An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve Tommaso Albertini, Andrea Caruso, Riccardo Facchetti Thermo Fisher Scientific, Milan, Italy

2 An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve

An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve Tommaso Albertini, Andrea Caruso, Riccardo Facchetti Thermo Fisher Scientific, Milan, Italy

The configuration in Figure 7 has been tested with different gas mixes in krypton and argon. Figure 8 shows that the CF4 and C2F6 peaks are separate from the large krypton peak. Figure 9 shows the analysis of impurities in xenon.

Conclusion A PDD is an excellent detector for the characterization of gas samples due to its high sensitivity, allowing for the detection of trace impurities. Combined with different column and valve configurations, this detector is applicable to a vast range of analyses. The Thermo Scientific Instant Connect PDD module provides outstanding sensitivity and unmatched flexibility. PDD installation requires no modifications to the GC frame or plumbing.

Overview Purpose: Introduce a novel, innovative PDD detector module for the Thermo Scientific™ TRACE™ 1300 Series Gas Chromatograph (GC) and show some examples of its applicability to the analysis and characterization of gas samples.

Introduction The pulsed discharge ionization detector (PDD) uses metastable helium atoms as an ionization source. These atoms are generated by electric sparks pulsed in a high purity grade helium flow. Ionization of the compounds is due mainly to a broad band emission (Hopfield emission) arising from the transition of the diatomic helium He2 into dissociative 2He ground state. The energy of the photons produced by this transition falls into the interval between 13.5 and 17.7 eV. This energy is high enough to ionize practically any compound present in the carrier gas, and therefore to detect it in concentrations in the low ppb range. The PDD is a universal, non-destructive, high sensitivity detector particularly suited for the analysis of permanent gases. The chromatographic analysis of gases may present some difficulties and typically involves the use of multiple columns and complex column switching to properly separate the analytes of interest. Column switching is typically performed using valves.

In this poster, we introduce the innovative Thermo Scientific™ Instant Connect PDD, a versatile and self-sufficient module, including the electronic and pneumatic circuits necessary for its control and gas supply. The detector can be installed on any TRACE 1300 Series GC regardless of its previous configuration.

The examples below illustrate the versatility of this detector, coupled with the Thermo Scientific TRACE 1310 Auxiliary Oven, for a variety of applications with multiple column setups suitable for the analysis of pure gases

Methods Gas analysis typically requires use of various packed or Plot columns to effectively separate all the compounds of interest. Sample injection is performed by a valve-and-loop injector and the path of the analyte is controlled by switching valves in a time-based way to send the different portions of the effluent carrier gas to the different columns, to the detector, or to the vent.

All of the examples in this poster use a TRACE 1310 GC equipped with an Instant Connect PDD Module and an auxiliary oven. Valve and column configurations differ from one example to the other.

Sample acquisition, system control and valve switching is handled by the Thermo Scientific Dionex™ Chromeleon™ 7.2 Chromatography Data System software.

Analysis of Impurities in Bulk Gases For this application, the hardware configuration comprises three purged valves (VICI Valco Co. Inc.): one six-port sampling valve with a 0.5 mL external loop for the sample and two four-port switching valves. Two wide-bore Plot columns are used for the analyte separation: a 30m Thermo Scientific TracePLOT™ TG-BOND Q GC column and a 30m Thermo Scientific TracePLOT TG-BOND Msieve 5A GC column. The sample is split by a needle valve (VICI Valco Co.Inc.) mounted just before the first column connection. The analysis is performed by simply switching Valve 2 and Valve 3 in a time-based way, depending on the compound being analyzed.

The system pneumatic scheme is illustrated in Figure 2. The gas mixtures analyzed are listed in Table 1.

Results The repeatability of the areas of all analyzed samples showed a %RSD below 1.5. Figure 3 shows the chromatograms of the analysis for the impurities in helium and argon. The peak intensity for all analytes indicates the high sensitivity achieved in all of these analyses.

Analysis of Impurities in Breathing Oxygen In this application, two valves are used for gas sampling and column switching. The sampling valve is a six-port valve, while a ten-port valve is used for column switching. The columns used are a 30m TracePLOT TG-BOND Msieve column, 0.53mm ID and a 30m TG-BOND Q column, 0.53mm ID. The configuration is shown in Figure 4. The analyzed compounds are listed in Table 2.

Results Figure 5 shows the linearity plots for ethylene and acetylene tested on the oxygen mixture. Both show a R2 greater than 0.999.

VICI is a registered trademark of Valco Instruments Co., Inc. and VICI AG. Porapak is a trademark of Waters. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries

This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.

The repeatability of the areas of all samples analyzed showed an %RSD lower than 1.5, as reported in Table 3 along with the minimum detectable quantities. A chromatogram of the analysis is reported in Figure 6.

Xenon and Krypton Analysis The system for this application includes two analytical channels. This first channel includes three packed columns: a 7 m Porapak QS column, a 2 m, 1/8” Porapak Q column installed in the valve oven; and a 2 m MolSieve column installed in the GC oven. The sample is introduced through a valve (4) with 1 mL sample loop. This channel should be used to analyze impurities that elute in the tail of Kr and Xe.

The second channel includes a 3 m MolSieve 5Å column, installed in the GC oven. The sample is introduced through a valve (1), with 1 mL sample loop. This channel should be used to analyze impurities such as C2F6, H2, O2, N2, Kr, CH4, and CO in pure Xe or C2F6, H2, O2, N2, and Xe in pure Kr. Valves 1 and 4 are used for sample injection and for backflushing the packed column. Valves 2 and 3 direct the eluted sample eluted out of the long Porapak QS column to the 2 m Porapak Q (2) or to the 2m MolSieve (3) column. The system scheme is illustrated in Figure 7.

