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GCE

Chemistry

Context study

Edexcel Advanced Subsidiary GCE in Chemistry


(8CH01)

Edexcel Advanced GCE in Chemistry (9CH01)

Analysis of Chemicals for A2

October 2007
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Contents

Introduction 1
Analysis of chemicals 3
Electromagnetic radiation as a diagnostic tool 3
Technically differentiating between spectroscopy and spectrometry 3
Ultraviolet radiation 4
NMR 4

Gas chromatography 8
Introduction 8
Food analysis 9

References 11
Introduction

This document is designed to help teachers to understand the contemporary context of the
analysis of chemicals. It should give teachers information on this context and on how to
research it further if they wish. This document could also be given to students as introductory
material.

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Analysis of chemicals

Electromagnetic radiation as a diagnostic tool


Electromagnetic radiation in its various forms is an excellent diagnostic tool for chemists. The
energy of a given wave E = h v (where h is Planck’s constant and v the frequency of the
radiation) has the same magnitude as variety of properties of interest to chemists, such as
vibrational energy of a bond, or the energy of an electronic level.
Quantum theory predicts that energy levels within systems are quantized: they only exist in
certain discrete magnitudes. Electromagnetic radiation may be absorbed by a system and raise
the energy level of an electron or nucleus. Conversely, if a particle moves back down to a
lower level then electromagnetic radiation will be emitted. A spectrum arising from a given
portion of electromagnetic radiation consists of a series of peaks (absorptions or emissions)
characteristic of the molecule under examination. Typically though, in spectra these peaks
may be broadened as a result of thermal collisions and interacting atoms or groups adjacent to
the absorbing species.

Technically differentiating between spectroscopy and


spectrometry
Spectroscopy 1 is the study of the electromagnetic radiation with which physical systems
interact or that they produce. Spectrometry is the measurement of such radiations as a
means of obtaining information about the systems and their components. In certain types of
optical spectroscopy, the radiation originates from an external source and is modified by the
system, whereas in other types, the radiation originates within the system itself.
Molecules have rotational energy as they tumble by virtue of their kinetic energy E=3/2 kT
(k= Boltzmann constant, T the temperature in kelvin). Microwave radiation has energies
comparable with rotational energy levels within molecules and can induce transitions between
levels. Chemists can measure the distance between absorptions in a spectrum of a molecule
such as HCl and find information such as the bond length between atoms. Infrared radiation
has a higher energy level than that of microwaves and can thus induce transitions between
vibrational levels within molecules as well as rotations (a vibration-rotation spectrum thus
results).
Infrared absorption is restricted to molecules whose vibrations change the dipole moment as
they stretch or bend. There is no requirement for there to be a permanent dipole moment.
The ability of molecules in the atmosphere such as water, carbon dioxide and methane to
absorb infrared radiation that has been reflected from the surface is of great importance to
climate science. Houghton (2004) likens this to a thermal blanket.
The retention of thermal energy that would otherwise be emitted to outer space is a possible
cause of observed global warming. It must be remembered that the Sun is highly variable in
terms of energy output and could be a cause of 25 to 30 per cent of current rising average
temperatures. Well documented ‘wobbles’ 2 in Earth’s orbit may also be responsible for ice
ages and correspondingly warm interglacials. This subject is still a matter of vigorous debate
and controversy.

1
1986, 58, 1738
IUPAC Compendium of Chemical Terminology 2nd Edition (1997)
2
The Milankovich cycles.

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Ultraviolet radiation
Of greater energy still is ultraviolet radiation (UV). This radiation induces transitions between
electronic levels in the molecule. In absorption, energy is always taken in by the molecule and
a transition to a higher level takes place. In emission spectra, electromagnetic energy is
emitted when a transition to a lower energy level takes place.
Chemists are particularly interested in conjugated systems where systems of π electrons may
overlap, as in benzene, or where carbonyl groups may be adjacent to carbon multiple bond
systems. Here UV spectra are particularly informative as to chemical structure. Conjugation
changes the absorption to longer wavelengths and gives a more intense absorption.

