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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 relationship 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.

log P

ct

(Eq 1)

One of the subjects in the course on Heat and Chemical Elements that Dalton gave in Manchester in 1805 (by subscription, 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 experiments 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 (18101878) discredited Daltons Eq 1.[2] Jean-Baptiste Biot (17741862) extended Daltons equation and wrote[3] log P a b

t

(Eq 2)

Earlier Equations

John Dalton (17661844) 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 progression, while the temperatures, T, increased in arithmetic progression. (In Daltons 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.

where a, b, c, , and were constants to be determined by means of five experiments. Biots 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 temperature 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 convenient zero. Regnault[2] used Biots 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)

t n, that is, was a temperature measured where 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

General Interest One of the few experimental works that Amedeo Avogadro (17761856) conducted in his scientific career concerned the determination of the vapor pressure of mercury at temperatures 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, Avogadro 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)

and concluded that the predicted values were manifestly impossible. The different functionalities developed by Jacques-Louis Bertrand (18221900) are of particular interest because of their relation to Antoines equation[79] (Eq. 29). Bertrand started from the following approximation for the ClausiusClapeyron equation: dP dT

H ATv

(Eq 7)

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

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 P K T

(T a) (Eq 8)

(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 temperatures and lower pressures, where the experimental errors became very large, the fit was not good. Previous measurements by others, such as Michael Faraday (17911867), had already established that near 0 C the vapor pressure of mercury 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 Biots Eq 2 to the form

log P at bt 2 ct 3 (Eq 6)

For water, he obtained 79.623, 88.623, a 126.37, and log K 34.21083. (b) For many substances, it was APv/ H, was a very weak function known that the ratio, 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 P G T

T

n

(Eq 10)

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

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 absolute 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 Faradays 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 Biots relation to try to determine the critical pressure of some 30 odd substances[6]

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)

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 equation 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 derivation starts from the following TdS equation:[11] TdS cVdT T P T

dV

V

(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 dV dT

(Eq 13)

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

SV VG SL VL

HV HL T (VG VL)

H 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 (18311879) 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 Clapeyrons 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 Pv P0 v0 (267 267 t0

t) (Eq 15)

Fig. 1 Clapeyron cycle: (a) ideal gas and (b) saturated fluid. In both figures, TC TH dTH

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)

R (Eq 16) According to Clapeyron, B and C were undetermined functions 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.

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 Clapeyrons scheme was that separating the two isotherms by a differential amount yielded a quadrilateral cycle that could be approximated by a parallelogram.

624

General Interest V T

dP P

TdS

cp dT

cp dT

cp dT

T

RT

dP

P

(Eq 18)

RTd ln P

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 dP V G 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 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 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.

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 produced by magneto electricity, 438 for the mechanical 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 ClausiusClapeyron 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

d ln P dT

H RT 2

(Eq 23)

In 1850, Clausius used Carnots monograph and Clapeyrons paper, as well as new experimental data that had accumulated thence, to change the expression of Mariotte-Gay Lussacs law to[13] (as also used by Bertrand)[79] Pv

Pv

(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 temperature interval). Under these assumptions, Eq 23 can be integrated to yield ln P H RT

c (Eq 24)

where c is the integration constant. Integrating between the limits (P1, T1) and (P2, T2): ln P2 P1

H 1 R T1

1 T2

(Eq 25)

R(a

t)

t)

(Eq 20)

(Eq 21)

P0 v0 (a 273 t0

where a was a constant, the same for all gases; and R was a constant equal to P0v0/R(a t0). According to the Clausius, the experimental evidence indicated that the best value for a (at that time) was 273 C and that this value would become more precise as better experimental data become available. Furthermore, Clausius concluded that function C of Clapeyron had the structure C A(a t) where 1/A represented the work equivalent of the unit of heat. He then proceeded to write the Clapeyron equation in the form

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

(Eq 22)

Equations 24 and 25 are also known as the ClausiusClapeyron 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 ClausiusClapeyron 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 vaporization (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

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General Interest data in a short temperature interval. One common way to improve the fitting ability was to express the heat of vaporization as a function of the temperature, using the facts that Hvap H sat H at , cP ( H/ T )P , and that the specific vapor liq 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 T T.... as a polynomial in temperature, Hvap 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 T, where temperature, Hvap d ln P dT

log P A

T

RT 2 B T

C log T

(Eq 27)

