U.S. patent number 3,812,355 [Application Number 05/206,353] was granted by the patent office on 1974-05-21 for apparatus and methods for measuring ion mass as a function of mobility.
This patent grant is currently assigned to Franklin Gno Corporation. Invention is credited to David I. Carroll, Martin J. Cohen, Wallace D. Kilpatrick, Roger F. Wernlund.
United States Patent |
3,812,355 |
Wernlund , et al. |
May 21, 1974 |
APPARATUS AND METHODS FOR MEASURING ION MASS AS A FUNCTION OF
MOBILITY
Abstract
Ion mass is determined directly as a function of the drift time
in a chamber containing gas at atmospheric pressure. The drift time
is a function of approximately the cube root of the ion mass for
ion mass greater than the mass of the drift gas and a function of
approximately the square root of the ion mass for ion mass less
than the mass of the drift gas. A measure of the ion mass may be
obtained by recording the ion-current output of the drift tube with
the time base adjusted to an exponential function of the drift
time. Corrections may be made automatically for variations in
temperature, pressure and drift field.
Inventors: |
Wernlund; Roger F. (Lake Worth,
FL), Carroll; David I. (Lantana, FL), Kilpatrick; Wallace
D. (North Palm Beach, FL), Cohen; Martin J. (West Palm
Beach, FL) |
Assignee: |
Franklin Gno Corporation (West
Palm Beach, FL)
|
Family
ID: |
22765986 |
Appl.
No.: |
05/206,353 |
Filed: |
December 9, 1971 |
Current U.S.
Class: |
250/283 |
Current CPC
Class: |
G01N
27/622 (20130101) |
Current International
Class: |
G01N
27/64 (20060101); H01j 039/34 () |
Field of
Search: |
;250/41.9TF,41.9SE,41.9G,41.9S |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lawrence; James W.
Assistant Examiner: Anderson; B. C.
Attorney, Agent or Firm: Semmes; Raphael
Claims
1. In a method wherein ions are caused to drift through a drift
space containing a drift gas of known mass and at a pressure
sufficient to ensure that the length of the mean free path of said
ions in said space is substantially less than the dimensions of
said space, the improvement for producing a measure of ion mass
which comprises producing an output which varies approximately as a
cube function of the drift time for ion masses
2. A method in accordance with claim 1, wherein said output is
produced approximately as a square function of the drift time for
ion masses less
3. A method in accordance with claim 1, wherein the ions are
produced by ion-molecule reactions in a reaction space maintained
at a pressure such that the length of the mean free path of the
ions is substantially less
4. A method in accordance with claim 1, wherein the pressure is
such that the ions reach substantially constant statistical drift
velocity in the
5. A method in accordance with claim 1, wherein the ions are caused
to drift in said space by the application of an electric drift
field thereto.
6. A method in accordance with claim 5, wherein the producing of
said output comprises producing an ion current at a time delayed
with respect
7. A method in accordance with claim 6, wherein the producing of
said output comprises making a recording of said ion current along
a time base
8. A method in accordance with claim 7, wherein the time base
varies as a function of the temperature and pressure of the gas in
said space and the
9. A method in accordance with claim 6, wherein said ions are
segregated in accordance with their mobility in the drift space and
the ion current is
10. A method in accordance with claim 8, wherein the segregating of
the ions comprises gating a group of ions into the drift space and
later
11. In apparatus including a drift chamber, means including a pair
of spaced electrodes for producing a drift field in said chamber,
means providing a drift in said chamber at a pressure such that the
length of the mean free path of ions in said chamber is
substantially less than the dimensions of the drift space between
said electrodes, means for providing ions adjacent to one of said
electrodes, means for producing an ion current in response to ions
adjacent to the other electrode, the improvement which comprises
means for producing an output measure of ion mass in response to
said ion current as an exponential function of the
12. Apparatus in accordance with claim 11, said function being
initially approximately a square function of the drift time and
then being
13. Apparatus in accordance with claim 11, said function being
14. Apparatus in accordance with claim 11, said output producing
means comprising a recorder having a time base which varies in
accordance with
15. Apparatus in accordance with claim 11, wherein said function
includes factors corresponding to the temperature and pressure of
said gas and the
16. Apparatus in accordance with claim 11, said output producing
means
