Determination of bloncondensables in
Gas
AARON E. MARKHAM, Research Department, Y a k Corporation, York, Pa. concentration desired. A complete analysis requires from I O t e 15 minutes, exclusive of calculation.
An apparatus ir described lor the quantitative determination 01 amall percentages 01 noncondenrsble in an easily condensed gas. The apparatus should bo useful for analyses of many gaseous systems, especially in the cam of gases for which no chemical absorbrntl are available. Tho vapor pressure and liquid density of the condensable gar must be known. The method has been applied to the determination of noncondenrsble In commercial difluarodichloromethane, Freon-I 2.
PRINCIPLE OF THE METHOD The g a is liquefied by e ~ o l i n gin a graduated tube. The amount of noncondensahle 1s observed and corrected for the presence of condensable gsJ. The volume of condensate is o h served, and converted to pss volumc through the known densities of the two phases. Frum the volumes of condensable and noneondensable, the percentaxe of noncondensahle is calculated to any desired basis.
THE
need has arisen in this laboratory in connection with research work on refrigeration for a method of quantitative determination of noncondensable in the presence of large amounts of easily condensed gas. Routine determinations were required for such analyses of dichlorodifluoromethane, boiling point -30' C., when the noncondensable was in the range of 0.001 to 3%. Atmospheric gmes constituted the noncondensable. A method developed by the Kinetic Chemicals Corporation (I) was available far the determination of nonabsorbable in keroBene, which in this case is nearly the same as noneondensable. Their method involves the absorption of the condensable gas in kerosene which bas been freshly boiled and then saturated with air. However, the method was not satisfactory for the author's purposes, for several reasens. First, a rather large correction (1.6%) must be applied to compensate for air driven out of the kerosene h y the dichlorodifluoromethane. Such a correction Leads to inacouracies in the low rmge of nonabsorbahles. Furthermore, a method was desired which meamred actual noncondcnsable without the sasumption that it w a the same 88 nonabsorbable. The apparatus described here proved to be rapid in operat,ion and to give reproducible results in the whole range of
APPARATUS
The apparatus, shown in Figures 1 and 2, is of glass, with a ruhher tube connection from A to a mercury leveling bulb. Tubes A, C, and J are of 7-mm. inside diameter. The capillary tubes have about 2-mm. bore. Bulbs F and E have volumes of about 0.5 and 1.5 ml., respectively. Tube G is graduated from point 0 in convenient, increments of volume, depending on tube diameter. The first graduations below 0 are on the capillary, hence corm spnnd to very small increments of volume. The next are on a 6-mm. tnhe, and the next on a 12-mm. tube, which is the main body of G. At the bottom of G is a short 4-mm. capillary, graduated a t 2-mm. intervals to the mark above F. The tot,al volume of G is 7.5 ml. The dimensions were calculated to 've the maximum accuracy throughout the range of noneondensafles expected. This calculation is based on the ranxe of noncondensables to be covered, the relative densities of gas and liquid and the operating temperature. The apparatus was accurat.ely calibrated hv the use of mercury. The cold zone is an unsilvered I-liter vacuLm flask, fille 1 siIh ilimet huxyierracr hylenc ylyvoi. sntl cooled w i t h Jrv iw (2). A rempcmrirre or h h w t -31' C. e m be mamiiiiiicd cnsilv fGr lorw iieriodi in rhia wav. The flask can he lowered readily io allow the apparatus to warm. A scale is placed behind C , for reading pressure, and the height from a reference point on the scale to the graduations of G is known. The graduations are calibrated for hei ht, so that a n observation of t,he mercury levels in C and G caoRbe reduced to a pressure difference. MANlPULAllON
By proper manipulation of the stopcocks, with the leveling hulh raised, the apparatus is filled completely with mercury up to the tip of tube K, and up tubes C and J to points about 20 cm. above the cocks. Connection is then made at K t o the source of gas to be analyzed, and cocks B and H a r e turned to shut off the mercury in C and J , hut to allow flow from K through t a the mercury bulb. The mercury bulb is then lowered eiowly, drawing in sample, until the mercury level is in bulb F. The vacuum flask, a t the low temperature, is then raised to surround the apparatus, and condensation h e ~ n s . During condensation, the merclrry level is adjusted exactly to the mark a t the bottom 01. F or E, B is shut off, and condensation continued till F or hoth bulbs are nearly filled with liquid. (This choice depends on the probable amount of noncondensble present, the larger sample . when hotb bulbs are used permittin,"mOreaccuratemeasurement if the percentage of noneondensable 18 small.) When the condensed liquid nearly reaches the mark a t the top of F, cock H is turned off, apd then turned to allow mercury to run down from J into the capillary to 0, thus sealing the tube and driving all gas into the cold eone. (It is evident that the mercury height in J must be sufficient to overcome the pressure in the apparatus.) The apparatus is then alloved to stand for severd minutes, to allow the liquid to drain into F. With 6ome practice, it is possible to stop the flow, so that this draining will fill the bulb slmost exactly to the mark. Any excess c8u readily he estimated by the gsaduatiom on the capillary tube above F. The volume of condensable is thus measured as liquid, and its temperature eatimated from that in the bath. The mercury bulb is then raised above B, and cock B turned to connect A, C, and D. T h e height of mercu in C, the top of the liquid meniscus in G the mercury level in and the temperatye pf the Fath are observed., B y manipulation of t.he pressure, I t i s possrhle to adjust the liquid level to a favorable location for reading. From the barometric ressure and the mercury levels, corrected for a mall head of &quid above the mercury in 0, the total pressure on the psa is known. From the t,emperature and the thermodynamic tables of the liquid, the partial pressure of the liquid is known. Hence the partial prensure of the noncondensable in found. and this,
17[
Figure 1
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
682
combined with its volume and temperature, leads to the amount of noncondensable, expressible in any desired way, since the amount of condensable is known. The amount of condensable in the vapor phase can be calculated, and added to the volume of condensate, but this correction is negligible. To empty the apparatus, tlie mercury from J is slowly draw11 through H into G, then H is opened, and the varuum flask is removed. h a t h e l i q u i d boils, it escapes through J . .I mercury trap a t the top of J is desirable.
