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Spectroscopy is an instrumentally aided studies of the interactions between matter (sample being analyzed) and energy (any portion of the electromagnetic spectrum, EMS) EMS refers to the seemingly diverse collection of radiant energy, from cosmic rays to X-rays to visible light to microwaves, each of which can be considered as a wave or particle traveling at the speed of light. Chemists can use portions of the EMS to selectively manipulate the energies contained within a molecule, to uncover detailed evidence of its chemical structure and bonding.
=>
Energy (E)
where h is Plancks constant, c is the speed of light, n is frequency or the number of vibrations per second and l is the wavelength
E = hn = hc/l
Wavenumber (n)
given in cm-1
n = 1/ l
= hcn
Period (P)
P = 1/n
The four most common spectroscopic methods used in organic analysis are:
Method
Abbrev.
Energy used UV-Vis ultravioletvisible IR infrared NMR MS radio frequencies electron volts
Units
nm
mm or cm-1 Hz amu
What actually happens to the sample during an analysis? {How do the sample and energy interact?}
Matter/Energy Interactions
What happens when a sample absorbs UV/Vis energy?
excitation of ground state electrons (typically p and n electrons) Eelectronic increases momentarily
p* UV/Vis
(200 nm)
sample
p p*
transition
p
What happens when a sample absorbs IR energy?
stretching and bending of bonds (typically covalent bonds) Evibration increases momentarily
-O-H
IR
(3500 cm-1)
- O H
Infrared spectroscopy (IR) measures the bond vibration frequencies in a molecule and is used to determine the functional group Mass spectrometry (MS) fragments molecule and measures the masses the
Nuclear magnetic resonance (NMR) spectroscopy detects signals from hydrogen atoms and can be used to distinguish isomers
The IR Region
Just below red in the visible region Wavelengths usually 2.5-25 mm
More common units are wavenumbers, or cm-1, the reciprocal of the wavelength in centimeters (104/mm = 4000-400 cm-1)
Wavenumbers are proportional to frequency and energy
The IR region is divided into three regions: the near, mid, and far IR. The mid IR region is of greatest practical use to the organic chemist.
Molecules are made up of atoms linked by chemical bonds. The movement of atoms and chemical bonds like spring and balls (vibration)
What is a vibration in a molecule? Any change in shape of the molecule- stretching of bonds, bending of bonds, or internal rotation around single bonds
Vibrations
There are two main vibrational modes : 1. Stretching - change in bond length (higher frequency)
Stretching vibration
Stretching Types
Symmetric
Asymmetric
In-plane (Scissoring)
Out-plane (Twisting)
Modes of vibrations
Stretching: change in bond distance. Occurs at higher energy: 4000-1250 cm1. Bending: change in bond angle. Occurs at lower energy: 1400-666 cm1.
H 2O
-CH2-
Asymmetrical stretching/bending and internal rotation change the dipole moment of a molecule. Asymmetrical stretching/bending are IR active.
moment
Fundamental Vibrations (Absorption Frequencies) A molecule has as many as degrees of freedom as the total degree of freedom of its individual atoms.
Each atom has 3 degree of freedom (x,y,z) A molecule of n atoms therefore has 3n degrees of freedom. Non linear molecules (e.g. H2O) Vibrational degrees of freedom or Fundamental Vibrations = 3n 6
H O H H O H H O H
For linear molecule (e.g. CO2) : Vibrational degrees of freedom or Fundamental Vibrations = 3n 5
O C O O C O
BACKGROUND
H-O-H
H-O-H O=C=O
The theoretical no. of fundamental vibrations will seldom be observed because overtones (multiples of a given frequencies) and combination tones (sum of two other vibrations) increase the no. of bands.
H2
N2
Cl2
Why?
MM =2 g/mole
MM =254 g/mole
For a vibration at 4111 cm-1 (the stretch in H2), how many vibrations occur in a second?
120 trillion vibration per second!!!!
Hookes Law
M1
M2
= The vibration frequency (cm-1) c = Velocity of light (cm/s) f = force constant of bond (dyne/cm)
The relative contributions of bond strength is also considered in vibrational frequencies. In general functional groups that have a strong dipole give rise to strong absorptions in the IR.
n=
c =
frequency in cm-1
velocity of light
( 3 x 1010 cm/sec )
n = 2pc
where
K = force constant
in dynes/cm
m1 m2 = m1 + m2
C C > C C >C C
multiple bonds have higher Ks
m = atomic masses
This equation describes the vibrations of a bond.
m = reduced mass
n = 2pc
constants
1650
1200
Stretching Frequencies
Frequency decreases with increasing atomic mass. Frequency increases with increasing bond energy.
