US3066220A - Means for the quantitative analysis of deuterium in hydrogen-containing compounds - Google Patents

Means for the quantitative analysis of deuterium in hydrogen-containing compounds Download PDF

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US3066220A
US3066220A US836529A US83652959A US3066220A US 3066220 A US3066220 A US 3066220A US 836529 A US836529 A US 836529A US 83652959 A US83652959 A US 83652959A US 3066220 A US3066220 A US 3066220A
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hydrogen
deuterium
spectrometer
line
tube
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US836529A
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Nief Guy
Botter Rene
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/22—Hydrogen, per se

Definitions

  • the invention relates to improvements in means for the quantitative analysis of deuterium in hydrogen-containing compounds.
  • a principal object of the present invention is the provision of means for quantitatively analysing deuterium in hydrogen-containing compounds which overcome the disadvantages described above and enable a high degree of accuracy to be obtained.
  • This invention consists broadly in quantitatively analysing the deuterium contained in hydrogen-containing compounds, by means of a mass spectrometer which separates ions having an atomic mass of two (i.e. that of a hydrogen molecule) from ions having an atomic mass of three (i.e. that of a molecule consisting of a hydrogen atom and a deuterium atom), the said hydrogen-containing compounds being reduced in a device known as a gas line located before the mass spectrometer and in which the actual reduction takes place in a uranium reduction oven disposed between the leak via which gas is introduced intothe spectrometer and the spectrometer itself.
  • the uranium in the reduction oven is in the form of one or more tapes or the like, of, for example, between 4 and 24 cms. long, between 1 and mms. wide, and very thin, preferably between 0.1 and 0.4 mm. thick, the said uranium being heated to a temperature of the order of 600 C.;
  • the strip or strips of reducing uranium are disposed in a U-shaped silica tube, while the remainder of the gas line preferably consists of a glass based on aluminium borosilicate and sodium, such as that commercially available under the name Pyrex.
  • the invention further comprises additional arrangements which are preferably used at the same time. They are apparent from the detailed description which follows, but the following among them will be particularly mentioned:
  • FIGURE 1 is a diagrammatic overall view of apparatus for carrying out quantitative analysis by means of a mass spectrometer
  • FIGURE 2 is a diagrammatic view of the gas line forming a part of the apparatus illustrated in FIGURE 1;
  • FIGURE 3 is an electrical circuit diagram of an arrangement incorporating the present invention adapted to give expression to the analysis carried out by the spectrometer;
  • FIGURE 4 is a graph illustrating another arrangement according to the invention adapted to make still more advantageous use of the results given by a mass-spectrometer analysing apparatus according to the invention.
  • FIGURE 1 shows a tube 1 of a mass spectrometer and details of the device for pumping out the tube 1, said device being connected to the tube 1 of the spectrometer by a pipe 4a.
  • the gas line itself is included in a rectangle gas line which conveys the gases which are to be analysed to the tube 1, a primary pump 4, which sets up the desired vacuum in said gas line, is connected thereto by a pipe 4a.
  • the gas line itself is included in a rectangle outlined at 5; its construction which comprises the use of a plurality of the features of the invention, is shown in detail in FIGURE 2.
  • the mass spectrometer used is a modification of a conventional spectrometer in which the tube 1 is curved through 60 (in technical language, such a spectrometer is said to have a 60 magnetic prism), with a mean radius of curvature of 5 cms., at the bend 6.
  • the spectrometer also comprises a source of ions 7, a source magnet 8 which focusses the ions in the source, slots 9 related to the side of the source, a main magnet 10 which imparts different deflections to the two ion beams produced, an electrical collector 11 for H? ions of mass 2, and a collector 12 for HD+ ions of mass 3; the spectrometer in question is therefore a mass spectrometer of the two-three type.
  • the tube 1 is pumped out by means of three pumps in series, i.e. a primary pump 13, which is generally of the vane type, and two mercuryditfusion secondary pumps 14 and 15.
  • the pump 14 is equipped with an ejector. It is strongly heated, and provides primary vacuum for the pump 15, which has a nominal delivery of 30 litres per second.
  • the pumping rate depends especially on the power with which the pumps are heated (and moreover that it depends thereon in a different manner for the respective molecules of H and HD, which could have unfavourable repercussions on the accuracy of measurements being carried out)
  • a gauge 17 of known type and various traps and safety devices illustrated at 18 and 19 complete the pumping unit.
  • the various pumping arrangements described enable pumping to be kept up for more than six months without interruption, the device according to the invention meanwhile remaining highly eflicient and strictly accurate in operation, without the heating of the pumps having any effect on the measurements obtained.
  • Another particular arrangement relevant to the spectrometer concerns the source of ions for the latter.
  • a filament emission current of 4 milliamperes is used, while the output slot 9 is 1.5 mm. wire; this produces a strong electric field, of approximately 50 v./cm., in the ionisation chamber of the tube 1, and, in particular, almost completely prevents the formation of H? ions, which would be undesirable since in this case measurements are only carried out on H and I-ID ions.
  • Another arrangement concerns the receiving slots which are one of the elements of the collector members 11 and 12 for each of the two ion beams and which enable the strength of the said beams to be measured.
  • these slots are made relatively wide (for example 0.5 mm.).
  • the planes of the two slots are respectively disposed perpendicularly to the mean axis of each of the two electron beams and, at least sub- Ztantially, at the focal points of the corresponding ion eam.
  • the mass spectrometer and the collectors enable the ion currents to be measured, preferably by means of an electrical circuit as shown in FIGURE 3, which will be described later. It is nevertheless important for the gaseous currents of H and HD reaching the spectrometer via the tube 3 (FIGURE 1) to have a quantitative compipe 3 which provides a connection to the mass spectrometer, comprises the following principal integers: a liquid 'nitrogen tra'p 21 of known type; four taps 22a, 22b, 22c,
  • the tap 22a serves to isolate the gas line from the vacuum-pumping device 4.
  • the tap 22b enables an inlet 25 to be placed in communication with the expansion bulb 23, while the inlet 25 enables a sample of any particular liquid hydrogen-containing compound (this will often 'the gas introduced into the oven.
  • the tap 22c enables a gaseous hydrogen-containing compound, such for example as hydrogen sulphide, to be directly introduced; for this purpose it comprises a ground inlet 26 which can be fitted to a container filled with the gas to be investigated.
  • a gaseous hydrogen-containing compound such for example as hydrogen sulphide
  • the uranium reduction oven 24 is disposed, as stated above, between the leak 27 through which the hydrogencontaining gas in introduced into the spectrometer and the spectrometer itself.
  • the uranium contained in the oven 24 is in the form of two very thin tapes 28a and 28b, each disposed in one branch of a U-shaped tube 29 which is preferably made of silica.
