Mpemba effect: The story of rediscovery by a Tanzanian high school pupil named Mpemba

"Inspiring young scientist to pursue scientific studies."

The Mpemba effect is named after a Tanzanian student called Erasto Mpemba, who observed
that hot ice cream mix froze before the cold mix. Scientists have known for generations
that hot water can sometimes freeze faster than cold, an effect known as the Mpemba effect,
but until now have not understood why. Several theories have been proposed, but one
scientist believes he has the answer (J. and A. 2015; Bregovi, n.d.).

Theories for the Mpemba effect have included (Auerbach 1995):

a. Faster evaporation of hot water, which reduces the volume left to freeze
b. Formation of a frost layer on cold water, insulating it
c. Different concentrations of solutes such as carbon dioxide, which is driven off when
the water is heated

The problem is that the effect does not always appear, and cold water often freezes faster than
hot water.

The story of its rediscovery by a Tanzanian high school pupil named Mpemba is written up
in the New Scientist. The story provides a dramatic parable cautioning scientists and teachers
against dismissing the observations of non-scientists and against making quick judgements
about what is impossible(The Times 2013).

In 1963, Mpemba was making ice cream at school, which he did by mixing boiling milk 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 in without cooling it. To his surprise, he
found that his hot milk froze into ice cream before that of other pupils (The Mpemba Effect:
When Can Hot Water Freeze Faster than Cold? 2006). He asked his physics teacher for an
explanation, but was told that he must have been confused, since his observation was
impossible.

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 when making ice cream, he
put the hot liquids in the refrigerator to make them freeze faster. Mpemba found that other
ice cream sellers in Tanga had the same practice.

Later, when in high school, Mpemba learned Newton's law of cooling, that describes how
hot bodies are supposed to cool. Mpemba asked his teacher why hot milk froze before cold
milk when he put them in the freezer. The teacher answered that Mpemba must have been
confused (Thomas 2007).

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 would criticize
Mpemba's mistakes in mathematics and physics by saying "That is Mpemba'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. Dr Osborne said that
he could not think of any explanation, but would try the experiment 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 result." However, repeated tests gave the same result, and in 1969
Mpemba and Osborne wrote up their results.

In the same year, in one of the coincidences so common in science, Dr Kell independently
wrote a paper on hot water freezing sooner than cold water. Kell showed that if one assumed
that the water cooled primarily by evaporation, and maintained a uniform temperature, the
hot water would lose enough mass to freeze first. Kell thus argued that the phenomenon
(then a common urban legend in Canada) 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 water in a closed container, eliminating the effects of
evaporation, and still found that the hot water froze first.
Together with a physics professor at University College at Dar es Salaam, he published a
paper in 1969 that showed equal volumes of boiling water and cold in similar containers
would freeze at different times, with the hot water freezing first.

Dr Denis Osborne, a lecturer at University College in Dar es Salaam who published the paper
with Mr Mpemba on the effect they had observed, said: "Several different mechanisms may
cause or contribute to an Mpemba effect(The Telegraph. 2013; The Daily Mail 2013).

The Mpemba effect is the name given to the assertion that:-

It is quicker to cool water to a given temperature when the initial temperature is higher.
The experiments were carried out to explore evidence on Mpemba effects by cooling water in
carefully controlled conditions.

The statement hot water does not cool more quickly than cold is vague and imprecise; hot
water can be made to cool more quickly than cold by supplying more energy to the cooling of
hot water, but it is under such a non-specific premise that the Mpemba effect has become an
artefact in popular science.

Broadly speaking, when two samples of water are cooled to the same temperature, in the
same manner with the two samples being identical except for their initial temperature, and
the initially hotter sample cools in less time, one can consider the Mpemba effect to have
been observed. The temperature at which cooling times are compared has often been chosen
to be 0C (or below) making careful measurements more difficult because of the phase
change that occurs as water freezes.

The Royal Society of Chemistry offered a 1,000 prize to anyone who could explain how the
Mpemba effect worked. Nikola Bregovic, a chemistry research assistant at the University of
Zagreb, was announced as the winner for the prize (Bregovi, n.d.).

He conducted experiments using beakers of water in his laboratory and his resulting paper
suggested that the effect of convection was probably responsible.

