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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 One of the subjects in the course on Heat and Chemical

cycle (Genesis 2:6): “But there went up a mist from the earth,

and watered the whole face of the land.” Experience indicates scription, under the auspices of the Royal Society) carried

that the vapor pressure of a pure liquid depends only on the name: “Expansive force of vapour of water, ether, &c., the temperature, provided that the external pressure is not in geometrical progression with equal increments of heat.” excessive (over 50 atm) and that the material is not subject Dalton was especially interested in the question of vapor

to other fields, such as magnetic, electric, and/or surface pressure because of its relation to meteorology. His experi- effects. It is also independent of the relative amounts of the ments seemed to indicate that air humidification was not liquid and vapor phases present. dependent on pressure, only on temperature. He believed that

Many different formulas and graphical representations have been suggested for the vapor pressure-temperature rela-

one “cubic foot of air will imbibe the same weight of vapour, if the temperature be the same. Eventually, Victor Regnault

tionship for pure liquids and their mixtures. Many of these (18101878) discredited Daltons Eq 1. [2]

are empirical, but some of them have a theoretical basis. As Jean-Baptiste Biot (17741862) extended Daltons equa- we will see, the different equations involve several parameters tion and wrote [3] 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

An interesting aspect of Eq 2 is that Biot put the tempera- Antoine equation. 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

Earlier Equations 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

and was a temperature measured from a conve-

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 .

(Eq 2)

Elements that Dalton gave in Manchester in 1805 (by sub-

(Eq 1)

log P b ct

log P a b t c t

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

that the vapor pressures, P, increased in geometric progres-

sion, while the temperatures, T, increased in arithmetic pro- as follows:

gression. (In Dalton’s words: “That the force of steam is in

geometrical progression to equal increases of temperature

intensity of heat.”). That is, P P 0 a t with t being temperature

in the Celsius scale so that

surface,

nient zero.

Regnault

[2]

used Biot’s equation to correlate his extensive

observed measurements of the vapor pressure and observed that a

much better fit was obtained if the equation was modified

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.

or

Jaime Wisniak, Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel 84105. Contact e-mail:

wisniak@bgumail.bgu.ac.il.

622

Journal of Phase Equilibria Vol. 22 No. 6 2001

General Interest

and concluded that the predicted values were manifestly

(1776–1856) conducted in his scientific career concerned the impossible.

determination of the vapor pressure of mercury at tempera-

tures very close to its boiling point.

used an inverted glass siphon, connected to a flask, and their relation to Antoine’s equation [79] (Eq. 29). Bertrand immersed in a bath of olive oil that could be heated to a started from the following approximation for the Clausius-

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):

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

where T rel was the mercury pressure and was a measure

relative temperature in the sense that T rel 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

For water, he obtained 79.623, 88.623, a 126.37,

and log K 34.21083. (b) For many substances, it was P (1 at) m (Eq 5) known that the ratio, APv/ H, was a very weak function

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-

had

ments by others, such as Michael Faraday (1791–1867),

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 where G was a constant, n 1/b, and b/a.

C it was necessary to employ an equation having

parameters, such as the one proposed by Biot. Avogadro

(Eq 10)

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

(Eq 9)

of temperature. For this situation, Eq 7 could be integrated to

(Eq 8)

T rel P(1 l/L)

(Eq 7)

The different functionalities developed by Jacques-Louis Bertrand (1822–1900) are of particular interest because of

One of the few experimental works that Amedeo Avogadro

[5] For this purpose, he

Clapeyron equation:

dP

dT H

ATv

(Eq 4)

of

T

(T a)

P K

P kT n

n

P G T

T

According to Bertrand, Eq 10 had the remarkable property that for an immensity of pairs ( , n) it gave exact values of

modified Biot’s Eq 2 to the form the vapor pressure; nevertheless, he recommended using the value, n 50, and then determining the pertinent value of log P at bt 2 ct 3 (Eq 6) . As shown subsequently, Antoine used Eq 10 to develop his relation.

by considering that the vapor pressure of mercury at 0 C

was 1 mm mercury (so that in Eq 2 a 0) and

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.

