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CHEM10812: Introduction to
Forensic & Analytical Chemistry
Lecture VI
Pyrolysis as an analytical technique
Define pyrolysis Define pyrolysis
Interface with GC and MS
Some examples
Roy Goodacre, 2.027 MIB, roy.goodacre@manchester.ac.uk
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Why pyrolysis?
Not all analytes are amendable to GC or LC
Samples of low volatility
Polymers - Man made fibres - Paints Polymers - Man made fibres - Paints
Also not amenable to MS
Too big - especially polymers
cf. MALDI and ESI
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Pyrolysis is:
The thermal degradation of complex material in
an inert atmosphere or a vacuum.
It causes molecules to cleave at their weakest It causes molecules to cleave at their weakest
points to produce smaller, volatile fragments
called pyrolysate.
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Considerations
Sensitive technique
Clean preparation
Sample has to be dried
Need an inert
atmosphere
O
2
oxidation rather
than pyrolysis
No volatile or low
volatile analytes
No H
2
O hyrolysis
rather than pyrolysis
than pyrolysis
Pyrolysate is sticky
Need to limit
condensation during
analysis
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Is it possible to control
temperature?
Needs to be accurately controlled
Different temp: different bonds break
tune into analyte class tune into analyte class
Ratio monomer/dimer
in the pyrolysis of
natural rubber
(polyisoprene)
0
0.2
0.4
0.6
0.8
1
300 350 400 450 500
Temperature (C)
M
o
n
o
m
e
r
/
D
i
m
e
r
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How?
Resistive heated filament
Pt coil, resistive conductor
Electric current generates heat
wood
charcoal
tars H
2
CH
4
H
2
O
Furnace
Introduce sample into a hot zone
Radiative heating
Laser
Curie-point pyrolysis
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Ferromagnetic alloy conductors
High frequency (RF)
electromagnetic field induces
an oscillating current
Eddy currents (induction of
-
+
Eddy currents (induction of
electric current) and
hysteresis cause the
temperature to increase
+
N S
-
Curie-point of alloy:
Ferromagnetic Paramagnetic
Thermostatic switch
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Curie points of some
ferromagnetic alloys
Fe % Ni % Co % Curie point
temp. C
0 100 0 358 0 100 0 358
61.7 0 38.3 400
55 45 0 400
50 50 0 530
100 0 0 770
0 0 100 1128
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Temperature profile of pyrolysis
400
500
600
T
e
m
p
e
r
a
t
u
r
e

(

C
)
Total heating time (THT)
Temperature equilibrium (Teq)
530
0 1 2 3 4 5
0
100
200
300
Time (s)
T
e
m
p
e
r
a
t
u
r
e

(
Total heating time (THT)
Temperature rise time (TRT)
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Pyrograms
A plot of GC retention time vs. FID or total ion count
Would be matched against reference materials.
Plastics for example:
Chromatographic retention times
MS spectra of monomers
For complex samples; e.g., paints
Pattern recognition algorithms often necessary
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Chemical composition of
natural and man-made fibers
Motor vehicle crime
Automotive paint binders can
be identified from g of topcoat
Wampler, T.P. (1995) Applied Pyrolysis Handbook. CRC Press.
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Pyrolysis-methylation
In pyrolysis get conventional free radical pyrolysis
processes. You can conduct chemical reactions:
Thermally assisted hydrolysis and methylation (THM)
Uses quaternary alkyl ammonium compounds Uses quaternary alkyl ammonium compounds
Reacts with (macro)molecules susceptible to hydrolysis to
give alkyl derivatives.
Tetramethylammonium hydroxide (TMAH)
Very useful reagent because the methyl derivatives
are sufficiently volatile to be analysed by GC.
Often aids identification of parent product
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Typical base used in lipsticks
Py-GC
Surface coat natural resins and
pigments. TMH-GC used to
establish the authenticity of oil
paintings and works of art
THM-GC
TMH-GC
Wampler, T.P. (1995) Applied Pyrolysis Handbook. CRC Press.
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Application areas
Forensics
Man-made fibres
(automotive) Paints

Break down a polymeric


chain to monomers,
oligomers, and other
fragments
Adhesives
Plastics and rubbers
Bacteria
Foodstuffs
fragments
Recycling
Nylon carpets monomer
Plastics
Tyres pyrolysis oil
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Pyrolysis-Mass Spectrometry
Sample
Volatile organic fragments
Singly positively charged fragments
Curie-point pyrolysis
Low-energy ionization
p
y
r
o
l
y
s
i
s
Singly positively charged fragments
Ions of specific mass
Detector
Spectrum
Data storage
Ion separation
(quadrupole)
Electron multiplier
Computer
Screen or printer
M
a
s
s

S
p
e
c
t
r
o
m
e
t
e
r
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A pyrolysis mass spectrometer
Speed < 2mins sample
Automated - 300 samples/day
Quick sample preparation
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Sampling
bacteria
Sample tube
Cultures need to be:
pure and cultured in the same way
Phenotypic typing method, physiology and
biochemistry of the sample important.
Foil
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PyMS spectrum of a bacterium
2
2.5
3
3.5
4
P
e
r
c
e
n
t
a
g
e

t
o
t
a
l

i
o
n

c
o
u
n
t
Library Matching
Identify bacteria using
pattern recognition
on a computer
60 80 100 120 140 160 180 200
0
0.5
1
1.5
2
P
e
r
c
e
n
t
a
g
e

t
o
t
a
l

i
o
n

c
o
u
n
t
Mass (m/z)
Quantitative profile of 150 m/z intensities
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Field portable instrumentation
McClennen, W.H., Arnold, N.S. and
Meuzelaar, H.L.C. (1994) Field-
portable hyphenated instrumentation -
the birth of the tricorder. TRAC-Trends
in Analytical Chemistry 13, 286-293.
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Py-GC-DMS of bacteria
Cheung, W. et al.
(2009) Analyst 134, 557-563
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QC of extra virgin olive oil
8
6
4
2
r
c
e
n
t
a
g
e

o
f

t
o
t
a
l

i
o
n

c
o
u
n
t
Virgin olive oil - Dritta cultivar,
adulterated with 5% soya oil
8
6
4
2
r
c
e
n
t
a
g
e

o
f

t
o
t
a
l

i
o
n

c
o
u
n
t
Virgin olive oil
- Dritta cultivar
Adulteration
Provenance
Cultivar
Geographic distribution
200 180 160 140 120 100 80 60
0
Mass range (m/z)
P
e
r
200 180 160 140 120 100 80 60
0
Mass range (m/z)
P
e
r
Goodacre, R. et al. (1992) Nature 359, 594.
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Lecture VI: Take Homes
Pyrolysis used to get non-volatile (usually
complex) materials into the gas phase
Temperature can be highly controlled
Roy Goodacre, 2.027 MIB, roy.goodacre@manchester.ac.uk
Temperature can be highly controlled
Analysis by GC, MS, GC-MS, IMS/DMS
Many examples for forensics
Man-made fibres, paints, adhesives,
Plastics and rubbers, bacteria, foodstuffs

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