FIGURE 1. IC PDD Detector Module

FIGURE 2. System schematics for gas impurities analysis.

He/N2

He

Ar

N2 10% N2 2.0 ppm H2 50.0 ppm O2 2.0 ppm O2 0.5 ppm N2 6.0 ppm

CO2 0.7 ppm CO2 0.5 ppm O2 2.6 ppm CH4 0.2 ppm H2 0.4 ppm CH4 0.2 ppm

CO 0.2 ppm CH4 0.03 ppm

TABLE 1. Analyzed gas mixes.

FIGURE 5. Linearity plot for ethylene and acetylene.

Ethylene

Acetylene

FIGURE 3. One argon, two helium, and three helium/nitrogen analyses.

FIGURE 4. System schematics for analysis of breathing oxygen.

TABLE 2. Impurities in oxygen.

O2

CH4 26.6 ppm

CO 5.8 ppm

CO2 5.3 ppm

N2O 4.1 ppm

C2H6 2.3 ppm

C2H4 1.0 ppm

C2H2 1.1 ppm

Compound

Area RSD%

Retention Time RSD%

MDQ (pg) S/N 3

CH4 0.494 0.0963 0.6

CO 0.975 0.0936 4

CO2 0.9 0.056 0.9

N2O 0.579 0.0279 0.9

C2H6

0.612 0.0876 0.7

C2H4

1.184 0.0409 0.7

C2H2 0.463 0.0457 1

TABLE 3. Analysis results.

FIGURE 6. Oxygen analysis chromatogram.

FIGURE 7. System schematics for Xenon an Krypton analysis.

Xe + C2H4

C2F6

Kr Air

CF4 C2F6

Kr

CF4

Air

FIGURE 8. Krypton impurities analysis.

CF4

Kr

SF6

Air

CO2

N2O

Xe

FIGURE 9. Xenon impurities analysis.

PO10437

3Thermo Scienti� c Poster Note • PITTCON • PN10437-EN 0215S

An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve Tommaso Albertini, Andrea Caruso, Riccardo Facchetti Thermo Fisher Scientific, Milan, Italy

The configuration in Figure 7 has been tested with different gas mixes in krypton and argon. Figure 8 shows that the CF4 and C2F6 peaks are separate from the large krypton peak. Figure 9 shows the analysis of impurities in xenon.

Conclusion A PDD is an excellent detector for the characterization of gas samples due to its high sensitivity, allowing for the detection of trace impurities. Combined with different column and valve configurations, this detector is applicable to a vast range of analyses. The Thermo Scientific Instant Connect PDD module provides outstanding sensitivity and unmatched flexibility. PDD installation requires no modifications to the GC frame or plumbing.

Overview Purpose: Introduce a novel, innovative PDD detector module for the Thermo Scientific™ TRACE™ 1300 Series Gas Chromatograph (GC) and show some examples of its applicability to the analysis and characterization of gas samples.

Introduction The pulsed discharge ionization detector (PDD) uses metastable helium atoms as an ionization source. These atoms are generated by electric sparks pulsed in a high purity grade helium flow. Ionization of the compounds is due mainly to a broad band emission (Hopfield emission) arising from the transition of the diatomic helium He2 into dissociative 2He ground state. The energy of the photons produced by this transition falls into the interval between 13.5 and 17.7 eV. This energy is high enough to ionize practically any compound present in the carrier gas, and therefore to detect it in concentrations in the low ppb range. The PDD is a universal, non-destructive, high sensitivity detector particularly suited for the analysis of permanent gases. The chromatographic analysis of gases may present some difficulties and typically involves the use of multiple columns and complex column switching to properly separate the analytes of interest. Column switching is typically performed using valves.

In this poster, we introduce the innovative Thermo Scientific™ Instant Connect PDD, a versatile and self-sufficient module, including the electronic and pneumatic circuits necessary for its control and gas supply. The detector can be installed on any TRACE 1300 Series GC regardless of its previous configuration.

The examples below illustrate the versatility of this detector, coupled with the Thermo Scientific TRACE 1310 Auxiliary Oven, for a variety of applications with multiple column setups suitable for the analysis of pure gases

Methods Gas analysis typically requires use of various packed or Plot columns to effectively separate all the compounds of interest. Sample injection is performed by a valve-and-loop injector and the path of the analyte is controlled by switching valves in a time-based way to send the different portions of the effluent carrier gas to the different columns, to the detector, or to the vent.

All of the examples in this poster use a TRACE 1310 GC equipped with an Instant Connect PDD Module and an auxiliary oven. Valve and column configurations differ from one example to the other.

Sample acquisition, system control and valve switching is handled by the Thermo Scientific Dionex™ Chromeleon™ 7.2 Chromatography Data System software.

Analysis of Impurities in Bulk Gases For this application, the hardware configuration comprises three purged valves (VICI Valco Co. Inc.): one six-port sampling valve with a 0.5 mL external loop for the sample and two four-port switching valves. Two wide-bore Plot columns are used for the analyte separation: a 30m Thermo Scientific TracePLOT™ TG-BOND Q GC column and a 30m Thermo Scientific TracePLOT TG-BOND Msieve 5A GC column. The sample is split by a needle valve (VICI Valco Co.Inc.) mounted just before the first column connection. The analysis is performed by simply switching Valve 2 and Valve 3 in a time-based way, depending on the compound being analyzed.

The system pneumatic scheme is illustrated in Figure 2. The gas mixtures analyzed are listed in Table 1.

