Gas Purity Analysis

at Air Liquide
Martine Carr (Laboratory & Analysis
European Platform)
Jrme Perrin (Centre de Recherche
Claude Delorme)

Outline
ALPHAGAZ

Impurity specifications for pure gases

Examples : Air, N2, Ar, He
Relation between gas purity and GC detector in analysis

Analytical Methods

H2O and O2
H2, CO, CO2, CH4
NOx and S Compounds
ALMAX : IR diode laser hygrometry
APIX : Atm. Pressure Ion Mass Spec
Analytical services : VOC in ambient Air

Round Robin :

Inter-laboratory comparison of gas mixture analysis within

Air Liquide

Gas Purity Workshop, LNE, 8 Sept. 2003

ALPHAGAZ
2 standard
specifications of gas
purity
www.airliquide.com

Shop@Air Liquide

Gas Purity Workshop, LNE, 8 Sept. 2003

ALPHAGAZ & other Air qualities

Gas Purity Workshop, LNE, 8 Sept. 2003

ALPHAGAZ & other N2 qualities

Gas Purity Workshop, LNE, 8 Sept. 2003

ALPHAGAZ Ar qualities

Gas Purity Workshop, LNE, 8 Sept. 2003

ALPHAGAZ & other He qualities

Gas Purity Workshop, LNE, 8 Sept. 2003

Relationship between Gas Purity, GC

detectors, and level of analysis
ALPHAGAZ 2

GC detectors

ALPHAGAZ 1

Publications

CD (Sulfur)
DID or HID
PDHID

Caution: For GC columns can be

damaged by O2 or H2O:
ALPHAGAZ 2 should be used.

M. Gastiger
& B. Jurcik

ELCD

Guideline to hep
to choose the
right gas and
gas equipment
in your
laboratory;
Parts 1, 2 ,3 & 4

AED
PID
TCD
FID
ECD
NPD (N)
NPD (P)

International
Laboratory
(1999,2000)

FPD (S)
FPD (P)
FTIR
MS (SIM)

MS (Scan)
Initial
concentration
in solution
Initial molar
concentration in
gaseous phase

> 100 g/l

1 g/l

vol %

1 g/l

1 ppmv

Alphagaz 1
EQUIPMENT

1 mg/l

Pure
installation & procedures

Alphagaz 2

1 ppbv

Alphagaz 2

Highly pure
Gas Purity Workshop, LNE, 8 Sept. 2003

Ultra pure

H2 O & O2
Analysis

Target : high-purity gases in cylinders for the

laboratory & analysis, and electronics market
O2 ANALYSIS

SAMPLE

ELECTROCHEMICAL
CELL

H2O ANALYSIS
QUARTZ CELL

PURIFIER

SAMPLE
REFERENCE

DIFFERENTIAL ANALYSIS
OF WATER

H2O
trapped
Gas Purity Workshop, LNE, 8 Sept. 2003

AMETEK Model 5800

detection limit 20 ppb

CYLINDER
REFERENCE

10

H2,CO, CO2, CH4

Analysis

Target : high-purity gases in cylinders for the laboratory &

analysis, and electronics market

Trace Analytical RGA5

Sample Gas/Impurity

H2

CO

CO2

CH4

Oxygen

2ppb

1ppb

5ppb

2ppb

Nitrogen

2ppb

1ppb

1ppb

1ppb

Argon

2ppb

1ppb

1ppb

1ppb

Hydrogen

4ppb

1ppb

2ppb

Helium

2ppb

1ppb

1ppb

1ppb

Gas Purity Workshop, LNE, 8 Sept. 2003

11

NO, NO2 & NH3

Analysis

high-purity gases and low N calibration mixtures in cylinders

for the laboratory & analysis market
Environnement SA, Model AC32M
NO, NO2 & NH3 in Air
by chemiluminescence
DL ~ 10 ppb for NOx

Gas Purity Workshop, LNE, 8 Sept. 2003

12

Sulfur Compounds
Analysis

development
In partnership
with Varian
and Sievers

high-purity gases and low S calibration mixtures in cylinders

for the laboratory & analysis market
Comparison of the PFPD and Chemiluminescence Detectors for
the Analysis of Low Level Sulfur Compounds
Compound

PFPD
dL (ppb)

OCDL*

SCD
10X **

dL (ppb)

OCDL*

10X **

H2S

24.3

4.86

2.07

0.9

0.18

3.95

COS

26.7

5.34

2.10

1.3

0.26

3.94

SO2

29.4

5.88

2.10

Methyl Mercaptan

20.0

4.0

2.09

1.1

0.28

4.07

Ethyl Mercaptan

20.6

4.12

2.09

1.4

0.22

3.83

Thiophene

38.8

7.76

2.08

1.5

0.30

3.93

* OCDL : on-column detection limit for a split ratio of 5

** dynamic range
Gas Purity Workshop, LNE, 8 Sept. 2003

13

APIX

Atmospheric
Pressure
Ionisation Mass
Spectrometry
On-line analysis of major impurities -down to ppt level
in Semiconductor bulk gases N2, Ar, He , H2 and O2

Real time contamination measurements in the entire distribution

network from Source to Point Of Use
The Multigas APIX System is the result of a successful
collaboration between Air Liquide and VG Gas Analysis (ONIX)
more than 60 references over the world

Multi
Sampler

N2
He
Ar
H2
O2

API

MS

Gas Purity Workshop, LNE, 8 Sept. 2003

H2O
O2
CO
CO2

CH4
N2
others

14

ALMAX

Tunable Diode Laser Infrared

Absorption Spectroscopy

On-line analysis of water in any gas, including corrosive gases

Absolute measurement, down to ppb level
High sensitivity Hygrometer
Air Liquide technology industrialized with SOPRA

