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Atkins 10th Ch4 PhysicalTransformationsOfPureSubstances
Atkins 10th Ch4 PhysicalTransformationsOfPureSubstances
Atkins 10th Ch4 PhysicalTransformationsOfPureSubstances
Physical transformations of
pure substances
Vaporization, melting (fusion), and the conversion of graph- diagram. The practical importance of the expressions we derive
ite to diamond are all examples of changes of phase without is that they show how the vapour pressure of a substance varies
change of chemical composition. The discussion of the phase with temperature and how the melting point varies with pres-
transitions of pure substances is among the simplest applica- sure. Transitions between phases are classified by noting how
tions of thermodynamics to chemistry, and is guided by the various thermodynamic functions change when the transition
principle that the tendency of systems at constant temperature occurs. This chapter also introduces the ‘chemical potential’, a
and pressure is to minimize their Gibbs energy. property that will be at the centre of our discussions of mix-
tures and chemical reactions.
➤➤ Why do you need to know this material? Brief illustration 4A.1 The number of phases
Phase diagrams summarize the behaviour of substances
under different conditions. In metallurgy, the ability to A solution of sodium chloride in water is a single phase
control the microstructure resulting from phase equilibria (P = 1). Ice is a single phase even though it might be chipped
makes it possible to tailor the mechanical properties of the into small fragments. A slurry of ice and water is a two-
materials to a particular application. phase system (P = 2) even though it is difficult to map the
physical boundaries between the phases. A system in which
➤➤ What is the key idea? calcium carbonate undergoes the thermal decomposition
CaCO3(s) → CaO(s) + CO 2 (g) consists of two solid phases
A pure substance tends to adopt the phase with the lowest
(one consisting of calcium carbonate and the other of calcium
chemical potential.
oxide) and one gaseous phase (consisting of carbon dioxide),
➤➤ What do you need to know already? so P = 3.
This Topic builds on the fact that the Gibbs energy is a Self-test 4A.1 How many phases are present in a sealed, half-
signpost of spontaneous change under conditions of full vessel containing water?
constant temperature and pressure (Topic 3C). Answer: 2
156 4 Physical transformations of pure substances
Liquid
cooling
Temperature, T
Liquid
Tf freezing
Solid
(a) (b)
cooling
Figure 4A.1 The difference between (a) a single-phase
solution, in which the composition is uniform on a microscopic
scale, and (b) a dispersion, in which regions of one component
Time, t
are embedded in a matrix of a second component.
Figure 4A.2 A cooling curve at constant pressure. The flat
Two metals form a two-phase system (P = 2) if they are section corresponds to the pause in the fall of temperature
immiscible, but a single-phase system (P = 1), an alloy, if they while the first-order exothermic transition (freezing) occurs.
are miscible. This example shows that it is not always easy to This pause enables Tf to be located even if the transition cannot
decide whether a system consists of one phase or of two. A be observed visually.
solution of solid B in solid A—a homogeneous mixture of the
two substances—is uniform on a molecular scale. In a solution, Detecting a phase transition is not always as simple as seeing
atoms of A are surrounded by atoms of A and B, and any sam- water boil in a kettle, so special techniques have been developed.
ple cut from the sample, even microscopically small, is repre- One technique is thermal analysis, which takes advantage of
sentative of the composition of the whole. the heat that is evolved or absorbed during any transition. The
A dispersion is uniform on a macroscopic scale but not on transition is detected by noting that the temperature does not
a microscopic scale, for it consists of grains or droplets of one change even though heat is being supplied or removed from the
substance in a matrix of the other. A small sample could come sample (Fig. 4A.2). Differential scanning calorimetry (Topic
entirely from one of the minute grains of pure A and would 2C) is also used. Thermal techniques are useful for solid–solid
not be representative of the whole (Fig. 4A.1). Dispersions transitions, where simple visual inspection of the sample may
are important because, in many advanced materials (includ- be inadequate. X-ray diffraction (Topic 18A) also reveals the
ing steels), heat treatment cycles are used to achieve the pre- occurrence of a phase transition in a solid, for different struc-
cipitation of a fine dispersion of particles of one phase (such tures are found on either side of the transition temperature.
as a carbide phase) within a matrix formed by a saturated solid As always, it is important to distinguish between the ther-
solution phase. modynamic description of a process and the rate at which the
process occurs. A phase transition that is predicted from ther-
modynamics to be spontaneous may occur too slowly to be
(b) Phase transitions significant in practice. For instance, at normal temperatures
A phase transition, the spontaneous conversion of one phase and pressures the molar Gibbs energy of graphite is lower than
into another phase, occurs at a characteristic temperature for a that of diamond, so there is a thermodynamic tendency for dia-
given pressure. The transition temperature, Ttrs, is the temper- mond to change into graphite. However, for this transition to
ature at which the two phases are in equilibrium and the Gibbs take place, the C atoms must change their locations, which is an
energy of the system is minimized at the prevailing pressure. immeasurably slow process in a solid except at high tempera-
tures. The discussion of the rate of attainment of equilibrium is
Brief illustration 4A.2 Phase transitions a kinetic problem and is outside the range of thermodynamics.
In gases and liquids the mobilities of the molecules allow phase
At 1 atm, ice is the stable phase of water below 0 °C, but above transitions to occur rapidly, but in solids thermodynamic insta-
0 °C liquid water is more stable. This difference indicates that bility may be frozen in. Thermodynamically unstable phases
below 0 °C the Gibbs energy decreases as liquid water changes
that persist because the transition is kinetically hindered are
into ice and that above 0 °C the Gibbs energy decreases as ice
called metastable phases. Diamond is a metastable but persis-
changes into liquid water. The numerical values of the Gibbs
tent phase of carbon under normal conditions.
energies are considered in the next Brief illustration.
Self-test 4A.2 Which has the higher standard molar Gibbs
energy at 105 °C, liquid water or its vapour?
(c) Thermodynamic criteria of phase stability
Answer: Liquid water All our considerations will be based on the Gibbs energy of a
substance, and in particular on its molar Gibbs energy, Gm. In
4A Phase diagrams of pure substances 157
Figure 4A.3 When two or more phases are in equilibrium, 4A.2 Phase boundaries
the chemical potential of a substance (and, in a mixture, a
component) is the same in each phase and is the same at all The phase diagram of a pure substance shows the regions of
points in each phase. pressure and temperature at which its various phases are ther-
modynamically stable (Fig. 4A.4). In fact, any two intensive
fact, this quantity plays such an important role in this chap- variables may be used (such as temperature and magnetic field;
ter and the rest of the text that we give it a special name and in Topic 5A mole fraction is another variable), but in this Topic
symbol, the chemical potential, μ (mu). For a one-component we concentrate on pressure and temperature. The lines separat-
system, ‘molar Gibbs energy’ and ‘chemical potential’ are syno- ing the regions, which are called phase boundaries (or coex
nyms, so μ = Gm, but in Topic 5A we see that chemical poten- istence curves), show the values of p and T at which two phases
tial has a broader significance and a more general definition. coexist in equilibrium and their chemical potentials are equal.
