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Sostmann
OF
THERMOMETRY I
1: THE
ABSOLUTE,
OR THERMODYNAMIC
KELVIN,
TEMPERATURE
SCALE
Temperature is a measure of the hotness of something. be rational (and useful between people), there must scale of numerical values (the most familiar of which Centigrade
VdUfZS.
Scale),
and
on
devices
for
interpolating
only
temperature
scale of
with
a real
basis
in
nature
is
the
the * mark), and since it reference point is needed to was chosen, in the original
273.15K,
OC is a temperature with which we all have a common experience. It is the temperature at which water freezes, or, coming from the other side, ice melts; at which water exists under ideal conditions as both a liquid and a solid under atmospheric pressure. In 1954 the reference point was changed to a much more precisely reproducible point, O.OlC. This is known as the triple point of water, and is the temperature at which water exists simultaneously as a liquid and a solid under its own vapor pressure. The triple point of water will be the subject. of extended discussion important in a later reference article in this series point in thermometry. of articles. It is the most
The unit of temperature temperature interval K, and C or K (the indicate a temperature 1K or lC, but the
of the TKTS is the kelvin, abbreviated K. The C is identically equal to the temperature interval latter without the symbol) may be used also to interval. The difference between 1C and 2-C is 1-C = the temperature 274.15K.
temperature
Measurements of temperature employing the TKTS directly are hardly suitable for practicable thermometry. Most easily used thermometers are not based on functions of the First and Second Laws. The practicable thermometers that will be discussed later in this series of articles depend upon some function that is a repeatable and single-valued analog
of, or consequence of, temperature, and they are used as devices of utilitarian temperature scales (such as the Temperature Scale) which are themselves artifacts. The main the realisation of the TKTS is to establish relationships Thermodynamic Scale of nature and the practical thermometers of the laboratory or of industry, so that made by non-thermodynamic means can be translated into TKTS, and rational temperature scales can be constructed related to real&able physical phenomena. There points. two or ture is exist in nature a number These are physical states three of the three possible constant. of in what which phases
A two-phase equilibrium is represented by the earlier example of the freezing point of water, or, more properly, the coexistence of liquid and solid water. For this equilibrium to represent a constant temperature, OC, pressure must be specified, and the specification is a pressure of 1 standard atmosphere, 10 1325 Pascal. (A two-phase fixed point at 1 standard atmosphere is called the normal point). The variation due to pressure from the defined temperature of a liquid-solid equilibrium is not large (which is not to say that it may not be significant). The freezing point of water is reduced approximately O.OlK for an increase of pressure of 1 atmosphere. The variation due to pressure for a liquidvapor equilibrium is relatively very large. A three-phase equilibrium is represented by the triple point the coexistence of liquid and solid water under its own vapor at 0.Ol.C. Because all three possible phases are determined physical state, it is generally possible to realise a triple point curately than a two-phase point. This may be seen from the Phase Rule of Gibbs: of water, pressure, by the more ac-
P-C-2=F where P is an integer equal to the number of phases present, C is the number of kinds of molecule present (for an ideally pure material, C = 1) and F is an integer giving the number of degrees of freedom. Obviously, for the two-phase equilibrium there is one degree of freedom, pressure, and for the three-phase equilibrium F = 0; that is, the temperature is independent of any other factor. Fig.1 illustrates one, two and three-phase equilibria.
3a
Fig. 1: The Phase Rule of Gibbs. P = the number of phases C = the number of components (1 for a pure material); degrees of freedom. la is uncontrolled. lb is a melt point. Ic is a triple point. A typical since the (or rather device for realizing the TKTS is vapor pressure of an ideal gas a statistical mechanical function, transfer function in pressure of of a gas a gas kept
the helium gas thermometer, is a thermodynamic function which for the purpose is the thermometer at constant may be volume, chosen or the
change in volume of a gas kept at constant to measure accurately change in pressure in volume, constant-volume gas thermometers than constant-pressure gas thermometers. A rudimentary gas illustrated by using low the temperature Celsius Scale.
pressure. Since it is easier than it is to measure change are more common in use
be bethe
Fig. 2 shows a cylindrical bulb of constant volume, connected by tubing defined as constant-volume, to a U-tube manometer. A second connection to the manometer leads to a reservoir of mercury, which contains a plunger, P, by means of which the column height of the manometer may be varied. The constant-volume bulb and tubing contain an ideal gas.
