CHE 18 REVIEWER • Transition Temperature, 𝑻𝒕𝒓𝒔 :

temperature when chemical

Phase Transformation
potentials are equal; for example,
How do we know the phase of a substance at μ𝑖𝑐𝑒 = μ𝑙𝑖𝑞𝑢𝑖𝑑 𝑤𝑎𝑡𝑒𝑟 at T = 0
a given pressure and temperature?

The Gibbs energy can give us the answer to

this question:

• Spontaneous processes have

negative changes in Gibbs free
energy
• For example, if you want to know the
most stable phase of water at a given
pressure and temperature, you can
calculate the Gibbs energies for each Rates of Phase Transitions
of the phases, compare them and
pick the lowest one Distinguish between them:
• Chemical potentials are equivalent • Spontaneity of Transition:
to molar Gibbs energies for pure thermodynamics may predict the
substances, so the phase with the spontaneity of the physical
lowest chemical potential will be the transformation, but not the rate at
most stable phase which it occurs
Stabilities of Phases • Rate of Transition: kinetics predicts
the rate at which a transition occurs,
• Phase: a form of matter that is but not the spontaneity
uniform throughout in both chemical
composition and physical state Consider the phase transition from diamond
• Phase Transition: Spontaneous to graphite:
conversion of one phase into Normal pressure and temperature,
another, occurring at a characteristic μ𝑑𝑖𝑎𝑚𝑜𝑛𝑑 > μ𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒
temperature for a given pressure
For change to take place, C atoms must
Consider water at p = 1 atm exchange positions, which is an incredibly
Ice is stable when T < 0, μ𝑖𝑐𝑒 < μ𝑙𝑖𝑞𝑢𝑖𝑑 𝑤𝑎𝑡𝑒𝑟 slow process for solids (except high
when T < 0 temperatures)

Liquid water is stable phase when T > 0, In gases and liquids, these changes can take
μ𝑖𝑐𝑒 > μ𝑙𝑖𝑞𝑢𝑖𝑑 𝑤𝑎𝑡𝑒𝑟 when T > 0 place rapidly, but in solids, thermodynamic
instability may be inherent in the system
 • Metastable Phases:
thermodynamically unstable phases
that persist due to kinetic hindrance

Phase Boundaries

• Phase Diagram: shows regions of

pressure and temperature where
phases are thermodynamically stable
Critical Points and Boiling Points
• Sublimation Vapor Pressure:
pressure of gas in equilibrium with In an open vessel, at the temperature where
solid phase the vapor pressure is equal to the external
• Phase Boundaries: separate regions pressure, free vaporization occurs
and show p and T where two phases throughout the liquid, and vapor can expand
exist in equilibrium freely into the surroundings. Free
• Vapor Pressure: pressure of a gas in vaporization is known boiling.
equilibrium with the liquid phase
• The normal boiling point, T𝑏 : is the
Vapor pressures increase with increasing T, temperature of free vaporization at a
as the Boltzmann distribution populates the pressure of 1.0 atm
higher energy states with increasing • The standard boiling point: is the
temperature temperature of free vaporization at a
pressure of 1.0 bar (0.987 atm) (e.g.,
water: 99.6°C for T𝑏 = 100°C)

In a closed vessel, boiling does not occur –

rather the vapor pressure and density of the
vapor increase with increasing temperature
(a) equilibrium, (b) increasing density & (c)
two densities equal, surface between phases
disappears

• Critical Temperature, T𝑐 and Critical

Pressure, P𝑐 : where interphase
surface disappears
• Supercritical Fluid: fills container and
interface no longer exists (figure c)
 • The solid-liquid boundary shows
variation of melting point with
temperature
• Glacier motion may result from
decrease in m.p. with increasing p
• At extremely high pressures,
different phases of ice come into
existence, as bonds between
The temperature at a specified pressure molecules are modified by huge
where the liquid and solid phases coexist in stresses
equilibrium is called the melting • Multiple triple points exist within the
temperature (or freezing temperature or diagram other than the lowest where
fusion temperature) vapor, liquid and ice coexist

• The standard freezing point, T𝑓 : is

the temperature of freezing at a
pressure of 1.0 atm (for water, T𝑓 =
0°)
• The standard freezing point: is the
temperature of freezing at a pressure
of 1.0 bar (0.987 atm) (negligibly
different from T𝑓 )

The point where all three phases exist in

equilibrium is called the triple point,
T3 (three phase boundaries meet)

• T3 occurs at a specific temperature

and pressure which are characteristic
of a substance
• T3 marks lowest pressure in which a Phase Diagram of Carbon Dioxide
liquid phase of a substance can exists • Positive slope of solid-liquid
Example: water, T3 = 273.16 K and 611 Pa boundary is characteristic of most
(6.11 mbar, 4.58 Torr) substances (m.p. increases as
pressure is increased)
Phase Diagram of Water
• Triple point lies above 1 atm,
• The liquid-vapor boundary shows implying that liquid CO2 cannot exist
variation of vapor pressure with at normal pressures (solid sublimes
temperature
 at normal pressures, hence the
name, “dry ice”)
• To obtain liquid CO2, p = 5.11 atm is
the minimum. For a cylinder of CO2(l)
at 25°C, the pressure of the gas must
be greater than 67 atm – gas comes
out of a Joule-Thomson throttle,
emerging into p = 1 atm, condenses
into a snow-like solid
• Supercritical CO2 (highly
compressed) is used in supercritical
fluid chromatography which
separates lipids are phospholipids,
and fuel oils into components; also, it
is used to decaffeinate coffee
Temperature Dependence of Phase
Stability

Temperature dependence of Gibbs energy is

ժG
expressed in terms of entropy, (ժT)𝑝 = -S.
Since the chemical potential of a pure
substance is the same as the molar Gibbs
energy, we can write:

As T increases, μ decreases and S𝑚 > 0, so:

slope of μ vs. T is negative
Phase Stability and Phase Transitions
Plot of μ vs. T is steeper for gases than
The thermodynamic criterion of equilibrium
liquids, since the S𝑚 (g) > S𝑚 (l). For solids and
is:
liquids, usually S𝑚 (s) < S𝑚 (l)
• At equilibrium, the chemical
Solids and Liquids:
potential of a substance is the same
throughout a sample, regardless of - Steep negative slope of μ(l) falls
how many phases are present below μ(s) when the temperature is
high enough (liquid becomes stable
phase and solid melts)
Liquids and Gases: Sample Problem 1

