Exercise M1 Infrared Spectroscopy Part I M1: Recording the IR

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Transcript Exercise M1 Infrared Spectroscopy Part I M1: Recording the IR

Infrared Spectroscopy

Dr. Milkevitch Organic Chem II Lab Spring 2010 Feb 11 & 13, 2010

Introduction

The purpose of this experiment

  

To introduce the student to spectroscopy Discuss the specific technique of Infrared Spectroscopy

Which is used to acquire structural information on organic molecules Use this technique in the laboratory

First: In order to Understand Spectroscopy

Must understand electromagnetic radiation (EMR)

EMR is a form of energy

Has a particle and wave nature

Examples: Light, microwaves, radiowaves

We Use Symbols to Designate Properties of Waves

λ is the wavelength of the waves

ν is the frequency of the waves

c is the speed of light

of all EMR actually

Relationships Between These Variables

Speed = wavelength x frequency

Therefore:

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c = λν λ = c/ν ν = c/λ

For electromagnetic waves, the speed (c) is constant

3 x 10 8 m/s

What This Means

Wavelength has a direct, inverse relationship with frequency:

λ

1/ν

The higher the frequency, the shorter the wavelength

The longer the wavelength, the smaller the frequency

Summary of Relationships

Wavenumbers

When the wavelength is measured in centimeters:

the reciprocal of the wavelength (1/cm) Is directly proportional to the frequency

1/cm Is called the wavenumber and is a commonly used term in spectroscopy

The Electromagnetic Spectrum

Spectroscopy Is the Study of the Interaction of Matter and Electromagnetic Radiation

In Organic Chemistry, the common techniques include:

Infrared Spectroscopy

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Nuclear Magnetic Resonance Spectroscopy UV/Visible Spectroscopy

What Spectroscopy Tells Us

Specific information on the structural features of the molecules being studied

The presence or absence of specific patterns of chemical bonding in a molecule

Infrared Spectroscopy: The use of infrared radiation to determine the presence or absence of specific patterns of bonding in a molecule (i.e., functional groups)

The Infrared Region

      

When IR Radiation is Applied to a Molecule Some passes through it, but some does not Some of it is absorbed All bonds in a molecule have a vibrational frequency If the frequency of the IR energy matches the specific vibrational frequency of a bond in a molecule

The molecule will absorb the IR radiation at that frequency The bond is excited from a lower to a higher vibrational state

Amplitude of vibration increases dramatically We can measure this absorbance of IR radiation We can come up with a graph of absorbance intensity vs. Wavelength

What an IR Spectrum Looks Like

Graph of absorption intensity vs. radiation frequency

Given as % transmittance E = hv = hc

Units are in wavenumbers (cm -1 ), (sometimes microns

)

λ

Now, Organic Molecules are Quite Diverse

Millions of organic compounds exist

Remember the 12 families of organic compounds?

Structurally different molecules can have different functional groups

Do not absorb exactly the same frequencies of IR radiation

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Therefore, give different patterns of absorption Specific bonds and functional groups in a molecule

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Have specific vibrational frequencies Therefore, will absorb characteristic frequency ranges of IR radiation

This means:

IR spectroscopy is a valuable tool for identifying different functional groups

Also, a valuable tool for helping identify the structure of an organic compound

Ways Molecules Vibrate: Vibrational Modes

Vibrational Modes:

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Fancy way to describe the ways a molecule can vibrate 2 most important vibrational modes in IR spectroscopy:

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Stretching: involves a change in interatomic distance Bending: involves a change in bond angles Change in interatomic distance Change in bond angles

IR-Active and Inactive Bonds

Stretching and bending must:

Change the molecule’s dipole moment in order

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absorption This is really important

Polar bonds will absorb strongly

Does a polar bond have a dipole moment?

A nonpolar bond will absorb weakly or not at all

Does a nonpolar bond have a dipole moment?

Some Trends in Vibrational Frequency

The smaller the atoms in a bond, frequency increases

Larger the atoms in a bond, frequency decreases

Bond strength also effects frequency of absorption

Stronger bonds, higher frequency of absorption Alkyne 2250 – 2100 cm -1 Alkene 1680 – 1600 cm -1 Alkane 1200 – 800 cm -1

Trends: Carbon-Hydrogen Stretching

Bonds with more s character absorb at a higher frequency

More s character, shorter and stronger bond

  

sp 3 sp 2

C-H, just below 3000 cm C-H, just above 3000 cm sp C-H, at 3300 cm -1 -1 -1 (to the right) (to the left)

The Three Most Important Regions of the IR Spectrum

3600 – 3100 cm -1

Where OH and NH stretching occur

Region around 1700 cm -1

Where C=O stretching occurs

Region around 1650 cm -1

Where C=C stretching occurs

Many of the important functional classes are identified by the presence (or absence) of absorptions in these regions

An Infrared Spectrophotometer

=>

FT-IR Spectrometer

“The modern IR spectrometer”

Small and compact

Computer controlled

Has better sensitivity than dispersive instruments

Irradiate the sample with all IR frequencies at the same time

Does multiple scans quickly

Averages the results

An Alkane IR Spectrum: Notable Peaks (or absorbances)

An Alkene IR Spectrum: Notable Peaks

An Alkyne IR Spectrum: Notable Peaks

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Correlation Table:

Summary of Notable IR absorbances for the functional Groups

Very important For the organic Chemist

Procedure

Each group should choose one of the following compounds: Chlorooctane Dodecane Chlorodecane Cyclohexane Cyclohexene 3,3-dimethyl-1-butene Heptane Hexane 1-heptyne 1-hexene

Procedure (2)

Obtain an IR spectrum

See Dr. M in the instrument lab

Interpret major absorption frequencies

Using tables in this handout

Annotate the spectrum with your interpretations

Your Report

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Your introduction should include a discussion of IR spectroscopy

Your textbook also has a chapter on IR Spectroscopy, use it if necessary No reaction mechanism or balanced equation in this experiment Physical properties section should be the relevant physical properties of your chosen compound

Your results section should include the spectrum of your chosen compound

Annotated

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What do the peaks correspond to?

If it’s not annotated, it is meaningless

Make a table of relevant absorbances, along with their identity

Conclusions: Things to think about

 

Did you successfully obtain your IR spectrum?

Is the spectrum clean? Crappy? Easy to obtain?

What does your IR spectrum look like?

What major peaks do you have?

What stretches do these peaks correspond to?

Do the peaks correspond to what type of compound you have (alkane, alkene or alkyne)?

Prove this: correlate your peaks to what peaks these compounds should have in an IR spectrum

Prove it further: find an IR spectrum of the compound and compare it to your spectrum

Overall, what did you learn about IR spectroscopy?

Additional Questions to answer: 1.

Which absorbs at a higher frequency: a C-H bond or a C-D bond? Explain.

2.

Why does H 2 not have an IR spectrum?

3.

Explain why the C=C stretch for a trans-disubstituted alkene is weaker than for a cis-disubstituted alkene.