NMR
Nuclear Magnetic Resonance spectroscopy (nmr) and its lesser known cousin Electron Spin
Resonance (ESR) use energy radiation in the radio frequency range. Nmr involves transitions of
nuclei from one spin state to another. ESR involves unpaired electron spins, rather than the
spins of atomic nuclei. Proton Magnetic Resonance spectroscopy is particularly suitable for
organic chemists as there are only two levels (+½ and -½) and the interpretations of the
spectra are reasonably straightforward. Chemists also use carbon-13 nmr as this shows the
carbon environments as well as coupling between hydrogen and carbon nuclei. Inorganic
chemistry is also well served as various nuclei such as 31P and 19F have the appropriate spin
states.
Nmr spectra arise from a property that some nuclei have, loosely termed spin. This is a
quantum effect; a simplified model of it imagines the nucleus spinning on its axis, this spin
being quantised ie having only two directions (up and down). The nuclear spin is a
characteristic property of the nucleus.
The circulation of positive nuclear charge generates a magnetic moment along the axis of
spin. In effect, the nuclei act like tiny bar magnets. If an external magnetic field is applied,
for example to the proton nucleus, then its magnetic moment can be aligned in one of two
ways: with or against the field. Alignment with the field is the more stable and energy must
be absorbed to flip the proton magnet over to the less stable alignment, against the field. The
fields are shown by arrows in figure 1.

B E2: external and nuclear


nuc
fields opposed
B external
ΔE = E2 – E1

E1: external and nuclear


fields aligned
B nuc

Figure 1 — Splitting of nuclear energy levels in a magnetic field

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Transitions between the nuclear spin states are accomplished through the input of radio
frequency waves together with the applied magnetic field. For proton magnetic resonance the
frequency and field strength are related via the following formula.
μB
v=

Where v is the frequency, B the applied magnetic field strength (Tesla or gauss) and µ is a
nuclear constant, the magnetogyric ratio is 26750 for the proton. Thus the radio frequency
used depends upon the strength of the magnetic field. In a field of 14092 gauss (1.4092 Tesla)
a frequency of 60 MHz will induce transitions. Using superconducting magnets, very higher
magnetic fields of around 5 T (50 kG) allow resonances of 200 MHz to be used. The nmr
spectrum arises because nuclei in different parts of the molecule experience different local
magnetic fields according to the molecular structure, and so have different frequencies at
which they absorb. This difference is called the chemical shift.
In practice the radio frequency is kept constant, and the magnetic field is then swept over a
narrow range of field strength. The absorptions are plotted on a graph where the frequency
differences (in reality magnetic field differences) are plotted relative to some standard
compound which defines the zero; for proton magnetic resonance. The compound normally
chosen as a standard is TMS, tetramethylsilane, Si(CH3)4.
The chemical shift given by a particular proton is the frequency difference between its
absorption and the absorption from tetramethylsilane, TMS, Si(CH3)4. The actual chemical shift
depends on the radio frequency used, which in turn depends on the magnetic field strength.
The shift can be made field-independent by defining it as shown.
(ν − ν o ) x 10 6 Δν x 10 6
δ= =
ν0 ν0
The value of δ is quoted in parts per million. This means for frequencies of approximately 200
MHz the shifts correspond to frequency differences of a few hundred Hz.
The chemical shift depends on the environment of the hydrogen atom concerned. The local
external magnetic field, the one with which the nucleus interacts, is not the same as the
applied external field. This is because the nucleus is shielded from this field to a greater or
lesser extent by the other atoms in the vicinity and their electrons. The effect can be seen in
the low-resolution spectrum of ethanal, CH3CHO, in figure 2.

-CH3; heavy shielding


H H
O
C C
H
H
ethanal

-CHO; light shielding


TMS

9.8 2.2 0

Figure 2 — Low-resolution spectrum of ethanal

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The less the nucleus is shielded, the higher the chemical shift. The relatively exposed
hydrogen in the aldehyde group has δ = 9.8, so oxygen charge clouds shift the absorption
downfield. The more heavily shielded hydrogen atoms in the methyl group are found at
δ = 2.2. TMS hydrogen atoms are have a chemical shift of δ = 0.

