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Analysis of Polymers
LC/ LCMS
Content
Chromatography
Basics of chromatography
Gas Chromatography
Sample introduction
Injection systems
Columns
4
Detection systems
Classification
Applications
History
1906-Tswett described the use of glass columns packed with
adsorbent for separation
1941-Martin and Synge- Gas could replace liquid as mobile phase
1952- First GC- Martin and James
1954-Ray-Thermal conductivity detector
1955-First Commercial GC
GC-Powerful analytical tool in modern laboratory
History
Mikhail Tswett, Russian Botanist, 1872-1919
In 1906 Tswett used to chromatography to separate
plant pigments.
He called the new technique chromatography because
the result of the analysis was 'written in color' along
the length of the adsorbent column.
Chroma means color and graphein means to write
Chromatography
A separative technique
Physical separation of
components:
Gas, Liquids, Solids
What is chromatography?
Chromatography is a dynamic separation process based on the
selective distribution of the different components between two phases.
One of the phases, the stationary phase, is held immobilised inside the
column while the other phase, the mobile phase travels through the
column, flowing through the stationary phase. Compounds that exhibit
a higher affinity for the stationary phase will travel more slowly than
compounds exhibiting a lower affinity. The different sample
components travel at different speed through the column and are
eluted from the column at different times.
Light Object
Direction of flow
Heavy Object
Riverbed
Mobile
phase
Strong
Weak
Stationary
Phase
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12
13
14
Chromatographic Areas
SEC
HPLC
GC
Mol. wt
15
10
10e2
10e3
1oe4
10e5
10e6
10e7
Chromatographic Modes
Stat.
Solid
Liquid
Liquid
(ionic)
Solid
(Pores)
Gas
G.S.C.
G.L.C.
------
G.S.C.
Liquid
L.S.C.
T.L.C.
L.L.C.
I.E.C.
G.P.C.
S.E.C.
Phase
Mobile
Phase
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Gas Chromatography
CHROMATOGRAPHIC PROCESS
The sample injected onto the column and are carried through the column
by an inert gas (carrier gas).
The different component of sample is partitioned between the carrier gas
and the stationary phase.
The stationary phase selectively retards the sample components
according to their partition coefficient.
The components separate as they pass through the column and
eventually elute from the column one after another and are recorded as a
function of time
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19
20
Detector
Carrier Gas
Thermal
Conductivity
He
Flame Ionization
He or N2
Electron Capture
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22
23
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PTV injection
First describe by VOGT in 1979.
Closely resemble to split/splitless inlet. 2 main differences:
inlet is kept cool during injection- allowing the analyte to condence
inside the liner, while solvent is vented via split.
Inlet has very low thermal mass, allow rapid heating for analyte
transfer
Large volume may be injected at control speed into the inlet allowing
the injection of very large volume.
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PTV
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Column type
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Column type
Internal diameter
Carrier flow
Capillary column
3 - 4 ml/min
0.53 mmID
5 10 ml/min
0.1 mmID
1 1.5 ml/min
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30
31
Efficiency
The efficiency of a column is the capability of the
system to maintain the subtances molecules
dispersed in small phase volumes.
The efficiency depends on different parameters
diameter
length
linear rate
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Detectors overview
NPD
FID
ECD
FPD
PID
PDD
PFPD
TCD
Up to three
detectors can be
mounted and
controlled
33
Sensitivity (or
Selectivity
Detector efficiency
to convert the
sample in an
electrical signal
Noise
Short term: high
frequency baseline
fluctuation
Long term: low
frequency baseline
perturbation
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Minimum
Detectability
Amount of sample for
which the peak height
is three times the
noise (S/N=3)
Dynamic
Range
Range of sample
concentration for
which the detector
can provide a
detectable signal
variation with
analyte amount
Detectors classification
Universal
Selective
Specific
They respond to
everything eluting
from the column
TCD
PDD
(FID)
ECD
PID
PDD
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NPD
FPD
PFPD
universal response
non-destructive
physical detection principle
concentration-dependent
detector
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Application fields
Petroleum industry
Chemicals (gas analysis)
Semiconductor industry
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CHO+ + e-
39
Petroleum industry
Enviromental
Pharmaceuticals
Food and flavors
Sensitivity in the ppm - % range
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ECD
This establishes a high current flow
between detector body (foil) and
centrally located collector.
Halogenated analyte elute and capture
some of the electrons
Negative ions formed are low energy
and are not collected on the electrode.
Reduction in the current flow.