17. Apparatus in accordance with claim 16, wherein said potential
generating means comprises means for producing a ramp voltage and
an
18. Apparatus in accordance with claim 17, wherein said function
generator
19. Apparatus in accordance with claim 17, wherein said drift
chamber has means for initiating a drift period synchronously with
the commencement of
20. Apparatus in accordance with claim 17, further comprising means
for producing a voltage proportional to the drift field, means for
producing a voltage proportional to the absolute temperature of
said gas, means for producing a voltage inversely proportional to
the absolute pressure of said gas, and means for obtaining the
product of said voltages and
21. Apparatus in accordance with claim 17, said output producing
means comprising a recorder having orthogonal coordinate axes, one
of which is a time base axis, means for controlling the time base
in accordance with the output of said function generator, and means
responsive to the ion current
22. Apparatus in accordance with claim 11, wherein said ion
providing means comprises means including an ion source adjacent to
said one electrode for
23. Apparatus in accordance with claim 11, wherein said chamber has
a pair of ion gates spaced apart between said electrodes and means
for opening and gates sequentially, whereby ions produced adjacent
to said one electrode are admitted to the space between said gates
and become segregated in accordance with their mobility and whereby
a portion of the segregated ions is passed by the second gate to
the other electrode.
Description
BACKGROUND OF THE INVENTION
This invention relates to Plasma Chromatography and is more
particularly concerned with the measurement of ion mass directly
from a Plasma Chromatograph chamber operating at atmospheric
pressure.
The basic concepts of Plasma Chromatography are now well-known.
See, for example, "The Plasma Chromatograph", Research/Development,
March, 1970. In the Plasma Charomatograph, which preferably
operates at atmopsheric pressure, product ions are produced by
ion-molecule reactions, and the ions are caused to drift in an
electric field toward a detector, becoming segregated in accordance
with their mobility in the drift field. The output of the Plasma
Chromatograph may be a recording in which ion species are
represented by the peaks of a curve of ion current versus drift
time. In order to measure the mass of the ion species, it has been
necessary to inject ions from the Plasma Chromatograph chamber into
a conventional mass spectrometer (lacking the usual ion
source).
BRIEF DESCRIPTION OF THE INVENTION
It is a principal object of the present invention to provide a
measure of ion mass directly from the Plasma chromatograph.
Another object of the invention is to provide a method and
apparatus for measuring the mass of trace molecules at atmospheric
pressure.
Still another object of the invention is to provide apparatus and
method for measuring the mass of molecules over a very wide range,
and up to the order of 5,000 to 10,000 atomic mass units.
A further object of the invention is to provide simple
instrumentation for measuring the mass of molecules on a linear or
logarithmic scale.
A still further object of the invention is to provide
instrumentation of the foregoing type in which variations due to
pressure, temperature, or drift field changes may be compensated
automatically or manually.
Briefly stated, in a preferred embodiment of the invention trace
molecules are converted to ions by ion-molecule reactions and are
subjected to a drift field in a chamber containing a drift gas at
atmospheric pressure. The ions are segregated in accordance with
their mobility in the drift field and are collected to produce an
ion current, pulses of which correspond to ion species of different
mobility. By recording these pulses with respect to a time base
which varies exponentially as a function of drift time, a direct
measure of the mass of the molecules (ions) is obtained.
BREIF DESCRIPTION OF THE DRAWINGS
The invention will be further described in conjunction with the
accompanying drawings, which illustrate preferred and exemplary
embodiments, and wherein:
FIG. 1 is a block diagram of a system in accordance with the
invention;
FIG. 2 is a somewhat diagrammatic longitudinal sectional view of a
Plasma Chromatograph drift chamber;
FIG. 3 is a waveform diagram illustrating the output of the Plasma
Chromatograph as a function of drift time;
FIG. 4 is a graphical diagram illustrating the relationship of
drift-mass and reduced mobility in accordance with the
invention;
FIG. 5 is a graphical diagram illustrating the relationship of
drift-mass and time of drift in accordance with the invention;
and
FIG. 6 is a waveform diagram illustrating the output of an
instrument of the invention from which drift-mass can be read
directly.
