JOURNAL OF RESEARCH of the Na tional Burea u of Standards-A.

Physics and Chemistry

Vol. 69A, No. 6, November-December 1965

Isotherms Determined by the National Bureau of Standards

Acoustical Thermometer in the Liquid Helium
Temperature Range
G. Cataland and H. Plumb
(.July 7. 1965)

Is ulh e rm s u f Ih e s pee d uf s uuncl in he lium 4 g:as as a fun c l iun uf press ure have bee n meas ure d.
Fi ve (If Ih e isu lh e rm s in Ih e liquid he lium 4 1e mpe ra lure ra n ge Ilave bee n a na lyze d , a nd Ihe res ull s a re
di scussed . The acoustically d e t e rmine d valu es of te mpe rature are co ns is te ntly hig he r than Ih e va lu es
of le mpe ralul'e a ss (lc ia led wilh Ih e liquid he lium 4 vapo r p ress u re sc a le (T ,.). T he d ev iali uns arc
0.006 OK a l 2 .323 OK. 0.007 OK a l 2. 807 OK. 0.008 OK a l 3 .211 OK, 0.0]0 OK a l 4.212 OK a nd 0.01 2 OK a l
5. 024 oK.

Key Wurd s : Ac uu s li ca l Ih c nnuill e lc r, iso l he rlll a l low Ic mp e ra lllrc . S pee d of s uund in he lium
~as . th e rmom e try at lu w te mpe ratur e.

1. Introduction th erm o me t.ri c gas a nd the press ure meas ured at so me

ass um ed valu e of te mperature. Thi s ass umption is
A program of absolute and seco nd ary lo w tempera- criti cal and receiv es carefu l co nsidera ti on, na turall y,
ture th erm ome tr y has bee n co ndu c ted for som e years but a cascad ing of errors from on e te mperature ran ge
at the Nati onal Bureau of Stand ards . Certain of th e to another is possible. Thi s type of error is also
results are in th e pro cess of being re ported a nd thi s avo id ed in our approach to the rm o me try .
paper prese nts a bsolute te mperature de termination s Th e me th od of te mper a ture de termin at io ns whi c h
in the lower range of inves tigati on . we have purs ued is base d on th e s peed of so und in
Thu s far , absolute thermome tr y at th ese te mpera- helium gas as a fun c ti o n of the gas press ure. Sin ce
tures has bee n co ndu c ted by e mployin g eith e r a gas tran slational di s pers ion of s peed s in our experim e nts
thermom e ter or ap parat us desig ne d for P - V isoth erm is negli gible, one ca n proceed ho m th e ba sic equation
de terminati o ns. Each of th ese me thods i s s ubj ec t to 117 = VifiP wh e re 117 is th e s peed of so und ;
inacc uracies whi c h req uire correc ti o ns in order to ob-
tain " the thermod ynami c te mperature." Th e correc - E , the ad ia batic bulk (1)
tion s are ca used by or related to " dead s pace volu mes",
devia tion s of th e th ermom e tri c fluid from " ideal gas" modulu s 0 (' th e medium ; a nd p th e de nsity. Thi s
be havior, conservation of th e thermom etric fluid dur- can be writte n as
in g meas ure ments, and volume c hanges accompany-
ing necessary temperature c hanges. In some cases
the pressure meas ure me nts , the require me nts of whic h (2)
are far from b ein g trivial, mu st be modifi ed to allow
for thermomolecular effects. To some extent, these If the equation of s tate for helium gas is assum ed to be
co rrections have been co nsidere d as exis ting nuisan ces of the form
but not always necess arily crucial in determining t he
-e nd res ult , a te mperature. While it is not the iriten- (3)
tion of thi s paper to trea t the preceding correction s, the
inves ti gation be in g re ported was initiated with an
inte nti on of avoidin g the m. Additionally we felt that
a fundam e ntall y differe nt approach to low te mperature
the partial derivative, (~p)
uV T
, can be s ub stituted into
th ermom e try was comple tely ju stifi ed and would prove eq (2) and CvlC v can be related to an id eal gas with
to be be ne fi cial in contributing knowl edge about ex ist- the result
in g te mperature de te rm ina ti o ns and scales.
A s ali e nt feature of gas th ermom e try s hould be 1172= (Cc p ) RMMT (1 + ap+ (3p2 + . . .). (4)
menti oned. The th ermom e te r mu st be filled with the v p=O He

