U.S. patent number 3,850,579 [Application Number 05/359,854] was granted by the patent office on 1974-11-26 for ionization current detector for chromatographic analysis.
This patent grant is currently assigned to Ceskoslovenska akademie ved. Invention is credited to Hanniel Dubsky.
United States Patent |
3,850,579 |
Dubsky |
November 26, 1974 |
IONIZATION CURRENT DETECTOR FOR CHROMATOGRAPHIC ANALYSIS
Abstract
An ionization current detector of improved efficiency includes
facilities for directing heated nitrogen gas upward against a test
sample, which is disposed on an aligned periphery of a rotary
conveyor. The gaseous product resulting when the test sample is
volatilized by the hot nitrogen is in turn sucked upward into a
partial vacuum formed in an overlying, axially aligned nozzle
having a venturi-like construction into which heated hydrogen gas
is introduced. The hydrogen gas thereby admixed with the gaseous
sample is ignited by the further application of forced air at the
output of the nozzle, and the resulting hydrogen flame ionizes the
sample. A pair of electrodes positioned above the air inlet
measures the ionization current increase in the detector caused by
the ionization of the sample.
Inventors: |
Dubsky; Hanniel (Brno,
CS) |
Assignee: |
Ceskoslovenska akademie ved
(Praha, CS)
|
Family
ID: |
5372120 |
Appl.
No.: |
05/359,854 |
Filed: |
May 14, 1973 |
Foreign Application Priority Data
|
|
|
|
|
May 15, 1972 [CS] |
|
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3259-72 |
|
Current U.S.
Class: |
422/54 |
Current CPC
Class: |
G01N
30/70 (20130101); G01N 30/68 (20130101) |
Current International
Class: |
G01N
30/00 (20060101); G01N 30/70 (20060101); G01N
30/68 (20060101); G01n 031/12 () |
Field of
Search: |
;23/254EF,232C |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Reese; Robert M.
Claims
What is claimed is:
1. In an ionization apparatus for the chromatographic analysis of a
test sample:
an elongated nozzle including a central chamber having input and
output ends and an intermediate portion, and a gas port disposed at
the nozzle periphery in radial communication with the intermediate
portion of the chamber;
means disposed in axially spaced relation to the input end of the
nozzle for directing a first heated gas axially toward the input
end of the nozzle chamber;
conveyer means for transporting a test sample to a position axially
aligned with and intermediate the directing means and the input end
of the nozzle chamber whereby the heated first gas from the
directing means volatilizes the test sample;
means for passing a heated second gas through the nozzle gas port
and into the intermediate portion of the nozzle chamber to form a
partial vacuum in the nozzle and to thereby draw the volatilized
test sample into the nozzle chamber for admixture with the second
gas; and
means associated with the output end of the nozzle chamber for
ionizing the volatilized test sample passing through the nozzle
chamber.
2. Apparatus as defined in claim 1, in which the apparatus further
comprises a pair of electrodes for sensing the ambient level of
ionized current.
3. Apparatus as defined in claim 1, in which the intermediate
portion of the nozzle chamber is constricted with respect to the
input and output ends.
4. Apparatus as defined in claim 1, in which the conveyer means is
a rotary centrifugal mechanism whose peripheral portion is aligned
with and intermediate the directing means and the input end of the
nozzle chamber.
5. Apparatus as defined in claim 1, in which the gas directing
means includes an axially aligned heated cylinder through which the
first gas is passed.
6. Apparatus as defined in claim 1, in which the apparatus further
comprises means for heating the nozzle.
7. Apparatus as defined in claim 1, in which the ionizing means
comprises means for introducing forced air adjacent the output end
of the nozzle chamber to ignite the heated second gas to form a
flame, said flame serving to ignite and ionize the volatilized test
sample.
8. Apparatus as defined in claim 7, in which the ionizing means
further comprises an auxiliary rectifying screen disposed above the
forced air introducing means.
