Scribd
Upload
2 views

CT_Ch4_2022

Chapter 4 of 'Chemical Thermodynamics' discusses the physical transformations of pure substances, focusing on phases, phase transitions, and the criteria for phase stability. It explains the concept of phases, phase diagrams, and the phase rule, detailing how temperature and pressure affect the stability and coexistence of different phases. Additionally, it covers specific examples like water and helium, illustrating their unique phase behaviors and transitions.

Uploaded by

limsohee3537
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
2 views

CT_Ch4_2022

Chapter 4 of 'Chemical Thermodynamics' discusses the physical transformations of pure substances, focusing on phases, phase transitions, and the criteria for phase stability. It explains the concept of phases, phase diagrams, and the phase rule, detailing how temperature and pressure affect the stability and coexistence of different phases. Additionally, it covers specific examples like water and helium, illustrating their unique phase behaviors and transitions.

Uploaded by

limsohee3537
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
You are on page 1/ 15

Chemical Thermodynamics

Chapter 4: Physical transformations of


pure substances
Phases

Phases
: A form of matter that is uniform throughout in chemical composition
and physical state. e.g.) gas, liquid, solid…

• Number of phases in a system “ P ”


ex) a gas, or gaseous mixture : single phase, P=1
a crystal of substance : single phase, P=1
two fully miscible liquids (H2O and CH3OH) : single phase, P=1
NaCl(aq) : single phase, P=1
ice : single phase, P=1
a slurry of ice and water : two phases, P=2
CaCO3(s)  CaO(s) + CO2(g) : two solid phases and one gas phase, P=3

For a system of two metals,


two phases if they are immiscible: P=2
single phase if they are miscible (i.e. alloy) : P=1
Phases
(a) Single phase solution:
A homogeneous mixture of two substances.
The composition is uniform on a molecular (microscopic) scale.

(b) Dispersion :
The composition is uniform on a macroscopic scale
but not on a microscopic scale.
Grains or droplets of one substance embedded in a matrix of the other.

Single phase Two phases


Phase Transition

: Spontaneous conversion of one phase into another phase.


occurs at a characteristic temperature for a given pressure.
ex) - Stable phase of water at 1 atm,
Ice is the stable phase of water below 0°C.
Liquid water is more stable above 0°C.
- Phase transition of water at 1 atm
Below 0°C, Gibbs energy decreases as liquid water changes into ice.
Above 0°C, Gibbs energy decreases as ice changes into liquid water.

At transition temperature (Ttrs), the two phases are in equilibrium.

• Metastable phase
: thermodynamically unstable phase that persists because the transition is
kinetically hindered.
e.g.) Diamond is a metastable phase of carbon under normal conditions
Graphite is thermodynamically more stable than diamond.
i.e. Gm(graphite) < Gm(diamond)
Activation energy for conversion of diamond to graphite is very high.
kinetically long.
Phase transition
Detecting a phase transition
Thermal analysis
Phase transition is detected by noting that T does not change even though heat
is being supplied or removed from the sample.
ex) differential scanning calorimetry

• A cooling curve at constant pressure


Temperature doesn’t change
when the freezing take place (exothermic process) .
Released heat from the sample is use
to maintain the temperature at Tf.
Criteria of phase stability

Thermodynamic criteria of phase stabilities


Chemical potential ( ):

For one component system,


 ≡ Molar Gibbs energy

i e. Spontaneous change  A decrease in chemical potential (Gibbs energy)


μ ≡ Gm

i.e. Criterion of phase equilibrium


: a consequence of 2nd law of thermodynamics
At equilibrium, the chemical potential of a substance
is the same throughout a sample, regardless of how
μ2
many phases are present.
* Calculation of Gibbs energy change when the infinitesimal dn
amount dn of the substance is transferred from one location
to the other. μ1
Gibbs energy The overall change of Gibbs energy is
dG = − μ1dn + μ2dn = (μ2 − μ1)dn
At equilibrium, dG=0 , μ2 = μ1
Phase boundaries
• Phase diagram :
A phase diagram of a pure substance shows the
regions of pressure and temperature at which its
various phases are thermodynamically stable.

