GC-MS and TG-MS Analysis Techniques

Institutul ‘Petru Poni’ Iasi, aprilie 2009
Mass selective detector

coupled to gas chromatography (GC-MSD)
and to thermogravimetry (TG-MSD)
Dr. Mihai Brebu
1. Gas chromatography (GC)

2. Thermogravimetry (TG)
3. Mass selective detector (MSD)
4. Gas chromatography - Mass selective detector (GC-MSD)
5. Thermogravimetry - Mass selective detector (TG-MSD)
1. Gas chromatography (GC) Institutul ‘Petru Poni’ Iasi, aprilie 2009
Gas chromatography: analysis technique for qualit./quantit. determination of compounds in mixtures
Vaporisation, mixing with carrier gas,

Inlet
injection in the column
Compounds separation by selective adsorption/desorption
Column
affected by temperature, gas flow (for a given column)
Detector Detection of compounds based on specific properties
Recorder Recording/analysis/display of signal

1. Gas chromatography (GC) Institutul ‘Petru Poni’ Iasi, aprilie 2009
retention time (rt) depends on: response

Sc Sa
 characteristics of the column 1.0e+7 Sb Vc Vanilin (V) in EtOH as solvent (S)
(length, diameter, filling) Va
o
GC-FID a: 100(1),10>220 C; 1ml/min
 polarity of compounds 0.8e+7
Vb b: 150(1),10>220oC; 5ml/min
(rt izooctan < octena < octan)
0.6e+7
c: 150(1),10>220oC; 10ml/min
 molecular weight of compounds
(rt heptan < octan < nonan) effect of temperature and flow rate
0.4e+7
 temperature program
(rt decreases at high temperatures) effect of flow rate
0.2e+7
 carrier gas flow
(rt decreases at high flows) 0
retention
0 2 4 6 8 10 12 14 16 18 20 22 24 time (min)
abundance
1.5e+7 31(8) oC; 1ml/min Ambient gas sample
1.0e+7
good balance between short analysis time
and good separation of compounds
0.5e+7
1.5e+7
1.0e+7 26(8) oC; 1ml/min

qualitative analysis:
0.5e+7
- from retention times
- from MSD
1.5e+7
quantitative analysis:
26(4),10>70 oC; 0.6ml/min
1.0e+7 - from peak area
0.5e+7
retention time
2 3 4 5 6 7 (min)
2. Thermogravimetry (TG) Institutul ‘Petru Poni’ Iasi, aprilie 2009
Thermogravimetry: analysis technique for thermal processes involving mass loss (thermal degradation)
Polyurethane
thermal behaviour - described by: thermal behaviour - affected by:

 temperature for onset of the degradation step  temperature program (heating rate)
 temperature for maximum rate of degradation  atmosphere (air, inert gas)
 temperature for end of the degradation step  sample mass
 final mass loss of degradation step
aplications: thermal stability - lifetime predictions

100
PET ABS PP HDPE

PVC
DTG - derivative weight loss

80
ABS-Br
PE
Sample weight , wt%
HIPS-Br
PP
60
PS
HIPS-Br
40 ABS
ABS-Br
HIPS-Br: DTG
PVC
20 PET
PS
0
250 300 350 400 450 500 550 600
Temperature , oC
aplications: kinetic studies: activation energy (Ea), reaction order (n), pre-exponential factor (A)
Mass/% Mass/%
Polyurethane
90 90 20 oC/min
10 oC/min
5 oC/min
70 70
10 oC/min
50 50
30 30
10 10
100 200 300 400 500 600 100 200 300 400 500 600
Temperature/°C Temperature/°C
the kinetic model should correspond to a plausible degradation mechanism !!!
3. Mass selective detector (MSD) Institutul ‘Petru Poni’ Iasi, aprilie 2009
Mass selective detector: qualitative identification of compounds based on fragmentation pattern (EI)
MS spectra for aliphatics
MS spectra for aromatics

MS spectra for brominated compounds

79+15
Br: 79.904; g mol-1 81+15
79Br (50.69%); 81Br (49.31%)
M=95
79+14 79+81+14
81+14
79*2+14 81*2+14
M=174
79+81+13
79*2+13 81*2+13
M=253
79+12 81+12
79*2+81+13 79+81*2+13
81+13
79*3+13 81*3+13
4. Gas chromatography - mass selective detector (GC-MSD) Institutul ‘Petru Poni’ Iasi, aprilie 2009
Abundance
1.2e+7 TIC HIPS-Br degradation oil
1.0e+7
0.8e+7
0.6e+7
0.4e+7
0.2e+7
Time
100000 HBr ion 81 ???
80000
60000
40000
20000
PhCHBrCH3
???
0
5 10 15 20 25 30 35 40 45 50 55 60 65
HIPS-Br degradation oil - detail TIC
I HIPS-Br degradation oil - scan at 34.59 min
II
II
ambient gas sample – TIC

