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Historical Development of the Vapor Pressure Equation from Dalton to Antoine

Article  in  Journal of Phase Equilibria · November 2001

DOI: 10.1007/s11669-001-0026-x

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General Interest

Historical Development of the Vapor Pressure Equation

from Dalton to Antoine
Jaime Wisniak

(Submitted 14 August 2001)

The vapor pressure of a pure liquid or of a solution is a property that has been observed since
antiquity. Here, we trace the different equations that have been suggested to describe the variation
of the vapor pressure with the temperature, until the time when Antoine proposed his equation,
a functionality that has survived the test of time and is the one mostly widely used today.

Phase change phenomena have been known and described
since ancient times. For instance, the second chapter of the
Bible describes in these words an evaporation-condensation
cycle (Genesis 2:6): “But there went up a mist from the earth,
and watered the whole face of the land.” Experience indicates
that the vapor pressure of a pure liquid depends only on
the temperature, provided that the external pressure is not
excessive (over 50 atm) and that the material is not subject
to other fields, such as magnetic, electric, and/or surface
effects. It is also independent of the relative amounts of the
liquid and vapor phases present.
Many different formulas and graphical representations
have been suggested for the vapor pressure-temperature rela-
tionship for pure liquids and their mixtures. Many of these
are empirical, but some of them have a theoretical basis. As
we will see, the different equations involve several parameters
that have to be determined by regression using experimental
data. The resulting expression is then used to interpolate
between known values on the vapor-pressure curve, as well
as calculating other important physical properties, such as
the heat of vaporization.
The purpose of this paper is to review these representations
of vapor-pressure data, with special emphasis on the
Antoine equation.
Earlier Equations
John Dalton (1766–1844) made the earliest satisfactory
measurements of vapor pressures using a water-jacketed
barometer filled with the substance in question and measuring
the depression of a mercury column.[1] He measured the vapor
pressure of several liquids, such as water, ether, spirit of
wine, ammonia, mercury, and sulfuric acid, and observed
that the vapor pressures, P, increased in geometric progres-
sion, while the temperatures, T, increased in arithmetic pro-
gression. (In Dalton’s words: “That the force of steam is in
geometrical progression to equal increases of temperature or
intensity of heat.”). That is, P ⫽ P0at with t being temperature
in the Celsius scale so that
Jaime Wisniak, Department of Chemical Engineering, Ben-Gurion
University of the Negev, Beer-Sheva, Israel 84105. Contact e-mail:
wisniak@bgumail.bgu.ac.il.
log P ⫽ b ⫹ ct (Eq 1)
One of the subjects in the course on Heat and Chemical
Elements that Dalton gave in Manchester in 1805 (by sub-
scription, under the auspices of the Royal Society) carried
the name: “Expansive force of vapour of water, ether, &c.,
in geometrical progression with equal increments of heat.”
Dalton was especially interested in the question of vapor
pressure because of its relation to meteorology. His experi-
ments seemed to indicate that air humidification was not
dependent on pressure, only on temperature. He believed that
one “cubic foot of air will imbibe the same weight of vapour,
if the temperature be the same.” Eventually, Victor Regnault
(1810–1878) discredited Dalton’s Eq 1.[2]
Jean-Baptiste Biot (1774–1862) extended Dalton’s equa-
tion and wrote[3]
log P ⫽ a ⫹ b␣ t ⫹ c ␤ t (Eq 2)
where a, b, c, ␣, and ␤ were constants to be determined
by means of five experiments. Biot’s equation became very
popular, mostly in the simplified form, log P ⫽ a ⫹ b␣ t.
An interesting aspect of Eq 2 is that Biot put the tempera-
ture as the exponent and not as the basis of the exponential.
This type of functionality was not new, Newton had suggested
that the rate of cooling of a body was followed by a geometric
progression with the temperature, and Dulong and Petit[4]
had developed the first model of radiant emittance, R(␪ ), as
R(␪ ) ⫽ ␮a␪, where a was a universal constant, ␮ was a factor
determined by the mass of the body and by the nature of its
surface, and ␪ was a temperature measured from a conve-
nient zero.
Regnault[2] used Biot’s equation to correlate his extensive
measurements of the vapor pressure and observed that a
much better fit was obtained if the equation was modified
as follows:
log P ⫽ a ⫹ b␣ ␪ ⫹ c ␤ ␪ (Eq 3)
where ␪ ⫽ t ⫹ n, that is, ␪ was a temperature measured
from a convenient zero (such as the lowest temperature in
the series of experiments used to determine the constants),
similar to what Dulong and Petit had used for their
correlations.

