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Pergamon

Int. J. Heat Mass Transfer, Vol. 40, No. 15, pp. 3497-3502, 1997 © 1997 Elsevier Science Ltd, All rights reserved Printed in Great Britain 0017-9310/97 $17.00+0.00

PH: S0017-9310(97)00021-5

**A new method for determining binary diffusion coefficients in dilute condensable vapors
**

C. C. M. LUIJTEN, K. J. BOSSCHAART and M. E. H. VAN DONGEN Eindhoven University of Technology, Department of Applied Physics, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

(Received 26 April 1996 and in final form 10 January 1997)

Abstract--A new method

for determining binary diffusion coefficients in dilute condensable vapors is outlined. The method is based on condensational droplet growth. It can be used in a large range of pressures and temperatures, even below the freezing point of the condensing vapor. Results are obtained for the mixtures weLter-nitrogenand water-helium in the pressure range 11-44 bar. The product of pressure and diffusivity is found to be constant. New temperature correlations for the binary diffusion coefficientare proposed, valid for the range 235-375 K. For water-nitrogen the temperature dependence is significantly stronger than predicted by the Fuller correlation; for water-helium, it is weaker. © 1997 Elsevier Science Ltd.

1. I N T R O D U C T I O N

The binary diffusion coefficient is one of the key transport properties of a gas mixture. According to Fick's first law it is defined as the proportionality constant between molecula:r flux and concentration gradient of a species. In irtdustrial chemical processes, mass transfer rates are often governed by diffusion equations. The spreading of air polluting waste gases into the atmosphere is an application of environmental interest, closely related to the field of meteorology. Even in astronomy, diffusion processes can readily be identified. A wide range of techniques exists to determine diffusion coefficients in binary mixtures of dilute gases. An extensive review was provided by Marrero and Mason [1], who also summarized and evaluated about all of the reported data up to 1968. Some reported techniques make use of unsteady droplet evaporation. We present here what could be considered as the opposite of this principle : a method based on the condensational growth of liquid droplets. One advantage of this technique is that it can be used to determine binaJ;y diffusion coefficients in a wide range of Knudsen numbers (Kn) by varying the total pressure. As we will point out in the next section, especially small Knudsen number systems are suitable for diffusion coefficient determination. Very small Kn values are easily obtained with the present method. Another useful aspect of the presented technique is its ability to determine binary diffusion coefficients at supercooled conditions (below the freezing point of the condensable vapor). Droplet growth rates, which form the basis of the method, are determ.ined using an expansion wave tube designed by Looijmans et al. [2]. The particular advantage of this setup is that droplet formation

(nucleation) and droplet growth stages can be separated in time, which greatly facilitates both nucleation rate and growth rate measurements. We illustrate our method using a measurement series of the binary diffusion coefficient of supercooled water in nitrogen and in helium. The validity of extrapolating existing correlations to lower temperatures will be investigated. Since measurements were performed at three different pressures of approximately 11, 27 and 44 bar, the influence of pressure on the diffusion coefficient is also discussed.

2. CONDENSATIONAL DROPLETGROWTH

In order to derive a diffusion coefficient from a condensation experiment, a growth model is needed. The model used in this study is described in detail by Gyarmathy [3]. It takes into account the whole range of Knudsen numbers, from very large ( free molecular flow) down to very small (usually referred to as the continuum regime). In the latter, case, droplet growth is controlled by diffusion and can accurately be described by : dr~ p~ - - = 2~12--(Y+--Y+,m)" dt p~ (1)

The Knudsen number is defined here as the ratio of the mean free path of a vapor molecule to the droplet diameter, Kn = l/(2rd). It is readily verified that under typical experimental conditions in this work, the Knudsen number is very small indeed : l ranges from 10 -8 m at 10 bar to 10 - 9 m at 40 bar and rd lies typically between 10 -6 m at 10 bar and 10-7 m at 40 bar. Although the model covers the entire range of Knudsen numbers--as do our calculations--we men-

