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NATIONAL ADVISORY COMMITTEE FOR AERONAUTICS TECHNICAL MEMORANDUM 1368 SUPERSATURATION IN THE SPONTANEOUS FORMATION OF NUCLEI IN WATER VAPOR*1 By Adolf Sander and Gerhard Damkohler I. STATEMENT OF THE PROBLEM According to experience, a certain supersaturation is required for condensation of water vapor in the homogeneous phase; that is, for incep- tion of the condensation, at a prescribed temperature, the water-vapor partial pressure must lie above the saturation pressure. The condensation starts on so-called condensation nuclei. Solid or liquid suspended par- ticles may serve as nuclei; these particles may either a priori be present in the gas phase (dust, soot), or may spontaneously be formed from the vapor molecules to be condensed themselves. Only the second case will be considered below. Gas ions which facilitate the spontaneous formation of nuclei may be present or absent. The supersaturations necessary for spontaneous nucleus formation are in general considerably higher than those in the presence of suspended particles. The condensed, thermodynamically stable phase pertaining to water vapor below 00 is the ice. According to all experiences so far, one must nevertheless assume in this temperature range the spontaneously formed primary particles to be predominantly liquid, in accordance with Ostwald's law of stages. The question is whether this is still valid at arbitrarily low temperatures, or whether not perhaps, after all, below a certain tem- perature the nuclei themselves already originate as (minute) crystals. This problem has so far been treated only theoretically2 but not experi- mentally. Thus the supersaturation of water vapor required for sponta- neous formation of nuclei was measured in a temperature range as wide as possible, namely between +350 and -750. *"Ubersattigung bei der spontanen Keimbildung in Wasserdampf." Die Naturwissenschaften, vol. 31, nos. 39/h0, Sept. 24, 1943, pp. 460-465. From the department for motor research of the Hermann Goring Institute for Aviation Research. 2R. Becker and W. During, Ann. Physics 24, pp. 719-752, 1935. - M. Volmer, Kinetik der Phasenbildung, p. 200 ff. Dresden-Leipzig 1939. NACA TM 1368 II. METHOD OF INVESTIGATION AND APPARATUS The operating principle was as follows: Especially purified air of known pressure, known temperature, and water-vapor content (lying still below saturation) is adiabatically expanded to a certain terminal pressure. During this process cooling off and, also, for a corresponding high expan- sion ratio, supersaturation occur. If the supersaturation is sufficiently high, fog formation will be observed. The critical supersaturation ( P partial pressure of water vapor at the final temperature p. saturation pressure of water vapor at the final temperature/ is attained when due to the expansion about one fog droplet per cubic centimeter and second becomes visible. The purification of the initial air and the preadjustment of the water- vapor content were carried out according to the scheme represented in figure 1. This scheme also contains the various methods of operation used. The suspended particles of the initial air could be removed optionally either by a Schott bacteria filter (G5 on 3, fictitious pore diameter according to Bechhold = 1.48i) or by a layer of absorbent cotton of 100-cm length (it is true that such a layer of only 10-cm length also had proved to be sufficient). The drying was done in two exchangeable freezing traps containing a cotton wool filter of 5-cm length and cooled by liquid oxygen. The water-vapor saturator through which was sent the entire air or only a partial flow line (for the latter case the two flow manometers) con- sisted of two washing bottles connected in series with adjoining moist cotton wool filter; the entire arrangement was kept at a certain temper- ature by a Hoppler thermostat. The final adjustment of the water-vapor content was made in the sepa- rator as shown in figure 2 which was kept at the same temperature as the observation sphere b proper. The gas flow leaving the separator a, being fully saturated there, was no longer completely saturated later in the expansion sphere b since a pressure drop of about 10-mm Hg appeared in the capillary connecting tubing between a and b at the steady flow velocity of 5-cubic cm/sec used for flushing through and filling. A methanol bath was used as a cold thermostat which was disposed in a large Dewar vessel (500-mm height, 250-mm inside diameter) with observa- tion strips. The cooling agent was liquid oxygen which was from time to time injected into an immersed glass tube g. The stirring was done mechanically, by means of an electrically driven