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Regnault's "Determination of the Specific Heat of Steam"

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1882 Proc. Phys. Soc. London 5 87

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 PK 0CE E D IN G S

T H E PHYSICAL S O C I E T Y
OF L O N D O N ,
.-......
_..._.
^_.
~ ~~ _..........z._

JULY
188%.
IX. Rcgnault’s Determination of the Spec$c Ileut of X t r u ~ , ~ .
By J. &fACFAItLANE GRAY+.
IlEGNhULT’S experiments on the specific heat of‘ vapours havr!
Imri iiiterprcted by Regnault as giving results not at :~11
in accordance with tho deduction from the kinetic theory
of gam, that, for matter travelling in single moleculos,
the product of the molecular weight by the specific heat is
:L constant for all substanccs. I have been led, by considor-
i tig tlic order of‘ teiiipcrature-pi.essures for steam, t o conclude
that the above deduction is true for stcam; and I have no doubt,
nlso for all inattcr travelling in binfile molecules. When, in
1880, I laid my conclusions before the Physical Society :is
being corroborated by Rcgnault’s dynamicd esperinients, it
was objected that Ilcgnault’s direct thermal cxpei-imcnts gave
results widcly different from my conclusions ; and the report
on my paper was that that difference provcd that, in the cor-
roborations I had pointed out, I had been led away by mcrely
numerical coincidence.
I will now show that Rcgnault’s thermal experiments have
Imxi inisinterpreted by Ilegn:LuIt himself, and that he ouglit to
have m:td tlic specific heat of s t e m , according to his e s p r i -

Rend February 36, 1883.

\’OL. v I
88 YR. J. M. GRAY ON REGNAULT'S DETERMINATION

ments, to be exactly in accordance with the deduction of the

kinetic theory.
The method of the experiments was to generate steam at
100' C., to superheat it under atmospheric pressure to (say)
125' in one set ofesperiments, condeiising it in a calorimeter
to ascertain what quantity of heat was given up, clowii to 0'.
In a second set of experiments with the same apparatus, tlie
teinpernture was raised to (say) 225', while the steam was
still at atmospheric pressure ; this was also condensed in the
eame calorimeter. I t was found tliat the heat given up by the
steam nt 225' exceeded that given u p by thc stenni at 125'by
413.051 units of heat ; and, dividing by the JiRerence of tcm-
p x t u r c (loo), Itcgnault found 0.48051 for the specific hcat
of steam at constant pressure.
I n these cspcrimcnts the superlieating to 125' was, no
doubt, inknded to thoroughly dry the steam, so as to get, in
the quantity of heat abandoned in tlie first sct of experiments,
the entire heat of complete gaseficatioii, bccausc, if still soni(?
moisture remained in thc steam, the latent lieat of evaporm1' t'ion
of that inoisture would be included in the diff"x+quantity
supposed to be due to the specific heat of tempcrature-raising,
and, by that amount, tlie result would be too high.
It appears to me that the completion of tho evaporation of
suspended rnoisturc cannot be accotn1)lislicclbctween 100' and
125'; but it will be inore likely to be carried on between 125'
and 225'. Particles of liquid remain at tho pressure-tempe-
raturc whatever be the superheated temperature of tho gas in
which they are suspended. The rate of evaporation of those par-
ticles will therofore depend upon the temperature-difference ;
and in the lower range of temperatures but little of the mois-
ture will bo evaporated in its rapid passage through a worm
heated to only 25' in excess of the pressure-temperature. I n
the second set of experiments the excess of temperature
was 125'.
To test this, let similar experiments be made at 100';
and if the resulting apparent specific heats between 100'
and 125Oare higher than those obtained by Regnault b e
tween 125' and 225O, then my argument is demolished; but
if the results are snialler, then my suspicions have been jus-
tified, and a correction is required on the results as given by
 OF THE SPECIFIC HEAT OF STEAM. 89
Ilcgnault. Fortunately for my object, Regnault has left us (in
vol. i., :it page 695) the d i l h of thirty-eight reliable esperi-
mwts on the “ total hcnt ” ofstc:iin at 100’ down to Oo,giving
thc incnii = 636.70 units of heat. I have, with this total
11e:it” for looo, compared the results of the esperiments on tho
stentn of 12.j0-in precisely the same way as Ibcgnault worked
ti)r tile i n t e n d between 125’ and 225’ (these espcrimcnts arc
rccordcd in vol. ii., pngas 167-178). The results of niy cdcu-
1;~tionsare given below. The first two series were merely pre-
Ixrattory trials to arrive at the best form of apparatus; and only
:L few gramrncs of vapour were passed. through the worm at
onch of tliose csperiinents. In the third and t h fourth series
tan tiiiics as much vapour was passed through on each occasion.
Ilcgnault s:iys:--“ J’ni pu opdrer a i d sur dcs quantitds de
wpcnr beaucoup plus considdmbl~s,et diniinucr 1’iniport:ince
wl:\tivc>dcs corrections produites par les causcs perturbatriccs.”
This consideration is still more important when tho rangc of
tcnipcrature is limited to 25°-onIy one fourth of the riinge
froin which Iiegnault deduccd his result. The large cnlori-
Ineter was used-only in the third and fourth :rios.
I;irst series. Fourth series.
~280 -386
-4G5 -381
~417 .Y4G
*377 *309
-463 Mean ,567 ~400 -427
- -411 *463
DIcaii -400 .349
~ 4 1 3 Mea11 -3853
Preparatory trials.
I( ,405
-415
--
c
/I Mean ,3721

