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NIELSEN 721
MAGNETIC ANALYSIS OF NEGATIVE IONS IN MERCURY
VAPOR
BY WALTER M. NIELSEN*
BARTOL RESEARCH FOUNDATION, FRANKLIN INSTITUTE
vawilm
0 2 Cmn
C/ec t rometer
0 cl
EJ aL . fetnholIz
Col/s
FIGURE 1
Diagram of apparatus.
current to G is plotted along the ordinate and the ratio of the mass (m)
of the charged particle to the charge (e) carried by the particle is plotted
along the abscissa. Such effective values of m/e were calculated from a
knowledge of the radius of curvature of the ion path, the applied voltages
and the magnetic field intensities as measured by a Grassot fluxmeter.
In these runs, the drawing out potential (Vc) was 20.2 volts and the ac-
celerating potential (Va) for ions was 54.8 volts. The driving potential
for electrons was 70 volts. The maximum value of the magnetic field
intensity employed in the runs was 2000 gauss. The height of the Hg+
724 PHYSICS: W. M. NIELSEN PROC. N. A. S.
peak has been reduced by dividing the ordinate of the three points near the
maximum by a factor of two so as to make evident some of the smaller peaks.
The negative ion currents observed by reversing all accelerating voltages
and the direction of the magnetic field are indicated by the crosses. The
magnitude of the negative ion currents should be divided by a factor of
800 in comparing them with the positive ion currents.
We ascribe to mercury the negative ion peak which appears at a value
of m/e equal to 200. Within the accuracy of the determination it has the
same effective value of m/e as
I- Hg+. The pressure range over
r
I9g which the apparatus was capa-
ble of giving reliable data was
limited at higher pressures by a
7 - positive space charge as already
indicated. It is also of interest
-t 64 to point out that it was nec-
essary to cool the jacket for sev-
Aso-ffi<
_ _ _ l eral hours before beginning a
<> run in order that the space be-
-P - -I tween the slits and the analyzing
v6 l l l region was relatively free of
-tl. l__ - __mercury vapor. In this respect
the behavior of the negative
____ ions was markedly different
-_ ___- - T r from that of the positive ions.
___\ Apparently such ions are either
- 7E< of low stability or have a large
collision area or possibly both.7
0= D to120/6O ; 0V0 The ion which has a value of
FIGURE 2
mi/e equal to 29 is probably due
to carbon monoxide (m/e = 28)
Analysis of positive and negative ions. since the resolving power of the
apparatus was not sufficient to
separate ions for which m/e differs by one unit in this region. This
impurity is quite frequently observed in work on positive ion analy-
sis.6'8 The ion having an m/e value of 12 is undoubtedly due to carbon,
probably produced by ionization of carbon, monoxide. A similar ion is
observed in the work of Hogness and Harkness,9 in their work on the
ionization of carbon monoxide.
The ions which have effective values of m/e of 19 and 60 have not been
identified with certainty. Water vapor is suggested as the origin of the
former.
All of the above ions appear in the analysis of the positive ions as well
VOL. 16, 1930 PHYSICS: W. M. NIELSEN 725
as in the negative ion analysis. The failure of others who have made a
search for negative ions, as here reported, may have been due to the forma-
tion of positive ion sheaths., It is very possible that the presence of such
sheaths may throw doubt upon the interpretation of results obtained by
positive ion analysis, unless such sheaths are recognized or avoided. It is
also necessary in considering the ability of the present apparatus to detect
negative ions to recall that slow electrons present in the beam as a result
of inelastic collisions or as secondary electrons are constrained to remain
there by the collimating magnetic field for a larger period of time than in
the methods used heretofore. That slowly moving electrons are present
in the electron beam is indicated by the abundance of the CO and CO+
ions as determined by the areas under their respective peaks. An inspec-
tion of the curves leads to the conclusion that the number of CO- ions is
approximately 1/100 of the number of CO+ ions, a ratio much greater than
would be expected from a consideration of the magnitude of the attach-
ment constant (average number of impacts between electrons and mole-
cules of a gas which result in one attachment to form a negative ion) and
the efficiency of ionization of similar gases, unless a large number of slowly
moving electrons are present in the beam. Because of this fact, a calcula-
tion of the attachment constant for mercury from the known pressure
total electron current and negative ion current becomes meaningless.
We may, however, avoid this difficulty, and, by making what appear to be
fairly justifiable assumptions, calculate a value for the attachment constant
for mercury.
We first assume that the efficiency of ionization of carbon monoxide to be
of the same order of magnitude as that of N210 at the same electron energy.
A knowledge of the abundance ratio of Hg+ and CO+ ions may be obtained
by a measurement of the respective peak areas properly corrected to take
account of the effective slit width for the two types of ions.6',1 This
abundance ratio, together with the known partial pressure of mercury,
the efficiency of ionization of mercury, and the assumed efficiency of
ionization of carbon monoxide lead, by a simple calculation to a value of
3.6 X 10-6 mm. of mercury for the partial pressure of CO present as an
impurity in the experimental tube. 12
Our knowledge of the attachment constants are limited to pressures very
much greater than those employed here, and because of lack of knowledge
of the mechanism of the attachment process, the effect of de-attachment,
etc., an extrapolation to a very low pressure may not be justified. It is
of interest, however, to make such an extrapolation and from the ratio
of ion currents, the partial pressures of mercury and carbon monoxide, as
estimated above, to calculate the order of magnitude of the attachment
constant for mercury. The value1 of the attachment constant n for car-
bon monoxide is 1.6 X 108.
726 PHYSICS: W. M. NIELSEN PROC. N. A. S.
where n is the total number of charges with paths having radii between P1 and p. The
integral required in order to compare the abundancies of two different types of ions is
2H dn dP ~~d(HA).
I -
H2 dp d(H2)
I
dp
If we assume that is a constant over the region of integration corresponding to a
d(Hl)
single peak
VOL. 16, 1930 PHYSICS: DR YDEN A ND HILL 727
[I = dp A
d(H2)
From the equations of motion we have
H2p2 = and d-
d(H2)
= (constant) m,
=-
Hl
and therefore
]= A1 (constant) -.
We conclude that the areas of the peaks due to the different kinds of ions should be
divided by the corresponding value of m/e in comparing ion abundancies.
12I+ = RIP g where +' represents the ratio of the abundance of positive mer-
co Pco PCO Ico
cury ions to positive carbon monoxide ions as measured, pHg and Pco represent the
partial pressures of mercury and carbon monoxide, respectively, and Pig and Pco
represent the probabilities of ionization by impact between electrons and mercury atoms
and between electrons and carbon monoxide molecules, respectively.
13L. Loeb, Kinetic Theory of Gases, p. 513.
14 Ico = nlg Pco where - represents the ratio of the abundance of carbon mon-
Ijjg nCO PHg IHg
oxide negative ions to mercury negative ions, nHg and nco represent the attachment
constants for mercury and carbon monoxide, respectively, and where pg and Pco
are defined as in note 13.