- μ (g) plunges downward as 1. Calculate the effect of chemical

temperature is raised (S𝑚 (g) high!), potentials of ice and water of
so the gas is the stable phase and the increasing the pressure from 1.0 bar
liquid vaporizes to 2.0 bar at 0°C. The density of ice is
p = 0.97 g cm^-3, and water is p =
Melting Response to Applied Pressure
0.999 g cm^-3
Most substances melt at a higher
temperature when subjected to pressure
(the pressure prevents the formation of a
less dense liquid phase) – an exception is
water, with p(l) > p(s) [i.e., V𝑚 (s) > V𝑚 (l)]

The variation of chemical potential with

pressure is:

So, the slope of chemical potential vs.

pressure is equal to molar volume

• Increase in pressure raises the

chemical potential of most pure
substances, because V𝑚 must be
greater than zero
• In (a), the freezing temperature
increases, and in (b) the freezing
temperature is lowered (these are
plots of negative entropy)
Applied Pressure and Vapor Pressure Location of Phase Boundaries

When pressure is applied to a condensed Locations of phase boundaries are found by

phase, the vapor pressure rises (molecules recognizing that when two phases are in
are squeezed out and escape as a gas) equilibrium, chemical potentials are equal
(phase α and β):
• Pressure can be exerted on the
condensed phase: (a) mechanically
or (b) subjecting it to an inert
pressurizing gas
• In case (b), vapor pressure is the Solve the equation for p in terms of T to get
partial pressure of the vapor in the boundary equation
equilibrium with the condensed
• When pressure is applied to a system
phase – this is the partial vapor
in which the two phases are in
pressure of the substance (it is
equilibrium (at a) the equilibrium is
possible that some of the inert gas
disturbed
can dissolve in the condensed phase
• It can be restored by increasing the
if it is a liquid, or perhaps solvate
temperature (moving the system to
some of the liquid molecules but we
state b)
will not treat these complications)
• So, there is a relationship between
The relationship between the vapor dp and dT, ensuring that the system
pressure, p, after an applied pressure change stays in equilibrium as each variable
of ΔP, and vapor pressure p*, in absence of is changed
additional pressure, is:

Vapor pressure increases when pressure

acting on condensed phase increases

Slopes of Phase Boundaries

P and T are changed infinitesimally such that

two phases stay in equilibrium with one
another – chemical potentials are initially
qual, and remain equal after these changes
(i.e., dμ𝛼 = dμ𝛽 ). For each phase:

After integration, an approximate equation

of the solid and liquid phase boundary is
written as
𝛥 𝐻 𝑇
Which rearranges to give the Clapeyron p = p* + 𝛥𝑓𝑢𝑠 𝑉 ln (𝑇∗)
𝑓𝑢𝑠
equation:
when T is close to T* (the melting
dp 𝛥𝑡𝑟𝑠 𝑆
= temperature when pressure is p*)
𝑑𝑇 𝛥𝑡𝑟𝑠 𝑉
𝑇 𝑇−𝑇∗ 𝑇−𝑇∗
Where 𝛥𝑡𝑟𝑠 𝑆 = S𝛼,𝑚 and 𝛥𝑡𝑟𝑠 𝑉 = V𝛽,𝑚 − ln(𝑇∗) = ln(1 + )≈
𝑇∗ 𝑇∗

V𝛼,𝑚 are entropy and volume of the because ln(1+x) ≈ x when x ‹‹ 1, we can
transition (exact expression for the slope of rewrite the above equation:
a phase boundary – applies to phase
(𝑇−𝑇∗)𝛥𝑓𝑢𝑠 𝐻
equilibrium of any pure substance) p ≈ p* + 𝑇∗(𝛥𝑓𝑢𝑠 𝑉)

Solid-Liquid Boundary plotting this equation as a function of T

Melting (fusion) has an enthalpy change yields a steep straight line
𝛥𝑓𝑢𝑠 𝐻 occurs at T. molar entropy at melting Liquid-Vapor Boundary
at T is 𝛥𝑓𝑢𝑠 𝐻/T, and we write the Clapeyron
equation as • Entropy of vaporization at
temperature T is equal to 𝛥𝑓𝑢𝑠 𝐻/T.
𝑑𝑝 𝛥𝑓𝑢𝑠 𝐻
= The Clapeyron equation for the
𝑑𝑇 𝑇(𝛥𝑓𝑢𝑠 𝑉) liquid-vapor boundary is
𝛥𝑓𝑢𝑠 𝑉 is change in molar volume on melting 𝑑𝑝 𝛥𝑣𝑎𝑝 𝐻
=
𝑑𝑇 𝑇(𝛥𝑣𝑎𝑝 𝑉)
• Enthalpy of melting is positive
(except He^3) and volume change is 𝛥𝑣𝑎𝑝 𝐻 is positive, 𝛥𝑣𝑎𝑝 𝑉 is large and
usually +ve and small, so dp/dT is positive, so dp/dT is positive, but not as
steep and positive steep a slope as for the solid-liquid boundary
• Formula for boundary is obtained by dT/dp is large, boiling temperature is more
integration assuming that 𝛥𝑓𝑢𝑠 𝐻 and responsive to pressure than the freezing
𝛥𝑓𝑢𝑠 𝑉 are constant (very small temperature
changes):
to estimate the size of the effect of Solid-Vapor Boundary
increasing p on the b.p. of liquids:
This is treated exactly in the manner as the
𝛥𝑣𝑎𝑝 𝑉 = V 𝑚 (𝑔) − V𝑚 (𝑙) ≈ V𝑚 (𝑔), (since liquid-vapor boundary, replacing 𝛥𝑣𝑎𝑝 𝐻 with
V𝑚 (𝑔) ›› V𝑚 (𝑙)) 𝛥𝑠𝑢𝑏 𝐻, the enthalpy of sublimation
dP 85 J K−1 mol−1 Since 𝛥𝑣𝑎𝑝 𝐻 < 𝛥𝑠𝑢𝑏 𝐻, the equation predicts
= = 3.4 x 10^3 Pa K^-1
𝑑𝑇 25 𝑥 10−3 m3 mol−1 K
a steeper slope for the sublimation curve
This is 0.034 atm K^-1, so dT/dP = 30 atm^-1 than the vaporization curve at similar
(+0.1 atm pressure change alters the boiling temperatures
point by approximately +3 K)