The name ‘chemical potential’ is also instructive: as we develop
the concept, we shall see that μ is a measure of the potential (a)Characteristic properties related to phase
that a substance has for undergoing change in a system. In this
chapter and Chapter 5, it reflects the potential of a substance
transitions
to undergo physical change. In Chapter 6, we see that μ is the Consider a liquid sample of a pure substance in a closed vessel.
potential of a substance to undergo chemical change. The pressure of a vapour in equilibrium with the liquid is called
We base the entire discussion on the following consequence the vapour pressure of the substance (Fig. 4A.5). Therefore,
of the Second Law (Fig. 4A.3): the liquid–vapour phase boundary in a phase diagram shows
how the vapour pressure of the liquid varies with temperature.
equilibrium
Temperature, T
Brief illustration 4A.3 Gibbs energy and phase transition
Figure 4A.4 The general regions of pressure and temperature
The standard molar Gibbs energy of formation of water where solid, liquid, or gas is stable (that is, has minimum molar
vapour at 298 K (25 °C) is –229 kJ mol−1 and that of liquid water Gibbs energy) are shown on this phase diagram. For example,
at the same temperature is –237 kJ mol−1. It follows that there the solid phase is the most stable phase at low temperatures
is a decrease in Gibbs energy when water vapour condenses and high pressures. In the following paragraphs we locate the
precise boundaries between the regions.
158 4 Physical transformations of pure substances
Vapour
pressure,
Vapour p
Liquid
or solid
(a) (b) (c)
Figure 4A.5 The vapour pressure of a liquid or solid is the Figure 4A.6 (a) A liquid in equilibrium with its vapour.
pressure exerted by the vapour in equilibrium with the (b) When a liquid is heated in a sealed container, the density
condensed phase. of the vapour phase increases and that of the liquid decreases
slightly. There comes a stage (c) at which the two densities are
equal and the interface between the fluids disappears. This
more molecules have sufficient energy to escape from their
disappearance occurs at the critical temperature. The container
neighbours. needs to be strong: the critical temperature of water is 374 °C
When a liquid is heated in an open vessel, the liquid vapor- and the vapour pressure is then 218 atm.
izes from its surface. When the vapour pressure is equal to the
external pressure, vaporization can occur throughout the bulk
of the liquid and the vapour can expand freely into the sur- called the melting temperature. Because a substance melts at
roundings. The condition of free vaporization throughout the exactly the same temperature as it freezes, the melting tempera-
liquid is called boiling. The temperature at which the vapour ture of a substance is the same as its freezing temperature. The
pressure of a liquid is equal to the external pressure is called freezing temperature when the pressure is 1 atm is called the
the boiling temperature at that pressure. For the special case of normal freezing point, Tf, and its freezing point when the pres-
an external pressure of 1 atm, the boiling temperature is called sure is 1 bar is called the standard freezing point. The normal
the normal boiling point, Tb. With the replacement of 1 atm by and standard freezing points are negligibly different for most
1 bar as standard pressure, there is some advantage in using the purposes. The normal freezing point is also called the normal
standard boiling point instead: this is the temperature at which melting point.
the vapour pressure reaches 1 bar. Because 1 bar is slightly less There is a set of conditions under which three different
than 1 atm (1.00 bar = 0.987 atm), the standard boiling point phases of a substance (typically solid, liquid, and vapour) all
of a liquid is slightly lower than its normal boiling point. The simultaneously coexist in equilibrium. These conditions are
normal boiling point of water is 100.0 °C; its standard boiling represented by the triple point, a point at which the three phase
point is 99.6 °C. We need to distinguish normal and standard boundaries meet. The temperature at the triple point is denoted
properties only for precise work in thermodynamics because T3. The triple point of a pure substance is outside our control: it
any thermodynamic properties that we intend to add together occurs at a single definite pressure and temperature character-
must refer to the same conditions. istic of the substance.
Boiling does not occur when a liquid is heated in a rigid, As we can see from Fig. 4A.4, the triple point marks the low-
closed vessel. Instead, the vapour pressure, and hence the den- est pressure at which a liquid phase of a substance can exist.
sity of the vapour, rise as the temperature is raised (Fig. 4A.6). If (as is common) the slope of the solid–liquid phase bound-
At the same time, the density of the liquid decreases slightly as ary is as shown in the diagram, then the triple point also marks
a result of its expansion. There comes a stage when the density the lowest temperature at which the liquid can exist; the critical
of the vapour is equal to that of the remaining liquid and the temperature is the upper limit.
surface between the two phases disappears. The temperature at
which the surface disappears is the critical temperature, Tc, of
Brief illustration 4A.4 The triple point
the substance. The vapour pressure at the critical temperature
is called the critical pressure, pc. At and above the critical tem- The triple point of water lies at 273.16 K and 611 Pa (6.11 mbar,
perature, a single uniform phase called a supercritical fluid fills 4.58 Torr), and the three phases of water (ice, liquid water, and
the container and an interface no longer exists. That is, above water vapour) coexist in equilibrium at no other combina-
the critical temperature, the liquid phase of the substance does tion of pressure and temperature. This invariance of the tri-
not exist. ple point was the basis of its use in the about-to-be superseded
The temperature at which, under a specified pressure, the definition of the Kelvin scale of temperature (Topic 3A).
liquid and solid phases of a substance coexist in equilibrium is
4A Phase diagrams of pure substances 159
F =3−P A one-component system The phase rule (4A.2) This relation is actually two equations for two unknowns, μ(α;
p,T) = μ(β; p,T) and μ(β; p,T) = μ(γ; p,T), and therefore has a
solution only for a single value of p and T (just as the pair of
By a constituent of a system we mean a chemical species that is
equations x+y = xy and 3x − y = xy has the single solution x = 2
present. The variance (or number of degrees of freedom), F, of a
and y = 2). That conclusion is consistent with F = 0. Four phases
system is the number of intensive variables that can be changed
cannot be in mutual equilibrium in a one-component system
independently without disturbing the number of phases in because the three equalities
equilibrium.