• Phase boundary:
lines separating the regions in a phase diagram
showing the values of p and T. Two phases
coexist in equilibrium at the phase boundaries.
• Vapor pressure of a liquid or solid is
the pressure exerted by
the vapor in equilibrium with the
condensed phase.
Vapor pressure of a substance increases
with temperature.
Characteristics of phase transitions

In an open vessel,
When a liquid is heated, a liquid vaporizes
from its surface.
When the vapor pressure is equal to the
external pressure,
vaporization occurs throughout the bulk of
the liquid.

Boiling temperature
: the temperature at which the vapor
pressure of a liquid is equal to the external
pressure.
Normal boiling point
: the boiling point when the external Pex
pressure is 1 atm.
Standard boiling point
: the boiling point when the external
pressure is 1 bar
Characteristics of phase transitions
In a closed vessel,
(a) A liquid is in equilibrium with its vapor.
(b) Boiling does not occur when a liquid is heated.
The density of the vapour increases as the temperature is raised.
At the same time, the density of the liquid decreases slightly as a result of its
expansion.
(c) The surface between the two phases disappears when the density of the
vapour is equal to that of the remaining liquid.
- Critical temperature (Tc)
: Temperature at which the surface between two phases disappears
- Critical pressure (Pc)
- Critical volume (Vc)
- At and above Tc, a single uniform phase  supercritical fluid
Characteristics of phase transitions
Melting temperature (freezing temperature)
: The liquid and solid phases of a substance coexist in
equilibrium
under a specified pressure,
Normal freezing point
: The freezing temperature when the pressure is 1 atm.
Standard freezing point
: The freezing temperature when the pressure is 1 bar.

Triple point: a point on a phase diagram at which the


three phase boundaries meet and all three phases are in
mutual equilibrium.
Phase rule
Phase rule:

F=C–P+2

F : variance, (number of degrees of freedom) = number of intensive variables.


C: number of components
= minimum number of independent species (ions or molecules).
ex) a mixture of ethanol and water  C=2
NaCl(aq) C=2 (NaCl and water. )
cf) Na+ ion, Cl− ion, and water
P: number of phases at equilibrium.
ex) ice : single phase, P=1
a slurry of ice and water : two phases, P=2
CaCO3(s)  CaO(s) + CO2(g) : two solid phases and one gas phase, P=3
* Single-component and single-phase system (C=1 and P=1), F=2
: Pressure and temperature may be changed independently.
* Two phases (i.e. ice and water) are in equilibrium (C=1, P=2) , F=1
: Temperature (or pressure) can be changed.
In this case, temperature and pressure can not be changed independently.
Phase diagrams
For a one-component system (e.g. water), F = 3 – P
* One phase (P=1), F=2
: Both p and T can be varied independently w/o changing the number of phases
 Single phase is represented by an area on a phase diagram.

* When two phases are in equilibrium (P=2), F=1


: P is not freely variable if T is set.
 At a given T, a liquid has a characteristic vapor pressure.
 Equilibrium of two phases is represented by a line.

* When three phases are in equilibrium (P=3), F=0


: The system is invariant.  Equilibrium of three
phases is represented by a point.

* Four phases can not be in equilibrium


in a one component system.
Phase diagram of CO2
*The liquid–vapor boundary
 how the boiling temperature varies with the pressure
*The solid–liquid boundary
 how the melting temperature varies with the pressure

Typical phase diagram


1) Positive slope of the solid–liquid boundary
 Melting temperature of solid carbon dioxide rises
as the pressure is increased.
2) Triple point lies above 1 atm,
 Liquid cannot exist at 1 atm whatever the temperature
 Solid sublimes when left in the open (dry ice).
3) At or above 5.11 atm, liquid can exist.
Phase diagram of water

The solid–liquid boundary has a negative slope up to 2 kbar


 Melting temperature decreases as the pressure is raised.
® More favorable for the ice to transform into the liquid water

as the pressure is raised.


 Liquid water has smaller volume than ice.
: partial collapses of ice-I structure on melting
Phase diagram for He

Helium behaves unusually because (1) the mass


of its atoms is so low and (2) their small
number of electrons results in less effective
interactions with their neighbors.
ex) Solid and gas phases of He are never in
equilibrium.
Helium (4He)
Two liquid phases
- He-I : a normal liquid
- He-II : a superfluid
(liquid phase that flows without viscosity)
Phase boundary between He-I and He-II : λ-line

You might also like