Chem 5

Chapter 13

Liquids, Solids, and Intermolecular Forces

Part 2

December 4, 2002
Phase Equilibria
And Phase Transitions

Key Concepts:
Vapor pressure, Clausius-Clapeyron Eq.
Phase diagram
Boiling point, normal boiling point
Melting and freezing point
Sublimation
Triple point
Critical point
Vapor Pressure
The vapor pressure of a liquid is the pressure exerted by its
vapor when the liquid and vapor states are in dynamic equilibrium.

Initially only Condensation begins Rate of vaporization is

vaporization occurs equal to rate of condensation
Dynamic Equilibrium
 A mercury Vapor pressure Vapor pressure Vapor pressure Vapor pressure
barometer depresses the independent of independent of increases with
mercury level the volume of the volume of an increase in
liquid vapor present temperature

Pvap is only dependent on T (independent of V and n) as long as both phases exist!

 Vapor Pressure vs. Temperature

Normal Boiling Point

P is not proportional to T! Does PV = nRT apply ?

Yes, PV = nRT does hold for the vapor phase!
For a fixed vapor phase volume, V, n is not const when T is increased,
because the liquid phase is a reservoir.
Demo: Boiling at reduced pressure
 ( )
lnP = - A (1/T) + B
P2 ∆H vap 1 1
Clausius-Clapeyron Eq. ln = −
P1 R T1 T2
∆Hvap, enthalpy of vaporization
Why Logarithm Dependence?

− E/RT Probability of having kinetic

P∝ e energy higher than E
A Molecular Picture

− ∆ H vap /RT
P(T) ∝ e

∆Hvap  1 
lnP = -   + B
R T

EE

Distributions of kinetic energies of surface molecules of a liquid at two

temperatures. Only the molecules having kinetic energy higher than E can
escape from the intermolecular interaction in liquid. The higher the temp.,
the larger the fraction of escaping molecules.
Phase Diagram
A graphic representation of the conditions of temp. and pressure
at which solids, liquids and gases exist, either as single phases or
as two phases in equilibrium with one another.

∆Hvap
lnP = - +B
RT

∆Hsub
lnP = - +C
RT
Phase Diagram of H2O Heating Curve for H2O

Enthalpy
of vaporization

Enthalpy
of fusion

Temperature ( C ) Heat capacities from the slopes

Demo: Reaching Triple Point of H2O

A closed system

Temperature ( C )
Ice Skating

According to one theory:

the pressure of the skate
blades melts the ice, and the
skate skims along a thin
lubricating film of water.

Temperature ( C )
Sublimation ∆Hsub = ∆Hfus+∆Hvap

Temperature ( C )
A Story of Stanford Library

Some years ago, a Stanford University library suffered flooding

that soaked thousands of books. Hoping to preserve the books,
Stanford took an unusual approach: they froze them and allowed the
ice to sublimate.

How did it work? When paper gets wet, it becomes less rigid.
The process of evaporation, which occurs quickly, creates stress
between the dry and wet parts of a page, causing wrinkles.

By freezing the wet books, the original structure of the paper was
maintained. Sublimation is a slower process than evaporation and
creates essentially no stress on the paper. The library collection was
saved!
Sublimation of Iodine

Sublimation of CO2 (s)

- Dry Ice
 Demo: Liquification of CO2 in a Coke Bottle

Tc,Pc

Critical temp., Tc: the highest temp. at which a distinct liquid phase can form.
Critical pressure: the pressure required to bring about liquefaction at Tc.
Demo: Critical Point of CO2

Vapor
Vapor

Liquid Liquid

Capillaries sealed with CO2 Meniscus disappears

above Tc.
 Chemistry Goes Green!
“Over recent decades, the chemical industry has been increasingly regulated
and leaned that it is often best to cooperate with environmental legislators.
Organic solvents are particularly problematic, because many are toxic and are
not broken down easily in the environment. Green chemistry focuses on
making whole chemical processes less wasteful and damaging to the
environment.”
C&E News, August 2002
Green chemistry is defined as “The design, development and
implementation of chemical processes and products to reduce or eliminate
substances hazardous to human health and the environment”
Science 297, 807 (2002)

Supercritical Fluid Extraction Technology

- supercritical fluids as solvents

Solubility of Naphthalene
(C10H8) in Supercritical CO2
How is decaffeinated coffee made?

O
Decaffeinated coffee is made through
CH3
caffeine extraction from coffee beans by
CH3 N
N
supercritical fluid CO2. Afterwards the
beans are roasted.
N
O N

CH3
How is instant coffee made?

High-quality instant coffee is made by freeze-

drying with dry ice. Fresh-made coffee is frozen
and undergoes sublimation under vacuum. The
dried coffee flakes are then packed and ready to
serve by adding hot water. Compared to instant
coffee made by drying at high temperature, this
method preserves the flavor of coffee better and
has a longer shelf life.
Super cooled liquid How is artificial rain made?

Clouds are composed of small water

droplets; in order to condense them into
raindrops, nucleation sites are needed. In
principle, small ice crystals formed at 0°C
can be used as the nucleation site.
However, because of the supercooling,
rain does not form even at –10°C. In
order to accelerate the formation of the
crystal nucleus, dry ice is dispersed in
clouds. Sublimation of dry ice cools down
the water droplets and creates nucleation
sites that result in rain formation over a
small region.