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INFRARED SPECTROSCOPY

REGION X-ray UV/Visible Infrared Microwave Radio Frequency (nmr)

PROCESS Bond-breaking Electronic Vibrational Rotational Nuclear and Electronic Spin

Infrared Spectrometer

Fourier Transform Infrared (FTIR) Spectrometer

Energy Levels: Basic Ideas

Basic Global Warming: The C02 dance

About 15 micron radiation

Wavelength and Wavenumber

Wavelength = 1 / Wavenumber For the IR, wavelength is in microns. Wavenumber is typically in 1/cm, or cm-1. 5 microns corresponds to 2000 cm-1. 20 microns corresponds to 500 cm-1.

15 microns corresponds to 667 cm-1. Much terrestrial IR energy at the wavenumber.

FTIRs Often Use MCT Detectors: Mercury Cadmium Telluride

HgCdTe or Mercury cadmium telluride (also Cadmium Mercury Telluride, MCT or CMT) is an alloy of CdTe and HgTe and is sometimes claimed to be the third semiconductor of technological importance after Silicon and Gallium(III) arsenide. The amount of cadmium (Cd) in the alloy (the alloy composition) can be chosen so as to tune the optical absorption of the material to the desired infrared wavelength. (from http://en.wikipedia.org/wiki/Mercury_cadmium_telluride)

Outline

Introduction
Design Applications Measurements Discussions

What is a FTIR Spectrometer?

A spectrometer is an optical instrument used to measure properties of light over a specific portion of the electromagnetic spectrum, 5 microns to 20 microns. FTIR (Fourier Transform InfraRed) spectrometer is a obtains an infrared spectra by first collecting an interferogram of a sample signal using an interferometer, then performs a Fourier Transform on the interferogram to obtain the spectrum. An interferometer is an instrument that uses the technique of superimposing (interfering) two or more waves, to detect differences between them. The FTIR spectrometer uses a Michelson interferometer.

FOURIER TRANSFORMS

Fourier transform defines a relationship between a signal in time domain and its representation in frequency domain. Being a transform, no information is created or lost in the process, so the original signal can be recovered from the Fourier transform and vice versa. The Fourier transform of a signal is a continuous complex valued signal capable of representing real valued or complex valued continuous time signals.

Fourier Transforms cont.

The Continuous Fourier Transform, for use on continuous signals, is defined as follows:

And the Inverse Continuous Fourier Transform, which allows you to go from the spectrum back to the signal, is defined as:

F(w) is the spectrum, where w represents the frequency, and f(x) is the signal in the time where x represents the time. i is sqrt(-1), see complex number theory.

Fourier Transforms cont.

A computer can only work with finite discrete signals, not with continuous signals. Thus, we need to define the Discrete Fourier Transform (DFT). In DFT, the infinite borders of the integrals can be replaced by finite ones, and the integral symbol can be replaced by a sum. So the DFT is defined as:

And the inverse DFT is defined as:

Figure 1.

Schematic of Michelson Interferometer

Figure 2.

Source: MS thesis submitted by Carl George Schmitt, UNR , 1998.

Wave Interference

Figure 3.

Sample interferograms and their theoretical source intensity Source: MS thesis submitted by Carl George Schmitt, UNR , 1998.

APPLICATIONS

Identification of inorganic compounds and organic compounds Identification of components of an unknown mixture Analysis of solids, liquids, and gasses In remote sensing In measurement and analysis of Atmospheric Spectra - Solar irradiance at any point on earth - Longwave/terrestrial radiation spectra Can also be used on satellites to probe the space

ATTENUATED TOTAL REFLECTION SPECTROSCOPY

Outline
Introduction to ATR technology Evanescent Waves Crystal Composition Data Collection Advantages & Disadvantages

Sample Analysis
Challenges Future Applications Conclusion

How an ATR accessory works


Internal reflection spectroscopy passes infrared radiation through an infraredtransmitting crystal of high refractive index, allowing the radiation to reflect in the crystal one or more times
An attenuated total reflection accessory measures the totally reflected infrared beam when the beam comes in contact with a sample In this way, an evanescent wave penetrates into the sample in contact with the crystal, producing a spectrum of the sample

Evanescent Waves

The infrared radiation interacts with the sample through a series of standing waves, called evanescent waves

An evanescent wave is a penetrating electromagnetic field whose intensity quickly decays as it moves away from its source

