[Physics FAQ] - [Copyright] Written Nov, 1998 by Monwhea Jeng (Momo), Department of Physics, University of California Can hot

water freeze faster than cold water? Yes a general explanation History of the Mpemba Effect More-detailed explanations References Yes a general explanation

Hot water can in fact freeze faster than cold water for a wide range of experime ntal conditions. This phenomenon is extremely counterintuitive, and surprising even to most scientists, but it is in fact real. It has been seen and studied i n numerous experiments. While this phenomenon has been known for centuries, and was described by Aristotle, Bacon, and Descartes [1 3], it was not introduced to the modern scientific community until 1969, by a Tanzanian high school pupil nam ed Mpemba. Both the early scientific history of this effect, and the story of M pemba's rediscovery of it, are interesting in their own right Mpemba's story in particular providing a dramatic parable against making snap judgements about wha t is impossible. This is described separately below. The phenomenon that hot water may freeze faster than cold is often called the Mp emba effect. Because, no doubt, most readers are extremely skeptical at this po int, we should begin by stating precisely what we mean by the Mpemba effect. We start with two containers of water, which are identical in shape, and which hol d identical amounts of water. The only difference between the two is that the w ater in one is at a higher (uniform) temperature than the water in the other. N ow we cool both containers, using the exact same cooling process for each contai ner. Under some conditions the initially warmer water will freeze first. If th is occurs, we have seen the Mpemba effect. Of course, the initially warmer wate r will not freeze before the initially cooler water for all initial conditions. If the hot water starts at 99.9C, and the cold water at 0.01C, then clearly under those circumstances, the initially cooler water will freeze first. However, un der some conditions the initially warmer water will freeze first: if that happen s, you have seen the Mpemba effect. But you will not see the Mpemba effect for just any initial temperatures, container shapes, or cooling conditions. This seems impossible, right? Many sharp readers may have already come up with a common proof that the Mpemba effect is impossible. The proof usually goes som ething like this. Say that the initially cooler water starts at 30C and takes 10 minutes to freeze, while the initially warmer water starts out at 70C. Now the initially warmer water has to spend some time cooling to get to get down to 30C, and after that, it's going to take 10 more minutes to freeze. So since the init ially warmer water has to do everything that the initially cooler water has to d o, plus a little more, it will take at least a little longer, right? What can b e wrong with this proof? What's wrong with this proof is that it implicitly assumes that the water is cha racterized solely by a single number its average temperature. But if other fact ors besides the average temperature are important, then when the initially warme r water has cooled to an average temperature of 30C, it may look very different t han the initially cooler water (at a uniform 30C) did at the start. Why? Becaus e the water may have changed when it cooled down from a uniform 70C to an average 30C. It could have less mass, less dissolved gas, or convection currents produc ing a non-uniform temperature distribution. Or it could have changed the enviro

nment around the container in the refrigerator. All four of these changes are c onceivably important, and each will be considered separately below. So the impo ssibility proof given above doesn't work. And in fact the Mpemba effect has bee n observed in a number of controlled experiments [5,7 14] It is still not known exactly why this happens. A number of possible explanatio ns for the effect have been proposed, but so far the experiments do not show cle arly which, if any, of the proposed mechanisms is the most important one. While you will often hear confident claims that X is the cause of the Mpemba effect, such claims are usually based on guesswork, or on looking at the evidence in onl y a few papers and ignoring the rest. Of course, there is nothing wrong with in formed theoretical guesswork or being selective in which experimental results yo u trust; the problem is that different people make different claims as to what X is. Why hasn't modern science answered this seemingly simple question about cooling water? The main problem is that the time it takes water to freeze is highly sens itive to a number of details in the experimental setup, such as the shape and si ze of the container, the shape and size of the refrigeration unit, the gas and i mpurity content of the water, how the time of freezing is defined, and so on. B ecause of this sensitivity, while experiments have generally agreed that the Mpe mba effect occurs, they disagree over the conditions under which it occurs, and thus about why it occurs. As Firth [7] wrote "There is a wealth of experimental variation in the problem so that