Results The repeatability of the areas of all analyzed samples showed a %RSD below 1.5. Figure 3 shows the chromatograms of the analysis for the impurities in helium and argon. The peak intensity for all analytes indicates the high sensitivity achieved in all of these analyses.

Analysis of Impurities in Breathing Oxygen In this application, two valves are used for gas sampling and column switching. The sampling valve is a six-port valve, while a ten-port valve is used for column switching. The columns used are a 30m TracePLOT TG-BOND Msieve column, 0.53mm ID and a 30m TG-BOND Q column, 0.53mm ID. The configuration is shown in Figure 4. The analyzed compounds are listed in Table 2.

Results Figure 5 shows the linearity plots for ethylene and acetylene tested on the oxygen mixture. Both show a R2 greater than 0.999.

VICI is a registered trademark of Valco Instruments Co., Inc. and VICI AG. Porapak is a trademark of Waters. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries

This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.

The repeatability of the areas of all samples analyzed showed an %RSD lower than 1.5, as reported in Table 3 along with the minimum detectable quantities. A chromatogram of the analysis is reported in Figure 6.

Xenon and Krypton Analysis The system for this application includes two analytical channels. This first channel includes three packed columns: a 7 m Porapak QS column, a 2 m, 1/8” Porapak Q column installed in the valve oven; and a 2 m MolSieve column installed in the GC oven. The sample is introduced through a valve (4) with 1 mL sample loop. This channel should be used to analyze impurities that elute in the tail of Kr and Xe.

The second channel includes a 3 m MolSieve 5Å column, installed in the GC oven. The sample is introduced through a valve (1), with 1 mL sample loop. This channel should be used to analyze impurities such as C2F6, H2, O2, N2, Kr, CH4, and CO in pure Xe or C2F6, H2, O2, N2, and Xe in pure Kr. Valves 1 and 4 are used for sample injection and for backflushing the packed column. Valves 2 and 3 direct the eluted sample eluted out of the long Porapak QS column to the 2 m Porapak Q (2) or to the 2m MolSieve (3) column. The system scheme is illustrated in Figure 7.

FIGURE 1. IC PDD Detector Module

FIGURE 2. System schematics for gas impurities analysis.

He/N2

He

Ar

N2 10% N2 2.0 ppm H2 50.0 ppm O2 2.0 ppm O2 0.5 ppm N2 6.0 ppm

CO2 0.7 ppm CO2 0.5 ppm O2 2.6 ppm CH4 0.2 ppm H2 0.4 ppm CH4 0.2 ppm

CO 0.2 ppm CH4 0.03 ppm

TABLE 1. Analyzed gas mixes.

FIGURE 5. Linearity plot for ethylene and acetylene.

Ethylene

Acetylene

FIGURE 3. One argon, two helium, and three helium/nitrogen analyses.

FIGURE 4. System schematics for analysis of breathing oxygen.

TABLE 2. Impurities in oxygen.

O2

CH4 26.6 ppm

CO 5.8 ppm

CO2 5.3 ppm

N2O 4.1 ppm

C2H6 2.3 ppm

C2H4 1.0 ppm

C2H2 1.1 ppm

Compound

Area RSD%

Retention Time RSD%

MDQ (pg) S/N 3

CH4 0.494 0.0963 0.6

CO 0.975 0.0936 4

CO2 0.9 0.056 0.9

N2O 0.579 0.0279 0.9

C2H6

0.612 0.0876 0.7

C2H4

1.184 0.0409 0.7

C2H2 0.463 0.0457 1

TABLE 3. Analysis results.

FIGURE 6. Oxygen analysis chromatogram.

FIGURE 7. System schematics for Xenon an Krypton analysis.

Xe + C2H4

C2F6

Kr Air

CF4 C2F6

Kr

CF4

Air

FIGURE 8. Krypton impurities analysis.

CF4

Kr

SF6

Air

CO2

N2O

Xe

FIGURE 9. Xenon impurities analysis.

PO10437

4 An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve

An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve Tommaso Albertini, Andrea Caruso, Riccardo Facchetti Thermo Fisher Scientific, Milan, Italy

The configuration in Figure 7 has been tested with different gas mixes in krypton and argon. Figure 8 shows that the CF4 and C2F6 peaks are separate from the large krypton peak. Figure 9 shows the analysis of impurities in xenon.

Conclusion A PDD is an excellent detector for the characterization of gas samples due to its high sensitivity, allowing for the detection of trace impurities. Combined with different column and valve configurations, this detector is applicable to a vast range of analyses. The Thermo Scientific Instant Connect PDD module provides outstanding sensitivity and unmatched flexibility. PDD installation requires no modifications to the GC frame or plumbing.

Overview Purpose: Introduce a novel, innovative PDD detector module for the Thermo Scientific™ TRACE™ 1300 Series Gas Chromatograph (GC) and show some examples of its applicability to the analysis and characterization of gas samples.

Introduction The pulsed discharge ionization detector (PDD) uses metastable helium atoms as an ionization source. These atoms are generated by electric sparks pulsed in a high purity grade helium flow. Ionization of the compounds is due mainly to a broad band emission (Hopfield emission) arising from the transition of the diatomic helium He2 into dissociative 2He ground state. The energy of the photons produced by this transition falls into the interval between 13.5 and 17.7 eV. This energy is high enough to ionize practically any compound present in the carrier gas, and therefore to detect it in concentrations in the low ppb range. The PDD is a universal, non-destructive, high sensitivity detector particularly suited for the analysis of permanent gases. The chromatographic analysis of gases may present some difficulties and typically involves the use of multiple columns and complex column switching to properly separate the analytes of interest. Column switching is typically performed using valves.

