Physical Chemistry II

(CHE21M5)

Lecture #6:
Phase Equilibria: Pure substances
Elements Of Physical Chemistry, Peter Atkins & Julio de Paula, 5th
Ed, Chapter 5, From page 105
The thermodynamics
of transition

Phase 1: Liquid, Phase 2: vapour

Derivation 5.1: The variation
of G with Pressure (not for exam)
Δ𝑮𝒎 = VmΔP

From the derivation of ΔH = qp

Derivation 5.1: The variation
of G with Pressure (cont.)
 dG = VdP – SdT
At const P: VdP = 0
𝑷𝒇 dG = -SdT
𝑮𝒎(Pf) =𝑮𝒎(Pi) + 𝒏𝑹𝑻 𝒍𝒏
𝑷
Phase Diagrams: Definitions: Figure: Phase Diagram

• Phase: state of matter (solid, liquid and gas)

• Phase transitions: Phase changes without change of
chemical composition. Ice  water  gas (vapour)
• Phase diagram: graphical representation
of the variations in physical states of a substance
Phase
under different conditions of T and P. Shows which
boundary
state is thermodynamically most stable (Points A – E)
• Phase change occurs when phase boundary is crossed
• The transition temperature, Ttrs, between two
phases, such as between liquid and solid is the
temperature, at a given pressure, at which the molar
Gibbs energies of the two phases are equal
• A – Vapour phase is most stable, B –Liquid  vapour (boiling), C – Liquid phase
most stable, D – Solid  liquid (melting), E – Solid phase most stable
Phase Diagrams:
• Triple Point (TP): A point at which all 3 states coexist
• Critical Point (CP) is the point at which two phases of a substance
initially become indistinguishable from one another. It is the end
point of a phase equilibrium curve, defined by a critical pressure Tp
and critical temperature Pc. At this point, there is no phase boundary.
Example: The meniscus between steam and water vanishes at
temperatures above 374°C and pressures above 217.6 atm,
forming what is known as a supercritical fluid.
• Fusion(melting) (or freezing) curve – the curve on a phase diagram which represents the transition between
liquid and solid states
• Vaporization (or condensation) curve – the curve on a phase diagram which represents the transition
between gaseous and liquid states
• Sublimation (or deposition) curve – the curve on a phase diagram which represents the transition between
gaseous and solid states
• If the pressure exerted on a liquid is increased, while the temperature is held constant, what type of phase
transition will eventually occur? (see pink arrow)
Gibbs Phase Rule: F=1
F=2

• Gibbs Phase Rule for a system at equilibrium states: F = C – P + 2

F=1
• F = the number of degrees of freedom, intensive variable F=2
(T, P, mole fraction) that can be changed independently without
disturbing the number of phases in equilibrium F=0 F=2
F=1
• C = number of components in a system, minimum number of
independent species (matter) necessary to define the composition of
all the phases present in the system. C = 1 for pure water, C =2 for water/ethanol mixture
• P = number of phases at a specific point
• Examples: Pure water: One-component system. C = 1, simplifies to F = 3-P.
For 1 phase present: F = 3-1 = 2 (P & T can be varied independently)
For 2 phases present: F = 3-2 = 1 (we cannot freely vary P if we have set T)
- The equilibrium of 2 phases is represented by a line which shows how one variable
must change if another varied.
- This means any transition occurs at a definite temperature and given pressure.
For 3 phases present: F = 3 = 0 (there is no freedom to change either variable, its fixed,
Triple point)
Phase Diagram for H2O
• The S/l line (blue) has negative slope, as you
increase T the line decreases. So at high P, liquid
is favoured instead of solid. Hence liquid water
has higher density (mass/volume) than ice. This
is why ice floats on liquid water. (See red arrow
at 0 °C: solid  liquid) 6x10-3
atm
• At P = 1 atm: P is above the triple point: As you
increase T, solid will melt, then vaporize
• When P is below triple point: Solid will go
directly to gas when T is increased (sublimation
process)
• For melting: The melting point decreases as the P • The triple point for water occurs at a
increases (blue melting line) very low pressure
• For vaporization: The boiling temperature • Critical temperature is 374°C
increases as the pressure increases • The normal melting and boiling points of
water indicated at 1 atm
Phase Diagram for CO2
• Positive s-l line slope (typical of most substances). The
density of CO2 (s) > CO2(l) because solid is favoured at
high P. Melting T increases as P increases.
• The triple point (TP) is above atmospheric pressure. It
is impossible to get any liquid carbon dioxide at P ≤
5.11 atm regardless of T. When heated at 1 atm, solid
does not melt but sublimes.
• That means that at 1 atm pressure, carbon dioxide
will sublime at a T = -78°C. This is the reason that solid
carbon dioxide is often known as "dry ice". You can't Dry ice
get liquid carbon dioxide under normal conditions –
only the solid or the vapor.
• For a CO2 (s)  CO2(l) transition to be observed, T
must increase at P ≥ 5,11 atm
Phase Diagram for Helium
• Helium behaves unusually at low temperatures:
The solid and gas phases of helium are never in
equilibrium.
Liquid He-I Tcr = -271 OC
• However at low T: the atoms are so light that they
vibrate with a large amplitude motion even at very
low temperatures and the solid simply shakes Liquid
Superfluid
itself apart.
• Solid helium is obtained only by holding the atoms
together by applying pressure.
• Helium has two liquid phases: The phase marked
He-I in the diagram behaves like a normal liquid;
He-II is a superfluid because it flows without
-273 OC
viscosity
• Helium is the only known substance with a liquid–
liquid boundary in its phase diagram
 Phase diagram of Sulfur
• Sulfur exhibits a very complicated phase behavior The difficulty arises from the tendency of
S8 molecules to break up into chains (especially in the liquid above 159 OC) or to rearrange into
rings of various sizes (S6 to S20). Even the vapor can contain a mixture of species S2 through S10.
• Two solid phases: rhombic (Srh) and monoclinic (Smo). The names refer to the crystal structures in
which the S8 molecules arrange themselves. This gives rise to three triple points, indicated by the
numbers on the diagram.
• Total No. of phases: 4 (all 4 can never coexist)
• Srh changes into Smo at 96 only when heated slowly.
{Srh  Smo  S (g)}
• If heating is fast, Srh changes directly to liquid phase
{Srh  S(l)  S (g)}
• Three Triple Points: Srh <-> Smo <-> Sg
Smo <-> Sl <-> Sg
Srh <-> Smo <-> Sl
• Normal boiling at 445 OC
Rearrangements of the sulphur crystal
structure