AccuTOF GCv 4G - JEOL USA...There is no need to break vacuum when you switch ion modes. It is ... FD...

JEOL

“AccuTOF GCｖ 4G“ : Petroleum Sample Analysis with EI/FI/FD combination ion source and Applications.

JEOL USA, Inc.

JEOL

Topics

1. Instrument

2. Samples and Measurement conditions

3. TIC chromatogram

4. Mass spectra of EI and FI

5. Conclusion

6. Examples of other hydrocarbon

applications

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1. Instrument

• JMS-T100GCV “AccuTOF GCv 4G” basic unit • Resolving power: R≥8,000 (FWHM) @ m/z 617

• Mass range: m/z 4-5000

• Mass accuracy: 1.5 mDa or 4 ppm (RMS)

• Sensitivity: S/N ≥ 100 for 1pg OFN (using with EI standard ion source)

• Acquisition rate: 50 spectra/s

• Auto Tuning for all ionization modes

• “EI/FI/FD Combination Ion Source” option • EI, FI and FD modes can be switched without breaking vacuum

• Suitable for petroleum analysis

• Additional options • CI mode (Positive and Negative)

• Direct insertion: DEP, DIP, FD, LIFDI*

Liquid Injection Field Desorption Ionization:

Allows continuous sample introduction onto the FD emitter without removing the probe.

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1. EI/FI/FD Combination Ion Source

EI, FI and FD modes can be switched without breaking vacuum

Cathode for FI/FD

Filament for EI

Lens unit

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2. Samples and Measurement Conditions

• Sample: • Diesel oil

• Measurement conditions: • Column: DB-5ms, 30 m x 0.25 mm, 0.25 um

• Oven: 50 C(1min) → 20 C/min → 300 C(6.5 min)

• Inlet: 300 C, Split 200:1, 0.2 uL inj.

• EI: 70 eV, 300 uA

• FI: -10 kV (Cathode), 45 mA (30 msec: Refreshed every spectra

recording

• Mass range: m/z 35-800

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3. TIC Chromatograms TIC[1]; / EI+(eiFi) / EI+(eifi)_DieselOil_1023_003 0.2uL Inj, Split200

0

2

4

6

8

10

12

14

16

Intensity (17885739)x106

9.819.22

8.61 10.89

4.907.96 11.39

5.74 6.53 7.27

11.87

9.50

4.01 12.339.00

8.357.53

12.766.23 7.065.38 11.114.59 13.19

TIC[1]; / FI+(eiFi) / FI+(eifi)_DieselOil_1024_002 0.2uL Inj, Split200

2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0Time[min]

0

500

1000

1500

2000

2500


9.23 9.81 10.37

8.61

11.39

7.96

11.87

7.27

6.5312.33

5.75 9.014.9012.778.36

GC/EI

GC/FI

C11H24 C12H26 C13H28

C14H30

C15H32

C16H34

C17H36

C18H38

C19H40

C20H42

C21H44

C22H46

C23H48

C10H22

+

C9H12

C24H50

C25H52

C26H54

C9H20

C9H20

C10H22

+

C9H12 C11H24

C12H26

C13H28

C14H30

C15H32

C16H34 C17H36 C18H38

C19H40

C20H42

C21H44

C22H46

C24H50

C25H52

C23H48 C26H54

m/z 207.0329 (Background)

is used as external calibrant

m/z 226.26605 (C16H34)

is used as external calibrant

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4. Mass spectra of the component at R.T. 4.90 MS[1];4.89..4.91;-1.0*MS[1];4.93..4.94; / EI+(eiFi) / EI+(eif i)_DieselOil_1023_003

0.2uL Inj, Split200

0

50

100

150

200


57.07143.055

105.070

71.085

85.100

120.093

56.062

70.07755.054

84.093

119.085142.17299.11691.054

58.07351.023

MS[1];4.89..4.91; / FI+(eiFi) / FI+(eif i)_DieselOil_1024_002

0.2uL Inj, Split200

40 60 80 100 120 140 160 180 200

m/z

0

5

10

15

20

25


142.172

120.095

143.176

121.100

EI

FI

M+・, C10H22

(0.8 mDa)

M+・, C9H12

(1.6 mDa)

M+・, C10H22

(-0.2 mDa)

M+・, C9H12

(-0.7 mDa)

C8H9

(-0.4 mDa)

C6H13

(-1.0 mDa)

C5H11

(-0.8 mDa)

C4H9

(0.9 mDa) C3H7

(0.6 mDa)

No fragment ions

FI spectrum showed that

the component at R.T. 4.90 (min)

consists of different two

hydrocarbons.