9. Apparatus as defined in claim 8, in which the volatilized test
sample contains a material selected from the group consisting of
phosporous and the halogens, and in which the apparatus further
comprises an alkaline metal salt disposed on the auxiliary screen.
Description
BACKGROUND OF THE INVENTION
In the present designs of ionization detectors employing a hydrogen
burner for chromatographic analysis of gaseous test products, the
normal ionization current level in the detector resulting from the
hydrogen flame is increased when the gaseous test product is
ignited by the flame.
Such gaseous test product is generally introduced into the detector
on a moving linear conveyer (typically a wire) on which a test
sample is coated. Inside the detector the sample is either directly
volatilized by the hydrogen flame itself or, in more complex
designs, is volatilized first in a separate pyrometer portion of
the detector, and the resulting gaseous product is forced by a gas
stream into the hydrogen flame. In either case, the increase in
ionization current in the presence of the gaseous product is
employed for chromatographic analysis of the product in the normal
manner.
These existing schemes have several disadvantages. They tend to
have a low detection sensitivity and are susceptible to noise.
Moreover, because of their relatively small burner area and their
association with a wire or other linear conveyer, only a small
portion of the available test sample is actually ignited in the
hydrogen flame, resulting in a low efficiency; and while more
efficient mechanical conveyers such as rotary centrifugal types are
available, they are not compatible with presently known detector
designs or with convenient modifications of such designs.
SUMMARY OF THE INVENTION
The present invention contemplates an improved ionization detector
that is more sensitive, efficient and noise-free than existing
designs and that is compatible with a rotary conveyer. In one
embodiment, particularly suitable for liquid chromatography, the
detector is provided with a nozzle having an elongated central
chamber centered on a longitudinal axis of the detector. The nozzle
has a gas port in radial communication with an intermediate portion
of the chamber.
The input end of the nozzle is positioned in axially spaced
relation to, and concentric with, a heat source including a heated
cylinder through which a first gas (such as nitrogen) is directed
upward toward the nozzle. The test sample-collecting periphery of a
rotary conveyer is disposed at the longitudinal axis of the
detector intermediate the heated tube and the input of the nozzle.
In this position, the hot nitrogen directed at the conveyer
periphery volatilizes the collected test sample.
The resulting gaseous test product is sucked up into a partial
vacuum formed in the nozzle when a second heated gas (e.g.,
hydrogen) is forced through the gas port into the intermediate
portion of the nozzle, which is advantageously constricted relative
to the input and output ends of the nozzle.
The hydrogen constituent of the resulting admixture of gases in the
nozzle is ignited when mixed with air introduced into a diffusor
section coupled to the upper end of the nozzle. The resulting
hydrogen flame ionizes the gaseous test product, and the increase
in ionization current level in the diffusor is sensed by a pair of
electrodes therein.
One feature of the invention is the provision of an auxiliary
rectifying screen in the diffusor above the air inlet, such screen
serving to reduce the noise level and to maintain a uniform
hydrogen flame. Where the gaseous product contains phosphorous or a
halogen such as chlorine, an additional order of detection
sensitivity may be obtained by disposing a layer of an alkaline
metal salt on the auxiliary screen.
BRIEF DESCRIPTION OF THE DRAWING
The invention will be further set forth in the following detailed
description taken in conjunction with the appended drawing, in
which the single FIGURE depicts an improved ionization detector in
accordance with the invention for use with a rotary (centrifugal)
conveyer.
DETAILED DESCRIPTION
In the drawing, an illustrative ionization detector constructed in
accordance with the invention has a longitudinal axis 30 which is
intersected by a peripheral region of a rotary conveyer designated
as 3. Such conveyer may be arranged in a conventional manner to
rotate a column of a raw material sample (not shown) and to collect
the sample, after centrifugal action, on the conveyer
periphery.
The test sample (not shown) on the conveyer periphery is exposed to
an axial stream of a first gas from a source 31 (illustratively
nitrogen). Such gas is heated to a temperature illustratively in
the range of 200 - 800.degree.C by passing it through the interior
of a cylinder 1 which is heated via a surrounding coil 2. The
heated gas serves to volatilize the overlying test sample on the
conveyer periphery.
