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SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Transportable Miniature FTMS for Analysis of Corrosives and Chemical
Warfare Agents
Wayne V. Rimkus, Dean V. Davis, Kenneth Gallaher
Siemens Applied Automation, 500 West Highway 60, Bartlesville, OK 74003
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Introducing the Quantra• Rugged• Transportable• Accurate• Fast• Cheap• Small (by FTMS standards!)• 1 torr to 2 Atmosphere sampling• Self contained
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
The relative size, absence of external pumping requirements and full battery backup of critical systems lead to the portability of the system. This translates to “field-ability” .
24”
42”
Miniature FTMS Quantra
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Transportable
The author transporting the FTMS system – a small truck with a ramp was used. The Quantra is on wheels and is in the crate.
System was setup in a hotel room. Elapsed time - truck to 20,000 resolution – 15 minutes.
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Unique Design Features
• Permanent Magnet (1 tesla)• Ion Getter Pump (10-10 torr)• Pulsed Valve – picoliter sampling• Filament current in Nanoamps• Battery Backup – All Critical Systems• LOD 10 ppm, with trapping < 10 ppb (ppt?)• Resolution at m/z 131 is 20,000• Ion Manipulation
– Ion Ejection– MS/MS– Chemical Ionization– Negative Ion Detection
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Measurement ChamberSensor
Valve manifold
Ion pump
power supplyVacuum chamber
crimp tube
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Theory of Fourier TransformIon Cyclotron Resonance
Mass Spectrometry
FTICR or FTMS
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
The FT-ICR Measurement Cell
Trapping Plates
Transmitter Plates
Detector Plates
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
FT
Time DomainThe FT produces a Frequency Domain
Subsequent non linear inversion yields Mass/Charge
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Mixed Hydrogen, Helium, Deuterium sample
Resolution > 540,000
m/z 4 Spectrum
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Resolving PowerFTMS vs Quadrupoles
NitrogenCarbon Monoxide
What the FTMS “sees”What the Quadrupole “sees”
m/z 28
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Resolution Zoom
Resolution > 8,000
Quantra exhibits very high resolving power
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Quantra Instrument Sensor and Electronics
Example Applications
• Trace organics in bulk gases
• Identification of materials during catalysis
• Headspace and Solids analysis
• Residual Solvents
• Ambient air monitoring
• Characterization of semi-conductor reaction mixtures
• Incinerator monitoring
• Chemical Threat
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
MS/MS in Direct effluent analysis
FTICR Spectral Trace of SF6 W ithout N 2 M atrix Ejection
14 14.5
28
29
3032
40 44 1270
5000
10000
15000
Ion
Abu
ndan
ce (a
rb. u
nits
)
50 100 150
M ass (m /z)
Sulfur Hexafluoride not readily seen
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Study of process effluent with Nitrogen ejection
F T IC R S p e c tra l T ra c e o f S F 6 W ith N 2 M a tr ix E je c t io n
4 1
7 0
8 9
1 0 8
1 2 7
0
5 0
1 0 0
Ion
Abu
ndan
ce (a
rb. u
nits
)
5 0 1 0 0 1 5 0
M a s s (m /z )
N2 completely ejected
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Isolated SF5+ Ion for MS/MS
0
2000
4000
6000
8000
10000
12000
20 40 60 80 100 120 140
SF5+ 126.964 amu
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
MS/MS Spectrum of SF5+
0
