44 INDUSTRIAL AND ENGINEERING CHEMISTRY
1
are introduced by the lengthy procedure of the Vanselow and
Laurance modified combination of the two methods. In fact,
there seems to be no advantage in using the spectrograph for
the final determination of zinc in place of the iodide titration
in the chemical method.
Summary
Comparisons of analyses for zinc by a spectrographic
method with analyses for zinc by a chemical method have
been made on about forty samples of several varieties of
plants. Agreement has been attained on only half the
samples. It has been found that zinc is frequently retained
in the residue from the hydrochloric acid extraction em-
The Microanalysis of Gases
IV. Nitrous Oxide and Methane
FRANCIS E, BLACET AND DAVID H. VOLMAN, University of California at Los Angeles, Calif.
T HE methods of microanalysis of gases previously de-
scribed (1, b, 5) have been extended to include a new
procedure for the combustion of gases. This procedure has
been applied in the analysis for nitrous oxide and methane
and presents the possibility of application in the case of several
other gases. It ie assumed that the preceding articles are
available to the reader and in the interest of brevity refer-
ence to them will be made frequently.
Analysis with the aid of a combustion in which an ex-
plosion occurs (1) has two important limitations. In the
first place, the mixture must exceed a certain minimum
richness before an explosion will occur. This means that a
small percentage of gases such as methane or ethane cannot
be detected readily by this method. In the second place,
certain gases do not burn completely upon the passage of a
spark through the system containing them. These fac-
tors may be over-
come, however, by
c a r r y i n g out the
reaction on a hot
surface placed in the
system (4). This
was accomplished,
in the present in-
stance, by means of
a p l a t i n u m loop
shown in the operat-
ing position in Fig-
ure 1. Other de-
t a i l s of t h e g a s
microanalysis appa-
r a t u s h a v e been
described (3).
The mounting for
the p l a t i n u m was
made from a piece
of soft glass tubing
of the same length
and diameter as an
absorbent holder ( I ,
a). A 7-cm. length
of 24-gage platinum
wire was placed in the
tube in such a man-
ner that about 1 cm.
of it extended beyond
FIGURE 1. 'COMBUSTION COIL IN one end of the tube.
OPERATING POSITION Starting at this end,
VOL. 9, NO.
ployed in the chemical method, which may explain some of the
lack of agreement between the two methods. A modification
of the extraction procedure seems indicated. A discussion of
a modified combination of the two methods is given.
Literature Cited
(1) Hibbard, P. L., IND. ENQ.CHEM.,Anal. Ed., 6,423(1934).
(2) Rogers, L. H., Ibid., 7,421 (1935).
(3) Ruthardt, K.,and Hirachmann, H., Centr. aZZgem. Path., 61, 275
(1934).
(4) Vanselow, A. P.,and Lauranoe, B. M., IND.
ENQ.CHEW,Anal.
Ed., 8, 240 (1936).
RECEIVIDD
September 23, 1936.
a narrow portion of the tubing was heated carefully, so that a
fusion of glass to platinum occurred. By slowly moving the
tube through the flame the platinum wire was encased in glass
for a length of about 5 cm. It is important that no air bubbles
be trapped in this process. The glass and wire were then bent
to assume the shape shown in the diagram.
The exposed platinum was bent so that the top of the loop
was about 1 mm. above the end of the glass and the tip of the
loop could be immersed in the mercury within the gas holder.
The top of the loop was worked down for a distance of 1 mm.
by careful filing and the use of Crocus cloth, until the cross
section was approximately one-third of the original. By placing
a small amount of mercury in the unconstricted portion of the
mounting, electrical contact could be made, as indicated. The
large mercury reservoir served to complete the circuit.
In the use of this combustion coil, it was found convenient to
have available an electrical potential of about 10 volts and t o
regulate the glow of the coil by means of a slide wire rheostat
pIaced in the circuit.