622 Journal of Phase Equilibria Vol. 22 No. 6 2001


One of the few experimental works that Amedeo Avogadro
(1776–1856) conducted in his scientific career concerned the
determination of the vapor pressure of mercury at tempera-
tures very close to its boiling point.[5] For this purpose, he
used an inverted glass siphon, connected to a flask, and
immersed in a bath of olive oil that could be heated to a
desired temperature. In addition to the measurements, Avoga-
dro derived the following equation to compute the vapor
pressure of mercury at very high temperatures (up to 300 ⬚C,
which was the upper limit of most mercury thermometers
then used):
Trel ⫽ P(1 ⫺ l/L) (Eq 4)
where Trel was the mercury pressure and was a measure of
relative temperature in the sense that Trel ⫽ 0 when l reached
the height L (mm) in the open branch; P was the total pressure,
and l (mm) was the height that air alone would have reached
at the same temperature and pressure according to the ideal
gas laws. Avogadro proceeded then to state his experimental
results using an expression of the form
P ⫽ (1 ⫹ at) m
(Eq 5)
where P was the vapor pressure in atmospheres, and t was
the temperature relative to the boiling temperature of mercury,
in units of 100 ⬚C (for example, in this scale, the boiling
temperature of water would be (360 ⫺ 120)/100 ⫽ 2.4)).
Avogadro found that for the range 230 to 300 ⬚C a ⫽ 0.4548
and m ⫽ 2.875 and that Eq 5 predicted results very close to
the experimental ones. He also found that at lower tempera-
tures and lower pressures, where the experimental errors
became very large, the fit was not good. Previous measure-
ments by others, such as Michael Faraday (1791–1867), had
already established that near 0 ⬚C the vapor pressure of mer-
cury was almost zero. Avogadro considered that in order to
describe the vapor pressure of mercury in the range 0 to 100
⬚C it was necessary to employ an equation having more
parameters, such as the one proposed by Biot. Avogadro
modified Biot’s Eq 2 to the form
log P ⫽ at ⫹ bt 2 ⫹ ct 3 (Eq 6)
by considering that the vapor pressure of mercury at 0 ⬚C
was 1 mm mercury (so that in Eq 2 a ⫽ 0) and expressing
the temperature in the same relative units as in Eq 5. On the
basis of the experimental measurements, he determined the
values: a ⫽ ⫺0.64637, b ⫽ 0.075956, and c ⫽ 0.18452. For
temperatures below the boiling temperature of mercury, the
relative value of the temperature was to be taken as its abso-
lute value. Application of Eq 6 to a low temperature, such
as 0 ⬚C (that is, t ⫽ 360/100 ⫽ 3.6), led to P ⫽ 8.498 ⫻ 10⫺8
mmHg; a result that did not agree with Faraday’s findings that
at 0 ⬚C the vapor pressure was 0 mmHg (the actual value
is 0.00001846 mmHg). Avogadro attributed the numerical
difference to physical reasons not related to the law that
described the vapor pressure.
Years later (1909), Young used Biot’s relation to try to
determine the critical pressure of some 30 odd substances[6]
Journal of Phase Equilibria Vol. 22 No. 6 2001
General Interest
and concluded that the predicted values were manifestly
impossible.
The different functionalities developed by Jacques-Louis
Bertrand (1822–1900) are of particular interest because of
their relation to Antoine’s equation[7–9] (Eq. 29). Bertrand
started from the following approximation for the Clausius-
Clapeyron equation:
dP ⌬H
⫽ (Eq 7)
dT ATv
where A is constant, ⌬H is the heat of vaporization, and v
is the molar volume of the vapor. Bertrand integrated it for
several situations. (a) The available information for water
indicated that a better equation of state for steam was Pv ⫽
R(T ⫹ a) with v ⫽ m ⫺ nT, where a, m, and n were constants.
Substitution in Eq 7 yielded
T␣
P⫽K (Eq 8)
(T ⫹ a) ␤
For water, he obtained ␣ ⫽ 79.623, ␤ ⫽ 88.623, a ⫽ 126.37,
and log K ⫽ 34.21083. (b) For many substances, it was
known that the ratio, ␸ ⫽ APv/⌬H, was a very weak function
of temperature. For this situation, Eq 7 could be integrated to
P ⫽ kT n (Eq 9)
where n ⫽ 1/␸. It should be noticed that Eq 9 corresponds
to Eq 5. (c) For other substances, the parameter, ␸, was found
to vary linearly with temperature, that is, ␸ ⫽ aT ⫺ b.
Integration of Eq 7 then yielded
冋 册
n
T⫺␭
P⫽G (Eq 10)
T
where G was a constant, n ⫽ 1/b, and ␭ ⫽ b/a.
According to Bertrand, Eq 10 had the remarkable property
that for an immensity of pairs (␭, n) it gave exact values of
the vapor pressure; nevertheless, he recommended using the
value, n ⫽ 50, and then determining the pertinent value of
␭. As shown subsequently, Antoine used Eq 10 to develop
his relation.
The Clapeyron Equation[10]
Every student of thermodynamics becomes familiar with
the equation of Clausius- Clapeyron when learning about the
influence of temperature on the vapor pressure of a pure
compound.
dP ⌬H
⫽ (Eq 11)
dT T⌬V
where ⌬H and ⌬V are the changes in enthalpy and volume
that take place during the phase change process. Textbooks
normally use the derivation of the Clausius-Clapeyron equa-
tion as an example of the large number of relations that can
623
General Interest