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 where H and V are the changes in enthalpy and volume

described the vapor pressure.

more

expressing

For

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

dT H

T

V

(Eq 11)

that take place during the phase change process. Textbooks

Years later (1909), Young used Biot’s relation to try to normally use the derivation of the Clausius-Clapeyron equa-

[6]

determine the critical pressure of some 30 odd substances tion as an example of the large number of relations that can

Journal of Phase Equilibria Vol. 22 No. 6 2001

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]

TdS c V dT T P

T

V

dV

(Eq 12)

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

dS dP

dT dV

(Eq 13)

Equation 13 is now integrated for the phase change, liquid (L) to vapor (V ), to yield

dP

S V S L

H V

H

L

H

dT

V G V L

T (V G V L )

T

V

(Eq 14)

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 the form

P v

P 0 v 0

267 t 0 (267 t)

and then defined R as

P 0 v 0

267 t 0 R

(Eq 15)

(Eq 16)

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.

eral cycle that could be approximated by a parallelogram. Fig. 1 both figures, T C T
eral cycle that could be approximated by a parallelogram. Fig. 1 both figures, T C T

Fig. 1

both figures, T C T H dT H

Clapeyron cycle: (a) ideal gas and (b) saturated fluid. In

Clapeyron went on to determine the following expression for the heat transferred, Q, from the heat source.

Q R(B C log P )

(Eq 17)

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

TdS c p dT T V

Clausius used Eq 22 to calculate the value of 1/A as 421 kg m/kcal and explained this last figure saying that the work equivalent of the unit of heat was the lifting of something over 400 kg of water to the height of 1 m. He also compared this potential equivalent with those of Joule: 460 for the heat

c p dT RT dP

produced by magneto electricity, 438 for the mechanical c p 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

are in remarkable agreement with the actual value of 427. Inspection of Eq 22 shows that Clausius had already arrived at the definition of absolute temperature and that his equation is equivalent to the modern expression for the Clausius- Clapeyron equation. The Clausius-Clapeyron equation can be easily integrated for the phase changes, liquid to gas and solid to gas, if we make the following simplifying assumptions. (a) The gas volume is much larger that that of the liquid (or the solid). This will always be true if we are not very close to the critical point where the volume of the gas is equal to that of the liquid. (b) The vapor phase behaves similar to an ideal gas. Equation 11 now becomes

T P dP

P

(Eq 18)

The next stage was to repeat the arguments this time using a saturated vapor as the working substance. The final result was

k

C 1 V L

V

G dP dt

(Eq 19)

where k was the latent heat of vaporization (which Clapeyron

called latent caloric per unit volume of vapor).

According

to Clapeyron, k could never become infinite but could become

zero when the two

phases achieved the same density (that

is, at the critical point). Equation 19 is essentially the same as Eq 11, if C is taken as the absolute temperature multiplied by the conversion factor between heat and mechanical work units. In his paper, Clapeyron indicated that no experimental data were available to determine the value of C, except for t 0. Using the value c P /c V 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 the mechanical equivalent kg m/kcal. Although Eq 19 was determined using a cycle in the liquid-vapor envelope, it was clear that the same result would be obtained if the cycle were performed either in the solid-gas or in the solid-liquid envelopes.