A b u n d a n c e
(26(4),10>100; 0.6ml/min)
A b u n d a n c e
T I C : G A Z E 0 5 . D \ d a t a . m s
I o n 2 7 . 0 0 ( 2 6 . 7 0 t o 2 7 . 7 0 ) : G A
1 . 2 e + 0 7 2 4 0 0 0
1 . 1 5 e + 0 7
1 . 1 e + 0 7
detailed TIC at rt 2.03 – 2.06 2
2
3
2
0
0
0
0
0
0
ion 27 – HCN at rt 2.05
1 . 0 5 e + 0 7 2 1 0 0 0
1 e + 0 7 2 0 0 0 0
9 5 0 0 0 0 0 1 9 0 0 0
9 0 0 0 0 0 0 1 8 0 0 0
8 5 0 0 0 0 0 1 7 0 0 0
8 0 0 0 0 0 0 1 6 0 0 0
7 5 0 0 0 0 0 1 5 0 0 0
7 0 0 0 0 0 0 1 4 0 0 0
6 5 0 0 0 0 0 1 3 0 0 0
6 0 0 0 0 0 0 1 2 0 0 0
5 5 0 0 0 0 0 1 1 0 0 0
5 0 0 0 0 0 0 1 0 0 0 0
4 5 0 0 0 0 0 9 0 0 0
4 0 0 0 0 0 0 8 0 0 0
3 5 0 0 0 0 0 7 0 0 0
3 0 0 0 0 0 0 6 0 0 0
2 5 0 0 0 0 0 5 0 0 0
2 0 0 0 0 0 0 4 0 0 0
1 5 0 0 0 0 0 3 0 0 0
1 0 0 0 0 0 0 2 0 0 0
5 0 0 0 0 0 1 0 0 0
0
2 . 0 2 2 . 0 2 2 . 0 3 2 . 0 4 2 . 0 4 2 . 0 4 2 . 0 5 2 . 0 6 2 . 0 6 2 . 0 6 2 . 0 27 . 02 . 00 8 2 .2 0 8. 2 0 2 . 4 0 2 . 6 0 2 . 8 0 3 . 0
T im e - - > T i m e - - >
2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00
4. Gas chromatography - mass selective detector (GC-MSD) A bundance Institutul ‘Petru Poni’ Iasi, aprilie 2009
Io n 5 4 .0 0 (5 3 .7 0 to 5 4 .7 0 ): G A Z E 0 5 .D \d a ta .m s
10000
9500
ambient gas sample – TIC 9000
8500
A b u n d a n c e
8000
I o n 4 1 . 0 0 ( 4 0 . 7 0 t o 4 1 . 7 0 7 5G
) : 00 A Z E 0 5 . D \ d a t a . m s
6 0 0 0 0 0 0
7000
ion 54
5 5 0 0 0 0 0
ion 41 6500
6000 – 2-propenenitrile: 2.97
– acetonitrile: 2.78
5 0 0 0 0 0 0
– propanenitrile: 3.60
5500
4 5 0 0 0 0 0
5000
4 0 0 0 0 0 0
4500
3 5 0 0 0 0 0
4000
3 0 0 0 0 0 0
3500
2 5 0 0 0 0 0 3000
2 0 0 0 0 0 0 2500
2000
1 5 0 0 0 0 0
1500
1 0 0 0 0 0 0
1000
5 0 0 0 0 0
500
0
2 . 5 0 3 . 0 0 3 . 5 0 4 . 0 0 4 . 5 0 5 0. 0 0 5 . 5 0 6 . 0 0 6 . 5 0
T i m e - - > 2 .6 0 2 .8 0 3 .0 0 3 .2 0 3 .4 0 3 .6 0 3 .8 0 4 .0 0 4 .2 0 4 .4 0 4 .6 0 4 .8 0
T im e -->
A b u n d a n c e
Io n 8 6 .0 0 ( 8 5 .7 0 to 8 6 .7 0 ) : G A Z E 0 5 .D \d a ta .m s
Io n 1 0 1 .0 0 ( 1 0 0 .7 0 to 1 0 1 .7 0 ) : G A Z E 0 5 .D \d a ta .m s
ion 86; ion 101

2 4 0 0 0 0 0
2 2 0 0 0 0 0
2 0 0 0 0 0 0 – triethylamine: 6.07
1 8 0 0 0 0 0
1 6 0 0 0 0 0
1 4 0 0 0 0 0
1 2 0 0 0 0 0
1 0 0 0 0 0 0
8 0 0 0 0 0
6 0 0 0 0 0
4 0 0 0 0 0
2 0 0 0 0 0
0
5 .5 0 6 .0 0 6 .5 0 7 .0 0 7 .5 0 8 .0 0 8 .5
T im e - - >
2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00
5. Thermogravimetry - mass selective detector (TG-MSD) Institutul ‘Petru Poni’ Iasi, aprilie 2009
2.0E-09 100
2 12 15 16 17 18 26
1.8E-09
28 29 30 43 44 Tic Tg
1.6E-09 80
1.4E-09 Pc: 5.6 mg

