3.

11 Evaporative cooling

Evaporative cooling is a popular and intuitive
mechanism for explaining the Mpemba effect,
which causes a liquid (water in this case) to
vaporise at its exposed surface. This results in
faster cooling and a mass loss in the
remaining liquid. The rate of evaporation
increases for increasing temperatures where
it reaches its maximum at the boiling point
100C for water. [Cite]
Therefore water at a higher initial
temperature will have a greater mass loss
throughout its cooling process than water at a
lower initial temperature; where the effects
of evaporation and mass loss are negligible
[cite]. In his paper The Freezing of Hot and
Cold Water, G. P. Kell provided an explanation
of how evaporation can allow hot water to
cool and freeze faster than cold water:
If equal masses are taken at two starting
temperatures, more rapid evaporation from
the hotter one may diminish its mass enough
to compensate for the greater temperature
range it must cover to reach freezing [Kell].
Kell claims that the cooling (and freezing)
process of water inside wooden pails is partly
Newtonian and partly by evaporation. Kell
argues that at sufficiently high temperatures
evaporation is more important. Kell assumes
that the loss of heat (enthalpy) for the body of
water is solely due to the latent heat of
vaporization of water.
Where m is the mass of vapour and K is a
proportionality constant, which depends on
the surface area; and other variables assumed
to be constant.
By combining equations and , the
following equation is produced:
= ( ) (3)
The latent heat - , the specific heat capacity
- and the vapour pressure - , vary with
temperature and hence are implicitly
functions of temperature. The vapour
pressure varies with values ranging from
to [cite]
In addition to this equation Kell describes the
freezing process where the loss of heat (and
mass loss) due to vaporization is provided by
the latent heat released in the liquid to ice
phase transition:
= (1)
Where Lf is the latent heat of fusion (due to
freezing) and M is the mass of ice formed.
The temperature of the body of water, T0, is
now the temperature at which water begins
to freeze i.e. its freezing point. The mass loss
for the freezing process is still given by
equation where the vapour pressure, is
now evaluated at the freezing point, T0.