IR
laser
diode

power

HCl , HBr , HF,

NH3, NF3, SF6
He , Ar , CnHm ,

Optical
System
10m
GAS
CELL

Detection Limit :
10 ppb for H2O
(50 ppb for NH3)

Photoelectric signal
Detector

Gas Purity Workshop, LNE, 8 Sept. 2003

15

VOC
Analysis

Sampling method in Air

Analytical
Service

Canisters : no preparation, long lasting ( 6L canister ~ 1 to 8h )

Thermal extraction, cryogenic focusing, improve GC/MS sensitivity

Applications in electronics:
Clean room air monitoring
Analysis of mini-environment of tools
Clean Room

H2 O

SAMPLING

Tenax

Glass beads

Canister

CO2

Mass Spectrometry

GC MS

Cryogenic
Focuser

CONCENTRATION

SEPARATION ANALYSIS

Gas Purity Workshop, LNE, 8 Sept. 2003

16

ROUND ROBIN : inter-laboratory

comparison of gas mixture analysis
within Air Liquide
1998

1999-2000

1 mixture
CO in N2

2 mixtures
O2 in N2
CO, CO2, C3H8,
O2 in N2

11 European
laboratories
+ Canada
+ Singapore

11 European
laboratories
+ Canada
+ Singapore

2001
12 European laboratories
+ Singapore
2 mixtures
NO in N2
CH4, C2H2, C2H4,
C2H6, C3H8 in N2
12 American laboratories
(US + Canada + Brazil)
1 mixture
02, CO, CO2, C3H8
in He

Gas Purity Workshop, LNE, 8 Sept. 2003

17

Objectives of the Round Robin

Determination of the accuracy (trueness and precision) for one
specific method:

Comparison of the global mean value to gravimetric value

Determination of within laboratory variance (repeatability)
Determination of between laboratories variance
Determination of reproducibility (repeatability + between lab variance)

Assessing the performance of one laboratory

Determination of trueness and precision of each laboratory

First step for european uniformity of uncertainties

Determination of the repeatability and reproducibility is useful for the

calculation of global uncertainties
Data on repeatability and reproducibility can be used by each lab for
calculation of their own uncertainty
Identification of the main sources of uncertainty and calculation of
the combined uncertainties

Gas Purity Workshop, LNE, 8 Sept. 2003

18

Data treatment
Based on norm ISO 5725:
Description of specific conditions for interlaboratory experiments:
Use one standard measurement method
Samples have to be identical when dispatched to the laboratories
Samples have to remain identical during transport and during the time
interval before measurement
one sample per lab and short time between preparation and analysis

Description of statistical model and statistical tests used for

determination of outliers:
Cohran test, Grubbs test for outliers data
Mandels between laboratory consistency test statistic: h
Mandels within laboratory consistency test statistic : k

Using specific excel macro developed by M. Feinberg (INA) for

statistical calculations

Gas Purity Workshop, LNE, 8 Sept. 2003

19

Analysis of NO in N2
Evaluation of trueness
4

h, statistique de Mandel

Trueness:

Labo 6

3
2
1
0

Labo 1

Labo 2

Labo 7

Labo 4

Labo 8

Labo 5

-1

Labo 9

Very good trueness is observed for

all laboratories :
Except Labo 6: Outside the
acceptable range and Labo 3
(closed to the limit at 5%)
Global Mean value: 9.07 ppm
Gravimetric value: 9.12 0.08 ppm

Labo 3

-2
-3

h1%

h5%

h1%

h5%

Precision:

Evaluation of precision
k, statistique de Mandel

2.500
Labo 9
2.000

Similar variance is obtained for all

laboratories:

Labo 8

1.500

Labo 2

1.000
0.500

Labo 1
Labo 4 Labo 5

0.000

Labo 3
k

Labo 6
k1%

Labo 7

k5%
Gas Purity Workshop, LNE, 8 Sept. 2003

Except labo 9 which is above the

limit for a risk of 1% and labo 8
between both limits
Srepeatability = 0.03 ppm
Sreproductibility = 0.12 ppm

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Analysis of both mixtures

All laboratories give a value closed to the true value with few exceptions:
NO analysis: labo 6
C2H2: labo 6; C2H4: labo 10 and 11

TRUENESS OF LABORATORIES
4
3

NO
CH4
C2H2
C2H4
C2H6
C3H8

2
1
0
-1
-2

La
bo
6
La
bo
7
La
bo
8
La
bo
9
La
bo
10
La
bo
11

La
bo

La
bo

La
bo

La
bo

-3

La
bo

h of Mandel

1% risk limit

Gas Purity Workshop, LNE, 8 Sept. 2003

21

Analysis of both mixtures

The precision is different from one laboratory to the other but always below the maximum
limit with few exceptions:
labo 8 and 9: bad precision for all impurities
Labo 10: bad precision only for C2H2

PRECISION OF LABORATORIES
2.5
2

NO
CH4

1.5

C2H2
C2H4

C2H6
C3H8

0.5

Gas Purity Workshop, LNE, 8 Sept. 2003

La
bo
10
La
bo
11

La
bo
9

La
bo
8

La
bo
7

La
bo
6

5
La
bo

4
La
bo

3
La
bo

2
La
bo

La
bo

k of Mandel

1% risk limit

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Results Summary
In general the agreement between the gravimetric value
and the global analytical mean value is good within the
gravimetric uncertainty
A slight discrepancy between gravimetric value and global
analytical mean value has helped identifying a problem
with a C2H2 source
Corrective measures are taken for laboratories outside of
acceptable limit of deviation from global mean value
The regular and systematic practice of these internal
"Round Robin" is continued

Gas Purity Workshop, LNE, 8 Sept. 2003