stirrer of propeller type f. The temperature measurement was performed with a Hg-thermometer cali- brated at the PTR or with a self-manufactered NH -tension thermometer con- nected to it which was moreover compared with a second model arrangement. INACA TM 1368 For expansion of the gas under investigation, in the observation sphere b (0.71) the glass stopcock c (boring 10-mm) was opened quickly toward a large prevacuum vessel (121) (not shown in figure 2) in which various pressures could be measurably adjusted. In special tests with an expansion sphere of the same size as the observation sphere which contained, however, a metal membrane manometer for mirror reading, it was possible to determine with the aid of films that the expansion time lasted about 0.1 second and the subsequent time of constant pressure more than 0.3 second. No gas vibrations were observed with the connecting tubing used (about 2-m length and 20-mm inside diameter) between expansion sphere (0.72) and prevacuum vessel (12Z). The observation sphere was coated on the outside with a black lacquer (graphite + vinidur adhesive solution PC 20) in order to keep off scattered light. The illuminating light ray came from an arc lamp through a lens system, entered from below into the observation sphere b through the observation strips of the Dewar vessel and was lost in the expansion cock c. In the first tests, we had operated with a small film projector. However, the intensity of light of that projector was found to be too slight to recognize reliably the condensate particles which are extremely small just at low temperatures. The observation was made obliquely from above through the observation strips of the Dewar vessel. The content of ions of the expansion gas was either the natural one or it had been reduced to zero in the customary manner, by applying a field of about 50 volt/cm. For this purpose, two opposite inner segments of the observation sphere had been silver-plated and connected with four B-batteries in series (a 500 v) by platinum fused through the wall. The observation sphere as well as the entire remaining apparatus could be pumped out with a low-absolute-pressure aggregate, and pould then, after it had been left standing for a while, be examined as to density by means of a Geissler tube. III. TEST RESULTS If figure 3, the critical supersaturations measured p /p are rep- resented as a function of the absolute temperature T. Therein p. sig- nifies the saturation pressure of the supercooled water as it was taken from Robitzsch's tables3.. Only for the curve branch on the upper right, with a jump at the onset, reference was made to the saturation pressure 3M. Robitzsch, AusfUhrliche Tafeln zur Berechnung der Luftfeuchtigkeit. Leipzig 1941. NACA TM 1368 of ice, again using Robitzsch's figures. In order to exclude systematic errors as far as possible the measuring points were obtained by very dif- ferent methods. There were three possibilities of variation: (a) The type of air purification and preadjustment of the water-vapor content according to the scheme in figure 1 (marked by capital Latin letters). (b) The type of final water-vapor content according to the scheme in figure 3 (marked by Roman numerals). (c) Selection of the initial temperature in the observation sphere so that for a certain expansion end temperature various temperature dif- ferences (from 240 to 350) could be adjusted between center and wall of the sphere. In figure 3, the measuring points are distinguished only with respect to variation possibility (b). However, none of the methods used for adjust- ment of the water-vapor content shows any systematic deviations. On the contrary, all measuring points lie so satisfactorily about the solidly drawn curve of mean values that one is quite justified in excluding a falsification of the measured values by insufficient purification of the air (variation possibility (a)) or by insufficiently adiabatic expansion (variation possibility (c)). Only at the lowest temperatures the meas- uring points show somewhat more scatter the cause of which is, however, in the poor visibility of the condensate particles, reduced more and more with decreasing temperature. In the temperature region investigated, the critical supersaturations measured pl/P. (speed of nucleus formation J = 1 particle/cubic cm/sec) can be satisfactorily represented by the following interpolation formulas: In P1 = 780. 1.521 above -620 without ions4 (1) p T In !-= 1.537 above -62o with ions4 (2) p T In Pl = 13 3.748 below -620 with or without ions5 (3) p = saturation pressure of liquid water. 5p = saturation pressure of ice. NACA TM 1368 From the curves in figure 3 one can read off: 1. The influence of the gas ions favoring condensation disappears at -62. 