any laboratory undertaking such investigations is guaranteed different results from all others." So with the limited number of experiments done, often under very different condi tions, none of the proposed mechanisms can be confidently proclaimed as "the" me chanism. Above we described four ways in which the initially warmer water could have changed upon cooling to the initial temperature of the initially cooler wa ter. What follows below is a short description of the four related mechanisms t hat have been suggested to explain the Mpemba effect. More ambitious readers ca n follow the links to more complete explanations of the mechanisms, as well as c ounter-arguments and experiments that the mechanisms cannot explain. It seems l ikely that there is no one mechanism that explains the Mpemba effect for all cir cumstances, but that different mechanisms are important under different conditio ns. Evaporation As the initially warmer water cools to the initial temperature o f the initially cooler water, it may lose significant amounts of water to evapor ation. The reduced mass will make it easier for the water to cool and freeze. Then the initially warmer water can freeze before the initially cooler water, bu t will make less ice. Theoretical calculations have shown that evaporation can explain the Mpemba effect if you assume that the water loses heat solely through evaporation [11]. This explanation is solid, intuitive, and evaporation is und oubtedly important in most situations. However, it is not the only mechanism. Evaporation cannot explain experiments that were done in closed containers, wher e no mass was lost to evaporation [12]. And many scientists have claimed that e vaporation alone is insufficient to explain their results [5,9,12]. Dissolved Gasses Hot water can hold less dissolved gas than cold water, and large amounts of gas escape upon boiling. So the initially warmer water may hav e less dissolved gas than the initially cooler water. It has been speculated th at this changes the properties of the water in some way, perhaps making it easie r to develop convection currents (and thus making it easier to cool), or decreas ing the amount of heat required to freeze a unit mass of water, or changing the boiling point. There are some experiments that favor this explanation [10,14], but no supporting theoretical calculations. Convection As the water cools it will eventually develop convection currents

and a non-uniform temperature distribution. At most temperatures, density decr eases with increasing temperature, and so the surface of the water will be warme r than the bottom: this has been called a "hot top." Now if the water loses heat primarily through the surface, then water with a "hot top" will lose heat faste r than we would expect based on its average temperature. When the initially war mer water has cooled to an average temperature the same as the initial temperatu re of the initially cooler water, it will have a "hot top", and thus its rate of cooling will be faster than the rate of cooling of the initially cooler water a t the same average temperature. Got all that? You might want to read this para graph again, paying careful distinction to the difference between initial temper ature, average temperature, and temperature. While experiments have seen the "h ot top", and related convection currents, it is unknown whether convection can b y itself explain the Mpemba effect. Surroundings A final difference between the cooling of the two containers re lates not to the water itself, but to the surrounding environment. The initiall y warmer water may change the environment around it in some complex fashion, and thus affect the cooling process. For example, if the container is sitting on a layer of frost which conducts heat poorly, the hot water may melt that layer of frost, and thus establish a better cooling system in the long run. Obviously e xplanations like this are not very general, since most experiments are not done with containers sitting on layers of frost. Finally, supercooling may be important to the effect. Supercooling occurs when the water freezes not at 0C, but at some lower temperature. One experiment [12] found that its initially hot water supercooled less than its initially cold wate r. This would mean that the initially warmer water might freeze first because i t would freeze at a higher temperature than the initially cooler water. If true , this would not fully explain the Mpemba effect, because we would still need to explain why initially warmer water supercools less than initially cooler water. In short, hot water does freeze sooner than cold water under a wide range of cir cumstances. It is not impossible, and has been seen to occur in a number of exp eriments. However, despite claims often made by one source or another, there is no well-agreed explanation for how this phenomenon occurs. Different mechanism s have been proposed, but the experimental evidence is inconclusive. For those wishing to read more on the subject, Jearl Walker's article in Scientific Americ an [13] is very readable and has suggestions on how to do home experiments on th e Mpemba effect, while