531
In eq (4), T is the desired temperature; require a day it was not possible for all points on an
isotherm to be taken at exactly the sam e temperature.
Cp )
( -C =5/3; R,/=8.314 X 10 7 (ergr K mol) ;1 Consequently, s mall deviations in te mperature oc-
/) }J = O c urred (not exceedi ng 3 mdeg) and t he speeds were
M Hc = 4.0026 g/mol [2] ;2 corrected using the german ium thermometer indi ca-
tions. The speeds in table 1 have bee n treated in
this manner.
and a=~ (2B +1 T dB +..±.. T2 d 2B) Band Care
RT 3 dT 15 dT2' TABLE 1. Isotherm data (s!,eed-rnelers/sec ; I,ressllre-
the second and third virial coefficients, respectively, allllO sl, h eres)
for helium 4 gas. Equation (4) suggests the form
I. 2.323 OK 4. 4.212 OK
. ~ - -~~ .--

T
i' W IV' t." I' W IV' LI
(5) - --
0.0/35 88.99 1 7.919.4 - 12.4 0.0.122 120.24 1 14.46 1 -1),5
.01541 88.968 7.915.3 - 1.1 .0328 120.182 14.4'~1 -2 1.6
.02005 88.806 7.886 ...5 -7.6 .0501 120.030 14.407 4.0
in whi c h Wo is the s peed of sound in an ideal gas. .025 1 88.528 7.837.2 -1.0 .0507 11 l),l)l)6 14.:191 - I.Y
Wand fJ are meas ured experimentally and treated so .0251
.02076
88.527
88.740
7.837.4
7.874.8
- 1.2
1.6
.06638
.0668
11 9.76
11 9.766
14.342
14.344
-2.2
- 0.7
that W7; may be det ermin ed. In practi ce thi s may be .02966 88.292 7.7%.5 - 5.9 .0801 11 9.566 14.287 .6
.021)C)] 88.3 12 7.791).0 - 0.4 .Ol)~.l7 119.262 14.22:1 - 1.6
don e in two ways. W2 and I) as in eq (5) may be fitted .03837 87.942 7.733.7 2.7 .1021 1 11 9.2.32 14.2 16 -. 1
by a leas t squares me thod with th e interce pt Wij , a t '---- .1027 1
. 1204
J JIJ.26R
11 8.% 8
14.22.\
14. 14.5
10.7
2.8
p = 0 res ulting. Another approach is to obtain 2. 2.807 OK .1.10.\ 11 8.498 14.042 - 0. 7
.1674 118.25 13.975 1.2
Wo or W7; from a lin ear extrapolation (either graphi· .1986 11 7.786 13.874 3.8
cally or a nalyti c ally). The impli cation is, naturally. 0.01601 98.043 9.612.5 -8.4 .11)76 11 7.76 13,867 - 5.\)
.0233 1)7.87<) 9.612.3 3.5 .20 17 11 7.707 13.855 - 3.7
that in eq (5) ap is s mall co mpared with 1, and term s .030 11 97.648 9.535. 1 - 0.6 1.2357) 11 7.28 1 13,746
.03666 Y7.44S 9.4%.4 - .7 1.3( 24) 116.1 39 13.481
involving higher ord e rs of pre ss ure negligible. Values .04333 97.24 1 9.455.8 ~. I 1.2.1.\5) 116.859 13.646
of Wij obtained by the me thods desc ribed afford a - - 1.3805) 11 4.743 13. 160

simple calc ulation of th e te mperature. Obviou sly, 3. 3.211 OK

thi s trea tment can produce information on helium 4
virial coeffi cient s, but thi s will be prese nted in a follow·
ing pape r.
0.03U'18
.04007
.0.101
104.647
104.448
104 . 162
10.9.1 1.
10.909.4
I
- 5.3
3.7
10.849.7 . - 3.0
(/.U644
.0988
5. 5.024 OK