μ (α; p,T ) = μ (β; p,T )
μ (β; p,T ) = μ ( γ ; p,T )
Brief illustration 4A.5 The number of components μ ( γ ; p,T ) = μ (δ; p,T )
A mixture of ethanol and water has two constituents. A solu- are three equations for two unknowns (p and T) and are not
tion of sodium chloride has three constituents: water, Na + consistent (just as x + y = xy, 3x − y = xy, and x + y = 2xy2 have no
ions, and Cl− ions but only two components because the num- solution).
bers of Na + and Cl− ions are constrained to be equal by the Now consider the general case. We begin by counting the
requirement of charge neutrality. total number of intensive variables. The pressure, p, and tem-
Self-test 4A.5 How many components are present in an aque- perature, T, count as 2. We can specify the composition of a
ous solution of acetic acid, allowing for its partial deprotona- phase by giving the mole fractions of C − 1 components. We
tion and the autoprotolysis of water? need specify only C − 1 and not all C mole fractions because
x 1 + x 2+ … +x C = 1, and all mole fractions are known if all
Answer: 2
except one are specified. Because there are P phases, the total
number of composition variables is P(C − 1). At this stage, the
total number of intensive variables is P(C − 1) + 2.
In a single-component, single-phase system (C = 1, P = 1), the At equilibrium, the chemical potential of a component J
pressure and temperature may be changed independently with- must be the same in every phase:
out changing the number of phases, so F = 2. We say that such a
system is bivariant, or that it has two degrees of freedom. On μ (α; p,T ) = μ (β; p,T ) = … for P phases
160 4 Physical transformations of pure substances
Pressure, p
Phase
( ) ( )
F = P C −1 + 2 − C P −1 = C − P + 2
α
F = 2,
Phase
β P = 4,
P=1 forbidden
F = 0,
which is eqn 4A.1.
P=3 Phase
F = 1,
P=2 δ
67
Figure 4A.7 shows a reasonably typical phase diagram of a sin-
gle pure substance, with one forbidden feature, the ‘quadruple B D
5.11
point’ where phases β, γ, δ, and ε are said to be in equilibrium. Triple
point Vapour
Two triple points are shown (for the equilibria α β γ 1
and α β δ, respectively), corresponding to P = 3 and
298.15
A
304.2
216.8
194.7
Self-test 4A.6 What is the minimum number of components Figure 4A.8 The experimental phase diagram for carbon
necessary before five phases can be in mutual equilibrium in dioxide. Note that, as the triple point lies at pressures well
a system? above atmospheric, liquid carbon dioxide does not exist under
Answer: 3 normal conditions (a pressure of at least 5.11 atm must be
applied). The path ABCD is discussed in Brief illustration 4A.7
4A Phase diagrams of pure substances 161
gas and liquid are present in equilibrium. When the gas squirts
through the throttle it cools by the Joule–Thomson effect, so
when it emerges into a region where the pressure is only 1 atm,
it condenses into a finely divided snow-like solid. That carbon
dioxide gas cannot be liquefied except by applying high pres-
sure reflects the weakness of the intermolecular forces between
the nonpolar carbon dioxide molecules (Topic 16B).
Brief illustration 4A.7 Figure 4A.10 A fragment of the structure of ice (ice-I). Each
A phase diagram 1
O atom is linked by two covalent bonds to H atoms and by two
Consider the path ABCD in Fig. 4A.8. At A the carbon diox- hydrogen bonds to a neighbouring O atom, in a tetrahedral
ide is a gas. When the temperature and pressure are adjusted array.
to B, the vapour condenses directly to a solid. Increasing the
pressure and temperature to C results in the formation of the
pressure is raised. The reason for this almost unique behaviour
liquid phase, which evaporates to the vapour when the condi-
tions are changed to D. can be traced to the decrease in volume that occurs on melting:
it is more favourable for the solid to transform into the liquid
Self-test 4A.7 Describe what happens on circulating around as the pressure is raised. The decrease in volume is a result of
the critical point, Path E. the very open structure of ice: as shown in Fig. 4A.10, the water
Answer: Liquid → scCO2 → vapour → liquid molecules are held apart, as well as together, by the hydrogen
bonds between them but the hydrogen-bonded structure par-
tially collapses on melting and the liquid is denser than the
solid. Other consequences of its extensive hydrogen bonding
are the anomalously high boiling point of water for a molecule
(b) Water
of its molar mass and its high critical temperature and pressure.
Figure 4A.9 shows the phase diagram for water. The liquid– Figure 4A.9 shows that water has one liquid phase but many
vapour boundary in the phase diagram summarizes how the different solid phases other than ordinary ice (‘ice I’). Some of
vapour pressure of liquid water varies with temperature. It also these phases melt at high temperatures. Ice VII, for instance,
summarizes how the boiling temperature varies with pressure: melts at 100 °C but exists only above 25 kbar. Two further
we simply read off the temperature at which the vapour pres- phases, Ice XIII and XIV, were identified in 2006 at –160 °C but
sure is equal to the prevailing atmospheric pressure. The solid– have not yet been allocated regions in the phase diagram. Note
liquid boundary shows how the melting temperature varies that five more triple points occur in the diagram other than the
with the pressure; its very steep slope indicates that enormous one where vapour, liquid, and ice I coexist. Each one occurs at a
pressures are needed to bring about significant changes. Notice definite pressure and temperature that cannot be changed. The
that the line has a negative slope (down from left to right) up to solid phases of ice differ in the arrangement of the water mol-
2 kbar, which means that the melting temperature falls as the ecules: under the influence of very high pressures, hydrogen
bonds buckle and the H2O molecules adopt different arrange-
1012 ments. These polymorphs of ice may contribute to the advance
X XI VII of glaciers, for ice at the bottom of glaciers experiences very
VI C
VIII B high pressures where it rests on jagged rocks.
109 V D
II
A Liquid
Pressure, p/Pa
III
106 F Brief illustration 4A.8 A phase diagram 2
I
Consider the path ABCD in Fig. 4A.9. At A, water is present
103 Vapour as ice V. Increasing the pressure to B at the same temperature
results in the formation of a polymorph, ice VIII. Heating to C
1 leads to the formation of ice VII, and reduction in pressure to
0 200 400 600 800
D results in the solid melting to liquid.