Since V𝑚 (𝑔) ›› V𝑚 (𝑙), 𝛥𝑣𝑎𝑝 𝑉 ≈ V𝑚 (𝑔). If

gas behaves perfectly, V𝑚 (𝑔) = RT/p
dP 𝛥𝑣𝑎𝑝 𝐻 d ln 𝑝 𝛥𝑣𝑎𝑝 𝐻
= , =
𝑑𝑇 𝑇(𝑅𝑇/𝑝) 𝑑𝑇 RT2

Since dx/x = d ln x. if 𝛥𝑣𝑎𝑝 𝐻 is independent

of temperature, then integration of this
equation yields • Note the very similar slopes where
the solid and liquid boundaries meet
𝛥𝑣𝑎𝑝 𝐻 1 1
p = p* e^-x, X = (𝑇 - T∗)
R Ehrenfest Classification of Phase
where p* is the vapor pressure when Transitions
temperatures is T*, and p for T (as shown in
• Common phase transitions: fusion
the plot) – this plot will not extend beyond,
vaporization
T𝑐 , since there is no liquid phase at that point
• Less common phase transitions:
solid-solid conducting-
superconducting fluid-superfluid
• Paul Ehrenfest – came up with a
classification scheme for phase
transitions, based on the
thermodynamic properties of
substances

Many phases transitions are accompanied by

changes in enthalpy and volume – these
changes can alter the chemical potentials on
both sides of the phase transition. For
example, phase α changing to phase β:
 ժ𝜇𝛽 ժ𝜇𝛼 increases well before the transition, and
( )𝑇 − ( ) = 𝑉𝛽,𝑚 − 𝑉𝛼,𝑚 = 𝛥𝑡𝑟𝑠 𝑉
ժ𝑝 ժ𝑝 𝑇 occurs in:

ժ𝜇𝛽 ժ𝜇𝛼 • Order-disorder transitions in alloys

( )𝑇 − ( ) = −𝑆𝛽,𝑚 + 𝑆𝛼,𝑚
ժ𝑝 ժ𝑝 𝑇 • Ferromagnetic materials
𝛥𝑡𝑟𝑠 𝐻 • Fluid-superfluid transition in liquid
= −𝛥𝑡𝑟𝑠 𝑉 = −
𝑇𝑡𝑟𝑠 helium
𝛥𝑡𝑟𝑠 𝑉 and 𝛥𝑡𝑟𝑠 𝐻 are nonzero for fusion and
vaporization, so slopes of μ as functions of p
or T on each side of the phase transition are
different

• First order phase transition: first

derivative of μ w.r.t T is
discontinuous
• Second order phase transition: first
derivative of μ w.r.t T is continuous,
but second derivative is
discontinuous

C𝑝 of a substance is the slope of the plot of

enthalpy wrt temperature; at the transition,
H changes by a finite amount, so at the
• Order-disorder transition in β-brass
transition, the heat capacity is infinite: i.e.,
(CuZn) is λ-transition
heat drives the transition instead of raising
a) Low T phase: orderly arrangement of
temperature
atoms
λ-transition b) Islands of disorder appear as T
increased
The λ-transition is a phase transition that is
c) Islands grow and merge at the
not first-order, but has infinite heat capacity
transition temperature (742 K),
at the transition – the heat capacity
 where heat capacity increases an – after which, all sides of the unit cell
drives the transition increase at the same rate
• This tetragonal-cubic solid-solid
Second-Order Phase Transition in a Solid
phase transition does not involve
Change of symmetry of a crystal structure in discontinuity in energy between
a solid is an example of a second-order atoms of the volume they occupy: so,
phase transition it is not a first-order transition

• At first, the crystal has a unit cell Liquid Surfaces: Surface Tension
(smallest repeating unit in the
A unique feature of behavior of liquids is that
crystal) which is tetragonal in
they typically adopt a shape which
symmetry, meaning that one axis of
minimizes their surface area
the unit cell is longer than the other
two, which are equal • Smallest surface-to-volume ratio:
• As T is increased, the shorter spherical droplet
dimensions of the unit cell increase • Maximum number of molecules in
faster than the longer dimension the bulk volume interacting with
neighboring molecules
• Other forces may compete against
tendency to form an ideal shape
(e.g., gravity flattens droplets into
puddles, lakes ad oceans)
• Helmholtz and Gibbs energies are
used to describe the amount of work
needed to change the surface area.
Under different conditions, dA and
dG are equal to the work done in
changing the energy of a system

Work needed to change surface area, σ, of a

sample by an infinitesimal amount dσ is
proportional to dσ

dw = ϒ dσ

where ϒ is a proportionality constant known

• At some point, the sides of the cell as surface tension, having dimensions J m^-
become equal, and the crystal is said 2 or N m^-1 (since 1 J = 1 N m). At constant V
to have cubic symmetry at this point and T:

dA = ϒ dσ
Helmholtz energy decreases, dA < 0, if At the surface things are different. There is
surface area decreases, dσ < 0, so surfaces no up pull for very down pull, since of course
have a natural tendency to contract there is no liquid above the surface; thus, the
surface molecules tend to be pulled back
Example: calculate work need to raise a wire
into the liquid. It takes wok to pull a
of length L and to stretch the surface
molecule up to the surface. If the surface is
through liquid of height h as shown on the
stretched – as when you blow up bubble – it
left.
becomes large in area, and more molecules
are dragged from within the liquid to
become part of this increased area. This
“stretchy skin” effect is called surface
tension. Surface tension plays n important
role in the y liquid behave. If you fill a glass
with water, you will be able to add water
above the rim of the glass because of surface
When wire o length L is raised by height h in tension
increases the liquid surface area by twice the
area of the rectangle (there is a surface on
each side)