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1000
1500
2000
2500
20 40 60 80 100 120 140
SF4+ 107.964
amu
SF3+ 88.966
amu
SF2+ 69.968
amuSF+ 50.970amu
SF5+ 126.962
amu
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Fermenter 1Headspace Spectrum
0
2000
4000
6000
8000
10000
10 20 30 40 50 60
10 sets of “Mass Doublets” – Isobars
1 Triplet (Nominal mass 16 – O, CH4, NH2)
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Mass 16
0
500
1000
1500
2000
2500
3000
15.99 16 16.01 16.02 16.03 16.04 16.05
0
500
1000
1500
2000
2500
3000
15.99 16 16.01 16.02 16.03 16.04 16.05
O
NH2 CH4
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Mass 17
0
50
100
150
200
250
16.99 17 17.01 17.02 17.03 17.04 17.05
0
50
100
150
200
250
16.99 17 17.01 17.02 17.03 17.04 17.05
OHNH3
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Mass 43
0
500
1000
1500
2000
42.98 43 43.02 43.04 43.06 43.08 43.1 43.12 43.14 43.16
0
500
1000
1500
2000
42.98 43 43.02 43.04 43.06 43.08 43.1 43.12 43.14 43.16
C2H3O
C3H7
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Summary Of Components DetectedPeak Number Observed mass Fragment Assignment Theory Corrected obs Corrected Delta
1 12.0029 C C 12.0000 11.9989 -0.00112 14.0069 N N 14.0037 14.0023 -0.00143 14.0226 CH2 CH2 14.0156 14.0180 0.00244 14.7103 noise? noise 14.7055 5 15.0281 CH3 e/butane/propane 15.0234 15.0232 -0.00026 15.99996 O H2O 15.9949 15.9948 -0.00017 16.0239 NH2 NH3 16.0187 16.0187 0.00008 16.0362 CH4 CH4 trace 16.0312 16.0310 -0.00029 17.0084 OH H2O 17.0027 17.0029 0.000210 17.0322 NH3 NH3 17.0265 17.0267 0.000211 18.0167 H2O H2O 18.0106 18.0109 0.000312 19.9884 Ar+2 Ar+2 19.9812 19.9820 0.000814 25.0149 C2H butane/propane 25.0078 25.0070 -0.000815 26.0235 C2H2 butane/propane 26.0157 26.0153 -0.000416 26.0121 CN HCN 26.0031 26.0039 0.000817 27.0195 HCN HCN 27.0109 27.0110 0.000118 27.0313 C2H3 butane 27.0235 27.0228 -0.000719 28.0058 CO CO 27.9949 27.9970 0.002120 29.0117 CHO acid? 29.0027 29.0026 -0.000121 29.0224 HN2 HN2 29.0140 29.0133 -0.000722 30.0067 NO NO 29.9980 29.9973 -0.000723 32.0002 O2 O2 31.9898 31.9902 0.000427 39.0352 C3H3 propane 39.0235 39.0231 -0.000429 39.9747 Ar Ar 39.9624 39.9623 -0.000132 41.051 C3H5 propane 41.0391 41.0383 -0.000833 42.0224 C2H2O acetone 42.0106 42.0094 -0.001234 42.0598 C3H6 butane 42.0469 42.0468 -0.000135 43.0327 C2H3O acetone 43.0184 43.0194 0.001036 43.0677 C3H7 butane &? 43.0548 43.0544 -0.000437 44.0006 CO2 CO2 43.9898 43.9870 -0.002838 44.0145 N 2O N2O 44.0010 44.0009 -0.000139 45.0117 COOH acid? 44.9977 44.9978 0.000140 50.0291 C4H2 butane 50.0157 50.0137 -0.002042 58.0619 C3H6O acetone 58.0419 58.0441 0.002243 58.0949 C4H10 butane 58.0782 58.0771 -0.0011
Average delta
0.00015 AMU
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Fermenter 2 N2, Ar, and CO2 Ejection
0
500
1000
1500
2000
2500
10 20 30 40 50 60 70
0
500
1000
1500
2000
2500
10 20 30 40 50 60 70
Arbitrary Y / Mass (m/z) Paged X-Zoom CURSOR
File # 1 = REG-FERM1B-T7_P#3 @258 Seconds 2/28/03 11:17 AM Res=None
Profile data
SO2
NO2
CH3S
Ar
ArH
36ArH2S
NO or CH2O
N2
HCN& C2H3
CN &C2H2
Ar++
H20
O
N
C
OH & NH3
Sulfur Eating Bacteria
Hot Spring
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
m/z 17
-100
-50
0
50
100
150
200
250
16.85 16.9 16.95 17 17.05 17.1 17.15 17.2 17.25
-100
-50
0
50
100
150
200
250
16.85 16.9 16.95 17 17.05 17.1 17.15 17.2 17.25
Arbitrary Y / Mass (m/z) Paged X-Zoom CURSOR
File # 1 = REG-FERM1B-T7_P#3 @258 Seconds 2/28/03 11:17 AM Res=None
Profile data
OHObserved 17.0046Theory 17.0027
NH3Observed 17.0283Theory 17.0265
DifferenceObserved 0.0237Theory 0.0238
Fermenter 2
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
