Materials Science and Engineering, A178 (1994) 35-41 35

Thermodynamic properties of liquid metals

R. I. L. Guthrie
McGill Metals Processing Centre, McGill University, 3450 University Street, Montreal, Que. H3A 2A 7 (Canada)
T. Iida
Department of Materials Science and Processing, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suita,
Osaka 565 (Japan)

Abstract

Some of the more important thermodynamic properties of liquid metals are their vapour pressures, heat capacities and
their rates of transmission of shock waves (sound velocities). Thus changes in the vapour pressure of liquid metals are
related to changes in the cohesive or binding energy of the liquid with temperature. No theoretical approaches have yet
been successful in predicting values of heat capacities, owing to the extremely complex motion of atoms in the liquid state.
Experimental measurements at constant pressure (Cp) are therefore essential. Measurements of the sound velocity, which
is thermodynamically related to the isentropic compressibility x and to Cp/Cv, allow such properties to be measured. A
review of values of U~, Cp and Pv for a wide range of pure liquid metals, together with the underlying thermodynamic
relations, are briefly reported in this paper.

1. Introduction zinc and magnesium, and in refining processes. Since

This paper reviews some of the more important
thermodynamic properties of liquid metals. These
comprise vapour pressure, heat capacity, and sound
velocity. Theoretical and empirical equations describ-
ing these thermodynamic properties are therefore
presented, together with data and an explanation of
their relationships with the underlying atomic structure
of metallic metals. This is of interest to researchers
studying amorphous or glassy solids, since the atomic
structures of such materials closely resemble those of
the liquid state. Further, the thermodynamic properties
of liquid metals in their undercooled state can be
estimated by extrapolation.
2. Vapour pressure of pure liquid metals
the equilibrium vapour pressure of a condensed phase
varies exponentially with temperature, liquid metals
tend to evaporate more rapidly with rising tempera-
ture.
2.1. Thermodynamic equation for vapour pressure
From the standpoint of thermodynamics, application
of the Clausius-Clapeyron relation to equilibrium
between a condensed liquid phase and a gaseous phase
provides an expression for changes in vapour pressure
with temperature. However, the thermodynamic
equation contains an integration constant which has to
be determined experimentally. Thus, for two phases a
and fl in equilibrium with each other, the following
relation exists between the temperature and equilib-
rium vapour pressure P:

The vapour pressure of a liquid metal is an impor- dP H ~- H ~ Aa~H

tant property which is related to the liquid's cohesive d T - T ( V ~ - V ~) TA~V (1)
or binding energy. From an engineering standpoint,
knowledge of a liquid metal's vapour pressure is of Using the superscripts 1 for liquid and g for the gas,
obvious importance. For instance, it is sometimes of assuming the gas is ideal and neglecting the volume of
technological importance that loss of a pure metal by liquid compared with that of the gas: vg,> V l, and
evaporation must be minimized during processing Vg = R T/P, we obtain
operations. Alternatively, rates of evaporation of
metallic elements or impurities may be utilized in the 1 dP AlgH
pyrometallurgical production of mercury, cadmium, P dT RT 2

