TAKACHIHO TRADING CO., LTD.TAKACHIHO CHEMICAL INDUSTRIAL CO., LTD.

Kanako Nishi, Toshikatsu Hayase, Tsutomu Nakanoya

Jun Hashimoto, and Yusuke Yoshida

Preparation of Stable Hydrogen Chloride Standard Gases at Low Concentrations

8th APMP/TCQM Gas CRM Workshop

June 10th, 2010

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I． Background

II． Conditions to Make Low Concentration HCl Gas Standards

Ⅲ. Traceability

IV． Cylinder Treatment Methods

V． Stability Test

VI. Accuracy

VII. Conclusion

VIII．Current and Future Development Work

CONTENTS

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I. Background

Japan first passed legislation on HCl emissions in the 1960s

In 2006 Japanese Industrial Standard (JIS) revised the legislation to allow dry analytical method using gas standards

This led to:• Increased demand for HCl standard gas

• New requirements for low concentration HCl gas standards

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Ⅱ. Conditions to Make Low Concentration HCl Gas Standards

SI Traceability

Concentration Stability

(cylinder inner treatments are required)

Ⅲ. Traceabilty

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Gas Standard Preparation (SI Traceable)Preparation based on ISO-6142 （Gravimetric Method)

Analysis Method

Ion ChromatographyComparative analysis against Ion Chloride standard

solution per Japan Calibration Service System (JCSS)

III. Traceabilty (cont’d)A. Preparation of Gas Standard

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Use of high precision giant balance

Standard method based on SI Unit

Preparation of gas standard with small uncertainty and high accuracy

Model LK-100 LK-30

Maximum Capacity of Scale

100 kg 30 kg

Readability of Scale 1 mg 0.5 mg

III. Traceabilty (cont’d)B. Analysis Method

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1) Fill the glass vessel with the sample gas

2) Measure the pressure and temperature to calculate the moles (Gmol) of the sample gas

3) Add absorber liquid to the glass vessel

4) Agitate the glass vessel to absorb the HCl into absorber liquid

5) Analyze the concentration of the HCl in the absorber liquid by ion chromatography

B. Analysis Method (cont’d)

(Vol × Gatm) / (R × Gtemp ) = Gmol

(Gmol × HClc × Clg) / L = Ca

(Ca × L) / (Gmol × Clg) = HClc

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Gmol: Volume of extracted gas (mol)

Vol : Interior volume of sample cylinder (ℓ)

Gatm : Pressure of sample gas (atm)

Gtemp : Temperature of sample gas (K)

R: Gas constant (1 atm/mol K) 0.082057

HClc : Density of standard gas (mol/mol)

Clg : Molecular weight of Cl (g/mol) 35.453

L: Absorber Liquid volume (ℓ)Ca: Calculated volume of HCl in Absorbed Liquid (g/ ℓ)

Comparative analysis between standard solution and HCl 100 μmol/mol absorbed liquid

B. Analysis Method (cont’d)

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Reference Gas Concentration: 99.833 μmol/mol

Number of Samplings: 12 times

The HCl concentration in the gas standard is traceable and the analytical method is verified

Grav.Value(μmol/mol)

Analysis Value (Average)

(μmol/mol)

StandardDeviation

(μmol/mol)

99.833 98.889 1.457

T-Coat TM：Trademark of Takachiho’s unique and original cylinder inner treatment

IV. Cylinder Treatment Methods

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IV. Cylinder Treatment Methods (cont’d)Metal Coating (M.C.) and Cylinder Inner Treatments (C.I.T.)

1) M. C.

2) M. C. + Gas Aging (G.A.) (HCl)3) M. C. + T-Coat-I TM

4) M. C. + T-Coat-II TM

Concentration of HCl: HCl (90 μmol/mol) / N2

Measurement period: 180 Days

IV. Cylinder Treatment Methods (cont’d)

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Cylinder Treatment vs. Long-Term Stability

70

75

80

85

90

95

0 50 100 150 200

(days）

HC

l Con

c.

（μm

ol/m

ol）

1) M.C.

2) M.C.+G.A.

3) M.C.+ T-Coat-I

4) M.C.+ T-Coat-II

The HCl concentration in the (1) metal coating cylinder and (2) metal coating

plus gas aging cylinder declined about 10% after a few days

The HCl concentration of standard gas in the (3) metal coating plus T-Coat-I TM

cylinder declined 10% after 14 days

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The gas in the (4) metal coating plus T-Coat-II TM cylinder is very stable

T-Coat-II TM cylinder inner treatments was adopted and tested

IV. Cylinder Treatment Methods (cont’d)

70

75

80

85

90

95

0 50 100 150 200

(days）

HC

l Con

c.

（μm

ol/m

ol）

1) M.C.

2) M.C.+G.A.

3) M.C.+ T-Coat-I

4) M.C.+ T-Coat-II

V. Stability Test

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Gas: HCl/N2

Concentration: 75 μmol/mol

Number of sample cylinders: 5

Measurement period: 365 days

New gas standard:(prepared gravimetrically)

@ 3 months@ 6 months@ 12 months

V. Stability Test (cont’d)

40

50

60

70

80

90

100

0 100 200 300 400(days)

HC

l Con

c. (μ

mol

/mol

)

3

2

4

1

5

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Stable concentration for 12 months

Stability Test HCl/N2 (T-Coat-II TM)

6062646668707274767880

0246810Pressure （MPa）

HC

l Con

c. （μm

ol/m

ol）

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Pressure Dependence on HCl/N2 (T-Coat II TM)

Stable concentration between 1 MPa and 9 MPa

V. Stability Test (cont’d)

HCl / N2 T-Coat-II

HCl concentration of 100 μmol/mol was calculated using the equation below (uncertainty value of 95%)

U95 = √｛(S)2 + (A)2｝ = 2.96 μmol/mol

A : Uncertainty of analysis ± 2.9μmol/mol(Standard deviation in 30 analyses)

VI. Accuracy

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U95 : Uncertainty value

S : Uncertainty of reference gas (gravimetrical method) ± 0.6μmol/mol

VII. Conclusion

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Metal Coating + T-Coat -II TM combinedperformed the best

The HCl concentration was stable for a minimum of 12 months

The concentration was stable at the minimum cylinder working pressure of 1 MPa

SI Traceable

VIII. Current and Future Development Work

To produce even lower concentration HCl gas standards(HCl 5μmol /mol N2 balance is in development)

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Stability of HCl 5μmol /mol N2 balance

3.03.54.04.55.05.56.0

0 100 200 300 400 500

（days）

HC

l Con

c.（μm

ol/m

ol）

VIII. Current and Future Development Work (cont’d)

To continue as pioneers by staying on the leading edge of

new environmental standards

To develop and test these standards as well as new

cylinder treatment processes for other reactive gas

standards

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Tel: +81-3-3444-0231Fax: +81-3-3444-0462E-mail：info_1@takachiho.bizhttp://www.takachiho.biz

TAKACHIHO TRADING CO., LTD.TAKACHIHO CHEMICAL INDUSTRIAL CO., LTD.

Thank You For Your Attention!

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