be derived using the four Maxwell relations that summarize

the first two laws of thermodynamics. The common deriva-
tion starts from the following TdS equation:[11]

冢⭸T冣 dV
⭸P
TdS ⫽ cVdT ⫹ T (Eq 12)
V

Considering that a phase change occurs at temperature, T,

when P is fixed and vice versa at fixed T vapor pressure
independent of the volume, Eq 12 reduces to

dP
dS ⫽ dV (Eq 13)
dT

Equation 13 is now integrated for the phase change, liquid

(L) to vapor (V ), to yield

dP SV ⫺ SL HV ⫺ HL ⌬H
⫽ ⫽ ⫽ (Eq 14)
dT VG ⫺ VL T (VG ⫺ VL) T⌬V

which is Eq 11.
Few are aware that Benoit-Pierre-Emile Clapeyron (1799–
1864) derived the first expression of Eq 11 in 1834 when
the second law was still to be stipulated, entropy was a
nonexistent concept, and James Clerk Maxwell (1831–1879)
was three years old. Clapeyron came to his equation after
putting the Carnot cycle on a mathematical and graphical
basis. In order to do so, he compared the performance of two
differential reversible Carnot cycles (Fig. 1) that differed in
the working substance and compared the way heat was added
and removed from the cycle. The first cycle used an ideal
gas and took place between two isotherms separated by dT
(Fig. 1a). In the second cycle, a saturated liquid was first
evaporated and then the vapors condensed at a slightly lower
temperature (Fig. 1b).
The actual mathematics in Clapeyron’s paper is less
straightforward and reflects the knowledge available at his
time. For the first cycle, Clapeyron wrote the Mariotte-Gay
Lussac law (he did not use the expression ideal gas) in
Fig. 1 Clapeyron cycle: (a) ideal gas and (b) saturated fluid. In
the form both figures, TC ⫽ TH ⫺ dTH
P0 v0
Pv ⫽ (267 ⫹ t) (Eq 15)
267 ⫹ t0 Clapeyron went on to determine the following expression
for the heat transferred, Q, from the heat source.
and then defined R as