The Clausius-Clapeyron Equation

In 1850, Clausius used Carnot’s monograph and Clapey-

ron’s paper, as well as new experimental data that had accu-

Mariotte-Gay

Lussac’s law to [13] (as also used by Bertrand) [79]

mulated thence, to change the expression of

d ln P

H

RT 2

dT

(Eq 23)

(c) To integrate the differential Eq 23, we need to know the dependence of H on T (or P). We know that H decreases as the temperature increases and becomes zero at the critical point. If we consider a temperature interval not too large (probably about 10 C), we can assume a constant value for H (or, if not, we take its average value in the tempera- ture interval). Under these assumptions, Eq 23 can be integrated to yield

ln P RT H

c

(Eq 24)

where c is the integration constant. Integrating between the limits (P 1 , T 1 ) and (P 2 , T 2 ):

P v R(a t)

Pv

P 0 v 0 273

t 0 (a t)

(Eq 20)

(Eq 21)

where a was a constant, the same for all gases; and R was

a constant equal to P 0 v 0 /R(a t 0 ). According to the Clausius, the experimental evidence indicated that the best value for

become

more precise as better experimental data become available.

Furthermore, Clausius concluded that function C of Cla-

peyron had the structure C A(a t) where 1/A

the work equivalent of the unit of heat. He then proceeded to write the Clapeyron equation in the form

a (at that time) was 273 C and that this value would

represented

r

A(a t)(V G V L ) dP dT

(Eq 22)

where r was the latent heat of vaporization.

ln P 2

H

P

1

R

1

T 2

1

T

1

(Eq 25)

Equations 24 and 25 are also known as the Clausius- Clapeyron equation. Equation 24 can be written in the general form

log P A B T

(Eq 26)

Thus, if a substance behaves according to the Clausius- Clapeyron equation, a plot of log P against 1/T (semilog graph) should yield a straight line with slope H/2.303R. The slope of the line allows us to calculate the heat of vapor- ization (or sublimation). The assumption that the heat of vaporization is constant was soon found to be one of the main reasons why the 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 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.

heat c P of the gas and the liquid may be expressed as a

polynomial, c

information together the heat of vaporization could be written

as a polynomial in temperature, H vap 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 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 Acade´mie de Sciences, where it was read on the session held on April 12. Eventually, extracts of this and other memoirs were published in Comptes

Rendu, the journal of the Acade´mie. Antoine began the development of his equation by using the functionality suggested by Bertrand, Eq 10, for the vapor pressure. [7,9] Differentiating the equation with respect to the absolute temperature, he obtained: [22]

d ln P

temperature, H vap T, where

improve the fitting ability was to express the heat of vaporiza- tion as a function of the temperature, using the facts that

H

vap H sat

vapor H at liq , c P ( H/ T) P , and that the specific

P a bT cT 2 . By putting all this

T

RT 2

dT

(Eq 27)

[15–29]

log P A

B T C log T

(Eq

28)

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]

dT

T 2 T

d ln P

(Eq 29)

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

Antoine’s Equation

P G t 55

t

5.5

(Eq 30)

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, dT

1898 (Fig. 2). He was the son of Charles Joseph Antoine, who worked as a schoolmaster in Rambervillers, and Marie

where P was in atmospheres, and t was in C. Also,

d ln P

t 55

5.5

(Eq 31)

´

Anne Euge`ne Thiriet. He attended the E cole

between 1842 and 1845 and, after graduation, continued his

In

1846, he joined the French Navy as Sous-Inge´nieur (subengi- neer) and eventually reached the rank of Inge´nieur 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 Le´gion 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. Eq 26 and 33 shows that the Clausius-Clapeyron equation

studies in the School of Naval Engineering (1845–1846).

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 ze´ro spe´cial [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

Polytechnique

log P A B

log P A

B

t C

(Eq 32)

(Eq 33)

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

626

Journal of Phase Equilibria Vol. 22 No. 6 2001

General Interest

General Interest Fig. 2 Antoine’s birth certificate can be considered a special case of Antoine’s equation

Fig. 2

Antoine’s birth certificate

can be considered a special case of Antoine’s equation with In a following publication, [23] Antoine reported the val-

C 233.15.