Typical 1H chemical shifts relative to TMS = 0


RCOOH carboxylic acids +9 to +13 Can be broad and solvent-dependent
RCONH2 amide +5 to +12 Broad and solvent-dependent
RCHO aldehyde +8 to +10 Sharp
C6H6 etc aromatics +6 to +10
R2C=CHR alkene +4 to +8
RNH2 amines +1 to +6 Broad and solvent-dependent
ROH alcohols +0.5 to +8 Broad and solvent-dependent
RCH2R methylene +1.5 to +4.5
RCH3 methyl 0 to +4

Table 1 — NMR data for typical 1H chemical shifts (Sources: Morrison and Boyd)

Figure 3 — The nmr (H1) spectrum of ethyl ethanoate

The nmr spectrum is presented in figure 3. This is an example of a non-complex spectrum with
the peaks separated for straightforward analysis.

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Note that in some spectra an integration line is provided which can be used to calculate the
number of protons under each peak. This is extremely useful. The radio of the peak heights
can also give us this information. The triplet at δ ∼1.2 and the singlet at δ = 2 are low
chemical shifts, indicative of well-shielded CH3 protons. The former is due to the CH3 next to
the Ch2 and the latter the CH3 bonded to the C=O group. The methylene (CH2) protons are in a
higher chemical shift range at δ =4 (see table 2).
The multiplet structure is in fact extremely informative and we can demonstrate spin-spin
coupling using the ‘n+1 splitting rule’. Looking at the structure of ethyl ethanoate, see
figure 4 and the numbering of the carbon atoms.

CH3 – C –OO CH2 CH3

4 3 2 1

Figure 4 — Structure of ethyl ethanoate

Focus on the methyl group carbon number 1, and look at its leftward neighbour the methylene
group carbon number 2. Count the number of protons on the neighbour, 2, and add 1. This
rule predicts the number of peaks present in the carbon number 1 environment. Pascal’s
triangle, summarised in table 2, helps to identify a ratio of height, in this case 1:2:1.
Similarly focussing on carbon number 2, its neighbour, the right has three protons, add 1 to
give a quartet. We say colloquially that the methyl protons split the methlylene protons in the
ratio of 1:3:3:1.
Finally carbon number 4 is not adjacent to a carbon atom with protons, so no splitting occurs
and a single peak at Δ = 4 is observed. Note also this methyl group is ‘downfield’ of the first
methyl due to the electron-withdrawing properties of the oxygen atoms.

No of protons in No of leaks expected Pattern of peaks


neighbouring carbon
1 2 1:1
2 3 1:2:1
3 4 1:3:3:1

Table 2 — ‘n+1 splitting rule’ for H1 nmr

Note that, if there are two neighbours with protons, a complex multiplet results. Use the n+1
splitting rule on the first neighbour, then split the lines again using the same rule for this
second neighbour. For example, in propanal (CH3CH2CHO) the CH2 protons will be spilt into a
quartet 1:3:3:1 by the methyl group, then each of these lines is split again by the CH proton
giving an octuplet.
Symmetry in a molecule is also extremely useful to the nmr spectroscopist, as equivalent
protons in a molecule will only show as the one peak. For example ethane has two equivalent
methyl groups but only one peak is observed.

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Gas chromatography

Introduction
Gas chromatography (GC) is a chromatographic technique that can be used to separate
volatile organic compounds. A gas chromatograph consists of a flowing mobile gaseous phase,
an injection port, a separation column containing the stationary phase, a detector, and a data
recording system. The organic compounds are separated because of differences in their
partitioning behaviour between the mobile gas phase and the stationary phase in the column.

