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October 10, 2001 Reading: Chapter VII Homework: 7.1, 7.3, 7.5, 7.7, 7.8, 7.9 More On Vapor Pressure Over The Solid Phase

1) The document discusses vapor pressure over solid, liquid, and solid-liquid phases. Equations are derived relating the change in vapor pressure to the change in enthalpy of sublimation or evaporation. 2) Vapor pressure over liquid water is examined as a specific example. Equations are provided relating the enthalpy of evaporation to temperature and calculating vapor pressure as a function of temperature from 273K to 373K. 3) Polymorphism in solid materials is discussed, where multiple solid phases can exist at different temperatures and pressures, leading to additional triple points on phase diagrams.

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48 views

October 10, 2001 Reading: Chapter VII Homework: 7.1, 7.3, 7.5, 7.7, 7.8, 7.9 More On Vapor Pressure Over The Solid Phase

1) The document discusses vapor pressure over solid, liquid, and solid-liquid phases. Equations are derived relating the change in vapor pressure to the change in enthalpy of sublimation or evaporation. 2) Vapor pressure over liquid water is examined as a specific example. Equations are provided relating the enthalpy of evaporation to temperature and calculating vapor pressure as a function of temperature from 273K to 373K. 3) Polymorphism in solid materials is discussed, where multiple solid phases can exist at different temperatures and pressures, leading to additional triple points on phase diagrams.

Uploaded by

claudio
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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October 10, 2001

Reading: Chapter VII


Homework: 7.1, 7.3, 7.5, 7.7, 7.8, 7.9
More on vapor pressure over the solid phase:
We have shown that
dP H g (T ) H s (T )
=
dT
P
RT 2
What is H g (T ) H s (T ) ?
This is simply the enthalpy of sublimation (evaporation). Suppose we known Hg-Hs at
some temperature T0, then
T

H g (T ) H s (T ) = H (T ) = H (T0 ) + C P dT
T0

In the above, T0 could be any temperature at which H s g (T0 ) is known. It maybe the
standard sublimation temperature, Ts, at which the vapor pressure is 1 atm. In that case,
T

H s g (T ) = H s g (Ts ) + C P dT
Ts

Thus,
dP H s g (T )
=
dT
P
RT 2
And
ln P( s ) = (Const )1 +

H s g (T )
RT 2

dT

(1)

The above describes the vapor pressure over the solid-gas coexisting line.
P
s
g

A similar calculation can be done for vapor pressure over the liquid phase.
dP H l g (T )
=
dT
P
RT 2
Where,
T

H l g (T ) = H l g (T0 ' ) + (C Pg C Pl )dT


Ts '
T

= H l g (T0 ' ) + C P (l g ) dT
Ts '

Thus,
ln P( l ) = (Const ) 2 +

H l g (T )
RT 2

dT

(2)

For s-l equilibrium, we have shown,


Hl Hs
H s l (T )
dP
=
=
dT T (Vl Vs ) TVs l (T )
If we know Hsl at some temperature T0, then
T

H s g (T ) = H s g (T0 ' ' ) + (C Pl C Ps )dT


Ts ''

Usually, the temperature dependence of Vsl can be neglected. One can, however, take
it into account, if required.
So,
H s l (T )
(3)
dP = Psl = (Const ) 3 + TVsl (T ) dT
All three lines, defining respectively the s-g, l-g, and s-l equilibrium, pass through the
triple point.
(3)
P

(2)
(1)
g

Soild-solid equilibrium:
Before in a P-T diagram of a one-component system, we have one triple point at which s,
l, and g are in equilibrium. However, in many solid materials there are several
crystallographic transitions. An example of such a system is shown in the schematics
below.

l
S3

S2

S1

T
S1, S2, and S3 are three crystallographic polymorphs. For this system, there are three
points corresponding to S1, S2, and g; S2, S3, and g; and S3, l, and g equilibria. In some
systems, certain solid phases are present only at high pressures (high-pressure phases).
An example of such a system is shown below
P

S3
l
S1

S2
g

T
Here, three are four triple points corresponding to S1, S2, and g; S2, l, and g; S1, S2, and S3;
and S2, S3, and l equilibria.
Let us return to a one-component system with s, l and g phases.
Consider point A corresponding to s-l equilibrium as shown in the figure below.
P

Note that there is no gas phases present. Physically, the system would consist of l and s in
a box as shown below at appropriate P and T. there is no void space.

void

l
l
s

Now, lets introduce void space as shown above. As soon as void space is introduced, the
pressure drops to zero. To maintain equilibrium, some materials evaporate to establish a
gas phase. Since the pressure is below PA at the same temperature, the solid will melt (for
the case shown herewith Vs<Vl). The required heat will flow into the vessel fro the
surroundings heat reservoir. Equilibrium will be established when all of the solids melt
and the two phases present are l and g. The corresponding equilibrium will be on the l-g
line- given here by point A.

A
g

Vapor pressure over liquid water:


CP(v) heat capacity of vapor
CP(l) hear capacity of liquid
Normal boiling point is defined as the temperature at which the vapor pressure is equal to
1 atm. Suppose Hevap at the boiling point (T0=373K) is known, then
T

H evap (T ) = H evap (T0 ) + {C P (v) C P (l )}dT


T0

Now (from textbook):

C P (v) = 30 + 10.7 10 3 T +
C P (l ) = 75.44 J / K mol

0.33 10 5
T2

J / K mol

So,
C P ( l v ) = C P (v) C P (l ) = 45.44 + 10.7 10 3 T +

0.33 10 5
T2

Also,
H evap (T0 = 373K ) = 41,090 J / mol
So,
H evap = 58,872 45.44T + 5.35 10 3 T 2
Now,
d ln P =

H evap
RT 2

0.33 10 5
T

J / mol

dT

So,
ln P =

58,872 45.44
5.35 10 3
0.33 10 5

T+
+C
ln T +
RT
R
R
2 RT 2

(Here, P is in Pa)
At T=373K, we have P=1 atm, so we can solve C=51.092
In terms of log10, we have P in units of atm.
log10 P (atm) =

3075
862
5.465 log10 T + 0.279 10 3 T + 2 + 22.155
T
T

This is the standard vapor pressure-temperature relationship for H2O from 273 to 373K.

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