PO-CON1406E

New Applications UsingGC BID Detector

Pittcon 2014 530-1P

Zhuangzhi “Max” Wang, Nicole Lock,

Richard Whitney, Clifford M. Taylor

Shimadzu Scienti�c Instruments, Columbia, MD

2

Introduction

New Applications Using GC BID Detector

The Barrier Ionization Discharge (BID) detector generates a 17.7 eV helium plasma that ionizes almost all compounds except Neon. A newly designed quartz dielectric chamber allows for a lower discharge current and higher operating temperature. The BID is a universal detector with sensitivity greater than 100 times that of a TCD. It is an ideal detector for trace levels of permanent gas, water, volatile fatty acids and light hydrocarbons. Two customized GC applications are presented. Two 6-port valves are used to inject, trap and release permanent gases. A 4-port switching valve was used to direct high concentration sample components to a TCD.

Materials and Methods

A plasma is generated by applying a high voltage to a quartz dielectric chamber, in the presence of helium. Compounds that elute from the GC column are ionized by this He plasma, then captured with collection electrodes and described as peaks. The photon energy of He is extremely high (17.7 electron volt). Therefore it makes possible to detect every compound except Ne (neon) and He which is the plasma gas, with high sensitivity. BID is truly a universal plasma detector.

BID-2010 Plus Principals for Detection

Column

Quartz tube(dielectric substances)

He plasma

Principle of Ionization Reaction

BID was developed thru collaborative research with Dr. Katsuhisa Kitano, Center of Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, resulting in 3 U.S. patents and 4 patents pending.

Plasma

Compounds

BID-2010 PlusCross Section Drawing

3

New Applications Using GC BID Detector

BID-2010 Plus of Tracera is a novel universal detector based on dielectric barrier plasma ionization. Tracera makes it possible to conduct many kinds of applications and achieve simple and high sensitive analysis.

1. High Sensitivity Detection Sensitivity over 100x Higher Than TCD, 2x Higher than FID

2. Novel Universal Detector Single Detector Approach for Your Complex Analyses

3. Long-Term Stability Long-Term Stability with New Discharge Design

Structure of BID

Features of BID-2010 Plus

Structure of BID

Three electrodes are placed on the quartz tube. High voltage is applied to electrodes, and plasma is generated

Compounds are ionized by plasma, and signal is collected at collection electrode

column

Quartz glass tube(Dielectric) Helium plasma

He

Low frequency power supply

High voltageelectrode

Collection electrode

First purge line

Second purge line

Plasma generation zone

Peak detection zone

The BID can replace multiple detection schemes

TCD

TCD

He carrier

Ar carrier

Analysis of O2,N2,CH4, CO

Analysis of H2

ppm levels of CO and CO2 are detected

TCDHe

Impossible to detect

FIDMTN-1He

Analysis of H2, O2, N2, CH4, CO Analysis of ppm level of CO, CO2

Using two TCDs Using a Methanizer and FID

BID will detect all of these analytes at low levels

4

New Applications Using GC BID Detector

GC-2010Plus BID with Valves

Main body of BID-2010 Plus

• Permanent gases are trapped in a MolSieve column, and then released and analyzed by BID.

• Light hydrocarbons are analyzed by the BID directly, bypassing the MolSieve column.

System I System I ChromatogramData�le Name:BID_TogasRep 005.gcdSample Name:Unknown SampleSample ID:UNK-0005

Concentration(ppm)

Hydrogen Oxygen Nitrogen Methane CarbonMonoxide

CarbonDioxide

Ethylene Ethane Acetylene

100 2500 16900 100 100 400 100 100 100

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 min

-100000

0

100000

200000

300000

400000

500000

600000

uV

MET

HA

NE

CA

RBO

N D

IOX

IDE

AC

ETY

LEN

E,ET

HY

LEN

E

ETH

AN

E

H2

O2

N2

CA

RBO

N M

ON

OX

IDE

BID1

5

New Applications Using GC BID Detector

System I Standard Repeatability

System I Hydrocarbon Standard Repeatability • Permanent gases are trapped in a MolSieve column, and

then released and analyzed by BID.• High concentration sample components are directed to

the TCD via a 4 port switching valve.

System II

System I Hydrocarbon StandardData�le Name:BID_C1-C6Rep 005.gcdSample Name:Unknown SampleSample ID:UNK-0005

Concentration(ppm)

Methane

100

Ethane

100

Propane

400

N-Butane

100

N-Pentane

100

N-Hexane

100

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 min

0

25000

50000

75000

100000

125000

150000

175000uV

MET

HA

NE

ETH

AN

E

PRO

PAN

E

N-B

UTA

NE

N-P

ENTA

NE

N-H

EXA

NE

BID1

New Applications Using GC BID Detector

Conclusions

System II Low Standard- BID System II High Standard - TCD

• The new Shimadzu GC BID is a universal, sensitive, and rugged detector that can be used in a variety of applications.

Data�le Name:DDF210-BID-11-8-13-006.gcdSample Name:HIGH GAS STDSample ID:DDF210-BID-11-8-13-006

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 min

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

uV

CO

2

C2H

4/C

2H6

C2H

2

H2

O2

N2

CH

4

CO

Data�le Name:DDF210-TCD only-11-12-13-006.gcdSample Name:High Gas STDSample ID:DDF210-TCD only-11-12-13-006

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 min-10000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000uV

CO

2

C2H

4/C

2H6

C2H

2

O2

N2

CH

4

CO

For Research Use Only. Not for use in diagnostic procedures.The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu. The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject to change without notice.

© Shimadzu Corporation, 2014

First Edition: March, 2014

www.shimadzu.com/an/

Concentration(ppm)

Hydrogen Oxygen Nitrogen Methane CarbonMonoxide

CarbonDioxide

Ethylene Ethane Acetylene

100 2500 16900 100 100 400 100 100 100Concentration

(ppm)

Hydrogen Oxygen Nitrogen Methane CarbonMonoxide

CarbonDioxide

Ethylene Ethane Acetylene

4990 125310 829675 3740 5000 20040 3750 3750 3745

BID1 TCD1