the articles by Auerbach [12] and Wojciechowski [14] are two of the more modern papers on the effect. History of the Mpemba Effect The fact that hot water freezes faster than cold has been known for many centuri es. The earliest reference to this phenomenon dates back to Aristotle in 300 B. C. The phenomenon was later discussed in the medieval era, as European physicis ts struggled to come up with a theory of heat. But by the 20th century the phen omenon was only known as common folklore, until it was reintroduced to the scien tific community in 1969 by Mpemba, a Tanzanian high school pupil. Since then, n umerous experiments have confirmed the existence of the "Mpemba effect", but hav e not settled on any single explanation. The earliest known reference to this phenomenon is by Aristotle, who wrote: "The fact that water has previously been warmed contributes to its freezing quic kly; for so it cools sooner. Hence many people, when they want to cool hot wate r quickly, begin by putting it in the sun. . ." [1,4] He wrote these words in support of a mistaken idea which he called antiperistasi s. Antiperistasis is defined as "the supposed increase in the intensity of a qu ality as a result of being surrounded by its contrary quality, for instance, the

sudden heating of a warm body when surrounded by cold" [4]. Medieval scientists believed in Aristotle's theory of antiperistasis, and also s ought to explain it. Not surprisingly, scientists in the 1400s had trouble expl aining how it worked, and could not even decide whether (as Aristotle claimed in support of antiperistasis), human bodies and bodies of water were hotter in the winter than in the summer [4]. Around 1461, the physicist Giovanni Marliani, i n a debate over how objects cooled, said that he had confirmed that hot water fr oze faster than cold. He said that he had taken four ounces of boiling water, a nd four ounces of non-heated water, placed them outside in similar containers on a cold winter day, and observed that the boiled water froze first. Marliani wa s, however, unable to explain this occurrence [4]. Later, in the 1600s, it was apparently common knowledge that hot water would fre eze faster than cold. In 1620 Bacon wrote "Water slightly warm is more easily f rozen than quite cold" [2], while a little later Descartes claimed "Experience s hows that water that has been kept for a long time on the fire freezes sooner th an other water" [3]. In time, a modern theory of heat was developed, and the earlier observations of Aristotle, Marliani, and others were forgotten, perhaps because they seemed so c ontradictory to modern concepts of heat. However, it was still known as folklor e among many non-scientists in Canada [11], England [15 21], the food processing i ndustry [23], and elsewhere. It was not reintroduced to the scientific community until 1969, 500 years after Marliani's experiment, and more than two millennia after Aristotle's "Meteorolog ica I" [1]. The story of its rediscovery by a Tanzanian high school pupil named Mpemba is written up in the New Scientist [4]. The story provides a dramatic p arable cautioning scientists and teachers against dismissing the observations of non-scientists and against making quick judgements about what is impossible. In 1963, Mpemba was making ice cream at school, which he did by mixing boiling m ilk with sugar. He was supposed to wait for the milk to cool before placing it the refrigerator, but in a rush to get scarce refrigerator space, put his milk i n without cooling it. To his surprise, he found that his hot milk froze into ic e cream before that of other pupils. He asked his physics teacher for an explan ation, but was told that he must have been confused, since his observation was i mpossible. Mpemba believed his teacher at the time. But later that year he met a friend of his who made and sold ice cream in Tanga town. His friend told Mpemba that whe n making ice cream, he put the hot liquids in the refrigerator to make them free ze faster. Mpemba found that other ice cream sellers in Tanga had the same prac tice. Later, when in high school, Mpemba learned Newton's law of cooling, that describ es how hot bodies are supposed to cool (under certain simplifying assumptions). Mpemba asked his teacher why hot milk froze before cold milk when he put them i n the freezer. The teacher answered that Mpemba must have been confused. When Mpemba kept arguing, the teacher said "All I can say is that is Mpemba's physics and not the universal physics" and from then on, the teacher and the class woul d criticize Mpemba's mistakes in mathematics and physics by saying "That is Mpem ba's mathematics" or "That is Mpemba's physics." But when Mpemba later tried the experiment with hot and cold water in the biology laboratory of his school, he again found that the hot water froze sooner. Earlier, Dr Osborne, a professor of physics, had visited Mpemba's high school. Mpemba had asked him to explain why hot water would freeze before cold water. D r Osborne said that he could not think of any explanation, but would try the exp