= (1) Kell solves these equations by integrating

In addition he assumes that the rate of
change of mass of water vapour is
proportional to the difference in vapour
pressure, Pv and the surrounding ambient
pressure of the air, Pa.
= ( ) (2)
numerically using a computer program. The
calculations for a unit mass at different
temperatures shows that evaporative cooling
can explain why hot water cools (and freezes)
faster than cold water.
Fig. 3 shows the graph produced by Kell
showing the cooling (a and c) and the freezing
times (b and d) against the initial temperature
of the body of water using Kells model. The
observed maxima occurring at and for a
non-zero ambient (partial) pressure; indicates
that increasing the temperature past this
maxima causes both the freezing and cooling
times to decrease hence for this temperature
interval the mpemba effect is predicted to
occur.
As seen in fig. the cooling (and freezing)
times for the temperatures and are the
roughly equal. This shows that if the two
initial temperatures are less than (or equal) to
the temperature corresponding to maximum
cooling (or freezing) time; or if the two initial
temperatures are too wide apart i.e. one
temperature below the maxima and one
above, then the model predicts that no
Mpemba-Effect will be observed.
Fig. - Cooling and freezing time, maxima
for vacuum pressure and not vacuum.
Kells model predicts that water initially at
100oC will lose 16% of its mass throughout
the cooling process (cooling to 0oC) and an
additional 10% mass loss after it has comp-
letely frozen. Kell verified the mass loss
predicted by his model using dewar flasks
containing water at 88oC and 61oC with an
equal mass of 1550 g. Kell showed that when
the warmer water cooled to 39oC it had a
mass of 1440 g. These results were consistent
with the predicted mass of 1430 g (within
experimental precision of the measurements)
computed from Kells model. [Kell]
Walker also supports Kells model, claiming
that his own experiments appear to be in line
with Kells calculations. [Walker] However,
some of Walkers results had large deviations
from the expected results, despite most of the
results being reproducible [Walker, Jeng].
One of the main issues concerning the role of
evaporative cooling in the Mpemba effect
concerns the mass loss predicted by Kells
model.
Many experimenters have claimed that the
amount of mass-loss measured is not
sufficient for evaporative cooling to solely
explain the Mpemba effect. [Bregovic, JH
Thomas, Ibekwe, Brownridge, Mpemba,
R.P.Gamage and S.R.D.Rosa, Elizabeth H.
Oakes, Auerbach] This was the case for
Osbourne, who only reported a mass loss of
up to 6%. Osbourne ruled out the role of
evaporation as a valid explanation for the
Mpemba effect. [Osbourne, Mind on Ice]
However, there is much variation in the mass
loss reported by different experiments [cite];
this could be due to the different factors that
affect the evaporation rate, for example the
surface area of the exposed water, the shape
of the containers. [Jeng, Firth, Walker].
Thomas reported that in his experiments none
of the samples of water reduced their mass by
more than 3.0% regardless of the initial
temperature. [Joseph H. Thomas, 2007]
He argues that such a small mass reduction
would require a very large difference in the
thermal energy transfer to explain the
difference in freezing times on the order of
thousands of seconds [Joseph H. Thomas,
2007]. Freeman reported a more optimistic
mass loss of 10% for water cooling from 100oC
and a mass loss of 1% for an initial
temperature of 20oC. However, he claims that
for this amount of mass loss that Kells model
is not applicable to this experimental
situation. [Freeman]
The disagreement in the mass loss predicted
by Kells model compared with measurements
by other experimenters can be partly
explained by the assumptions made in Kells
model. Kells model is a lumped mass model,
which assumes the temperature to be
uniform throughout the body of water.
[Vynnycky]. This implies that the water has no
variation in temperature and hence no
temperature gradients within the water.
[Firth] The model neglects the effects of
conduction and convection [Vynnycky], which
rely on temperature gradients within the
water and at the boundaries - the container.
In addition, Kell assumes there is no heat loss
through the sides of the container - the
water is assumed to be in a container with
adiabatic walls without a lid. [Vynnycky]
Kell argues that hot water will only freeze
faster than cold water when using wooden
pails since metal pails lose too much heat.
[Kell] This might be one explanation why the
effect is not commonly observed and
understood since most are metal pails. [Kell]
One possible explanation suggested by Firth is
that wood has a much lower thermal
conductivity than metal [Firth] [textbook],
and thus has less heat loss at the sides of the
container as compared to the metal pails.
This is further supported in Kells experiment,
which uses dewar flasks with a low thermal
conductivity [Firth]. This suggests that the
Mpemba effect may be more likely to occur
with containers of low thermal conductivity. It
is evident that the effects of heat loss through
the sides could be an important factor in
observing the Mpemba effect. Walker claims
that faster conduction through the walls and
the bottom of the container may diminish the
importance of evaporation [Walker]
The effects of heat loss through the container
can be investigated by using:
1. Containers with different amounts of
thermal insulation [Jeng] [Walker]
2. Containers made from different
materials [Walker], [Jeng]
Freeman compared the freezing times for a
plastic and aluminium beaker with the same
dimensions. Freeman observed no Mpemba
effect for either beaker but noted that the
aluminium beaker froze 30% faster than the
plastic beaker. [Freeman] A more important
quantity to observe the effects of
evaporation, is the ratio between the surface
area of the exposed water and the sides of
the container. [Walker]