Vol. 16, No. 11
might reduce the leakage, but under the conditions used such refinements appear unnecessary. Sampling of a gas mixture for analysis is just as important as the analysis, and frequently more difficult to do accurately. I n this special case, uniform samples were available of sufficient quantity for an analysis (ca. 100 to 400 ml.), Frequently, however, gas of uniform composition might not be available, or might be available only in very small quantity. The sampling then could easily be a real problem, especially if two phases were present. GENERAL APPLICATION
CHECK RESULTS
Some commercial material of high purity was analyzed by the method just described, giving reproducible results in the range 0.013 to 0.020% noncondensable. To this material was added Figure 2 air inmeasured proportions, after which the mixture was analyzed as described. The following results illustrate the reproducibility of the analyses as checked by the author in his work: % Air Added
‘36 Noncondensable Found
1.25 1.52 0.34 1.16 1.01 0.62
1.23 1.46 0.32 1.13 1.03 0.64
The discrepancy is probably due as much to the uncertainties in preparing the mixtures as to the analyses. A source of error lies in the solubility of noncondensable in the condensate. This error, of course, depends on the system under investigation, and in some systems could easily be excessive. By keeping the partial pressure of the noncondensable low, the error can be minimized. I n the measurements cited, the temperature of the condensate has been kept about 1’ below its normal boiling point, and the pressure during condensation only a few inches greater than atmospheric. Hence the partial pressure of the gas is not more than 7.5 or 10 cm. (3 or 4 in.) of mercury. The temporary increase of partial pressure to about 25 or 30 cm. (10 or 12 inches) when the volume is observed probably results in little increase in the noncondensable dissolved. Condensation near the normal boiling point is probably most satisfactory, since with a small positive pressure in the apparatus the partial pressure of noncondensable is kept small. Furthermore, the vapor pressure of the condensable is frequently better known or more satisfactorily estimated near the normal boiling point. If the noncondensable data are to be used a t temperatures other than that of the analyses, it is well to remember that “noncondensable” is a relative term and what is noncondensable a t one temperature may be condensable a t other temperatures. If water is present in quantity, it must be removed before the analysis, or the tube will clog with frost. I t is advisable to keep a slight positive pressure in the apparatus to avoid the possibility ,of leaks inward. There is some tendency for dichlorodifluoromethane to leak through ordinary stopcocks. The manipulations described were planned to reduce leakage to a minimum, by t h e use of moderate pressures, and by separating the gas and liquid from the stopcocks with mercury when possible. Repeated use of the apparatus tends to saturate the stopcock lubricant with gas, which may reduce the leakage. I n the range of noncondensable considered here, small losses of condensable are much less important than leakage, either inward or outward, of aoncondensable. The use of special stopcocks or of special grease
The apparatus should be useful with a wide variety of gases, especially those for which no chemical absorbents are available. Other temperatures of condensation can be used. Tube C can be connected a t point A to cover lower pressures, and to provide for the simultaneous measurement of gas and liquid volumes. The addition of more liquid bulbs, or the change of relative volumes of the apparatus, could make the apparatus cover a different range of noncondensable. Provision can be made to withdraw and analyze the noncondensable. This has not been done. It is necessary t o know the liquid density and vapor pressure of the condensable gas. LITERATURE CITED
(1) Kinetic Chemicals, Inc., Wilmington, Del., Tech. Paper 8
(1931).
( 2 ) Wikoff, Cohen, and Grousman, IND.ENG.CHEM.,. ~ N A L . ED., 12, 92 (1940).
General M o t o r s Spectrographic Conferences A series of spectrographic conferences has been initiated by the General Motors Corp., under the chairmanship of G. M. Rassweiler, Research Laboratories Division, to develop further the applications of these analytical tools. Application of spectrochemical analysis has expanded so rapidly in connection with war production problems that 24 General Motors plants now have spectrographic installations in operation or on order. Attended only by General Motors men, these conferences provide for frank and critical examination of methods now in use or contem-. plated. The fundamental physical and chemical aspects are discussed, together with closely associated problems of physics, chemistry, and metallurgy. Five conferences have already been held, attended by from 40 to 60 men. Papers have been presented by R. E. Nusbaum and D. L. Fry of the Research Laboratories Division, 5. F. Simpson of Chevrolet, W. N. Hatfield of Delco-Remy, R. W. Smith of AC Spark Plug, H. H. Grossman of Harrison Radiator, E. Osborne of Buick, F. D. Brookshire and W. R. O’Neill of Cadillac Motor, L. A. Danse of Standards Section, and R. B. Schenck of Buick. Further meetings are planned, as well as such other activities as cooperative preparation of standards and extensive study of methods and equipment.
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