3497

Using the complete model--covering the whole range of Knudsen numbers--is correct. Due to the particular form of the temperature pattern. our results for 212 are only weakly dependent on the particular form of the growth model used. Latent heat release due to condensation does not violate this assumption : the amount of heat is negligible in view of the large heat capacity of the carrier gas at the high pressures concerned. [5]). An optical setup monitors the growth process. Following rupture of the membrane. Secondly. However. the choice of the interpolation method.M. NOMENCLATURE 912 Kn l n p rd t T x y binary diffusion coefficient Knudsen number mean free path index of refraction pressure droplet radius time temperature position vapor fraction. LUIJTEN et al. described by Smolders et al. Therefore. the saturation ratio S--defined as the ratio of vapor pressure to saturated vapor pressure at a given temperature---peaks during the pressure dip. At the same time. In Fig. followed by a weak recompression as it reaches the narrowing. but is still larger than unity. an expansion wave travels into the high pressure section (HPS). The temperature follows a similar pattern. are very well defined. EXPERIMENTAL METHOD 3. Figure 1 shows a schematic drawing of the setup. Firstly. but does not provide a clear interpretation. The droplet temperature Td differs from the far field gas temperature Tg by at most 1. of course. whose signal oscillates to an equilibrium value--typically in 10 min. the continuum limit provides considerable insight into diffusion-controlled droplet growth. A condensation experiment proceeds in the following way. significant nucleation only takes place during the small period of lowest pressure. Therefore. since the process can be considered as isentropic. that calculates the experimental diffusion temperature from Td and Tg. for a quantitative determination of diffusion coefficient values. tion the continuum limit because of several reasons. 90 ° light scattering is used for time-resolved radius determination. liquid water is injected. however. The preparation stage of the experiment involves several steps. both theoretical and experimental scattering patterns . 4] . the new droplets grow to macroscopic sizes. 3. one should be as accurate as possible and thus use the complete set of implicit equations. Several droplet growth models exist. the carrier gas is let in and the mixture is homogenized by the circulation pump MP.4K for the lowest pressures used in this work. Besides the small Knudsen numbers. our growth experiments are clearly in the continuum regime. [6]. the tube is evacuated to a residual pressure below 10 -2 Pa. After this so-called 'nucleation pulse'. 0 6 2 scattering angle scattering angle wavelength of laser. 3. The gasdynamic aspects are discussed in more detail in Ref. the continuum limit is important because of its generality. As a last point. Growth rates In our expansion wave tube. It is reflected at the local widening as another small expansion. Firstly. is of minor importance. after which evaporation and wall adsorption stabilize the vapor pressure within half an hour. the saturation ratio decreases. a shock wave travels into the LPS. Secondly. 2. Thirdly. An x-t-diagram of the wave propagation is shown in Fig.3498 C.1. Greek symbols p density Subscripts 12 binary d droplet eq equilibrium exp experimental g gas 1 liquid v vapor.C. Because of the extreme sensitivity of nucleation rates on S. for small K n values they all coincide to the same continuum limit. Using the continuum approximation throughout our calculations would yield only small deviations (up to about 6%). Therefore. Homogeneity is monitored by the humidity sensor RH. which differ considerably in describing the transition regime for intermediate Knudsen numbers [3. whereas measurement of the transmitted intensity yie!ds the droplet concentration. there is an additional advantage of our experiments being in the continuum regime : the experimental temperatures at which the droplets are growing. separation of nucleation and droplet growth stages is accomplished by means of a local widening in the low pressure section (LPS). together with the resulting pressure history at the HPS endwall (calculations were done using the Random Choice Method.