That the method of calculation may be perfectly clear, I

give the particulars for the first experiment in the fourth series.
Superheating’to 124O.81, each unit of vapour gave up 646.28
nnits of heat down to 0’. Steam at 100’ gave up 636.70
down to 0’.
646.28 - 636.70
__ =*38G.
124.31 -100
I 2
 MR. s. BIDWELL ON THE ELECTRICAL RESISTANCE

Thc qnantity of vapour in tliis esperi~nentwas 102.62 g r i ~ i;~ .

the quantity in tlie first of the first series was only ti.!iCii firms.
Tlic fourth series W:IS mndc Jvitf-i :in apparatus wliidi w : i , ~;;Ti
iinprovcnient on t h t used in thc third scrics ; and, taking tli:,t
series only, adding tlic proLaClr1 aniount of' nioisturc w l i i ( s ] i
would remain :It 100' t ~ n i p c r a t ~ r(say
e 1 pcr cent. 011 t I i , b

*38ri), the result is -389; this, on 0 t h grounds, I h l' 'l e v ( ' tc,
1)c: iie:trly corrcck. If, lion.ever, ncglccting the other g i ~ c ) i i i i ~ I ~
I'or 1 i i y ol)inion, we takc the mcnn of the m x n s of' the tLirxI
:incl tlic fourth series, wc g e t
~3721
~-
+ -3853 -
- ,3787,
2
Tliis is what R r p d t , might fairly have done.
If we iiow c:ilculate what Regnault's experiments wonlti
give :is tho kinetic-theory result, we Act tlie specific 1ic:it of
ligtlrogon, :it page 121, U mean = 3.4090 ;" :ind taking tlic
iiiolecular weight of steam = 17*9G, we find the specific he:d
of stearn
2
3.409 x -==3i96.
17.Y6
Tliat is to say, the kinvtic theory and the thermal determinn-
tion give :illnoit itlcntically the snmc nuniber.
Tliis is, I bclicvc, the first experimental proof that the 1:iv
of in\.ersely as the molecuhr weights " applies to compound
gases.

X. T?/e 32Tec.t Twipcratzwe on the Electrical Rpsisimrc

U/'

qf J(isfures q/ S'lcklLur cind Cwbon. B y SHELFO~~I)

13IDKE I, L, M,A., LL.B.*
SINCRDcccmber 1880 I h a w from time to time made a nun;-
1)cr of experiments with tho object of asccrt:iining whetlic~r
sul~iliurcould, undchr any circuinstnnces, be made to exhibit
thc reinarkable property possessed by seleniuni, and in :t
sin:~llerdegree by tellurium, of having its electrical resistance
diniinislicd ?JJ- the action of light.
Amongst other things, tho cffect was tried of mixing it with
* Rend llnrch 25, 1882,