EXAMPLE: Calculate the fundamental frequency expected in the infrared absorption spectrum for the C - O stretching frequency. The value of the force constant is 5.0 X 105 dynes/cm.
wave number = 1 = ------- * ((k(m1 + m2))/(m1 m2))1/2 2pc 1 = ---------------------- cm-1 2(3.14)(3.0E10) * ((5.0E5(12+16)(6.02E23))/(12*16))1/2
= 1112 cm-1
Vibrational Spectroscopy
100%
Transmission
0%
50%
4500
4000
3500
3000
Wavenumber
2500 (cm-1)
2000
1500
IR Correlation Diagram
Region I 3600-2700 cm-1
100
Transmittance (%)
80 60 40 20 0 4000 2.5
C=O
acid chlorides anhydrides (below 1500 cm-1) esters ketones aldehydes carboxylic acids amides
Fingerprint Region
3500 3.0
3000
2500 4.0
2000 5.0
1500 6.0
1000 10.0
Instrumentation
1. Radiation source 3. Solvents, sample cells, samples 2. Monochromator 4. Readout / Recorder
Solvents
1. Must be transparent in the region studied: no single solvent is transparent throughout the entire IR region 2. Water and alcohols are seldom employed to avoid O-H band of water . 3. Must be chemically inert (does not react with substance or cell holder). CCl4, CS2, or CHCl3; may be used but we should consider its IR spectrum
Cells
- NaCl or KCl cells may be used (moisture from air and sample should be avoided: even with care, their surfaces eventually become fogged
Samples
1. Solid KBr disk (1 mg solid sample + 100 mg KBr pressed into a disk)
Mull: 1 mg solid sample suspended in Nujol (heavy liquid hydrocarbon)
2. Liquid Neat (thin film of liquid between two NaCl plates solution in
CCl4 and put in special NaCl cells.
Interferogram
The interferogram at the right displays the interference pattern and contains all of the spectrum information. A Fourier transform converts the time domain to the frequency domain with absorption as a function of frequency.
Use of IR spectra
Identification of functional groups on a molecule this is a very important tool in organic chemistry Spectral matching can be done by computer software and library spectra Since absorbance follows Beers Law, can do quantitative analysis
FEATURES OF AN IR SPECTRUM
An IR spectrum is a plot of per cent transmittance (or absorbance) against wavenumber (frequency or wavelength). A typical infrared spectrum is shown below.
A 100 per cent transmittance in the spectrum implies no absorption of IR radiation. When a compound absorbs IR radiation, the intensity of transmitted radiation decreases. This results in a decrease of per cent transmittance and hence a dip in the spectrum. The dip is often called an absorption peak or absorption band. Different types of groups of atoms (C-H, O-H, N-H, etc) absorb infrared radiation at different characteristic wavenumbers.
IR Spectrum
Baseline
Absorbance/ Peak
No two molecules will give exactly the same IR spectrum (except enantiomers) Simple stretching: 1600-3500 cm-1 Complex vibrations: 400-1400 cm-1, called the fingerprint region
80
70
60 50 40
30 20 10
C=O
0 4600 3800 3000 2200 1800 1400 1000 800 600 400
Wavenumber (cm-1)
Describing IR Absorptions
IR absorptions are described by their frequency and appearance. Frequency (n) is given in wavenumbers (cm-1) Appearance is qualitative: intensity and shape conventional abbreviations:
vs
s m w br sh
very strong
strong medium weak broad sharp OR shoulder
In general, the IR spectrum can be split into four regions for interpretation: 4000 2500 cm-1: Absorption of single bonds formed by hydrogen and other elements e.g. OH, NH, CH 2500 2000 cm-1: Absorption of triple bonds e.g. CC, CN 2000 1500 cm-1: Absorption bonds e.g. C=C, C=O of double
1500 400 cm-1: This region often consists of many different, complicated bands. This part of the spectrum is unique to each compound and is often called the fingerprint region. It is rarely used for identification of particular functional groups.