Characteristic:
Minimum detectability:
Response: selective to halogen containing
compound
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TCD
FID
ECD
PID
NPD (N)
NPD (P)
FPD (S)
FPD (P)
PFPD
PDD
10-15
ppt
fg
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10-12
ppb
pg
10-9
ppm
ng
10-6
0.1%
ug
10-3 GRAMS
100%
mg
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Fixed gases
Hydrocarbons
Halogenated compounds
How to identify in GC ?
By Injecting Standards!
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100
31
100
29
100
44
OH
50
45
50
50
58
43
29
15
15
27
26
15
42
14
12
16
13
10
12
(mainlib) Acetaldehyde
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17 18 19
14
16
18
24 25
21
20
22
24
26
27 28
28
41
30 31
30
34
36
38
40
10
(mainlib) Ethanol
45
40
32
12 13 14
42
44
46
48
17 18
19
15
24
20
13
30
10
25
16
15
25
28
(mainlib) Acetone
25
30
46
27
14
0
20
25
30
41
35
36
31
42
33
42
29
43
44
40
35
38
39
41
44
40
57
45
50
55
59
60
65
47
45
50
55
60
50
31
100
31
100
45
100
32
OH
H
50
50
O
H
29
50
13
15
0
0
46
10
28
14
12 13 14
16 17 18 19
16
14
19
15
12
18
10
27
(mainlib)
29 1-Propanol
22
10
15
26
28
(mainlib) Isopropyl Alcohol
24
30
33 34
30
26
16
18 19
15
20
32
25
34
26
42
38
30
38
35
40
30
25
30
35
50
55
36
38
59
41
39
32 33
40
40
43
60
45
53
45
50
65
70
41
39
28
36
42
28
24 25
43
20
31
20
15
OH
29
27
40
44
59
46
45
60
60
55
55
57
61
60
65
70
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GC-MS why?
Nearly Universal and specific
Sensitive
For compound identification with standard or library spectrum and mass
interpretation
Interference-free quantitation
Combines separation (GC)and identification techniques (MS).Nothing but
hyphenation GC-MS
Provides both qualitative and quantitative information about sample
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48
Mass Spectrometer
Introduction of mass ions in a
separation field
+
_
Ion Source
49
Mass Analyzer
Detector
TRACE 1300
Series
ISQ Series
ITQ Series
TSQ Duo
Single Quadrupole MS
Single / Triple
Quadrupole MS
Triple Quadrupole MS
Confirmation by Mass
Spectrum or SIM
Pesticides, PCBs,
Volatiles
Petrochemical and
Chemical
Pharma, Chemicals,
Toxy/Forensic
Pesticides Multiresidual,
Dioxin, POPs
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54
55
56
57
58
Avoid extraction
Gas phase
Eliminates losses
(Head space)
Avoids non-volatiles entering GC column
Septum
Thermostated
vial
the GC system
Sample phase
Liquid or solid
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of
volatiles
reaches
dynamic
60
K = CL/Cg
K = Partition coefficient
CL = Concentration in the liquid phase
Cg = Concentration in the gas phase
Cg
CL
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Factor:
Time
Temperature
Shaking
Matrix modifiers
62
COMPOUND
50OC
60oC
80oC
ETHANOL
1220
630
240
n-PROPANOL
520
350
150
IPA
445
250
120
t-BUTANOL
280
150
60
ACETONE
270
110
55
ETHYL ACETATE
42
30
18
BENZENE
1.2
0.4
TOLUENE
0.8
TRICHLOROETHYLENE
0.7
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65
Pressure/Loop System
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67
ISO Standard
ISO 6401-1985 Determination of Residual Vinyl Chloride Monomer in
Homopolymers and Copolymers by Gas Chromatography
68
RTs
(min)
A
8.32
B 10.76
1 12.147
2 12.463
C 13.15
3
15.78
D+E 17.39
F 17.72
4 18.275
G 18.91
5 19.367
6 19.833
H 21.33
Peak
7+8 21.533
9 22.738
I
23.82
10 24.97
L
25.71
M 25.84
N 27.91
O 29.69
11 32.748
P 34.23
69
compound
Methanol
Ethanol
Acetone
2-Propanol
Methyl acetate
1-Propanol
Ethyl acetate & 2-Butanone
2-Butanol
Tetrahydrofuran
Cyclohexane
2-Methyl-1-propanol
Isopropyl acetate
1-Butanol
1-Methoxy-2-propanol & 2Methoxyethanol
Propyl acetate
2-Ethoxyethanol
4-Methyl-2-pentanone
Toluene
Isobutyl acetate
Butyl acetate
2-Methoxyethyl acetate
2-Ethoxyethyl acetate
Cyclohexanone
Static Headspace
Advantages
Lower contamination
Disadvantages
Cannot detect less than 1 ppb
Small fraction of sample extract
injected
1-10% efficiency
70
CDS Pyrolyser
72
Theory of Pyrolysis
Pyrolysis can be a preparatory step for high molecular weight, low
volatile samples prior to GC analysis
Bond breaking needs to be reproducible in order for this to be a useful