P 0 v0 Q ⫽ R(B ⫺ C log P ) (Eq 17)

⫽R (Eq 16)
267 ⫹ t0
Inspection of Eq 15 and 16 tells us that Clapeyron not only
did not employ the concept of absolute temperature, but he
used the gas law with a zero located at 267 ⬚C. He then
proceed to draw a differential Carnot cycle in the P-V plane,
using the words heat source and impermeable envelope to
define what today we call isotherms and adiabatics. The
brilliant idea behind Clapeyron’s scheme was that separating
the two isotherms by a differential amount yielded a quadrilat-
eral cycle that could be approximated by a parallelogram.
According to Clapeyron, B and C were undetermined func-
tions of the temperature; function B would formally vary
from one gas to another but was probably identical for all
simple gases. This conclusion was based on the (wrong)
information that all gases had the same heat capacity. In
addition, constant C, in particular, was assumed to be positive
and independent of the nature of the gas. Equation 17 was
arrived at by making the (wrong) assumption that dQ was
an exact differential. In modern terms, Eq 17 corresponds to
the second TdS equation[12] applied to an ideal gas.

624 Journal of Phase Equilibria Vol. 22 No. 6 2001

 General Interest

冢⭸T冣 dP
⭸V Clausius used Eq 22 to calculate the value of 1/A as 421
TdS ⫽ cp dT ⫺ T kg ⭈ m/kcal and explained this last figure saying that the work
P
equivalent of the unit of heat was the lifting of something over
dP 400 kg of water to the height of 1 m. He also compared this
⫽ cp dT ⫺ RT (Eq 18) potential equivalent with those of Joule: 460 for the heat
P
produced by magneto electricity, 438 for the mechanical
⫽ cp dT ⫺ RTd ln P expansion of a gas, and 425 for the heat produced by the
friction of water, mercury, and cast iron. All these values
The next stage was to repeat the arguments this time using a are in remarkable agreement with the actual value of 427.
saturated vapor as the working substance. The final result was Inspection of Eq 22 shows that Clausius had already arrived
at the definition of absolute temperature and that his equation

冢 冣
V L dP is equivalent to the modern expression for the Clausius-
k⫽C 1⫺ (Eq 19) Clapeyron equation.
V G dt
The Clausius-Clapeyron equation can be easily integrated
where k was the latent heat of vaporization (which Clapeyron for the phase changes, liquid to gas and solid to gas, if we
called latent caloric per unit volume of vapor). According make the following simplifying assumptions. (a) The gas
volume is much larger that that of the liquid (or the solid).
to Clapeyron, k could never become infinite but could become
This will always be true if we are not very close to the critical
zero when the two phases achieved the same density (that
is, at the critical point). point where the volume of the gas is equal to that of the
Equation 19 is essentially the same as Eq 11, if C is taken liquid. (b) The vapor phase behaves similar to an ideal gas.
Equation 11 now becomes
as the absolute temperature multiplied by the conversion
factor between heat and mechanical work units. In his paper,
d ln P ⌬H
Clapeyron indicated that no experimental data were available ⫽ (Eq 23)
to determine the value of C, except for t ⫽ 0. Using the dT RT 2
value cP/cV ⫽ 1.412 found by Dulong and Petit,[4] Clapeyron
calculated 1/C to be 1.41 at 0 ⬚C, and thus, the value 386 as (c) To integrate the differential Eq 23, we need to know the
the mechanical equivalent kg ⭈ m/kcal. Although Eq 19 was dependence of ⌬H on T (or P). We know that ⌬H decreases
determined using a cycle in the liquid-vapor envelope, it was as the temperature increases and becomes zero at the critical
clear that the same result would be obtained if the cycle were point. If we consider a temperature interval not too large
performed either in the solid-gas or in the solid-liquid (probably about 10 ⬚C), we can assume a constant value for
envelopes. ⌬H (or, if not, we take its average value in the tempera-
ture interval).
Under these assumptions, Eq 23 can be integrated to yield
The Clausius-Clapeyron Equation
⌬H
In 1850, Clausius used Carnot’s monograph and Clapey- ln P ⫽ ⫺ ⫹c (Eq 24)
RT
ron’s paper, as well as new experimental data that had accu-
mulated thence, to change the expression of Mariotte-Gay
where c is the integration constant. Integrating between the
Lussac’s law to[13] (as also used by Bertrand)[7–9]
limits (P1, T1) and (P2, T2):
Pv ⫽ R(a ⫹ t) (Eq 20)
冢 冣
P2 ⌬H 1 1
ln ⫽ ⫺ (Eq 25)
P0 v0 P1 R T1 T2
Pv ⫽ (a ⫹ t) (Eq 21)
273 ⫹ t0
Equations 24 and 25 are also known as the Clausius-
where a was a constant, the same for all gases; and R was Clapeyron equation.
a constant equal to P0v0/R(a ⫹ t0). According to the Clausius, Equation 24 can be written in the general form
the experimental evidence indicated that the best value for
a (at that time) was 273 ⬚C and that this value would become B
log P ⫽ A ⫺ (Eq 26)
more precise as better experimental data become available. T
Furthermore, Clausius concluded that function C of Cla-
peyron had the structure C ⫽ A(a ⫹ t) where 1/A represented Thus, if a substance behaves according to the Clausius-
the work equivalent of the unit of heat. He then proceeded Clapeyron equation, a plot of log P against 1/T (semilog
to write the Clapeyron equation in the form graph) should yield a straight line with slope ⌬H/2.303R.
The slope of the line allows us to calculate the heat of vapor-
dP ization (or sublimation).
r ⫽ A(a ⫹ t)(V G ⫺ V L) (Eq 22)
dT The assumption that the heat of vaporization is constant
was soon found to be one of the main reasons why the
where r was the latent heat of vaporization. Clausius-Clapeyron equation would only fit the experimental

