practical gas chromatographic analyses using … gas chromatographic analyses using icp-ms detection...
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Practical Gas Chromatographic Analyses Using
ICP-MS Detection
William M. Geiger Consolidated Sciences
www.conscicorp.com
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Why GC-ICP-MS
7.4ppb Germane
MDQ ~ 1 ppb
GC/MS MDQ ~ 5 ppb
GC-AED MDQ ~ 5 ppb
Chapter 3 “ (ICP-MS) is too costly to use as a GC detector except for the most demanding applications.” W.M. Geiger
GC-ICP-MS Effort in 1995
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4.1 ppb Germane
MDQ ~ 2 - 4 ppt
GC-ICP-MS Effort in 2014
Why GC-ICP-MS
Column: 100 m X 0.53 mm X 5.0 um DB-1
Detector Agilent 8800 QQQ using ORS with O2, m/z 74 -> m/z 90
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Why GC-ICP-MS
Advantages
• Universal and Specific
• Extremely Sensitive
• Robust Plasma
• Single Tune for Most Elements
• Compound Independent Calibration (CIC)
• Isotope Measurement
Disadvantages
• Insensitive to Carbon *
• Cannot measure, H2, N2, O2, F
• Very Expensive Detector
• Uses a Lot of Argon
• Very Expensive
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Petroleum and
Petrochemical Applications
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Full Time Range EIC(32) : 018SMPL.d
RT(min)
8.0 16.0 24.0
Co
un
t
6x10
0
2
4
018SMPL.d
017SMPL.d
Methyl Mercaptan + n-Butane
Ethyl Mercaptan + Dimethyl sulfide + n-Pentane
Column: 100 m X 0.53 mm X 5.0 um DB-1 Carrier: Helium @ 12 psig Initial Temperature: 30 deg C Initial Time: 5.4 minutes Ramp: 15 deg C/ minute Final Temperature: 220 deg C
Sulfur in n-Gas
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Sulfur in Naphtha
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
Time-->
Abundance
TIC: NAPHTHA_7-23-2005_8-48-29_PM_-RUN-_1-.D
Methyl
Thiophenes
Dimethyl
Thiophenes
Thiophene
H2S
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Sulfur in Jet Fuel
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
6000000
6500000
Time-->
Abundance
TIC: 32JET_7-24-2005_12-23-44_AM_-RUN-_1-.D
Methyl Thiophenes
Dimethyl Thiophenes Benzothiophenes
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0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00
14500
15000
15500
16000
16500
17000
17500
18000
18500
19000
19500
20000
20500
21000
21500
22000
22500
23000
23500
Time-->
Abundance
Ion 48.00 (47.70 to 48.70): WAX_100_PPBIN_BENZENE_3
100 ppb Thiophene
Column: Carbowax 20M
Thiophene in Benzene
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35Cl chromatogram (ISTD)
13C chromatogram
204Pb chromatogram
Aviation Gasoline 100 LL Analysis
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Compound MW BP C (F) vp mmHg
Hexamethylcyclotrisiloxane 222 D3 135 (275) 10
Octamethylcyclotetrasiloxane 296 D4 175, (348) 1.3
Decamethylcyclopentasiloxane 370 D5 211, (412) 0.4
Dodecamethylcyclohexasiloxane 444 D6 245, (473) 0.02
Hexamethyldisiloxane 162 L2, MM 106, (224) 31
Octamethyltrisiloxane 236 L3, MDM ? 3.9
Decamethyltetrasiloxane 310 L4, MD
2M ? 0.55
Dodecamethylpentasiloxane 384 L5, MD
3M ? 0.07
Siloxanes
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L2
Siloxanes in Gasoline, ~ 5 ppm
L3
L4
Column: 60 meter x 0.32 mm x 1.8 um VOCOL (Supelco) Carrier: He @ constant flow 2 mls/minute, Split 15:1 Initial Temperature: 40 oC for 5 minutes Ramp 1: 5 oC /minute to 70 oC Hold: 0 minutes Ramp 2: 10 oC /minute to 230 oC Hold: 20 minutes Top Chromatogram: ICP-MS, conventional hard extract (m/z 28) Bottom Chromatogram: ICP-MS, hard extract (m/z 13)
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L2
L3
L4
Siloxanes in Gasoline, ~ 5 ppm
Column: 60 meter x 0.32 mm x 1.8 um VOCOL (Supelco) Carrier: He @ constant flow 2 mls/minute, Split 15:1 Initial Temperature: 40 oC for 5 minutes Ramp 1: 5 oC /minute to 70 oC Hold: 0 minutes Ramp 2: 10 oC /minute to 230 oC Hold: 20 minutes Top Chromatogram: ICP-MS, hard extract (m/z 28), 3.5 mls/min H2 to ORS Bottom Chromatogram: ICP-MS, conventional hard extract (m/z 28), No H2 to ORS
L2
L3
L4
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D3, 3 ppm D4, 2.7 ppm
D5, 1.7 ppm
D6, 0.93 ppm
Column: 30 meter x 0.32 mm x 0.25 um HP-5
Carrier: Helium @ 2.5 mls/min
Initial Temp.: 50 oC
Hold: 2 minutes
Ramp: 15 oC/minute
Final Temp.: 270 oC
ICP-MS 8800 QQQ was used for detection. Spectrometer was run in MS/MS mode using hydrogen in the octapole reaction system (ORS) in order to minimize hydrocarbon interference.