Total area: 2Lh

Work done: 2ϒLh
Because: w = F x d = 2ϒL x h

ϒL is an opposing force on the wire of the

length this is why ϒ is called tension, and
units are chosen to be N m^-1

High Surface Tension of Water

• Within the water, at least a few

molecules away from the surface,
every molecule is engaged n a tug of • Water has a much high surface
war with its neighbors on every side tension than most other liquids, due
– strong hydrogen bonding to the strong cohesive
interactions. For every “up” pull intermolecular interactions within
there is a “down” pull, and for every the bulk material arising from
“left” pull there is a “right” pull, an hydrogen bonding. At the surface,
so on, so that any given molecule there are additional adhesive forces
feels no net force at all.
The square area shown below on the surface The difference in pressure decreases to zero
of water is subject to forces of tension (N as the radius of the curvature becomes
m^-1) in each direction, making the surface infinite (i.e., flat surface)
behave as a stretchy skin

Curved Surfaces Small cavities, small radii of curvature,

Surface area may be minimized by the produce huge pressure differences
formation of a curved surface, such as Cavities in a liquid are at equilibrium when
bubble. There are two consequences of this tendency for their surface rea to decrease is
curvature: balanced by a corresponding rise in internal
1. Vapor pressure of liquid depends on pressure
the curvature of its surface • If pressure in a cavity is p𝑖𝑛 & radius
2. Capillary rise and fall of liquids in = r outward force is p x A = 4π𝐫 𝟐 𝐩𝒊𝒏
narrow tubes • Inward Forces: arise from external
• Bubble: a region in which vapor pressure and surface tension, with
(possibly air as well) is trapped by a magnitude 4π𝐫 𝟐 𝐩𝒐𝒖𝒕 + 8πϒr
thin film – two surfaces, one on each
side of the film The latter is calculated as follows, the change
• Cavity: a vapor-filled hole in a liquid in surface area when radius changes from r
(gas bubbles in liquids are strictly to r+ dr is
defined as cavities) – one surface dσ = 4π(r + dr)2 - 4πr 2 = 8πr dr
touching a vapor
• Droplet: small volume of liquid at Ignoring the small (dr)2, work done on the
equilibrium surrounded by a vapor surface is
• Laplace Equation: pressure on the dw = 8πϒr dr
concave side of the interface, p𝑖𝑛 is
Since w = F x d, force opposing stretching
always greater than the pressure on
through when radius is r is F = 8πϒr
the convex side, p𝑜𝑢𝑡 , and these
pressures are related Total inward force is 4πr 2 p𝑜𝑢𝑡 + 8πϒr. At
2ϒ equilibrium, outward and inward forces are
p𝑖𝑛 = p𝑜𝑢𝑡 +
𝑟 balanced, so

4πr 2 p𝑖𝑛 = 4πr 2 p𝑜𝑢𝑡 + 8πϒr

The vapor pressure of a liquid depends on close the opening by flipping the
the pressure applied to a liquid – since wand over, the tension in the bubble
curving the surface gives rise to pressure skin tries to shrink the bubble into a
difference of 2ϒ/r, the vapor pressure above shape with the smallest possible
a curved surface should be different from a surface area for the volume of air it
flat surface. We can use the Kelvin equation contains. That shape happens to be
to calculate the vapor pressure of a liquid a sphere
when dispersed as droplets of radius r
Nucleation
𝑉𝑚𝛥𝑃/𝑅𝑇
p = p*e
For water droplets of radius 1 μm and 1nm,
If the applied pressure ΔP = 2ϒ/r, then ratios p/p* at 25°C are about 1.001 and 3,
2ϒ𝑉𝑚
respectively (though in the latter case, the
p = p*e 𝑟𝑅𝑇 droplet is only 10 molecules in diameter, and
where p* is the vapor pressure of the liquid the calculation is bit suspect)

The effect is small, but can have some

• An analogous expression for the
important consequences
vapor pressure inside the cavity can
also be obtained from the above Consider cloud formation:
equation: since the pressure outside
• Warm moist air rises into
the cavity is less than the pressure
atmosphere
inside, we simply change the sign of
the exponent • Temperature decreases, at some
point vapor becomes
Shapes of Bubbles thermodynamically unstable (i.e.,
• A bubble, like a balloon, is a very thin wants to condense
skin surrounding volume of air. The • Swarm of water molecules
rubber skin of the balloon is elastic congregates into a small droplet, so
and stretches when inflated. The small, that it has an enhanced vapor
liquid skin of the bubble is stretchy, pressure – it is so small, instead of
somewhat like piece thin rubber, growing it evaporates (the vapor is
and like a balloon it pushes the air stabilized, tendency to condense is
out of the bubble, leaving a flat circle overcome by heightened tendency
of soap in a bubble wand. Unlike a to evaporate) that is, it
sheet of rubber that when supersaturated:
unstretched loses all tension, a - Thermodynamically unstable
bubble always has its “stretch” no with respect to liquid
matter how small the surface - Not unstable wrt small droplets
becomes. If you blow a bubble and before bulk liquid phase is
formed
 sharp-edged glass or porous
activated carbon flakes in the
beaker prevent this, providing
nucleation centres for the
molecules in the heated liquid to
attach themselves

Nucleation is necessary for phase transitions

to occur at the normal phase transition
temperatures – this is the formation of a
small bubble (heating liquid-vapor) or crystal
Two mechanisms of cloud formation:
(cooling liquid-solid) that acts as the
1. Sufficiently large number of interface between the two phases. In the
molecules congregate into a large absence of nucleation sites, phase transition
droplet so big that enhanced T’s change dramatically. Homogenous or
evaporation is negligible spontaneous nucleation is very improbable
(spontaneous nucleation) – very low
Example: H2O freezes at -42°C if it is cooled
probability of this happening in a
in a perfectly smooth container with no dust
cloud
particles, crystals, etc. present to act as
2. Minute dust particles and other
nucleation sites.
foreign matter nucleate
condensation (i.e., centres are Example: for boiling liquids, nucleation most
provided around which the often happens on the heating surface, at so-
condensation can occur) – water called nucleation sites, which may be tiny
molecules attach and condense crevices on a rough surface or rough
Liquids may be superheated above boiling particles introduced into the solution (e.g.,
temperature and supercooled below CO2 bubbles in pop bottles; bubbles on side
freezing temperatures – thermodynamically of container during boiling). At these sites,
stable phase is not achieved, on account of tiny gas-liquid interfaces (surfaces) are
kinetic stabilization occurring in the absence thermodynamically stabilized. If a liquid is
of nucleation centres degassed, and heating surfaces are clean
and smooth, superheating happens
• Superheating: vapor pressure inside
of a cavity that form tend to collapse • Suitably, sized nuclei must grow or
(encountered in heating water in be present in order for phase
breaker without stirring – violent transitions to occur. So, it is possible
bumping occurs, from spontaneous to superheat liquids above T𝑏 and to
nucleation leads to large bubbles big supercool liquids below T𝑓 since
enough to survive) – small piece of there are energy barriers between
 the phases; a bubble or microcrystal
(of the new phase) must form before
the phase transition can proceed.
So, a bubble can’t grow b/c of the
surface tension σ: small bubbles pay
a large cost in the surface tension for
small gain in volume of the new
phase. A nucleation surface helps to
bypass this barrier