Journal of Phase Equilibria Vol. 22 No. 6 2001 625

General Interest
data in a short temperature interval. One common way to
improve the fitting ability was to express the heat of vaporiza-
tion as a function of the temperature, using the facts that
⌬Hvap ⫽ H sat
vapor ⫺ H liq, cP ⫽ (⭸H/⭸T )P , and that the specific
at
heat cP of the gas and the liquid may be expressed as a
polynomial, cP ⫽ a ⫹ bT ⫹ cT 2 ⫹ ⭈⭈⭈. By putting all this
information together the heat of vaporization could be written
as a polynomial in temperature, ⌬Hvap ⫽ ␣ ⫹ ␤T ⫹ ␥T . . . .
This polynomial could then be replaced in Eq 23 to yield a
more accurate equation for the vapor pressure. The simplest
expression for ⌬H corresponds to a linear variation with the
temperature, ⌬Hvap ⫽ ␣ ⫹ ␤T, where
d ln P ␣ ⫹ ␤T
⫽ (Eq 27)
dT RT 2
B Rendu, the journal of the Académie.[15–29]
log P ⫽ A ⫹ ⫹ C log T (Eq 28)
T the functionality suggested by Bertrand, Eq 10, for the vapor
Equation 28 is known as the Rankine-Kirchhoff equation.
As will be shown subsequently, Antoine considered this pos-
sibility but discarded it.
An interesting point is that Ramsay and Young calculated
the values of the right-hand side of Eq 11 (without mentioning
it by the name Clausius-Clapeyron) for different liquids and,
on the basis of their results, claimed that the heat of vaporiza-
tion per unit increase in volume at normal conditions was
approximately constant, that is, ⌬H/⌬V ⫽ constant.[14]
Antoine’s Equation
Before proceeding to discuss this equation, some words
are needed regarding Antoine. Very little is known about
Louis Charles Antoine. He was born (Fig. 2) on May 29,
1825, in Rambervillers, Vosges and passed away on April 1,
1898 (Fig. 2). He was the son of Charles Joseph Antoine,
who worked as a schoolmaster in Rambervillers, and Marie
Anne Eugène Thiriet. He attended the École Polytechnique
between 1842 and 1845 and, after graduation, continued his
studies in the School of Naval Engineering (1845–1846). In
1846, he joined the French Navy as Sous-Ingénieur (subengi-
neer) and eventually reached the rank of Ingénieur de 1⬚
Classe (1871). Between the years 1862 to 1864, he saw action
in China and Cochinchine (the Opium Wars). In 1860, he
was appointed Chevalier de la Légion d’Honneur, and in
1871, he was promoted to Officier. Antoine served in the
Navy for a little over thirty years and was stationed mostly
in Brest.
While in the Navy, Antoine published a series of reports
on subjects related to the mechanical aspects of ships (for
example, “Design of helical propellers” and “Determination
of the coefficient for calculating the flow resistance of hulls”)
and on thermodynamics. His interest in thermodynamics orig-
inated in work he was doing on the steam engines of ships
and the methods of propulsion for torpedoes. At that time,
torpedoes were propelled by air compressed to 50 atm, con-
tained within the weapon. Motion of the torpedo was achieved
by a helix propelled by controlled release of the air.
626 Journal of Phase Equilibria Vol. 22 No. 6 2001
Antoine also published a series of reports related to the
thermodynamic properties of gases and superheated vapor
(density, compressibility, coefficient of thermal expansion,
and heat content). In these papers, he described his experi-
mental measurements and developed the analytical equations
that related the different properties. The most important of