131.)78
130.90
17.208
17. 13.\
- 12.5
6.2
.0.168 l o:J.996 10.81..5.2 -3.3 .1340 130.5 1 17.033 - 2.0
Th e experim e nt a ll y de te rmin ed quantity , s pee d , .0668 103.769 10.768.0 3.4 .1676 130. 166 16.943 2.2
.08366 103.324 10.67 ..5.8 .2 .1978 129.87 16.866 1.2
has bee n obtained with an apparatu s whi c h is generally .OV8l) 102.942 ' 1O.5Y7. 1.9
called an acous ti cal interfe romet e r [3]. This in stru- .1003 102.884 10.585.1 - 2.6
1.1340) lOl.lJl)5 10.403.0
me nt e mploys a quartz c ry stal , operating at its resonant 1.16721 101.049 10.210.9
1.2(36) W.l)75 9.99.\.0
frequency (1 megahertz) , and it is assumed that the
crystal acts as a plan e wave radiator. Press ure
H 'flit"' cn iumn s undn d ('un l ain lilt" dif-Tt: n :nce between the experi men t a l
mea sure me nt s are made with a merc ury manom e ter W2 al th e ind icated pre ssures an d the II/~ of linear fU ll c ti on del('rrnillt'd 1)\
the compU I t:'r least s qu a re~ fill in).!. .
which is accurate to 70 J.L of mercUl:Y in the range of
meas ure ment s. While th ere are a few refe ren ces to
our in strument in th e lit erature [4 , 5, 61, a de tailed
description has not bee n publi she d (see footnot e 3). For eac h isotherm. values of p and W2 have been
treated analytically by computer and graphica lly to
2. Results obtain Wa.
Equation (5) demon s trates that a linear
treatment of the data will be inadequate at s uffi-
The re are li sted in table 1 values of pressure. s pee d cien tl y high press ures. It is not s urprising, therefore ,
and speed squared for each isotherm. The tem- that in figure 1, whi c h depicts the 3.2 OK isotherm , the
perature of an "isotherm" was maintained nearly data points markedly depart from a strai ght lin e above
constant by an automati c regulator which operated 0.17 atm of pressure. In order to represent the
from a germanium resistor co nn ec ted to a Wheats tone isotherms lin early , we noted the d eparture of the
bridge. This and other germanium resistors we re highe st point and , assumin g that su c h departures
located in th e rmal co ntac t with th e acoustical th er- are proportional to p 2, di scarded all point s for which
mometer apparatus so that allowance could be made th e d ev iation from linearity would exceed th e experi-
for small relativ e tem pe rat ure chan ges whi ch occurred me ntal re producibilities. Accordingly, the data
durin g measurement s of a n isotherm. Since four or above 0.1003 and 0.2017 atm for isotherms 3.2 and 4.2
fiv e press ure-s peed de termination s on a given isoth erm OK, respective ly, were omitt e d in th e lin ear co mput er
analys is. For the remaining isot herms, comparable
data selec tion was unnecess ary si nce correspo ndingl y
1 Th e value of the gas co ns tan t is tak e n from refere nce Ill·
high press ure data had not been acquired.
Z Fi gure s in brackets ind icate the lit era ture references al the end of thi s paper. In general , th e low est press ure points on an isoth erm
3 Note adde d in proof: Th e in s trum ent is desc ribed in Science 150, No. 3693, p. 155
(8 Oct. 1965). warrant lesser weightings. Th e inaccuracy of these

