Elemental Combustion System CHNS-O analyzer

1. Elemental Combustion System CHNS-O analyzer

2. It is designed to analyser organic materials such as those produced in a chemical laboratory. • It is not designed for inorganicseg carbon in steel.

3. It represents an evolution in the technique of elemental analysis by “Flash combustion-Gas Chromatographic Separation”.

4. During normal system operation, helium carrier gas circulates within the analytical circuit which consists either of a combustion reactor for CHNS or a pyrolysis reactor for Oxygen. The carrier gas brings the combustion (for oxygen analysis: pyrolysis) gases to a gas chromatographic separation column and TCD detector for CHNS-O analysis.

5. Three running modes according to the weight of sample: 1- Micro <2 mg 2- Semi-micro 2-5 mg 3- Macro 5-10 mg In order to modulate the oxygen injection volume. Gases : Helium and O2 @ 99.995 % (30 -40 psi) N2 or Air for the Pneumatics @ 99.95 to 99.99% (60-70 psi)

6. Purging prior to analysis Purging is required to make sure the analyser and gas lines are free of contamination before starting. In addition contaminants from the atmosphere get into the instrument and gas lines, particularly overnight and when the system is left unused. For unused periods, it is better to go in Stand-by and not turning off the instrument. In stand-by, oxygen and helium flow should be off. Temperature will decrease in furnaces by 200 degrees.

7. C/H/N/S - Combustion Analysis 1- At the start of the analytical cycle the helium carrier gas is switched to a volume of oxygen which is chosen by the operator depending on the size and composition of the sample. 2- The samples are dropped automatically into the combustion reactor prior to the arrival of oxygen in the combustion reactor. 3- The sample and tin capsule react with oxygen and combust at temperatures of 1700-1800 °C and the sample is broken down into it’s elemental components, N2, CO2, H2O and SO2. (interfere gases) High performance copper wires absorb the excess oxygen not used to combust the sample. 4- The gases flow through the gas chromatographic (GC) separation column which is kept at a constant ± 0.1 °C temperature. As they pass through the GC column, the gases are separated and are detected sequentially by the TCD.

8. 5- The TCD generates a signal, which is proportional to the amount of element in the sample. 6- The ECS software compares the elemental peak to a known standard material (after calibration) and generates a report for each element on a weight basis For Continuous Flow Isotope Ratio Mass Spectroscopy, the separated gases are carried to the mass spectrometer interface and into the MS source.

9. Oxygen Analysis - Pyrolysis Helium carrier gas circulates through the analytical circuit, which consists of a pyrolysis reactor which is filled with a special nickelized carbon wool contact material heated to 1080 °C, a trap for acidic gases formed by the pyrolysis, a GC column which will separate the gas mixture, and a TCD. 1- Samples are dropped automatically into the pyrolysis reactor, break down and the released oxygen reacts with the nickel carbon wool to form CO (2C + O2 = 2 CO) and N2, if present in the sample. 2- The mixture of N2 and CO gases flow through the gas chromatographic (GC) separation column which is kept at a constant temperature (± 0.1 °C). 3- As they pass through the GC column, the gases are separated and are detected sequentially by the TCD.

10. 4- The TCD generates a signal, or peak, which is proportional to the amount of element in the sample. 5- The ECS software compares the elemental peak to a known standard material (after calibration) and generates a report for each element on a weight basis. In the Oxygen mode, the operating gas is helium when using silver vials or helium/hydrogen mixture when using tin vials.

11. Packing reactors N, NC, NCH Reactor packing Replace the inside every 200 samples

12. NCS, NCHS Reactor packing Sulphur burns to SO3 and SO2 The SO3 must be removed (reduced) immediately because of its reactivity This is achieved by adding copper to the combustion tube

13. Oxygen reactor packing • Helium / hydrogen (approx 5%) gas stream enhances conversion to CO and allows the use of tin capsules. • Copper is used to convert any CO2 formed back to CO.

