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F e a t u r e : l Vp e mb a e f f e c t

hotwaterfreeze
first?
Does
freezes
faster
thetimeofAristotle,
some
scientists
haveclaimed
thathotwater
thancold.
Since
phenomenon
PhilipBalll00ks
atcurrent
attempts
t0shedlightonthispuzllng

It soundslike the kind of questionyou would be dismayed to hear schoolchildrengetting wrong: which
takeslesstime to tieeze,cold or hot water?Common
senseand the lawso{ thcrmodynamicsappeartoinsist
that cold water must freezefirst. For example,Newton'slaw ofcooling statesthat the rate at which a body
cools is proportional to the temperature difference
betweenthe object and its surroundings.But, infact, it
doesseemasthoughhot watersometimes"overtakes"
cold asit cools.
Indeed,Aristotle, FrancisBacon and Rene Descartes
all claimed that hot water doesfreezemore quickly.
Erasto Mpemba, a secondary-school
studentin Tanzania,mayhavebccnunawareof theirclaims,but itwas
somethinghe alsoobservedin 1963.To make ice cream
for a schoolprojcct, he was told to boil milk and then
let it coolbefore puttingit in the reliigerator. But, fearful of losing his place, Mpemba put his mixture in the
fridge while itwas still hot. He found that it ftozc before
the other,cooledmL\tures.
Others have since claimed to have observedthis
"Mpemba effect" in their own experiments.Nevertheless,many scientistsfind it hard to acceptsuch a
seeminglycountedntuitive phenomenon.The problem
is that the effect is frustratinglyhard to reproduccsometimesit appears,and sometimesnot. In fact, noone hasagreedexactlyhow the experimentsshould be
conducted in the first place. And even if the Mpemba
P h y s l c sW o r l d A p r i i 2 0 0 6

efl'ectis real - ifhot water can sometimesfreeze mote 0n thir ice

nk
quicklythan cold - it is not clearwhether the explan- Intuitvelyweth
thatcoldwater
ationwould be trivial or illuminatins.
Againstthe grain
MonwheaJengofSouthCondensed-matterphysicist
ern Illinois Universityin the US, who hasresearched
the history of the Mpemba effect, believesthat scientistsare much more likely to react with disbelief
than laypeoplewhen they first hear about the phenomenon. That is becausescientistsknowwhy it "cannot" be right, he says.Indeed,when Mpemba learned
about Newton's law ofcooling a few yean after making
his discoveryand askedhis teacherhow this could be
his teacherreplied,
reconciledwith his obser,,ations,
'All I can sayis that is Mpemba'sphysicsand not the
universalphysics."
Fortunately,Mpembawasnot deterredby this cruel
put-down, and he went on to carry out further experiments of his own. When local physicsprofessor Denis
Osborneof University College in Dar esSalaamvisited
the school,Mpemba seizedthe chanceto ask for an
cxplanation for his findings. Osborne had none, but he
was lessscepticalthan Mpemba'steacherand wisely
concludedthat "it is dangerousto passjudgementon
what can and cannotbe". Osbornethen askeda technician at his university to repeat the experiments,and
the resultsseemedto showthat Mpembawasright. In

shouldtakelesstime
to freeze
thanhot
water,butAistote
have
andotherssince
fo!ndthlsnotto be
thecase.

Phi'ipBallisa
sctence
wnteT
andjournalist
basedin London,
emailp.ball@
nalute.c0ra

19

r
: a S t ari e :
,ust desserts
TheMpembaetfect
is namedaftera
sec0ndary-scll00l
studentfrcm
Tanzania
whofound
thatanice-cream
mlfr!refrozequicker
whent wasst lhot.

effect

Many
findit
scientists
hardto accept
sucha
seeminglycounterintuitive
phenomenon
asthe
Mpembaeffect