m/z 27
0
100
200
300
400
26.99 27 27.01 27.02 27.03 27.04 27.05 27.06
0
100
200
300
400
26.99 27 27.01 27.02 27.03 27.04 27.05 27.06
Arbitrary Y / Mass (m/z) Paged X-Zoom CURSOR
File # 1 = REG-FERM1B-T7_P#3 @258 Seconds 2/28/03 11:17 AM Res=None
Profile data
HCNObserved 27.0126Theory 27.0109
C2H3Observed 27.0249Theory 27.0235
DifferenceObserved 0.0123Theory 0.0126
Fermenter 2
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Fermenter 3 m/z 28
0
500
1000
1500
27.94 27.96 27.98 28 28.02 28.04 28.06 28.08
0
500
1000
1500
27.94 27.96 27.98 28 28.02 28.04 28.06 28.08
Arbitrary Y / Mass (m/z) Paged X-Zoom CURSOR
File # 1 = REG-FERM2B-T3_P#2 @72 Seconds 2/28/03 10:20 AM Res=None
Profile data
COObserved 27.9978Theoretical 27.9949
N2Observed 28.0086Theoretical 28.0061
DifferenceObserved 0.0107Theoretical 0.0115
Sulfur Eating Bacteria
Deep Sea Ocean Vent
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Fermenter 3
0
200
400
600
28.94 28.96 28.98 29 29.02 29.04 29.06 29.08
0
200
400
600
28.94 28.96 28.98 29 29.02 29.04 29.06 29.08
Arbitrary Y / Mass (m/z) Paged X-Zoom CURSOR
File # 1 = REG-FERM2B-T3_P#2 @72 Seconds 2/28/03 10:20 AM Res=None
Profile data
N2HObserved 29.0160Theoretical 29.0140
Protonated 28 ions
COHObserved 29.0051Theoretical 29.0027
Difference Observed 0.0109Theoretical 0.0113
29 AMU
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Fermenter 332 AMU
0
200
400
600
31.92 31.94 31.96 31.98 32 32.02 32.04 32.06
0
200
400
600
31.92 31.94 31.96 31.98 32 32.02 32.04 32.06
Arbitrary Y / Mass (m/z) Paged X-Zoom CURSOR
File # 1 = REG-FERM2B-T3_P#2 @72 Seconds 2/28/03 10:20 AM Res=None
Profile data
O2Observed 31.9908Theoretical 31.9898
SObserved 31.9744Theoretical 31.9721
DifferenceObserved 0.0164Theoretical 0.0177
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Fermenter 3 m/z 64
-20
0
20
40
60
80
100
63.7 63.8 63.9 64 64.1 64.2 64.3 64.4
-20
0
20
40
60
80
100
63.7 63.8 63.9 64 64.1 64.2 64.3 64.4
Arbitrary Y / Mass (m/z) Paged X-Zoom CURSOR
File # 1 = REG-FERM2B-T3_P#2 @72 Seconds 2/28/03 10:20 AM Res=None
Profile data
Observed 63.9466S2 Theoretical 63.9441error of -0.002not SO2 Theoretical 63.9619error of 0.0152(error for CH3S at 47 is -.0014)
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
observed theory Adjusted Diff. fragment assignment
14.0171 14.0031 0.0014 N N215.0414 15.0235 -0.0024 CH316.0137 15.9949 -0.0018 O O216.0489 16.0313 -0.0006 CH4 CH417.0228 17.0027 -0.0015 OH H2O18.0319 18.0106 -0.0010 H20 H2O19.0429 ?20.0061 19.9812 -0.0011 Ar++ Ar26.0536 26.0157 -0.0021 C2H2 Ethane27.0517 27.0189 0.0052 HCN HCN27.0634 27.0234 -0.0020 C2H3 Ethane28.0436 27.9949 0.0027 CO CO28.0504 28.0061 -0.0153 N2 N229.0492 29.0027 -0.0040 COH COH29.0594 29.014 -0.0028 N2H N2H30.0456 29.998 -0.0027 NO NO32.0428 31.9898 -0.0032 O2 O239.095 39.0234 -0.0027 C3H3
40.0369 39.9624 -0.0028 Ar41.1163 41.0391 -0.0022 C3H542.1271 42.047 -0.0020 C3H643.1023 43.01839 -0.0028 CH3O44.0795 43.9898 -0.0055 CO245.0866 44.9977 -0.0014 CHO253.1565 53.0391 -0.0017 C4H555.1796 55.0548 -0.0014 C4H756.1913 56.0626 -0.0014 C4H858.179 58.0418 -0.0020 C3H6O acetone
65.2052 65.0391 -0.0013 C5H5 benzene67.2285 67.0547 0.0001 C5H768.2394 68.0626 0.0017 C5H870.2652 70.0783 0.0011 C5H10 cyclopentane?78.2719 78.047 0.0027 C6H6 Benzene91.3506 91.0548 0.0045 C7H7 Toluene92.3709 92.0626 -0.0019 C7H8 Toluene
0.00037 4/10 of a millimass unit
Average difference 0.4 Millimass Unit
Data from a Cigarette “smoked”
via an aspirator35 ml volume
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Spectrum #1 - NF3
NF2
NF3
5,550 countsNormal Electron Ionization
systems will fail within 1hour NF3 consumes the filament