Temperature, T/K
Self-test 4A.8 Describe what happens on circulating around
Figure 4A.9 The experimental phase diagram for water the critical point, Path F.
showing the different solid phases. The path ABCD is discussed Answer: Vapour → liquid → scH2O → vapour
in Brief illustration 4A.8.
162 4 Physical transformations of pure substances
λ-line point and therefore (from ΔfusS = ΔfusH/Tf ) at the melting point the
Liquid
1 He-II
entropy of the liquid is lower than that of the solid.
(super-
fluid) B
A
0.1 C Gas Brief illustration 4A.9 A phase diagram 3
Triple
D point
0.01
Consider the path ABCD in Fig. 4A.11. At A, helium is pre-
0 1 2 3 4 5 6 sent as a vapour. On cooling to B it condenses to helium-I,
Temperature, T/K
and further cooling to C results in the formation of helium-
Figure 4A.11 The phase diagram for helium (4He). The λ-line II. Adjustment of the pressure and temperature to D results
marks the conditions under which the two liquid phases are in a system in which three phases, helium-I, helium-II, and
in equilibrium. Helium-II is the superfluid phase. Note that a vapour, are in mutual equilibrium.
pressure of over 20 bar must be exerted before solid helium Self-test 4A.9 Describe what happens on the path EFGH.
can be obtained. The labels hcp and bcc denote different
Answer: He-I → solid → solid → He-II
solid phases in which the atoms pack together differently:
hcp denotes hexagonal closed packing and bcc denotes
body-centred cubic (see Topic 18B for a description of these
structures). The path ABCD is discussed in Brief illustration 4A.9. 1 Water might also have a superfluid liquid phase.
Checklist of concepts
☐ 1. A phase is a form of matter that is uniform throughout ☐ 5. The phase rule relates the number of variables that
in chemical composition and physical state. may be changed while the phases of a system remain in
☐ 2. A phase transition is the spontaneous conversion of mutual equilibrium.
one phase into another and may be studied by tech- ☐ 6. Carbon dioxide is a typical substance but shows fea-
niques that include thermal analysis. tures that can be traced to its weak intermolecular
☐ 3. The thermodynamic analysis of phases is based on the forces.
fact that at equilibrium, the chemical potential of a sub- ☐ 7. Water shows anomalies that can be traced to its exten-
stance is the same throughout a sample. sive hydrogen bonding.
☐ 4. A substance is characterized by a variety of parameters ☐ 8. Helium shows anomalies that can be traced to its low
that can be identified on its phase diagram. mass and weak interactions.
4A Phase diagrams of pure substances 163
Checklist of equations
Property Equation Comment Equation number
Solid ∂μ
Liquid
∂p = Vm Variation of chemical potential with p (4B.2)
T
Vapour
This equation shows that the slope of a plot of chemical potential
against pressure is equal to the molar volume of the substance.
Solid Liquid Vapour An increase in pressure raises the chemical potential of any
stable Tf stable Tb stable pure substance (because Vm > 0). In most cases, Vm(l) > Vm(s)
Temperature, T and the equation predicts that an increase in pressure increases
the chemical potential of the liquid more than that of the solid.
Figure 4B.1 The schematic temperature dependence of the As shown in Fig. 4B.2a, the effect of pressure in such a case is
chemical potential of the solid, liquid, and gas phases of a
to raise the melting temperature slightly. For water, however,
substance (in practice, the lines are curved). The phase with
Vm(l) < Vm(s), and an increase in pressure increases the chemi-
the lowest chemical potential at a specified temperature
cal potential of the solid more than that of the liquid. In this
is the most stable one at that temperature. The transition
case, the melting temperature is lowered slightly (Fig. 4B.2b).
temperatures, the melting and boiling temperatures (Tf and
Tb, respectively), are the temperatures at which the chemical
potentials of the two phases are equal.
Example 4B.1 Assessing the effect of pressure on the
Brief illustration 4B.1 The temperature variation of μ chemical potential
The standard molar entropy of liquid water at 100 °C is 86.8 Calculate the effect on the chemical potentials of ice and water
J K−1 mol−1 and that of water vapour at the same temperature of increasing the pressure from 1.00 bar to 2.00 bar at 0 °C. The
is 195.98 J K−1 mol−1. It follows that when the temperature is density of ice is 0.917 g cm−3 and that of liquid water is 0.999
raised by 1.0 K the changes in chemical potential are g cm−3 under these conditions.
166 4 Physical transformations of pure substances
Pressure, ΔP
Method From eqn 4B.2 in the form dμ = Vm dp, we know
that the change in chemical potential of an incompressible
substance when the pressure is changed by Δp is Δµ = Vm Δp. Vapour Vapour plus
Therefore, to answer the question, we need to know the inert pressurizing
molar volumes of the two phases of water. These values are Piston gas
permeable to
obtained from the mass density, ρ, and the molar mass,
vapour but
M, by using Vm = M/ρ. We therefore use the expression not liquid
Δµ = MΔp/ρ.
(1.802 ×10−2 kg mol −1 ) × (1.00 ×105 Pa ) Figure 4B.3 Pressure may be applied to a condensed phase
∆μ(ice) = = +1.97 Jmol −1 either (a) by compressing the condensed phase or (b) by
917 kg m −3
subjecting it to an inert pressurizing gas. When pressure is
(1.802 ×10−2 kg mol −1 ) × (1.00 × 105 Pa ) applied, the vapour pressure of the condensed phase increases.
∆μ(water) =
999 kg m −3
= + 1.80 Jmol −1 (c)The vapour pressure of a liquid subjected
We interpret the numerical results as follows: the chemical to pressure
potential of ice rises more sharply than that of water, so if they When pressure is applied to a condensed phase, its vapour pres-
are initially in equilibrium at 1 bar, then there will be a ten- sure rises: in effect, molecules are squeezed out of the phase and
dency for the ice to melt at 2 bar. escape as a gas. Pressure can be exerted on the condensed phase
Self-test 4B.2 Calculate the effect of an increase in pressure mechanically or by subjecting it to the applied pressure of an
of 1.00 bar on the liquid and solid phases of carbon dioxide inert gas (Fig. 4B.3). In the latter case, the vapour pressure is
(molar mass 44.0 g mol−1) in equilibrium with densities 2.35 the partial pressure of the vapour in equilibrium with the con-
g cm−3 and 2.50 g cm−3, respectively. densed phase. We then speak of the partial vapour pressure of
the substance. One complication (which we ignore here) is that,
Answer: Δµ(l) = +1.87 J mol−1, Δµ(s) = +1.76 J mol−1; solid forms
if the condensed phase is a liquid, then the pressurizing gas
might dissolve and change the properties of the liquid. Another
complication is that the gas phase molecules might attract
High molecules out of the liquid by the process of gas solvation, the
pressure attachment of molecules to gas-phase species.