Summary of IR Absorptions
BASE VALUES
(+/- 10 cm-1)
C=O C=C C O
O-H STRETCH
WAVELENGTH (mm)
5 5.5 6.1 6.5 15.4
O-H N-H
C-H
C N C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800
1650
FREQUENCY (cm-1)
broadens
shifts
FREE H-BONDED
3600
3300
HYDROGEN-BONDED HYDROXYL
R H R O H R O O R H O H R O H H O R
Many kinds of OH bonds of different lengths and strengths This leads to a broad absorption.
Neat solution.
FREE HYDROXYL
The free hydroxyl vibrates without interference from any other molecule.
Distinct bond has a welldefined length and strength.
CCl4
ALCOHOL
,
O-H H-bond
OH
CH2 C-O
C-H
CARBOXYLIC ACID
O R C
H O C R O H O
Strong hydrogen bonding in the dimer weakens the OH bond and leads to a broad peak at lower frequency.
N-H STRETCH
WAVELENGTH (mm)
5 5.5 6.1 6.5 15.4
O-H N-H
C-H
C N C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800 1650
FREQUENCY (cm-1)
H N H
1-Butanamine
CH3
CH2
3-Methylbenzenamine
benzene
CH3
Ar-H
SECONDARY AMINE
N -Ethylbenzenamine
NH
NH CH2 CH3
CH3 benzene
Ar-H
TERTIARY AMINE
N,N -Dimethylaniline
Ar-H -CH3
CH3 N CH3
no N-H
CH3
benzene
Ar-H
C-H STRETCH
C-H
O-H N-H C-H
WAVELENGTH (mm)
4 5 5.5 6.1 6.5 15.4
C N C C X=C=Y (C,O,N,S)
4000
2500
2000
1800 1650
1550
650
FREQUENCY (cm-1)
We will look at this area first
C-H sp stretch ~ 3300 cm-1 C-H sp2 stretch > 3000 cm-1 C-H sp3 stretch < 3000 cm-1
UNSATURATED
3000 divides
SATURATED
C-H aldehyde, two peaks (both weak) ~ 2850 and 2750 cm-1
STRONGER BONDS HAVE LARGER FORCE CONSTANTS AND ABSORB AT HIGHER FREQUENCIES increasing frequency (cm-1)
3300 = =C-H
sp-1s
3100
3000
=C-H
2900
-C-H sp3-1s
2850 2750
-CH=O
(weak)
sp2-1s
aldehyde
ALKANE
Hexane
CH bending vibrations discussed shortly
CH stretching vibrations
C-H BENDING
CH3 bending (asym) appears near the CH2 value ~ 1460 cm-1
CH3 bending (sym) ~ 1375 cm-1
H C H H C H
~1465 cm-1
H C H
H C
~1250 cm-1
~720 cm-1
H C H
H C
~1250 cm-1
Rocking
in-plane
Twisting
out-of-plane
Bending Vibrations
CH3
C-H Bending, look near 1465 and 1375 cm-1 sym
1465
1460
1375
C H H
CH2
asym
CH3
sym
The sym methyl peak splits when you have more than one CH3 attached to a carbon.
C CH3
1465
1460
1375
CH3 C CH3
one peak
1380 1390
1370 1370
two peaks
two peaks
ALKANE
Hexane
CH2 rocking CH2 bend CH stretch CH3 bend
ALKENE
1-Hexene
=CH
C=C
CH
AROMATIC
Toluene
Ar-H
CH3
CH3
ALKYNE
1-Hexyne
HC
Fingerprinting
C10H22
C12H26
C N AND C C STRETCH
C=C =
C N
WAVELENGTH (mm)
5 5.5 6.1 6.5 15.4
O-H N-H
C-H
C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800 1650
FREQUENCY (cm-1)
The cyano group often gives a strong, sharp peak due to its large dipole moment. The carbon-carbon triple bond gives a sharp peak, but it is often weak due to a lack of a dipole. This is especially true if it is at the center of a symmetric molecule. R C C R
NITRILE
Propanenitrile
BASE = 2250
= C=N
CH3 CH2 C
ALKYNE
BASE = 2150
1-Hexyne
= =C-H
= C=C
HC
C=O STRETCHING
C=O
5.5 6.1 6.5 15.4
O-H N-H
C-H
C N C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800 1650
FREQUENCY (cm-1)
KETONE
2-Butanone
1715
overtone 2x C=O
BASE = 1715
C-H
CH bend
O
C=O C=O
CH3 C CH2 CH3
ester
aldehyde
ketone
amide
O R C Cl
O R C OR'
O R C H
O R C R
O R C OH
O R C NH2
1800
anhydride
1735
O
1725
1715
BASE VALUE
1710
1690
R C O C R
1.225 A
1.231 A
SUMMARY
Ketones are at lower frequency than Aldehydes because of
the second electron-donating alkyl group.