(Eq 28)

Equation 28 is known as the Rankine-Kirchhoff equation. As will be shown subsequently, Antoine considered this possibility 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 vaporization per unit increase in volume at normal conditions was approximately constant, that is, H/ V constant.[14]

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 experimental 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 wellknown 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 Academie 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 Academie.[1529] 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]

dT d ln P

T2 T

(Eq 29)

the equation of a parabola. Now, in a previous publication,[15] Antoine had demonstrated that the vapor pressure of water could be satisfactorily represented by P G t

t

Antoines 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 Eugene Thiriet. He attended the Ecole Polytechnique between 1842 and 1845 and, after graduation, continued his studies in the School of Naval Engineering (18451846). In 1846, he joined the French Navy as Sous-Ingenieur (subengi neer) and eventually reached the rank of Ingenieur 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 Legion dHonneur, 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 originated 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, contained within the weapon. Motion of the torpedo was achieved by a helix propelled by controlled release of the air.

55

5.5

(Eq 30)

t 55 5.5

(Eq 31)

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 zero special [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 log P A B

(Eq 32) B

t C

log P

(Eq 33)

where coefficients A, B, and C were to be determined from the experimental data. Equation 33 is Antoines equation for the vapor pressure of a saturated liquid. Comparison of Eq 26 and 33 shows that the Clausius-Clapeyron equation

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General Interest

can be considered a special case of Antoines 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 Regnaults 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.

In a following publication,[23] Antoine reported the values 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. Antoines 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.[3032] According to Thomson,[33] although the equation is an appropriate three-constant regressor for interpolation 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 Antoines constants for the

627

General Interest range 0.0004 to 10 mmHg and another for the range 10 to 1500 mmHg. Antoines equation and Eq 23 can be used to predict the heat of vaporization at a given temperature as follows: d ln P dT

H RT 2

2.303B (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, 18081863), as another possible model but rejected it because the variable: dT d ln P

T2 2.303A

CT (Eq 35)

had the shape of a hyperbola and, thus, did not fit the experimental evidence. To complete the historical background of Antoines equation, we must say that Porter compared Bertrands 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 publication, 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 Duhring (18331921) used Regnaults results on the vapor pressure of organic compounds to develop what is now known as Duhrings 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, Duhrings 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 Francois-Marie Raoult (18301901), in his paper describing the general law of the vapor pressure of solutions[36] (eventually to be known as Raoults law), made no mention of Regnaults results on the subject. Several attempts have been made to develop a theoretical basis for Antoines 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 characteristic frequency of the liquid. Wall applied van der Waals equation of state to pressures sufficiently low so that the liquid could be considered incompressible and the vapor to behave ideally. Under these conditions, the vapor pressure could be equated to the fugacity of the liquid. Now, the fugacity, f, of a fluid is given by[11]

v

Fig. 3 Document from the French Navy allowing Antoine to publish his work

ln f

ln P*

1 PV RT

RT

v*

PdV

(Eq 36)

628

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

b

V b 2a VRT

RT

V b

identify the constant C of the Antoine equation with (273.16 3 0/8), and the C could be calculated from the maximum vibrational frequency of the oscillator: log P A B 273.15

A B 3 0 /8

(Eq 44)

3 0 /8

ln f

ln

(Eq 37)

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 a

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 (18521914) 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

G nRT ln P Psat

P

(Eq 38)

Substitution of Eq 38 into 36 and assuming that at low pressures the fugacity was equal to the vapor pressure yielded, finally a b2

a bRT

ln P

ln

(Eq 39)

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.

a (V V2

V LdP

Psat

V L (P

Psat)

(Eq 45)

b)

(T )

(Eq 40) where VL is the volume of the liquid. In todays terms, we would use the concept of fugacity and write Eq 45 in the more precise manner:

(Eq 41) G nRT ln f

f sat

P

(T )

RT

3R 8

RT 2 0 2 20T

V LdP

Psat

V L (P

Psat)

(Eq 46)

V

a b2

ln f

2a V (T )

a b (T )

ln

(T ) b

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 Psat

(0.001127)(18)(1000 3.169) (298.15)(82.06)

0.000827 (Eq 45a)

P Psat

1.0008 (Eq 45b)

ln P

ln

(Eq 43)