Siloxanes in Coker Naphtha
Si, 28 > 28 ion chromatogram
C, 13 > 13 ion chromatogram
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Compound ppmv as Si
D3 2.24
L3 0.08
D4 2.08
D5 5.56
TMS 0.32
Siloxanes in Town Gas
D3 D4
D5
L3
TMS
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Propylene Propylene contaminants include phosphine (PH3), Arsine (AsH3), Hydrogen Sulfide (H2S), and Carbonyl Sulfide (COS). A desirable method for analyzing these contaminants would be use of a single column and a single detector. Megabore (0.53mm) boiling point have been useful for this analysis, but suffer from the fact that COS elutes with the propane/propylene matrix. The Agilent PLOT U column also works well, but presence of ethane can give a false peak. It has been found that the Agilent Select Low Sulfur column satisfies all separation problems.
Carrier: Helium @ 20 psig Column: Select Low Sulfur 60 m x 0.32 mm
Temperature: 35 degrees isothermal Sample Size: 400 ul
Split: ~ 4:1 Detection: 8800 QQQ MS MS
Acquisition: m/z 31 -> m/z 47 0.4 seconds/mass m/z 32 -> m/z 48 0.4 seconds/mass m/z 74 -> m/z 90 0.1 seconds/mass m/z 75 -> m/z 91 0.1 seconds/mass
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AsH3, 11.4 ppb
Propylene Contaminants, Arsine
DL ~30 ppt
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PH3, 1.7 ppb spike
Ethane, 1.04 % Methane, 1.77 %
PH3 DL ~ 0.15 ppb. This chromatogram illustrates positive interference for P.
Propylene Contaminants, PH3
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H2S Standard COS Standard
H2S Spike
COS Spike
The matrix effect is more pronounced as the analyte is closer to the matrix. This chromatogram also illustrates the negative interference hydrocarbons have on the sulfur response. DL for H2S and COS ~ 3 ppb
Propylene
Propylene Contaminants, H2S and COS
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Carrier
Column
Sx Loop
Std
Loop
Std
Loop
Carrier
Column
Sx Loop
LoadInject
10 port GSV for Standard Addition
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Health and
Environmental
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Single column analysis of PBDE mix containing 14 common congeners from tri to deca 50 pg on column, 250 pg Deca- 10.5 minutes
Courtesy of Steve Wilbur and Emmett Soffey
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Tin Species in Landfill Gas Courtesy of Eva Krupp 2008 Plasma Winter
Conference
0
20000
40000
60000
80000
100000
120000
140000
160000
180000
200000
150 200 250 300 350 400 450
1
6 5 4 3
2
12, 13
7, 7a
8
14 11 10
9
16
1 Me4Sn; 2 Me3SnEt; 3 Me3Sni-Pr; 4 Me3SnPr; 5 Me2SnEt2; 6 Me2SnEtiPr; 7 Me3SnBu; 7a Me2SnEtPr; 8 MeSnEt3; 9 Me2SnPr2; 10 Et4Sn; 11 Et3SnPr; 12 Et2SnPr2; 13 BuSnEt3; 14 EtSnPr3; 15 Bu2SnEt2; 16 Bu2SnPr2