2. At the same temperature, a break in the supersaturation temper- ature curve appears, in such a manner that the supersaturation pressures measured at lower temperatures may lie higher but certainly not lower than one should expect on the basis of the curve branch valid at higher tem- peratures. (Compare the dashed extrapolation curve.) In addition to these two quantitative findings there is a qualitative one: 3. At very low temperatures, one finds a scintillating of the con- densate particles; at -620 it is observable with certainty, at higher temperatures one sometimes imagines seeing it. A rigorous temperature limit for the start of scintillating cannot be defined. IV. DISCUSSION OF THE TEST RESULTS AND COMPARISON WITH THE THEORY USED SO FAR From the quantitative findings 1 and 2, one may conclude that at -620 there starts a more or less sudden change in the spontaneous process of nucleus formation. The disappearing of the ion influence below -620 would suggest that the nucleus forming at lower temperatures is in a higher order state requiring more space than the nucleus type originating at higher temper- atures, for surely the ion influence favoring the condensation must be understood to mean that the water dipoles in the inhomogeneous field of the ion are attracted and tend to arrange themselves as closely as pos- sible around the latter whereby part of the surface work to be expended for nucleus formation is compensated by electrostatic attraction energy. This molecule grouping of maximum density about a central ion will hardly be the molecule arrangement which must take place in ice and thus also in the crystal nucleus as is suggested by the difference in density between water and ice at 00. It would therefore be understandable if the gas ions would favor the spontaneous formation of crystal nuclei either not at all or at least less than the formation of droplet nuclei. The scintillating of the formed condensate particles, observed with certainty at -620, also supports the theory of a primary crystal-nucleus formation although the latter cannot be proved directly by that fact, in our opinion, for a water droplet, too, could suddenly crystallize throughout NACA TM 1368 after a certain time and be transformed into a scintillating minute crys- tal. In what time this would be possible under our test conditions, we are not able to tell. The break in the supersaturation temperature curve found at -62 likewise points at a sudden variation in the process of nucleus formation. However, the direction of this break is strange and in contradiction to the theory used so far. According to Becker and D'ring as well as to Volmer- there should always be favored that type of nucleus which requires for its formation the lesser partial pressure in the vapor phase. This conception has the advantage of representing a perfect analogy to the selection of the condensed phase thermodynamically stable in the respective case where, for a prescribed temperature, there always forms the phase which possesses the lower saturation pressure. However, the present report would indicate another process for the formation of the nucleus because of the required partial pressures, for below -620 there would have originated precisely that type of nucleus which requires for its formation a higher water vapor partial pressure than the type of nucleus stable at higher temperature, as one can recognize by comparing the extrapolation curve plotted in dashed lines with the actual measuring points. According to Becker and Doring as well as to Volmer, the break in the supersaturation temperature curve in.figure 3, seen from below, should not be convex, but concave; however, this precisely could not be observed within the comparatively high measuring accuracy. In the theoretical treatment of the spontaneous process of nucleus formation (in absence of ions), Becker and Doring as well as Volmer start out from the same fundamental physical concept: To a vapor molecule, further vapor molecules attach themselves on the basis of the natural fluctuations in successive single steps. Thus aggregates of a higher num- ber of molecules originate each of which may go over into the next highest aggregate by addition of another vapor molecule, into the next lowest aggregate by subtraction of a vapor molecule. The process of nucleus for- mation itself is interpreted as a stationary chain of reactions so that every aggregate occurs with a certain frequency. Then an expression for the speed of nucleus formation may be derived, in principle, in a simple manner. An explicit evaluation requires, of course, certain simplifying assumptions; they were made in a somewhat different manner