In this poster, we introduce the innovative Thermo Scientific™ Instant Connect PDD, a versatile and self-sufficient module, including the electronic and pneumatic circuits necessary for its control and gas supply. The detector can be installed on any TRACE 1300 Series GC regardless of its previous configuration.

The examples below illustrate the versatility of this detector, coupled with the Thermo Scientific TRACE 1310 Auxiliary Oven, for a variety of applications with multiple column setups suitable for the analysis of pure gases

Methods Gas analysis typically requires use of various packed or Plot columns to effectively separate all the compounds of interest. Sample injection is performed by a valve-and-loop injector and the path of the analyte is controlled by switching valves in a time-based way to send the different portions of the effluent carrier gas to the different columns, to the detector, or to the vent.

All of the examples in this poster use a TRACE 1310 GC equipped with an Instant Connect PDD Module and an auxiliary oven. Valve and column configurations differ from one example to the other.

Sample acquisition, system control and valve switching is handled by the Thermo Scientific Dionex™ Chromeleon™ 7.2 Chromatography Data System software.

Analysis of Impurities in Bulk Gases For this application, the hardware configuration comprises three purged valves (VICI Valco Co. Inc.): one six-port sampling valve with a 0.5 mL external loop for the sample and two four-port switching valves. Two wide-bore Plot columns are used for the analyte separation: a 30m Thermo Scientific TracePLOT™ TG-BOND Q GC column and a 30m Thermo Scientific TracePLOT TG-BOND Msieve 5A GC column. The sample is split by a needle valve (VICI Valco Co.Inc.) mounted just before the first column connection. The analysis is performed by simply switching Valve 2 and Valve 3 in a time-based way, depending on the compound being analyzed.

The system pneumatic scheme is illustrated in Figure 2. The gas mixtures analyzed are listed in Table 1.

Results The repeatability of the areas of all analyzed samples showed a %RSD below 1.5. Figure 3 shows the chromatograms of the analysis for the impurities in helium and argon. The peak intensity for all analytes indicates the high sensitivity achieved in all of these analyses.

Analysis of Impurities in Breathing Oxygen In this application, two valves are used for gas sampling and column switching. The sampling valve is a six-port valve, while a ten-port valve is used for column switching. The columns used are a 30m TracePLOT TG-BOND Msieve column, 0.53mm ID and a 30m TG-BOND Q column, 0.53mm ID. The configuration is shown in Figure 4. The analyzed compounds are listed in Table 2.

Results Figure 5 shows the linearity plots for ethylene and acetylene tested on the oxygen mixture. Both show a R2 greater than 0.999.

VICI is a registered trademark of Valco Instruments Co., Inc. and VICI AG. Porapak is a trademark of Waters. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries

This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.

The repeatability of the areas of all samples analyzed showed an %RSD lower than 1.5, as reported in Table 3 along with the minimum detectable quantities. A chromatogram of the analysis is reported in Figure 6.

Xenon and Krypton Analysis The system for this application includes two analytical channels. This first channel includes three packed columns: a 7 m Porapak QS column, a 2 m, 1/8” Porapak Q column installed in the valve oven; and a 2 m MolSieve column installed in the GC oven. The sample is introduced through a valve (4) with 1 mL sample loop. This channel should be used to analyze impurities that elute in the tail of Kr and Xe.

The second channel includes a 3 m MolSieve 5Å column, installed in the GC oven. The sample is introduced through a valve (1), with 1 mL sample loop. This channel should be used to analyze impurities such as C2F6, H2, O2, N2, Kr, CH4, and CO in pure Xe or C2F6, H2, O2, N2, and Xe in pure Kr. Valves 1 and 4 are used for sample injection and for backflushing the packed column. Valves 2 and 3 direct the eluted sample eluted out of the long Porapak QS column to the 2 m Porapak Q (2) or to the 2m MolSieve (3) column. The system scheme is illustrated in Figure 7.

FIGURE 1. IC PDD Detector Module

FIGURE 2. System schematics for gas impurities analysis.

He/N2

He

Ar

N2 10% N2 2.0 ppm H2 50.0 ppm O2 2.0 ppm O2 0.5 ppm N2 6.0 ppm

CO2 0.7 ppm CO2 0.5 ppm O2 2.6 ppm CH4 0.2 ppm H2 0.4 ppm CH4 0.2 ppm

CO 0.2 ppm CH4 0.03 ppm

TABLE 1. Analyzed gas mixes.

FIGURE 5. Linearity plot for ethylene and acetylene.

Ethylene

Acetylene

FIGURE 3. One argon, two helium, and three helium/nitrogen analyses.

FIGURE 4. System schematics for analysis of breathing oxygen.

TABLE 2. Impurities in oxygen.

O2

CH4 26.6 ppm

CO 5.8 ppm

CO2 5.3 ppm

N2O 4.1 ppm

C2H6 2.3 ppm

C2H4 1.0 ppm

C2H2 1.1 ppm

Compound

Area RSD%

Retention Time RSD%

MDQ (pg) S/N 3

CH4 0.494 0.0963 0.6

CO 0.975 0.0936 4

CO2 0.9 0.056 0.9

N2O 0.579 0.0279 0.9

C2H6

0.612 0.0876 0.7

C2H4

1.184 0.0409 0.7

C2H2 0.463 0.0457 1

TABLE 3. Analysis results.

FIGURE 6. Oxygen analysis chromatogram.

FIGURE 7. System schematics for Xenon an Krypton analysis.

Xe + C2H4

C2F6

Kr Air

CF4 C2F6

Kr

CF4

Air

FIGURE 8. Krypton impurities analysis.

CF4

Kr

SF6

Air

CO2

N2O

Xe

FIGURE 9. Xenon impurities analysis.