means for analysis (same polymer should yield the same pyrrogram
every time)
There are three types of bond breaking observed depending on relative
bond strengths of the compound (chain scission, side group scission,
unzipping)
Useful to understand bond breakage patterns when interpreting
pyrograms
73
Theory of Pyrolysis
74
Theory of pyrolysis
75
Theory of pyrolysis
76
Theory of pyrolysis
Bond breaking is reproducible when the following parameters are
constant:
1. Temperature
2. Heating Rate
3. Time of Heating
Pyrolyzers are instruments that rapidly heat and pyrolyze samples
Each pyrolyzer offers different options when trying to adjust for the
optimal temperature, heating rate, and time of heating
77
Pyrolysers
78
Pyrolyzers:
- capable of heating up to 1400C
- operate between 500 and 800C for most analytical work
- designed to connect directly to GC
- three basic types (each with its own advantage and disadvantage)
Sample Loading:
1. into a boat or tube and dropped into pyrolysis
zone (solids, liquid)
2. syringe injects sample directly into pyrolysis
zone (liquid only)
Advantages:
no condensation
Disadvantages:
large pyrolysis chamber increases volume (band
broadening), increase flow to account for band
broadening (wastes sample, need higher split
ratio)
79
Sample Loading:
sample either coated onto (dipped in soln.
or applied with syringe) the wire or wrapped
in ferromagnetic foil, dropped into pyrolysis
zone
Advantages:
final temp is set (no calibrating), very rapid
heating, reproducible heating, sample
insertion simple
Disadvantages: temperature optimization
difficult (only set temperatures available), no
adjusting the heating rate (need resistively
heated filament)
80
Sample Loading:
similar to Curie-point, typically coated onto the
filament using a syringe (liquid), melted in place
(solids), quartz tube with quartz wool (solids)
Advantages:
temperature optimization, heating rate
optimization
Disadvantages:
temperature monitoring based on current through
entire filament loop, (not localized, may be
inaccurate), area where filament is housed is
heated (heats sample prior to pyrolysis)
81
increments to 1400C
TIMES: Settable in units of 0.01 second to 999.99 sec. or
in units of 0.01 minute to 999.99 min.
HEATING RATES: Settable in units of 0.01C/millisecond
0.01 to 999.99C/Second, or
0.01 to 999.99C/Minute
INTERFACE TEMPERATURE: Settable in 1C increments
to 350C
TIMES: Settable in units of 0.01 minute to 999.99 minutes
HEATING RATES: Settable in units of 0.01C/minute to
60.00 C/minute.
DRY MODE: User selectable
CLEAN MODE: User selectable
SEQUENCE: Up to 8 methods, each with GC start
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Applications
TYPES OF SOLID MATERIALS ANALYZED
Plastics films, foams, fibers, molded parts
Paints alkyd, latex, art, varnish
Rubber tires, bumpers, building materials
Adhesives rubber, acrylic, urethanes
Petrochemicals resins, waxes, asphalts, oils
Printing ink, toners, coatings
Consumer goods cosmetics, surfactants, food, soaps, detergents
84
Vulcanized Rubber
85
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87
Polymer-Polyurethan polymer
Automobile paint
Peak Identifications.
1 Methyl Methacrylate
2 Methacrylic Acid
3 Styrene
4 Butyl Acrylate
5 Butyl Methacrylate
6 Hydroxyethyl
Methacrylate
7 Hydroxypropyl
Methacrylate
8 Octyl Methacrylate
90
Fiber Analysis
Polyester(PET)
Cotton
91
92
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Thermal Desorption
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Application areas
Environmental and workplace air monitoring (Occupational Health & Safety at
workplace)
EPA methods (clean air act) e.g. TO-14 (canister), TO-15 () & TO-17 (tubes)
ISO- 16017-2; ASTM D6196-03; MDHS 80 (UK HSE)
Ozone precursor (PAMS)
Forensic analysis
Arson residue analysis- Gasoline vapours
Materials and materials emissions testing
VDA- 278 (VOC and FOG emissions by Thermal Desorption GCM)
ISO-22219-4(2013)- emission of VOCs for vehicle interior parts & material
Automobile industry
VOCs in vehicle exhaust
Food, flavour and fragrance profiling
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