For someone reading only this particular paper of vapors that included ammonia, nitrogen dioxide, hydrogen

Antoine,

special zero by a fortuitous accident. This is not the case;

Antoine had already used the concept of the special zero over that of Clausius-Clapeyron. It is the most widely used in several papers he had published before. According to today, and its parameters are extensively reported in the

although the

equation is an appropriate three-constant regressor for inter-

Antoine used Regnault’s experimental data for the vapor polation purposes, it cannot be extrapolated above a

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 for different temperature ranges. For example, the TRC

gave a much better fit than Eq 30.

lists one set of Antoine’s constants for the

ues of the constants A, B, and C for seventeen additional

[22] it would seem that he came into the idea of a

sulfide, silver iodide, methanol, sulfur, and methyl chloride. Antoine’s equation represents a significant improvement

literature. [3032] According to Thomson, [33]

reduced temperature of about 0.85 without serious error. This is the reason why different sets of constants are given

database

[31,32]

him, the value of the special zero was the temperature at which the vapor pressure of the particular gas was zero.

Journal of Phase Equilibria Vol. 22 No. 6 2001

627

General Interest

General Interest Fig. 3 Document from the French Navy allowing Antoine to pub- lish his work

Fig. 3 Document from the French Navy allowing Antoine to pub- lish his work

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

 

dT

RT 2

(T

C) 2

(Eq 34)

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 Dupre´ equation (Anastase Dupre´, 1808–1863), as another possible model but rejected it because the variable:

 

dT

T

2

d

ln P

2.303A CT

(Eq 35)

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 CS 2 . [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 (CS 2 , ether, ethanol, benzene, CCl 4 , CHl 3 , acetone, and turpentine) [2] at different pressures. Karl Eugene Du¨hring (1833–1921) used Regnault’s results on the vapor pressure of organic com- pounds to develop what is now known as Du¨hring’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, Du¨hring’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 Franc¸ois-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]

ln f ln P*

v

RT PV RT v* PdV

1

(Eq 36)

628

Journal of Phase Equilibria Vol. 22 No. 6 2001

General Interest

where the superscript (*) represents a low pressure where the gas behaves ideally. Substitution of P from van der Waals’ expression and assuming that V* is very large so that (V* b) can be replaced by RT /P* and a/V 2 can be neglected, led to

ln f

b

VRT ln

2a

V b

RT

V

b

b

(Eq 37)

identify the constant C of the Antoine equation with (273.16

3

/8), and the C could be calculated from the maximum

vibrational frequency of the oscillator:

0

log P A

B

t 273.15 3 0 /8 A

B

T 3 0 /8

(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,

V b b 2 RT

a

Substitution of Eq 38 into 36 and assuming that at low pres- sures the fugacity was equal to the vapor pressure yielded, finally

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

(Eq 38) 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

ln P ln

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

bRT (Eq 39) by John Henry Poynting (1852–1914) in 1881, very close

a

a

b 2

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.

P

a 2 (V b) (T )

V

(T ) RT 3R 0

8

RT 2

20T 2

0

(Eq 40)

(Eq 41)

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 P sat 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

G nRT ln

P

P

sat

P

P sat V L dP V L (P P sat )

(Eq 45)

where V L 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:

G nRT ln

f

f sat

P

P sat V L dP V L (P P sat )

(Eq 46)

where 0 was a characteristic temperature. For this situation, Eq 37 and 40 became

ln f

b

V b

V (T) ln

2a

(T)

b

V

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

(Eq 42)

ln

P sat (0.001127)(18)(1000 3.169)

P

(298.15)(82.06)

0.000827

ln P ln

a

b 2

a

b (T)

(Eq 43)

(Eq 45a)

P

P sat 1.0008

(Eq 45b)

According to Gutmann and Simmons, if only the first term of the (T ) series was retained, then, Eq 43 became of the form of the Clausius-Clapeyron equation; retention of the first two terms yielded an expression that had the same

form as that of Antoine. Furthermore, it was possible to may become of importance in many modern processes that

As we see, under normal conditions, the effect of the external pressure on the vapor pressure is negligible, but it

Journal of Phase Equilibria Vol. 22 No. 6 2001

629

General Interest

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

References

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630

Journal of Phase Equilibria Vol. 22 No. 6 2001