0921-5093/94/$7.00 © 1994 - Elsevier Sequoia. All rights reserved

SSD10921-5093(93)04507-E
36 R. L L. Guthrie, T. lida
or
d(ln P ) = , A,~H
d(1/T) R
From Kirchhoff's law, we have
T
&g = Ho + J AlgCp d T
0 (6) and (7), we obtain the following equation for the
where H 0 is the enthalpy of evaporation at 0 K, and
AlgCp= Cpg-Cp I. Since A1gH o r AlgCp varies slowly
with temperature, we can approximate the change
(AlgCp) with the following simple algebraic expression
for the temperature variation of AIgH:
AlgH = A + B T + C T 2
where A , B and C are constants. On substituting this
empirical equation into eqn. (2) and integrating,
A B C evaporation of a liquid at its boiling point AHv, b.
lnP .... + - - I n T+~-- T + D
RT R R
where D is the constant integration.
Taking the enthalpy of evaporation as constant, eqn.
(2) can be integrated immediately, to give
l n P = - - AtgH
- + lnA
RT
or
AIgH]
P = A exp - - R T - ]
where In A is a constant of integration. Equation (5)
can provide approximate values for equilibrium vapour
pressures over a wide range of temperature. The
relationship shows that vapour pressures should
increase exponentially with temperature and that their
temperature sensitivities depend on their A~gH values.
2.2. A n equation based on lattice theory
In the harmonic oscillator model based on a lattice
theory of liquids, it is assumed that the liquid has a
quasicrystalline structure, and that each molecule of
the liquid vibrates about a lattice point, i.e. a position
of minimum potential energy, as an isotropic three-
dimensional harmonic oscillator with an effective
frequency v. According to this model, one can describe
the partition function and the chemical potential of the
liquid. When the liquid is in equilibrium with its vapour
at temperature T, the vapour pressure P is given as [ 1]:
p =(27rm)3/2v 3 AHv]
(kT),/2 e x p - N k T ]
/ Properties of liquid metals
where m is the molecular mass and AHv, the enthalpy
of vaporization. Using the modified Lindemann
(2) equation proposed by the authors [2],
v=6.8x1011 (7)
where M is the molecular weight (M = Nm) and a the
(3a) surface tension of the liquid metal. By combining eqns.
vapour pressure of liquid metals [3]:
p = 3 . 0 x 1 0 1 2 03/2 ( AHv/
T55 exp - N k r ] (8)
Equation (8) can easily be applied to various pure
(3b) liquids since it does not explicitly contain the molecular
weight. Since P is 1 atm, i.e. 1.013 x 105 Pa, at the
boiling point, only the value of the surface tension is
required to calculate the value of the enthalpy of
(4) Figures l(a) and l(b) provide a comparison between
calculated and experimental data for AHv.m, and
AHv, ~ respectively, the experimental values being
taken from Kubaschewski and Alcock [4]. To our
knowledge, the enthalpies of Nd, Gd, Ta and Os are
not known at their boiling points. Predicted values for
Amv, b based on eqn. (8) are Nd 337, Gd 356, Ta 643
(5a)
and Os 610 kJ mol 1.
2.3. Empirical equations for vapour pressure:
Trouton's rule
It follows from eqn. (2) that if we plot In P against
(5b)
1/T, the curve so obtained should, at each point, have a
slope equal to ALgH/R. Saturated vapour pressures of
metals have frequently been represented by empirical
formulae having the same form as eqn. (5), i.e.
In P--- a - b/T, where a and b are constants. The form
of eqn. (5) provides a good approximation, and is
useful for interpolation between tabulated values.
Closer fits are obtained when a further term is added:
P = a - b / T + Cln T.
The temperature at which the vapour pressure
of a saturated vapour is equal to one atmosphere ( P =
1 atm = 1.01325 × 105 Pa) is also known as the normal
boiling point of a liquid T~. We then have from eqn. (5)
that
AlgHb
- In A (9)
~eTb
This relationship is known as Trouton's rule. In A is a
constant that is approximately the same for all metals.
To obtain enthalpies of evaporation AIgH, or of sub-
limation ACH, plots of ln P against 1 / T can be
(6) constructed by measuring P at several known
 R. L L. Guthrie, T. Iida / Properties of liquid metals 37

600 , . . . . /j// 900 I I I I I t I I

/ ,U 800
500 / //
700

Z~ 400 Fe ,Sl.~, LI 600

0
E ©
Cuc~/c/Ge E
Sn/<el"• 5oo
--. 300

pl,/~ 6' ~ 400

Pu////Pt
oy// -°It
> 200 o'~ei F~pdo;, Oil
Ca / II >" 300
,B~o,"~^u
Zn'"~¢2"-St ~Sb tin ^g~°r-~Cu Cr
100

0
/3/,, I I I I I
2OO

100
SK pbn~l~ ~"~1
I"eC~ 1 8 I

0 100 200 300 400 500 600 0 I I I I I I I I

(a) 0 I00 200 300 400 500 600 700 800 900
(~r-/~,.O ~p~./KJ mol-~
(Z2d-/~,b) e×vt./ KJ mol -I
900 Fig. 2. Comparison of the calculated enthalpies of evaporation
i , I , I ,IIIIVI/ for liquid metals at their melting points using Trouton's rule
800 (AHv,b)calc with the experimental data (AHv,b)expt. The broken
curve represents a tendency to vary with the plots of (AH,,~>).
700 /
I II "/ I_
z

600 I /.~ i i
ii /o ~ i/
/ %,°,r'" Figure 2 provides a comparison of the calculated
~.~ 5 0 0 i1: V,.~O0 ill'l enthalpies of evaporation for liquid metals at their
400 melting points using Trouton's rule.

