000 2000 1000

Wavenumbers (cm-1)

## What is the Spectrum?

A representation of the interaction between our sample and the
frequencies of light we are measuring
The pattern of frequencies interacting tells us what the molecular
structure of our sample is Qualitative analysis
The intensities of those interactions tell us about how much sample we
have in the analysis Quantitative analysis
We typically view the data as the % of light that passed through our
sample (units of %T) or we look at the amount of light that was
absorbed by the sample (units of ABS)

% Transmission
100%

6 ABS

0%

O ABS

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Absorbance

These are general guidelines:
0% Transmission = 6 ABS = no energy to the detector for that group of
frequencies. Data not reliable when energy measured is 0, or close to 0.
Quantitative analysis Use frequencies where the maximum energy
interaction is >10%T or <1 ABS
Qualitative analysis If the data looks good, it is probably good enough.
Never use system cutoffs for measurements. ie. KBr cuts off at 350cm-1.
Never perform quant using 400-350cm-1.
Software corrections can fix data qualitatively. Quantitatively if corrections
are needed it is better to find a different collection technique.
The lower the resolution, the better. But you still need to solve the problem.

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FTIR Instruments
Nicolet iS5 Simple, Robust, Inexpensive, Limited

## Nicolet iS50 Highest capability and Versatility.

If FTIR can do it, the iS50 can do it.

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NIR Theory
The same technology as Mid-infrared.
Source, beamsplitter, detector perform the same function with a
different set of frequencies.
Data collected represents combinations of interactions generating
spectral change. Data is a more general representation.
Quantitatively, data is excellent.
Qualitatively, data is harder to interpret.
Benefits of NIR:
Can analyze through glass and plastic. These materials absorb all of the
mid-infrared light.
Can use fiber optic cables
Can handle much larger sample sizes
Better for real time, process control data analysis
Excellent hardware and software validation tools. Essential for some
industries
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NIR Spectrum
Fundamental
Vibration
1st Overtone
3rd

2nd Overtone

Overtone

12000 cm-1

9000 cm-1

6000 cm-1

3000 cm-1

1.2
1.1

Combinatio
n

Absorbance

1.0
0.9
0.8
0.7
0.6
0.5
0.4

2nd
Overtone

0.3
0.2
0.1

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3rd
Overtone
11000

10000

9000

1st
Overtone

8000
7000
Wavenumbers (cm-1)

6000

5000

4000

NIR Spectrum

3rd Overtone

IR Spectrum
Fundamental

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1st Overtone

2nd Overtone

20

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## Build a Calibration Curve

NIR is a secondary technique
Concentration values are used to build a calibration curve
The curve is then used to calculate real numbers from samples which
are unknown

Samples
With
Known
Values

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## NIR For Controlling the Process

The Antaris II
Multiple sampling choices for varied application

Antaris MX
When Fiber Optics is all you need

Antaris Target
Attach it to the Blender/Dryer and Go.

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Raman Theory
Based on Laser excitation of the sample. Sample is the source
Sample emits light based on wavelength of Laser
Common Lasers used 780nm, 633nm, 532nm, and the new 455nm

## Signal goes up as laser wavelength goes down

Signal originates at the focal point of the excitation laser

LASER

LASER

I scattering
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Sample

1
(excitation)4

Laser Wavenumber
18796 cm-1

17795 cm-1

Laser Wavenumber
15798 cm-1

14801 cm-1

Laser Wavenumber
12820 cm-1

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11819 cm-1

Laser
1001 cm-1

1001 cm-1

1001 cm-1

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## Benefits Offered by Raman Complementary to IR

Complementary use of Raman and FT-IR for structural
elucidation

FT-IR

## Example: Trans-cinnamyl acetate

C=O

Raman

C=C

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C=C
C-O
C=C
C-O

C=O

Raman Hardware
Laser -1064nm, 780nm, 633nm, 532nm, 455nm
Detector NIR CCD or InGaAs detectors used
Filter
Need to remove the laser frequency
Intensity at the laser frequency is too great
Filter cutoff determines low end spectral cutoff

Grating
Disperses raman scatter in predictable angles like a prism
Acts to separate frequencies for individual measurement
The greater the separation, the higher the resolution

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## Benefits Offered by Raman Complementary to IR

Highly Complementary to Infrared

## Weak IR absorbers often strong Raman emitters

Symmetric bonds represented more in Raman (S-S, C-C, etc.)
Molecular backbone emphasized more than end groups
Sample preparation not needed for Raman, just place sample at laser focus
Analyze through glass, through plastic, in water
Can penetrate into sample without manipulation
Raman provides Far-IR information
Can use fiber optic technology
Extremely high spatial resolution: <1 micron
IR (photo)
Microscopic or macroscopic
Great for qualitative subtractions
Essential in Pharmaceutical and Forensic labs
Excellent for Polymer studies
Raman (x-ray)

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## Problems with Raman

Safety issues with lasers
Raman systems have safety locks Class1 Laser safe

## Weak signal at times

Can adjust laser power to magnify signal

Sample heating
Dark samples exhibit more heating
Samples can heat to the point of burning

## Almost impossible to analyze gases

Gases need to be at very high concentration or pressure

Fluorescence
If sample fluoresces it will give off measureable signal that distorts data
Fluorescence can complete wipe out sample spectrum

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Fluorescence Avoidance
Spectral correction after collection
Several specialized baseline correction algorithms exist
Not viable in cases where fluorescence saturates detector

## Confocal optics signal comes from laser focus point

Can work well when the source of fluorescence is the substrate rather than
the sample

## Excitation laser change

Most reliable means of avoiding fluorescence
Switch to an excitation frequency that does not stimulate fluorescence in the
sample
Typically this means switching to longer (NIR) wavelengths
FT-Raman operating with 1064 excitation rarely exhibits fluorescence

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Raman DXR
Micro
And
Macro

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Review

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## FTIR and NIR work because the samples absorb light

Raman works by the sample emitting light
FTIR and Raman show fundamental frequencies of vibration
NIR shows combinations of frequencies and overtones
FTIR and NIR give excellent quantitative results
FTIR and Raman give excellent qualitative results
FTIR looks at the outside of the molecule
Raman looks at the backbone or inside of the molecule
Raman and NIR both work through glass, plastic, and fiber optics