2 Prezentare Metoda Ms GC Ms TG

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
characteristics of the column Sb Sa Vc
1.0e+7 Vanilin (V) in EtOH as solvent (S)
Va
(length, diameter, filling) o
a: 100(1),10>220 C; 1ml/min
GC-FID
polarity of compounds 0.8e+7
Vb b: 150(1),10>220oC; 5ml/min
(rt izooctan < octena < octan) c: 150(1),10>220oC; 10ml/min
0.6e+7
molecular weight of compounds
(rt heptan < octan < nonan) effect of temperature and flow rate
0.4e+7
temperature program
(rt decreases at high temperatures) 0.2e+7 effect of flow rate
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
0.5e+7
qualitative analysis:
- from retention times
1.5e+7
- from MSD
26(4),10>70 oC; 0.6ml/min
quantitative analysis:
1.0e+7
- from peak area
0.5e+7
2 3 4 5 6 7 retention time
(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
80
DTG - derivative weight loss

ABS-Br
PE HIPS-Br
Sample weight , wt%
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 C/min
o
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 81+15
Br: 79.904; g mol-1
79
Br (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

Abundance (26(4),10>100; 0.6ml/min) Abundance
TIC: GAZE05.D\data.ms
Ion 27.00 (26.70 to 27.70): GAZE05.D
1.2e+07 24000
1.15e+07
1.1e+07
detailed TIC at rt 2.03 2.06 23000
22000
ion 27 HCN at rt 2.05
1.05e+07 21000
1e+07 20000
9500000 19000
9000000 18000
8500000 17000
8000000 16000
7500000 15000
7000000 14000
6500000 13000
6000000 12000
5500000 11000
5000000 10000
4500000 9000
4000000 8000
3500000 7000
3000000 6000
2500000 5000
2000000 4000
1500000 3000
1000000 2000
500000 1000
0
2.02 2.02 2.03 2.04 2.04 2.04 2.05 2.06 2.06 2.06 2.07 2.08
2.00 2.082.20 2.40 2.60 2.80 3.00
Time--> Time-->
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) Abundance Institutul Petru Poni Iasi, aprilie 2009
Ion 54.00 (53.70 to 54.70): GAZE05.D\data.ms
10000
9500
ambient gas sample TIC 9000
8500
Abundance
8000
Ion
7500
41.00 (40.70 to 41.70): GAZE05.D\data.ms
7000
ion 54
6000000
6500
ion 41
5500000
5000000
6000
2-propenenitrile: 2.97
acetonitrile: 2.78 5500
propanenitrile: 3.60
4500000
5000
4000000
4500
3500000
4000
3000000
3500
2500000 3000
2000000
2500
2000
1500000
1500
1000000
1000
500000
500
0
2.50 3.00 3.50 4.00 4.50 0
5.00 5.50 6.00 6.50
Time--> 2.60 2.80 3.00 3.20 3.40 3.60 3.80 4.00 4.20 4.40 4.60 4.80
Time-->
Abundance

2400000
2200000 ion 86; ion 101

2000000
1800000
triethylamine: 6.07
1600000
1400000
1200000
1000000
800000
600000
400000
200000
0
5.50 6.00 6.50 7.00 7.50 8.00 8.5
Time-->
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 in ten sity , 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
Te mperatu re , 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 in ten sity , 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
Te mperatu re , 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

2 Prezentare Metoda Ms GC Ms TG

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2 Prezentare Metoda Ms GC Ms TG

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Institutul Petru Poni Iasi, aprilie 2009

Mass selective detector

Dr. Mihai Brebu

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

ambient gas sample TIC 9000

Ion 86.00 (85.70 to 86.70): GAZE05.D\data.ms

2200000 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

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