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Spectrum #2000 - NF3
17 hours later NF2
NF3
5,450 counts The Quantra has a double advantage the filament is
impervious to these corrosives and the detection system does not rely on any impact of ions to count the
signal – No Multiplier Fadeout
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Calibration curve
5
4.54
3
2
10.5
y = 1290.5x - 230.38R2 = 0.9996
0
1000
2000
3000
4000
5000
6000
7000
0 1 2 3 4 5 6
% NF3
Inte
nsity
calibration curve NF3 Linear (calibration curve NF3)
m/z 52 peak
NF3 in Nitrogen calibration
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
m/z 52 Peak from NF3
quant plot
0
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8000
150 250 350 450 550 650 750 850 950 1050
scan number
inte
nsity
mass 52
7 point Calibration Stability
Serial Dilution
Random Introduction
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Random validation points
actual calc 95% confidence % NF3 %NF3 Conc RSD
1.25 1.21 1.28 1.14 3.513.33 3.19 3.26 3.11 1.332.56 2.45 2.49 2.40 0.914.38 4.24 4.35 4.13 1.353.15 3.02 3.07 2.97 0.851.01 0.99 1.05 0.93 3.763.70 3.61 3.73 3.49 1.735.00 5.01 5.13 4.89 1.28
1 – 4% RSD
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Semiconductor Gas Sampling
Semiconductor applications (Etch process and abatement) involving highly corrosive fluorocarbon species were readily analyzed with the Quantra Mini FTMS. Response times are similar to FTIR (data presented in part at 50th ASMS - 2002).
Once again the design features of this miniature FTMS allow aggressive and corrosive species to be directly sampled with no ill effects to the mass spectrometer. Placement of the filament, very low filament current, very high vacuum, extremely small sample volume and fast pumping are equally important in this design scheme and yield an extremely rugged system.
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
CF4/CHF 3 Etch Process Emissions (FTICR)
0.00
0.50
1.00
1.50
2.00
2.50
0 5 10 15 20
Scan Number
Ion
Abu
ndan
ce (a
rb. u
nits
)
CF3+CF2+
0
200
400
600
800
1000
50 100 150 200
CF3+
C2F4+
CHF2+
C2F5+
C3F5+C2F3
+ C3F7+ C4F7
+CF2
+
CN+, C2H2+
COF2+
O+
C+
N+
0
200
400
600
800
1000
50 100 150 200 0
200
400
600
800
1000
50 100 150 200 0
200
400
600
800
1000
50 100 150 200
CF3+
C2F4+
CHF2+
C2F5+
C3F5+C2F3
+ C3F7+ C4F7
+CF2
+
CN+, C2H2+
COF2+
O+
C+
N+
CF3+
C2F4+
CHF2+
C2F5+
C3F5+C2F3
+ C3F7+ C4F7
+CF2
+
CN+, C2H2+
COF2+
O+
C+
N+
FTMS Spectrum During CF4/CHF3/Ar Etch Process
16
51 66
69
85
93
100119
131
138 169181
0
200
400
600
800
1000
50 100 150 200 250 300
File # 1 = DATA2_P#3 @ 15 Seconds 9/18/01 4:09 PM
C 4F8 Etch of X LK (Spin-O n Low K )
2629
M ass-to-Charge (m /z)
Abu
ndan
ce (a
rb. u
nits
)
16
2629
51
69
85
119
0
100
200
300
400
500
50 100 150 200 250 300
File # 1 = DATA2_P#4 @ 21 Seconds 9/18/01 4:15 PM
C 4F6 Etch of X LK
M ass-to-Charge (m /z)
Abu
ndan
ce (a
rb. u
nits
)
Courtesy of Motorola APRDL – Austin Texas
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Process Monitoring During High-Density Plasma Etch
C4F8 Etch of F54P
0
50
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150
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250
0 20 40 60 80 100
Time (sec)
Ion
Inte
nsity
(arb
. uni
ts)
Mass 16Mass 26Mass 29Mass 41Mass 42Mass 51Mass 66Mass 69Mass 81Mass 82Mass 85Mass 93Mass 100Mass 113Mass 119Mass 131Mass 138Mass 169Mass 181
CF3+
C3F5+
C2F5+
C2F4+C4F7
+
Portability and effective sample introduction make the Quantra a particularly useful instrument for process monitoring. Generally it is impervious to aggressive species that will damage filaments or electron multipliers.
