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How does evaporation work? Well, lets take what we know.

The Second Law requires that for


the system as a whole
P
d i mi gi (T, p)
dG
=
<0
dt
dt
The Gibbs-Duhem relationship gives us the relationship between pressure and temperature gradients and potential gradients
Hm,p + V pH,V = m gH,p
If there is no energy barrier to initiating flows, we can constrain further for constant temperature
(or enthalpy)
m g=V p
or
g=

1
p

or as, a continuum expression


1
rg = rp

Finally, pressure (or density) gradients drive flows:

@m
A
=D
@t T,p
x
1. Show that over a plane surface of pure water at constant temperature, where RH is the
relative humidy, that the difference in the chemical potential between the vapor and liquid
phase is
= v (T ) l (T ) = kT ln (RH/100)
where
G=m gN

where N refers to the amount of matter (typically molecules) and is the amount of
potential energy per molecule. The trick in the above is recognizing that, just above the
liquid surface, vapor is in saturation (or equilibrium), such that its pressure is the same as the
liquid water beneath it and p. Consequently, moving a vapor molecule from just above the
liquid surface to the air above it is equivalent to moving it from the liquid phase to the vapor
phase.
Essentially this transfer is an example of the isothermal expansion (or compression) of an
ideal gas as it goes from saturation to RH , where the gas we are interested in is water
vapor. We are intested in the change of potential energy per molecule as it undergoes this
transition. From the above
1
g=
p

or, in terms of chemical potential, using the symbol e for vapor pressure and noting that
e = nkT
1
e
=
e = kT
' kT d ln e
n
e
1

The change in chemical potential required to move a vapor molecule from right at the liquid
surface to some distance farther away phase is thus
= v

sat
v = kT ln

e
esat

= kT ln

RH
100

The value sat


v refers to the chemical potential of water vapor at saturation where it is in
equilibrium with the liquid phase and sat
v = l .
2. On the basis of the above, why does a puddle evaporate in dry conditions? Note that a system
always work towards equilibrium. In this case a system always works towards a state where
pv = pl . Hint: the chemical potential of vapor molecules just above a flat surface is what the
chemical potential would be at saturation. Draw a box around the vapor and liquid system,
and do an accounting of the total gibbs free energy in the box for the transfer of molecules,
with their respective chemical potentials , from the liquid phase to the vapor phase.
The system acts to minimize the potential difference , such that in a spontaneous process
d| | < 0. If ln e/esat is non-zero, then the imbalance between v and l must be reduced
according to the second law. The way the system can do this is through material transfer
from high potential at saturation to low potential at RH<100%. Remember we derived that

@
|T,m
=
@t T,p

so a gradient in vapor density from the puddle to the dry air leads to a less dense system
with more vapor in dry air.
Alternatively, consider a volume that contains dry air and liquid.The liquid potential is
Gl = Nl sat
l
In the rest of the volume
G v = Nv v
The the total potential is
G = Nv v + Nl sat
l
At constant temperature

dG
dNv
dNl sat
=
v +

dt
dt
dt l
But molecules are neither created or destroyed so, in a close system, what leaves the surface
adds to the rest of the volume (and vice versa)
dNl
=
dt
So

dNv
dt

dG
dNv
dNv
dNv
=
v sat
=
=
kT ln e/esat
l
dt
dt
dt
dt
Since dG/dt < 0 through the second law, if e < esat then = kT ln e/es < 0 and dNv /dt
must be positive (i.e. evaporation). Likewise, if e > esat , then = kT ln e/es > 0 and
dNv /dt must be negative (i.e. condensation).
2

3. It is often stated that the air can hold more water on a warm day. Comment
The amount of water vapor has nothing to do with the air itself, only the temperature, according to Clausius-Clapeyron.