Figure 5 — Gas chromatograph (Source: Wikipedia)

Mobile phases are generally inert gases such as helium, argon, or nitrogen. The injection port
consists of a rubber septum through which a syringe needle is inserted to inject the volatile
sample. The injection port is maintained at a higher temperature than the boiling point of the
least volatile component in the sample mixture. Since the partitioning behaviour depends on
temperature, the separation column is usually contained in a thermostat-controlled oven.
Components with a wide range of boiling points are separated by starting at a low oven
temperature and increasing the temperature over time to.
Most columns contain a liquid stationary phase on a solid support. Gases with low molecular
weight are separated with solid adsorbents. HPLC (high performance liquid chromatography) is
invaluable to organic chemists for separating similar molecules such as peptides in a complex
mixture or a mixture of diastereoisomers. The compounds must be in the liquid phase. HPLC
uses high pressure to force the mobile phase through a closed column packed with
micrometric particles. This allows rapid separation of complex mixtures.

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There is a wide variety of stationary and variable phases in use which makes the technique
very versatile. In normal phase (NPHPLC) the sample should be non-ionic and soluble in a
hydrophobic solvent (eg hexanoic acid). The mobile phase is non-polar and the stationary
phase is polar (eg silica), or containing cyano or amino groups. The sample is introduced via a
rotatory valve. Most HPLC systems are linked to a continuous monitoring detector of high
selectivity. Examples include UV/visible detectors good for phenols or diode array detection
(DAD) and fluorescence detection for aromatic compounds. Electrochemical detectors can
detect femto amounts of electro active compounds such as vitamins and purines. In GC and
HLPC connection to software records and calculates the retention times and sizes (areas) of
peaks for quantitative analysis.
Typically, GC is useful for analyzing non-polar and semi-polar, volatile and semi-volatile
chemicals. Without chemical derivatization, GC is often used for the analysis of sterols, oils,
low chain fatty acids, aroma components and off-flavors, and many contaminants, such as
pesticides, industrial pollutants, and certain types of drug in foods.

Food analysis
As a case study the application of chromatography to the food industry will be examined. GC
is used widely in applications involving food analysis. Typical applications pertain to the
quantitative and/or qualitative analysis of food composition, natural products, food additives,
flavor and aroma components, a variety of transformation products, and contaminants, such
as pesticides, fumigants, environmental pollutants, natural toxins, veterinary drugs, and
packaging materials.
Since the commercial introduction of GC 50 years ago, it has been used to help determine
food composition, discover our nutritional needs, improve food quality, and introduce novel
foods. GC has been the only adequate approach to measure many of the organic contaminants
that occur at trace concentrations in complex. Figure 6 shows how each possible contaminant
a food may contain may be adequately resolved when present together.

Figure 6 — Contaminants in a food sample


(Source: Cochran 2002)

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The contaminants in figure 6 are found to be (via fast GC analysis of pesticides):

1 alpha BHC 2 gamma BHC 3 beta-BHC 4 delta BHC


5 heptachlor 6 aldrin 7 isodrin 8 heptachlor epoxide
9 gamma-chlordane 10 alpha-chordane 11 p.p’-DDE 12 endosulfan I
13 dieldrin 14 p,p’-DDD 15 endosulfan II 16 p.p’ –DDT17
17 endriun aldehyde 18 endosulfan 19 methoxychlor 20 endrin ketone
sulfate

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References

Krane K S — Introductory Nuclear Physics (Wiley, 1987)


Lee M S — Spectroscopic methods of analysis — Mass spectrometry Vol 1 issue 1, pp 2535-2551
(available online www.dekker.com/sdek/linking~db=enc~content=a713491567, 2002)
Morrison R T and Boyd R N — Organic Chemistry, 5th edition (Allyn and Bacon, Inc, 1987)
Structure spectroscopy examples for GCE
Chapman B — Transition Metal, Quantitative Kinetics and Applied Organic Chemistry (Nelson,
2001)
Houghton J — Global warming: The complete briefing, 3rd edition (Cambridge University
Press, 2004)
Extra reading
A detailed and in-depth overview of current MS technologies and applications can be obtained
from the recent proceedings of the American Society for Mass Spectrometry Conference on
Mass Spectrometry and Allied Topics (www.asms.org) and the Association of Biomolecular
Resource Facilities (www.abrf.org).
Websites
Dr Rod Beavon’s Chemistry http://home.clara.net/rod.beavon/chemistry_contents.htm
pages
Extended periodic table www.apsidium.com/ext_pt/expertab.htm

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