A basic Plasma Chromatograph chamber 10 is shown in FIG. 2 and
comprises an envelope 12 containing a pair of spaced electrodes 14
and 16 adjacent to opposite ends of the envelope, the electrodes
being separated by several centimeters, for example. An inlet 18 is
provided adjacent to electrode 14 for the admission of a sample,
and an outlet 20 is provided also. An ionizer 21 is provided
adjacent to electrode 14 and may comprise a tritium film supported
on the electrode, for example. A sample, which may comprise a host
gas, such as air at atmospheric pressure, containing trace
molecules, such as DMSO, is admitted by the inlet 18, passes the
ionizer 21, and leaves the envelope by way of the outlet 20.
Reactant ions of a reactant gas, which may be part of the sample,
are produced by the ionizer, and product ions of the trace
molecules are formed as the result of ion-molecule reactions
involving the reactant ions. The length of the mean free path of
the ions is very much less than the dimensions of the reaction
region.
An electric drift field is established between electrodes 14 and 16
by a high voltage power supply. The polarity of the field is
selected to cause the ions to drift from the reaction region
adjacent to electrode 14 toward the collection region at electrode
16. A non-reactive (inert) gas, such as nitrogen, is admitted to
the chamber by an inlet 22, leaving the chamber by way of outlet
20. The drift gas fills the drift region between a pair of spaced
shutter grids 24 and 26, the first of which is in the vicinity of
the electrode 14 and the second of which is adjacent to the
collector electrode 16. Each grid comprises a pair of coplanar,
interdigitated, parallel-wire grid sections, whereby alternate
wires of the grid may normally be held at equal and opposite
potentials with respect to a grid average potential, which may be
applied to the grids from taps of a voltage divider across the high
voltage power supply. Uniformity of field between the electrodes 14
and 16 may be maintained by a series of guard rings (not shown)
also connected to taps of the voltage divider.
A mixed ion population, represented by the letters A, B, and C in
FIG. 2, is presented to the first shutter grid 24 from the reaction
region between electrode 14 and shutter grid 24. At a predetermined
time the shutter grid is opened, by driving each of the grid
sections to the grid average potential, and remains open long
enough to pass a group of ions to the drift region between the
grids 24 and 26. The various ion species, A, B, and C, become
segregated in the drift region in accordance with their mobility,
each species reaching substantially constant statistical drift
velocity characteristic of the ion species. The separate species
may then be passed to the collector 16 by opening the second
shutter grid 26 at an appropriately delayed time with respect to
the opening of the first shutter grid 24. The collector may be
connected to an electrometer, for example, which integrates the ion
current over successive cycles. By scanning the time of opening of
grid 26 relative to grid 24, substantially the entire ion
population within the drift region may produce output pulses as a
function of drift time as shown in FIG. 3.
The Plasma Chromatograph has very high sensitivity for the
detection of trace molecules capable of engaging in ion-molecule
reactions, but in the past it has been necessary to employ a
conventional mass spectrometer in tandem with the Plasma
Chromatograph chamber in order to determine the mass of the
molecules (ions). In accordance with the present invention,
however, it has been discovered that a measure of the mass can be
taken directly from the Plasma Chromatograph output, thereby making
it possible to perform mass measurements at atmospheric pressure
and avoiding the need for the complexity and high vacuum of the
mass spectrometer. The term "drift-mass" will be utilized herein to
connote the measured ion mass, to account for the fact that in some
instances the measured mass may be affected by the molecule
configuration. The term "reduced mobility" connotes the measured
mobility normalized to standard temperature and pressure
conditions.
