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MEASUREMENT OF GASEOUS DIFFUSION COEFFICIENTS AT
AND ABOVE THE NORMAL BOILING POINT TEMPERATURE
OF THE LIQUID BY THE STEFAN-WINKELMANN METHOD

Ricardo ALVAREZ, Julio L. BUENOand Jose COCA


Department of Chemical Engineering, University of Oviedo, Oviedo, Spain

Introduction
vents, benzene and toluene were used as boiling liquids
in an Othmertype adiabatic still where the evapora-
The Stefan-Winkelmann method has been widely tion tube was immersed18). Temperatures above the
used to measure gas-vapor diffusion coefficients, in boiling points of the solvents were obtained by means
spite of its limitations16K It has been stated that pre- of azeotropic mixtures of /i-butyl alcohol-water and n-
cision is not good for vapors of liquids which have butyl alcohol-0-xylene which were used to thermostate
the system in a range of ±1°C.
very high or very low vapor pressure, and that meas- The gas flow was 250 ncm3/min, and the total pres-
urements cannot be madeabove the boiling tempera- sure of the system was kept within ±2mmH2O.
ture of the liquid phase23\ Partial pressure of the solvent-benzil mixtures was
The former drawbackscan be overcomein many
systems by using a high-boiling point substance- determined by vapor pressure osmometry2)and vapor
solvent mixture as evaporation source, in this way pressures were calculated using the Antoine equa-
tion13).
making the temperature range of the experimental
measurements wider. Thus, measurements can be The solvents benzene and toluene (Fluka analytical
made at and above the normal boiling point tempera- reagents) were distilled in a packed column and used
ture of the liquid solvent without pressure modifica- as solvent; their purity was checked by gas chromato-
tions. graphy, Benzil (Aldrich analysis grade) was used
In this work, diffusivity data are reported for the air- without further purification.
benzene and air-toluene systems at 80.1 and 110.4°C
2. Experimental Results and Conclusions
respectively and 1 atm pressure. These are the boiling
temperatures of the liquids, at which diffusion measure- Diffusion coefficients can be calculated from data of
ments are difficult by the conventional Stefan-Winkel- the interface depth as a function of time, using the
equation9} :
mann technique. Measurements have also been car-
ried out at temperatures above the solvent boiling <A^>12= (zo +z)dz (1)
point, but results maynot be as reliable as those at the PMA(h- h) «1 ln{(P~pAi)/P}
boiling point. that describes the evaporation model shown in Fig. 1.
Corrections of the initial interface depth, z0, were
1. Experimental Apparatus and Procedure
madefollowing the methods reported in the litera-
The Stefan-Winkelmann technique used in ture4'1^. (DAB}12 is defined for the interval dtlt2,
this work has been reported previously in more but as can be shown experimentally the gaseous dif-
detail2'6-9'17'20*. The evaporation tube is filled with fusion coefficient does not depend, in our case, on the
a solution of a high-boiling point compound (benzil liquid-phase composition.
in this work), and the solvent (benzene or toluene). Results at the normal boiling-point temperature of
As the solvents used have a lower density than benzil, benzene, 80.1°C, and toluene, 110.4°C, with air as the
composition gradients could be avoided in the experi- gas flowing phase are given in Table 1. In addition,
ments ; the uniformity of the liquid phase was checked the method used in this work has been used to obtain
under the operating conditions by holographic inter- gaseous diffusion data above these temperatures, and
ferometry22).
the results are also reported in Table 1. Nevertheless,
To obtain the boiling-point temperature of the sol- these last data may not be so accurate, because of the
Received July 24, 1980. Correspondence concerning this article should be
high rate of evaporation of the solvent that, eventually,
addressed to J. Coca. can yield disturbances at the interphase.
VOL. 14 NO. 3 1981 239
Fig. 1 Evaporation tube
Fig. 2 Experimental data of gaseous diffusion coefficients (at 1 atm)