Capillary Action

The tendency of liquid to climb up capillary Capillary Depression

tubes (narrow bore tubes) is known as
capillary action, and it results from surface • if adhesive forces between the liquid
tension and the wall are weaker than
cohesive forces in the liquid (e.g., Hg
• Narrow tube is immersed in water, in glass) liquid in the tube retracts
any liquid entering the tube adheres from the walls, curving the surface
to the walls with the high-pressure concave side
• Energy is lowest when thin film downwards (this is capillary
covers as much of the glass as depression). To equalize pressure at
possible the same depth, surface falls to
• As the film creeps up the wall, the compensate for heightened pressure
liquid surface becomes curved arising from its curvature
(meniscus) • mercury in a thermometer or
• The pressure beneath the meniscus barometer exhibits capillary
is less than the atmosphere by 2ϒ/r, depression
where r is the tube radius (assume
hemispherical surface, and p𝑖𝑛 =
p𝑜𝑢𝑡 + 2ϒ/r)
• Pressure immediately under the flat
surface outside the tube is p, under
the curved meniscus p - 2ϒ/r
• Excess external pressure forces the
liquid up the tube until hydrostatic
equilibrium has been achieved
(equal pressures at equal depths)
Capillary Rise process itself and to a lesser extent with the
types of non-ideal interactions which can
• pressure exerted by a column of
take place between different substances.
liquid of density of p and height h is
We will also start to learn how to deal with
ρ = ρgh
liquid solutions, which will increase the
• hydrostatic pressure matches the
arsenal of the systems that we know how to
pressure difference 2ϒ/r and ρgh
2ϒ
deal with
h = ρgr
• Mainly, we will deal with non-
This is an easy way of now measuring the reactive binary mixtures, which have
surface tension of liquids, which tend to components A and B, making use of
decrease with increasing temperature (e.g., the relation:
water is shown on the left) X𝑎 + X𝑏 = 1
• We have already used such mole
If water at 25°C rises 7.36 cm in 0.20 mm
fractions to escribe the partial
capillary tube, surface tension is
pressures of mixtures of gases which
give rise to a total pressure

Partial Molar Volume

• The partial molar volume: is the

contribution that one component in
a mixture makes to the total volume
of a sample

SIMPLE MIXTURES

We now go from the behavior of simple

single substances systems to mixtures of The difference increase in total volume in
substances. In general, these will still be non- the H2O/EtOH example depends on the
reacting substances and we will be dealing identity of the molecules that surround H20.
mostly with the energetics of the mixing The EtOH molecules pack around the water
molecules (i.e., solvate) differently than how • The partial molar volume: is the
water molecules pack around water slope of a plot of total volume as the
molecules: the increase in the molar volume amount of J in the sample is changed
is only 14 cm^3/mol (volume vs. composition)
• For a binary mixture, the
• Partial molar volume of substance A
composition can be changed by
in a mixture is the change in volume
addition of dn𝐴 of A and dn𝐵 of B,
per mole of A added to the large
with the total volume changing by
volume of the mixture
• The partial volume of components of
a mixture vary as the mixture goes
from pure A to pure B – that is
because the molecular environments
of each molecule change (i.e.,
packing, solvation, etc)
• If partial molar volumes are known
for the to components, then at some
temperature T, the total volume V
(state function, always positive) of
the mixture is
V = 𝑛𝐴 𝑉𝐴 − 𝑛𝐵 𝑉𝐵

• Partial molar volumes of a water-

ethanol binary mixture are show at
25°C across all possible compositions
• The partial molar volume, V𝑗 , of a
substance J is defined as

• Partial molar volumes vary with

composition (different slope at
compositions a and b) – partial molar
volume at b is negative (i.e., the
overall sample volume decreases as
- where n signifies that all other
A is added)
substances present are constant
 • The partial molar volume can be
measured by fitting the observed
volume (as function of composition)
using a curve fitting program (find
the parameters that give the best fit
• So chemical potential of a substance
of a particular function to the
is the slope of the total Gibbs energy
experimental data)
of a mixture wrt amount of substance
If the function is found, the slope at any of interest, J
point (any composition) can be determined
Total Gibbs energy is
by differentiation; for example, if V has the
following function G = 𝑛𝐴 𝜇𝐴 − 𝑛𝐵 𝜇𝐵

V = A + Bn𝐴 + C(n2𝐴 − 1) Where 𝜇𝐽 are chemical potential of the

substances in a mixture make a contribution
With constants A, B and C (note this is not A
to the total Gibbs energy of the substance
and B), then the partial molar volume of A at
any composition is • Gibbs energy depends on
composition, pressure and
temperature (so, G may change if any
of these variables change – which
they may). For a system with
components A, B, …
And the partial molar volume of component
dG = V dp – SdT + 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵
B is obtained by rearranging
• Which is a fundamental equation of
V = 𝑛𝐴 𝑉𝐴 − 𝑛𝐵 𝑉𝐵 classical thermodynamics
𝑉 − 𝑛𝐴 𝑉𝐴 𝐴 − (n2𝐴 − 1)𝐶
𝑉𝐵 = = At constant temperature and pressure,
𝑛𝐵 𝑛𝐵
Partial Molar Gibbs Energy dG = 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵 + ⋯

• The concept of partial molar In chapter 4, we saw that under these

quantity can be applied to any conditions, dG = d𝑤𝑒,𝑚𝑎𝑥 (the maximum
extensive state function. For non-expansion work)
example, for a substance in a d𝑤𝑒,𝑚𝑎𝑥 = 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵 + ⋯
mixture, the chemical potential ca be
defined as the partial molar Gibbs what does this mean? Non-expansion work
energy can happen just from changing system
composition at constant pressure and
temperature (e.g., battery, chemical rxn in
two sites called electrodes, and the work the
battery produces comes from reactants 𝑛𝐴 𝑑𝜇𝐴 + 𝑛𝐵 𝑑𝜇𝐵 = 0
going to products)
This special case holds for multiple
More on Chemical Potential components, and is the Gibbs-Duhem
equation
Chemical potentials tell us even more than
just about variation in G