- h ~w
2.4, Experimental data for vapour pressures
200 ~ / ~ . l n/ " Most normal metals are monatomic in the vapour
¢
form. However, the vapour species of semi-metals and
non-metals (e.g. phosphorus, sulphur) are often poly-
merized. For example, bismuth vapour contains both
0 I I I I I I I I Bi and Bi 2 gas species. For most metals, even for
0 100 200 300 400 500 600 700 800 100
copper, silver, and gold, small amounts of dimer gas
(b) (AHv,b) ~xp,./ KJ mol"l molecules have been observed.
Fig. 1. (a) Comparison of the calculated enthalpies of evapora- Figure 3 shows typical plots of changes in the
tion for liquid metals at their melting points (AHv,m)~alcwith the vapour pressure of various metals over the tempera-
experimental data (AHv,~)~xm. The broken lines represent the ture range 900-1700 K, while experimental values for
+_5% error band. (b) Comparison of the calculated enthalpies of
pure liquid metals are available in ref. 2.
evaporation for liquid metals at their boiling points (AHv,b)~ai~
with the experimental data (AHv,b)~pt. The broken lines repre-
sents the __20% error band.
3. Heat capacity of pure liquid meals
temperatures. The slope of such a plot is, from eqn. (5),
The heat capacity C of a substance is equal to the
AIgH d(ln P ) T 2 dP quantity 6q added to, or withdrawn from, the sub-
Slope = (10a) stance, divided by the resultant change in temperature
R d(]/r> P dr
dT of that substance: C = 6q/dT. The heat capacity is
When eqn. ( 1 ) is combined with the above relation, we one of the most fundamental thermodynamic prop-
have erties of matter. Calculations of changes in enthalpy or
entropy of a substance with temperature require
T AjgH knowledge of the temperature dependence of heat
Slope = (10b)
P AIgv capacity.
38 R. L L. Guthrie, T. lida / Propertiesof liquid metals
b.p.
104
10 x
1 10-2
I0 -2
10~
10--6
10-s
900 1000 1100 1 2 0 0 1300 1400 1500 1600
Temperature/K
Fig. 3. Equilibrium vapour pressures of liquid metals as a function of temperature: o melting point.
Investigations of the heat capacities of solid ele-
ments have been carried out for many years. Dulong
and Petit, in 1819, proposed the empirical law that
most solid metals have values of heat capacity lying
around 26 J tool -1 K -1 (6.2 cal mo1-1 K -1) under
standard conditions of pressure, 1 atm at room tem-
perature. The theoretical work of Einstein, Debye, and
others on heat capacity of a solid element is well
known. The values of the heat capacity of the solid
calculated by the Einstein and the Debye models,
which are based on statistical thermodynamics and
quantum mechanics, are in moderately good agree-
ment with those measured.
Clearly, thermodynamics gives no information about
the numerical values of heat capacities nor of their
temperature dependence. Various theoretical ap-
proaches have been made concerning the heat capaci-
ties of liquids. None have been successful, because the
motion of atoms in the liquid state is extremely com-
plex. Furthermore, no empirical relationship has been
successful in providing reliable estimates of a liquid
metal's heat capacity. Accurate experimental data for
the heat capacities of liquid metals and alloys are,
therefore, highly desirable. For most liquid metals the
values of heat capacity Cp are assumed to be constant
over relatively wide ranges of temperatures, because
there is insufficient experimental data available to
allow the temperature dependence of Cp to be deter-
mined. In general, the influence of temperature on
10'
1
~tJ
m
E
10-~
10-6
10-s
700
liquid metal heat capacities tends to be small, as also
noted by Baykara et al. [5].
Table 1 lists values of constant-pressure heat
capacity for various liquid elements. At their melting
points, most liquid metals have Cp values ranging
between 30 and 40 J tool- ~K - 1 (7-10 cal mol- ~ K- l).
The values of the heat capacities of liquid alloys
have often been estimated by proportional addition of
the heat capacities of the constituent elements, Le. the
Neumann-Kopp law.
4. Ultrasonic v e l o c i t y ( c o m p r e s s i b i l i t y )
Only a few studies have been made of the velocity of
sound in liquid metals, even though this represents one
of their most fundamental thermodynamic properties
on the atomic scale, given its relationship to isentropic
compressibility.
4.1. Thermodynamic relationship between velocity of
sound and compressibility
The relationship between isentropic or adiabatic
compressibility 1cs (~cs ~ - V -1 [OV/OP]s), and the
velocity of sound U (m s- 1) is given by
1 1
lCS-pU2-Bs (11)
 R. L L. Guthrie, 7". lida / Properties of liquid metals 39