532

11 100
10900
! 10700
u
~
~ 10500
N;: 10300
10100
o
9900 L _ _ _--L_ _ _ _-'-_ _ _ _--'-:-_ _ _ _",:-_ _
o .05
PRESSU RE (ol m ) P ~
FI GU Il E l. W" (IS ulilll Clivll aIpressure
point s is c a used b y a lac k of res oluti o n res ultin g fro m
th e hi gh att e nuati o n of so und e ner gy in t he th e rm o-
m e tric ga s_ C on sequently, the italic ize d d a ta received
one quarte r weights in all compute r fit s.
Column 1 of t a ble 2 co nt a in s th e W§ int erce pts
obtain ed fr om g ra phi cal trea tm e nt of th e da ta whe re
JF2 was plo tted as a fun c tio n of p . Th e procedure
was s tra ightfo rw a rd in th a t s traight li nes we re o bvio us
re prese nt a ti ons in th e gra ph s if th e hi ghes t press ure
point s fo r th e 3.2 a nd 4 .2 oK is oth e rm s we re no t co n-
s id e re d. Column 8 of ta bl e 2 c o nt a in s th e te mpe ra-
tures de rive d from the W 5's o f c olumn l.
In th e c o m pute r a na lys is of th e ap pa re ntl y li ne ar
d a ta, ea c h isoth e rm was fitt e d b y th e me th od of le as t
s qu a re s to a polynomi al in whi c h th e s q uare of th e
s peed is e q u a te d to a po we r se ri es of th e press ure , i.e.,
W2= W~+ W~ap+ Wij{3p2+ ~yp3+. . .. Th e firs t
a na lys is in vo lved th e co ns ta nt a nd lin e a r te rm s, th e
s econd includ ed the qua dra ti c , a nd for the thi rd th e
c ubi c was a ls o a dd ed . E ac h of th e se cases yie lds a
va lu e fo r Wij . C olumn s 2 a nd 9 of table 2 lis t th e
int e rce pts and te m pe ra tures o bt ai ne d from t he Ii ne a r
co mpute r fittin g. Th e hi g he r ord e r fit s, with one
e xception , prove d ' to be of little signifi c an ce s in ce the
add iti o na l coe ffi cie nt s we re s ta t is ti ca ll y u nce rt ain .
T he e xce pti on was th e q uad ra ti c fit fo r th e 4.2 OK
is o th e rm . In thi s ca se a Wij va lu e of 14 ,570 wi th a n
unce rtain ty of 6 was o b ta in ed fro m whi c h a te mpe ra-
ture of 4.209 (± 0. 002) OK res ult ed .4 In th e above
a nalys es th e brac ke te d hi gh press ure da ta po int s fo r
o
th e 3.2 a nd 4 .2 O K we re no t in clud e d .
E qu a ti o n (5) c an be acc ura te ly re prese nte d b y a
lin e a r e xp ress ion (fo r a co ns ta nt a ) if th e p ress ure is
15.2 s uffi c ie ntly low. (Ou r in put da ta fo r th e majo rit y of
is oth e rm s have bee n se le cted to mee t thi s c rit e ri o n
or. mo re s pec ifi c a ll y, da ta hav e bee n used th a t g rap hi -
(II .~ . 2 J1 oK.
c a ll y ex hibit a lin e ar re la ti o ns hip within th e limit s of
th e e xpe ri me nt a l e rro r.) Fo r thi s re as o n we b e li e ve
th a t th e mo s t acc ura te de te rmi na ti o ns of is othe rm
te mpe ra t ures a re th ose wh ic h have res ulte d fr o m a
lin e ar tre a tm e nt. Ne ve rth e less fo r c om pl e te ness, it
is necess a r y to e xte nd the comp ut e r ana lys is to hi ghe r
o rde rs of press ure a nd inc lu de th e hi ghe r p ress ure
da ta for iso t he rm s 3. 2 and 4.2 OK. I n t hi s c ase th e
lin ea r re prese nt a ti o n is inacc ura te , b ut th e re e xi s ts
no a p rio ri a pproac h to p red ic t t he sig n ifi ca nce of pa r-.
ti c u lar hi ghe r o rde r press u re te rms s in c e th e a na lyti ca l
re prese nta ti o n of hi ghe r urd e r viri al co e ffi c ie nt s is
un k no wn . Co n se qu e ntl y we hav e app roa c he d th e
a na lyses e mp ir ica ll y, b y in c lu d in g q uad ra ti c. a nd
quadrati c and c ub ic te rm s for t he press u re.
W he n o nl y th e q uad ra tic te rm is add ed _ a s t a ti s ti -
c a lly mea nin gful coe ffi c ie nt fo r fJ 2 of e q (5) res ult s .
Co lum ns 5 and 11 li s t t he W6and T va lu es whi c h res u It
fro m e xtrapo lati o ns of th e q uadra ti c an a lyses . T h e
a ddition of a c u bic te rm wa s not he lpfu l s ince th e
I Th l ' \ul ut."!' rt"p'lrlt-'d Iwre an' 1111' til Ill' ( ' llnrll ... pd \\i l ll i llt' \allh' rt, ... uhill l! rnlill tilt-' tII • •rt'
('()Illp le te q uad ra tic fltlin~ <.1:- rtyorted i n ('ldU Ill Il !oo S. 6. a nd 7 uf lalJlt, 2,