1969 Osborne wrote about thc work with Mpemba ter to settlethe issueonce and for all by carryingout
(then at the College of African Wildlife Management expefiments?That tums outtobe surprisingll'difficult,
in Moshi) and published it in the journal Ph)slc-r not least becausethc statement"hot water fr eezcs
Education. Coincidentally. a physicistnamed George fasterthan cold" is ill-defined.In a recentpaper.Jeng
Kell at the National ResearchCouncil of Canadain suggestsa more precisewording (arXiv.org/abs/physics/
Ottawa reported the samephenomenonthat year in 0512262v1):
"There existsa set of initial parameters,
theAmeicqn Jour al ofPhysics.
and a pair oftemperatures,suchthatgiventwo bodiesof
These reports revealedthat the Mpemba effect was water identical in theseparameteff, and differing only
alreadyfamiliar in folk wisdom. Kell, hailing liom a in their temperatures,
the hot one will freezesooner."
countrywithample experienceoffreezingwater,stated
There are manysuchparametcrsthat could affectthe
that "somesaythata carshouldnot be washedwith hot rate offreezing, the most obviousincludingthe volume
water becausethewaterwill freezeon it more quickly and type ofwater used,the sizcand shapeof the conthao cold water will, or that a skzltingrink should tre taineIS,andthe temperatureofthe fridge.Thispresents
flooded wilh hot water becauseit will freeze more a significant challengelor the experimentalist,who in
quicklv". Mpcmba, mearwhile,pointed out that Thn- principlcwould haveto setup avastmultidimensional
zanianice-creanrmakcrs routinely lioze theirmixtures array of experimcnts involving contail1erswith differwhile theywerehot, becausethat wasa fastermethod. ent sizesand shapes,while independcntlyyaryingthe
Andwhen Mpemba'swork wasdcscribedin an article massesand gascontent of the water and the refriger
1n New Scientislin 1969,it prompted a rush of ar- ation methodused,in order to testfor thc cifcct.
ecdotcsabout food-freezingpracticesand hot-water
There is also the key problem of horvto dcfine the
pipesfreezingwhile cold onesdid not.
timc of freezing.Does this refer to the mon]entwhcn
Thosemaking suchclaimsarc in good company.In the first ice crystalsappear or to thc timc when the
his Meteorologicafrom about 350 BC. Aristotle wrote entire body ofliquid is frozen? "Both of thcsctimes can
thal "if water has been previouslyheated,this con- be very hard to obscrve,perhaps especiallyin a refrigtributes to the rapidity with which it treezes,for it cools erator," saysice specialistCharlcsKnight of the Namore quickly". The idea wasquestionedby the great tional Center for Atmospheric Rescarchin Boulder,
medievalchampionof experimcntationRogerBacon, Colorado,US.
but his namesakeFrancisassertcdin the 17thcentury
that "water a little warmed is morc easilyfrozen than Lookingfor clarity
that which is quite cold". FrancisBacon was deeply Thesecomplexiticspcrhapscxplainwhy the Mpemba
interestedin freezingand refrigeration he is saidto effect remainsa puzzleto this day.A number of scihave caught a fatal chill while conductingan experi- entistshave investigatedMpemba's claim, but thcir
ment on preserving a chicken by stuffing it with snow. resultsremaininconclusive.In1977.for example,Jearl
Around the sametime, Descartesmadecarefulobser- Walker reported in SciantficAmaican that he had obvations of thc freezingof water that enabled him to ser,'edthe time it took a beakerofwater to cool to 0'rC
identirythe Iiquid'sunusualdensitymaximurnat 4"C. fiom differentinitial temperaluresundcl variousconThcsc studiesconvincedhim that "water which has ditions. These testsprovided some clarification of tl.re
been kept hot for a long time freezesfaster than any effect (seefigure). But although Walker rcportcd that
other sort".
he couldreproducemostofhisresults,he stillobtained
But were all thesereportsjust the result of bad ex- large deviationsin some of them. "I have not been abie
perimental technique?Surelyit shouldbc a simplc mat- to rcsolvcthc controversy,"he said.

20

P h y s i c sW o r l d ' \ p|

2006

F e r r i r r r :M p e m b ae f f e c t

However,despitethe continuinguncertaintiessurroundingthe effect,PabloDebenedetti,a physicistat