As shown in the following Justification, the quantitative rela-
Chemical potential, µ
High Liquid
Liquid tion between the vapour pressure, p, when a pressure ΔP is
pressure
Solid applied and the vapour pressure, p*, of the liquid in the absence
of an additional pressure is
Low Low
pressure pressure p = p*eV
m( l ) ∆P /RT Effect of applied pressure
(4B.3)
Solid ΔP on vapour pressure p
Figure 4B.2 The pressure dependence of the chemical Justification 4B.1 The vapour pressure of a pressurized
potential of a substance depends on the molar volume
liquid
of the phase. The lines show schematically the effect of
increasing pressure on the chemical potential of the solid We calculate the vapour pressure of a pressurized liquid by
and liquid phases (in practice, the lines are curved), and the using the fact that at equilibrium the chemical potentials
corresponding effects on the freezing temperatures. (a) In this of the liquid and its vapour are equal: µ(l) = µ(g). It follows
case the molar volume of the solid is smaller than that of the that, for any change that preserves equilibrium, the resulting
liquid and μ(s) increases less than μ(l). As a result, the freezing change in µ(l) must be equal to the change in µ(g); therefore,
temperature rises. (b) Here the molar volume is greater for the we can write dµ(g) = dµ(l). When the pressure P on the liquid is
solid than the liquid (as for water), μ(s) increases more strongly increased by dP, the chemical potential of the liquid changes by
than μ(l), and the freezing temperature is lowered. dµ(l) = Vm(l)dP. The chemical potential of the vapour changes
4B Thermodynamic aspects of phase transitions 167
Then, with ΔtrsS = Sm(β) − Sm(α) and ΔtrsV = Vm(β) − Vm(α), which
are the (molar) entropy and volume of transition, respectively,
Solid
∆ trs SdT = ∆ trsVdp
Pressure, p
This relation rearranges into the Clapeyron equation:
Liquid
dp ∆ trs S Clapeyron equation (4B.5a)
=
dT ∆ trsV
Temperature, T
The Clapeyron equation is an exact expression for the slope
of the tangent to the boundary at any point and applies to any Figure 4B.5 A typical solid–liquid phase boundary slopes
phase equilibrium of any pure substance. It implies that we can steeply upwards. This slope implies that, as the pressure is
use thermodynamic data to predict the appearance of phase raised, the melting temperature rises. Most substances behave
diagrams and to understand their form. A more practical appli- in this way.
cation is to the prediction of the response of freezing and boil-
ing points to the application of pressure, when it can be used in
the form obtained by inverting both sides: where ΔfusV is the change in molar volume that occurs on melt-
ing. The enthalpy of melting is positive (the only exception is
dT ∆ trsV helium-3) and the volume change is usually positive and always
= (4B.5b)
dp ∆ trs S small. Consequently, the slope dp/dT is steep and usually posi-
tive (Fig. 4B.5).
We can obtain the formula for the phase boundary by
integrating dp/dT, assuming that ΔfusH and ΔfusV change so
Brief illustration 4B.3 The Clapeyron equation little with temperature and pressure that they can be treated
The standard volume and entropy of transition of water from as constant. If the melting temperature is T* when the pres-
ice to liquid are −1.6 cm3 mol−1 and +22 J K−1 mol−1, respectively, sure is p*, and T when the pressure is p, the integration
at 0 °C. The slope of the solid–liquid phase boundary at that required is
temperature is therefore
p ∆ fus H T dT
dT −1.6 ×10 m mol
=
−6 3 −1
= −7.3 ×10−8
K
= −7.3 ×10−8 K Pa −1
∫ p*
dp =
∆ fusV ∫
T* T
dp 22 J −1 mol −1 Jm −3
Therefore, the approximate equation of the solid–liquid bound-
which corresponds to −7.3 mK bar−1. An increase of 100 bar
therefore results in a lowering of the freezing point of water ary is
by 0.73 K.
∆ fus H T
Self-test 4B.4 The standard volume and entropy of transi-
p = p*+ ln (4B.7)
∆ fusV T *
tion of water from liquid to vapour are +30 dm 3 mol−1 and
+109 J K−1 mol−1, respectively, at 100 °C. By how much does This equation was originally obtained by yet another
the boiling temperature change when the pressure is reduced Thomson—James, the brother of William, Lord Kelvin. When
from 1.0 bar to 0.80 bar? T is close to T*, the logarithm can be approximated by using
Answer: −5.5 K
T T −T * T −T *
ln = ln 1+ ≈
T* T * T*
dp ∆ fus H (4B.6) This expression is the equation of a steep straight line when p is
= Slope of solid–liquid boundary
dT T ∆ fusV plotted against T (as in Fig. 4B.5).
4B Thermodynamic aspects of phase transitions 169
Brief illustration 4B.4 The solid–liquid boundary Example 4B.2 Estimating the effect of pressure on the
boiling temperature
The enthalpy of fusion of ice at 0 °C and 1 bar (273 K) is 6.008
kJ mol−1 and the volume of fusion is –1.6 cm3 mol−1. It follows Estimate the typical size of the effect of increasing pressure on
that the solid–liquid phase boundary is given by the equation the boiling point of a liquid.
6.008 ×103 Jmol −1 Method To use eqn 4B.9 we need to estimate the right-hand
p ≈ 1 bar + (T − T *)
(273 K ) × (−1.6 ×10−6 m3 mol −1 ) side. At the boiling point, the term Δ vapH/T is Trouton’s con-
≈ 1 bar −1.4 ×107 Pa K −1(T − T *) stant (Topic 3B). Because the molar volume of a gas is so
much greater than the molar volume of a liquid, we can write
∆ vapV = Vm (g) − Vm (l) ≈ Vm (g) and take for Vm(g) the molar
That is,
volume of a perfect gas (at low pressures, at least).
p/bar = 1 −140(T − T *)/K
Answer Trouton’s constant has the value 85 J K−1 mol−1. The
with T* = 273 K. This expression is plotted in Fig. 4B.6. molar volume of a perfect gas is about 25 dm3 mol−1 at 1 atm
and near but above room temperature. Therefore,
15 dp 85 J K −1 mol −1
≈ = 3.4 × 103 Pa K −1
(a) Water dT 2.5 × 10−2 m3 mol −1
10
atm K−1 and hence to dT/dp = 29 K atm−1. Therefore, a change of
(b) Benzene
pressure of +0.1 atm can be expected to change a boiling tem-
perature by about +3 K.
