The Essay of M. M. Dulong and Petit, in the 10th vol. of the An. de chimie (see An. of Philosophy, vol. 14th, 1819) manifests great ingenuity. It does not appear, however, so fortunate either in theory or experiment as the former one. It would be difficult to convince any one, either by reasoning or by experience that a number of particles of mercury at the temperature of -40°, whether in the solid,, liquid, or elastic state, have all the same capacity for heat. Indeed the experiments of De la Roche and Berard, if they are to be credited, demonstrate the inferior capacity of condensed air to rarefied air; and if the same body changes its capacity in the elastic form, it may well be concluded that all the three forms have not the same capacity. M. M. Dulong and Petit have themselves shewn, in their former essay, ([see page 276]) that solid bodies vary in their capacities for heat, and that scarcely any two bodies, vary alike; hence it is impossible that the product of the weight of the atom and specific heat of the body should be a constant quantity. Their specific heat of certain metals differ greatly from what is found by others. For instance, they make the specific heat of lead .0293; the lowest authority I have seen is Crawford, .0352, and the highest Kirwan .050; from repeated trials I have lately found it, upon an average, .032. The weights of some of the atoms in their table, differ materially from what are commonly received; for instance, bismuth is 13.3 instead of 9; also copper, silver, and cobalt, are only half the weights of some authors. The gases too are unfortunate examples. Oxygen gas gives a product of .236 instead of .375; azotic gas gives a product .1967, if oxygen be to azote as 7 to 5, but a product of .393 if oxygen be to azote as 7 to 10: by Dr. Thomson’s ratio of oxygen to azote, 4 to 7, the product will be .482, very different from .375. Hydrogen will give a product of .47 or .41 instead of .375. All these differences, it may be said, are occasioned by errors in the specific heats of the gases; but if errors of this magnitude can still subsist after all the care that has been taken, we shall scarcely know what to trust in experimental philosophy.
If M. Dulong would assume all his simple elements in an elastic state and under one uniform pressure, the hypothesis would then make a part of mine (vol. 1. page 70), and there is great reason to believe it would be either accurately true or a good approximation; but to suppose that some of the bodies should be in a solid state, having their particles united by various degrees of attraction, others fluid, and others in the elastic state, without any material modifications of their heat arising from these circumstances, appears to me to be in opposition to some of the best established phenomena in the mechanical philosophy.
Their observations on the specific heat of compound elements, on the relation of the heat developed by combination, as compared with the heat of the elements before and after the combination, &c., are not supported by a detail of actual experience. Heat given out by chemical changes they suppose not to have been previously in a state of combination with the elements. As an argument, the heat given out by charcoal kept in a state of ignition, by a current of galvanic fluid, is adduced. It is true this case is most easily explained, by allowing that the galvanic fluid is in such circumstances converted into heat. But the charcoal does not undergo any chemical change, and therefore this is not a case in point.
All modern experience concurs in shewing that the heat of combustion is primarily dependent on the quantity of oxygen combining. The heat evolved by the combustion of phosphorus and hydrogen is very nearly, if not accurately, in proportion to the oxygen spent. The heat by the combustion of charcoal is not in a much less ratio: and I find the heat in burning carbonic oxide, carburetted hydrogen and olefiant gas is the same as in burning hydrogen gas, provided the combining oxygen is the same.
One difficulty seems to have occurred to M. M. Dulong and Petit. They all along conceive that the specific heats of bodies, that is, the heats producing equal increments of temperature, must necessarily be proportionate to their whole heat. This is purely hypothetical, till established by experiment. The generality of writers on specific heat had conceived it almost confirmed by experiment. The results of Delaroche and Berard have shewn that in elastic fluids the increments of heat are not proportional to the whole quantities, but on the contrary are less when a body is elastic than when liquid. Indeed some writers have argued this should be the case; because a body nearly saturated with another has less affinity for it left.[27] It is plain then that oxygen gas or any other elastic fluid, may have a small specific heat in the sense above defined, and yet have an almost unlimited quantity of heat. I am not aware of any one established fact that does not admit of an explanation upon the hypothesis that heat exists in definite quantities in all bodies, and is incapable of any change, except perhaps into one of the other equally imponderable bodies, light or electricity.
NEW TABLE OF THE
Forces of Vapours in Contact with the
Generating Liquids at Different Temperatures.
- (A) = Temperatures by the common thermometer.
- (B) = Ether vapour, ratio 2 Spec. Gravity .72
- (C) = Sulphuret of carbon vapour, ratio 1.978
- (D) = Alcohol vapour, ratio 2.7 Spec. Gravity .82
- (E) = Acetic acid vapour, ratio 2.57
- (F) = Water, ratio 2.602()
| (A) | (B) | (C) | (D) | (E) | (F) |
|---|---|---|---|---|---|
| Inches of M. | Inches of M. | Inches of M. | Inches of M. | Inches of M. | |
| 7° | 3.75 | 3.134 | .193 | .11 | |
| 35 | 7.5 | 6.20 | .560 | .27 | .29 |
| 65+ | 15. | 12.26 | 1.51 | .69 | .75 |
| 97 | 30 | 24.26 | 4.07 | 1.77 | 1.95 |
| 133 | 60 | 48. | 11.00 | 4.54 | 5.07 |
| 173 | 120 | 29.70 | 11.7 | 13.18 | |
| 220 | 240 | 80.2 | 30. | 34.2 | |
| 272 | 88.9 | ||||
| 340 | 231 |
This is an improved and extended table of the force of vapour, similar to that at page 14, vol. I. It shews that the different vapours increase inforce in geometrical progression, to certain intervals of temperature, the same to most or all liquids. These intervals of temperature were presumed in the former table, to be in reality equal to one another; but the accuracy of this last notion has been questioned.
TABLE
Shewing the expansion of air, and the elastic
force of aqueous and ethereal vapour,
at different temperatures.