PrincetonUniversityanda specialist
in phasetransitionsofwater,is happyto believeMpemba'saccount.
"I do not seeanyreasonto doubtobservations
show- ^ 6 0
ingthatundersomecircumstances
hotwatercanfreeze
fasterthancoldwater,"he says.
But what causesthe effect?Both Debenedettiand E " "
Knightpoint out that therecouldbe at leastoneobvio40
ousexplanationfor it. If the containersare left open,
the hot waterwill evaporatemorequicklyandits vof
umewilldeclinecomparedwith
thatofthecoldwater.
With a smallervolume,the coolingof the hot water
couldthenovertakethatof the cold.That shouldbe
easyto test,accordingto Debenedetti,
because
the
evaporationrate is proportionalto the areaof the liquidsurface."This canbe systematically
controlledin
0L
experiments
conductedin pairsof containerswith dif20
ferentgeometry,"he says.
(.C)
initiat
tempercture
Arother possibilityis thatthefreezingprocess
could
Does
hotwater
In1977lea/
coolfaster
than
cold?
Walkerobseved
thetime
taken
fora
beaffectedbydissolved
gas.Hot watergenerallyholds
beaker
oiwaterto
reach
0 oCfroma range
ofinitialtemperatures
andina number
ofdifferent
lessdissolvedgas
thancold,whichmeansthattwosam- conditions:
(yellow);
50mlofwater
ina small
Pyrex
beaker
50mlofwater
ina large
beaker(dark
plesthat differ onlyin their initial temperaturewould blue);50mlofwaterin
(lightbl!e)j100mloft{aterina large
a large
beaker
inafrost-free
freezer
not contain"identical"substances.
Debenedettipoints beaker,
(thermometer)
(green);
withthethermocouple
nearthe
bottom
ofthebeaker
100mlof
out thattinybubblesofgascanprovidenucleationsites waterin
a large
beaker,
covered
withplasticfood
wrap,
withthethermocouple
nearthe
bottom
whereicecrystalsstartto form.In principle,thismight (purple);andl00mloiwaterinalargebeaker,withthethermocoupleneartheto
be expected
tomakeiceformationeasierincoldwater, l\4pemba
gradient.
isseenintheponions
effect
ofthegraphsthat
have
a negative
contraryto the Mpembaeffect.But Debenedettisays
that the solubilityof nonpolargasessuchasnitrogen fect. But what he found only made things more comor methanedo not necessarilyvary
smoothlywithtem- plicated. He observedthat hot water ftoze at a higher
perature,sotherecouldbetemperaturerangeswithin temperature than cold and therefore in a sensefroze
whichthe hotterwatercontainsmoredissolvedsas. "first". However, the coldwatgrtook lesstime to reach
E x p e r i m e nt tosp i n p o i ntth e s ei n l l u e n c ewso u l dr e - its supercooledstateand so seemedto freeze "faster".
quirethewaterto be thoroughlydegassed.
The effects To add to the confusion, earlier researchers had reof otherdissolvedimpuritiescouldbe evenharderto ported the opposite: that initially hot water could be
probe:for example,onecoulddividethewaterup into supercooledto lower temperaturesthan cold water. In
tiny dropletsin an oil-water emulsionso that mostof 1948Noah Dorseyofthe US National Bureau ofStanthemaretoo smallto containanyimpurilyparticles. dards argued that this is because heating expels imThenthereis theroleofchance.sincethenucleation pudtyparticles that acted asnucleation sitesfor ice. It
ofice in freezingwaterdependson enoughwatermo- has been claimed that this effect leads to hot-water
leculescomingtogetherto form thecoreofan icecrys- pipes bursting more readily than cold, since deeper
tal that can then grow indefinitely.The further the supercooling leads to ice fingers that advance right
water is belowfreezingpoint, the more likely this is across the pipe and block the flow, while freezing
to happen.But becauseit cantake sometime for ice nearerto 0oCjustproducesa sheathofice on the pipe
crystalsto nucleate,watercanoftenbe "supercooled" surfaceswith an open channel in the centre.
suchthatit remainsliquidwellbelowfreezing.Random Such contradictions continue to make the MDemba
impuritiesin the liquid, suchasspecksof dust,can, effectaspuzzlingasever.Knightis happyto leav; it rhat
however,increasethe rateofnucleationandsuppress way, becausehe thinks that attempts to clarily itwould
supercooling.
"Keepingeverythingconstantfrom ex- demand too much effort for little return. But Jeng is
pedmentto experimentmaynot be possiblewithout more positive. He saysthat despite the complexity of
resortingto purposefulnucleation,and that might the effect, the experiments needed to study it can be
destroytheeffectoneis lookingfor," saysKnight.
canied out by undergraduates and high-school students
Knightaddsthathewasremindedofthe partplayed - so long asthey are planned carefully.As well asthinkby chancewhileconductingsomerecentexperiments ing about exactlyhow to heat thewater and the kind of
on iceformation."I hadto sit in a coldroomat -15 oC thermometer that should be used. exDerimenters
andwatchwaterfreezingin ice-cubetrayson a table shouldalsoconsiderprecisedetailsof the invironment
top.This exerciseemphasized
that everythingis vari- surrounding the container. "It can make a difference
able.Somecompartmentsstartedfreezingin about whetherthewaterisin the middleofan emptyfteezer,
15minutes,but manydid not for an hour ormore."
orjammed betweena frozen pizza and a frost-covered
tub ofice cream," he says.

Further
testingrequired
Though it is not perhapsthe most hi-tech type of
In 1995GermanphysicistDavidAuerbachat the Max experiment, it is one that could help resolve a puzzle
Planck Institute for Fluid Dynamicsin Gottingen that has intrigued scientistsfor over two millennia.
lookedat the role ofsupercoolingin the Mpembaef- Any takers?
P n y . l c sW o r l d A 0 r 2 Q 0 6

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