4 lowpressuresection VP diaphragm section MP photomultiplier IP photodiode Pa lens Pk humidity (VaisalaHMP 124B) valves vacuum pump mixing pump injection point staticpressure(DruckPDCR200) dynamic pressure(KisUer603 B) Fig. are shown for a typical experiment. .n 5 re I I ~/" 2nr#% r . . i . described in the book by Reid et al.15° // /'~ / / 15 II ~ II II v ~'10 0 2 4 6 8 (a) Exp. 3. We used a Vaisala Humicap 124B humidity transducer. 2. 1. From equation (1) it is clear that vapor fractions must be known in order to calculate theoretical growth rates. ' LPs Va Va .. based on changes in capacitance of a polymer film as it absorbs water. the device was calibrated with both humidity and pressure as independent variables. . Since the absorption process is influenced by ambient pressure. special effort is required to measure the water content of the mixture. it can be used for high pressure humidity determination. Both peaks and valleys are used as reference points. The resemblance is striking • the radiLus can be determined accurately as a function of time by simple pattern recognition. . .. (a) Theoretical Mie-pattern and (b) corresponding experimentally measured Mie-pattern.. The point of observation is situated at the endwall of the high pressure section (HPS) 20 II 83. however. . [7].~ V4 gas supply highpressuresection V1. 20 10 I 0. .5 HPS p (bar) 1 x (m) ~ 1. . Schematic drawing of the expansion wave tube setup. (b) time (ms) Fig. Calculations were performed using the Random Choice Method..Binary diffusion coefficients in condensable vapors 3499 PD P" Pd / t V VP 1 . the relative error is estimated to be no smaller than 5%.7a°<~<98.ll IAr-ionlaser HPS LPS DS PM PD L RH HPS i ~DS 'l . Since the tube is operated at high total pressures. x-t diagram cf wave propagation in the pulse expansion tube with schematic tube configuration and pressure history at the HPS endwall. In this way. = . Vapor fractions By comparison of measured and theoretical growth rates. 3.2. . RH MP IP . the diffusion~ coefficient ~ 2 is obtained. i 0 10 20 30 O D Fig. .28° 88.85° < 0 < 91. The saturated vapor fraction is obtained from the Wagner equation.5 LPS 2 .

235K < T < 355K.3.4--is neglected. Such considerations show that this effect introduces no systematic error : one should indeed use the least squares fit for a correct interpretation. obtained between 280K and 380K. 0 5 10 . to save computational cost. LUIJTEN et al.15 E For water-helium.M.2. As a last step (total) pressure and temperature during the growth period are averaged. Average values for PN~2 are given for each pressure range studied.8 and 1. each triplet of data in Table 1 is averaged to a single point in Figs. 6 and 7.5 ( T K . the influence of the water vapor--with a molar fraction of about 10.2 p = 27 bar T=24 0. the best fit to new and existing data is given by p~lz=4. and the least squares fit using the corrected value of the diffusion coetticient (solid line). Calculation of ~12 The experimental diffusion coefficient is defined as the particular value for which experimental and theoretical growth patterns coincide. The temperature and density in the middle of the pulse are calculated from the pressure. respectively) can be understood by taking the background of the scattered signal into account. the growth model yields 0. 4 and 5. and recommended by Marrero and Mason [1]. 235K < T < 375K. 4. It is clear from the table that no significant pressure dependence of the product P~12 can be deduced from the present results. the improved correlation reads : P ~ 1 2 = 1 . the calculation method will be described in some detail. 9]. together with the numbers of experimental runs on which these averages are based. All the correction factors ~exp/~Ansatz were between 0.35x10 3(TK-J) 1-338 ( P a m 2 s . The alternate positive and negative deviations from the best fit (for valleys and peaks. For the binary diffusion coefficient of water-nitrogen. therefore.1 0.05 0 15 20 25 30 t (ms) Fig. the correlation according to Fuller is chosen [7]. Clearly. [8. This causes no significant error. typical experimental growth patterns are shown (markers). Finally. Experimental droplet growth curve (markers) for water droplets in nitrogen. 1 3 x I 0 . using isentropic relations and real gas equations of state. The results of our experiments are summarized in Table 1. proposed by Sychev et al. 6 and 7. Only part of the recorded pressure signal is used for the growth calculation. Once the temperature is known. Continuing from this starting point. as well as new correlations. Also represented are data for water-nitrogen from O'Connell [10]. 4. data from Schwertz and Brow [11] and Lee and Wilke [12] are indicated. The 'Ansatz' correlations are shown.3500 C. qualitatively correct results: correcting the diffusion coefficient with a constant factor yields an almost perfect match between theory and experiment.~ ) 2-a59 (PamZs-1). (3) o. Also shown is the theoretical pattern using the Fuller correlation for ~ 2 (dashed fine). In Figs. an existing correlation for the diffusion coefficient as a function of temperature is used as an 'Ansatz' to calculate the growth pattern. This period consists of roughly 150 pressure samples. variations of temperature and density at each sample point are calculated using the ideal gas law. Then the 'Ansatz' value for ~12 is multiplied by a correction factor. since the pressure fluctuations during the growth stage are only very slight. It is this correction factor that is fitted to match theory with experiment.C. starting from the middle of the 'nucleation pulse' (where all droplets are assumed to be formed) up to the reflection of the shock wave from the LPS endwall (which heats the mixture and forces the droplets to evaporate). The corrected diffusion coefficient value is assigned to the average temperature and pressure. which are based on the combined new and existing data. To this end. Also represented are the calculated curves using the 'Ansatz' diffusion coefficient (dashed lines) and the fitted theoretical curves (solid lines). our results are plotted in Figs. In this section. demonstrating that extrapolation of the Fuller correlation is accurate within 20% for the water-nitrogen and water-helium systems. For water-helium.l ) . RESULTS AND DISCUSSION (2) 3. In all these calculations.

