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66
CALORIMETRY

the method. The absolute value of the specific heat deduced necessarily depends on the absolute values of the electrical standards employed in the investigation. But for the determination of relative values of specific heats in terms of a standard liquid, or of the variations of specific heat of a liquid, the method depends only on the constancy of the standards, which can be readily and accurately tested. The absolute value of the E.M.F. of the Clark cells employed was determined with a special form of electrodynamometer (Callendar, Phil. Trans. A. 313, p. 81), and found to be 1.4334 volts, assuming the ohm to be correct. Assuming this value, the result found by this method for the specific heat of water at 20° C. agrees with that of Rowland within the probable limits of error.

§ 15. Variation of Specific Heat of Water.—The question of the variation of the specific heat of water has a peculiar interest and importance in connexion with the choice of a thermal unit. Many of the uncertainties in the reduction of older experiments, such as those of Regnault, arise from uncertainty in regard to the unit in terms of which they are expressed, which again depends on the scale of the particular thermometer employed in the investigation. The first experiments of any value were those of Regnault in 1847 on the specific heat of water between 110° C. and 192° C. They were conducted on a very large scale by the method of mixture, but showed discrepancies of the order of 0.5%, and the calculated results in many cases do not agree with the data. This may be due merely to deficient explanation of details of tabulation. We may probably take the tabulated values as showing correctly the rate of variation between 110° and 190° C., but the values in terms of any particular thermal unit must remain uncertain to at least 0.5% owing to the uncertainties of the thermometry. Regnault himself adopted the formula,

s = 1 + 0.00004t + 0.0000009t2 (Regnault),   (3)

for the specific heat s at any temperature t C. in terms of the specific heat at 0° C. taken as the standard. This formula has since been very generally applied over the whole range 0° to 200° C., but the experiments could not in reality give any information with regard to the specific heat at temperatures below 100° C. The linear formula proposed by J. Bosscha from an independent reduction of Regnault's experiments is probably within the limits of accuracy between 100° and 200° C., so far as the mean rate of variation is concerned, but the absolute values require reduction. It may be written—

s = S100 + .00023(t − 100)  (Bosscha-Regnault)   (4).

The work of L. Pfaundler and H. Platter, of G. A. Hirn, of J. C. Jamin and Amaury, and of many other experimentalists who succeeded Regnault, appeared to indicate much larger rates of increase than he had found, but there can be little doubt that the discrepancies of their results, which often exceeded 5%, were due to lack of appreciation of the difficulties of calorimetric measurements. The work of Rowland by the mechanical method was the first in which due attention was paid to the thermometry and to the reduction of the results to the absolute scale of temperature. The agreement of his corrected results with those of Griffiths by a very different method, left very little doubt with regard to the rate of diminution of the specific heat of water at 20° C. The work of A. Bartoli and E. Stracciati by the method of mixture between 0° and 30° C., though their curve is otherwise similar to Rowland's, had appeared to indicate a minimum at 20° C., followed by a rapid rise. This lowering of the minimum was probably due to some constant errors inherent in their method of experiment. The more recent work of Lüdin, 1895, under the direction of Prof. J. Pernet, extended from 0° to 100° C., and appears to have attained as high a degree of excellence as it is possible to reach by the employment of mercury thermometers in conjunction with the method of mixture. His results, exhibited in fig. 6, show a minimum at 25° C., and a maximum at 87° C., the values being .9935 and 1.0075 respectively in terms of the mean specific heat between 0° and 100° C. He paid great attention to the thermometry, and the discrepancies of individual measurements at any one point nowhere exceed 0.3%, but he did not vary the conditions of the experiments materially, and it does not appear that the well-known constant errors of the method could have been completely eliminated by the devices which he adopted. The rapid rise from 25° to 75° may be due to radiation error from the hot water supply, and the subsequent fall of the curve to the inevitable loss of heat by evaporation of the boiling water on its way to the calorimeter. It must be observed, however, that there is another grave difficulty in the accurate determination of the specific heat of water near 100° C. by this method, namely, that the quantity actually observed is not the specific heat at the higher temperature t, but the mean specific heat over the range 18° to t. The specific heat itself can be deduced only by differentiating the curve of observation, which greatly increases the uncertainty. The peculiar advantage of the electric method of Callendar and Barnes, already referred to, is that the specific heat itself is determined over a range of 8° to 10° at each point, by adding accurately measured quantities of heat to the water at the desired temperature in an isothermal enclosure, under perfectly steady conditions, without any possibility of evaporation or loss of heat in transference. These experiments, which have been extended by Barnes over the whole range 0° to 100°, agree very well with Rowland and Griffiths in the rate of variation at 20° C., but show a rather flat minimum of specific heat in the neighbourhood of 38° to 40° C. At higher points the rate of variation is very similar to that of Regnault's curve, but taking the specific heat at 20° as the standard of reference, the actual values are nearly 0.56% less than Regnault's. It appears probable that his values for higher temperatures may be adopted with this reduction, which is further confirmed by the results of Reynolds and Moorby, and by those of Lüdin. According to the electric method, the whole range of variation of the specific heat between 10° and 80° is only 0.5%. Comparatively simple formulae, therefore, suffice for its expression to 1 in 10,000, which is beyond the limits of accuracy of the observations. It is more convenient in practice to use a few simple formulae, than to attempt to represent the whole range by a single complicated expression:—