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Mass Spectra of n - Paraffins 1

EI FI

C11H24

C12H26

C13H28

C9H20

C11H24

C12H26

C13H28

C9H20

M+・ (0.6 mDa)

M+・ (0.8 mDa)

M+・ (1.1 mDa)

M+・ (-0.7 mDa)

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EI FI

C15H32

C16H34

C17H36

C14H30

C15H32

C16H34

C17H36

C14H30

M+・ (1.2 mDa)

M+・ (-0.1 mDa)

m/z 226.26605

is used as

external

calibration

M+・ (1.0 mDa)

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EI FI

C19H40

C20H42

C21H44

C18H38

C19H40

C20H42

C21H44

C18H38

M+・ (-0.9 mDa)

M+・ (-0.6 mDa)

M+・ (-0.9 mDa)

M+・ (-2.2 mDa)

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EI FI

C23H48

C24H50

C25H52

C22H46

C23H48

C24H50

C25H52

C22H46

M+・ (-2.4 mDa)

M+・ (-1.5 mDa)

M+・ (-0.5 mDa)

M+・ (-2.9 mDa)

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MS[1];3.35..14.33; / FI+(eiFi) / FI+(eif i)_DieselOil_1024_002-Centroided

0.2uL Inj, Split200

100 200 300 400 500 600 700 800

m/z

0

500

1000

1500

Intensity (1835)

226.270 240.285

212.252 268.313

174.143282.327

160.127

43.053296.340

146.111310.357

120.095324.372

MS[1];1.32..14.80;-1*MS[1];16.21..17.98; / EI+(eiFi) / EI+(eif i)_DieselOil_1023_003-Centroided

0.2uL Inj, Split200

100 200 300 400 500 600 700 800

m/z

0

10

20

30

40

50


57.070

71.085

85.101

97.100

133.100

165.070

Sum Over the Entire R.T. Range

EI

FI FI is well suited for petroleum analysis because it is

the only soft ionization method that works well for

saturated hydrocarbons.

We can detect molecular ions for hydrocarbons with

FI and calculate molecular weight distributions.

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5. Conclusion

• The AccuTOF GCv has a unique EI/FI/FD combination ion source.

There is no need to break vacuum when you switch ion modes. It is

only necessary to replace the EI repeller probe with the FI/FD

emitter probe without breaking vacuum.

• FI method is well suited for petroleum analysis, because it can

generates molecular ions for saturated hydrocarbons with minimal

fragmentation.

• EI and FI mass spectra both showed excellent mass accuracy.

• The AccuTOF GCv can be used for GCxGC measurement. We have

also demonstrated applications for GCxGC/FI with high-resolution

mass spectra.

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6. Other Hydrocarbon Applications

• Commercial Lubricants Analysis with GC/FI

• Crude Oil Measurement with GC/FI

• Type Analysis of Crude Oil using a FI Mass Spectrum

• Microcrystalline Wax measurement with FD

• Rapid analysis using inactivated fused silica tube as a sample inlet

• GC x GC/EI - Dibenzothiophenes analysis in Kerosene

• GC x GC/FI technique with normal and reverse column set

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Commercial Lubricants Analysis with GC/FI

C13H28 (M+･: m/z 184.2191, external calibrant)

*

Hydrocarbons Fatty acid esters

A B

C

D

min

Formula Calc. m/z Meas. m/z Mass error (mDa)

A C11H24 156.1878 156.1868 -1.0

B C12H26 170.2034 170.2030 -0.4

C C20H40O2 312.3028 312.3046 1.8

D C22H44O2 340.3341 340.3356 1.5

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Crude Oil Measurement with GC/FI

TIC Chromatogram

FI Mass Spectrum

Accumulation over entire time range

Hydrocarbons could be detected as molecular ions

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Type Analysis of Crude Oil by using an FI Mass Spectrum

* Polymerix software (Sierra Analytics, Inc.)