TABLE 1. Molar heat capacities at constant pressure Cp for TABLE 1. (continued)

liquid elements
Element Cp Temperature range
Element Cp Temperature range (J mol-1 K- I) (K)
(J moI-L K-l) (K)
W'~ 53.0 mp
Be 29.46 1560-2800
Pt '' 36.5 22(t2-2631
B 31.38 2453-3500 Au 29.29 1336-1600
Mg 32.64 922-1150
T1 3(1.1 577-1760
AI 31.8 933-2400
Th 46.0 2023-3000
Si 25.61 1685-1873
U ~' 48 mp
P 26.32 317-870
Data from ref. 4; additional data ~'from ref. 5.
Ca 29.29 1112-1757
Over the stated of temperature, ('p is constant.
Ti a 45.5 1969-2315 rap, melting point.
V 47.49 2175-2600
V" 48.7 2205-2638
Cr 39.33 2130- in which p is the density of the medium and B s is the
Cra 50.71 1641-2395 isentropic bulk modulus. This equation forms the basis
Mn 46.0 1517-2333 for determining ~cs or B s from measurements of the
velocity of sound. T h e isothermal compressibility KT
Fe 41.8 1809-1873
Fen 43.05 1804-2142 can be calculated if the thermal expansion coefficient
a ( I / K ) and the specific heat cp (J tool -1 K -I) are
Co 40.38 1768-1900 known, since
Co" 48.45 mp
Ni 38.49 1726-2000 KT= KS+ (12T/pCp (121
NP 39.3 mp
T h e constant-volume heat capacity Cv and the ratio
Cu 31.38 1356-1600 of the heat capacities Yh ( 7h ~ Cp/C v ) can be calculated
Cw' 33.0 1388-1887 through the thermodynamic relations
Zn 31.38 693-1200
Ge 27.61 1210-1600 / c T Cp C pp= I+--a'-VT (13)
Se 35.1 493-800 ~Cs Cv Cv /¢sCp
Y 39.79 1799-2360
It is difficult to determine values for the isothermal
ya 39.8 1799-2360
compressibility and constant-volume heat capacity
Zr a 4(/.7 2125 experimentally, but their values can be computed using
64.0 3000
these formulae together with sound velocity measure-
Nba 41.8 2031-3159 ments.
Mo ~' 34.3 mp
Pd" 41.0 mp 4.2. Semi-empirical equations for the velocity of
Ag 30.54 1234-1600
sound in liquid metals
According to Einstein, a simple relationship exists
Cd 29.71 594-1100 between the velocity of sounds in solids and the mean
Sb 31.38 904-1300 frequency of atomic vibrations v [6]~ His relation can
Te 37.7 723-873 be written as
Cs 31.88 303-330 UocvV j/3 (141
Ba 48.1 1002-1125
in which V is the atomic volume. By using Linde-
Ce 37.70 1071-1500 mann's formula, for the mean atomic frequency vl.
Ce" 31.6 1077-2500
(eqn. (711,
Pr 42.97 1204-1500
Pr" 41.57 1460-2289
gm °C (15)
Nd 48.79 1289-1400
Nd" 44.0 1446-2246
Ta 41.8 3250-4000 This relationship shows that the velocity of sound in
Ta~ 42.28 2653-3358 solids at their melting points U m is proportional to the
40 R. L L. Guthrie, T. lida / Properties of liquid metals

6
/ /
/// ///
/F ."
/ /*
5 / //
ii /" L i
/I / /"/
//I TFC ¢1/'''''~
// / NiTo~.,/" Mg .81
"7
// / • ///
E / Cu/.- "'//
// ~ -'""Ca
"-£ 3
• G~ , / z~
- a/ g .".">'",Slope of 99
S l o r of
. Sn/OAu/ / Na .

