WM4 Instrumental analysis

The 3 key instrumental techniques

How do we know that salicylic acid contains –

OH and –COOH groups?

 Mass spectroscopy (m.s.).

 Infrared (i.r.) spectroscopy.
 Nuclear magnetic resonance (n.m.r.)
spectroscopy.
Making use of infrared spectroscopy

 Any unidentified, new substance has its i.r. spectrum

recorded.
6.4 Infrared spectroscopy

 Energy in molecules is quantised.

 In i.r., molecules are exposed to radiation
between 1014Hz – 1013Hz (wavelengths 2.5µm
-15 µm). Remember: c = λ v
 Bonds vibrate and stretch (pull apart then
push together again) as they absorb energy.
Vibrational changes of CO2

Asymmetric stretch

Symmetric stretch

bending
Infrared spectra: signals = stretches

 An IR spectrum hangs down from a baseline (100%

transmittance = no absorbtion).
 The signals (look like ‘icicles’) on an IR spectra
correspond to bonds absorbing a packet of energy
and vibrating more.
 The –OH and –CO bonds in salicylic acid absorb
energy at specific wavelengths (λ)/µm and so
wavenumbers (1/ λ)/ cm-1 .
Generally, particular bonds can be matched
to a particular absorption region.

Bond Location Wavenumber/cm-1 Intensity

C-H Alkanes 2850 -2950 M-S
C=C Alkenes 1620 – 1680 M
Arenes Sev peaks 1450-1650 Variable
C C Alkynes 2100 – 2260 M
C=O Aldehydes 1720 – 1740 S
C-O Alcohols, ethers 1050 - 1300 S
phenols
C-F fluoroalkanes 1000 – 1400 S
O-H Alcohols 3600 – 3640 S
N-H 1o amines 3300 - 3500 M-S
Interpreting spectra: 2-ethylbut-1-ene

?
Interpreting spectra: propanone
 Regions in the IR spectrum where
typical absorptions occur

Absorption range/cm-1 Bonds responsible Examples

4000 – 2500 Single bonds to hydrogen O-H, C-H, N-H,

2500 – 2000 Triple bonds C C, N N

2000 – 1500 Double bonds C=C, C=O

Below 1500 Various C-O,

(fingerprint region) (not used to ID functional groups) C-X (halogen)

Label these regions on the previous two examples; sketch the structures and
link them to the main signals. Do this for the following examples, too.
Examples of infrared spectra

Butane
 Strong
absorption at
2970 cm-1
characteristic of
C-H stretching
in aliphatic
compounds.
 No indication of
any functional
groups.
 Examples of infrared spectra

Methylbenzene
 2 types of C-H
absorption ~3000
cm-1 (above = C-
H on benzene;
below = C-H on
methyl group).
 No indication of
any functional
groups.
 Absorption pattern
~700 cm-1 is typical
of a benzene ring
with a substituted
group.
Examples of infrared spectra
Benzoic acid
 A sharp
absorption at
3580 cm-1 is due
to O-H bond.
 A strong
absorption at
1760 cm-1 is the
C=O group.
 Position of C-H
absorption
suggests an
aromatic
compound.
Summary of IR spectroscopy

 An IR spectrum measures the extent to

which electromagnetic radiation is
transmitted through a sample of substance.
 Frequency ranges absorbed give clues about
functional groups which are present.
 IR spectrum of salicylic acid gives evidence
of C=O and –OH groups.
Evidence from nuclear magnetic
resonance (n.m.r.) spectroscopy.

 This technique helps to determine structure,

as it investigates the different environments
in which (hydrogen) nuclei are situated. The
n.m.r. spectrum for salicylic acid shows
signals for the different environments of the 6
protons:
 One proton in a –COOH environment.
 One proton in a phenolic –OH environment.
 Four protons attached to a benzene ring.
n.m.r. spectrum for salicylic acid
Absorption

12 11
The evidence so far….

A combination of i.r. and n.m.r. spectroscopy

shows that salicylic acid has an –OH group
and –COOH group both attached to a
benzene ring; we can now rename it
HYDROXYBENZOIC ACID.
 However, it could be one of 3 possible
isomers: 2-hydroxybenzoic acid, 3-
hydroxybenzoic acid and 4-hydroxybenzoic
acid.
 Mass spectroscopy can determine which
isomer we have.
The mass spectrum of salicylic acid

 Signals correspond to positively charged ions formed

from the parent compound, and fragment ions.

The fragmentation pattern

is characteristic of a particular
Parent or
compound…the fragment at
molecular ion
120 can only come from 2-
hydroxybenzoic acid…can
you see why?

mass
Fragmentation

 Positiveions in a mass spectrometer can

break down into ‘building blocks’.
Example: 2-ethoxybutane. +
CH3-CH2-CH-O-CH2CH3
?
Loss of (M=87)
CH3 ?
Loss and +
CH3-CH2-CH-O-CH2CH3 ? +
rearrangement of CH3-CH2-CH
CH3CH=CHCH3
CH3 (M=102)
+ (M=87) CH3
HO-CH-CH3 (M=45) Loss of
? CH3-CH2
+ ?
CH3-CH2 (M=29)
Positively charged fragments form.
Mass difference suggests functional groups.

For each fragmentation, Mass Group that is

one product has a Difference suggested
positive charge: 15 CH3
17 OH
M+ A+ + B 28 C=O or C2H4
A + B+
29 C2H5
43 COCH3
The most stable ion
usually forms. 45 COOH
77 C6H5
Isotope peaks: heights are in the same
ratio of abundance for particular elements.

Pairs of peaks correspond to

isotopes of 35 Cl and 37 Cl in the
ratio of 75%:25% ie. 3:1.
Highlight these.

mass
Now it’s over to you!

 Do activity WM4: use accurate Mr values,

isotope peaks and a database to lead you to
the formula of salicylic acid.
It shows you how chemists use fragmentation
patterns to deduce or confirm a molecular
structure.
 Do assignments 1 and 2 C.S. p110-111
 Do ‘Problems for 6.5’ on mass spectrometry,
C.I., p145-146.