  • Each of the two uranium tapes has the following dimensions, length: 8 cms.; width: 2.5 mm., thickness: 0.2 mm.
  • the advantage of using such a very thin sheet of uranitun is that the time taken for the gas to become diffused in the metal, which is proportional to the square of the thickness of the latter, is reduced. Reaction equilibrium, corresponding to saturation of the metal, is thus reached in a very short time under the above conditionsapproximately a minute.
  • the hydrogen which passes out of the oven when the reducing uranium is saturated with dissolved gas has the same isotope composition as Nevertheless, the quantity of uranium metal is preferably limited to that present in tapes having dimensions of the order indicated above since the quantity of hydrogen-containing compound to be reduced is only that which gives rise to the hydrogen which must, in fact, be introduced into the ion source of the spectrometer tube.
  • the pressure of hydrogen on the metal is very low, and the time taken for the uranium to become saturated is consequently short, which acts in the same sense as the fact, indicated above, that the metal is very thin.
  • the gas line illustrated in FIGURE 2 also incorporates a further preferred feature of the invention, namely the provision of a capilliary tube on each side of the oven 24.
  • capillary tube 27 constitutes the leak through which the gas to be reduced is introduced into the oven. Suitable dimensions for the tube 27 are 10 cms. long and an internal diameter of 0.2 mm.
  • the other capillary tube 30, which is disposed between the reduction oven 24 and the spectrometer tube, is 5 cms. long and has an internal diameter of 0.1 mm.
  • a liquid for example water
  • it is introduced with the aid of a small helix 31 of platinum wire mounted on a polyvinyl plug 32.
  • Platinum is chosen because it is readily wetted by water and because it resists corrosion; moreover, it is very simply cleaned by heating the wire to red heat.
  • the plug 32 is attached to the inlet 25, and the taps 22b and 22d are opened, while the tap. 22a and 220 are closed. Opening of the tap 22d causes the Water held by the small helix 32 to vaporise in the expansion bulb 23; the latter advantageously has a volume of 250 cubic centimetres.
  • the small quantity of air (approximately 0.05 cubic centimetre) between the plug 32 and the tap 22d is, of course, simultaneously introduced into the bulb 23, but this does not involve any disadvantage, since air combines with uranium at 600 C. to give oxides and nitrides.
  • the water vapour diffused through the capillary tube 27 then passes into the oven 24, Where it is reduced to hydrogen which then passes on to the ion source of the spectrometer.
  • FIGURE 2 Two further details of the improved gas line illustrated in FIGURE 2 are as follows: one is that it is advantageously constructed, before the U-shaped tube 29, of a glass based on aluminum borosilicate and sodium, for example that known by the trade name Pyrex; the other is that the taps are advantageously heated to approximately 85 C. in order to prevent water from being absorbed on the walls (the taps are therefore preferably lubricated with a silicone grease), while the other parts of the line are heated to approximately 160 C.; such heating is conveniently effected with electric heater wires E-E.
  • FIGURES l and 2 The apparatus illustrated in FIGURES l and 2 is employed in conjunction with a device for measuring ion currents, the latter device preferably incorporating one or more of the features of the electrical circuit diagram illustrated in FIGURE 3.
  • the two ion currents produced by the source 7 in the tube 1 (which is illustrated here in a conventional simplified form), having been deflected in the tube as described above with reference to FIGURE 1, are respectively received by the collector member 11 in the case of H ions of molecular mass two and by the collector member 12 in the case of HD+ ions of molecular mass three.
  • the ion currents received by these collectors are respectively fed by connections 33a and 34a to amplifiers 33 and 34 via pre-amplifiers 33b and 34b respectively; the ratio of the output currents of the amplifiers 33 and 34 is measured by a decade box 35a, 35b and a galvanometer 36. If R is the ratio thus measured, the concentration C of deuterium with respect to H is expressed by a mathematical function of R and the output voltage V of the amplifier 33 relative to the ions of mass two, this function being:
  • f(V) and F (V) are functions which take into account certain undesirable phenomena in the mass spectrometer.
  • the constants f(V and F(V are determined by calibrating the mass spectrometer according to the invention before it is used for analyses; this calibration leads to two linear curves which are indicated at 37 and 38 in FIGURE 4. These curves are obtained by plotting the concentration C of deuterium, in the liqiud and vapour phase respectively, in a plurality of mixtures of standardised waters and hydrogen sulphide, as ordinates, against the corresponding values of the ratio R, as abscissae, the axes of the graph having an arbitrary origin.
  • the experimentally determined points on the curves 37 and 38 do not extend as far as the intersection point P, but they are graphically extrapolated to the point P.
  • the ordinate of the point P represents the actual Zero concentration of deuterium as this point represents the condition of H 8 and H 0 in equilibrium having the same concentration of deuterium, which can only happen with zero concentration of deuterium.
  • the standardised waters are obtained by mixing light water and known quantities of substantially pure heavy water.
  • the device according to the present invention is employed in the following way in order to obtain a quantitative determination of the deuterium content of the hydrogen-containing compound under investigation.
  • the ratio R is determined for different decreasing values of output voltage V of the amplifier 33, the said values being between 30 and 20 volts and being reduced by reducing the pressure in the expansion bulb 23 of the gas line by pumping out that part of the gas between the taps 22a and 22b. Each determination of the ratio R takes approximately five minutes and the results are then interpolated to obtain the reference value R of the ration R corresponding to the reference output voltage of 25 volts.
  • the device according to the invention is characterised by the possession of very appreciable advantages, more particularly the high degree of accuracy obtainable in circumstances in which such accuracy has hitherto appeared to be unattainable, other things being equal, and the relative rapidity with which such highly accurate results may be obtained.
  • the field of use of a prototype constructed as above described with reference to FIGURES 1 and 2 extends from zero to 10 parts per million of deuterium in hydrogen, and that the degree of accuracy obtained is 0.2 ppm. for concentrations of the order of a hundredth of a p.p.m., and 0.1% for stronger concentrations.
  • a mass spectrograph In an apparatus for isotopic separation by mass spectrography of hydrogen elements of hydrogen containing substances reduced prior to separation, a mass spectrograph, an ionisation chamber for said spectrograph, means for delivering a reduced hydrogen containing substance to said chamber comprising a gas line, a tubular extremity for said gas line, a leak in said extremity from said line leading to said chamber, a valve in said line, vacuum creating means connected to said valve, a second valve in said line, means for admitting hydrogen containing substances through said second valve to said line, a tubular member under low pressure connected to said extremity and to said chamber and means in said member for completely reducing the hydrogen containing substances including a reducing metal.