He He He N2 N2 N2 He He He N2 N2 N2 P*@12 p (bar) 11. and the least squares fit using the corrected value of the diffusion coefficient (solid line).8 237.4 7.6 254. For each series of experiments.5 42.05 0 0 5 10 15 t (ms) Fig.9___0. 6 and 7.1 10. C O N C L U S I O N S Looking carefully at Figs.5+0.9 10. Solid line is the new correlation.1 1. O3 4 E ft. at higher temperatures. This observation can be made only now.4 7. Dashed line is the correlation according to Fuller [7]. Experimental droplet growth curve (markers) for water droplets in helium.0 T (K) 239. our d~. Also shown is the theoretical pattern using the Fuller correlation for ~ 2 (dashed line). Table 1.4 6. of runs 1 3 3 3 4 5 2 5 5 6 5 4 obtained at higher temperatures.4+0. A new method.6 255.2 27.ta are fairly in line with the recommended data from other experimentalists.9_+0.3+0. the deviations from the Fuller relation seem to be hardly significant.7 26. Binary diffusion coefficient data obtained in this study.7 235. because our method is based on isentropic cooling of the gas mixture.0+0.9 255.7 43. Diffusion coefficient of water-nitrogen as a function of temperature. we cannot reproduce the data at temperatures above r o o m temperature. 5.1 1. especially for w a t e r helium.0 26.4 1.2 p = 41 bar T = 255 K 0.4+0. ---. The uncertainty in temperatures is smaller than 1K.4_+0. two conclusions can be drawn.1 No. Secondly.1 1.15 3501 E "~ 0.8+0.6 11. 2 """ Z~ 1 200 I I 250 300 350 40 T (K) Fig.2 254. 5. the spreading in pressures is approximately 1 bar 2nd comp.7 1.3 255. with our low temperature data included in the picture. has been introduced to determine binary diffusion coefficients for mixtures o f a condensable vapor and a gas at small Knudsen numbers. Firstly.3+0.1 238. A pulse expansion wave tube setup was applied for measuring droplet growth rates.1 1.8 238.6 26. the average result over the indicated number of runs is given.1 0.6_+0.1 7.5 237. the Fuller correlation--for which P ~ z oc Tt 75-----does not accurately describe the temperature dependence of the product P ~ 2 . v 3 Fuller new correlat~n O'Connell presentdata I ca o. Unfortunately. based on condensational droplet growth.9 44.6 43.2 + 0.2 (Pam 2 s-1) 7.Binary diffusion coefficients in condensable vapors 0. starting from r o o m temperature.8 255. 6. This is an important argument of support for the reliability of our new method.6 6. .

