Determination of Oxides of Nitrogen (NOx) in

Analytical Smoking Part 1 : Complexities in

Calibration Methods.
Authors
James Vincent, Ceulean, Rockingham Drive, Linford Wood East, Milton
Keynes , United Kingdom
Tim Mason: Ceulean, Rockingham Drive, Linford Wood East, Milton Keynes ,
United Kingdom
Ian Tindall, Ceulean, Rockingham Drive, Linford Wood East, Milton Keynes ,
United Kingdom

Abstract
Regulatory demands for reporting of larger numbers of analytes in tobacco
and tobacco smoke has rekindled interest in quantification of oxides of
nitrogen (NOx) in tobacco smoke. Confounding measurement accuracy is the
shortened lifetime of free NO within the tobacco smoke vapour phase matrix
and the relationship between experiment equipment design and the calibration
process.
Various arrangements have been devised where by standard smoking
machines have been converted to capture and analyse NOx using bag
systems but this approach has inherent compromises between accuracy and
simplicity. In contrast the design of commercially available analytical smoking
engines in a puff by puff manner were unsuitable for truly accurate
measurements of NOx so an optimised smoking platform was devised and
built using the chemiluminescent method for NO/NOx analysis.
The accuracy of measurement of calibration gas introduction at three points,
at analyser, through vapour path and through whole smoke path were
compared for a clean system and one where smoking had been conducted.
The influence of vapour phase condensate within the system on the
calibration and by inference the analysis of smoke vapour was investigated
and an estimate formed of the error introduced by calibration by these three
different paths.

Introduction
The calibration of any analyzer is critical to the accuracy of results and is a
key consideration in instrument design. This especially true in the case of
quantifying oxides of nitrogen generated in the smoking process due to their
short lifetime in the smoke matrix and their propensity to stick and/or react
with the inner surfaces of the smoking machine. By designing a machine
where calibration of the NO/NOx analyzer is, as far as possible, via the
smoking path, as well as by delivering gas direct to the inlet ports of the
analyzer, it has been possible to estimate the effect of calibration method on
the ultimate accuracy of the NOx analysis.

Equipment and Methods

The SM450N linear smoking machine (Figure 1) was developed for the
analysis of NO/NOx in mainstream smoke. The airflows and smoking hood
section was identical to the well characterized SM450. The puff engines are
relocated to reduce dead volume and modifications to the valves enabled the
inclusion of two puff by puff NOx analyzers, each serving 10 channels of
smoking.
The gas drawn into the puff engines is delivered to the analyzers using an
initial pulse to purge the lines and then at a controlled rate that exceeds the
analyzers draw. The analyzers were modified to incorporate an internal bypass that reduced the dead time from delivery of fresh gas to the analyzer
inlet to its first detection from 15 s to 6 s. Any gas remaining in the puff
engines at the end of the exhaust cycle is dumped rapidly to the extract. A
schematic of the valve design is shown in Figure 2

Figure 1: SM450N showing two Thermo Scientific chemiluminescence analyzers

mounted below the smoking hood

Figure 2: Valve layout schematic of SM450N

Calibration of the NO/NOx analyzers can be undertaken in two modes. The

calibration gas can be delivered either directly to the analyzer inlet port (direct
calibration) or drawn into the puff engines via ports CS1 &/or CS11 and then
pushed forward towards the analyzers as for a smoking run (smoke path
calibration). For this experiment calibration gas was also introduced via the
smoking port through a specially designed fixture to mimic the smoking
procedure as closely as possible (Figure 3).

Cylinder Gas

Figure 3: special fixture for delivering calibration gas

Experimental
Each analyzer was directly calibrated in both NO and NOx mode using either
of two calibration gases
1013 ppm NO / 7 ppm NO2 = 1020 PPM NOx

515 ppm NO / 2 ppm NO2 = 517 PPM NOx

The calibration gases were then drawn into the analyzers through the smoking
path and the special calibration path (via CS1 and CS2) and the
concentrations of NO and NOx determined. It was noted that three 55ml puffs
were needed to purge the system and achieve saturation values.
Twenty full flavor king size cigarettes were then smoked through each port
using the CI regime and vent blocking holders.
A recalibration of the analyzer was performed and the same calibration NO/
NOx introduced through the smoking path for comparison purposes.

Results
Immediately after calibration the analyzers were typically capable of reading
back the gas composition to within 2 ppm (~0.2%). The results for both
analysis of calibration gas before and after smoking when introduced through
the smoking port is shown in Figure 4.
Table 1 shows the discrepancies between measurements made when
compared to the nominal value of the gases used when the analyzer is
calibrated directly.
Table 1 : Comparison of measured values of cylinder gas
Smoking Condition
Saturation
Comment
NO/NOx Content
Before smoking cigarettes
Gas introduced via
7 ppm less than
~0.7% apparent NO/NOx
calibration manifold
cal value
loss due to calibration
(most direct path)
manifold path
Gas introduced via
14 ppm less than
~1.4% apparent NO/NOx
smoking ports
cal value
loss due to smoking path
After smoking cigarettes
Gas introduced via
30 - 40 ppm less
~3 - 4% apparent NOx loss
smoking ports
than cal value
due to smoking path - slight
evidence of greater loss of
NOx (i.e. NO2) than NO

Discussion
The smoking experiments showed that the SM450N gave yields of TNC
compatible with the SM450 range indicating that the modifications to the
puffing engines and analyzer had no influence on the smoking process or
airflows.

It can be seen from Figure 4 and Table 1 that there is only a small difference
between the measured NO/ NOx values when these are passed through the
smoking path before any smoking has taken place. After even a moderate
amount of smoking has taken place there is a significant difference between
the true concentration of NO/ NOx and that measured at the analyzer. It is
possible that this effect has not reached a maximum and could increase as
more smoking takes place or change after an interruption to use.
Figure 4: Graph showing measured calibration gas concentration when introduced
through the new calibration path and the smoking path for an analyzer directly
calibrated before and after smoking.
Puff-by-Puff NO/NOx Content Relative to the Calibration Gas
0
-10
Cal manifold - 55/30

-20

Smoking ports 1013 NO

Smoking ports 1013 NO

NO / NOx (ppm)

-30

Smoking ports 517 NOx

Smoking ports 1020 NOx
Smoking ports 517 NOx

-40

Smoking ports (Post Cig) 1020 NOx

Smoking ports (Post Cig) 1020 NOx

-50
-60
-70
-80
-90
-100
0

10

Puff Number (9 Smoking Puffs)

It is speculated that this is due to adsorption of some vapor phase chemicals

upon the smoke path. These could be physisorbed or chemisorbed and so it is
difficult to predict where these vapor phase components will adsorb or if this is
permanent or temporary state.
It is quite clear that direct analyzer calibration has the potential for
underestimating the NO/ NOx content and the magnitude of this effect is not
easily estimated from theory.
The alternate path, through the smoking engines and manifold would reduce
this effect considerably and this would be the preferred route for calibration.
The nature of the unpredictable influence of coating of the smoke path also
would demand that calibration is performed on a regular basis, at least twice
daily.

Conclusions
If a NO/ NOx analyzer is calibrated by delivering gas directly to its inlet port
then the process of smoking, which results in coating of the walls of the
smoking path, will result in an underestimation of NO/ NOx concentration in

the vapor phase by at least 3 to 4%. A better calibration scheme is to pass

calibration gas along the smoke pathway. It is also recommended that
calibrations of the analyzers are conducted at regular intervals as the
adsorption/desorption of vapor phase components is not well characterized or
understood.