It is impossible to obtain in the market absolutely chemically pure oxygen. All the oxygen that we have thus far been able to purchase contains nitrogen and, in some instances, measurable amounts of water-vapor and carbon dioxide. The better grade of oxygen, that prepared from liquid air, is practically free from carbon dioxide and water-vapor, but it still contains nitrogen, and hence with every liter of oxygen admitted there is a slight amount of nitrogen added. This amount can readily be found from the gasometric analysis of the oxygen and from the well-known relation between the weight and the volume of nitrogen the weight can be accurately found. This addition of nitrogen played a very important rôle in the calculation of the oxygen consumption as formerly employed. As is seen later, a much abbreviated form of calculation is now in use in which the nitrogen admitted with the oxygen does not influence the calculation of the residual oxygen.
REJECTION OF AIR.
In long-continued experiments, where there is a possibility of a noticeable diminution in the percentage of oxygen in the chamber—a diminution caused either by a marked fall in barometer, which expands the air inside of the chamber and permits admission of less oxygen than would otherwise be required, or by the use of oxygen containing a high percentage of nitrogen, thus continually increasing the amount of nitrogen present in the system—it is highly probable that there may be such an accumulation of nitrogen as to render it advisable to provide for the admission of a large amount of oxygen to restore the air to approximately normal conditions. In rest experiments of short duration this is never necessary. The procedure by which such a restoration of oxygen percentage is accomplished has already been discussed elsewhere.[25] It involves the rejection of a definite amount of air by allowing it to pass into the room through the gas-meter and then making proper corrections for the composition of this air, deducting the volume of oxygen in it from the excess volume of oxygen introduced and correcting the nitrogen residual in order to determine the oxygen absorption during the period in which the air has been rejected.
INTERCHANGE OF AIR IN THE FOOD-APERTURE.
The volume of air in the food-aperture between the two glass doors is approximately 5.3 liters. When the door on the inside is opened and the material placed in the food-aperture and the outer door is subsequently opened, there is by diffusion a passage outward of air of the composition of the air inside of the chamber, and the food-aperture is now filled with room air. When the inner door is again opened this room air enters the chamber and is replaced by air of the same composition as that in the chamber. It is seen, then, that there may theoretically be an interchange of air here which may have an influence on the results. In severe work experiments, where the amount of carbon dioxide in the air is enormously increased, such interchange doubtless does take place in measurable amounts and correction should undoubtedly be made. In ordinary rest experiments, where the composition of the air in the chamber is much more nearly normal, this correction is without special significance. Furthermore, in the two forms of calorimeter now in use, the experiments being of but short duration, provision is made to render it unnecessary to open the food-aperture during the experiment proper. Consequently at present no correction for interchange of air in the food-aperture is made, and for the same reason the slight alteration in volume resulting from the removal or addition of material has also not been considered here.
USE OF THE RESIDUAL BLANK IN THE CALCULATIONS.
To facilitate the calculations and for the sake of uniformity in expressing the results, a special form of blank is used which permits the recording of the principal data regarding the analyses of air in the chamber at the end of each period. Thus at the head of the sheet are recorded the time, the number of the period, kind of experiment, the name or initials of the subject, and the statement as to which calorimeter is used. The barometer recorded in millimeters is indicated in the column at the left and immediately below the heading, together with the temperature of the calorimeter as expressed in degrees centigrade. The temperature of the calorimeter as recorded by the physical observer is usually expressed in the arbitrary scale of the Wheatstone bridge and must be transposed into the centigrade scale by means of a calibration table.
The apparent air-volumes in the subsections of the ventilating system are recorded under the headings I, which represents the volume of air containing water-vapor and therefore is the air in the chamber plus the air in the piping to the surface of the acid in the first sulphuric-acid absorber; I-II, which represents the air containing carbonic acid and includes volume I plus the volume of the air in the first sulphuric-acid vessel and the volume of air in the potash-lime absorber; I-III, which includes the total confined volume of the whole system, since this air contains both oxygen and nitrogen. These volumes change somewhat, depending upon the size of the body of the subject, the volume of the materials taken into the chamber, and the type of calorimeter.
The data for the residual analyses are recorded in the lower left-hand corner: first the weight of the water absorbed from 10 liters of air passing through the meter; to the logarithm of this is added the logarithm of volume I; the result is the logarithm of the total weight of water-vapor in the ventilating air-current. To convert this into liters the logarithmic factor 09462[26] is added to the logarithm of the weight of water and (a) is the logarithm of water expressed in liters. A similar treatment is accorded the weight of carbon dioxide absorbed from the air-sample, (b) being ultimately the logarithm of the volume of carbon dioxide.