
this field. Only ions having a charge-to-mass ratio that corresponds to a given
radio frequency reach an orifice at the end of that path and pass into an electron
multiplier, whose signal is proportional to the number of incoming ions.
Such instruments deliver a signal for each molecule having a given charge-
to-mass ratio. A given molecule may give several signals at different radio
frequencies, since ionization may often break the molecule into several ions.
For example, water vapour gives a peak not only at mass 18 (H
2
O
þ
), but also
at mass 17 (HO
þ
), 16 (O
þ
), 2 (H
þ
2
) and 1 (H
þ
). The electric current is propor-
tional to the concentration, but the sensitivity depends on the analysed gas.
Characteristics of mass spectrometers:
.
Analysable tracers – any tracer that can be distinguished from the normal
components of air. Confusion may occur if the molecule or a part of it has
the same charge-to-mass ratio as components of air. Exampl es are shown
in Table 7.5.
.
Sensitivity – 2 10
6
for tracers with low background concentration.
.
Interfering gases – any gas present in the sample may interfere with another,
but it is nevertheless possible to analyse up to seven tracers without there
being too much interference from the gases in the air or between the tracers
themselves.
.
Analysis time – a few milliseconds.
.
Accuracy – 1 per cent.
Table 7.5 Tracer gases most used in the mass spectrometer technique
Gas Ions Mass
Comments
SF6 SF
þ
5
127
SF
þ
51 7.6% of mass 127 peak. Interferes with Freon 22
Freon R22 CHF
þ
51 Interferes with SF
6
CHClF
þ
69 2.1% of peak 51. Interferes with R14 and R13B1
CHCl
þ
2
85 1.5% of peak at mass 51. Interferes with R12
Freon R12 CClF
þ
2
85 Freon R13B1
CF
þ
3
69
Freon R12B2
þ
CF
2
Br
þ
120 Not commonly available
n-Butane C
4
H
þ
10
58 Flammable above 2% concentration
C
3
H
þ
7
43
He He
þ
4 5.24 ppm background concentration
Ne Ne
þ
20 Expensive, 18 10
12
background concentration
Ar Ar
þ
40 Background of 1%. Not a tracer but a good
reference
Note:
Mass-to-charge ratio of the most common isotopes singly charged.
Source: Sherman and Dickerhoff, 1989.
Common Methods and Techniques 145
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