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

As we see, under normal conditions, the effect of the external pressure on the vapor pressure is negligible, but it may become of importance in many modern processes that

629

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

1. J. Dalton: Mem. Proc. Manchester Lit. Phil. Soc., 1802, vol. 5, pp. 535-602. 2. V. Regnault: Memoires de lAcademie des Sciences, 1862, vol. 26, pp. 1-928. 3. J.B. Biot: Traite de Physique Experimentale et Mathematique, Deterville, Paris, 1817, pp 264-90. 4. P.L. Dulong and A.T. Petit: Ann. Chim. Phys., 1818, vol. 7, pp. 337-67. 5. A. Avogadro: Ann. Chim., 1833, vol. 49, pp. 369-92. 6. S. Young: Proc. R. Dublin Soc., 1909, vol. 12, pp. 374-443. 7. J.L. Bertrand: Comp. Rendu, 1887, vol. 104, pp. 1568-71. 8. J.L. Bertrand: Comp. Rendu, 1887, vol. 105, pp. 389-94. 9. J.L. Bertrand: Thermodynamique, Gauthier-Villars, Paris, 1887, pp. 154-211. 10. E. Clapeyron: J. de lEcole Polytechnique, 1834, vol. 14, pp. 153-91. 11. S. Glasstone: Thermodynamics for Chemists, D. Van Nostrand Co., Princeton, NJ, 1947, pp. 253-54. 12. Reflections on the Motive Power of Fire by Sadi Carnot, and Other Papers on the Second Law of Thermodynamics by E. Clapeyron and R. Clausius; E. Mendoza, ed., Dover Publications, New York, NY, 1960. 13. R. Clausius: Ann. Phys., 1850, vol. 79, pp. 368-97 and 500-24. 14. W. Ramsay and S. Young: Phil. Mag., 1885, vol. 20 (5), pp. 515-23. 15. C. Antoine: Comp. Rendu, 1875, vol. 80, pp. 435-36. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. C. Antoine: Comp. Rendu, 1875, vol. 81, p. 574. C. Antoine: Comp. Rendu, 1886, vol. 102, pp. 863-64. C. Antoine: Comp. Rendu, 1886, vol. 103, pp. 1242-43. C. Antoine: Comp. Rendu, 1887, vol. 105, pp. 1242-43. C. Antoine: Comp. Rendu, 1888, vol. 106, pp. 57-60. C. Antoine: Comp. Rendu, 1888, vol. 106, pp. 116-17. C. Antoine: Comp. Rendu, 1888, vol. 107, pp. 681-84. C. Antoine: Comp. Rendu, 1888, vol. 107, pp. 836-37. C. Antoine: Comp. Rendu, 1888, vol. 107, pp. 1143-45. C. Antoine: Comp. Rendu, 1889, vol. 108, pp. 141-43. C. Antoine: Comp. Rendu, 1890, vol. 110, pp. 632-35. C. Antoine: Ann. Chim., 1891, vol. 22, pp. 281-88. C. Antoine: Comp. Rendu, 1892, vol. 114, pp. 1177-80. C. Antoine: Ann. Chim., 1892, vol. 26, pp. 426-32. Chemical Data Series, Vapor-Equilibrium Data Collection, E. Kreysa, ed., Dechema e.V., Frankfurt am Main, Germany, 1999. TRC-Thermodynamic Tables-Hydrocarbons, Thermodynamics Research Center, The Texas A&M University System, College Station, TX, extant 2000. TRC-Thermodynamic Tables-Non Hydrocarbons, Thermodynamics Research Center, The Texas A&M University System, College Station, TX, extant 2000. G.W. Thomson: Chem. Rev., 1946, vol. 38, pp. 1-40. A.W. Porter: Phil. Mag., 1907, vol. 13, pp. 724-25. J. Wisniak: J. Phase Equilibrium, 2001, vol. 22 (5). F.-M. Raoult: Comp. Rend., 1887, vol. 104, pp. 1430-33. F. Gutmann and L.M. Simmons: J. Chem. Phys., 1950, vol. 18, pp. 696-97. F.T. Wall: J. Chem. Phys., 1948, vol. 16, pp. 508-12. H. Tetrode: Phys. Z., 1913, vol. 14, pp. 212-15. J.H. Poynting: Phil. Mag., 1881, vol. 12 (4), p. 32.

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