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Specialty And
General Applications
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GC-ICP-MS Analysis of CF3I
1 Trace Sulfur compound
2 Octafluoropropane
3 Trifluoromethane
4 Carbon Dioxide
5 Pentafluoroethane
6 Hexafluoropropene
7 Octafluorobutene + Octafluorocyclobutane
8 Octafluorobutene +
9 Br compound 10 Pentafluoropropene +
11 Sulfur compound
12 Hexafluoropropane
13 Chlorodifluoromethane +
14 Br compound
15 Sulfur compound
16 Cl compound trace
17 Br compound trace
18 Methyl Bromide ?
19 Br compound trace
20 Sulfur compound trace
21 Cl compound trace
22 Br compound trace
Matrix Vent Region
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Full Time Range EIC(13) : 104SMPL.d
RT(min)
7.0 14.0 21.0
Co
un
t
7x10
-1
-0.5
0
0.5
1
2
3
4
5
6
7
8
9
13
28
32
35
1 Ethene, 15.68 % 2 COS, 27 ppm 3 Difluorodimethylsilane, 80 ppm 4 Butene, 0.21 % 5 Butene, 1.30 % 6 Butene, 1.29 % 7 2-Fluorobutene, matrix 8 Methylene Chloride, 0.23 % 9 Carbon Disulfide, 9 ppm
Fluorobutene Impurities
1
2
3
4
5 6
7
8
9
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Electronic and
Semi-Conductor
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Single Tune Detection for Phosphine Impurities Detector: Agilent 7700 ICP-MS, Column: 200 m x 0.53 x 5.0 µm DB-1 @ 30oC
Germane, GeH4, m/z 74 Arsine, AsH3, m/z 75
Silane, SiH4, m/z 28 Arsine, AsH3, m/z 75
33 ppb, DL ∼ 3 ppb
33 ppb, DL ∼ 100 ppt
234 ppt
33 ppb, DL ∼ 5 ppt
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H2S: 13 ppb
COS: 32 ppb standard H2S: 32 ppb standard
DL: ∼3 ppb based on 3 sigma
Single Tune Detection for Phosphine Impurities Detector: Agilent 7700 ICP-MS, Column: 30 m x 0.53 mm x 20 µm
df HP-PLOT/U @ 50°C, Sample size: 75 µl
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Full Time Range EIC(31) : 14357-003.d
RT(min)
4.0 8.0 12.0
Co
un
t
5x10
0
1
2
3
20 ppb Triphosphine
24 ppm Diphosphine
Phosphine 'tail'
Dean's Switch
Phosphine Homologs
24 ppm Diphosphine
20 ppb Triphosphine
Phosphine Tail
Phosphine Vent
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n-Tetragermane, 7 ppb
Trigermane, 22 ppb
iso-Tetragermane, 5 ppb neo-Tetragermane, 1ppb
Germane (GeH4) Homologs
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11B = 3431999
10B = 458
11B = 14738129
10B = 3495946
Found 11B = 80.82 %
Theoretical 11B = 80.1 %
Enriched 11B = 99.99 %
Isotopic Analysis
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Interfacing
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Column
Switching Valve
To Transfer Line/Torch
Vent
Needle Valve
Dilution Gas
Interfacing Agilent 7700, 7900, 8800
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Carrier/Nebulizer Gas
Make-up Gas Standard or Blank
Dilution Gas/GC Effluent
Simultaneous GC and Wet Plasma Interfacing Agilent 7700, 7900, 8800
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Interfacing
To Torch
Make-up Gas
Carrier/Nebulizer Gas
Dilution Gas/GC Effluent
Standard or Blank
Agilent 7700, 7900, 8800
Simultaneous GC and Wet Plasma
Spray Chamber End View
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Cross Calibration Using CIC
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Mo
Ni
Fe
Ni Co
Fe
Carbon Monoxide
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58Ni
54Fe
52Cr
Theory
%
Found
%
50Cr 4.35 3.91
52Cr 83.79 83.09
53Cr 9.50 10.23
54Cr 2.37 2.78
Carbon Monoxide
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Ni signal = 99,440
(0.17 umoles/L)
Counts/umole= 228,328
Br signal = 99,440 (12.8 umoles/L)
Counts/umole= 7801
X RRFNi = 7801/228,328 = 0.0342
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Nickel Carbonyl = 16711 x 0.0342 x 101 ppb / 18874 = 3.1 ppb
101 ppb Methyl Bromide
Unknown Ni(CO)4
DL ~ 80 ppt
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The obvious advantage to analyzing Fe in the H2
mode is illustrated by these two chromatograms. This is a sample of CO containing 0.72 ppb iron carbonyl. Nickel works better in the He mode.
Fe, H2 mode
Fe, He mode
DL ~ 46 ppt
DL ~ 140 ppt
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This chromatogram illustrates the switching time going from Helium in the ORS to Hydrogen. The acquisition time was also changed since the iron carbonyl was a broader peak.
Carbon Monoxide
mode switch
Ni, He mode
Fe, H2 mode
CO matrix
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Resources
Journal of Analytical Atomic Spectrometry
Handbook of Hyphenated ICP-MS Applications - Agilent
Agilent 8800 ICP-QQQ Application Handbook - Agilent
Practical Guide to ICP-MS – Robert Thomas, CRC Press
ICP Mass Spectrometry Handbook, Simon M. Nelms, CRC Press
Trace Analysis of Specialty and Electronic Gases, Geiger and Raynor, Wiley
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Acknowledgments
Emmett Soffey - Agilent
Steve Wilbur- Agilent
Jesus Anguiano – CONSCI, LTD
Blake McElmurry – CONSCI, LTD