Lord Rayleigh (1842-1919, born John William Strutt)

Density of Nitrogen

Nature 46, 512 (1892) [from Scientific Papers, vol IV (Cambridge, UK: Cambridge Press, 1903)]

I am much puzzled by some recent results as to the density of nitrogen, and shall be obliged if any of your chemical readers can offer suggestions as to the cause. According to two methods of preparation I obtain quite distinct values. The relative difference, amounting to about 1/1000 part, is small in itself, but it lies entirely outside the errors of experiment, and can only be attributed to a variation in the character of the gas.

In the first method the oxygen of atmospheric air is removed in the ordinary way by metallic copper, itself reduced by hydrogen from the oxide. The air, freed from CO2 by potash, gives up its oxygen to copper heated in hard glass over a large Bunsen, and then passes over about a foot of red-hot copper in a furnace. This tube was used merely as an indicator, and the copper in it remained bright throughout. The gas then passed through a wash-bottle containing sulphuric acid, thence again through the furnace over copper oxide, and finally over sulphuric acid, potash and phosphoric anhydride.

In the second method of perparation, suggested to me by Prof. Ramsay, everything remained unchanged, except that the first tube of hot copper was replaced by a wash-bottle containing liquid ammonia, through which air was allowed to bubble. The ammonia method is very convenient, but the nitrogen obtained by means of it was 1/1000 part lighter than the nitrogen of the first method. The question is, to what is the discrepancy due?

The first nitrogen would be too heavy, if it contained residual oxygen. But on this hypothesis, something like 1 per cent. would be required. I could detect none whatever by means of alkaline pyrogallate. It may be remarked that the density of the nitrogen agrees closely with that recently obtained by Leduc using the same method of preparation.

On the other hand, can the ammonia-made nitrogen be too light from the presence of impurity? There are not many gases lighter than nitrogen, and the absence of hydrogen, ammonia, and water seems to be fully secured. On the whole it seemed the more probable supposition that the impurity was hydrogen, which in this degree of dilution escaped the action of the copper oxide. But a special experiment seems to preclude this explanation.

Into nitrogen prepared by the first method, but before its passage into the furnace tubes, one or two thousandths by volumes of hydrogen were introduced. To effect this in a uniform manner the gas was made to bubble through a small hydrogen generator, which would be set in action under its own electro-motive force by closing an external contact. The rate of hydrogen production was determined by a suitable galvanometer enclosed in the circuit. But the introduction of hydrogen had not the smallest effect upon the density, showing that the copper oxide was capable of performing the part desired of it.

Is it possible that the difference is independent of impurity, the nitrogen itself being to some extent in a different (dissociated) state?

I ought to have mentioned that during the fillings of the globe, the rate of passage of gas was very uniform, and about 2/3 litre per hour.

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