Calculated values by the Slattery-Bird24) and Chap- Table 1 Diffusivity data DAB for binary systems at and
man-Enskog10) equations have been evaluated by using above boiling-point temperature of liquid

the parameters summarized in Table 2. Deviations System T


[°C]
DAB[cm2 - s' 1]
exptl. calc.ll) calc.12>
with respect to experimental values are less than -9 %.
Diffusivity data for the systems air-benzene and air- Air-benzene 80.1 0.1218 0.1241 0.1145
toluene have been reported for a wide range of Air-toluene 110.4 0.1310 0.1308 0.1200
Air-benzene 88.1 0.1320 0.1293 0.1247
temperatures. A summary of data available in the Air-toluene 116.4 0.1355 0.1348 0.1234
literature and those reported in this work are shownin
Fig. 2. Faced with non-availability of previous ex- Table 2 Data used to obtain calculated diffusion coeffi-
cient in Table l*>**w
perimental data at this temperature, we compared our Substance Tc[K] Pc[atm] a[A] e/k\K] MA
results with those from extrapolation of In DABvs.
In T plots for experimental and for estimated values. Air
Benzene
132
562.6
36.4
48.6
3.62
5.27
97
440
28.96
78.ll
Assuming a variation of diffusion coefficient with Toluene 591.7 41.6 5.64 575 92.13
temperature of the type DAB~Tm,a least-squares
analysis of the data shown in Fig. 2 gives a value of
/72=1.73 for the air-benzene system and m=1.71 for
R = gas constant [atm - cm3/K -mol]
the air-toluene system. xA = molar fraction in the liquid phase [-]
In conclusion, by using the Stefan-Winkelmann yA = molar fraction at the interface [-]
technique with a high-boiling point compound mixed z = drop in interface depth [cm]
with the solvent, gaseous diffusivities of solvent-gas z0 = initial interface depth [cm]
systems can be determined at the boiling-point tem- s = Lennard-Jones parameter [erg]
perature of the solvent and even at higher tempera- pA = density of the liquid phase [g/cm3]
tures. These results can be useful for design of eva- g = Lennard-Jones parameter [A]
poration-drying
tions.
units and polymer processing opera- <Subscrip
i
ts> = interface
Nomenclature j = point in the gaseous stagnant phase
1, 2 = two consecutive experimental runs
A = volatile compound in liquid phase
B = inert compound in gas phase Literature Cited
DAB = molecular diffusion coefficient in gas phase 1) Altshuller, A.P. and I. R. Cohen: Anal. Chem., 32, 802
[cm2/s] (1960).