PO10437

5Thermo Scienti� c Poster Note • PITTCON • PN10437-EN 0215S

An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve Tommaso Albertini, Andrea Caruso, Riccardo Facchetti Thermo Fisher Scientific, Milan, Italy

The configuration in Figure 7 has been tested with different gas mixes in krypton and argon. Figure 8 shows that the CF4 and C2F6 peaks are separate from the large krypton peak. Figure 9 shows the analysis of impurities in xenon.

Conclusion A PDD is an excellent detector for the characterization of gas samples due to its high sensitivity, allowing for the detection of trace impurities. Combined with different column and valve configurations, this detector is applicable to a vast range of analyses. The Thermo Scientific Instant Connect PDD module provides outstanding sensitivity and unmatched flexibility. PDD installation requires no modifications to the GC frame or plumbing.

Overview Purpose: Introduce a novel, innovative PDD detector module for the Thermo Scientific™ TRACE™ 1300 Series Gas Chromatograph (GC) and show some examples of its applicability to the analysis and characterization of gas samples.

Introduction The pulsed discharge ionization detector (PDD) uses metastable helium atoms as an ionization source. These atoms are generated by electric sparks pulsed in a high purity grade helium flow. Ionization of the compounds is due mainly to a broad band emission (Hopfield emission) arising from the transition of the diatomic helium He2 into dissociative 2He ground state. The energy of the photons produced by this transition falls into the interval between 13.5 and 17.7 eV. This energy is high enough to ionize practically any compound present in the carrier gas, and therefore to detect it in concentrations in the low ppb range. The PDD is a universal, non-destructive, high sensitivity detector particularly suited for the analysis of permanent gases. The chromatographic analysis of gases may present some difficulties and typically involves the use of multiple columns and complex column switching to properly separate the analytes of interest. Column switching is typically performed using valves.

In this poster, we introduce the innovative Thermo Scientific™ Instant Connect PDD, a versatile and self-sufficient module, including the electronic and pneumatic circuits necessary for its control and gas supply. The detector can be installed on any TRACE 1300 Series GC regardless of its previous configuration.

The examples below illustrate the versatility of this detector, coupled with the Thermo Scientific TRACE 1310 Auxiliary Oven, for a variety of applications with multiple column setups suitable for the analysis of pure gases

Methods Gas analysis typically requires use of various packed or Plot columns to effectively separate all the compounds of interest. Sample injection is performed by a valve-and-loop injector and the path of the analyte is controlled by switching valves in a time-based way to send the different portions of the effluent carrier gas to the different columns, to the detector, or to the vent.

All of the examples in this poster use a TRACE 1310 GC equipped with an Instant Connect PDD Module and an auxiliary oven. Valve and column configurations differ from one example to the other.

Sample acquisition, system control and valve switching is handled by the Thermo Scientific Dionex™ Chromeleon™ 7.2 Chromatography Data System software.

Analysis of Impurities in Bulk Gases For this application, the hardware configuration comprises three purged valves (VICI Valco Co. Inc.): one six-port sampling valve with a 0.5 mL external loop for the sample and two four-port switching valves. Two wide-bore Plot columns are used for the analyte separation: a 30m Thermo Scientific TracePLOT™ TG-BOND Q GC column and a 30m Thermo Scientific TracePLOT TG-BOND Msieve 5A GC column. The sample is split by a needle valve (VICI Valco Co.Inc.) mounted just before the first column connection. The analysis is performed by simply switching Valve 2 and Valve 3 in a time-based way, depending on the compound being analyzed.

The system pneumatic scheme is illustrated in Figure 2. The gas mixtures analyzed are listed in Table 1.

Results The repeatability of the areas of all analyzed samples showed a %RSD below 1.5. Figure 3 shows the chromatograms of the analysis for the impurities in helium and argon. The peak intensity for all analytes indicates the high sensitivity achieved in all of these analyses.

Analysis of Impurities in Breathing Oxygen In this application, two valves are used for gas sampling and column switching. The sampling valve is a six-port valve, while a ten-port valve is used for column switching. The columns used are a 30m TracePLOT TG-BOND Msieve column, 0.53mm ID and a 30m TG-BOND Q column, 0.53mm ID. The configuration is shown in Figure 4. The analyzed compounds are listed in Table 2.

Results Figure 5 shows the linearity plots for ethylene and acetylene tested on the oxygen mixture. Both show a R2 greater than 0.999.

VICI is a registered trademark of Valco Instruments Co., Inc. and VICI AG. Porapak is a trademark of Waters. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries

This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.

The repeatability of the areas of all samples analyzed showed an %RSD lower than 1.5, as reported in Table 3 along with the minimum detectable quantities. A chromatogram of the analysis is reported in Figure 6.

Xenon and Krypton Analysis The system for this application includes two analytical channels. This first channel includes three packed columns: a 7 m Porapak QS column, a 2 m, 1/8” Porapak Q column installed in the valve oven; and a 2 m MolSieve column installed in the GC oven. The sample is introduced through a valve (4) with 1 mL sample loop. This channel should be used to analyze impurities that elute in the tail of Kr and Xe.

The second channel includes a 3 m MolSieve 5Å column, installed in the GC oven. The sample is introduced through a valve (1), with 1 mL sample loop. This channel should be used to analyze impurities such as C2F6, H2, O2, N2, Kr, CH4, and CO in pure Xe or C2F6, H2, O2, N2, and Xe in pure Kr. Valves 1 and 4 are used for sample injection and for backflushing the packed column. Valves 2 and 3 direct the eluted sample eluted out of the long Porapak QS column to the 2 m Porapak Q (2) or to the 2m MolSieve (3) column. The system scheme is illustrated in Figure 7.