nb / /Sb o~.~
• /-- / ./1 Pr
B lem
/ "1"1../ / - ' C e
Hg• / /
1 i////'/R b eYb I Ba
/ 5///.e~ ~ "Se
/ / / ' ~ "- . z Cs •Te
/ /

0 I I I I I I [ 1 ,~
0 1 2 3 4 5 6 7 8
(RTmlM)1/2/102 ms -I
Fig. 4. The velocityof sound in liquid metals at their melting points as a function of (RTm/M) 1/2.The broken lines denote the + 20%
error band.

square root of the metal's melting point and inversely titanium 5230, vanadium 5150, chromium 4520, and
proportional to the square root of the metal's atomic manganese 3710.
weight. The expression has been known for a long time. Similarly, in closing, it is noted that few data are
In the semi-empirical treatment of Iida and co- available on the velocity of sound in liquid alloys.
workers, they proposed that the mean atomic vibra-
tional frequency of liquid metals could be represented
by the product of Lindemann's formula and a correc-
tion factor fl which incorporates the surface tension o n 5. Conclusions
of a metal at its melting point [2]. Figures 4 and 5
provide a comparison of sound velocities in liquid A n updated review of some of the more important
metals based on plots of ( R T J M ) 1/2 (eqn. (15)) and thermodynamic properties of liquid metals--vapour
(am~ M)I/2Vml/3" As seen, while both plots give satisfac- pressure, heat capacity, and sound velocity--largely
tory relationships, the latter provides a better correla- based on ref. 2, has been made. While theoretical
tion. These figures incorporate new values for the models exist for predicting these properties based on
velocity of sound in liquid lithium, calcium, manganese, the atomic structures and interactions, our lack of
barium, lanthanum, cerium and strontium which are knowledge of the complex interactions involved pre-
not reported in ref. 2. Furthermore, to our knowledge, cludes direct predictions. Nonetheless, correlations
there are no experimental data on the velocities of between the thermodynamic properties show that the
sound for liquids such as titanium, vanadium, chrom- underlying atomic mechanisms are reasonably well
ium, manganese, etc. Estimated values for these metals understood and that a priori predictions can be made
at their melting points have therefore been calculated, for various thermodynamic and transport properties of
using the corrected version of eqn. (15) (incorporating liquid metals. These properties are of relevance to
fl), leading to the following predictions for Um (m s-l): undercooled melts.
 R. 1. L. Guthrie, T. lida / Properties of liquid metals 41

/
7' //
///

/ /// / / /
/ ///

/////// /1/~/'//

I l/ / /
/i I
i /"

/ ~" ] • ~,lg /
~ 4 i / C o 7
ii Ctl / i Ix
E I t i /
I I
I I / C{~ i II
~E 3 Ag
• G
o
a
/
l i
."
/

Au
0/
1 / "/ •/
-" ..M I I
., I S l i ~ 1"" Na •
ca#in X,..-'"

~. ,*" ° I K?-"L~\SIope of 3.SX1041mol -~

/ ~ e/" "Hg.~
O/ Ba
Rb
/~.Cs - '

0
/i
__ I I k I ~ . _ _ [ __1 1 I 1
o 2 4 6 s 1o 14 1G 18 20

(ym/M) ~V~m/10-' m s - ' mol t

Fig. 5. The velocity of sound in liquid metals at their melting points as a function of (ym/M) ~/: V,, ~/~. The broken lines denote the
+ 20% error band.

References tion of the enthalpies of evaporation, High Temp. Mater.

Process., I0 (1992) 200-207.
1 R. H. Fowler and E. A. Guggenheim, Statistical Thermo- 4 0 . Kubaschewski and C. B. Alcock, Metallurgical Thermo-
dynamic, Cambridge University Press, Cambridge, 1956, chemistry, Pergamon, Oxford, 1979, p. 258.
p. 336. 5 T. Baykara, R. H. Hauge, N. Norem, P. Lee and J. L.
2 T. Iida and R. I. L. Guthrie, The Physical Properties of Liquid Margrave, A review of containerless thermophysical property
Metals', Clarendon, Oxford, 1988. measurements of liquid metals and alloys, II Ciocco Workshop
3 T. Iida, Y. Kita, H. Okano, 1. Katayama and T. Tanaka, An Proc., 199.7.
equation for the vapour pressure of liquid metals and calcula- 6 A. Einstein, Ann. Phys., .74(1911) 170-174.