eriment later. When back in his laboratory, he asked a young technician to test Mpemba's claim. The technician later reported that the hot water froze first, and said "But we'll keep on repeating the experiment until we get the right resu lt." However, repeated tests gave the same result, and in 1969 Mpemba and Osborn e wrote up their results [5]. In the same year, in one of the coincidences so common in science, Dr Kell indep endently wrote a paper on hot water freezing sooner than cold water. Kell showe d that if one assumed that the water cooled primarily by evaporation, and mainta ined a uniform temperature, the hot water would lose enough mass to freeze first [11]. Kell thus argued that the phenomenon (then a common urban legend in Cana da) was real and could be explained by evaporation. However, he was unaware of Osborne's experiments, which had measured the mass lost to evaporation and found it insufficient to explain the effect. Subsequent experiments were done with w ater in a closed container, eliminating the effects of evaporation, and still fo und that the hot water froze first [14]. Subsequent discussion of the effect has been inconclusive. While quite a few ex periments have replicated the effect [4,6 13], there has been no consensus on what causes the effect. The different possible explanations are discussed above. T he effect has repeatedly a topic of heated discussion in the "New Scientist", a popular science magazine. The letters have revealed that the effect was known b y laypeople around the world long before 1969. Today, there is still no well-ag reed explanation of the Mpemba effect. More-detailed explanations Evaporation One explanation of the effect is that as the hot water cools, it loses mass to e vaporation. With less mass, the liquid has to lose less heat to cool, and so it cools faster. With this explanation, the hot water freezes first, but only bec ause there's less of it to freeze. Calculations done by Kell in 1969 [11] showe d that if the water cooled solely by evaporation, and maintained a uniform tempe rature, the warmer water would freeze before the cooler water. This explanation is solid, intuitive, and undoubtedly contributes to the Mpemba effect in most physical situations. However, many people have incorrectly assum ed that it is therefore "the" explanation for the Mpemba effect. That is, they assume that the only reason hot water can freeze faster than cold is because of evaporation, and that all experimental results can be explained by the calculati ons in Kell's article. However, the experiments currently do not bear out this belief. While experiments show evaporation to be important [13], they do not sh ow that it is the only mechanism behind the Mpemba effect. A number of experime nters have argued that evaporation alone is insufficient to explain their result s [5,9,12]; in particular, the original experiment by Mpemba and Osborne measure d the mass lost to evaporation, and found it substantially less that the amount predicted by Kell's calculations [5,9]. And most convincingly, an experiment by Wojciechowski observed the Mpemba effect in a closed container, where no mass w as lost to evaporation. Dissolved Gasses Another explanation argues that the dissolved gas usually present in water is ex pelled from the initially hot water, and that this changes the properties of the water in some way that explains the effect. It has been argued that the lack o f dissolved gas may change the ability of the water to conduct heat, or change t he amount of heat needed to freeze a unit mass of water, or change the freezing point of the water by some significant amount. It is certainly true that hot wa ter holds less dissolved gas than cold water, and that boiled water expels most dissolved gas. The question is whether this can significantly affect the proper ties of water in a way that explains the Mpemba effect. As far as I know, there is no theoretical work supporting this explanation for the Mpemba effect.

Indirect support can be found in two experiments that saw the Mpemba effect in n ormal water which held dissolved gasses, but failed to see it when using degasse d water [10,14]. However, an attempt to measure the dependence of the enthalpy of freezing on the initial temperature and gas content of the water was inconclu sive [14]. One problem with this explanation is that many experiments pre-boiled both the i nitially hot and initially cold water, precisely to eliminate the effect of diss olved gasses, and yet they still saw the effect [5,13]. Two somewhat unsystemat ic experiments found that varying the gas content of the water made no substanti al difference to the Mpemba effect [9,12]. Convection It has also been proposed that the Mpemba effect can be explained by the fact th at the temperature of the water becomes non-uniform. As the water cools, temper ature gradients and convection currents will develop. For most temperatures, th e density of water decreases as the temperature increases. So over time, as wat er cools we will develop a "hot top" the surface of the water will be warmer tha n the average temperature of the water, or the water at the bottom of the contai ner. If the water loses heat primarily through the surface, then