by Becker-Doring and by Volmer. We checked their calculations and arrived under the same physical presuppositions of theory but on the basis of a somewhat more accurate calculation at a new formula. It yields numerical values for the speed of nucleus formation which lie between those of Becker-Doring and of Volmer. In the absence of ions, we have therefore for the spontaneous formation of droplet nuclei the following theoretical relations: 6Compare especially the figure on p. 202 of his book (cited in footnote 2). NACA TM 1368 Becker-DSring (= to Volmer II) Z 01 AK kT (4) J= V (4) nK 3kI Volmer I IA1KAK K Z1WlOK AK kT k~T Se e (5) nK 3ikT Sander-Damkxhler AK i 4 (6) ZW1OK AK ekT K] -- e - 2nK 13 k Therein signify: J number of nuclei formed per cubic cm per second (= to the number of fog particles observed per cubic cm) Z1 number of vapor molecules per cubic cm W1 number of vapor molecules impinging per second on 1 square cm at the partial pressure p 1 = NL Loschmidt number (= 6.0224 x 1023) R gas constant per g-mol (= 8.315 x 107 erg/deg) k R/NL = Boltzmann constant (= 1.3807 X 10-16 erg/deg) M molecular weight of the vapor to be condensed T absolute temperature 01 surface of the vapor molecule assumed to be spherical OK surface of the droplet nucleus assumed to be spherical which is in equilibrium with the external water-vapor partial pressure pl NACA TM 1368 number of vapor molecules in the drop nucleus (nK : 100) vaporization heat per molecule (for water X kJ 7.4 x 10-13 erg) surface tension 0OK/3 = work of nucleus formation may, with the Thomson equation S-- = kT In p dnK P. be traced back to and p. signify: pl partial pressure of pO saturation pressure ature T the supersaturation pl/P wherein pl the vapor to be condensed at the temperature T of the vapor to be condensed at the temper- With OK = CnK2/3 there follows AK "OK 4 J ( 3C\ 1 T = 3 =T 27 kT \ P%0 For spherical droplets there applies with the condensate density d c3 = 36i-M 2 (10) K;) and therewith AK l6NL M\2(, \3 1 3 = 3I n M 3R3W\; /^ (11) NACA TM 1368 According to equations (11) and (4) to (6), there pertains to a certain supersaturation pJ/P a perfectly defined speed of nucleus formation J. If the latter becomes 1 particle/cubic cm/sec, we obtain the critical supersaturation observed in our measurements which is plotted in figure 3. In figures 4(a) and 4(b), the experimental supersaturations (in the absence of ions) of the present report are compared to the theoretically calculated curves. For the latter, the numerical values of Moser7 were used for the surface tension of water above 00. They lie highest among the known values of literature8 (compare fig. 5) and are probably, for this reason, too, the most correct ones, all the more so because one can very easily lower the surface tension by slight contaminations with surface-active matter, but is hardly able to increase it. Below 00 the surface tension values had to be extrapolated. As may be recognized from figure 4, our new theoretical formula shows the best agreement with our measuring points, at least at and above 009. Below 00, however, our first extrapolation of the surface tension values performed at first arbitrarily (curve branch b in fig. 5) yields supersaturations which are too high. We employed therefore the inverse method. Under the assumption that our new formula (6) correctly renders the experimental data in the entire temperature range to -620, we calculated from them backward the surface tension of the water and obtained thus the curve branch c in figure 5. It is pronouncedly curved; however, in view of the still more pronouncedly cambered curves d and c of Ramsay and Shields and of Weinsteinl0 for water, and of the glycerin curve f and gll (glycerin is also strongly associated) this would not be unthinkable. It is noteworthy that the curve branch c has a maximum for the surface tension of the water at about -500, that is, not far from the point where the break in the supersaturation temperature curve (compare fig. 3) was found. 7Moser, L. B. Eg. IIa, 148. 8Compare also Ramsay and Shields, and Weinstein, L. B. I, 199. 9The slight differences between experiment and theory above 00 are most probably real and probably based on the fact that in our stationary chain of reactions for excessive water-vapor partial pressure the molecule aggregates exceeding the nucleus size are overheated because the conden- sation heat cannot be carried off with sufficient rapidity. This point, not yet taken into consideration in the theory used so far, will be discussed more thoroughly elsewhere. 10L. B. I, 199. 