MS intensity , a.u.
1.2E-09 60
TG , %
1.0E-09
8.0E-10 40
6.0E-10
4.0E-10 20
2.0E-10
0.0E+00 0
50 150 250 350 450 550 650 750 850
Temperature , oC
1.0E-11 100
2 12 15 16 17 18 26
9.0E-12
28 29 30 43 44 Tic Tg
8.0E-12 80
7.0E-12 Pc: 5.6 mg

MS intensity , a.u.
6.0E-12 60
TG , %
5.0E-12
4.0E-12 40
3.0E-12
2.0E-12 20
1.0E-12
0.0E+00 0
50 150 250 350 450 550 650 750 850
Temperature , oC
2.0E-09 100
2 12 15 16 17 18
1.8E-09 28 29 43 44 Tic Tg
Pc/CaNi: 37mg - 4.6 mg Pc
1.6E-09 80
1.4E-09
Ms intensity , a.u.
1.2E-09 60
Tg , %
1.0E-09
8.0E-10 40
6.0E-10
4.0E-10 20
2.0E-10
0.0E+00 0
50 150 250 350 450 550 650 750 850
Temperature , oC
3.0E-11 100
2 12 15 16 17 18
28 29 43 44 Tic Tg
2.5E-11
Pc/CaNi: 37mg - 4.6 mg Pc
80
2.0E-11
Ms intensity , a.u.
60
Tg , %
1.5E-11
40
1.0E-11
20
5.0E-12
0.0E+00 0
50 150 250 350 450 550 650 750 850
Temperature , oC
PEG
PEG
PU
changes in composition and structure of  -FeOOH during catalytic degradation of ABS
m/z 17 vs m/z 18 - ct.
 -FeOOH   -Fe2O3 • H2O Fe3O4

reaction of 4-phenylbutironitrile over  -FeOOH catalysts and its derivatives
toluene, ethylbenzene: 91
aliphatic nitriles:
41,14,15,16,28,29
alkyls: 27,28,29,14,15
NH3:14,15,16, 17/18
reduction of catalyst by
organic compounds
Institutul ‘Petru Poni’ Iasi, aprilie 2009
Conclusions:
- MSD is a powerful detector for qualitative identification of compounds

leaving a GC column or a TG furnace
- identification is facile in GC-MSD if compounds are well separated by GC

and their structure is included in databases
- careful interpretation of mass spectra is need if compounds are not well

separated by GC and their structure is not included in databases
- careful analysis of various mass signals is need for TG-MSD data since
compounds are not separated and the mass signals might represent a sum
of contributions from fragmentation of different compounds
Acknowledgements:
- Dr. Dan Rosu - Dr. Vasile Cornelia
- Dr. Nita Tudorache - Prof. Yusaku Sakata

GC-MS and TG-MS Analysis Techniques

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GC-MS and TG-MS Analysis Techniques

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Institutul ‘Petru Poni’ Iasi, aprilie 2009

Mass selective detector

1. Gas chromatography (GC)

Gas chromatography: analysis technique for qualit./quantit. determination of compounds in mixtures

Vaporisation, mixing with carrier gas,

Detector Detection of compounds based on specific properties

Recorder Recording/analysis/display of signal

retention time (rt) depends on: response

1.0e+7 26(8) oC; 1ml/min

thermal behaviour - described by: thermal behaviour - affected by:

aplications: thermal stability - lifetime predictions

PET ABS PP HDPE

DTG - derivative weight loss

MS spectra for aromatics

MS spectra for brominated compounds

1.2e+7 TIC HIPS-Br degradation oil

100000 HBr ion 81 ???

HIPS-Br degradation oil - detail TIC

I HIPS-Br degradation oil - scan at 34.59 min

ambient gas sample – TIC

ion 86; ion 101

1.4E-09 Pc: 5.6 mg

7.0E-12 Pc: 5.6 mg

changes in composition and structure of  -FeOOH during catalytic degradation of ABS

m/z 17 vs m/z 18 - ct.

 -FeOOH   -Fe2O3 • H2O Fe3O4

reaction of 4-phenylbutironitrile over  -FeOOH catalysts and its derivatives

- MSD is a powerful detector for qualitative identification of compounds

- identification is facile in GC-MSD if compounds are well separated by GC

- careful interpretation of mass spectra is need if compounds are not well

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