1 AS 3580.5.

1—1993

Australian Standard
Methods for sampling and analysis of
ambient air

Method 5.1: Determination of oxides of

nitrogen-Chemiluminescence method

PREFACE
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This Standard was prepared by the Standards Australia Committee on Methods for
Examination of Air to supersede AS 2447 — 1981, Ambient air — Determination of
oxides of nitrogen — Chemiluminescent method. The method is technically equivalent
to ISO 7996, Ambient air — Determination of the mass concentration of nitrogen
oxides — Chemiluminescence method. This Standard differs from AS 2447 in formatting
and includes additional information in the Foreword on the species being measured,
a procedure for determining converter efficiency and schematic representations of
chemiluminescence analysers. This edition also includes a modified procedure for
calibrating the chemiluminescence analyser to determine both nitrogen dioxide and
nitric oxide.

FOREWORD

Nitrogen oxides which are produced by combustion and industrial processes, are
emitted into the air predominantly as nitric oxide (NO) and, to a lesser extent, as
nitrogen dioxide (NO2 ). In the atmosphere, chemical reactions oxidize NO to produce
NO 2 which may undergo further reaction to produce nitric acid, and various gaseous
and particulate organic nitrates. This method provides a procedure for the direct
measurement of NO, and also for the quantitative conversion of NO 2 to NO, then its
measurement as the sum of the NO and NO 2 concentrations. In addition to NO 2 , other
gaseous nitrogenous species, e.g. peroxyacetyl nitrate (PAN) and nitric acid are also
converted to NO by the analyser and therefore are also detected. The efficiency of
conversion to NO of the other species can be variable and non-quantitative.
Oxides of nitrogen (NO x), as determined by this method, is the sum of the NO and NO 2
concentrations in the air sample, plus the concentration of NO produced by the
converter from other gas phase oxidized nitrogen species in the air sample.
It is usually found that where atmospheric nitrogen dioxide concentrations reach levels
of concern to health, NO x consists predominantly of NO and NO 2 .

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 AS 3580.5.1—1993 2

METHOD

1 SCOPE This Standard sets out a method for the determination of the
concentration of oxides of nitrogen in ambient air. The method is applicable to ambient
air containing oxides of nitrogen at a concentration of less than 1 p.p.m. by volume
(less than 1 mL/m 3). The method is specific for nitric oxide (NO) but total oxides of
nitrogen (NOx) may be measured by first passing the air sample over a converter to
reduce nitrogen dioxide (NO2 ) to nitric oxide (NO). Nitrogen dioxide (NO 2 ) may then
be calculated as the difference between NO x and NO.
NOTE: Substances which interf ere with the method are those which may be converted to nit ri c oxide
including ammonia, peroxyacetyl nitr ate, organic amines and organic nitr ates and nitr it es.

2 REFERENCED DOCUMENTS The following documents are referred to in this

Standard:
AS
2922 Ambient air — Guide for the siting of sampling units
3580 Methods for sampling and analysis of ambient air
3580.2.1 Method 2.1: Preparation of reference test atmospheres — Permeation tube
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method
3580.2.2 Method 2.2: Preparation of reference test atmospheres — Compressed gas
method
3580.4.1 Method 4.1: Determination of sulfur dioxide — Direct reading instrumental
method
3 DEFINITIONS For the purpose of this Standard, the definitions given in
AS 3580.4.1 and that below apply:
3.1 Oxides of nitrogen — nitric oxide (NO) and nitrogen dioxide (NO 2), collectively
known as NO x.
4 PRINCIPLE The sample air is passed through the analyser reaction chamber
where it is mixed with an excess of ozone. The resulting chemiluminescent reaction
produces radiation proportional to the amount of nitric oxide in the sample. Total
oxides of nitrogen in the air sample is determined by converting nitrogen dioxide to
nitric oxide prior to passing the sample through the reaction chamber.
The nitrogen dioxide content of the sample air is calculated from the difference
between the total oxides of nitrogen value and the value obtained from nitric oxide
when the air sample bypasses the converter.
5 REACTIONS The detection of nitric oxide is based on the following reactions:
NO + O 3 → NO 2* + O 2
NO *2 → NO 2 + hv
NO *2 + M → NO 2 + M
Under conditions of constant absolute pressure, a fixed proportion of the excited
molecules of nitrogen dioxide (represented in the reaction equations as NO 2* reaches
the ground state by the emission of radiation at the red or near-infrared wavelengths.
The remaining excited molecules of nitrogen dioxide have their electronic energy
dissipated by collision with another molecule (represented in the reaction equation
as M).
6 APPARATUS
6.1 Chemiluminescence analyser Analysers may be of the dual-chamber or
single-chamber type (see Figure 1). In the single-chamber analyser, there is only one
reaction chamber and detector and the output alternates between nitric oxide and total
oxides of nitrogen measurements, i.e. the air sample alternately bypasses and passes
through the converter. The analyser shall meet the following performance
requirements:
(a) Performance The instrument shall conform to the performance requirements
listed in Table 1. The converter shall have a conversion efficiency of nitrogen
dioxide to nitric oxide of not less than 95% (see Clause 8.4).
(b) Interference equivalent When reading 0.08 p.p.m. oxides of nitrogen, the
instrument shall not vary by more than 0.02 p.p.m. with each of the following
concentrations of interferent gases or by more than 0.04 p.p.m. when exposed to
a combination of all the interferent gases.

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AS 3580.5.1-1993, Methods for sampling and

analysis of ambient air Determination of oxides of
nitrogen - Chemiluminescence method
This is a free 2 page sample. Access the full version at http://infostore.saiglobal.com.

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