As shown in FIG. 4, it has been discovered that there is an
exponential relationship between the drift mass (expressed in
atomic mass units) and the reduced mobility K.sub.o. When the ion
mass M.sub.i is less than the mass of the drift gas M.sub.o, the
mobility approaches a Langevin polarization dependence, K.sub.0
.about.(M.sub.r).sup..sup.-1/2, where M.sub.r is the reduced mass
defined by 1/M.sub.r = 1/M.sub.i + 1/M.sub.0. For M.sub.i greater
than M.sub.o, the reduced mobility K.sub.o approaches an inverse
cubic dependence, K.sub.0 .about.M.sub.i.sup..sup.-1/3. This is
illustrated by the curve of FIG. 4 (where drift mass is on a
logarithmic scale), the portion to the right of the vertical line
being in accordance with the square root relationship and the
remainder of the curve, to the left of the vertical line, being in
accordance with the cube root relationship. The region where
M.sub.i = M.sub.o is a transition region. Where the drift air or
nitrogen at atmospheric pressure, it has been discovered that the
square root relationship holds up to M.sub.i .about.50 to 100 AMU,
and that above this, the cube root relationship exists. Since the
time of drift is inversely proportional to the reduced mobility,
the same relationship may be shown in terms of drift mass versus
time of drift as in FIG. 5 (drift-mass being shown on a linear
scale).
FIG. 1 illustrates a system of the invention for obtaining a direct
readout of drift mass. In effect, this system converts the drift
time axis of FIG. 2 to a drift-mass axis. The Plasma Chromatograph
chamber 10 (previously described) has its output connected to the
electrometer 28, which integrates the ion current as described
previously. The output of the electrometer is connected to the
Y-axis input of an X-Y recorder 30 which is employed to produce the
direct readout of ion current versus drift mass as shown in FIG. 6.
In order that the Y-axis ion current pulses from the electrometer
28 may be positioned along the X-axis so as to produce a direct
readout of drift mass, d.sub.pc, a time base v.sub.3 must be
generated in accordance with the equation:
v.sub.3 = f(k/K.sub.o) = d.sub.pc
such that the time base varies as a square function of drift time
for M.sub.i less than M.sub.o and as a cube function of drift time
for M.sub.i greater than M.sub.o (k being an arbitrary constant).
If the mass of the drift gas is low enough, the molecules of
interest may have a mass greater than that of the drift gas and the
cube function alone may suffice.
The reduced mobility K.sub.o is related to the electric field E
(volts per centimeter), drift length L (centimeters), absolute
temperature T (degress Kelvin), absolute pressure P (Torr) and
drift time t (seconds) by the relationship
1/K.sub.o = E/L .times. T/273 .times. 760/P .times. t.
Thus, to obtain the voltage v.sub.3, the factors E, L, T, P, and t
must be considered.
As shown in FIG. 1, a ramp voltage v.sub.1 = kt is obtained from
the Plasma Chromatograph controller 32. This is a ramp voltage
generator synchronized with the pulse which opens the first shutter
grid 24 of the Plasma Chromatograph chamber. Each time the shutter
grid 24 is opened, the ramp voltage generator commences the
generation of a ramp voltage v.sub.1, the amplitude of which varies
as a linear function of time t. The ramp voltage v.sub.1 is applied
to one input of a multiplier 34, the other input of which is a
voltage equal to
E/L .times. T/273 .times. 760/P. This voltage is obtained as
follows: A voltage E/L is derived from a voltage divider comprising
reisitors 36 and 38 connected in series across the high voltage
power supply 40 from which the drift voltage V is obtained. If the
applied voltage to the chamber is V (volts) and the overall length
of the chamber between the electrodes 14 and 16 is L.sub.1
(centimeters) then E/L = V/L.sub.1 L, and resistors 36 and 38 are
adjusted in value to produce the voltage E/L at the voltage divider
tap. This is applied as one input to a multiplier 41. The other
input is a voltage equal to T/273. This voltage is obtained by
applying the voltage output of an absolute temperature transducer
42 to a voltage divider comprising resistors 44 and 46 in series,
the values of which are adjusted to produce the voltage T/273 at
the divider tap. The absolute temperature transducer measures the
absolute temperature of the gas in the Plasma Chromatograph
chamber. Any conventional temperature transducer which produces an
output voltage which varies linearly with absolute temperature may
be employed. The product output of multiplier 41 is a voltage E/L
.times. T/273, and this is applied as one input to a multiplier 48,
the other input of which is a voltage equal to 760/P. This voltage
is obtained by applying a voltage P, the output of an absolute
pressure transducer 49, to a divider 50, the other input of which
is a voltage equal to 760. The pressure transducer measures the
pressure of the gas in the Plasma Chromatograph chamber and may be
any conventional absolute pressure transducer producing an output
voltage which varies linearly with pressure.