The bulb is first surrounded by an equilibrium mixture of ice and water (C, in Fig 2a). When the gas is in thermal equilibrium with the slurry in the bath, the pressure of the gas is adjusted by moving the plunger so that both columns of mercury in the U-tube are at the same height, corresponding to an index mark 1.
2a Fig.2: A rudimentary gas thermometer. B = mercury, C = water t ice (O-C), (100(Z), P = a plunger for adjusting A = helium gas. D = water t steam mercury level.
2b
Next, the ice bath is removed and replaced with a bath containing boiling water, or more correctly, an equilibrium mixture of liquid and vapor water at a pressure of 1 standard atmosphere, (D, in Fig 2b). As the manometric gas is heated by the boiling water it expands, and the mercury in the manometer is displaced. The plunger is actuated to reposition the surface of the mercury in the left leg at the index mark 1, restoring the criterion of constant volume in the closed gas system, a condition shown in Fig 2b. However the mercury in the right, open leg is not now at the index mark 1, but measurably higher. In fact, the difference in heights indicates that the pressure of the enclosed gas at the boiling point is 1.366099 times the pressure at the freezing point. We can then calculate: (100-c - OC)/(1.366099 - I) = 273.15 Eq.2
this we can understand ratio change between by 273.15 Celsius or reached therefore + 273.15 on the temperature reference which is the and 273.15K,
the Celsius degree OC and 1OOC. Thus kelvin intervals below zero of the TKTS. The
T = t
Eq.3 TKTS and t is temperature interval and the zero to the properties of on the Celsius of the TKTS have any specific sub-
where T is temperature Scale. Note that the been defined without stance. All terms constant of the P2 Ts the volume equation
gas
thermometer
measurements
can
be
expressed
in
PI /
where Scale, This that sure the and
= 01 - To) /
are TOs temperatures are the
(5
- To)
on the that TKTS, Scale. will the natural
Eq.4 temperature
zero
of
an ideal gas. The reader reflects Charles or Boyles gas, respectively, be held
gas is a gas whose behavior can be predicted exactly from Charles Law, which obeys it through all ranges of temperature sure, and where the relationship between concentration (n/V), temperature (n/V)(T/P) more commonly PV = nRT where R is the gas constant, identical for all ideal gases. and is known to about 30ppm. A second condition is that thus the internal energy, intermolecular forces acting, depend on the molecular distances, and (6E Unfortunately is a large / 6V)T = 0 is no real ideal gas, Helium comes closest, and the carbon uncertainty dioxide and absolute = I/R written pressure = a constant as is
Eq.5
there number.
real a in
approach in of
as Since zero
their
pres-
a gas
zero
volume)
requirement
an ideal gas is approached by making a number of measurements at a number of pressures and extrapolating to zero pressure. Such a system of measurements is shown in Fig. 3. Regardless of the nature of the gas, all gas thermometers at the same temperature approach the same reading as the pressure of the gas approaches zero.
374.0
gases at various point of steam. of the ideal gas law used, in to ac-
have
modifications
count for the non-ideality of real gases. of Clausius, is the virial equation, which of the density of the gas, and is written: nB, + -- n2Cv + ---2 B, n3Dv + ---3
is much expansion
that terms
PV = nRT(1
+...)
Eq.8
where
the
coefficients
C, D, etc.,
are
called
the
second,
third,
fourth,
etc., volume virial given temperature. mometry, it is coefficient. The departure accurate gas
are constants for a given gas at a range of gas densities in gas therto go beyond the second virial
from
ideality
is
only
one
of
the
problems
of
A second is the purely mechanical matter a real connection to convey the pressure ter. It is inconvenient to locate the bulb thermostatted enclosures, 2 to illustrate enclosure, and a common each carefully thermostatted. this configuration.
of dead space. There from the bulb to the and the manometer in practice Fig. is 4 is to use two a modification
Fig.4: Thermostatted gas thermometer. meter and the gas bulb are separately temperature; the (long, perhaps many is not. The length, price which paid is that goes through is The there the is a capillary wall of each
some and
relative to the capillary volume. capillary length can be measured at suitable intervals. The capillary volume can be kept small by providing a capillary of small diameter, but not so small as to introduce thermomolecular pressures where the tube a correction for passes through a temperature gradient, or , conversely, thermomolecular pressure can be made.
