use the apparatus, stop-cock d is closed and c opened, and gas allowed to pass from the gasholder into B, where it is condensed in the solid form. Stop-cock c then being closed and d opened, gas passes into the exhausted tube f, where it is examined with the spectroscope. The vessel D contains liquid air, in which the tube e is immersed in order to condense vapour of mercury which would otherwise pass from the pump into the sparking-tube. The success of the operation of separating all the gases which occur in air and which boil at different temperatures, depends on keeping the temperature of B as low as possible, as will be understood from the following consideration:—
The pressure p, of a gas G, above the same material in the liquid state, at temperature T, is given approximately by the formula
log p = A −BT,
where A and B are constants for the same material. For some other gas G′ the formula will be
log p1 = A1 −B1T,
and
log pp1 = A − A1 + B1 − BT,
Now for argon, krypton and xenon respectively the values of A are 6.782, 6.972 and 6.963, and those of B are 339, 496.3 and 669.2; so that for these substances and many others A − A1 is always a small quantity, while (B1 − B)/T is considerable and increases as T diminishes. Hence the ratio of p to p1 increases rapidly as T diminishes, and by evaporating all the gases from the solid state, and keeping the solid at as low a temperature as possible, the gas that is taken off by the mercurial pump first consists mainly of the substance which has the lowest boiling point, in this case nitrogen, and is succeeded with comparative abruptness by the gas which has the next higher boiling point. Examination of the spectrum in the sparking-tube easily reveals the change from one gas to another, and when that is observed the reservoirs into which the gases are pumped can be changed and the fractions stored separately. Or several sparking-tubes may be arranged so as to form parallel communications between b and e, and can be successively sealed off at the desired stages of fractionation.
Fig. 10.
Analytical operations can often be performed still more conveniently with the help of charcoal, taking advantage of the selective character of its absorption, the general law of which is that the more volatile the gas the less is it absorbed at a given temperature. The following are some examples of its employment for this purpose. If it be required to separate the helium which is often found in the gases given off by a thermal spring, they are subjected to the action of charcoal cooled with liquid air. The result is the absorption of the less volatile constituents, i.e. all except hydrogen and helium. The gaseous residue, with the addition of oxygen, is then sparked, and the water thus formed is removed together with the excess of oxygen, when helium alone remains. Or the separation may be effected by a method of fractionation as described above. To separate the most volatile constituents of the atmosphere an apparatus such as that shown in fig. 10 may be employed. In one experiment with this, when 200 c.c. was supplied from the graduated gas-holder F to the vessel D, containing 15 grammes of charcoal cooled in liquid air, the residue which passed on unabsorbed to the sparking-tube AB, which had a small charcoal bulb C attached, showed the C and F lines of hydrogen, the yellow and some of the orange lines of neon and the yellow and green of helium. By using a second charcoal vessel E, with stop-cocks at H, I, J, K and L to facilitate manipulation, considerable quantities of the most volatile gases can be collected. After the charcoal in E has been saturated, the stop-cock K is closed and I and J are opened for a short time, to allow the less condensable gas in E to be sucked into the second condenser D along with some portion of air. The condenser E is then taken out of the liquid air, heated quickly to 15° C. to expel the occluded air and replaced. More air is then passed in, and by repeating the operation several times 50 litres of air can be treated in a short time, supplying sparking-tubes which will show the complete spectra of the volatile constituents of the air.
The less volatile constituents of the atmosphere, krypton and xenon, may be obtained by leading a current of air, purified by passage through a series of tubes cooled in liquid air, through a charcoal condenser also cooled in liquid air. The condenser is then removed and placed in solid carbon dioxide at −78° C. The gas that comes off is allowed to escape, but what remains in the charcoal is got out by heating and exhaustion, the carbon compounds and oxygen are removed and the residue, consisting of nitrogen with krypton and xenon, is separated into its constituents by condensation and fractionation. Another method is to cover a few hundred grammes of charcoal with old liquid air, which is allowed to evaporate slowly in a silvered vacuum vessel; the gases remaining in the charcoal are then treated in the manner described above.
Fig. 11.Fig. 12.
Charcoal enables a mixture containing a high percentage of oxygen to be extracted from the atmosphere. In one experiment 50 grammes of it, after being heated and exhausted were allowed to absorb air at −185° C.; some 5 or 6 litres were taken up in ten minutes, and it then presumably contained air of the composition of the atmosphere, i.e. 20% oxygen and 80% nitrogen, as shown in fig. 11. But when more air was passed over it, the portion that was not absorbed was found to consist of about 98% nitrogen, showing that excess of oxygen was being absorbed, and in the course of a few hours the occluded gas attained a new and apparently definite composition exhibited in fig. 12. When the charcoal containing this mixture was transferred to a vacuum vessel and allowed to warm up slowly, the successive litres of gas when collected and analyzed separately showed the following composition:—
| 1st litre | 18.5% | oxygen |
| 2nd litre | 20.6% | ” |
| 3rd litre | 53.0% | ” |
| 4th litre | 72.0% | ” |
| 5th litre | 79.0% | ” |
| 6th litre | 84.0% | ” |
Table IX.
| Liquid Gases. | Boiling Point. | Liquid Volume of 1 gram at Boiling Point in c.c. | Latent Heat in gram Calories. | Volume of Gas at 0° C. and 760 mm. per gram Calorie in c.c. |
| Sulphurous acid | + 10°C. | 0.7 | 97.0 | 3.6 |
| Carbonic acid | − 78.0 | 0.65 (solid) | 142.4 | 3.6 |
| Ethylene | −103.0 | 1.7 | 119.0 | 7.0 |
| Oxygen | −182.5 | 0.9 | 53.0 | 13.2 |
| Nitrogen | −195.6 | 1.3 | 50.0 | 15.9 |
| Hydrogen | −252.5 | 14.3 | 125.0 | 88.9 |
| Helium | −269.0 | 7.0 | 13.0 | 450.0 |
Calorimetry.—Certain liquid gases lend themselves conveniently to the construction of a calorimeter, in which the heat in weighed quantities of any substance with which it is desired to experiment may be measured by the quantity of liquid gas they are able to evaporate. One advantage of this method is that a great range of temperature is available when liquid air, oxygen, nitrogen or hydrogen is employed as the calorimetric substance. Another is the relatively large quantity of gas yielded by the evaporation, as may be seen from table IX., which shows the special physical constants of the various gases that are of importance in calorimetry. In consequence it is easy to detect 150 gram calorie with liquid air and so little as 1300 gram calorie with liquid hydrogen.