5
Self-test 4B.6 Estimate dT/dp for water at its normal boiling
point using the information in Table 3A.2 and Vm(g) = RT/p.
1 Answer: 28 K atm−1
–0.1 –0.05 0 0.05 0.1
Temperature difference, (T – T*)/K
Figure 4B.6 The solid–liquid phase boundaries (the melting Because the molar volume of a gas is so much greater than
point curves) for water and benzene, as calculated in Brief the molar volume of a liquid, we can write ΔvapV ≈ Vm(g) (as in
illustration 4B.4. Example 4B.2). Moreover, if the gas behaves perfectly, Vm(g) =
RT/p. These two approximations turn the exact Clapeyron
Self-test 4B.5 The enthalpy of fusion of benzene is 10.59 kJ equation into
mol−1 at its melting point of 279 K and its volume of fusion
is close to +0.50 cm 3 mol−1 (an estimated value). What is the dp ∆ vap H p∆ vap H
equation of its solid–liquid phase boundary?
= =
dT T (RT /p) RT 2
Answer: p/bar = 1 + 760(T − T*), as in Fig. 4B.6
which, by using dx/x = d ln x, rearranges into the Clausius–
Clapeyron equation for the variation of vapour pressure with
temperature:
(c) The liquid–vapour boundary
The entropy of vaporization at a temperature T is equal to d ln p ∆ vap H Vapour is a Clausius–Clapeyron
= perfect gas equation (4B.10)
ΔvapH/T; the Clapeyron equation for the liquid–vapour bound- dT RT 2
ary is therefore
Like the Clapeyron equation (which is exact), the Clausius–
dp ∆ vap H Clapeyron equation (which is an approximation) is important
= Slope of liquid–vapour boundary (4B.9)
dT T ∆ vapV for understanding the appearance of phase diagrams, particu-
larly the location and shape of the liquid–vapour and solid–
The enthalpy of vaporization is positive; ΔvapV is large and posi- vapour phase boundaries. It lets us predict how the vapour
tive. Therefore, dp/dT is positive, but it is much smaller than for pressure varies with temperature and how the boiling tempera-
the solid–liquid boundary. It follows that dT/dp is large, and ture varies with pressure. For instance, if we also assume that
hence that the boiling temperature is more responsive to pres- the enthalpy of vaporization is independent of temperature,
sure than the freezing temperature. eqn 4B.10 can be integrated as follows:
170 4 Physical transformations of pure substances
and substitute this value into eqn 4B.11 with p* = 101 kPa. The Temperature, T
result is 12 kPa. The experimental value is 10 kPa.
Figure 4B.8 Near the point where they coincide (at the triple
A note on good practice Because exponential functions point), the solid–vapour boundary has a steeper slope than the
are so sensitive, it is good practice to carry out numerical liquid–vapour boundary because the enthalpy of sublimation
calculations like this without evaluating the intermediate is greater than the enthalpy of vaporization and the
steps and using rounded values. temperatures that occur in the Clausius–Clapeyron equation
for the slope have similar values.
4B Thermodynamic aspects of phase transitions 171
Figure 4B.9 The changes in thermodynamic properties 1 A metallic conductor is a substance with an electrical conductivity that
accompanying (a) first-order and (b) second-order phase decreases as the temperature increases. A superconductor is a solid that con-
transitions. ducts electricity without resistance. See Topic 18C for more details.
172 4 Physical transformations of pure substances
90
Equal
Slow
80 rates
70
Cp,m/(J K–1 mol–1)
Tetragonal
Cubic phase
60 phase
Fast Equal
50 Equal rates
Fast
rates
40
Phase
30 transition
(a) (b)
20
–6 –4 –2 0 +2 +4 +6 Figure 4B.11 One version of a second-order phase transition
(T – Tλ)/mK
in which (a) a tetragonal phase expands more rapidly in two
Figure 4B.10 The λ-curve for helium, where the heat capacity directions than a third, and hence becomes a cubic phase,
rises to infinity. The shape of this curve is the origin of the name which (b) expands uniformly in three directions as the
λ-transition. temperature is raised. There is no rearrangement of atoms
at the transition temperature, and hence no enthalpy of
transition.
(b) Molecular interpretation
First-order transitions typically involve the relocation of
atoms, molecules, or ions with a consequent change in the
energies of their interactions. Thus, vaporization eliminates
the attractions between molecules and a first-order phase tran-
sition from one ionic polymorph to another (as in the con-
version of calcite to aragonite) involves the adjustment of the
relative positions of ions.
One type of second-order transition is associated with a
change in symmetry of the crystal structure of a solid. Thus,
suppose the arrangement of atoms in a solid is like that repre-
sented in Fig. 4B.11a, with one dimension (technically, of the
unit cell) longer than the other two, which are equal. Such a (a) (b) (c)
crystal structure is classified as tetragonal (see Topic 18A).
Figure 4B.12 An order–disorder transition. (a) At T = 0, there is
Moreover, suppose the two shorter dimensions increase more
perfect order, with different kinds of atoms occupying alternate
than the long dimension when the temperature is raised. There
sites. (b) As the temperature is increased, atoms exchange
may come a stage when the three dimensions become equal. locations and islands of each kind of atom form in regions
At that point the crystal has cubic symmetry (Fig. 4B.11b), of the solid. Some of the original order survives. (c) At and
and at higher temperatures it will expand equally in all three above the transition temperature, the islands occur at random
directions (because there is no longer any distinction between throughout the sample.
them). The tetragonal → cubic phase transition has occurred,
but as it has not involved a discontinuity in the interaction
energy between the atoms or the volume they occupy, the tran- cooperative in the sense that, once two atoms have exchanged
sition is not first-order. locations, it is easier for their neighbours to exchange their
The order–disorder transition in β-brass (CuZn) is an exam- locations. The islands grow in extent and merge throughout the
ple of a λ-transition. The low-temperature phase is an orderly crystal at the transition temperature (742 K). The heat capacity
array of alternating Cu and Zn atoms. The high-temperature increases as the transition temperature is approached because
phase is a random array of the atoms (Fig. 4B.12). At T = 0 the cooperative nature of the transition means that it is increas-
the order is perfect, but islands of disorder appear as the tem- ingly easy for the heat supplied to drive the phase transition
perature is raised. The islands form because the transition is rather than to be stored as thermal motion.