Below 20° C. s = 0.9982 + 0.0000045(t − 40)2 − 0.0000005(t − 20)3. From 20° to 60°, s = 0.9982 + 0.0000045(t − 40)2   (5).

Above 60° to 200°{ s = 0.9944 + .00004t + 0.0000009t2  (Regnault corrd.)
s = 1.000 + 0.00022(t − 60)     (Bosscha corrd.)

The addition of the cubic term below 20° is intended to represent the somewhat more rapid change near the freezing-point. This effect is probably due, as suggested by Rowland, to the presence of a certain proportion of ice molecules in the liquid, which is also no doubt the cause of the anomalous expansion. Above 60° C. Regnault's formula is adopted, the absolute values being simply diminished by a constant quantity 0.0056 to allow for the probable errors of his thermometry. Above 100° C., and for approximate work generally, the simpler formula of Bosscha, similarly corrected, is probably adequate.

The following table of values, calculated from these formulae, is taken from the Brit. Assoc. Report, 1899, with a slight modification to allow for the increase in the specific heat below 20° C. This was estimated in 1899 as being equivalent to the addition of the constant quantity 0.20 to the values of the total heat h of the liquid as reckoned by the parabolic formula (5). This quantity is now, as the result of further experiments, added to the values of h, and also represented in the formula for the specific heat itself by the cubic term.

Specific Heat of Water in Terms of Unit at 20° C. 4.180 Joules

t° C. Joules. s. h Rowland.
4.208 1.0094 0 0
4.202 1.0054 5.037 5.037
10° 4.191 1.0027 10.056 10.058
15° 4.184 1.0011 15.065 15.068
20° 4.180 1.0000 20.068 20.071
25° 4.177 0.9992 25.065 25.067
30° 4.175 0.9987 30.060 30.057
35° 4.173 0.9983 35.052 35.053
40° 4.173 0.9982 40.044  
50° 4.175 0.9987 50.028  
60° 4.180 1.0000 60.020  
70° 4.187 1.0016 70.028  
80° 4.194 1.0033 80.052  
90° 4.202 1.0053 90.095 Shaw
100° 4.211 1.0074 100.158 Regnault
120° 4.231 1.0121 120.35  120.73
140° 4.254 1.0176 140.65  140.88
160° 4.280 1.0238 161.07  161.20
180° 4.309 1.0308 181.62  182.14
200° 4.341 1.0384 202.33   
220° 4.376 1.0467 223.20   

The unit of comparison in the following table is taken as the specific heat of water at 20° C. for the reasons given below. This unit is taken as being 4.180 joules per gramme-degree-centigrade on the scale of the platinum thermometer, corrected to the absolute scale as explained in the article Thermometry, which has been shown to be practically equivalent to the hydrogen scale. The value 4.180 joules at 20° C. is the mean between Rowland's corrected result 4.181 and the value 4.179, deduced from the experiments of Reynolds and Moorby on the assumption that the ratio of the mean specific heat 0° to 100° to that at 20° is 1.0016, as given by the formulae representing the results of Callendar and Barnes. This would indicate that Rowland's corrected values should, if anything, be lowered. In any case the value of the mechanical equivalent is uncertain to at least 1 in 2000.

The mean specific heat, over any range of temperature, may be obtained by integrating the formulae between the limits required, or by taking the difference of the corresponding values of the total heat h, and dividing by the range of temperature. The quantity actually observed by Rowland was the total heat. It may be remarked that starting from the same value at 5°, for the sake of comparison, Rowland's values of the total heat agree to 1 in 5000 with those calculated from the formulae. The values of the total heat observed by Regnault, as reduced by Shaw, also show a very fair agreement, considering the uncertainty of the units. It must be admitted that it is desirable to redetermine the variation of the specific heat above 100° C. This is very difficult on account of the

steam-pressure, and could not easily be accomplished by the electrical