He said that convection currents set up in the warm water cause it to cool more rapidly.
However, Dr Changqing and Dr Zhang have attempted to explain the effect further by
examining the process at a molecular level.

They said; the interaction between the hydrogen bonds and the stronger bonds that hold the
hydrogen and oxygen atoms in each molecule together, known as covalent bonds, is what
causes the effect.

Normally when a liquid is heated, the covalent bonds between atoms stretch and store
energy.

The scientists argue that in water, the hydrogen bonds produce an unusual effect that causes
the covalent bonds to shorten and store energy when heated.

This they say leads to the bonds to release their energy in an exponential way compared to
the initial amount stored when they are cooled in a freezer. So hot water will lose more
energy faster than cool water.

Dr Changqing said: Heating stores energy by shortening and stiffening the H-O covalent
bond.

Cooling in a refrigerator, the H-O bond releases its energy at a rate that depends
exponentially on the initially stored energy, and therefore, Mpemba effect happens.

The Royal Society of Chemistry received more than 22,000 responses to its call for a solution
to the Mpemba effect and it is still receiving theories despite the competition closing a year
ago, Dr Sun Changqing and Dr Xi Zhang from Nanyang Technological University, argue this
also determines the way water molecules store and release energy.

They argue that the rate at which energy is released varies with the initial state of the water
and so calculate that hot water is able to release energy faster when it is placed into a
freezer.

Dr Changqing said: The processes and the rate of energy release from water vary
intrinsically with the initial energy state of the sources.
Mr Bregovic, who was judged to have developed the best solution by a panel of experts a
conference at Imperial College London, said: This small simple molecule amazes and
intrigues us with its magic.

Aeneas Wiener, from Imperial College who helped to judge the competition, added: The new
paper demonstrates that even though a phenomenon seems simple, delving deeper reveals
even more complexity and that is certainly worth looking at. "What the authors describe as a
property of H-O bonding may be one of these."

More modern awareness of this apparent anomaly range from the accidental experiments of
the Tanzanian school boy, Mpemba (after whom the phenomenon is popularly known), to the
competition calling for explanations of the phenomenon by the RSC.

The Mpemba effect is an oft cited scientific anomaly and has been widely used in high-
school and undergraduate physics projects.

In the presence of an initially hot sample the freezer may remain on, and doing work, to drive
the cooling for longer. This, however, by no means explains the Mpemba effect; the hot water
must take some time to cool to the initial temperature of the cooler sample of water, after
which all else being equal one would expect the further cooling of the warm sample to take
the same time as the cooling of the colder sample.

Warm water, in total, would take longer to cool. Thus for the Mpemba effect to be observed
there must be some difference in the chemistry of the samples or the physics of their cooling
either initially or when at equivalent temperatures understanding and examining the various
mechanisms that might give rise to such differences remains the focus of scientific debate.

The winning entry to the RSC competition, for example, cites four factors as possibly
contributing to the Mpemba effect, namely:

a. Evaporation
b. Dissolved gases
c. Mixing by convective currents
d. Supercooling.
No doubt all four processes affect the cooling rate of water, albeit to differing extents, and
crucially their effects may be strongly coupled.

a. Evaporation

One explanation of the effect is that as the hot water cools, it loses mass to evaporation. 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 because there's less of it to freeze. Calculations done by
Kell in 1969 showed that if the water cooled solely by evaporation, and maintained a uniform
temperature, the warmer water would freeze before the cooler water (Thomas 2007).

This explanation is solid, intuitive, and undoubtedly contributes to the Mpemba effect in most
physical situations. However, many people have incorrectly assumed 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 calculations in Kell's article.

However, the experiments currently do not bear out this belief. While experiments show
evaporation to be important, they do not show that it is the only mechanism behind the
Mpemba effect. A number of experimenters have argued that evaporation alone is
insufficient to explain their results; in particular, the original experiment by Mpemba and
Osborne measured the mass lost to evaporation, and found it substantially less that the
amount predicted by Kell's calculations. And most convincingly, an experiment by
Wojciechowski observed the Mpemba effect in a closed container, where no mass was lost to
evaporation.

b. Dissolved Gasses

Another explanation argues that the dissolved gas usually present in water is expelled 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 of dissolved gas may change the ability
of the water to conduct heat, or change the amount of heat needed to freeze a unit mass of
water, or change the freezing point of the water by some significant amount (Thomas
2007). It is certainly true that hot water holds less dissolved gas than cold water, and that
boiled water expels most dissolved gas. The question is whether this can significantly affect
the properties 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 normal
water which held dissolved gasses, but failed to see it when using degassed water. However,
an attempt to measure the dependence of the enthalpy of freezing on the initial temperature
and gas content of the water was inconclusive.