4B Thermodynamic aspects of phase transitions 173
Checklist of concepts
☐ 1. The chemical potential of a substance decreases with ☐ 5. The Clausius–Clapeyron equation is an approximation
increasing temperature at a rate determined by its that relates the slope of the liquid–vapour boundary to
molar entropy. the enthalpy of vaporization.
☐ 2. The chemical potential of a substance increases with ☐ 6. According to the Ehrenfest classification, different
increasing pressure at a rate determined by its molar types of phase transition are identified by the behav-
volume. iour of thermodynamic properties at the transition
☐ 3. When pressure is applied to a condensed phase, its temperature.
vapour pressure rises. ☐ 7. The classification reveals the type of molecular process
☐ 4. The Clapeyron equation is an expression for the slope occurring at the phase transition.
of a phase boundary.
Checklist of equations
Property Equation Comment Equation number
Clausius–Clapeyron equation d ln p/dT = ΔvapH/RT 2 Assumes Vm(g) ≫ Vm(l) and vapour 4B.10
is a perfect gas
174 4 Physical transformations of pure substances
Exercises
4A.1(a) How many phases are present at each of the points marked in Fig. 4.1a? b
4A.1(b) How many phases are present at each of the points marked in Fig. 4.1b?
c c
4A.2(a) The difference in chemical potential between two regions of a system is
Pressure
Pressure
a
+7.1 kJ mol−1. By how much does the Gibbs energy change when 0.10 mmol of
a
a substance is transferred from one region to the other? d
4A.2(b) The difference in chemical potential between two regions of a system is b
–8.3 kJ mol−1. By how much does the Gibbs energy change when 0.15 mmol of d
a substance is transferred from one region to the other?
4A.3(a) What is the maximum number of phases that can be in mutual
(a) Temperature (b) Temperature
equilibrium in a two-component system?
4A.3(b) What is the maximum number of phases that can be in mutual Figure 4.1 The phase diagrams referred to in (a) Exercise 4A.1(a) and
equilibrium in a four-component system? (b) Exercise 4A.1(b).
For problems relating to one-component phase diagrams, see the Integrated
activities section of this chapter.
Exercises
4B.1(a) Estimate the difference between the normal and standard melting 4B.2(a) Water is heated from 25 °C to 100 °C. By how much does its chemical
points of ice. potential change?
4B.1(b) Estimate the difference between the normal and standard boiling 4B.2(b) Iron is heated from 100 °C to 1000 °C. By how much does its chemical
points of water. potential change? Take Sm< = 53 J K−1 mol−1 for the entire range.
Exercises and problems 175
4B.3(a) By how much does the chemical potential of copper change when the 4B.9(a) When benzene freezes at 5.5 °C its density changes from 0.879 g cm−3
pressure exerted on a sample is increased from 100 kPa to 10 MPa? to 0.891 g cm−3. Its enthalpy of fusion is 10.59 kJ mol−1. Estimate the freezing
4B.3(b) By how much does the chemical potential of benzene change when the point of benzene at 1000 atm.
pressure exerted on a sample is increased from 100 kPa to 10 MPa? 4B.9(b) When a certain liquid freezes at −3.65 °C its density changes from
0.789 g cm−3 to 0.801 g cm−3. Its enthalpy of fusion is 8.68 kJ mol−1. Estimate
4B.4(a) Pressure was exerted with a piston on water at 20 °C. The vapour
the freezing point of the liquid at 100 MPa.
pressure of water under 1.0 bar is 2.34 kPa. What is its vapour pressure when
the pressure on the liquid is 20 MPa? 4B.10(a) In July in Los Angeles, the incident sunlight at ground level has a
4B.4(b) Pressure was exerted with a piston on molten naphthalene at 95 °C. power density of 1.2 kW m−2 at noon. A swimming pool of area 50 m2 is
The vapour pressure of naphthalene under 1.0 bar is 2.0 kPa. What is its directly exposed to the sun. What is the maximum rate of loss of water?
vapour pressure when the pressure on the liquid is 15 MPa? Assume that all the radiant energy is absorbed.
4B.10(b) Suppose the incident sunlight at ground level has a power density of
4B.5(a) The molar volume of a certain solid is 161.0 cm3 mol−1 at 1.00 atm
0.87 kW m−2 at noon. What is the maximum rate of loss of water from a lake
and 350.75 K, its melting temperature. The molar volume of the liquid at
of area 1.0 ha? (1 ha = 104 m2.) Assume that all the radiant energy is absorbed.
this temperature and pressure is 163.3 cm3 mol−1. At 100 atm the melting
temperature changes to 351.26 K. Calculate the enthalpy and entropy of fusion 4B.11(a) An open vessel containing (i) water, (ii) benzene, (iii) mercury stands
of the solid. in a laboratory measuring 5.0 m × 5.0 m × 3.0 m at 25 °C. What mass of each
4B.5(b) The molar volume of a certain solid is 142.0 cm3 mol−1 at 1.00 atm substance will be found in the air if there is no ventilation? (The vapour
and 427.15 K, its melting temperature. The molar volume of the liquid at pressures are (i) 3.2 kPa, (ii) 13.1 kPa, (iii) 0.23 Pa.)
this temperature and pressure is 152.6 cm3 mol−1. At 1.2 MPa the melting 4B.11(b) On a cold, dry morning after a frost, the temperature was −5 °C and
temperature changes to 429.26 K. Calculate the enthalpy and entropy of fusion the partial pressure of water in the atmosphere fell to 0.30 kPa. Will the frost
of the solid. sublime? What partial pressure of water would ensure that the frost remained?
4B.6(a) The vapour pressure of dichloromethane at 24.1 °C is 53.3 kPa and its 4B.12(a) Naphthalene, C10H8, melts at 80.2 °C. If the vapour pressure of the
enthalpy of vaporization is 28.7 kJ mol−1. Estimate the temperature at which its liquid is 1.3 kPa at 85.8 °C and 5.3 kPa at 119.3 °C, use the Clausius–Clapeyron
vapour pressure is 70.0 kPa. equation to calculate (i) the enthalpy of vaporization, (ii) the normal boiling
4B.6(b) The vapour pressure of a substance at 20.0 °C is 58.0 kPa and its point, and (iii) the enthalpy of vaporization at the boiling point.
enthalpy of vaporization is 32.7 kJ mol−1. Estimate the temperature at which its 4B.12(b) The normal boiling point of hexane is 69.0 °C. Estimate (i) its
vapour pressure is 66.0 kPa. enthalpy of vaporization and (ii) its vapour pressure at 25 °C and 60 °C.