FIGURE 1. IC PDD Detector Module

FIGURE 2. System schematics for gas impurities analysis.

He/N2

He

Ar

N2 10% N2 2.0 ppm H2 50.0 ppm O2 2.0 ppm O2 0.5 ppm N2 6.0 ppm

CO2 0.7 ppm CO2 0.5 ppm O2 2.6 ppm CH4 0.2 ppm H2 0.4 ppm CH4 0.2 ppm

CO 0.2 ppm CH4 0.03 ppm

TABLE 1. Analyzed gas mixes.

FIGURE 5. Linearity plot for ethylene and acetylene.

Ethylene

Acetylene

FIGURE 3. One argon, two helium, and three helium/nitrogen analyses.

FIGURE 4. System schematics for analysis of breathing oxygen.

TABLE 2. Impurities in oxygen.

O2

CH4 26.6 ppm

CO 5.8 ppm

CO2 5.3 ppm

N2O 4.1 ppm

C2H6 2.3 ppm

C2H4 1.0 ppm

C2H2 1.1 ppm

Compound

Area RSD%

Retention Time RSD%

MDQ (pg) S/N 3

CH4 0.494 0.0963 0.6

CO 0.975 0.0936 4

CO2 0.9 0.056 0.9

N2O 0.579 0.0279 0.9

C2H6

0.612 0.0876 0.7

C2H4

1.184 0.0409 0.7

C2H2 0.463 0.0457 1

TABLE 3. Analysis results.

FIGURE 6. Oxygen analysis chromatogram.

FIGURE 7. System schematics for Xenon an Krypton analysis.

Xe + C2H4

C2F6

Kr Air

CF4 C2F6

Kr

CF4

Air

FIGURE 8. Krypton impurities analysis.

CF4

Kr

SF6

Air

CO2

N2O

Xe

FIGURE 9. Xenon impurities analysis.

PO10437

6 An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve

An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve Tommaso Albertini, Andrea Caruso, Riccardo Facchetti Thermo Fisher Scientific, Milan, Italy

The configuration in Figure 7 has been tested with different gas mixes in krypton and argon. Figure 8 shows that the CF4 and C2F6 peaks are separate from the large krypton peak. Figure 9 shows the analysis of impurities in xenon.

Conclusion A PDD is an excellent detector for the characterization of gas samples due to its high sensitivity, allowing for the detection of trace impurities. Combined with different column and valve configurations, this detector is applicable to a vast range of analyses. The Thermo Scientific Instant Connect PDD module provides outstanding sensitivity and unmatched flexibility. PDD installation requires no modifications to the GC frame or plumbing.

Overview Purpose: Introduce a novel, innovative PDD detector module for the Thermo Scientific™ TRACE™ 1300 Series Gas Chromatograph (GC) and show some examples of its applicability to the analysis and characterization of gas samples.

Introduction The pulsed discharge ionization detector (PDD) uses metastable helium atoms as an ionization source. These atoms are generated by electric sparks pulsed in a high purity grade helium flow. Ionization of the compounds is due mainly to a broad band emission (Hopfield emission) arising from the transition of the diatomic helium He2 into dissociative 2He ground state. The energy of the photons produced by this transition falls into the interval between 13.5 and 17.7 eV. This energy is high enough to ionize practically any compound present in the carrier gas, and therefore to detect it in concentrations in the low ppb range. The PDD is a universal, non-destructive, high sensitivity detector particularly suited for the analysis of permanent gases. The chromatographic analysis of gases may present some difficulties and typically involves the use of multiple columns and complex column switching to properly separate the analytes of interest. Column switching is typically performed using valves.

In this poster, we introduce the innovative Thermo Scientific™ Instant Connect PDD, a versatile and self-sufficient module, including the electronic and pneumatic circuits necessary for its control and gas supply. The detector can be installed on any TRACE 1300 Series GC regardless of its previous configuration.

The examples below illustrate the versatility of this detector, coupled with the Thermo Scientific TRACE 1310 Auxiliary Oven, for a variety of applications with multiple column setups suitable for the analysis of pure gases

Methods Gas analysis typically requires use of various packed or Plot columns to effectively separate all the compounds of interest. Sample injection is performed by a valve-and-loop injector and the path of the analyte is controlled by switching valves in a time-based way to send the different portions of the effluent carrier gas to the different columns, to the detector, or to the vent.

All of the examples in this poster use a TRACE 1310 GC equipped with an Instant Connect PDD Module and an auxiliary oven. Valve and column configurations differ from one example to the other.

Sample acquisition, system control and valve switching is handled by the Thermo Scientific Dionex™ Chromeleon™ 7.2 Chromatography Data System software.

Analysis of Impurities in Bulk Gases For this application, the hardware configuration comprises three purged valves (VICI Valco Co. Inc.): one six-port sampling valve with a 0.5 mL external loop for the sample and two four-port switching valves. Two wide-bore Plot columns are used for the analyte separation: a 30m Thermo Scientific TracePLOT™ TG-BOND Q GC column and a 30m Thermo Scientific TracePLOT TG-BOND Msieve 5A GC column. The sample is split by a needle valve (VICI Valco Co.Inc.) mounted just before the first column connection. The analysis is performed by simply switching Valve 2 and Valve 3 in a time-based way, depending on the compound being analyzed.

The system pneumatic scheme is illustrated in Figure 2. The gas mixtures analyzed are listed in Table 1.

Results The repeatability of the areas of all analyzed samples showed a %RSD below 1.5. Figure 3 shows the chromatograms of the analysis for the impurities in helium and argon. The peak intensity for all analytes indicates the high sensitivity achieved in all of these analyses.

