Hugh Longbourne Callendar

“ A bubble of vapour containing no air or gas could not exist at all in stable equilibrium in a liquid. If its radius r were such as to make 2T/r greater than p−P, it would collapse entirely. A bubble containing gas, on the contrary, is in stable equilibrium when its radius r is such that the pressure of the gas and vapour inside it balance the external pressure P together with the capillary pressure 2T/r. Any diminution of r produces an increase in the pressure of the gas which is more than sufficient to balance the increase of the capillary pressure 2T/r. ”

“ Without difference of temperature there is no transfer of heat. When two bodies have been brought to the same temperature by conduction, they are also in equilibrium as regards radiation, and vice versa. If this were not the case, there could be no equilibrium of heat defined by equality of temperature. A hot body placed in an enclosure of lower temperature, e.g. a calorimeter in its containing vessel, generally loses heat by all three modes simultaneously in different degrees. ”

“ Similarly if A is hotter than B, or if there is a gradient of temperature between adjacent layers, the diffusion of molecules from A to B tends to equalize the temperatures, or to conduct heat through the gas at a rate proportional to the temperature gradient, and depending also on the rate of interchange of molecules in the same way as the viscosity effect. Conductivity and viscosity in a gas should vary in a similar manner since each depends on diffusion in a similar way. The mechanism is the same, but in one case we have diffusion of momentum, in the other case diffusion of heat. ”

“ Forbes’s Bar Method.—Observation of the steady distribution of temperature along a bar heated at one end was very early employed by Fourier, Despretz and others for the comparison of conductivities. It is the most convenient method, in the case of good conductors, on account of the great facilities which it permits for the measurement of the temperature gradient at different points; but it has the disadvantage that the results depend almost entirely on a knowledge of the external heat loss or emissivity, or, in comparative experiments, on the assumption that it is the same in different cases. ”

“ A body may possess energy in virtue of its state (gas or steam under pressure) , or in virtue of its position (a raised weight) , or in various other ways, when at rest. In these cases it is said to possess potential energy. It may also possess energy in virtue of its motion or rotation (as a fly-wheel or a cannon-ball) . In this case it is said to possess kinetic energy, or energy of motion. In many cases the energy (as in the case of a vibrating body, like a pendulum) is partly kinetic and partly potential, and changes continually from one to the other throughout the motion. ”

“ The most obvious case of the production of work from heat is in the expansion of a gas or vapour, which served in the first instance as a means of calculating the ratio of equivalence, on the assumption that all the heat which disappeared had been transformed into work and had not merely become latent. ”

“ Prevost’s leading idea was that all bodies, whether cold or hot, are constantly radiating heat. Heat equilibrium, he says, consists in an equality of exchange. When equilibrium is interfered with, it is re-established by inequalities of exchange. If into a locality at uniform temperature a refracting or reflecting body is introduced, it has no effect in the way of changing the temperature at any point of that locality. ”

“ If we assume that the coefficient of expansion of platinum, the coefficient of increase of resistance, and the specific heat are all three linear functions of the temperature, we obtain results which are in agreement within the limits of error of observation up to the fusing-point of platinum itself. ”

“ Arbitrary Scales.—An arbitrary scale can be constructed by selecting any physical property of a substance which varies regularly with the temperature, such as the volume of a liquid, or the pressure or density of a gas, or the electrical resistance of a metal. ”

“ Helmholtz gives an admirable statement of the fundamental principle as applied to heat, but makes no attempt to formulate the correct equations of thermodynamics on the mechanical theory. He points out the fallacy of Holtzmann’s (and Mayer’s) calculation of the equivalent, but admits that it is supported by Joule’s experiments, though he does not seem to appreciate the true value of Joule’s work. He considers that Holtzmann’s formulae are well supported by experiment, and are much preferable to Clapeyron’s, because the value of the undetermined function F′t is found. ”

“ From the sense of heat, again, we naturally derive the idea of a continuous scale or order, expressed by such terms as summer heat, blood heat, fever heat, red heat, white heat, in which all bodies may be placed with regard to their degrees of hotness, and we speak of the temperature of a body as denoting its place in the scale, in contradistinction to the quantity of heat it may contain. ”

“ Irreversible Processes.—In order that a process may be strictly reversible, it is necessary that the state of the working substance should be one of equilibrium at uniform pressure and temperature throughout. If heat passes “of itself” from a higher to a lower temperature by conduction, convection or radiation, the transfer cannot be reversed without an expenditure of work. If mechanical work or kinetic energy is directly converted into heat by friction, reversal of the motion does not restore the energy so converted. ”

“ The converse process of freezing or solidification, the change from the liquid to the solid state, is subject to the same laws, and must be considered together with fusion. The solution of a solid in a foreign liquid, and the deposition or crystallization of a solid from a solution, are so closely related to the fusion of a pure substance, that it will also be necessary to consider some of the analogies which they present. ”

“ In space void of matter, we should have pure radiation, but it is difficult to obtain so perfect a vacuum that the effects of the residual gas in transferring heat by conduction or convection are inappreciable. In the interior of an opaque solid we should have pure conduction, but if the solid is sensibly transparent in thin layers there must also be an internal radiation, while in a liquid or a gas it is very difficult to eliminate the effects of convection. ”

“ In the case of substances like ice, which melt at a low temperature and are easily obtained in large quantities in a state of purity, the point of fusion may be very accurately determined by observing the temperature of an intimate mixture of the solid and liquid while slowly melting as it absorbs heat from surrounding bodies. But in the majority of cases it is more convenient to observe the freezing point as the liquid is cooled. ”