Amides
are at lower frequencies than ketones due to resonance involving the unshared pair on nitrogen. The electronwithdrawing effect of nitrogen is less important than the resonance. Note the electronegativity difference, O versus N, weights the two factors (resonance/ e-withdrawal) differently in esters than in amides.
KETONE
BASE = 1715
2-Butanone
overtone
C-H
CH bend
O
C=O
CH3 C CH2 CH3
3438
ALDEHYDE
BASE = 1725
Nonanal
CHO
CH bend C=O
O CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C H
3460
ACID CHLORIDE
Dodecanoyl Chloride
BASE = 1800
CH bend
O
C-H
C=O
C CH3 (CH2)10 Cl
3608
ESTER
Ethyl Butanoate
BASE = 1735
C-H
C-O
O
C=O
3482
CARBOXYLIC ACID
BASE = 1710
2-Methylpropanoic Acid
O-H
C-H
C=O
C-O
C CH3 CH CH3 OH
O R C
H O C R O H O
and also of O-H
Strong hydrogen-bonding in the dimer weakens the O-H and C=O bonds and leads to broad peaks at lower frequencies.
Propanamide
BASE = 1690
O C NH2
ALKENES AROMATICS
C=C STRETCHING
C=C
6.1 6.5 15.4
O-H N-H
C-H
C N C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800 1650
FREQUENCY (cm-1)
ALKENE
1-Hexene
=C-H
C-H aliphatic
C=C
C-H bend
oops CH CH2 CH2 CH2 CH3
CH2
AROMATIC
Toluene
benzene C-H
CH3
C-O
15.4
O-H N-H
C-H
C N C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800 1650
FREQUENCY (cm-1)
C-O STRETCHING
Look for one or more strong bands appearing in this range! Ethers, alcohols, esters and carboxylic acids have C-O bands
Dibutyl Ether
ETHER
BASE = 1100
C-H
AROMATIC ETHER
BASE = 1100
Anisole
C-H aromatic
O CH3
benzene
C-O
oops
ALCOHOL
Cyclohexanol
CH2 bend OH
OH
C-O C-H
CARBOXYLIC ACID
2-Methylpropanoic Acid
OH
O
CH
C=O
C-O
C CH3 CH CH3 OH
ESTER
Ethyl Butanoate
CH C-O C=O
CH3 CH2 CH2 O C O CH2 CH3
N=O STRETCHING
N-O
6.5 15.4
O-H N-H
C-H
C N C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800 1650
FREQUENCY (cm-1)
Often the 1550 cm-1 peak is stronger than the other one
NITROALKANE
2-Nitropropane
C-H N=O
NO2 CH CH3 CH3
gem-dimethyl
N=O
C-Cl
6.5 15.4
O-H N-H
C-H
C N C C X=C=Y (C,O,N,S)
C-Cl C-O C=C C-N C-C N=O N=O * C=N 1550 650
4000
2500
2000
1800 1650
FREQUENCY (cm-1)
C-Br and C-I appear outside the useful range of infrared spectroscopy.
C-F bonds can be found easily, but are not that common.
Often used as a solvent for IR spectra. When it is used, spectra show C-Cl absorptions.
Carbon Tetrachloride
Cl Cl C Cl Cl
C-Cl
Chlorobenzene
Cl
oops
benzene C=C
C-Cl
OUT-OF-PLANE BENDING
(OOPS) PLANE H ALKENES H H below above
ALKENES
Monosubstituted Disubstituted cis-1,2-
10
R C C H R C C H H H R C C R R H H C C R R H R C C R R H R C C R R H R H
11 s s
12
13
14
m 15
trans-1,2-
1,1-
Trisubstituted
Tetrasubstituted
BENZENES
Monosubstituted Disubstituted
10
11
12
13
14 s s
15 m s
m s
RING Hs OOPS
m s
m m 700 cm-1