the last group is “Du coefficient de dilatation des gaz et des
vapeurs sous pressions constants,” a 38-page document in
which he began to develop what would become the well-
known Antoine equation for the vapor pressure.
In 1886, he requested permission from the Ministry of the
Navy to make this work public. Permission was granted on
February 22, 1886 (Fig. 3), and on April 9 of the same year,
he sent it as a memoir to the Académie de Sciences, where
it was read on the session held on April 12. Eventually,
extracts of this and other memoirs were published in Comptes
Antoine began the development of his equation by using
pressure.[7,9] Differentiating the equation with respect to the
absolute temperature, he obtained:[22]
dT T 2 ⫺ ␭T
⫽ (Eq 29)
d ln P ␣␭
the equation of a parabola.
Now, in a previous publication,[15] Antoine had demon-
strated that the vapor pressure of water could be satisfactorily
represented by
5.5
冢 冣
t ⫹ 55
P⫽G (Eq 30)
t
where P was in atmospheres, and t was in ⬚C. Also,
dT t ⫹ 55
⫽ (Eq 31)
d ln P 5.5
the equation of a straight line.
Since, in Eq 10, there were many sets of the adjustable
parameters that could give a satisfactory fit of the data,
Antoine asked himself if temperatures were expressed from
a zéro spécial [special zero (C )] for every vapor, so that
␪ ⫽ t ⫹ C, would it be possible to find a parabola given
by dT /d ln P ⫽ E␪ 2 that would give a better representation
of the data than Eq 30.
Integrating equation dT /d ln P ⫽ E␪ 2 gave
B
log P ⫽ A ⫺ (Eq 32)
␪
B
log P ⫽ A ⫺ (Eq 33)
t⫹C
where coefficients A, B, and C were to be determined from
the experimental data. Equation 33 is Antoine’s equation
for the vapor pressure of a saturated liquid. Comparison of
Eq 26 and 33 shows that the Clausius-Clapeyron equation

Fig. 2 Antoine’s birth certificate
can be considered a special case of Antoine’s equation with
C ⫽ 233.15.
For someone reading only this particular paper of
Antoine,[22] it would seem that he came into the idea of a
special zero by a fortuitous accident. This is not the case;
Antoine had already used the concept of the special zero
in several papers he had published before. According to
him, the value of the special zero was the temperature at
which the vapor pressure of the particular gas was zero.
Antoine used Regnault’s experimental data for the vapor
pressure of water[2] to determine the values A ⫽ 8.9325,
B ⫽ 1884.3, and C ⫽ 230. A comparison of the calculated
data against the experimental one showed him that Eq 33
gave a much better fit than Eq 30.
Journal of Phase Equilibria Vol. 22 No. 6 2001
General Interest
In a following publication,[23] Antoine reported the val-
ues of the constants A, B, and C for seventeen additional
vapors that included ammonia, nitrogen dioxide, hydrogen
sulfide, silver iodide, methanol, sulfur, and methyl chloride.
Antoine’s equation represents a significant improvement
over that of Clausius-Clapeyron. It is the most widely used
today, and its parameters are extensively reported in the
literature.[30–32] According to Thomson,[33] although the
equation is an appropriate three-constant regressor for inter-
polation purposes, it cannot be extrapolated above a
reduced temperature of about 0.85 without serious error.
This is the reason why different sets of constants are given
for different temperature ranges. For example, the TRC
database[31,32] lists one set of Antoine’s constants for the
627
General Interest