<DAByX2= molecular diffusion coefficient in gas 2) Alvarez,


(1977).
R.: Ph. D. Thesis, University of Oviedo, Spain
phase defined by Eq. (1) [cm2/s]
/ = non-volatile compound in liquid phase 3) Arnold, J. H.: Ind. Eng. Chem. Fundam., 10, 36 (1971).
k = Boltzmann constant [erg/K] 4) Ben-Aim, R., R. Eggarter and J. H. Krasuk: Chim. Ind.,
MA = molecular weight Genie Chim., 97, 10 (1967).
m = exponent for thermal dependence of diffusion 5) Bird, R.B., W. E. Stewart and E.N. Light foot: "Feno-
c o effici ent menosde transporte", Reverte, Barcelona (1964).
NAz = molar flux [mol/cm2 à"s] 6) Bueno, J. L.: Ph. D. Thesis, University of Valladolid,
T = absolute temperature [K] Spain (1973).
t = time [s] 7) Bueno, J. L., J. Coca and R. Alvarez: /. Chem. Eng. Data,
P = total pressure [atm] 25, 27, (1980),
pAi = partial pressure at the interface [atm] 8) Coca, J., J. L. Bueno and R. Alvarez: PolymerBull, 1, 459
240 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
(1979).
Mato, F. and J. L. Bueno: An. Quim., 73, 108 (1977).
idem: Ind. Chem. Eng. Fundam., 19, 219 (1980). Othmer, D. F. : Ind. Eng. Chem., Anal Ed., 20, 763 (1948).
Chapman, S. and T. G. Cowling: "Mathematical Theory Perry, R. H. and C. H. Chilton: "Chemical Engineering
of Non-Uniform Gases", Cambridge University Press Handbook", McGraw-Hill, New York (1973).
(1951).
Pommersheim, J. M.: Ind. Eng. Chem. Fundam., 10, 154
Fuller, E. N., P. D. Schetler and J. C. Giddings: Ind. Eng. (1971).
Chem., 58, 19 (1966).
Reid, R. C. and T. K. Sherwood: "The Properties of Gases
Gilliland, E. R.: Ind. Eng. Chem., 26, 681 (1934). and Liquids", McGraw-Hill, New York (1966).
Gould, R. F., Ed. : "Physical Properties of Chemical Com- Sanchez, V.: Private communication, Laboratoire de
pounds", Am. Chem. Soc. (1959). Chimie-Physique, Universite Paul Sabatier, Toulouse
Lee, C. Y. and C. R. Wilke: Ind. Eng. Chem., 46, 2381 (1977).
(1954).
Seager, S. L., L. R. Geertson and J. C. Giddings: /. Chem.
Lugg, G. A.: Anal. Chem., 40, 7, 1072 (1968). Eng. Data, 8, 168 (1963).
Marrero, T. R. and E. A. Mason: /. Chem. Phys. Ref. Data, Slattery, J. C. and R. B. Bird: AIChEJ., 4, 137 (1958).
1, 1, (1972).

AN EQUATION TO CORRELATE BINODAL CURVES IN A


TERNARY LIQUID MIXTURE

Fukuji YAMASHITA, Akihiro IGUCHI, Sigefumi FUJITA and Hideo YOSHII


Department of Chemical Process Engineering, Ikutoku Technical University, Atsugi 243-02

can be determined analytically, they have been deter-


Introduction mined by the least squares method, linearizing Eq. (1).
Mutual solubility and equilibrium data are required It has become clear that Eq. (1) correlates fairly well
in liquid-liquid extraction. Though many methods of the data of systems whose maximumvalue of XAis
equilibrium data correlation have been previously pre- smaller than 0.6, though Eq. (1) does not give the best
sented for ternary liquid systems1'3'4'9'1^, there are correlation for any system.
only a few investigations of mutual solubility data 1. 2 The second equation
correlation5 '10'1^. Modifying Eq. (1), the following equation was
Namet al.10) have shown that mutual solubility devised.
xA=(xc-d1r(d2-xcy/[(xc-d1r+a(d,-xcy] (2)
data are correlated by plotting xA/(l -xB) against log
xB, but that not all systems obey their method. Wherea, m, n, and p are empirical constants to be
Hlavaty5) proposed a polynominal equation to cor- determined from data.
relate mutual solubility data. But it is not easy to From Eq. (2), the following equation was derived.
use this equation, because it contains many parameters. a(d2-xcy(xc -d1)-=(d2-xcyx^- i (iy
In this work two newequations of mutual solubility
data correlation are presented and comparedwith Ifp is given, a, m and n can be determined by the
least squares method from Eq. (2)' under the following
many data of various liquid-liquid systems with one conditions.
pair of immiscible liquids. d1 <Xc <d2 (3)
1. New Equations of Mutual Solubility Data Corre- a>0, (d2-Xcy>XA (4)
lation
From Eqs. (3) and (4), it follows that p is smaller
1. 1 The first equation than 1.0 or nearly equal to 1.0.
The following equation was first tested. Equation (2) was compared with the experimental
xA =a{xG -d,y{d,-xcy (i) data from the literature under the following cases.
where a, m and n are empirical constants to be deter- CASE2-a. p is determined by trial and error to give
the lowest root mean square deviation
mined from experimental data. Though a, m and n
Received September 17, 1980. Correspondence concerning this article
should be addressed to F. Yamashita. CASE2-b. p=1.0
VOL 14 NO. 3 1981 241

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