G = U + pV – TS

So for an infinitesimal change in U, we can

write So, for our binary mixture, if one partial
molar quantity increases, the other must
decrease
𝑛𝐴
𝑑𝜇𝐵 = − 𝑑𝜇
𝑛𝐵 𝐴
This holds for all partial molar quantities – in
binary mixtures, the partial mola quantity of
one component can be determined from
And at constant volume and entropy
measurements of the other
dU = 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵 + ⋯
Thermodynamics of Mixing
ժ𝑈
𝜇𝐽 = ( ) Dependence of Gibbs energy on mixture
ժ𝑛𝑗 𝑆.𝑉,𝑛′
composition is
And if that’s not enough… what about H and G = 𝑛𝐴 𝜇𝐴 − 𝑛𝐵 𝜇𝐵
A??? These too also depend upon the
composition of a mixture. Chemical And at constant T and p, systems tend
potential is IMPORTANT towards a lower Gibbs energy

ժ𝐻 ժ𝐴 • The simplest example of mixing:

(a) 𝜇𝑗 = (ժ𝑛 )𝑆,𝑝,𝑛 (b) 𝜇𝑗 = (ժ𝑛 ) 𝑇,𝑉,𝑛
𝑗 𝑗 what is the Gibbs free energy if we
Gibbs-Duhem Equation take two pure ideal gases and mix
them together? Consider gas A and
Since G = 𝑛𝐴 𝜇𝐴 − 𝑛𝐵 𝜇𝐵 , and 𝜇𝐽 depend on gas B, both in separate containers at
composition, for a binary mixture G may pressure p at temperature T.
change by
The chemical potentials are at their “pure
dG = 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵 + 𝑛𝐴 𝑑𝜇𝐴 + 𝑛𝐵 𝑑𝜇𝐵 values” at this point. Gibbs energy is
But at constant temperature and pressure,
since G is a state function
 𝛥𝑚𝑖𝑥 𝐺 = 𝑛𝑅𝑇 (𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 )

Since the mole fractions are never greater

than 1, the ln terms are negative, and 𝛥𝑚𝑖𝑥 𝐺
>0

This allows us to conclude that mixing

processes are spontaneous, and gases mix
We can simplify things by letting p denote spontaneously in all proportions
the pressure relative to p°, writing • Mixing of gas and effusion
𝐺1 = 𝑛𝐴 {𝜇𝐴° + 𝑅𝑇 ln 𝑝} + 𝑛𝐵 {𝜇𝐵° + 𝑅𝑇 ln 𝑝} Other Thermodynamic Mixing Functions

Since (ժG/ժT)𝑝,𝑛 = -S and 𝛥𝑚𝑖𝑥 𝐺 = nRT

(𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 ). It follows that for a
mixture of perfect gases, the entropy of
mixing is
ժ𝛥𝑚𝑖𝑥 𝐺
𝛥𝑚𝑖𝑥 𝑆 = − ( )
ժ𝑇 𝑝,𝑛𝐴 ,𝑛𝐵

= −𝑛𝑅(𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 )

Since ln x < 0, then 𝛥𝑚𝑖𝑥 𝑆 > 0 for all

compositions

• We expect this increase in disorder,

since dispersal of one gas into
Gibbs Energy of Mixing
another implies greater disorder in
After mixing, the partial pressures of the the system
gases are 𝑝𝐴 and 𝑃𝐵 , where the total
Example:
pressure is p = 𝑝𝐴 + 𝑝𝐵 . The total Gibbs
energy is then 𝛥𝑚𝑖𝑥 𝐺 = (4.0 mol)RT ln 2, so 𝛥𝑚𝑖𝑥 𝑆 = (4.0
mol)R ln 2 + 23 J K^-1
𝐺1 = 𝑛𝐴 {𝜇𝐴° + 𝑅𝑇 ln 𝑝𝐴 } + 𝑛𝐵 {𝜇𝐵°
+ 𝑅𝑇 ln 𝑝𝐵 } The isothermal isobaric enthalpy of mixing
of two gases is found from ΔG = ΔH – TΔS,
The difference in Gibbs energies, 𝐺𝑓 − 𝐺𝑖 , is
and we find
the Gibbs energy of mixing
𝑝𝐴 𝑝𝐵 𝛥𝑛𝑢% 𝐻 = 0
𝛥𝑚𝑖𝑥 𝐺 = 𝑛𝐴 𝑅𝑇 ln( ) + 𝑛𝐵 𝑅𝑇 ln( )
𝑝 𝑝
We use mole fractions, replacing 𝑛𝑗 with 𝑥𝑗 𝑛:
This is expected for a system in which there The chemical potential of A depends on its
are no interactions between the molecules partial vapor pressure, it follows that
in the mixture chemical potential of liquid A is related to its
partial pressure

Raoult’s Law
Chemical Potentials of Liquids
After experimenting with mixture of similar
• Quantities relating to pure liquids, the French chemist Francois Raoult
substances will be denoted with found the ratio of the partial vapor pressure
asterisks, so the chemical potential of of each component to its vapor pressure as a
pure liquid A is 𝜇𝐴 *(l). Since the vapor
pure liquid, 𝑝𝐴 /𝑝𝐴 *, is approximately equal
pressure of pure liquid is A is 𝑝𝐴 *, the to the mole fraction of a in the liquid mixture
chemical potential of a in the vapor is
𝜇𝐴 ° + RT ln 𝑝𝐴 * (𝑝𝐴 * as relative 𝑝𝐴 = 𝑥𝐴 𝑝𝐴 *
𝑝𝐴 */p°) • Some mixtures obey Raoult’s law
Chemical potentials are at equilibrium: very closely, especially when they are
structurally similar – these are called
𝜇𝐴 * = 𝜇𝐴 ° + RT ln 𝑝𝐴 *
ideal solutions, and they obey
If another substance is present (e.g., a solute
𝜇𝐴 = 𝜇𝐴 ° + RT ln 𝑥𝐴
in the liquid), chemical potential of A in the
liquid is 𝜇𝐴 and vapor pressure is 𝑝𝐴

