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    US3607076

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    Nitric acid literature

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    US3607076

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    saad
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    Nitric acid literature

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    US3607076[1]

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    Nitric acid literature

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    US3607076

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    Nitric acid literature

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    United States Patent [72] Inventors 7.0. Paine ‘Acting Administrator of the National ‘Aeronautics and Space Administration with respect toan invention of; Raffaele F. Muraca, Los Altos Hill, Calif, [21] Appl.No. 800,204 (22) Filed Feb. 18,1969 145] Patented Sept. 21,1971 [54] PROCEDURE AND APPARATUS FOR DETERMINATION OF WATER IN NITROGEN TETROXIDE 7 Claims, 3 Drawing Figs. (52) Us.ct + 23/230R, 23/252 C, 33/253 PC, 73/23.1 (51) Inte. seseseGOIn 31/08, Goin3i/i2 [50] Field ot Search, 23/230, 232, ‘C,253 PC; 73/23.1 00 3,607,076 (56) References Cited UNITED STATES PATENTS 3,224,499 12/1965 Reinecke. 7313.1 3,356,458 12/1967 Steinle etal. 23/230 3,428,432 2/1969. Stauntonetal... 23/253 PC X Primary Examiner—Morris 0. Wolk Assistant Examiner—R. M. Reese ‘Auorneys—I.H. Warden, Monte F, Mott and G. T, McCoy ABSTRACT: Nitrogen tetroxide is analyzed for water content by passing it through hot copper contained in a column ‘wherein al nitrogen and hydrogen containing compounds are ‘converted quantitatively to nitrogen and water. The resultant ‘material from the column is then passed into a gas chromato- graph whereupon the amount of water initially contained in the nitrogen tetroxide can be determined. Po concen 3,607,076 300034 SHEET 1 OF 2 6 PATENTED SeP2 1 187, V3 a wus a us | 0018 vcr are -oumouno v0 e INVENTOR, RAFFAELE F MURACA PATENTED sere 1 i971 3,607,076 SHEET 2 OF 2 PERCENT HQ ADDED. Qu10 __020 | 8 WATER PEAK HEIGHT — INCHES 6 yo aw ow 30 TOTAL HYOROGEN, AS PERCENT "WATER CONTENT" FIG.3 INTENSITY INVENTOR. Lig hit srorler T 2 RETENTION TIME — MINUTES 3,607,076 1 PROCEDURE AND APPARATUS FOR DETERMINATION ‘OF WATER IN NITROGEN TETROXIDE, ORIGIN OF THE INVENTION ‘The invention described herein was made in the per- forn...ce of work under a NASA contract and is subject to the provisions of section 305 of the National Aeronautics and Space Act of 1958, Public Law 83-568 (73 Stat. 435; 42 USC 2457). BACKGROUND OF THE INVENTION 1. Field of the Invention ‘This invention isin the field of gas detection and more par- ticularly i related to the detection of water in nitrogen tetrox- ide. 2. Description of the Prior Art Nitrogen tetroxide, N,O,, isan important rocket propellant. Small amounts of water may remain dissolved in nitrogen tetroxide for some time at 0 C. However, itis generally recog nized that within a short period of time, essentially all water is converted to a mikturo of nitric acid, nitrous acid and dinitrogen trioxide in accord with the following reactions: 1. HjO4N,O, = Ht+NO,'4+HNO, 2. 2HNO, = H,O+NO#NO, 3.2NO#N,0, = 2N.05 “The foregoing reaction products when formed by contact, with even a few tenths of 1 percent of water in the nitrogen tetroxide will seriously impair its usefulness because the products greatly increase the rate of the NO,’ attack on metals. As a result, procurement specifications place stringent limitations on the amount of water which has come in contact, ‘with nitrogen tetroxide propellant. Usually itis required that the amount of water be limited to 0.1 percent. ‘One method currently utilized to determine the water con- tent of nitrogen tetroxide is based on the removal of readily volatile nitrogen tetroxide by a stream of dry nitrogen and re- tention of the liquid residue which is assumed to consist of the fentire water, nitrous ackd and nitric acid content. This procedure, however, is time consuming, highly empirical, lacks sensitivity and often yields results that are questionable ‘The aforegoing method has been improved by a procedure of vaporizing a sample of nitrogen tetroxide and allowing its nitric and nitrous acid content to react with sodium carbonate at 280° C. and metallic copper at 600° C. Free water, if present, and water released by neutralization of nitric acid is absorbed by anhydrous calcium sulfate and weighed. Even this improvement, however, isnot suitable because itis atime con- suming gravimetric procedure. ‘Others have more recently developed an NMR method for determining the proton equivalent in nitrogen tetroxide, ‘Though this method is straightforward and precise, itis not at- tractive as a quality control procedure because of the high cost of instrumentation and the intricacy of sample prepara- tion required. ‘Additionally there has previously been described gas chro- matographic methods for the determination of a variety of im- purities in nitrogen tetroxide and other corrosive gases. How- ver, a method for the direct determination of water has not been reported. ‘OBJECTS AND SUMMARY OF THE INVENTION ‘Thus itis an object of this invention to provide a simple technique for the rapid determination of water in nitrogen tetroxide, ‘Another object of this invention is to provide a method for the utilization of gas chromatographic methods