In any extensive program involving gas microanalysis it is
necessary to save more samples than the main analytical ap-
paratus can accommodate. The authors have solved this
problem by using gas holder clips of the type sketched in Figure
2, which will fit on the side of any mercury reservoir in the
manner indicated. The clip is made of iron with one piece of
watch spring to hold it in place and another to support the gas
holder. By means of the pneumatic trough
scribed (2), gas samples may be transported, w i t ~ % % ~ ~ e
loss or contamination, from a storage reservoir t o the analytical
apparatus or vice versa.
Specific Methods of Analysis
NITROUS OXIDE. It has been suggested that a satisfactory
method of microanalysis for nitrous oxide in the presence of
air would be very useful in the field of anesthetics (6). This
problem has been solved by first removing the oxygen and
moisture by means of phosphorus and potassium hydroxide
(1) and then reducing the nitrous oxide with hydrogen gas
by the well-known reaction in which nitrogen gas and water
are produced (4). The procedure up to the analysis for
nitrous oxide is identical with that described for oxygen (1).
Thereafter, a measured volume of pure hydrogen is added
to the sample and the combustion coil placed in position as
shown in Figure 1. After adjusting the coil so that a small
amount of the glass insulation appears above the mercury
surface, the current is turned on and regulated until the thin
portion of the platinum wire appears reddish orapge in color.
With this condition it was found that in all cases complete
reduction of the nitrous oxide took place within 4 minutes,
Varying the excess of hydrogen does not seem to affect the
accuracy of the results in any way and has little effect on the
JANUARY 15, 1937 ANALYTICAL EDITION 45

combustion time. Upon completion of the reaction, the coil coil, it was found that methane
is removed and fused potassium hydroxide introduced to re- was oxidized completely within 2
move the water vapor. The volume decrease which is now minutes.
obtained is a direct measure of the amount of nitrous oxide In this work methane was pre-
present in the original sample. pared by heating a mixture of
In Table I are given typical results of the analysis of a sodium acetate and soda lime and
nitrous oxide sample obtained by heating ammonium nitrate collecting the gas over mercury.
and collecting the gas over mercury after removing the water Table I11 gives the results of the
vapor by means of a carbon dioxide trap. The deviation analysis of the sample thus pre-
from a 100 per cent sample is to be expected in this method of pared.
preparation of the gas (6). In order to test the value of the
Table I1 gives results obtained upon analysis of a sample method when small amounts of
made by diluting the sample represented in Table I with dry methane are present in a sample,
air. The theoretical percentage of nitrous oxide present is portions of the gas were diluted
20.01, calculated on the premise that the undiluted sample is FIGURE 2. Gas- with known volumes of air and then
99.25 per cent nitrous oxide as indicated in Table I. The HOLDER CLIP analyzed. The data thus obtained
oxygen was removed as previously described. Mounted on side.of stor- are shown in Table IV. The theo-
METHANE.It is frequently desirable to estimate the age reservoir retical percentage is based on the
amount of saturated hydrocarbons in small gas samples assumption that the analysis repre-
which do not contain enough of these substances to give an ex- sented in Table 111 is correct. The close agreement ofdhe
plosive mixture with oxygen. The combustion coil herein experimentally determined percentage with the theoretical
described has made this type of microanalysis possible in the appears to validate this assumption,
case of methane and there is little doubt but that the method
may be applied to certain other gases. Discussion
The procedure is essentially the same as that employed in The requirements of the combustion coil are such that it
the analysis for nitrous oxide, except that the gas to be must necessarily be fragile. An attempt was made to at-
analyzed in this case is oxidized instead of reduced and hence tach the end of the loop to the glass insulation of the incom-
an excess of oxygen, or carbon dioxide-free air, is added in ing wire, but for some reason which is not clear, it was more
place of hydrogen. After the water vapor has been removed, difficult to get the coil up to the desired temperature when this
the carbon dioxide produced in the reaction is determined in was done. However, with reasonable care one coil will last
the usual way. This, of course, represents the amount of for a long time when made as described and, when the tip
methane in the original sample. Using a reddish orange does break off, the rest of the wire can be salvaged in good
condition by simply heating the glass and platinum to redness
and plunging them into cold water.