𝜇𝐴 = 𝜇𝐴 ° + RT ln 𝑝𝐴

Combine to eliminate the standard

potential:
𝑝
𝜇𝐴 = 𝜇𝐴 ° + RT ln ( 𝑝 𝐴∗)
𝐴
 𝐾
𝑘𝑥𝐴 = 𝑘′𝑝𝐴 , 𝑝𝐴 = , 𝑥𝐴
𝐾

𝐾
For a pure liquid, 𝑥𝐴 = 1, so 𝑝𝐴 ’ = 𝐾

Departure from Raoult’s Law, Diute

Solutions

Some solution mixtures behave very

differently from Raoult’s law, notably with
mixtures of structurally and chemically
dissimilar liquids

• Ideal dilute solution, consider the

solute (B): Henry’s Law
𝑝𝐵 = 𝑥𝐵 𝐾𝐵
Molecular Interpretation of Raoult’s Law • Ideal solution, consider the solvent
(A): Raoult’s Law
We have to consider the rate at which 𝑝𝐴 = 𝑥𝐴 𝑝𝐴 *
molecules leave and enter solution to
• When the solvent is nearly pure (i.e.,
understand Raoult’s Law
B is the major component), it has a
• The presence of a second vapor pressure proportional to the
component hinders molecules from mole fraction with slope 𝑝𝐵 *
leaving the solution, but does not • When B is the minor component (the
inhibit the rate at which they return solute) the vapor pressure has a
• The rate at which A molecule leave different constant of proportionality
the surface is proportional to the Henry’s Law
number of them at the surface,
which is proportional to their mole The English chemist William Henry found
fraction that for real solutions at low concentrations,
Rate of vaporization = 𝑘𝑥𝐴 although the vapor pressure of the solute is
• Where k is a proportionality proportional to the mole fraction, the
constant. The rate at which constant of proportionality is not the vapor
molecules return is proportional to pressure of the pure substance
their gas phase concentration, which 𝑝𝐵 = 𝑥𝐵 𝐾𝐵
is proportional to their partial
pressure Here 𝑥𝐵 is the ole fraction of the solute B,
Rate of condensation = 𝑘′𝑝𝐴 and 𝐾𝐵 is an empirically determined
constant with pressure dimensions. 𝐾𝐵 is
At equilibrium, rates of vaporization and chosen so that a plot vapor pressure of B
condensation are equal, so
against mole fraction is tangent to the Liquid Mixtures
experimental curve at 𝑥𝐵 = 0
Gibbs energy of mixing for two liquids is
Such solutions are called ideal-dilute calculated the same as for gases. For two
solutions liquids A and B (note that * signifies pure
substance):
• Solvent: behaves like a slightly
modified pure liquid G𝑖 = 𝑛𝐴 𝜇𝐴 ∗ +𝑛𝐵 𝜇𝐵 ∗
• Solute: behaves entirely differently
Upon mixing, the chemical potentials are
from its pure state (since its
given by 𝜇𝑗 = 𝜇𝑗 ∗ + RT ln 𝑥𝑗
molecules are surrounded by solvent
molecules), unless the molecules of 𝐺𝑓 = 𝑛𝐴 {𝜇𝐴 *+ RT ln 𝑥𝐴 } + 𝑛𝐵 {𝜇𝐵 *+ RT ln 𝑥𝐵 }
the two components are very similar
Thus, the Gibbs energy of mixing is
Estimate the molar solubility of oxygen in
𝛥𝑚𝑖𝑥 𝐺 = 𝑛𝑅𝑇 (𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 )
water 25°C and partial pressure of 160 torr,
its partial pressure at sea level And the entropy of the mixing of two liquid
is
The amount of O2 dissolved is very small,
and 𝑥𝑗 = 𝑝𝑗 /𝐾, so 𝛥𝑚𝑖𝑥 𝑆 = −𝑛𝑅 (𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 )

Meaning that the ideal enthalpy of mixing is

zero

𝛥𝑚𝑖𝑥 𝐻 = 0

Same expressions as for mixing of two

perfect gas

Liquids Mixtures: Miscibility

Solution ideality is quite different from

So, the molar solubility of oxygen is 2.69 x perfect gas behavior:
10^-4 mol kg^-1 corresponding to
concentration of 2.7 x 10^-4 mol L^-1 • Perfect gases: no interactions
between the molecules
• Henry’s Law constants are very well • Ideal solutions: interactions
known by biochemists for treatment between molecules, but average of
of gas behavior in fats and lipids. interactions between A and B
Henry’s law is also very important in molecules is same as average
O2 is abnormal, such as in interactions A-A and B-B I pure
mountaineering, scuba diving, ang in liquids
the use of gaseous anesthetics
 • Real solutions: composed of but having different interactions with
molecules for which A-A, A-B, B-B another
interactions are all different from
a) The benzene/cyclohexane mixing,
one another
shows that mixing is endothermic
Sometimes, molecules of one type might b) Tetrachloroethane/cyclohexane
cluster together (additional contribution to mixing shows a volume contraction
entropy), so: at low, C2Cl4 fractions, and
expansion at high C2Cl4 fractions
• Enthalpy change might be large and
+ve Colligative Properties
• Negative entropy change Colligative properties literally denote
• Positive Gibbs energy for mixing properties which depend on a collection of
In this case, separation is spontaneous, and particles
liquids are immiscible (example, CCl4 and
• Boiling point elevation
H2O, which are non-polar and polar,
• Freezing point depression
respectively)
• Solubility of liquids and solids
• Liquids can also be partially miscible, • Osmotic pressure
which means that they are miscible
Each of these properties is going to depend
only in certain compositions
on the composition of the mixture (i.e., the
(partially dissolve in one another)
relative mole fractions of the components)
Real Solutions & Excess Functions
There is no reference in these properties to
• Thermodynamic properties of real the identities of the solutes and/or solvents
solutions are described with excess -strictly dependent upon composition
functions, 𝑋 𝐸
Important Assumptions:
• For example, the excess entropy, 𝑆 𝐸 ,
is the difference between the • Solute is not volatile, does not
observed thermodynamic function contribute to the chemical potential
and the function for an ideal solution: of the solvent vapor
𝑆 𝐸 = 𝛥𝑚𝑖𝑥 𝑆 - 𝛥𝑚𝑖𝑥 𝑆 𝑖𝑑𝑒𝑎𝑙 • Solute does not dissolve in solid
solvent (this is not the most common
So, the further excess energies re from zero
case, but does cut the mathematics
indicates the degree to which a solution is
down a lot) – so pure solid solvent
non-ideal – a regular solution has 𝐻 𝐸 − 0,
separates when the mixtures is
𝑆 𝐸 = 0, with two kinds of molecules
frozen
distributed randomly (like ideal solution),
All colligative properties result from • Liquid-solid equilibrium occurs at a
lowering of the chemical potential of the lower temperature (freezing point
solvent from the presence of a solute depression)

