Notes 21

HL ONLY

Topic 21 Spectroscopic Techniques (HL)

Essential idea: Although spectroscopic characterization techniques form the

backbone of structural identification of compounds, typically no one technique
results in a full structural identification of a molecule.
Nature of science: (1.8) Improvements in modern instrumentation—advances in
spectroscopic techniques (IR, 1H NMR and MS) have resulted in detailed
knowledge of the structure of compounds.

21.1 High Resolution NMR (HL only)

Reference Standard

 The position of absorption (the chemical shift) is measured relative to the

absorption of tetramethylsilane (TMS) mixed with the sample.

 TMS is chemically inert and produces one strong signal at and absorbs
upfield at a different frequency from most organic compounds.
Why does TMS only produce one signal? Why is the signal strong?

 The chemical shift of TMS is assigned a value of zero and all other
absorptions are measured relative to it.

Further Splitting (high resolution)

 Single peaks present in low resolution NMR can be split into clusters of
peaks due to spin-spin coupling with inequivalent hydrogen’s on
neighbouring carbon atoms.

 No. of lines = no. of inequivalent H’s on neighbouring carbons +1

(or n+1)

1
 signal singlet doublet triplet quartet

appearance

No. of lines 1 2 3 4

No. of
inequivalent
H’s on
neighbouring C

 Note: the H on an O-H is not affected by hydrogen’s on adjacent atoms so

the peak due to the H on an OH is not split – it always appear as a singlet

Summary High Resolution NMR

 No. of signals number of different chemical environments of

H atoms

 Chemical shift actual chemical environment of each H atom

(see Data Booklet Table 27)

 Area under peak number of H atoms in each environment

(peak areas are given as a ratio)

 Splitting number of inequivalent H atoms on adjacent

C atoms

ToK: The intensity ratio of the lines in the high resolution NMR spectrum is given
by the numbers in Pascal's triangle, a mathematical pattern known independently
over a thousand years ago by a number of different cultures. Why is mathematics
such an effective tool in science? Is mathematics the science of patterns?

2
 IHD = ½ [(2C+2) + N – X – H]
e.g. C2H6O = ½ [(4+2) + 0– 0 – 6]  Area 2 = two H atom (probably CH2)
= 0 (no bonds or rings  Quartet = three H on neighbouring C
(probably next to CH 3 )
 Area 3 =three
Chemical shift(probably
H atom 2.3 = close
CHto3) electroneg atom?
Suggests:
 3 signals = 3 different H environments
 Triplet =two
Suggest
H on CH 3CH2 grouping
neighbouring C (probably next to CH 2)
CH3CH2OH  Chemical shift 1.3 = R-CH3
 Suggest CH3CH2 grouping

 Area 1 = one H atom

 Singlet = no H on neighbouring C OR OH
 Chemical shift 5.3 = hydrogen in an
electroneg environment / R-O-H ?

Analyse the following NMR spectra in the same way:

e.g. C5H10O

3
e.g. C5H10O2

Sketch the spectra you would expect for each of the following compounds:

CH3CH2COCH3 CH3CH2CH2CH3

Now try Worksheet 11e High Resolution NMR’ OR Powerpoint “High Resolution NMR
Questions”on ISLE (more examples than on 11e)

Utilization:
Why is MRI replacing computerized tomography (CT) scans for some applications
but is used as a complementary technique for others?
MS (and other techniques such as TLC, GC, GC-MS and HPLC) can be used in
forensic investigations at crime scenes.

Analytical techniques can be used to test for drug abuse by high-performance

athletes.

4
21.1 X-Ray Crystallography (HL)

 We see objects by observing the light scattered from them. However, the
wavelength of visible light is too long for it to interact with individual atoms
and molecules.

 X-rays have a wavelength similar to the distance between atoms allowing

them to be used to determine the molecular and atomic structures of crystals.

 The structural technique of single crystal X-ray crystallography can be

used to identify the bond lengths and bond angles of crystalline
compounds.

 When X-rays pass through a crystalline solid they are scattered in an orderly
way by their interaction with electrons in the substance. A diffraction
pattern is produced.

 The diffraction pattern depends on:

- angle of incidence of the X-ray (
- wavelength of the incident ray )
- distance between atoms (d)
 The distance between atoms to be found
using the Bragg equation n= 2d sin
(no need to learn equation)

 An electron density map can be determined from the X-ray diffraction

pattern allowing bond lengths and angles to be determined.

 Contour lines connect points with the same electron density.

5
 The pattern in electron densities is related to the atoms electronic
configuration; hydrogen atoms are not visible as their electron density is too
low.
e.g. NaCl

Anthracene