11L. B. I, 255 and L. B. IIa, 156. NACA TM 1368 For the speed of crystal-nucleus formation Becker and Doring also had derived a formula which is based on the same fundamental physical concepts as the formula for the formation of droplet nuclei. It is true that a considerably larger number of simplifying assumptions was necessary in the derivation of the crystal-nucleus formula because in crystal forma- tion three dimensions may grow independently of each other and an aggregate of n molecules can therefore assume very different shapes, in contrast to the sphere-shaped droplet. The Becker-Dbring formula for the speed of crystal-nucleus formation in the absence of ions reads with our above symbols AK J 3 11 e (12) Therein AK = a0K/3 represents the work of formation of the solid crystal nucleus. It depends on the interfacial tension between solid and gaseous phase (still unknown at present) as well as on the surface of the determinative crystal nucleus; the form of the latter must be as compact as possible, according to Becker and Doring, but is not exactly defined. For a cube-shaped nucleus (we, too, shall calculate below with such a nucleus) there results from equation (8) S= 6 M2/3 (13) and hence from equation (9) AK 32NL 2 3 1 = -- () (in I)2 (14) kT 3 (in )2 One should not overrate the importance of single numerical values obtained with the equations (12) and (14); however, a temperature vari- ation of the critical supersaturation (l for J = 1 cm-3 8-1) P. NACA TM 1368 is significant since equation (12) represents solely the general Arrhenius expression for a reaction velocity with the activation heat A which K appears perfectly plausible and has been assumed by Volmer for the nucleus formation even before the report of Becker and Doring appeared. In figure 6, there are plotted as functions of the temperature the saturation pressure of supercooled water (curve a) and of ice (curve b), furthermore the critical supersaturation pressures measured in the present report (curve c) which are required for spontaneous nucleus formation in the absence of ions, and finally the supersaturation curves d60, d70, and d80 for the spontaneous formation of ice nuclei calculated with the equations (12) and (14). The arbitrarily assumed interfacial tensions a = 60, 70, and 80 erg/square cm between solid and gaseous phase correspond to those supersaturation curves. All curves were based on the saturation pressures of the tables of Robitzsch (footnote 3). One can see that the experimental curve for the supersaturation pressures of the droplet-nucleus formation can be intersected by an ice-nucleus curve in the temperature range investigated only when the interfacial tension of the ice crystals lies approximately between 68 and 72 erg/square cm. If it (the inter- facial tension) were independent of the temperature, a convex viewed from the abscissa axis break in the supersaturation pressure temperature curve would never occur but always only a concave one; however, such a concave break is precisely what was not found in the experiment. To explain a convex break, one would have to assume a slight dependence on temperature of the interfacial tension approximately as it is represented in figure 5 as the curve h12. 12The temperature coefficient to be read from figure 5, curve h: -di/dT = 0.062 erg/square cm degrees is, with respect to order of magnitude, completely in accord with a relation indicated by R. Fricke (Zur physikatischen Chemie, vol. 52, 1942, pp. 284-294) d= nk Z n i (15) dT Va wherein n = number of molecules per square cm surface, vi and va' respectively = fundamental frequencies of the centers of the molecules vibrating in the interior of the crystal or on the crystal surface, and the summation E is to be extended over all lattice vibrations. If one assumes that only one distinguishable lattice vibration is decisive and that the molecules situated on the surface are bound normal to it by about half the spring force as the molecules in the interior of the crystal, there applies footnote continued on following page NACA TM 1368 We cannot yet state reliably at present how the break at -620, indi- cated by our measuring points in figure 3, is to be explained. Should it be based on the transition of spontaneous droplet-nucleus formation to spontaneous ice-nucleus formation and we have named indications for this being the case we would have to give up the prevailing notion regarding the cause of such a transition (that always the type of nucleus forms which requires the least supersaturation pressure). One will give up this concept at first only reluctantly, particularly because of the above- mentioned analogy with the transition from the vapor-water to the vapor- ice equilibrium. Nevertheless this notion entertained so far, regarding the transition of one type of nucleus to the other, does not take