this means tha t the water should lose heat faster than one would expect based just on looking at the average temperature of the water. And for a given average temperature, t he heat loss should be greater the more inhomogenous the temperature distributio n is (that is, the greater the range of the temperatures seen as we go from the top to the bottom). How does this explain the Mpemba effect? Well, the initially hot water will coo l rapidly, and quickly develop convection currents and so the temperature of the water will vary greatly from the top of the water to the bottom. On the other hand, the initially cool water will have a slower rate of cooling, and will thus be slower to develop significant convection currents. Thus, if we compare the initially hot water and initially cold water at the same average temperature, it seems reasonable to believe that the initially hot water will have greater conv ection currents, and thus have a faster rate of cooling. To consider a concrete example, suppose that the initially hot water starts at 70C, and the initially c old water starts at 30C. When the initially cold water is at an average 30C, it i s also a uniform 30C. However, when the initially hot water reaches an average 3 0C, the surface of the water is probably much warmer than 30C, and it will thus lo se heat faster than the initially cold water for the same average temperature. Got that? This explanation is pretty confusing, so you might want to go back an d read the last two paragraphs again, paying careful attention to the difference between initial temperature, average temperature, and surface temperature. At any rate, if the above argument is right, then when we plot the average tempe rature versus time for both the initially hot and initially cold water, then for some average temperatures the initially hot water will be cooling faster than t he initially cold water. So the cooling curve of the initially hot water will n ot simply reproduce the cooling curve of the initially cold water, but will drop faster when in the same temperature range. This shows that the initially hot water goes faster, but of course it also has f arther to go. So whether it actually finishes first (that is, reaches 0C first), is not clear from the above discussion. To know which one finishes first would require theoretical modelling of the convection currents (hopefully for a range of container shapes and sizes), which has not been done. So convection alone m ay be able to explain the Mpemba effect, but whether it actually does is not cur rently known. Experiments on the Mpemba effect have often reported a "hot top" [5,8,10], as we would expect. Experiments have been done that looked at the con vection currents of freezing water [27,28], but their implications for the Mpemb

a effect are not entirely clear. It should also be noted that the density of water reaches a maximum at four C. S o below fourC, the density of water actually decreases with decreasing temperatur e, and we will get a "cold top." This makes the situation even more complicated. Surroundings The initially hot water may change the environment around it in some way that ma kes it cool faster later on. One experiment reported significant changes in the data simply upon changing the size of the freezer that the container sat in [7] . So conceivably it is important not just to know about the water and the conta iner, but about the environment around it. For example, one explanation for the Mpemba effect is that if the container is r esting on a thin layer of frost, than the container holding the cold water will simply sit on the surface of the frost, while the container with the hot water w ill melt the frost, and then be sitting on the bottom of the freezer. The hot w ater will then have better thermal contact with the cooling systems. If the mel ted frost refreezes into an ice bridge between the freezer and the container, th e thermal contact may be even better. Obviously, even if this argument is true, it has fairly limited utility, since m ost scientific experiments are careful enough not to rest the container on a lay er of frost in a freezer, but instead place the container on a thermal insulator , or in a cooling bath. So while this proposed mechanism may or may not have so me relevance to some home experiments, it's irrelevant for most published result s. Supercooling Finally, supercooling may be important to the effect. Supercooling occurs when water freezes not at 0C, but at some lower temperature. This happens because the statement that "water freezes at 0C" is a statement about the lowest energy stat e of the water: at less than 0C, the water molecules "want" to be arranged as an ice crystal. This means that they will stop zooming around randomly as a liquid , and instead form a solid ice lattice. However, they don't know how to form th emselves into an ice lattice, but need some small irregularity or nucleation sit e to tell them how to arrange themselves. Sometimes, when water is cooled below 0C, the molecules will not see a nucleation site for some time, and then water w ill cool below 0C without freezing. This happens quite often. One