Courtesy of Motorola APRDL – Austin Texas
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
0
50
100
150
200
250
300
350
400
450
500
0 50 100 150 200 250Time (sec)
Rela
tive
Peak
Inte
nsity
(arb
. uni
ts)
O+H3O+HF+C2H+C2H2+C2H3+N2+NO+CF+CF2+CHF2+CH2F2+COF2+CF3+C2F3+SiF3+C3F3+C2F4+C2F5+C3F5+
CF3+
C2F4+
C3F5+
Emission Trend Plot During an Etch Process
Very corrosive Fluorocarbon species – analyzed with no adverse affects to mass spectrometer performance
Mass-to-charge (m/z)
Rel
ativ
e In
tens
ity (a
rb. u
nits
)
0
100
200
300
400
20 40 60 80 100 120 140 160 180 200
CF3+
O+
SiF3+
C2F4+
C2F5+
C3F5+
C2F3+
Fluorocarbon fragments are dominant species
Mass-to-charge (m/z)
Rel
ativ
e In
tens
ity (a
rb. u
nits
)
0
100
200
300
400
20 40 60 80 100 120 140 160 180 200
0
100
200
300
400
20 40 60 80 100 120 140 160 180 200
CF3+
O+
SiF3+
C2F4+
C2F5+
C3F5+
C2F3+
Fluorocarbon fragments are dominant species Predominance of
Fluorocarbon species here indicated a plasma instability – this was corroborated by FTIR
Courtesy of Motorola APRDL – Austin Texas
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
PhosgeneLibrary
Phosgene spectrum
QuantraPhosgene spectrum
Library match of the low resolution Quantra spectrum was quite good.
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
%Phosgene
Phosgene reactor
startup modeFaulty Flow Controllers
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Phosgene reactor
Shutdown mode
Faulty Flow Controllers
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Chemical Warfare SurrogatesDMMP, DBBP
Chemical Warfare surrogates were obtained from Aldrich. Samples of DMMP (Dimethylmethylphosphonate C3H9PO3) and DBBP (Dibutylbutylphosphonate C12H27PO3) were analyzed using a direct liquid inlet. The samples were dissolved in methanol and a few microliters were injected into the mass spectrometer. Additional methanol laced DMMP and DBBP samples were added to a gasoline matrix. The aim of this experiment was two fold: 1. Determine what accuracy of mass measurement could be obtained on these compounds, and 2. Determine whether that accuracy would be sufficiently high enough to “target” these surrogates using their exact mass in a complex matrix.
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
DMMP Dimethylmethylphosphonate C3H9PO3 spectrum
(Actual mass)/Measured mass
(46.9687)/46.9706
(63.0000)/63.0030
(78.9949)/78.9952(94.0184)/94.0183
(109.0050)/109.0080
(124.0289)/124.0341
Actual Measured Delta46.9687 46.9706 -0.001963.0000 63.0030 -0.003078.9949 78.9952 -0.000394.0184 94.0183 0.0001
109.0050 109.0080 -0.0030124.0289 124.0341 -0.0052
Std Dev 0.00196
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
DMMP in a Gasoline Matrix
(Actual mass)/measured mass
(94.0183)/94.0179
(78.9949)/78.9942
Actual Measured Delta94.018 94.0179 0.000478.995 78.9942 0.0007
avg 0.0005
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
DBBP Dibutylbutylphosphonate C12H27PO3 Spectrum
Mol.wgt. 250.1698
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
DBBP Dibutylbutylphosphonate C12H27PO3 Spectrum
Hydrocarbon Matrix
(Actual mass)/Measured mass
(57.0704)/57.0723
Lock mass 91.0548
(96.9843)/96.9824
(138.9949)/138.9896
Actual Measured Delta57.0704 57.0723 -0.001996.9843 96.9824 0.0019
138.9949 138.9896 0.0053
avg 0.0018
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
DMMP
Unlikely chemical species
As can be seen from this typical exact mass fragment calculator, it is possible to “target” a compound such as DMMP, using a few millimass unit tolerance, thus drastically reducing the possible “hits” at any given mass. The mass accuracy provided by this mini FTMS is more than adequate for this type of an analysis.