into consideration a point which seems to us essential: the mobility of the molecules in the nucleus surface. A droplet nucleus of almost spherical shape can form only if the molecules being newly acquired push in between the surface molecules already present, that is, if they are absorbed by the surface. In the case of a crystal nucleus, in contrast, such a pushing-in need not take place since the molecule being newly acquired, is only added on, that is, in principle, adsorbed. The first process presupposes a considerable mobility of the surface particles, the latter does not. If a sort of two-dimensional melting point existed, that is, if the surface mobility of the particles would suddenly disappear at a certain temperature, no droplet nuclei could form any longer below this lIn In 1/r = 0.3464 a since, furthermore, n water molecules n .= 8 23) (.33 X 12)3 = 1.033 x 1015 fall to the share of 1 square cm of the crystal surface, one obtains according to (15) -da/dT w (1.033 x 1015) (1.3807 x 1016)0.3464 = 0.0494 erg/square cm deg since the tangential frequencies in the crystal surface also will differ somewhat from the corresponding frequencies in the crystal interior, this theoretical value of 0.0494 erg/square cm degree would have to be increased slightly and would then come surprisingly close to our value, inferred experimentally, of 0.062 erg/square cm degree. NACA TM 1368 temperature and the crystal nucleus would be left as the only primary condensation form, regardless whether the vapor partial pressure neces- sary for the formation of this crystal nucleus is higher or lower than that of the droplet nucleus. This conception could explain the strange break in the supersaturation temperature curve found by us. Also, this explanation does not perhaps imply an invalidation of the nucleus forma- tion theory used so far but merely limits in a special manner the temper- ature range of the droplet-nucleus and of the crystal-nucleus formulas. The two regions would not overlap, as was assumed a priori by Becker and During as well as by Volmer; rather, the two temperature regions would be separated by the melting point of the two-dimensional surface phase. If we denote it in the absolute temperature scale by TB, corresponding to the "baking temperature" known from fritting processes and if we denote likewise by TS the standard three-dimensional melting point, there would result from our measurements TB/TS = 211/273 = 0.77. This value can probably be fitted into the sequence determined by Tammannl3. TB/TS = 0.33 0.52 0.57 0.90 for metals oxides salts C-compounds Translated by Mary L. Mahler National Advisory Committee for Aeronautics 13G. Tammann, Z. angew. Chem. 39, 869, 1926 Gottinger Nachr. Math.- naturwiss. K1. 1930, 227. NACA TM 1568 Figure 1.- Air purification and preadjustment of the water-vapor content. Methods of operation Partial flow Partial flow Position of the stop cocks line I line II s p 5 6 7 A Bacteria filter Not used ( G ) S100 cm absorbent B cotton Not used e C Bacteria filter 100cm absorbent D 100 cm absorbent 100 cm absorbent ( ( S cotton cotton NACA TM 1568 vision thermometer External air (a) Separator (b) Observation sphere (c)Expansion stop cock (d) Silver plating (e)Feeler of the NH3-tension thermometer (f) Stirrer (g) Cooling tube (h) Mirror Figure 2.- Apparatus. NACA T 15368 Method of operation Partial flow lines Air ahead of separator Condensate in separator spheres Symbol without with ions I or 2 Too humid I or 2 Too dry Yes Yes I or 2 Separator not used I Separator not used 2 Separtor No No Yes No not used 0 0 9 t J.51 3.5 4.0 45 50 103/T- I i I I I I I I I I 300 280 260 240 220 200K --ir -e Z'.- >"-.-.--,. S:r:Sa'..'.I rdirg to .. 4. A-c A NACA TM 1568 First extrapolation of surface tension b o:Becker and DWring, o c(Volmer ll) b- Sander and Damkihler -c:Volmer I d: Experiment Second extrapolation -l/ b of surface tension C I 3.5 4.0 103/T 1 1 1 1 1 4.5 s 5.0 320 300280 260 240 220 ,---- T 2000K Figure 4.- Theoretical and experimental supersaturation curves for water vapor. C ; 2.0 1.5 1.0 /,0 f 1.5 NACA TM 1568 Erg/cm 2 nbI -I 'IN -4 Y =- h Ice h Interfacial tension ice/vapor from experiment and formula of Becker and Doring fI I I I I ' -80 I I I a: Experiments Moser b: Extrapolation I Water e: Experiments Ramsay SGlerf: Experiments Glycerin {gly 9: Experiments -d e - Weinstein Muller Figure 5.- Surface tension of water, glycerin, and ice. OC- 4 I - -60 -40 -20 0 20 40 60 80 oC 100 _ JZ~ - --' - NACA TM 1368 I I I I I 280 270 260 250 240 4.4 4.6 103/T . I I 230 220 B--o T I I I 210 200 1900K Figure 6.- Saturation pressures (p .) and supersaturation pressures (pl) of water vapor. 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