T A BI. E 2. Sum ma ry of data de ri ved fro m isotherms

W ! Extra polati on s frum

Qu a d rati (, a na l}s is Lillt'ar a na l)s is Q lIa drat i!'

of da ta Ana l}sis
-~~ --
C rap il iea l C rup h i('u l CUll11Hll t'r Cump ut el' COlJl pu tl'1'
.'.T
Co mput er

5" (J'" T T 5Th l' 01'"

-.--

Co lum n Nu, I 4 10 11 12 13
I - - - - t-----
17.3Y3 17.3Y2 9.6 5.4 5.024 5.024 0.002 0.0 12

14.580 14.583 3.1 5.0 14.568 6. 7.2 4.2 1I 4. 212 .00 1 4.208 0.002 .010

11.1 23 11.11 7 3.7 3. 1 11.104 4.4 2,lJ 3.2 13 3.211 .00 1 3.207 .001 .008

Y.722.5 Y.7 17.5 6.2 3. 1 2.808 2.80 7 .002 .007

- - - - ] - - - - -I- -I -- ----I--- + - +- - -+ - -+ ----"I -- t--
8.037.5 8.0~ 0.5 6.Y 4.5 2.322 2.323 .002 .006

" Thc o's In (,lIl um ll.s~~f t,-~ !'n~JIl COt' A1(~Je n b;, I~,
the UI1 ('("rtuln tlcs o f th t! in (ollJ lll ns 2 <ln d 5,
hTh t' S's !lf ( ' O llllllll~ 10 a nd 12 a rc th e (' ( ) rn's po n din ~ ull ce rtainti es uf th e t e mp e ra t urt~:; in c ol u mll s!) and I I ,
l' (J' i ~ the :5 la nd ard dt',i a tin ll in t he lea s t !5t lll a rt.'S fi ll in 1! of a n isotlwrlll,