experiment fo und that initially hot water would supercool only a little (say to about -2C), wh ile initially cold water would supercool more (to around -8C) [12]. If true, thi s could explain the Mpemba effect because the initially cold water would need to "do more work"; that is, get colder in order to freeze. However, this also cannot be considered "the" sole explanation of the Mpemba eff ect. First of all, as far as I know, this result has not been independently con firmed. The experiment described above [12] only had a limited number of trials , so the results found could have been a statistical fluke. Second, even if the results are true, they do not fully explain the Mpemba effec t, but replace one mystery with another. Why should initially hot water superco ol less than initially cold water? After all, once the water has cooled to the lower temperature, one would generally expect that the water would not "remember " what temperature it used to be. One explanation is that the initially hot wat er has less dissolved gas than the initially cold water, and that this affects i ts supercooling properties (see Dissolved Gasses for more on this). The problem with this explanation is that one would expect that since the hot water has les s dissolved gas, and thus fewer nucleation sites, it would supercool more, not l ess. Another explanation is that when the initially hot water has cooled down t o 0C (or less), its temperature distribution throughout the container varies more

than the initially cold water (see Convection for more on this). Since tempera ture shear induces freezing [26], the initially hot water supercools less, and t hus freezes sooner. Third, this explanation cannot work in all of the experiments, because many of t he experimenters chose to look not at the time to form a complete block of ice, but the time for some part of the water to reach 0C [7,10,13] (or perhaps the tim e for a thin layer of frost to form on the top [17]). While [12] says that it i s only a "true Mpemba effect" if the hot water freezes entirely first, other pap ers have defined the Mpemba effect differently. Since the precise time of super cooling is inherently unpredictable (see e.g. [26]), many experiments have chose n to measure not the time for the sample to actually become ice, but the time fo r which the sample's equilibrium ground state is ice; that is, the time when the top of the sample reached 0C [7,10,13]. The supercooling argument does not appl y to these experiments. References Historical 1. Aristotle in E. W. Webster, "Meteorologica I", Oxford U. P., Oxford, 192 3, pgs 348b 349a 2. Bacon F 1620 Novum Organum Vol VIII of "The Works of Francis Bacon" 1869 ed. J. Spedding, R. L. Ellis and D. D. Heath (New York) pp 235, 337, quoted in T.S. Kuhn 1970 "The Structure of Scientific Revolutions" 2nd edn (Chicago: Unive rsity of Chicago Press), pg 16 3. Descartes R 1637, "Les Meteores" 164 published with "Discours de la Meth ode" (Leyden: Ian Marie) 1637, quoted in "Oeuvres de Descartes" Vol. VI 1902 ed. Adam and Tannery (Paris: Leopold Cerf) pg 238 (trans. F. C. Frank) 4. Clagett, Marshall, "Giovanni Marliani and Late Medieval Physics", AMS pr ess, Inc., New York, 1967, pgs 72, 79, 94 Experiments on the Mpemba Effect 5. Mpemba and Osborne, "Cool", Physics Education 4, pgs 172 5 (1969) 6. Ahtee, "Investigation into the Freezing of Liquids", Phys. Educ. 4, pgs 379 80 (1969) 7. I. Firth, "Cooler?", Phys. Educ. 6, pgs 32 41 (1979) 8. E. Deeson, "Cooler lower down", Phys. Educ. 6, pgs 42 44 (1971) 9. Osborne, "Mind on Ice", Phys. Educ. 14, pgs 414 17 (1979) 10. M. Freeman, "Cooler Still", Phys. Educ. 14, pgs 417 21 (1979) 11. G.S. Kell, "The Freezing of Hot and Cold Water", American Journal of Ph ysics, 37, #5, pgs 564 5 (May 1969) 12. D. Auerbach, "Supercooling and the Mpemba effect: When hot water freeze s quicker than cold", American Journal of Physics, 63, #10, pgs 882 5 (Oct 1995) 13. J. Walker, "The Amateur Scientist", Scientific American, 237, #3, pgs 2 46 7 (Sept. 1971) 14. B. Wojciechowski, "Freezing of Aqueous Solutions Containing Gases", Cry st. Res. Technol., 23, #7, pgs 843 8 (1988) General discussion on the Mpemba Effect 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. New New New New New New New New New New Scientist, Scientist, Scientist, Scientist, Scientist, Scientist, Scientist, Scientist, Scientist, Scientist, 42, #652, 5 June 1969, pg 515 2 Dec. 1995, pg 22 42, #654, 19 June 1969, pgs 655 6 43, #657, 10 July 1969, pgs 88 9 43, #658, 17 July 1969, pgs 158 9 43, #658, 25 Sept. 1969, pg 662 44, #672, 23 Oct. 1969, pg 205 45, #684, 15 Jan. 1970, pgs 125 6 45, #686, 29 Jan. 1970, pgs 225 6 2 Dec. 1995, pg 57

25. New Scientist, 16 Mar. 1996, pg 58 Related Articles 26. J. Elsker, "The Freezing of Supercooled Water", Journal of Molecular St ructure, 250, pgs 245 51 (1991) 27. R.A. Brewster and B. Gebhart, "An experimental study of natural convect ion effects on downward freezing of pure water", Int. J. Heat Mass Trans. 31, #2 , pgs 331 48 (1988) 28. R.S. Tankin and R. Farhadieh, "Effects of Thermal Convection currents o n Formation of Ice", Int. J. Heat Mass Trans., 14, pgs 953 61 (1971)