Disadvantages ATR vs. Transmission

The ATR crystal absorbs energy at lower energy levels If the sample does not have good contact with the crystal, the data will not be accurate Most ATR crystals have pH limitations

Advantages ATR vs. Transmission


When an ATR accessory is used, most samples can be run neat, which means in their natural state ATR sampling is fast and easy because little or no sample preparation is required Other techniques, such as infrared transmission, often require the sample to be heated, pressed or ground in order to collect the spectrum

Crystal Composition
Crystals are typically made of:
Zinc Selenide (ZnSe) Germanium (Ge) Zinc Sulfide (ZnS) Silicon (Si) Diamond AMTIR: Germanium, Arsenic, Selenium (GeAsSe)

Solid analysis
ATR is an excellent technique for measuring the composition of solids Some examples of solids are films, fabrics, paper, hard polymer sheets, glass, rubber ATR is an ideal technique for measuring dark colored materials which often absorb too much energy to be measured by IR transmission

Liquid Analysis

ATR is an ideal technique for analyzing liquids Sample preparation is minimal Cleanup is easy and fast

Powder Analysis

Powders are easier to run by ATR than by IR transmission, because little or no preparation is required This category includes pure samples and mixtures that are available in powdered from Some examples of pure samples and mixtures are pharmaceuticals and pigments

Future Applications

Forensic Investigation

Biomedical applications

POLYPROPYLENE!

One Popular Polymer!

Whats so great about POLYPROPYLENE?


High Melting Point (dishwasher safe!) Intermediate crystallinity: tough without being brittle High resistance to fatigue (living hinge) Chemically Inert CHEAP to MAKE!!!

Polypropylene comes from Propylene!

Synthesis
1. Zeigler-Natta polymerization:
TiCl3 + Al(C2H5)2Cl, or TiCl4 + Al(C2H5)3

Synthesis
2) Kaminsky Catalysts: Metallocene
A metallocene is a positively charged metal ion sandwiched between two negatively charged cyclopentadienyl anions.

The era of Polypropylene & Polyethylene

Polypropylene is Useful. . .

How much polypropylene is out there?


PP generation in 1996 (tons)
Source: EPA, Characterization of Municipal Solid Waste in the United States: 1997 Update

Product Category
Durable Goods Non Durables*

Estimated US Generation
1,030,000 740,000

Other Plastic Containers


Bags, Sacks, Wraps Other Plastic packaging** Total Generated

70,000
430,000 310,000 2,580,000

* Includes plastics in disposable diapers, clothing, footwear, etc. ** Other plastics packaging includes coatings, closures, caps, trays, shapes, etc.

Polystyrene

Background Information
Polystyrene is a plastic polymer made from the monomer styrene.

It's used in many ways for various uses. Products such as disposable cutlery and CD or DVD cases are able to be made from it's solid state. Meanwhile, foam polystyrene (Styrofoam), is used for packaging, insulation and foam cups or plates.

Foam polystyrene is especially useful as it is a very light material while still being a great insulator.

Polystyrene: Why It Should Be Manufactured


It is sanitary for one-time food and beverage use.
Its low cost to manufacture. Less harmful to manufacture than manufacturing paper.

Biodegradability is not an issue in modern landfills.


Its rigid form makes it extremely useful and allows products of it to vary.

Polystyrene: Why It Should be Banned

It cannot break down out in the environment, away from a landfill.

Leaching can occur when heated, allowing poisonous neurotoxins into our food.

Recycling isn't economically justifiable; and we should therefore search for a product we can reuse better.

Foam polystyrene is made from non-renewable petroleum products.

Low-density Polyethylene (LDPE)


Small amount of branching on the chain gives a more open structure Melting point of 109 to 125 deg C Does not react at room temperature Resists alcohols, esters, acids, and bases. Limited resistance to aldehydes. Translucent to opaque Used for plastic food or garment bags, spray bottles, plastic lids.
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Polyethylene

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Formation and Structure

Ethylene-Ethylene bond yields polyethylene (CH2CH2)n


Crystalline regions lie in alternating fashion with amorphous regions, which creates scattering of light

polyethylene

Pure polyethylene, low-

and high-density polyethylene (LDPE, HDPE)