533
stati stical significance of coe ffi cients was lost. The
analysis was not extended for we felt that to be mean-
ingful it should include data over th e larges t possible
range of press ures_ Column 13 contains th e te mpera-
ture differences, Ti sotherm - T 58 , where T 58 is derived
from th e h elium 4 vapor press ure scale [7J - These
were obtain ed by calibratin g germanium resi stors
directly again st measured vapor press ures and co m-
paring them, in th e acousti cal thermom e ter, with
germanium re sistors whi ch had been calibrated by
the acoustical thermometer. In one or two cases, a
resistor associated with the acoustical thermome te r
during an isotherm measurement had been previously
calibrated at one or more vapor pressure temperatures _
The temperature values of Tisotherm are from column 9_
Thus o ur values of isotherm temperatures, column 9,
and th e indi cated departures from T5 8 (column 13)
afford a co mparison with the T 58 scale as portayed in
figure 2_ Ex ce pt for out data points, fi gure 2 is take n
from Van Dijk [8]- In essence he has plotted values
of absolut e te mperature de te rmination, in the liquid
helium range , relative to th e T5 8 sca le_ Whil e we are
15 r---------,-------- --,---------,----------,----,
o
. (Nov. 1963).
6,- -- --t-- ---j
<D
~ [51 C. Ca ta la nd a nd H. H. Plumb. 1. Acous t. Soc. Am. 34, 1145
, (1962).
~-5~------ xx x .' <9,-------~--------~--------_t-----
:i
-10 IL - - - ·-~.L.--------~-----------14----------~----'
FIGURE 2. A co mparison with T 58 of temperatares derived from
isotherm measurements , gas thermometry and th e acol/stico!
interferometer.
CD e O -Sc hmidt and Keeso m [9! (gas thermomet er. 1937).
• - Ki sle m ak er [lO J ( ~a s thermom ete r. 1(46),
x- Ki s le maker [101Ii sulherms. 1(46).
6 - Berma n and Swe nson [11 1 (gas thermumeter. 1954),
D - Kelle r [12] (heliu m 4 isotherms. 1955),
• - Ke ller [121 (h eli um 3 isot he rm s. 1(55).
£. _ Pre liminary re s ult s [4.51 (veloc it y of sou nd in
helium 4 ~ as . acous ti cal in terfero m ete r. 1962).
• _ Present work (isotherms determined by the NBS
acoustical therm ome ter).
534
not pre pared to present a value for the absolut e acc u-
racy of our values of temperature, if o ne believes that
th e T5 8 scale is s mooth with respec t to the true th e rmo-
dynami c te rn perature scale , the plot s uggests that
perhaps th e present data are t he most self consis tent
of any t e mperat ure meas ure ments th at have been made
below 5 oK. (The di spersion in temperature values
res ulting from our different method s of isotherm analy-
ses indi cates that our deduced values of te mpe rature
are not criti cally de pe nde nt upo n a particular me thod
of analysis _)
The reproducibilit y of points on an isotherm appears
to be within ± 0_002 OK although it is obvious that most
of the isotherms need a bett er defi nition , that is , a
greater numb er of points_ Nevertheless, we do feel
that th e indi ca ted co nclu sion s of our meas ure me nts
are important enough to be presented now rather than
be delayed until th e co mpl e te program in thi s t e m-
pe rature range has bee n fini shed_
3. References
llJ N BS T ec h. News Bu ll. 47 _ 175 (1965); N BS Misc . Publ. 253
121 F. Eve rlin ~. L. A. K(ini~, H. E. Mattu c h_ and A. H. Wapstra_
Re lati ve nu c li dic m asses . Nuclea r Ph ys . 18, 529 (1960).
[31 J. L. a nd E. S. S tewa rt. J. Acoust. Soc. A m . 24 ,22 (1952): M.
Green s pan . Ph ys ica l Aco usti cs 2A, 30 (Acade mi C Press .
In c .. New York . J965).
[41 C. Ca tal a nd _ M. Edlow. a nd H. H_ Plumb. T e m pe rature. It s
M eas ure ment and Control in Science and Indu stry , C. M.
Herzfe ld , ed., 3, F. G. Bri c kwed d e, e d., Pt 1 (R einhold Pub-
li s hin g Co rp. , New York, 1962).
161 C. C atuland a nd H. H. Plumb. Proce e din gs of th e Eil!hth In -
te rn a ti o na l C onference o n Low Temperature Ph ys ics (B ut -
[71
terwo rth s _W as hin gton, 1963).
F. G. Bri c kw edde_ H_ va li Dijk. M. Du rie ux_ J. R. C leme nt.
a nd J. K. Lo ga n. J. Resea rch NBS 64A Whys_ a nd C h e m .)
No. L 1 (1960).
[31 H. va n Dijk . Progress in C ryoge ni cs_ p. 123 (H eywood and Co m-
pany. Ltd .. Lo nd on , 1960).
[91 G. Sc hmidt an d W. H. Keesom. Leiden Co mmun. No. 250b:
Ph ys ic a 4, 963 (1937).
[10J J. Ki ste mak e r a nd W . H . Kee so lll_ Le id en Co mmun. No. 269b:
Phys ica 12 ,227 (1946).
[111 R. Berman and C. A. SW,e n son_ Ph ys_ Rev. 95, 311 (l954).
[121 W. E. Ke ll e r. Phys. Rev. 97, 1 (1955); P hys_ Rev. 100. 1790
(1955).
(Paper 69A6- 375)