range 0.0004 to 10 mmHg and another for the range 10 to

1500 mmHg.
Antoine’s equation and Eq 23 can be used to predict the
heat of vaporization at a given temperature as follows:

d ln P ⌬H 2.303B
⫽ ⫽ (Eq 34)
dT RT 2 (T ⫹ C )2

The value of the heat of vaporization predicted by Eq 34 is

usually within 15% (or less) of the experimental one.
Antoine also tested the Rankine-Kirchhoff equation (Eq
28), which he called the Dupré equation (Anastase Dupré,
1808–1863), as another possible model but rejected it
because the variable:

dT T2
⫽ (Eq 35)
d ln P ⫺2.303A ⫹ CT

had the shape of a hyperbola and, thus, did not fit the experi-
mental evidence.
To complete the historical background of Antoine’s equa-
tion, we must say that Porter compared Bertrand’s equation
(Eq 10) with that of Rankine-Kirchhoff (Eq 28) and found
the former to be more accurate.[34]
Regnault determined the vapor pressure as a function of
temperature not only of water but also of 28 other liquids,
such as vinyl alcohol, ether, and CS2.[2] In the same publica-
tion, he also reported his measurements of the vapor pressure
of mixtures of liquids, partially or totally soluble,[2] and the
heat of vaporization of eight substances (CS2, ether, ethanol,
benzene, CCl4, CHl3, acetone, and turpentine)[2] at different
pressures. Karl Eugene Dühring (1833–1921) used
Regnault’s results on the vapor pressure of organic com-
pounds to develop what is now known as Dühring’s rule, a
linear relation between the temperature at which a given
substance has the same vapor pressure as that of a reference
substance (usually water). Nowadays, Dühring’s rule is used
to calculate the increase in boiling point of a solvent caused
by a nonvolatile solute.[35]
Another interesting historical fact is that François-Marie
Raoult (1830–1901), in his paper describing the general law
of the vapor pressure of solutions[36] (eventually to be known
as Raoult’s law), made no mention of Regnault’s results on
the subject.
Several attempts have been made to develop a theoretical
basis for Antoine’s equation. For example, Gutmann and
Simmons[37] expanded the results of Wall[38] to show that Eq
11 could be developed from van der Waals’ equation of state
and the energy of an assembly of Einstein oscillators. The
value of parameter C was shown to be related to the character-
istic frequency of the liquid.
Wall applied van der Waals’ equation of state to pressures
sufficiently low so that the liquid could be considered incom-
pressible and the vapor to behave ideally. Under these condi-
tions, the vapor pressure could be equated to the fugacity of
the liquid. Now, the fugacity, f, of a fluid is given by[11]
v

冢 冮 PdV冣
1
Fig. 3 Document from the French Navy allowing Antoine to pub- ln f ⫽ ln P* ⫹ PV ⫺ RT ⫺ (Eq 36)
RT
lish his work v*

628 Journal of Phase Equilibria Vol. 22 No. 6 2001

 General Interest

where the superscript (*) represents a low pressure where identify the constant C of the Antoine equation with (273.16
the gas behaves ideally. Substitution of P from van der Waals’ ⫺ 3␪0/8), and the C could be calculated from the maximum
expression and assuming that V* is very large so that (V* ⫺ vibrational frequency of the oscillator:
b) can be replaced by RT /P* and a/V 2 can be neglected, led to
B B
log P ⫽ A ⫺ ⫽A⫺
t ⫹ 273.15 ⫺ 3␪0 /8 T ⫺ 3␪0 /8
冢 冣
b 2a RT
ln f ⫽ ⫺ ⫹ ln (Eq 37)
V ⫺ b VRT V⫺b (Eq 44)