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US836529A 1958-08-30 1959-08-27 Means for the quantitative analysis of deuterium in hydrogen-containing compounds Expired - Lifetime US3066220A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3208826A (en) * 1961-02-23 1965-09-28 Edward M Arnett Method of analyzing water samples for deuterium content
US3944824A (en) * 1973-09-21 1976-03-16 Entreprise De Recherches Et D'activites Petrolieres Elf Method and device for sampling gases
US4766081A (en) * 1985-03-26 1988-08-23 Kernforschungszentrum Karlsruhe Gmbh Method for the qualitative and quantitative determination of the hydrogen isotopes, protium, deuterium and tritium, and system for implementing the method
US5314827A (en) * 1989-09-20 1994-05-24 Fisons Plc Isotopic composition analyzer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2486199A (en) * 1945-09-10 1949-10-25 Univ Minnesota Method and apparatus for determining leaks
US2733135A (en) * 1956-01-31 huckabay

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2733135A (en) * 1956-01-31 huckabay
US2486199A (en) * 1945-09-10 1949-10-25 Univ Minnesota Method and apparatus for determining leaks

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3208826A (en) * 1961-02-23 1965-09-28 Edward M Arnett Method of analyzing water samples for deuterium content
US3944824A (en) * 1973-09-21 1976-03-16 Entreprise De Recherches Et D'activites Petrolieres Elf Method and device for sampling gases
US4766081A (en) * 1985-03-26 1988-08-23 Kernforschungszentrum Karlsruhe Gmbh Method for the qualitative and quantitative determination of the hydrogen isotopes, protium, deuterium and tritium, and system for implementing the method
US5314827A (en) * 1989-09-20 1994-05-24 Fisons Plc Isotopic composition analyzer

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