for the deter rmination of water in nitrogen tetroxide. “The above and other objects of this invention are accom plished by a procedure wherein a heated tube containing copper wire is disposed adjacent a gas chromatographic ‘column. Helium which is used as a carrier gas is continuously passed through the packed tube and into the gas chromato- raph column. A valve which is controltably cooled admits a 5 20 2s 50 55 60 65 0 2 Aesired size of nitrogen tetroxide sample into the helium gas stream prior to its entering the packed tube. The high tem- peratures in the presence of copper in the tube serve to ecompose the nitrogen tetroxide, nitric acid, nitrous acid, land other components to nitrogen, water and copper oxide. ‘Asa result, the nitric and nitrous acids are reduced to a water, ‘component which then can be detached in the gas chromato- fgraph. It is believed that the invention will be better un- derstood from the following detailed description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic representation of the apparatus uti ized to perform the procedure of the invention for the deter- ‘mination of water in nitrogen tetroxide. FIG. 2 is @ typical gas chromatograph resulting from the ‘method ofthis invention. FIG, 3s a typical calibration graph for the determination of ‘water in NO, DESCRIPTION OF THE PREFERRED EMBODIMENT [Asindicated, hereinbefore when water is mixed with N;O, it disappears and forms HNO,; and HNO,, and other products ‘which contain no hydrogen. Thus, its not the H,O content of 1,0; which i of concern herein, since it doesn’t exist as HO, but rather the hydrogen containing compounds, HNO, and HNO, resulting from the contact with water. Further, as in dicated, the HNO, and HNO, components actually invalidate the practical utilization of NO, asa propellant, since they in- duce corrosion of metals by N;O,. As a result of the aforego- ing, the only concern is the fact that N,O, was exposed to water and one must then determine how much of the hhydrogen-containing products are present as a result of that ‘exposure. Thus, if it were possible to run the contaminated 1,0, sample into a gas chromatograph and obtain values for the HNO, and HNNO;, the problem would be readily resolved. However, the foregoing wo substances are not separated reproducibly in a gas chromatograph and thus to date one has ‘been unable to make a determination of water content utliz- ing the chromatograph. Specifically, nitrogen tetroxide and nitic acid tend to attack the column packings providing asuc- cession of ill-defined peaks which cannot be readily correlated to the water content of the nitrogen tetroxide. Even columns. ‘prepared from entirely inert materials, such as perfluorinated polymers and oils, have failed to provide clean separation or yield reproducible and interpretable and chromatograms with NiO, HNO, of red-fuming nitric acid “The direct determination of water in nitrogen tetroxide is of| litle practical value because only a very small amount of ‘water is in equilibrium withthe ionic and molecular species in the NO, propellant, and the relationship of molecular specie 1,0 to the rates of corrosion of materials used in construction cof rockets has not been established. Additionally, and even of {greater importance is the fact that the ambient equilibrium in the sample would be shifted by removal of water in a chro- rmatographic procedure. Thus, the separated water would be a function of the sample composition as well as a function of c’chromatographic variables such as sample size, temperature, ‘column length and carrier gas flow. An extensive series of stu dies would be required to establish the relationship of such empirical results to the value of the propellant for rocket propulsion, 1 has been discovered that the foregoing problems relating to the determination of water in nitrogen tetroxide by gas chromatography can be averted by passing a sample of NsOy through hot copper contained in a column situated before the inlet ofthe gas chromatograph. In the copper-packed column all nitrogen and hydrogen-containing compounds are con- verted quantitatively to nitrogen and water, and if fee water is present it passes through unaltered in aceord with the follow- ing equation: 3,607,076 3 4. NsOt2HNOs#12Cu + 2Ner2HOFIZCLO since the resulting gases ae inert, selection of the chromato” Graphic substrate is simplified since it need only) provide arrtiuate separation of water from nitrogen and other Bases Such as earbon dioxide. Sse water added to NO, generates HNO, and HNO: 2sin- dicated above in equation 1, it then follows that by establish: ing conditions <0 that the HNO and HNOs content of NsO« ing com Gonverted to HO, then this water must be exactly Siqual in weight to the water which iitally cause the forma- tion of HNO, and HNO: "As indicated, the reducing column is initially packed with copper, However, after the first sample of N:Oy has been fared through, the packing consists of a mixture of OPPS pa copper oxide, as can be seen from the above equation 4 ee eefeault, when organic compounds are present in the ‘itrogen tetroxide sample, they willbe converted to water ang capt dioxide by the copper oxide. Organic compounds may Sho be directly oxidized by nitrogen dioxide at the elevated ‘emperatues in the columa. For example, greases contain ct Sanvsad hydrogen. Small amounts of grease dissolve in N:O. Whe hydrogen content of the grease will thus be converted to Nrater in aceord with the