Analysis of Impurities in Breathing Oxygen In this application, two valves are used for gas sampling and column switching. The sampling valve is a six-port valve, while a ten-port valve is used for column switching. The columns used are a 30m TracePLOT TG-BOND Msieve column, 0.53mm ID and a 30m TG-BOND Q column, 0.53mm ID. The configuration is shown in Figure 4. The analyzed compounds are listed in Table 2.

Results Figure 5 shows the linearity plots for ethylene and acetylene tested on the oxygen mixture. Both show a R2 greater than 0.999.

VICI is a registered trademark of Valco Instruments Co., Inc. and VICI AG. Porapak is a trademark of Waters. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries

This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.

The repeatability of the areas of all samples analyzed showed an %RSD lower than 1.5, as reported in Table 3 along with the minimum detectable quantities. A chromatogram of the analysis is reported in Figure 6.

Xenon and Krypton Analysis The system for this application includes two analytical channels. This first channel includes three packed columns: a 7 m Porapak QS column, a 2 m, 1/8” Porapak Q column installed in the valve oven; and a 2 m MolSieve column installed in the GC oven. The sample is introduced through a valve (4) with 1 mL sample loop. This channel should be used to analyze impurities that elute in the tail of Kr and Xe.

The second channel includes a 3 m MolSieve 5Å column, installed in the GC oven. The sample is introduced through a valve (1), with 1 mL sample loop. This channel should be used to analyze impurities such as C2F6, H2, O2, N2, Kr, CH4, and CO in pure Xe or C2F6, H2, O2, N2, and Xe in pure Kr. Valves 1 and 4 are used for sample injection and for backflushing the packed column. Valves 2 and 3 direct the eluted sample eluted out of the long Porapak QS column to the 2 m Porapak Q (2) or to the 2m MolSieve (3) column. The system scheme is illustrated in Figure 7.

FIGURE 1. IC PDD Detector Module

FIGURE 2. System schematics for gas impurities analysis.

He/N2

He

Ar

N2 10% N2 2.0 ppm H2 50.0 ppm O2 2.0 ppm O2 0.5 ppm N2 6.0 ppm

CO2 0.7 ppm CO2 0.5 ppm O2 2.6 ppm CH4 0.2 ppm H2 0.4 ppm CH4 0.2 ppm

CO 0.2 ppm CH4 0.03 ppm

TABLE 1. Analyzed gas mixes.

FIGURE 5. Linearity plot for ethylene and acetylene.

Ethylene

Acetylene

FIGURE 3. One argon, two helium, and three helium/nitrogen analyses.

FIGURE 4. System schematics for analysis of breathing oxygen.

TABLE 2. Impurities in oxygen.

O2

CH4 26.6 ppm

CO 5.8 ppm

CO2 5.3 ppm

N2O 4.1 ppm

C2H6 2.3 ppm

C2H4 1.0 ppm

C2H2 1.1 ppm

Compound

Area RSD%

Retention Time RSD%

MDQ (pg) S/N 3

CH4 0.494 0.0963 0.6

CO 0.975 0.0936 4

CO2 0.9 0.056 0.9

N2O 0.579 0.0279 0.9

C2H6

0.612 0.0876 0.7

C2H4

1.184 0.0409 0.7

C2H2 0.463 0.0457 1

TABLE 3. Analysis results.

FIGURE 6. Oxygen analysis chromatogram.

FIGURE 7. System schematics for Xenon an Krypton analysis.

Xe + C2H4

C2F6

Kr Air

CF4 C2F6

Kr

CF4

Air

FIGURE 8. Krypton impurities analysis.

CF4

Kr

SF6

Air

CO2

N2O

Xe

FIGURE 9. Xenon impurities analysis.

PO10437

PN10437-EN 0215S

An Innovative, Reliable, Easy Set-Up for the Analysis of Permanent Gases via PDD and Gas Sampling Valve Tommaso Albertini, Andrea Caruso, Riccardo Facchetti Thermo Fisher Scientific, Milan, Italy

The configuration in Figure 7 has been tested with different gas mixes in krypton and argon. Figure 8 shows that the CF4 and C2F6 peaks are separate from the large krypton peak. Figure 9 shows the analysis of impurities in xenon.

Conclusion A PDD is an excellent detector for the characterization of gas samples due to its high sensitivity, allowing for the detection of trace impurities. Combined with different column and valve configurations, this detector is applicable to a vast range of analyses. The Thermo Scientific Instant Connect PDD module provides outstanding sensitivity and unmatched flexibility. PDD installation requires no modifications to the GC frame or plumbing.

Overview Purpose: Introduce a novel, innovative PDD detector module for the Thermo Scientific™ TRACE™ 1300 Series Gas Chromatograph (GC) and show some examples of its applicability to the analysis and characterization of gas samples.

Introduction The pulsed discharge ionization detector (PDD) uses metastable helium atoms as an ionization source. These atoms are generated by electric sparks pulsed in a high purity grade helium flow. Ionization of the compounds is due mainly to a broad band emission (Hopfield emission) arising from the transition of the diatomic helium He2 into dissociative 2He ground state. The energy of the photons produced by this transition falls into the interval between 13.5 and 17.7 eV. This energy is high enough to ionize practically any compound present in the carrier gas, and therefore to detect it in concentrations in the low ppb range. The PDD is a universal, non-destructive, high sensitivity detector particularly suited for the analysis of permanent gases. The chromatographic analysis of gases may present some difficulties and typically involves the use of multiple columns and complex column switching to properly separate the analytes of interest. Column switching is typically performed using valves.