The product output of multiplier 48 is the voltage
E/L .times. T/273 .times. 760/P ,
which is applied to multiplier 34.
The product output of multiplier 34 is a voltage
v.sub.2 = kt .times. E/L .times. T/273 .times. 760/P .
This is applied to a diode function generator 52, which generates
the voltage v.sub.3 referred to previously.
The multipliers and dividers referred to above may be operational
amplifiers connected to muliply or to divide. The function
generator 52 may be an operational amplifier diode function
generator, the successive sections of which may be adjusted to
approximate many arbitrary functions. The multiplier or the divider
may be a Teledyne Philbrick Nexus Model 4450 or Model 4452, or Burr
Brown Model 4029/25 or Model 4030/25. The diode function generator
may be a Burr Brown Model 4062/45 or a Teledyne Philbrick Nexus
Model SPFX.
The diode function generator may be set empirically so as to
produce an X-axis time base which varies in the manner set forth
above. Thus, test runs may be made with known ion species and a
plot of drift mass (known) versus time of drift (measured) obtained
as in FIG. 5. The function generator 52 may then be adjusted to
modify the time base so that the ion current pulses (Y-axis) are
produced at times linearly (or logarithmically, if desired)
proportional to drift mass, as indicated in FIG. 6.
If desired, one or more of the functions providing automatic
correction of electric field, temperature, or pressure may be
replaced by a calibrated potentiometer, which may be manually set
to the proper value corresponding to the condition in the plasma
Chromatograph chamber, by breaking the circuit at point A, B, or C
and substituting the appropriate manually set voltage. The unused
portions of the circuit would then be replaced by the appropriate
voltage, temperature, or pressure indicator.
From the foregoing, it is apparent that the invention permits a
measurement of drift mass by a Plasma Chromatograph directly.
Empirically, it has been found that reduced mobility is
characteristic of the mass of each ion species when measurements
are performed at 760 Torr and E/P.about.0.5 volts/Torr-centimeter.
The relationship between ion mass and reduced mobility extends to
very high ion mass values, of the order of 10,000 AMU. The
measurement of drift-mass in accordance with the invention produces
highly useful data which may be used in conjunction with other
data, such as the output of a gas chromatograph or the output of
another Plasma Chromatograph drift-mass instrument using a
different drift gas. By employment of such a family of
instrumentation, chemical identification is possible.
In some instances two molecules of identical mass but of different
atomic arrangement may result in different mobility measurements.
Where the mass of the ion is the same as or double the drift gas
mass, spurious ion-molecule resonance effects can affect the
results. Therefore, the ion mass may be considered as lying in a
band centered on the drift mass-mobility calibration curve rather
than directly on the curve.
Resolution may sometimes be improved by employing a heavier drift
gas then a drift gas such as nitrogen, for example. With nitrogen
as the drift gas (molecular weight 28), an ion with the molecular
weight of 10 times this (280) loses drift-mass resolution from a
molecule of, say, 300 AMU, because the curvature of the drift-mass
calibration curve at the heavier masses has a steeper slope as
compared to the lighter masses, which are near the drift gas mass.
If, however, the drift gas is raised in weight to, say, 146
(SF.sub.6), then the same effect on resolution would not be
observed until 10 times this weight or mass, or until about 1,500.
Resolution of even heavier masses may be possible with the freons
as drift gas. Xenon is another suitable drift gas.
While preferred embodiments of the invention have been shown and
described, it will be apparent to those skilled in the art that
changes can be made in these embodiments without departing from the
principles and spirit of the invention, the scope of which is
defined in the appended claims.
* * * * *