A third
obvious
problem
is that
of
the
thermal thermal
expansion gas
of
the
materi-
the whole system is subject or estimated, and for which correction the system, required including effects from is that for
changes, which must be made. head itself. impurities in clean system, pressure
A fourth gas in
of
the
of
the
to the remaining
in which ideally
the are
gas, ab-
sorbed on the walls of the bulb and other parts of the thermometer system at the reference temperature, desorbed at a higher temperature, with the effect of elevating the measured gas pressure, and then reabsorbed as the temperature approaches the references temperature. Attention to the elimination of sorption has resulted in gas thermometry measurement Gas thermometry for some Edsinger, of the has normal claimed boiling the point attention of water of a as 99.975-C! of fine experi-
number
generations, followed
dards. This work forms much of the Practical Temperature Scale of 1968 Scale of 1990, in an effort to more
temperatures in a practicable Scale. A concise mometer and gas thermometry at the NBS is should be consulted by anyone interested Schooley provides an example of the accuracy work: Fixed point IC Steam pt Gas therm IC 99.975 231.924 419.514 IPTS-68 3 100.000 231.9681 419.58
account of the gas therand given by Schooley, in experimental elegance. and precision of this
Uncertainty
Tin pt Zinc pt
With the conclusion of work in preparation for ITS-90, is considered to be a finished matter at the NBS. The itself, which should have been preserved as a national ment, is now in the process of dismemberment. As a generality, namic values methods have gas the thermometry thermometric used largely has led the fixed points, to check its
of
been
include
acoustic and of
thermometry,
dielectric-constant each
gas
thermometry, to a
appropriate
2: THE
SCALE
OF
1990
International
a recommendation of its Consultative new practical temperature scale, Temperature Scale of 1968, which of previous Scales, those of 1948,
Committee
Thermometry
to replace the International had replaced, in turn, a suc1927, etc. The official text of of as word French, 1990. of will The be pubITS-90 is 1990. is is not de-
the ITS-90, in English translation lished in Metrologia, probably in officially in place as the international
1 January,
As in previous practical used in the title of the fined as tr,O/C and temperatures = TgO/K are -
substances (defining~ fixed points), interpolating instruments, and equations which relate the measured property to T(90). The defining fixed points and the values assigned to them are listed in Table 1, and the values which were assigned on IPTS(68) are listed also, for comparison. It is to be remembered that, while the Scale values assigned to a fixed point may have been changed, the fixed point has the identical hotness it always Several had. deep From device From 3.OK to the triple volume gas thermometer From gas From 3.OK thermometric to the gas triple point of neon with 3He or 4He as the 4.2K to the triple point of neon (24.5561K) using a constantcryogenic 0.65K to ranges 5.OK using are a provided. helium These vapor are: pressure interpolation
point
of
neon
with
4He
as
the
thermometric
10
These ranges cialists, and thermometer from 13.8033K of The subranges. below Scale slightly
are probably of interest to only a limited number of spewill not be dealt with in detail in this paper. The resistance portion of the Scale is divided into two major ranges, one to 0-C and the other from OC to 961,68C, with a number There to is third above short OC, in range Table which 2. embraces -38.8344 temperatures to +29.7646-C. slightly are specifically
ranges
summarised
The interpolations platinum resistance the resistance WT(90) a change OC, and one from at the
as the ratios of the (PRTs) at temperatures water; that is: Eq.10 of IPTS(68) which be used the
resistance of T(90)
of and
resistance
at
as denominator. The PRT must free; it is considered a measure two constrains are met: L 1.11807 L 0.844235 for use (gallium (mercury to the melt triple freezing
W(302.9146K) W(234.3156K) and a PRT acceptable meet this requirement: W(1234.93K) The ship: temperature
Z 4.2844 T(90) is
(silver calculated
point) resistance
W,T(90)
cific PRT from the reference function at T(90). (The reference functions represent the characteristics of a fictitious standard thermometer; the deviation function represents the difference between that thermometer and an individual real thermometer). The deviation function is obtained by calibration at the specified fixed points, and its mathematical form depends THE upon the temperature 13.8033k range TO 273.16K of calibration.