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Vacuum inlet
• Adsorption/Desorption• Membrane Probe• Direct Exposure Probe• Solids Probe• Liquid Injection• High Temperature Nozzle Inlet • Cryo Trapping
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Standard assembly for the Vacuum inlet System
AccumulationVolume
InjectionValve
ToQuantra
MeasurementCell
VacuumPump
BlockValve
PumpDischarge
+–
Direct ExposureProbe (DEP)
End changes for each type
of inlet device
Pressure range in Vacuum inlet 1 – 10 torr
Accumulation volume with heater and controller
Metering or block Valve
Small Vacuum pump and Vacuum gauge system
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
High Temperature Expansion Nozzle
(Molecular Leak)
AccumulationVolume
InjectionValve
ToQuantra
MeasurementCell
VacuumPump
BlockValve
PumpDischarge
Expansion Nozzle(High Temp)
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
2,6 di-tert-butylnapthaleneUsing expansion nozzle
0
2000
4000
6000
8000
50 100 150 200 250
0
2000
4000
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8000
50 100 150 200 250
Arbitrary Y / Mass (m/z) Paged Y-Zoom CURSOR
File # 1 = NOZZLE1_P#10 @411 Seconds 7/1/03 10:54 AM Res=None
Profile data
Melting point 146oC Boiling point 336oC
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Vacuum inlet – MIMS Probe
AccumulationVolume
InjectionValve
ToQuantra
MeasurementCell
VacuumPump
BlockValve
PumpDischarge
+–
Direct ExposureProbe (DEP)
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
MIMS/HR-FTMSTypical Isobaric Interferences – aliphatic ketone vs alkane
m/z 43
m/z 57 m/z 72
Methyl Ethyl Ketone & N-Pentane
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
MIMS/HR-FTMSm/z 43 and 57 doublets
57.0340
C3H5Ofrom MEK 57.0704
C4H9from Pentane
43.0184COCH3from MEK
43.0547C3H7 fromN-Pentane
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Vacuum inlet Adsorption/Desorption
AccumulationVolume
InjectionValve
ToQuantra
MeasurementCell
VacuumPump
BlockValve
PumpDischarge
+–
Direct ExposureProbe (DEP)
Vacuum Lock
Trapping Media
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
1 ppm Benzene and Toluene 8 ml/min for 5 minutes
(carboxen 563)
The interference is the S34 isotope of CS2
m/z 77.940 vs. benzene at m/z 78.047
~1200 resolution
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
100 ppb Benzene and Toluene 8 ml/min for 1 minute
(mol sieve 5A)
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
10 ppb Benzene and Toluene 20 ml/min for 15 minutes
(mol sieve 5A)
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Quantra as a field unit
At ambient temperature the Quantra will draw 300 watts, with heaters on approximately 700 watts, runs from a
generator or a voltage inverter, and typically uses a laptop
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Conclusion:
Adverse effects from corrosive and aggressive species are minimized due to design features of a new miniature FTMS.
The system is capable of process analysis as well as transportable field analysis of species ranging from phosgene gas and various fluorocarbons to NF3 and chemical weapons surrogates with little or no detriment to the mass spectrometer.
While pure elemental analysis, requiring 5 ppm or less mass accuracy is not readily seen above m/z 100 with this instrument, targeting species by their exact mass with subsequent identification – even in a complex background is definitely possible.
The system works very well in the field!
SIEMENS 4th Workshop on Harsh-Environment MS October 8, 2003
Acknowledgements:
Victor Vartanian, Brian Goolsby,
Motorola – Austin, Texas
Steve Beu
Beu Consulting – Austin, Texas
Dean Davis, Lonnie O’bannion
Siemens Applied Automation – Bartlesville, OK
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