described process. Thus, in effect. Though this invention relates to the determination of water in itregen tetroxide, actually the method involves determining {he total hydrogen content ofthe nitrogen tetroxide. However, from a practical standpoint, by far the major source of fydrogen compounds in the nitiogen tetroxide is water, and aaeestis said that the invention is determining the water con- tent in nitrogen tetroxide. ‘One of the most advantageous aspects of the particular method involved is that it also yields a quantitative value for The carbon dioxide formed from the oxidation of grease and tHE ike. Thus, ifone notes an unduly high amount of carbon ‘Hloxide, he would be led to believe «hat the presence of grease sr Miner carbon-hydrogen compouncls were present and thus Shatlenge the validity of the analytieal values, of fun & Separate determination for the grease content and make cot rections as required. {ts believed that the invention will be further understood with reference to the schematic block diagram of FIO. t. Hell vin carrier gas is stored in a pressure vessel 11, which is con- acted to.a valve 13, The helium gas carrier line 18 leading Tram the valve to the remaining apparatus first passes through trom jeoular sieve 17 which serves to remove traces of water Fram the helium. This main cartier line 18 passes through @ FoMfed aluminum block 19, whose function will be later Speeribed, through a reduction furnace 21 and into astandard fas chromatograph 23. A branch 25 ofthe ges carrier line 15 ars Gmmvents the cooling block 19 and 21 and passes directly Sate the chromatograph 23. This line 25 directly to the detec- for thermal conductivity detectors tor serves as a reference employed, “Phe nitvogen tetroxide sample is contained in a vessel 27 “which can be constructed of, for example, thick-walled glass ‘A short stainless steel Tine 29 connects the sample vessel 27 though a small intermediate valve 31 to a main sampling ‘lve 33. The smal valve 31 isoptional and is used to close the TEivple vessel of fom the system when there is no testing. The Tiqued sampling valve 3 is maintained at O° to 2° C. by cite Thling. ize" water through lines 38 entering a block 18 fabekated from aluminum to fit around the valve. Control of the temperature thus insures reproducibility of the samples of NiO. A vent lin 37 is additionally connected tothe sampling Mave 33 and serves, as will be explained, to vent a small por tion of the NO, sample. “tne reduction furnace 21 is a quartz tube column intially packed with copper wire. In the specific device utilized, the Fopper wire had a diameter of 0,016 inch, and ranged from Gabe 00 0.06 inch in length, It should be apparent that various Siaes of copper wire can be utilized provided that the re- 0 20 25 30 35 40 43 50 55 6s 0 18 4 sideney in the column is sufficient for the reduction of the ‘components passing therethrough. rPsitionally, the amount of packing can vary widely with the residency time in the column governing. The quartz tama is heated by an electrically heated furnace 38 t0 @ SShperature up to 900" C. Temperature as low as 300° C te be sufficient to transform HINO, and HNO; if sfficient areianes time can be established in the quartz column. The {Graperature of 800" the preferred operating temperature career has been demonstrated that carbon dioxide will not nee Tagbon monoxide and there is no possibility of eracking 1,0 into hydrogen and copper oxide. Above 800° C. itis ‘ostble that these reactions can possibly occur "The gas chromatograph is a conventional commercial item. “The chromatograph used herein is a dual column F & M Maral 810 made by F & M Scientific, @ Division of Hewlett- srefard, with a thermal conductivity detector operating at Flament current of 155 ma. A recorder 39 connected to the Tiatatograph is once again a conventional commercial tem serpin ingle-pen recorder with a response time of 0.50 to 1.0 second. DESCRIPTION OF PROCEDURE In order to calibrate the system and determine its effective ness as well calibration vessels of 75-mm. capacity. approx reately spherical in shape, were constructed from thick-walled Pyrex glass, The tubulatures were connected to stopcock Fuesd with Teflon plugs and terminated with glass-to-metal Kosar seals to which were affixed stanles steel fittings. Each motel was cleaned, dried, and evacuated and then weighed. vee vacuum was released and a measured volume of water at Tkown temperature was introduced through the stopcock fore with the aid of a hypodermic needle. The water was Fossen by immersing the vessel in liquid nitrogen. The vessel corthen attached fo a vacuum manifold made of Yerinch stain- Mee Noel tubing and fittings to which was connected a cylinder faitogen tetroxide, The manifold andthe vessel were evacu: ora nea about 50 ml. of nitrogen tetroxide was allowed to arver the vessel, The vessel stopcock was then closed. The coiments were allowed to come to room temperature and then {horoughly mixed. The vessel was reweighed at room tempera aooroa the percentage of water added to the nitrogen tettox- Wiowas computed. The contents were frozen again and the 1S cel vented to dry air. The stopcock was closed and the con- Tents allowed to come to room temperature. in performing the herein method, @ sample vessel i at tachelito the system with stainless ste! fittings, When thermal ‘ullbsium is established in the chromatograph and the valve~

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