Walker suggests that there might be a
particular advantageous ratio that might
enhance the Mpemba effect. [Walker]
This might also explain why the Mpemba
effect may not be observed when using less
favourable ratios. Walker noted that a beaker
with double the surface area (compared with
a smaller beaker) resulted in a greater rate of
evaporation. This suggests that evaporation
will have a greater advantage over the heat
loss through the sides of the
container.[Walker]
Therefore, Kells model becomes valid for
large exposed surface areas [Freeman],
[Balazovic], where evaporation dominates
over heat losses by/at the container. The
Effects of evaporation can be further
restricted or eliminated entirely by placing a
lid on a container or by adding a thin layer of
oil over the water. [Freeman] [Firth][Walker]
[Jeng] This could indicate whether evapor-
ation has a necessary role in causing the
Mpemba effect. If the Mpemba effect were
observed with restricted evaporation or
completely eliminated; this would suggest
that evapor-ation is not the sole explanation
for the Mpemba effect.
The Mpemba effect was observed in a closed
container by Worciejowski et al., whom
attributed the Mpemba effect to dissolved
solutes [Worciejowski]. However Jeng argues
that this does not disprove the role of
evaporation in the Mpemba effect; since
Worciejowskis experiment is the only
experiment that has observed the Mpemba
effect with a closed container.
A considerable amount of study into the role
of evaporation in the Mpemba effect has
been presented where other authors, critics
have simply dismissed due to insufficient
mass loss. [Bregovic, Burridge] Kells
calculations predict the Mpemba effect to
occur from evaporative cooling for specific
conditions mass loss of 16% in the cooling
process, in containers with low thermal
conductivity e.g. wooden pails, dewar flasks.
However these assumptions made by Kells
model make it limited in applicability. [Kell]
In addition the insufficient mass loss
measured by many experimenters makes
Kells model not applicable to these cases,
most notably with Mpembas original
experiments. [Osbourne cool, mind on ice]
Arguably, there is no unique explanation that
different explanations for different
circumstances.
This is only one model proposed by Kell can
be extended to 1D, 2D, 3D beyond lumped
mass model to account for non uniform
temperatures (greater)
Other heat transfer mechanisms can be
incorporated that could accelerate the
effects. More pronounced maxima and mass
loss.
Kells model does not apply to Mpembas
original experiments. Kells model is too
limited not general need an explanation that
applies to more circumstances.
Convection other effects could be included
to further boost the effects of the
evaporation.
1D, 2D or 3D models could be applied which
explain the role of temperature gradients
furthermore predict a lower mass loss and
more prominent maximum in the cooling-time
for initial temp.
 1. No heat loss at sides of the container predict less mass needed to produce
Kells model describes effects of wooden effect or more pronounced effects
pails metal pails lose too much heat. greater curvature in the maxima.
2. Firth low thermal conductivity of wood
Questions:
3. Walker heat loss diminishes effects of
evaporation. Does the mpemba effect need a specific
4. Sensitive interplay between the effects explanation.
of evaporation and heat loss at the sides
of the containers. Difficult problem isolating effects or not a
single parameter/mechanism responsible.
5. Walker effects of ratio of surface areas. Convective hot top.
- Firth experiments on different ratios
increase the effects of evaporation mass Not a single mechanism is responsible
loss multiple different mechanisms may validly
- Kells model becomes valid for large explain the same effect in different
exposed surface areas (freeman, balazovic) contexts/circumstances Kells model
- The Effects of evaporation can be provides one circumstance although not very
restricted or eliminated lid on container, general where evaporation is the driving force
oil film or other methods (firth, /mechanism.
jeng,walker, freeman). Jearl walker claims that faster conduction
6. The following arguments have outlined through the walls and the bottom of the
kells assumptions and the cases when container may diminish the importance of
the model are justified. evaporation
7. Sensitive parameters such as the ratio of
areas could indicate a region of golden Such assumptions are consistent with Kells
ratios were kells model is valid and motivations for explaining how the mpemba
indeed the mpemba effect can occur. effect arises from evaporation only.
8. This also suggests why the mpemba
effect is not observed when such
conditions are not met.
9. Many argue kells model does not apply
to Mpembas original experiments.
10. Mpemba effect observed in closed
container by Worciejowksi suggests that
in these cases evaporation does not
have a (significant) role in the effect.
11. Questions - more than one way t0o
explain the mpmeba effect- numerous
ways thermal parameters can combine
to give rise to the effect.
12. Focussed on outlining how one
parameter namely the mass can affect
the cooling of a system by evaporation.
13. Effects could be amplified by other
effects [jeng], vyynycky on lack of other
models could be improved by
assuming 1D,2D,3D models,
temperature gradients. This may
-We have only looked at one model limited
theoretical and experimental model.
Vynnycky.

Coupled effects of evaporation with other

heat transfers- difficult to isolate could
eliminate the conditions for mpemba effect to
occur some proposed arguments for how to
isolate the effects of evaporation jeng,
freeman, and firth.

Coupled effects ratio of areas, different

containers jeng etc.

OUTLINE VYNYCKY IMPROVEMENTS

Criticisms

- Mpemba effect has also been observed in

closed containers with no evaporation [9].
Wojciechovski B, Owczarek I and Bednarz G
1988 Freezing of aqueous solutions containing
gases Cryst. Res. Technol