RANGE
FROM
11
The
reference
function 12
for
this
range
is
ln[WrT(90)]
= A,
+ K Ai{[ln(T(90)/273.16K)+1.5]/1.5)i i=l of A, and Ai are over given the or in the text range, of
Kq.15
where If the
the PRT
values is to
the down
Scale. to 13.8033K,
be
calibrated
it must be calibrated at specified fixed tures determined by vapor pressure mometers will most likely be calibrated and this paper will of general interest 83.8058K (-189.3442-C), not to the include details, the primary triple point
The subrange from -189.3442 to 273.16-C triple point of argon (-189.3442C), the 38.8344-C) and the triple point of water to b. The deviation FROM function I] 0-C is: lllnW(T(90))
requires calibration at the triple point of mercury (obtain the coefficients a and
+ blW(T(90)) TO 961.76.C
Eq.16
from OC of silver,
point
of
water
to
the
WrT(90)
= C,
754.15)/4811i
Eq.17
and
the
coefficients
Ci are
specified
in
the
text
of the
over this entire range must be calibrated at and the freezing points of tin, zinc, aluminum a, b and c are derived from the tin, zinc and the reference below coefficient value at the
aluminum calibrations respectively, the deviation of WT(90) from the silver. For d = 0. The dWT(90) temperature deviation II3 measurements function is 11 + b[WT(90) + dCWt(90)
freezing
= a[WT(90) + c[WT(90)
II2
Eq. 18
- W(933.473KE2
12
PRTs
may
be
calibrated
over
the
whole
range
or
for
ranges shorter
terminating ranges of
at the freezing points Eq. 18, the equation is jJoner Aluminum Zinc limit
For
the
still
shorter
range
from
the
triple
point
of
water
to is:
the point
at the deviation
Eq.19 of water triple function to the freezing of water point and of the
indium, freezing dWT(90) For the gallium, equation For the gallium
the
point is:
triple point of water to required at these points, Eq.20 except for the
calibrations are gallium melting dT(90) However portion 0-c. For a = aCHT(90) the of the
required at the mercury point, and the deviation 11 + bCWT(90) function below OC, must and 112
reference Scale
for
relatively
simple
thermometer range from 1.5mK below, see the article Isotech Journal.
13
The
temperature thermometer
range as
above
the
freezing
point
of and
silver the
employs relationship
radiation is:
interpolating
instrument,
L X(TYD)/LX(TYO(X)
= (expCc2/
XT90(X)]
1) 1)
Eq.22
the spectral concentrations of radix in vacuum at TSO and at TSO(X). gold point or the copper point. C2 =
3: THE
1990
VALUE
OF
THE
OHM of the standard ohm also change effect, of the in the slight 1990. new but
The National The change international not insignificant various national resistors following Germany:
because resistance,
the ohm by the of the standard The resistance. States and West
NPL (England) increased the value of their ohm by t1.61 ppm. Thus a perfectly stable 1 ohm resistor calibrated at NPL prior to January 1, 1990, has a new value of 0.99999839 ohm. A 10 ohm resistor has a new value of 9.9999839 ohm. 1Q (NPL 1Q (NPL NIST ppm. 1990, value 90) 89) (United = 1.00000161Q = 0.99999839Q States) (NPL (NPL 89) SO) the value of their ohm by +I.69
increased
1 ohm resistor calibrated value of 0.99999831 ohm. ohm. = 1.00000169s2 = 0.99999831Q (NBS (NIST 89) 90)
at NIST A 10 ohm
prior to resistor
1~ (NIST 1Q (NBS
Germany) increased the 1 ohm resistor calibrated value of 0.99999944 ohm. ohm.
value of their ohm by to.56 at PTB prior to January 1, A 10 ohm resistor has a new
14
1~ (PTB 1Q (PTB
Other laboratories adjusted the ohm (a decrease); France, +O.?lppm; BIPM, The effects on calibrated the calibration by in 1989, and at of with 650-C
a standard a typical (f or
therOC as are
mometer
25.5249052)
t(89)
0-c
650-C where d(Q) and d(t) is
NBS 89 Q
NIST
90 Q
25.52490 85.28842
is the decrease the increase in
25.52486 85.28828
1 1 t a(tl 13 are
a and
is
conventionally
reported
at
25-C,
and
will
con-
t(90) of the ohm may be significant that the difference in the value resistor will require consideration.