In this poster, we introduce the innovative Thermo Scientific™ Instant Connect PDD, a versatile and self-sufficient module, including the electronic and pneumatic circuits necessary for its control and gas supply. The detector can be installed on any TRACE 1300 Series GC regardless of its previous configuration.

The examples below illustrate the versatility of this detector, coupled with the Thermo Scientific TRACE 1310 Auxiliary Oven, for a variety of applications with multiple column setups suitable for the analysis of pure gases

Methods Gas analysis typically requires use of various packed or Plot columns to effectively separate all the compounds of interest. Sample injection is performed by a valve-and-loop injector and the path of the analyte is controlled by switching valves in a time-based way to send the different portions of the effluent carrier gas to the different columns, to the detector, or to the vent.

All of the examples in this poster use a TRACE 1310 GC equipped with an Instant Connect PDD Module and an auxiliary oven. Valve and column configurations differ from one example to the other.

Sample acquisition, system control and valve switching is handled by the Thermo Scientific Dionex™ Chromeleon™ 7.2 Chromatography Data System software.

Analysis of Impurities in Bulk Gases For this application, the hardware configuration comprises three purged valves (VICI Valco Co. Inc.): one six-port sampling valve with a 0.5 mL external loop for the sample and two four-port switching valves. Two wide-bore Plot columns are used for the analyte separation: a 30m Thermo Scientific TracePLOT™ TG-BOND Q GC column and a 30m Thermo Scientific TracePLOT TG-BOND Msieve 5A GC column. The sample is split by a needle valve (VICI Valco Co.Inc.) mounted just before the first column connection. The analysis is performed by simply switching Valve 2 and Valve 3 in a time-based way, depending on the compound being analyzed.

The system pneumatic scheme is illustrated in Figure 2. The gas mixtures analyzed are listed in Table 1.

Results The repeatability of the areas of all analyzed samples showed a %RSD below 1.5. Figure 3 shows the chromatograms of the analysis for the impurities in helium and argon. The peak intensity for all analytes indicates the high sensitivity achieved in all of these analyses.

Analysis of Impurities in Breathing Oxygen In this application, two valves are used for gas sampling and column switching. The sampling valve is a six-port valve, while a ten-port valve is used for column switching. The columns used are a 30m TracePLOT TG-BOND Msieve column, 0.53mm ID and a 30m TG-BOND Q column, 0.53mm ID. The configuration is shown in Figure 4. The analyzed compounds are listed in Table 2.

Results Figure 5 shows the linearity plots for ethylene and acetylene tested on the oxygen mixture. Both show a R2 greater than 0.999.

VICI is a registered trademark of Valco Instruments Co., Inc. and VICI AG. Porapak is a trademark of Waters. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries

This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.

The repeatability of the areas of all samples analyzed showed an %RSD lower than 1.5, as reported in Table 3 along with the minimum detectable quantities. A chromatogram of the analysis is reported in Figure 6.

Xenon and Krypton Analysis The system for this application includes two analytical channels. This first channel includes three packed columns: a 7 m Porapak QS column, a 2 m, 1/8” Porapak Q column installed in the valve oven; and a 2 m MolSieve column installed in the GC oven. The sample is introduced through a valve (4) with 1 mL sample loop. This channel should be used to analyze impurities that elute in the tail of Kr and Xe.

The second channel includes a 3 m MolSieve 5Å column, installed in the GC oven. The sample is introduced through a valve (1), with 1 mL sample loop. This channel should be used to analyze impurities such as C2F6, H2, O2, N2, Kr, CH4, and CO in pure Xe or C2F6, H2, O2, N2, and Xe in pure Kr. Valves 1 and 4 are used for sample injection and for backflushing the packed column. Valves 2 and 3 direct the eluted sample eluted out of the long Porapak QS column to the 2 m Porapak Q (2) or to the 2m MolSieve (3) column. The system scheme is illustrated in Figure 7.

FIGURE 1. IC PDD Detector Module

FIGURE 2. System schematics for gas impurities analysis.

He/N2

He

Ar

N2 10% N2 2.0 ppm H2 50.0 ppm O2 2.0 ppm O2 0.5 ppm N2 6.0 ppm

CO2 0.7 ppm CO2 0.5 ppm O2 2.6 ppm CH4 0.2 ppm H2 0.4 ppm CH4 0.2 ppm

CO 0.2 ppm CH4 0.03 ppm

TABLE 1. Analyzed gas mixes.

FIGURE 5. Linearity plot for ethylene and acetylene.

Ethylene

Acetylene

FIGURE 3. One argon, two helium, and three helium/nitrogen analyses.

FIGURE 4. System schematics for analysis of breathing oxygen.

TABLE 2. Impurities in oxygen.

O2

CH4 26.6 ppm

CO 5.8 ppm

CO2 5.3 ppm

N2O 4.1 ppm

C2H6 2.3 ppm

C2H4 1.0 ppm

C2H2 1.1 ppm

Compound

Area RSD%

Retention Time RSD%

MDQ (pg) S/N 3

CH4 0.494 0.0963 0.6

CO 0.975 0.0936 4

CO2 0.9 0.056 0.9

N2O 0.579 0.0279 0.9

C2H6

0.612 0.0876 0.7

C2H4

1.184 0.0409 0.7

C2H2 0.463 0.0457 1

TABLE 3. Analysis results.

FIGURE 6. Oxygen analysis chromatogram.

FIGURE 7. System schematics for Xenon an Krypton analysis.

Xe + C2H4

C2F6

Kr Air

CF4 C2F6

Kr

CF4

Air

FIGURE 8. Krypton impurities analysis.

CF4

Kr

SF6

Air

CO2

N2O

Xe

FIGURE 9. Xenon impurities analysis.

PO10437

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