To calculate the fugacity of the liquid, Wall estimated the
volume of the liquid by considering it to be equal to the
smallest root of the cubic equation of state; namely,
b2RT
V⫽b⫹ (Eq 38)
a
Substitution of Eq 38 into 36 and assuming that at low pres-
sures the fugacity was equal to the vapor pressure yielded,
finally
a a
ln P ⫽ ln ⫺ (Eq 39)
b2 bRT
Inspection of Eq 39 shows that it is exactly the same form
as the Clausius-Clapeyron (Eq 26).
Gutmann and Simmons went a step forward and used the
expression developed by Tetrode[39] for the van der Waals
equation, where the thermal energy of a liquid was described
in terms of the vibrational energy possessed by an assembly
of Einstein oscillators.
Effect of the Pressure of the Vapor Pressure
It has already been mentioned that the vapor pressure of
a pure compound may be considered independent of the
external pressure. We will close our analysis with a general
discussion of the possible effect of the external pressure.
Experience tells us that most solids and liquids exist usually
under pressure greater than their vapor pressures. The
medium exerting pressure on a substance may be an insoluble
gas, insoluble liquid, piston, or other external force. As an
example, consider the common situation of water at 298.15
K; the vapor pressure of water is 3.169 kPa, while the external
one is near 100 kPa.
The possible effect of the external pressure was analyzed
by John Henry Poynting (1852–1914) in 1881, very close
in time to the publication of Antoine’ equation.[40] His basic
arguments were as follows. Consider a system consisting of
a pure liquid in equilibrium with its vapor. The gas phase is
now compressed isothermally from the initial pressure Psat
to a pressure P. From the Maxwell relation dG ⫽ VdP and
assuming, as a first approximation, that the vapor behaves
similar to an ideal gas and the liquid is incompressible, we get
冮
P
P
⌬G ⫽ nRT ln ⫽ V LdP ⫽ V L (P ⫺ Psat) (Eq 45)
Psat Psat

冢P ⫹ V 冣 (V ⫺ b) ⫽ ␾ (T )
a
2 (Eq 40)
where VL is the volume of the liquid.
In today’s terms, we would use the concept of fugacity
and write Eq 45 in the more precise manner:
3R␪0 RT␪ 20
␾ (T ) ⫽ RT ⫺ ⫹ ⫹ ⭈⭈⭈ (Eq 41)
8 20T 2
冮
P
f
⌬G ⫽ nRT ln sat ⫽ V LdP ⫽ V L (P ⫺ Psat) (Eq 46)
f Psat
where ␪0 was a characteristic temperature.
For this situation, Eq 37 and 40 became For example, consider saturated liquid water at 298.15 K. If
the pressure is increased from 3.169 to 1000 kPa, the vapor
pressure in the final state will from Eq 45 be approximately
␾ (T )
冢 冣
b 2a
ln f ⫽ ⫺ ⫹ ln (Eq 42)
V ⫺ b V␾ (T ) V⫺b
P (0.001127)(18)(1000 ⫺ 3.169)
ln ⫽ ⫽ 0.000827
Psat (298.15)(82.06)
a a
ln P ⫽ ln ⫺ (Eq 43) (Eq 45a)
b2 b␾ (T )
P
⫽ 1.0008 (Eq 45b)
According to Gutmann and Simmons, if only the first Psat
term of the ␾ (T ) series was retained, then, Eq 43 became
of the form of the Clausius-Clapeyron equation; retention of As we see, under normal conditions, the effect of the
the first two terms yielded an expression that had the same external pressure on the vapor pressure is negligible, but it
form as that of Antoine. Furthermore, it was possible to may become of importance in many modern processes that

Journal of Phase Equilibria Vol. 22 No. 6 2001 629

 General Interest
are conducted at very high pressures, such as supercritical
gas extraction.
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