D. Sychev.. J. V. J. D. providing a better accuracy over a n extended t e m p e r a t u r e range (down to 235K). D. 7. This result can be expected to hold for o t h e r mixtures as well. H. A. 2. Zuber. E. 11. 5. Diffusivity of water vapor in some common gases. 99-279. A. Experiments in Fluids. H.. A. K. 63-75. 2381-2387. H. 19(5).. Vasserman. E. J.. 61~4.. E. B. The o b t a i n e d diffusion coefficient data. C. Eindhoven University of Technology. F. B. Prausnitz. 7. Willems and A. H. J.. H. National Standard Reference Data Service of the USSR. Looijmans.. J. T h e m e t h o d can be used across large ranges o f pressures a n d temperatures. Sychev. H. o b t a i n e d at higher temperatures. ed... Looijmans. D. Kriesels. J. Thermodynamic Properties of Nitrogen. 3-118. Kozlov. Selover. The spherical droplet in gaseous carrier streams : review and synthesis. 1951... A. 4. and Van Dongen. J. Solid line is the new correlation. J. J. pp. M. // "7 ~i GI 8 J~/. The Properties of Gases and Liquids. 73. Spiridonov. P.. 640-646. V. and Poling. Kozlov. M. R. Gasdynamic aspects of a modified expansionshock tube for nucleation studies. 1987. G. o b t a i n e d at t e m p e r a t u r e s near 237K a n d 255K. Springer. and Wilke. The Netherlands. V. Diffusion coefficient of water-helium as a function of temperature. Hewitt. W. 1992. 6 / 4 / ~. 1982. J. J. Jager. 1(1). Gyarmathy. 1987. and Van Dongen.-'" ' [] (3 L e e /k present data ' 200 250 300 350 40 T (K) Fig. 1969. Diffusivities of water in nonpolar gases. E. i m p r o v e d correlation coefficients were proposed. which requires special techniques at high pressures. Smolders. describing the t e m p e r a t u r e dependence o f the p r o d u c t o f pressure a n d diffusivity. 1993. REFERENCES 10.. Measurements of vapor diffusion coefficient. N. Gillespie. Marrero. B. C. 1995. 6. A. A. 46(11). thesis. C . C. Schwertz. T h e m e t h o d was illustrated with m e a s u r e m e n t s in the systems w a t e r . National Standard Reference Data Service of the USSR. 2000-2004. Therefore. van Voorthuisen. even below the freezing p o i n t of the c o n d e n s a b l e vapor. A. Muitjens for carefully reading the manuscript.. A. In Multiphase Science and Technology 1. T. P. A. E. Homogeneous nucleation and droplet growth in the coexistence region of n-alkanemethane mixtures at high pressures.n i t r o g e n in the pressure range 11-44 bar.'" . N. Selover. 1. A. London.h e l i u m a n d w a t e r . and Tsymarny. 4th edn. G. M. E. Berlin. F. M .. We are grateful to M.ertz o. 1954. O'Connell. Niessen. 8. Springer. T.. Wasser.. F. ed. The Fuller correlation. 212 and 587. Reid. A. C. Its relative uncertainty (estimated to be 5 % in the present work) depends largely o n the accuracy o f v a p o r fraction m e a s u r e m e n t . K. The random choice method applied to non-linear wave propagation in gas-vapour~lroplet mixtures./ -new correlation Se. pp. A significant pressure dependence o f the p r o d u c t o f diffusion coefficient a n d pressure could n o t be identified. New York. McGraw-Hill.3502 12 C . D. P. Thermodynamic Properties of Helium. Ph. Young. V.. 1993. Lee. E. B. 9. M. International Journal of Heat and Mass Transfer. J.. R. A.. A. Industrial and Engineering Chemistry. and Tsymarny. . Gaseous diffusion coefficients. H. 1972. J. Eindhoven. Acknowledgements--The authors thank H. G.. and Prausnitz. Journal of Physical and Chemical Reference Data. Journal of Physical Chemistry.. Wijnands for their invaluable technical contributions.. LUIJTEN et al. Vasserman. M. ed. Delhaye and N.. McGraw-Hill. A. Krostek. 21. T. Dashed line is the Fuller correlation [7]. Journal of Physical Chemistry. and Brow. R. 15. V. M. The condensation and evaporation of liquid droplets at arbitrary Knudsen number in the presence of an inert gas. Computers and Fluids. Y. M. G. M. 12. Jr. E. 941-2956. V. 3. showed to be fairly in line with available data. Jr. 36(11). was f o u n d to be significantly in error for the present mixtures. and Mason. Spiridonov. Berlin. 1987.

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