14. Reduction reactor packing Removes excess oxygen Reduces NOX to Nitrogen

15. Nitrogen Configuration

16. Oxygen Configuration

17. Nitrogen/Carbon Configuration

18. Nitrogen/Carbon/Hydrogen/Sulfur configuration

22. Packing the H2O Trap

23. Packing the CO2 Trap

24. Thermal conductivity detector (TCD), also known as a Katharometer This detector senses changes in the thermal conductivity of the column eluent and compares it to a reference flow of carrier gas. Since most compounds have a thermal conductivity much less than that of the common carrier gases of helium or hydrogen, when an analyte elutes from the column the effluent thermal conductivity is reduced, and a detectable signal is produced. The TCD is often called a universal detector because it responds to all compounds. Also, since the thermal conductivity of organic compounds are similar and very different from helium, a TCD will respond similarly to similar concentrations of analyte. Therefore the TCD can be used without calibration and the concentration of a sample.  The TCD is also used in the analysis of permanent gases (argon, oxygen, nitrogen, carbon dioxide) 

25. Sulfur containing compounds: 30 min Oxygen: 10 min 6-8 min 4 min 2 min

26. Leak checking Once the reactors and traps are installed, a static leak check should be performed. 1- Place a cap on the He vent, wait 10-15 seconds for the pressure to stabilize, 2- then turn the He regulator off (counter clockwise). If there are no leaks the pressure on the He gauge will remain constant, if a leak is present the gauge will begin to fall. Sometimes the gauge will fall slightly, then remain constant. This only means that not enough time was allowed for the pressure to stabilize. If the pressure remains constant for 30-45 seconds, the ECS is tight enough to operate. If the pressure drops continuously after capping the vent, a leak is present in the system and must be sealed.

27. Helium The recommended flow rate for the helium carrier gas is between 80-120 ml/min. The pressure required to maintain the flow rate should not exceed 150 kPa. If the pressure is over 150 kPa there is a risk of breaking the quartz combustion reactor. A 2 meter GC column generally (column packing can vary slightly) needs 80-90 kPa to achieve a 100 ml/min flow rate, and a 3 meter column 100-110 kPa. A 4 meter column, due to the high backpressure, needs about 125-140 kPa to achieve a flow rate of 80-100 ml/min.

28. Oxygen The procedure to set the oxygen flow rate is different than the one for helium. The pressure in the oxygen volume, along with the size of the volume, will determine the amount of oxygen introduced for each sample combustion. This is very important to control and understand because there must be enough oxygen to combust the sample plus a small excess. Too little oxygen will result in poor or incomplete combustion, too much oxygen will consume the reduction (copper filled) reactor very quickly. a flow rate of 20-30 ml/min

29. Nitrogen/Carbon/Hydrogen/Sulfur Analysis These are the general operating parameters for automatic Nitrogen/Carbon/Hydrogen/Sulfur analysis. Modifications may be necessary for specific sample types or applications. Mode: CHNS Left furnace: 1000-1020 °C Right furnace: Off GC oven temp.: 65-80 °C GC Column: 2 meter

30. Oxygen Analysis These are the general operating parameters for automatic Oxygen analysis. Modifications may be necessary for specific sample types or applications. Mode: Oxygen Left furnace: 1070-1100 °C Right furnace: Off GC oven temp.: 65-80 °C GC Column: 1 meter molecular sievecolumn

31. Sample Preparation Tools Sample preparation plate: a metal plate with holes for holding sample capsules. Forceps: for closing the solid sample capsules Spatula: for filling the capsules. Capsules for solid samples Tin & silver capsules Capsules for liquid samples Add V2O5 for sulfur containig materials to increase the sensitivity of detector. (sample: V2O5, 1:5)