“ If a hot iron is placed on a cold iron plate, we may observe that the plate is heated and the iron cooled until both attain appreciably the same degree of warmth; and we infer from similar cases that something which we call “heat” tends to pass from hot to cold bodies, and to attain finally a state of equable diffusion when all the bodies concerned are equally warm or cold. Ideas such as these derived entirely from the sense of heat, are, so to speak, embedded in the language of every nation from the earliest times. ”

“ Balfour Stewart gave a number of striking illustrations of the qualitative identity of emission and absorption of a substance. Pieces of coloured glass placed in a fire appear to lose their colour when at the same temperature as the coals behind them, because they compensate exactly for their selective absorption by radiating chiefly those colours which they absorb. Rocksalt is remarkably transparent to thermal radiation of nearly all kinds, but it is extremely opaque to radiation from a heated plate of rocksalt, because it emits when heated precisely those rays which it absorbs. ”

“ Even if the expansion is adiabatic, in the sense that it takes place inside a non-conducting enclosure and no heat is supplied from external sources, it will not be is entropic, since the heat supplied by internal friction must be included in reckoning the change of entropy. Assuming that no heat is supplied from external sources and no external work is done, the intrinsic energy remains constant by the first law. The final state of the substance, when equilibrium has been restored, may be deduced from this condition, if the energy can be expressed in terms of the co-ordinates. ”

“ Accepting the conclusions of Davy and Rumford that heat is not a material substance but a mode of motion, there still remains the question, what definite conception is to be attached to a quantity of heat? ”

“ As the result of Joule’s experiments, we are justified in concluding that heat is a form of energy, and that all its transformations are subject to the general principle of the conservation of energy. ”

“ Heat equilibrium in an enclosure of constant temperature such as is here postulated by Prevost, has often been regarded as a consequence of Carnot’s principle. Since difference of temperature is required for transforming heat into work, no work could be obtained from heat in such a system, and no spontaneous changes of temperature can take place, as any such changes might be utilized for the production of work. ”

“ For every change of state a definite quantity of heat is required, without which the change cannot take place. Heat must be added to melt a solid, or to vaporize a solid or a liquid, and conversely, heat must be subtracted to reverse the change, i.e. to condense a vapour or freeze a liquid. The quantity required for any given change depends on the nature of the substance and the change considered, and varies to some extent with the conditions (as to pressure, &c.) ”

“ In reality the fraction of the heat of combustion available, even in an ideal engine and apart from practical limitations, is much less than might be inferred from the efficiency formula of the Carnot cycle. In applying this formula to estimate the availability of the heat it is usual to take the temperature obtainable by the combustion of the fuel as the upper limit of temperature in the formula. ”

“ The pressure of the air varies both on account of changes of volume and on account of changes of temperature; but it should be observed that for equal volumes, that is to say, for like positions of the piston, the temperature is higher during the dilatation than during the compression. Since the pressure is greater during the expansion, the quantity of motive power produced by the dilatation is greater than that consumed by the compression. We shall thus obtain a balance of motive power, which may be employed for any purpose. The air has served as working substance in a heat-engine ”

“ Each degree rise of temperature in a mass of water would then represent the addition of the same quantity of heat. The scale thus obtained would, as a matter of fact, agree very closely with that of a mercury thermometer, but the method would be very difficult to put in practice, and would still have the disadvantage of depending on the properties of a particular liquid, namely, water, which is known to behave in an anomalous manner in other respects. ”

“ The transition of any substance, from the state of liquid to that of solid or vapour under the ordinary atmospheric pressure, takes place at fixed temperatures, the freezing and boiling-points, which are very sharply defined for pure crystalline substances, and serve in fact as fixed points of the thermometric scale. A change of state cannot, however, be effected in any case without the addition or subtraction of a certain definite quantity of heat. ”

“ Assuming with Magnus that at least 10% of the heat from a source at 100° C. is absorbed in passing through a single foot of air, a very moderate thickness of atmosphere should suffice to absorb practically all the heat radiated from the earth into space. This could not be reconciled with well-known facts in regard to terrestrial radiation, and it was generally recognized that the result found by Magnus must be erroneous. Tyndall’s experiment on the great diathermancy of dry air agreed much better with meteorological phenomena, but he appears to have exaggerated the effect of aqueous vapour. ”

“ Similarly in thermal equilibrium between bodies at the same temperature, an indefinitely small difference of temperature suffices to reverse the transfer of heat. Carnot’s rule is therefore the criterion of the reversibility of a cycle of operations as regards transfer of heat. It is assumed that the ideal engine is mechanically reversible, that there is not, for instance, any communication between reservoirs of gas or vapour at sensibly different pressures, and that there is no waste of power in friction. ”

“ Heterogeneous Equilibrium.—In a system, as distinguished from a homogeneous substance, consisting of two or more states or phases, a similar condition of equilibrium applies. In an spontaneous irreversible change, if the system is heat-isolated, there must be an increase of entropy. The total entropy of the system is found by multiplying the entropy per unit mass of the substance in each state by the mass existing in that state, and adding the products so obtained. ”

“ If a hot body is placed in a cavity in a block of ice at 0° C., and is covered by a closely fitting slab of ice, the quantity of ice melted will be directly proportional to the quantity of heat lost by the body in cooling to 0° C. None of the heat can possibly escape through the ice, and conversely no heat can possibly get in from outside. The body must cool exactly to 0° C., and every fraction of the heat it loses must melt an equivalent quantity of ice. ”