One problem with this explanation is that many experiments pre-boiled both the initially hot
and initially cold water, precisely to eliminate the effect of dissolved gasses, and yet they still
saw the effect. Two somewhat unsystematic experiments found that varying the gas content
of the water made no substantial difference to the Mpemba effect.

c. Mixing by convective currents

It has also been proposed that the Mpemba effect can be explained by the fact that the
temperature of the water becomes non-uniform. As the water cools, temperature gradients
and convection currents will develop. For most temperatures, the density of water decreases
as the temperature increases (Vynnycky and Kimura 2015). So over time, as water cools we
will develop a "hot top" the surface of the water will be warmer than the average temperature
of the water, or the water at the bottom of the container. If the water loses heat primarily
through the surface, then this means that 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, the heat loss should be greater the more inhomogenous the temperature
distribution 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 cool 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 convection 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 cold water starts
at 30C. When the initially cold water is at an average 30C, it is also a uniform
30C. However, when the initially hot water reaches an average 30C, the surface of the
water is probably much warmer than 30C, and it will thus lose heat faster than the initially
cold water for the same average temperature.

d. Surroundings

The initially hot water may change the environment around it in some way that makes 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. So conceivably it is important not
just to know about the water and the container, but about the environment around it (The
Times 2013).

For example, one explanation for the Mpemba effect is that if the container is resting 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 will melt the frost, and then be sitting on the
bottom of the freezer. The hot water will then have better thermal contact with the cooling
systems. If the melted frost refreezes into an ice bridge between the freezer and the
container, the thermal contact may be even better (Bregovi, n.d.; J. and A. 2015; Auerbach
1995).

e. Supercooling

Finally, supercooling may be important to the effect. Supercooling occurs when water
freezes not at 0C, but at some lower temperature (Auerbach 1995). This happens because
the statement that "water freezes at 0C" is a statement about the lowest energy state 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 themselves into an ice lattice, but need some small
irregularity or nucleation site 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 will cool below 0C without freezing. This happens quite often.
One experiment found that initially hot water would supercool only a little (say to about
2C), while initially cold water would supercool more (to around 8C). If true, this could
explain the Mpemba effect because the initially cold water would need to "do more work";
that is, get colder in order to freeze.

For example, in two volumes of water, only differing in initial temperature and then cooled in
identical conditions, one would expect that different convective currents might develop.
Therefore, for significantly different initial temperatures the characteristic times that a given
water particle remains in contact with an imperfection in the container or impurity within the
water (e.g. dissolved gases) would vary between the two samples and so the level of
supercooling required to form ice crystals would vary also.

Thus it can be reasoned that the observed variations in the extent to which supercooling
occurs must arise, at least in part, due to differences in convective currents and the relative
levels of dissolved gases (further affected if evaporation occurs). Hence all the factors which
have been proposed to individually cause the Mpemba effect may alter the extent of
supercooling required to cause water to freeze.

Can hot water freeze faster than cold water?

Hot water can in fact freeze faster than cold water for a wide range of experimental
conditions. This phenomenon is extremely counterintuitive, and surprising even to most
scientists, but it is in fact real. It has been seen and studied in numerous experiments.

While this phenomenon has been known for centuries, and was described by Aristotle,
Bacon, and Descartes, it was not introduced to the modern scientific community until 1969,
by a Tanzanian high school pupil named Mpemba (The Telegraph. 2013; The New York
Times 2008).