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Microcrystalline Wax measurement with FD

FD Mass Spectrum

Mn Mw Mz PD DPn DPw DPzPercetSeries

PercentSpectrum

657.0 686.9 718.9 1.0 40.1 42.2 44.5 100.0 64.1

S1 CnH2n+2 571.1 617.3 665.3 1.1 33.6 36.9 40.3 17.3 11.1

S2 CnH2n 529.7 655.0 680.8 1.0 37.9 39.7 41.6 24.2 15.5

S3 CnH2n-2 670.5 692.3 715.6 1.0 41.0 42.5 44.2 13.1 8.4

S4 CnH2n-4 715.6 739.0 764.7 1.0 44.3 46.0 47.8 8.4 5.4

S5 CnH2n-6 688.3 717.9 751.1 1.0 42.5 44.7 47.0 22.5 14.5

S6 CnH2n-8 710.0 739.6 772.8 1.0 44.2 46.3 48.7 14.5 9.3

SeriesLabel

Total/Average

Type Analysis of Microcrystalline Wax

Mn：Number-average M.W. Mw：Weight-average M.W. Mz：Z-average M.W. PD：Mw/Mn DPｎ： Mn/R DPｗ： Mw/R DPｚ： Mz/R （R： Repeating unit）

FD type analysis can provide information such as component ratios and average molecular weight.

Unsaturated hydrocarbons Saturated

hydrocarbons

300 400 500 600 700 800 900 1000 1100 1200 1300 m/z

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Rapid analysis using inactivated fused silica tube (a.k.a. “guard column”) as a sample inlet

MS

GC Oven (prog.)

Inlet

GC Oven (iso.)

Fused silica tube

Capillary column:

　ZB-5ms, 30 m × 0.25 mm, 0.25 µm Fused silica tube: 3 m ×0.1 mm

Capillary column

MS

Inlet(a) (b)

Rela

tive

inte

nsi

ty /

%R

ela

tive

inte

nsi

ty /

%R

ela

tive

inte

nsi

ty /

%

m/z

m/z

m/z

Rela

tive

inte

nsi

ty /

%R

ela

tive

inte

nsi

ty /

%R

ela

tive

inte

nsi

ty /

%

m/z

m/z

m/z

Time / min

Time / min

Time / min

(A)

(B)

(C)

(a)

(b)

(c)

Fig.2 TICs of diesel oil

(a) blank tube inlet/FI,

(b) capillary GC/FI, (c) FD

Fig.3 Mass spectra of diesel oil

(A) blank tube inlet/FI,

(B) capillary GC/FI, (C) FD

MS

GC Oven (prog.)

Inlet

GC Oven (iso.)

Fused silica tube

Capillary column:

　ZB-5ms, 30 m × 0.25 mm, 0.25 µm Fused silica tube: 3 m ×0.1 mm

Capillary column

MS

Inlet(a) (b)

Fig.1 Schematic diagrams of sample

introduction system by using GC,

(a) capillary GC/FI. (b) blank tube inlet/FI.

• Short analysis time

• Loss of low boiling point components are

minimized compared with probe-based

methods, such as FD, DEI, and DCI, in

which the sample is deposited on the probe

at ambient pressure.

• Loss of high boiling point and trace

components is minimized compared to

GC/MS methods since there are no

interaction with a GC stationary phase.

• GC conditions are not critical; no need to

worry about separation parameters.

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GC x GC/EI – Kerosene and Diesel Oil

2-D TIC of

Kerosene (EI)

2-D TIC of

Diesel Oil (EI)

A time-of-flight mass spectrometer (TOFMS) is the best detector for GCxGC

because it is capable of rapid spectral acquisition with no spectral skewing.

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GC x GC/EI - Dibenzothiophenes in Kerosene

A, C12H8S

m/z 184.0343

Error: -0.4 mDa

B, C13H10S

m/z 198.0495

Error: -0.8 mDa

C, C14H12S

m/z 212.0654

Error: -0.6 mDa

TIC 2-D Mass chromatogram

A B C

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GC x GC/FI technique with normal column set

GCxGC condition ： 1st column : BPX5, 30mx0.25mm, I.D. 0.25um ： 2nd column : BPX50, 2mx0.1mm, I.D. 0.1mm ： Oven temp. prog.: 50℃(2min)→3℃/min→300℃

TOFMS condition : Mass range : m/z 35 ~ 500 : Data acquisition speed : 0.04 sec/spectrum : Ionization mode : FI, cathode voltage -10kV

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GC x GC/FI technique with reverse column set

GCxGC condition ： 1st column : DB-WAXETR, 30mx0.25mm, I.D. 0.1um ： 2nd column : DB-1, 1mx0.1mm, I.D. 0.1um ： Oven temp. prog.: 50℃(2min)→3℃/min→300℃

TOFMS condition : Mass range : m/z 35 ~ 500 : Data acquisition speed : 0.04 sec/spectrum : Ionization mode : FI, cathode voltage -10kV

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AccuTOF GCv 4G - JEOL USA...There is no need to break vacuum when you switch ion modes. It is ... FD...

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