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High-Density Polyethylene

Absence of branching results in a more closely packed structure, more crystalline, higher density, and chemical resistance slightly higher than that of LDPE. Resists alcohols, acids, bases, esters, and aldehydes Specific Gravity: 0.94 to 0.97 Melting point 130 to 135 deg C Carbon chains can are 10,000 to 100,000 carbon atoms long Translucent
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Low-density Polyethylene (LDPE)


Small amount of branching on the chain gives a more open structure Melting point of 109 to 125 deg C Does not react at room temperature Resists alcohols, esters, acids, and bases. Limited resistance to aldehydes. Translucent to opaque Used for plastic food or garment bags, spray bottles, plastic lids.
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Pure Polyethylene

Low density arises from minimal amount of branching in chain, gives a more open structure. Translucent to opaque Resists acids, bases, esters, alcohols, hydrocarbons. Limited resistance to aldehydes. Does not react at room temperature Translucent to opaque.

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Properties

Poylethylene is a solvent for fats, oils, and grease. Dissolving occurs slowly. Electrons are tightly trapped in their C-C and C-H bonds, which results in an inability of electrical current to flow. Also results in inability for water and ions to penetrate interior of solid.

Thin film of polyethylene photographed using polarized light. The pattern arises form the presence of spherulites, or regions where the polymer molecules have aggregated into spheres.
Picture and caption from Molecules

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R-E-C-Y-C-L-E, Recycle. . .

Polyethylene does not biodegrate unless first oxidized. Polyeofins are highly susceptible to photooxidation, or oxidation caused by the exposure to light. Hindered-amine light stabilizers are then used to prevent photooxidation.

Polyethylene film, which is widely used for packaging, is formed by extruding the molten plastic through a ring-like gap and inflating it like a balloon.
Photo and caption from Molecules

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Chap 11. Free Radical Copolymerization


Radical copolymerization

Regular copolymer Random copolymer Block copolymer Graft copolymer

Actual copolymer (case)

Copolymer Equation
Only Binary Case Two Monomers; M1 + M2

M1 .

+ + + +

M1 M2 M1 M2

k11 k12 k21 k22

M1.

M1 . M2 . M2 .

M2.
M1 . M2.

Steady State Assumption

d [ M 1] d [ M 2 ] 0 dt dt

and chain transfer & termination compared w/ propagation

k12 [ M1][ M 2 ] k21[ M 2 ][ M 1 ]

[ M 1 ] k 21[ M 1 ] [ M 2 ] k12 [ M 2 ]

Copolymer Equation

d[M 1 ] k11[ M 1 ][M 1 ] k 21[ M 2 ][M 1 ] dt


d[M 2 ] k12 [ M 1][M 2 ] k22 [ M 2 ][M 2 ] dt

d [ M 1 ] [ M 1 ] k11[ M 1 ] k 21[ M 2 ][M 1 ] d [ M 2 ] [ M 2 ] k12 [ M 1 ] k 21[ M 2 ][M 2 ]


Instantaneous ratio of monomers in copolymer From and

[M 1 ] d[M 1 ] [M 2 ] [M 2 ] d[M 2 ] 1 r2 [M 1 ] 1 r1

where

r2

k k 22 r1 11 k12 k 21 ,

monomer reactivity ratio

Copolymer Eq.

Ideal Copolymerization
Ideal Copolymerization
d [ M 1 ] [ M 1 ] r1[ M 1 ] [ M 2 ] d [ M 2 ] [ M 2 ] [ M 1 ] r2 [ M 2 ]
where r1 r2 1

r2

1 r1

r1
r1

[ M 1 ] r1[ M 1 ] [ M 2 ] [ M 2 ] r1[ M 1 ] [ M 2 ]
[M 1 ] [M 2 ]

F1

r1 f1 r1 f1 f 2

k11 k 22 1 k12 k 21

k11 k 21 k12 k 22

Most ionic copolymerizations are characterizes by the ideal type of behavior


When r1 1 r2 , the two monomers show equal reactivity toward both propagating species random copolymer

Ideal Copolymerization
r1 1
r2 1
or

r1 1

r2 1 One of the monomer us nire reactive than

The other toward both propagating spices. The copolymer will contain a larger proportion of the more reactive monomer in random placement 1

F1

0
Surfing to the internet

f1

For further details about Ideal Copolymerization Click next homepage. http://www.chem.rochester.edu/~chem421/copoly.htm

Result