The document discusses elemental analysis techniques using high temperature combustion. It focuses on the determination of sulfur and nitrogen using combustion tubes with and without catalysts. The key points made are: 1) Sulfur and nitrogen are oxidized at high temperatures and detected using UV fluorescence and chemiluminescence, respectively. 2) Catalysts in the combustion tubes allow for soot-free combustion, calibration with different injection volumes and rates, and improved recovery and sensitivity compared to tubes without catalysts. 3) Different catalyst materials and injection parameters were tested, showing the benefits of catalysts for quantitative analysis across various sample types with low detection limits.

1. Soot-free combustion of diesel, gasoline and other organic
liquids
25.11.2015
Ralf Dunsbach
Webinar elementar
Analysensysteme

2. The elementargroup – About us
30.11.2015 Webinar 2
• The technology leader in
• Elemental Analysis (EA)
• Isotope Ratio Mass Spectrometry (IRMS)
• Offers an unmatched combination of
• innovative technologies,
• tailor-made solutions and
• comprehensive support.

3. The elementargroup – Key Markets
30.11.2015 Webinar 3
AgricultureChemicals EnvironmentalEnergy MaterialsForensics

4. The elementargroup – Understanding Customers
30.11.2015 Webinar 4
• We provide highly competent application support
• This results in innovative, proprietary features
that address the needs of customers
• To deliver results faster, more accurate, more
sensitive, and in reliable high data quality

5. Determination of sulfur by high temperature
combustion
• Sulfur is oxidised to SO2 by high temperature combustion at >1100°C
• Detection of SO2 by UV fluorescence
30.11.2015 Webinar 5

6. Determination of nitrogen by high temperature
combustion
• Nitrogen is oxidised to NO at >1000°C
• NO is detected by chemoluminescence detection according to:
NO + O3 → NO2* + O2
30.11.2015 Webinar 6

7. Standard system
UV-F and CLD in-line
30.11.2015 Webinar 7
Source: PAC-Antek

8. trace SN cube
Separate combustion channels for S and N determination
30.11.2015 Webinar 8

9. Combustion tube without catalyst
30.11.2015 Webinar 9
Source:
ASTM D5453-12

10. Combustion tube with catalyst
30.11.2015 Webinar 10

11. Soot formation without catalyst
30.11.2015 Webinar 11
1 2 3
1: WO3 (S determination)
2: CeO2 (N determination)
3: Quarz (S+N)
Soot formation after 100
injections

12. Recovery with different tube fillings
WO3 CeO2 Quartz
1 mg/l toluene 0,941 <LOD 0,487
10 mg/l toluene 10,30 2,37 3,608
Diesel standard 93,99 33,34 26,26
Fuel oil 5,96 42,32* 5,19
30.11.2015 Webinar 12
*: carryover from diesel standard

13. Variation of injection rate
30.11.2015 Webinar 13
0
20000
40000
60000
80000
100000
120000
140000
0 20 40 60 80 100 120 140 160
1 ppm
2 ppm
5 ppm
10
ppm
Sample: quinoline in
toluene (N measurement)
Injection rate [µl/s]
Areacounts[rel.u.]

14. Calibration
30.11.2015 Webinar 14
Calibration with different
concentrations, IV 40µl
S/N [mg/l]
Injection volume [µl]
Calibration with different injection
volumes, 50mg/kg standard

15. Sensitivity
30.11.2015 Webinar 15
100µg/kg S
(benzothiophene in
toluene)

16. Carryover
30.11.2015 Webinar 16
50 mg/kg S, 80µl inj. vol., 640,000 area
counts
toluene, 80µl inj. vol., 760 area counts
eq. 0.106mg/kg S

17. Advantages of a catalyst
• Soot-free combustion
• Calibration by different injection volumes possible
• Simple design of the combustion tube
• Recovery independent of injection rate
• Increased sensitivity
30.11.2015 Webinar 17