32. Solid sample preparation technique - Select the appropriate capsule for the amount of sample material to be analyzed. - Tare the capsule on the microbalance and place it on the sample preparation plate. - Use the spatula to fill the capsule with your sample material. - Place the sample back on the microbalance, wait for it to stabilize, and record the weight. - Remove the capsule and place it back on the sample preparation plate. Using the forceps, squeeze the top of the capsule closed. Grabbing the capsule on the top at either end, push the ends toward the middle, forming a “Z” shaped fold. - Holding the capsule at the bottom with one set of forceps, fold down the top with the other set of forceps. Form the capsule into a roughly spherical shape. - Avoid flattening the capsule as this can cause jamming in the autosampler.

33. Liquid sample preparation technique • The easiest way to handle liquid samples is to treat them as solid samples if possible. • For example, if the liquid sample is relatively non-volatile, it can be absorbed onto a solid material such as Chromosorb W. • Add Chromosorb W (enough to absorb the liquid) to a standard solid capsule and tare it on the microbalance. • Add the liquid by pipette, syringe or wire, taking care that the sample is completely absorbed into the Chromosorb W. • - Seal the capsule as described above and place it on the microbalance. • When it stabilizes, take the weight. • - If the sample weight does not stabilize, then the samples are not suitable for this technique and must be sealed in the special liquid capsules. Samples such as gasoline, solvents, etc. must be hermetically sealed in a special liquid capsule.

34. Running an Analysis If the ECS is in standby, press “Work”, then confirm by pressing “Enter”. The ECS will immediately begin to heat the furnaces to the “Work” condition setpoints. When the set operating temperatures have been reached, all LED’s will turn green, indicating the ECS is ready for operation. In the “Work” condition the helium and oxygen flow rates will return to the operating setpoints, and the purge flow will be turned on. Set the ECS for Remote operation by pressing the “Remote” button, then “Enter”. REM will appear in the display, indicating ECS is in remote mode and ready to accept an external start signal. Load samples in the autosampler. If you are using the open carousel pneumatic autosampler, simply add samples to the carousel starting from the position which is aligned over the hole and going in a counterclockwise direction.

37. Quartz reactor

40. Oven can be set between 30-110 °C . It can also be turned off. A 2 meter GC column is recommended for CHNS analysis. For oxygen analysis a 1 meter molecular sieve column is used.

41. There are two sensitivity ranges for the TCD (Thermal Conductivity Detector), low and high. If you are analyzing large or concentrated samples, such as organic compounds, plant tissue, etc. then the low range with very little gain is required. If soils or sediment samples are analyzed, then a high gain is required to get enough detector sensitivity.

44. Analytical Troubleshooting Normal chromatogram

45. Nitrogen peak appears to get larger on subsequent samples The reduction reactor is exhausted and oxygen is eluting from the GC column. Nitrogen and oxygen have similar retention times, so the combined N2 and O2 peaks make it appear as though the N2 peak gets larger. The O2 may also first appear as a shoulder on the trailing edge of the N2 peak.

46. Poor or incomplete combustion Nitrogen peak will tail into the carbon peak. Carbon peak will have a long tail, indicating a long, slow combustion or pyrolysis. Possible causes: • Sample start time too long, sample drops after O2 has passed. • Not enough O2 for sample combustion. • No O2 injected for sample combustion • Large leak in analytical circuit. CO2 N2

47. Baseline drift after CO2 peak • H2O trap is exhausted and water is slowly bleeding through the GC column and detector. Replace H2O trap packing with fresh material.

48. Second peak after Nitrogen Carbon dioxide trap is exhausted and CO2 is breaking through and passing through the GC column and detector: repack CO2 trap with fresh material.

49. Long tail on Sulfur peak Possible causes: • Combustion is not optimized, reset sample drop time • Sulfate in sample, add V2O5 to the sample • Dead volume in combustion reactor packing, repack reactor.

50. Peak broadening Possible causes: • Slow carrier gas flow • Dead volume in reactors or traps