What causes the lowering of chemical a) Solvent with entropy S* & 𝑝𝐴 *, vapor
potential of a liquid? pressure reflects tendency to greater
entropy
• Not the energies of interactions
b) Solution with S > S*, therefore
between solvent and solute
weaker tendency to from gas (i.e.,
molecules, since lowering of energy
greater entropy), so 𝑝𝐴 < 𝑝𝐴 * and 𝑇𝑏𝑝
occurs even in idea solutions (𝛥𝑚𝑖𝑥 𝐻
= 0) is elevated
• Entropy mut be the driving force for
lowering the chemical potential of a
liquid once the solute has been
added

Solvents, Solutes and Entropy

There is no direct effect of the solute on the

chemical potential of the solvent vapor,
since solute is not in the vapor phase

Reduction of the chemical potential of the

solution (down from that of a pure liquid) Increased disorder in the liquid also opposes
implies that: tendency to freeze (go to higher order), so a
• Liquid-vapor equilibrium occurs at a lower temperature is required to hit solid-
higher temperature (boiling point liquid eqb.
elevation)
Boiling Point Elevation Where ΔT is the freezing point depression,
T* - T, and 𝛥𝑓𝑢𝑠 𝐻 replaces 𝛥𝑣𝑎𝑝 𝐻
Heterogenous equilibrium: between solvent
in solution and solvent vapor at 1 atm, where • Larger depressions are observed for
solvent is A and solute B (involatile) solvents with low 𝛥𝑓𝑢𝑠 𝐻 and high
melting points
• Equilibrium occurs at some
temperature when: • If solution is dilute, mole fraction ≈
𝜇𝐴 *(g) = 𝜇𝐴 *(l) + RT ln 𝑥𝐴 molality, b, of the solute, and
ΔT = 𝐾𝑓 𝑏
• The presence of some mole fraction
𝑥𝐵 causes and increase in the Where 𝐾𝑓 is the chemical potential
normal boiling point from T* to T* + cryoscopic constant
ΔT, where
𝑅𝑇∗2 Solubility
ΔT = 𝐾𝑥𝐴 , K = 𝛥
𝑣𝑎𝑝 𝐻
• Solubility: is a characteristic of the
The identity of solute is irrelevant: just the solute in a saturated solution. At a
mole fraction is important, so boiling point given temperature, the solubility of a
elevation is a colligative property value of ΔT substance is the concentration of a
depends on the solvent, biggest changes saturated solution at that
occur for solvents with high boiling points. temperature
For practical applications, mole fraction of B • Is solid and liquid are in contact, solid
is proportional to its molality, b (mol kg^-1), dissolves until the solution is
dilute solutions, and saturated (the equilibrium state).
ΔT = 𝐾𝑏 𝑏 Chemical potentials of solid solute,
𝜇𝐵 *, and B in the 𝜇𝐵 , are equal
𝐾𝑏 is the empirical (& unfortunately named)
ebullioscopic constant

Freezing Point Depression

Heterogeneous equilibrium: pure solid

solvent A and solution with solvent present
in mole fraction 𝑥𝐵 . At the freezing point:

𝜇𝐴 *(s) = 𝜇𝐴 *(l) + RT ln 𝑥𝐴

Only difference from boiling point elevation

is the presence of 𝜇𝐴 *(s) instead 𝜇𝐴 *(g).
Since: solute (in solution) – solute (solid)
Thus,
Then: μ (in solution) = μ (solid)
𝑅𝑇∗2
ΔT = 𝐾𝑥𝐵 , K = 𝛥
𝑣𝑎𝑝 𝐻
Solute (in solution): 𝜇𝐵 = 𝜇𝐵 *(l) + RT ln 𝑥𝐵
Eqb. μ’s is equal: 𝜇𝐵 *(s) = 𝜇𝐵 *(l) + RT ln 𝑥𝐵

• We wish to know the mole fraction of

solute B dissolved in solution at
temperature T, how do we get this?
Rearrange the eqb. Equation on the
previous slide, and substitute in the
Gibbs-Helmholtz equation:
∗ (𝑠)−𝜇 ∗ (𝑙) 𝛥𝑓𝑢𝑠 𝐺 𝛥𝑓𝑢𝑠 𝐻
𝜇𝐵 𝐵
ln 𝑥𝐵 = =− =− +
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝛥𝑓𝑢𝑠 𝑆
𝑅

𝛥𝑓𝑢𝑠 𝐻 𝛥𝑓𝑢𝑠 𝑆 𝛥𝑓𝑢𝑠 𝐻 𝛥𝑓𝑢𝑠 𝑆

ln 𝑥𝐵 = − + + −
𝑅𝑇 𝑅 𝑅𝑇∗ 𝑅

𝛥𝑓𝑢𝑠 𝐻 𝛥𝑓𝑢𝑠 𝐻
=− +−
𝑅𝑇 𝑅𝑇∗

𝛥𝑓𝑢𝑠 𝐻 1 1 𝛥𝑓𝑢𝑠 𝐻 𝑇−𝑇∗

=− (𝑇 − 𝑇∗) = ( 𝑇∗𝑇 )
𝑅 𝑅

• Where 𝛥𝑓𝑢𝑠 𝐻 and T* are for the pure

solute (which must be a non-
electrolyte). The expression becomes
les valis as we move further away
from T*, since 𝛥𝑓𝑢𝑠 𝐻 is known to
vary with temperature
• The plot on the RHS shows variation
of solute in saturated solution) with
temperature. Curve labels
=𝛥𝑓𝑢𝑠 𝐻/RT*. Solubility of B drops
exponentially as T is lowered from T*
(T/T* = 1 is the m.p. of pure B)