Three widely cited historical references to Mpemba-like effects in water

The cooling and freezing of water has intrigued some great scientific minds. Aristotle, Sir
Francis Bacon and Ren Descartes have all been credited with consideration of the Mpemba
effect15 and, although this list is by no means comprehensive, it is worth documenting the
precise observations of these three renowned scientists.
The fact that the water has previously been warmed contributes to its freezing quickly: for so
it cools sooner. Hence many people, when they want to cool hot water quickly, begin by
putting it in the sun. So the inhabitants of Pontus when they encamp on the ice to fish (they
cut a hole in the ice and then fish) pour warm water round their reeds that it may freeze the
quicker, for they use the ice like lead to fix the reeds.

The reference to ice as like lead in connection to fishing potentially raises confusion since
the use of lead to weight fishing lines is widespread in traditional fishing; ice being less dense
than water clearly makes it unsuitable for weighting fishing lines. It is our interpretation of
the description like lead to fix the reeds that it refers to the stiffening of the reeds by the
formation of ice so that the reeds can be plunged beneath the water, hence avoiding the need
to weight the reeds so that they might sink. It would, therefore, seem that Aristotle and the
peoples of ancient Greece believed that warming water did make it freeze faster.

No further discussion nor details are provided. Indeed, it is not clear whether any of Bacons

More recent scientific investigations of the Mpemba effect

The, now popular, adoption of the name Mpemba effect is owed to the lack of freezer space
at a Tanzanian school. While making ice-cream one pupil placed his mixture of milk and
sugar in the freezer without first boiling it; another pupil, Mpemba, worried that he would not
find space in the freezer and put his boiling mixture straight into the freezer without first
allowing it to cool. Both pupils returned an hour and a half later to find Mpembas mixture
had frozen while the other had not.

Mpemba did not brush this curious observation aside, instead he asked friends (some of
whom made a living selling ice-cream and apparently exploited the time saving effects of this
anomalous behaviour) and teachers to explain his observations but to no avail.

Mpemba eventually asked a visiting lecturer from the University of Dar es Salaam to explain
his observations. The open-minded Dr Osborne was intrigued by Mpembas observation and
later began investigating the effect with his students, ultimately publishing a scientific paper
with Mpemba on the observed effect (The New York Times 2008).

How to cite this article: Haule I.M. The story of its rediscovery by a Tanzanian high school
pupil named Mpemba: "Inspiring young scientist to pursue scientific studies." (2017)
References

Auerbach, D. 1995. Supercooling and the Mpemba Effect: When Hot Water Freezes
Quicker than Cold. American Journal of Physics 63: 882885.

Bregovi, N. n.d. Mpemba Effect from a Viewpoint of an Experimental Physical Chemist.

http://www.rsc.org/learn-chemistry/resource/res00001018/the-mpemba-
effect?cmpid=CMP00007615, (Date of access:05/01/2016) (2012).

J., Jin, and Goddard W. A. 2015. Mechanisms Underlying the Mpemba Effect in Water from
Molecular Dynamics Simulations. J. Phys. Chem. C 5 (119): 262229.

The Daily Mail. 2013. Mystery of Why Hot Water Freezes Faster than Cold Is Solved - and
Its All down to the Strange Behaviour of Atom Bonds.
http://www.dailymail.co.uk/sciencetech/article-2483383/Mystery-hot-water-freezes-
faster-cold-solvedstrange-behaviour-atom-bonds.html,.

The Mpemba Effect: When Can Hot Water Freeze Faster than Cold? 2006. American
Journal of Physics 75 (514).

The New York Times. 2008. The Claim: Cold Water Boils More Quickly than Hot Water.
http://www.nytimes.com/2008/03/18/health/18real.html,.

The Telegraph. 2013. Have Scientists Worked out Why Hot Water Freezes Faster than Cold
Water? http://www.telegraph.co.uk/news/science/science-news/10420496/Have-
scientists-worked-out-why-hot-water-freezes-faster-than-cold-water.html.

The Times. 2013. 22,000 Scientists Still Cant Explain the Boy Who Kept His Cool.
http://www.thetimes.co.uk/tto/science/physics/article3654099.ece.

Thomas, J. H. 2007. The Mpemba Effect: Studying the Effects of Initial Temperature,
Evaporation, and Dissolved Gasses on the Freezing of Water.

Vynnycky, M, and S Kimura. 2015. Can Natural Convection Alone Explain the Mpemba
Effect? Int. J. Heat Mass Transfer 80: 243225.