CONTROL EXPERIMENTS WITH THE CALORIMETER.
After providing a suitable apparatus for bringing away the heat generated inside the chamber and for preventing the loss of heat by maintaining the walls adiabatic, it is still necessary to demonstrate the ability of the calorimeter to measure known amounts of heat accurately. In order to do this we pass a current of electricity of known voltage through a resistance coil and thus develop heat inside the respiration chamber. While, undoubtedly, the use of a standard resistance and potentiometer is the most accurate method for measuring currents of this nature, thus far we have based our experiments upon the measurements made with extremely accurate Weston portable voltmeter and mil-ammeters. Thanks to the kindness of one of our former co-workers, Mr. S. C. Dinsmore, at present associated with the Weston Electrical Instrument Company, we have been able to obtain two especially exact instruments. The mil-ammeter is so adjusted as to give a maximum current of 1.5 amperes and the voltmeter reads from zero to 150 volts. The direct current furnished the building is caused to pass through a variable resistance for adjusting minor variations in voltage and then through the mil-ammeter into a manganin resistance-coil inside the chamber, having a resistance of 84.2 ohms. Two leads from the terminals of the manganin coil connect with the voltmeter outside the chamber, and hence the drop in potential can be measured very accurately and as frequently as is desired. The current furnished the building is remarkably steady, but for the more accurate experiments a small degree of hand regulation is necessary.
The advantage of the electrical method of controlling the apparatus is that the measurements can be made very accurately, rapidly, and in short periods. In making experiments of this nature it is our custom first to place the resistance-coil in the calorimeter and make the connections. The current is then passed through the coil, and simultaneously the water is started flowing through the heat-absorbing system and the whole calorimeter is adjusted in temperature equilibrium as soon as possible. When the temperature of the air and walls is constant and the thermal-junction system in equilibrium, the exact time is noted and the water-current deflected into the meter. At the end of one hour, the usual length of a period, the water-current is deflected from the meter, the meter is weighed, and the average temperature-difference of the water obtained by averaging the results of all the temperature differences noted during the hour. Usually during an experiment of this nature, records of the water-temperatures are made every 4 minutes; occasionally, when the fluctuations are somewhat greater than usual, records are made every 2 minutes.
The calculation of the heat developed in the apparatus is made by means of the formula C × E × t × 0.2385 = calories, in which C equals the current in amperes, E the electromotive force, and t the time in seconds. This gives the heat expressed in calories at 15° C. This procedure we have followed as a result of the recommendation of Dr. E. B. Rosa, of the National Bureau of Standards. In order to convert the values to 20°, the unit commonly employed in calorimetric work, it has been necessary to multiply by the ratio of the specific heat of water at 15° to that of water at 20°. Assuming the specific heat of water at 20° to be 1, the specific heat at 15° is 1.001.[16]
Of the many electrical check-tests made with this type of apparatus, but one need be given here, pending a special treatment of the method of control of the calorimeter in a forthcoming publication. An electrical check-experiment with the chair calorimeter was made on January 4, 1909, and continued 6 hours. The voltmeter and mil-ammeter were read every few minutes, the water collected in the water-meter, carefully weighed, and the temperature differences as measured on the two mercury thermometers were recorded every 4 minutes.
The heat developed during the experiment may be calculated from the data as follows: Average current = 1.293 amperes; average E. M. F. = 109.15 volts; time = 21,600 seconds; factor used to convert watt-seconds to calories = 0.2385. (1.293 × 109.15 × 21600 × 0.2385) × 1.001 = 727.8 calories produced.
During the 6 hours 237.63 kilograms of water passed through the absorbing system.
The average temperature rise was 3.04° C., the total heat brought away was therefore (237.63 × 3.04) × 1.0024[17] = 724.1 calories.
Thus in 6 hours there were about 3.7 calories more heat developed inside the apparatus than were measured by the water-current, a discrepancy of about 0.5 per cent.
Under ideal conditions of manipulation, the withdrawal of heat from the calorimeter should be at just such a rate as to exactly compensate for the heat developed by the resistance-coil. Under these conditions, then, there would be no heat abstracted from nor stored by the calorimeter and its temperature should remain constant throughout the whole experiment. Practically this is very difficult to accomplish and there are minor fluctuations in temperature above and below the initial temperature during a long experiment and, indeed, during a short experimental period. If a certain amount of heat has been stored up in the calorimeter chamber or has been abstracted from it, there should be corrections made for the variations in the temperature of the chamber. Such corrections are impossible unless a proper determination of the hydrothermal equivalent has been made. A number of experiments to determine this hydrothermal equivalent have been made and the results are recorded beyond, together with a discussion of the nature of the experiments. As a result of these experiments it has been possible to make correction for the slight temperature changes in the calorimeter.
It is interesting to note that these fluctuations are small and there may therefore be a considerable error in the determination of the hydrothermal equivalent without particularly affecting the corrections applied in the ordinary electrical check-test. The greatest difficulty experienced with the calorimeter as a means of measuring heat has been to secure the average temperature of the ingoing water. The temperature difference between the mass of water flowing through the pipes and the outer wall of the pipe is at best considerable. The use of the vacuum-jacketed glass tubes has minimized the loss of heat through this tube considerably, but it is advisable that the bulb of the thermometer be placed exactly in the center of the water-tube, as otherwise too high a temperature-reading will be secured. When the proper precautions are taken to secure the correct temperature-reading, the results are most satisfactory.
In testing both calorimeters a large number of electrical check experiments have led to the conclusion that discrepancies in results were invariably due, not to the loss of heat through the walls of the calorimeter, but to erroneous measurement of the temperature of the water-current.