TABLEI. ANALYSISOF NITROUS OXIDE PREPARED
BY THE The coil is so constructed that the gas may be brought to the
OF AMMONIUM
DECOMPOSITION NITRATE desired temperature a t the surface of the wire while the mer-
Volume Volume Deviation cury and surroundings are kept relatively cool. Because of
Determina- of of Nitrous from this the expansion of the gas volume is not great during the
tion Sample Hydrogen Oxide Mean
Cu. mm. Cu. mm. % % course of the combustion and the contamination of the sample,
1 53.73 71.77 99.05 -0.20 by adsorbed gases which may be driven from the glass sur-
2 54.58 71.78 99.56 +0.31
3 54.31 71.20 98.92 -0.32 face, is reduced to a minimum. It is important that the glass-
4 54.13 76.49 99.48 +o 23 enclosed platinum extend beyond the lower bend in the a p
Av. 99.25 *o 27
paratus; otherwise, foreign gases may be introduced into
a sample by the development of minute cracks in the glass.
TI. ANALYSISOF
TABLE AMIXTUREOF NITROUSOXIDE AND There was no evidence of the oxidation of mercury during
DRYAIR
the short time required for the reactions of nitrous oxide
Deter- Volume Volume Deviation Deviation
mina- of of Nitrous from from and methane However. continuous operation of the coil
tion Sample Hydrogen Oxide Mean Theoretical for 15minutes or more, gave some evidence of this reaction.
Cu. mm. Cu. mm. % % % It would appear that this method of analysis may be
1 54.79 47.89 19.60 -0.24 -0.41
2 57.07 50.37 19.96 4-0 12 -0.05 applied generally in cases where combustible gases are in-
3 56.27 49.44 19.87 $0.03 -0.14
Av. k0.13 -0.20
volved. Hydrogen may be determined by the use of oxygen
and oxygen may be determined by the use of hydrogen, etc.
However, an attempt to analyze for butane by this method
111. ANALYSISO F METHANEPREPARED
TABLE FROM SODIUM
was not quantitatively successful. The time required for
ACETATEAND SODA LIME
Determina- Volume of Deviation
the reaction to go to completion was of such length that the
tion Sample Methane from Mean entire system became hot and oxidation of mercury began
Cu. mm. % % to take place. It is possible that further experimentation
1 41.91 96.42 $0.18
with conditions would overcome these difficulties.
2 40.15 96.00 -0.24
3 39.98 96.20 -0.04
4 39.69 96.35 +O.ll Literature Cited
Av. 96.24 r O . 14
(1) Blacet and Leighton, IXD. ENQ.CHEM.,Anal. Ed., 3,266 (1931).
(2) Blacet and MacDonald, Ibid., 6,334(1934).
TABLEIv. k?ALYSES O F MIXTURESO F METHANEAND AIR (3) Blacet, MacDonald, and Leighton, I b i d . , 5,272 (1933).
Methane Methane (4) Dennis and Nichols, “Gas Analysis,” New York, Maomillan Co.,
Determi- Volume of Theoreti- Deter- 1929.
nation Sample cal mined Difference ( 5 ) Partington, “Text Book of Inorganic Chemistry,” 3rd ed.,
Cu. rnm. % % % London, Macmillan Co., 1930.
1 62.06 66.52 56.61 +0.09 (6) Sewers, M. H., Department of Pharmacology and Toxicology,
2 108.53 5.81 5.90 fO.09 University of Wisconsin, Madison, Wis., personal communica-
3 101.56 3.18 3.22 +0.04
4 101.29 3.19 3.41 f0.22 tion.
RECEIVED September 9, 1936.