************************************+***%%%%%%%%%%%%%%%%%%%% In our next issue, the fixed points realising them. we and will of discuss in detail the the equipment and physical operations embodiment involved of in
TABLE 1 FIXED POINTS OF THE IPTS-68 AND OF THE ITS(90) SUBSTANCE AS ADOPTED BY CIPM, OCTOBER 5 1989 CELSIUS TEMP. ITS-90 -259.3467
-218.7916
15
STATE CELSIUS TEMP. IPTS-68 Trip Trip Trip Boil Trip Trip Melt Freeze Freeze Freeze Freeze Freeze Freeze Freeze -259.34 -218.789
-189.352 -195.802 -38.842 0.01 29.772 156.634 231.9681 419.58 660.46 961.93 1064.43 1084.88
e-H2
02
Ar
N2 Hg H20 Ga
-189.3442 -195.794
-38.8344 0.01 29.7646 156.5985 231.928 419.527 660.323 961.78 1064.18 1084.62
in points
equilibrium are
between
the
ortho
and
para
at 1 standard
atmosphere
= 101 325
TABLE 2 RANGES OF THE ITS-90 THE PURCHASEROF A CALIBRATION MUST STATE THE RANGE REQUIRED*
LOW LIMIT -259.3467
16
(TP),
e-H2
(VP),
Ne (TP),
Hg
Hg (TP), H20
-218.7916
0.01
02
(TP) -189.3442
0.01
Ar
H$
(TP), (TP),
OF), Ga (ME)
Hz0
(TP)
0.01
0.01 0.01
H20 (TP).
H20 H20 (TP),
Ga (HP).
Ga (HP),
In (FP)
Sn (FP)
231.928
419.527 660.323
(TP).
Sn (FP),
Sn (FP),
Zn (FP)
2n (FP), Al
0.01
961.78
Zn (FP), Ga (MP)
(FP) at
Al
-38.8344
29.7646
pressure determination, (TP) = triple point. (VP) = a vapor (MP) = melting freezing point at 1 standard atmosphere, standard atmosphere *The purchaser may choose to specify -189.3442 to +419.527, for example, -200 to +500. example,
=
1
point
ranges, for
17
TABLE 3 THE COEFFICIENTS OF THE REFERENCE The values of the coefficients Eq. 15 and 17 Eq.15 CONSTANT OR COEFFICIENT VALUE FUNCTIONS functions of
A0
Al A2 A3 A4 A5 A6 A? A8 A9 A10 All A12
-2.135 3.183 -1.801 0.717 0.503 -0.618 -0.053 0..280 0.107 -0.293 0.044 0.118 -0.052
247 20 435 97 272 04 440 27 993 95 323 22 213 62 152 24 028 65 598 72 686 32 481 34
co
Cl c2 c3 c4 c5 c6 c7 c8 C
2.781 1.646 -0.137 -0.006 -0.002 0.005 0.001 -0.002 -0.000 0.000
572
54
Ar (TP)
Hg (TP) Hz0 (TP)
18
OF
PART
Th-o&y, thermometry
at
Twnpm
a, Academic
London
and
New
York
(1873)
F. Henning, H. Maser, Twnpucatuwn &wag, New York, 3rd edition (1977). German pressure thermometry by W. Thomas THE INTERNATIONAL Preston-Thomas 06 19 68 TEMPERATURE The (~e:ev-i-&on SCALE
t&&a
Ira.tea~od 04 1975
I Metrologia tie
P.wzc-GcaX Tanpeaduae 12, 1 (1976) the EPT-76, France. This at some future
Supp&mentcMy Inbomon Bureau International des publication continues to be date to include ITS-90
4oa
Poids valuable, et
R. E. Bedford, G. Bonnier, H. Maas, F. Pavese, appeoximetlng .#LQ I-tied Temp wt.aauAe BIMP, when published; no projected date is known. unofficial copies of a late draft indicate that this will e Scu& The Iti.awat.Lod TempcauUu/t official text of the new Scale, and it will Metrologia advises that it will be published 1990). THE 1990 OHM Ln tie Vdue 04 the UK Force and Redistance, England (1989) al, the NIST Technical New Rep~eaentetLon-6 of Commerce (1989) Neue Iwoti (1989) Re&xence National 06 be in
S+and4nda Physical
06 &&QCLaboratory,
Note
1263,
04
.the
40~ .the
d.-k