Disposed above the periphery of the conveyer 3 and axially aligned
with the heated tube 1 is the input end of an elongated nozzle 4
which serves as a fraction collector. The nozzle 4 has an interior
passage or chamber including an intermediate portion 32, which is
preferably constricted as shown so that the fraction collector
defines a Laval nozzle.
A second gas, illustratively hydrogen, is directed into the nozzle
4 via a tube 6. Such tube defines a gas in the nozzle which
communicates with the interior of the constricted intermediate
portion 32. The hydrogen gas thus introduced into the portion 32 is
preheated in a suitable manner to a temperature of about
500.degree.C. Such introduced hydrogen gas is transported upwardly
through the nozzle chamber and into a diffusor 7 that communicates
with the upper end of the nozzle chamber for ionizing the test
sample as described below and for measuring changes in the ambient
ionization current caused thereby.
Forced air is introduced via a tube 12 into the lower end of the
diffusor 7 to be mixed with the heated hydrogen gas, resulting in a
highly efficient hydrogen flame having a much larger burning area
(e.g., in the order of 10 mm) than burners typically used in prior
art detectors.
The hydrogen flame, which may be rectified and made more uniform by
the provision of an auxiliary screen 10 disposed in the diffusor 7
above the air inlet tube 12, results in the generation of ions of
hydrogen. The resulting ambient ionic current in the diffusor 7 (in
the absence of the test sample) is picked up by a pair of
electrodes 8,9 and passed through an amplifier 33 to a suitable
ionization current recorder 34, which may be calibrated to a
desired reference current level.
The flow of hydrogen through the inlet tube 6 and into the
constricted intermediate portion 32 of the nozzle chamber
establishes a partial vacuum therein by Venturi-type action to draw
the gaseous test sample from the conveyor 3 through the nozzle
chamber to be admixed with the introduced hydrogen. At this point,
the test sample constituent of the mixture is ignited by the
hydrogen flame. Because of the relatively large burner area
discussed above, a large part of the test sample is ionized by the
flame, resulting in increased efficiency.
The increased ionization current resulting from the ionization of
the gaseous test sample by the flame is registered in the recorder
34. Such increase, of course, has a well-known significance in the
chromatographic analysis of the test sample and will not be
discussed further here.
An enhancement of detector performance can be obtained if the
nozzle 4 is preheated to a temperature in the range of 200 -
800.degree.C. Such heating can be accomplished, e.g., by means of
an auxiliary heating coil 5 disposed around the nozzle 4.
Additionally, it has been found that when the gaseous test sample
contains a halogen or phosporous, an order of magnitude of
improvement in sensitivity can be obtained when a layer 11 of an
alkaline metal salt is disposed on the screen 10. Such layer can be
especially advantageous in another respect, since in appropriate
circumstances it can permit ionization of such gaseous products to
take place even in the absence of a hydrogen flame. Such
thermo-ionization phenomenon will of course be enhanced by the
pre-heating of the nozzle 4 via the coil 5.
Another advantageous characteristic of the described scheme is that
a high degree of noise suppression has been observed when the
auxiliary screen is used.
The electrodes 8 and 9 are shown as separate elements within the
diffusor 7. One of such electrodes may alternatively be constituted
by a portion of the detector wall (e.g., the wall of diffusor 7 or
nozzle 4, if conductive) or by an internal component of the
detector (e.g., the screen 10 or the supply tube 6, if
conductive).
In the foregoing, the invention has been described in connection
with a preferred arrangement thereof. Many variations and
modifications will now occur to those skilled in the art. For
example, such arrangements, while especially advantageous for
material analysis, can also be used for other purposes such as the
control of long-term separation processes. It is accordingly
desired that the scope of the appended claims not be limited to the
specific disclosure herein contained.
* * * * *