Patent GB-537486-A (GB)
Title: An electrical method and apparatus for analysing gaseous mixtures
IPC: G01N27/00
Filed: 1939-12-22
Abstract: 537,486. Gas analysis. FIFE, J. G. (Naamlooze Vennootschap de Bataafsche Petroleum Maatschappij). Dec. 22, 1939, No. 32733. [Class 1 (i)] [Also in Group XXXVI] A gaseous mixture, particularly one containing hydrocarbons, is analysed by exposing it to a heated element in the presence of oxygen to convert the hydrocarbons to carbon dioxide, and then passing the combustion products through an electrolytic liquid such as a dilute solution of a hydroxide of a metal forming substantially insoluble carbonates or carbonates having a very low solubility product, the concentration of carbon dioxide in the combustion products being determined from the variations in an electric current passed between electrodes immersed in the solution. The electrolytic liquid is maintained in a space comprising a reaction zone and a measurement zone in liquid communication with each other. The gas mixture is passed solely through the reaction zone and is caused to react completely with the solution within this zone. The solution is continuously circulated through the two zones and an electric current is passed through the solution along a path confined solely within the measurement zone, changes of conductivity of the solution caused by the reaction being observed. The sample of gas to be analysed is contained in a bag 1, Fig. 1, consisting of two concentric gas-tight bags 2, 3, the inner bag 2 being held within the outer bag 3 to prevent contamination of the gas sample by diffusion through the walls. Both bags are filled with the gas sample, but only that in the inner bag is analysed for its hydrocarbon content. The space within the outer bag 3 is connected to the atmosphere through a check valve 6 and pump 7. The space within the inner bag 2 is connected to towers 41, 42 through valves 9, 15, 24. The sample from the bag 2 may alternatively be passed through a coil 17 immersed in a liquid air chamber 18, wherein all hydrocarbons heavier than methane are condensed and removed to a container 29, while the non-condensible gas mixture comprising methane is passed to the towers 41, 42 through a pipe 23. The condensed hydrocarbons in the container 29 may be subsequently vaporized and passed to the towers 41, 42 through a valve 31, return to the coil 17 being prevented by a valve 28. The towers 41, 42 are filled with substances capable of removing carbon dioxide from the gas passing through, such as ascarite or a caustic alkali. The gas is passed from the towers 41, 42 through a flow meter 43 and a combustion chamber 45 containing an electrically heated platinum wire 46, the gaseous combustion products passing into a reaction chamber consisting of two cylindrical chambers 51, 52 connected by conduits 53, 54 and filled with an electrolytic solution which absorbs carbon dioxide. The orifice of the pipe 47 conveying the gases is situated at the lower part of the absorption chamber 52, the pipe entering through a plug 56 of cork, cotton, or other gas-permeable material. A solid glass coil 58 surrounds the pipe 47 so as to guide the gas bubbles along a spiral path. The electrode chamber 51 has a gas vent 59 and contains an inner electrode 60 and two outer electrodes 61, 62. These electrodes may be made of: platinum, platinum wire, platinized glass, platinized platinum, platinum black &c. and may be annular, as shown, or of other shape. The outer electrodes 61, 62 are connected in parallel by a mercury filled tube 64 to one terminal of the measuring circuit, the inner electrode 60 being connected to the other terminal through a similar tube 63. The measuring circuit comprising an alternating current wheatstone bridge formed of fixed resistances 73, 74 and a variable resistance 75, the electrolytic resistance between the electrode 60 and the electrodes 61, 62 forming the fourth arm. A modified analytical cell is shown in Fig. 2. The electrode chamber 51a has enlargements in which the electrodes 60a, 61a, 62a are fixed. The absorption chamber is in the form of a spiral coil 52a wound round the chamber 51a, the two chambers being connected at their upper and lower, portions. A cell 72a containing a platinized electrolytic resistance thermometer filled with a liquid having the same composition as that in the cell 51a, 52a is connected in the adjacent arm of the wheatstone bridge for temperature compensation. The whole system, including the analytical cell and the resistance thermometer, is kept at a constant temperature by thermostatic means or by immersion in melting ice. In the reaction cell shown in Fig. 3 the electrode chamber 51b is insulated from the absorption chamber 52b. The lower end of the electrode chamber 51b is formed as a dropper projecting into a chamber 54b while the conduit 53b connecting the chambers 52b, 51b is also made in the form of a dropper projecting into the upper enlarged portion 53c of the electrode chamber. The gaseous space in the chambers 53c, 54c is maintained by applying gaseous pressure through a tube 59b. The chambers 51, 52 are filled with an aqueous solution capable of reacting with carbon dioxide to form an insoluble precipitate or a non-ionised reaction product. Suitable solutions are those of the hydroxides of the alkaline earth metals, silver, or lead.