4B.7(a) The vapour pressure of a liquid in the temperature range 200 K to 4B.13(a) Calculate the melting point of ice under a pressure of 50 bar. Assume
260 K was found to fit the expression ln(p/Torr)=16.255 − 2501.8/(T/K). What that the density of ice under these conditions is approximately 0.92 g cm−3 and
is the enthalpy of vaporization of the liquid? that of liquid water is 1.00 g cm−3.
4B.7(b) The vapour pressure of a liquid in the temperature range 200 K to 4B.13(b) Calculate the melting point of ice under a pressure of 10 MPa.
260 K was found to fit the expression ln(p/Torr)=18.361 − 3036.8/(T/K). What Assume that the density of ice under these conditions is approximately 0.915
is the enthalpy of vaporization of the liquid? g cm−3 and that of liquid water is 0.998 g cm−3.
4B.8(a) The vapour pressure of benzene between 10 °C and 30 °C fits the 4B.14(a) What fraction of the enthalpy of vaporization of water is spent on
expression log(p/Torr) = 7.960 − 1780/(T/K). Calculate (i) the enthalpy of expanding the water vapour?
vaporization and (ii) the normal boiling point of benzene. 4B.14(b) What fraction of the enthalpy of vaporization of ethanol is spent on
4B.8(b) The vapour pressure of a liquid between 15 °C and 35 °C fits the expanding its vapour?
expression log(p/Torr) = 8.750 − 1625/(T/K). Calculate (i) the enthalpy of
vaporization and (ii) the normal boiling point of the liquid.
Problems
4B.1 The temperature dependence of the vapour pressure of solid normal boiling point of water. (c) By how much does the chemical potential of
sulfur dioxide can be approximately represented by the relation water supercooled to −5.0 °C exceed that of ice at that temperature?
log(p/Torr) = 10.5916 − 1871.2/(T/K) and that of liquid sulfur dioxide by
4B.5 Calculate the difference in slope of the chemical potential against
log(p/Torr) = 8.3186 − 1425.7/(T/K). Estimate the temperature and pressure
pressure on either side of (a) the normal freezing point of water and
of the triple point of sulfur dioxide.
(b) the normal boiling point of water. The densities of ice and water at 0 °C
4B.2 Prior to the discovery that freon-12 (CF2Cl2) was harmful to the Earth’s are 0.917 g cm−3 and 1.000 g cm−3, and those of water and water vapour at
ozone layer, it was frequently used as the dispersing agent in spray cans for 100 °C are 0.958 g cm−3 and 0.598 g dm−3, respectively. By how much does the
hair spray, etc. Its enthalpy of vaporization at its normal boiling point of chemical potential of water vapour exceed that of liquid water at 1.2 atm and
−29.2 °C is 20.25 kJ mol−1. Estimate the pressure that a can of hair spray using 100 °C?
freon-12 had to withstand at 40 °C, the temperature of a can that has been 4B.6 The enthalpy of fusion of mercury is 2.292 kJ mol−1, and its normal
standing in sunlight. Assume that ΔvapH is a constant over the temperature freezing point is 234.3 K with a change in molar volume of +0.517 cm−3 mol−1
range involved and equal to its value at –29.2 °C. on melting. At what temperature will the bottom of a column of mercury
4B.3 The enthalpy of vaporization of a certain liquid is found to be 14.4 kJ mol−1 (density 13.6 g cm−3) of height 10.0 m be expected to freeze?
at 180 K, its normal boiling point. The molar volumes of the liquid and the 4B.7 50.0 dm3 of dry air was slowly bubbled through a thermally insulated
vapour at the boiling point are 115 cm3 mol−1 and 14.5 dm3 mol−1, respectively. beaker containing 250 g of water initially at 25 °C. Calculate the final
(a) Estimate dp/dT from the Clapeyron equation and (b) the percentage error temperature. (The vapour pressure of water is approximately constant at
in its value if the Clausius–Clapeyron equation is used instead. 3.17 kPa throughout, and its heat capacity is 75.5 J K−1 mol−1. Assume that the
4B.4 Calculate the difference in slope of the chemical potential against air is not heated or cooled and that water vapour is a perfect gas.)
temperature on either side of (a) the normal freezing point of water and (b) the 4B.8 The vapour pressure, p, of nitric acid varies with temperature as follows:
176 4 Physical transformations of pure substances
Torr was passed slowly through the heated liquid, the loss of mass was 0.32 g.
θ/°C 0 20 40 50 70 80 90 100
Calculate the vapour pressure of geraniol.
p/kPa 1.92 6.38 17.7 27.7 62.3 89.3 124.9 170.9
4B.14 The vapour pressure of a liquid in a gravitational field varies with the
depth below the surface on account of the hydrostatic pressure exerted by
What are (a) the normal boiling point and (b) the enthalpy of vaporization of
the overlying liquid. Adapt eqn. 4B.3 to predict how the vapour pressure of a
nitric acid?
liquid of molar mass M varies with depth. Estimate the effect on the vapour
4B.9 The vapour pressure of the ketone carvone (M = 150.2 g mol−1), a pressure of water at 25 °C in a column 10 m high.
component of oil of spearmint, is as follows:
4B.15 Combine the ‘barometric formula’, p = p0e−a/H, where H = 8 km, for the
θ/°C 57.4 100.4 133.0 157.3 203.5 227.5 dependence of the pressure on altitude, a, with the Clausius–Clapeyron
equation, and predict how the boiling temperature of a liquid depends on the
p/Torr 1.00 10.0 40.0 100 400 760 altitude and the ambient temperature. Take the mean ambient temperature as
20 °C and predict the boiling temperature of water at 3000 m.
What are (a) the normal boiling point and (b) the enthalpy of vaporization of
4B.16 Figure 4B.1 gives a schematic representation of how the chemical
carvone?
potentials of the solid, liquid, and gaseous phases of a substance vary with
4B.10‡ In a study of the vapour pressure of chloromethane, A. Bah and N. temperature. All have a negative slope, but it is unlikely that they are truly
Dupont-Pavlovsky (J. Chem. Eng. Data 40, 869 (1995)) presented data for the straight lines as indicated in the illustration. Derive an expression for the
vapour pressure over solid chloromethane at low temperatures. Some of that curvatures (specifically, the second derivatives with respect to temperature) of
data is as follows: these lines. Is there a restriction on the curvature of these lines? Which state
of matter shows the greatest curvature?
T/K 145.94 147.96 149.93 151.94 153.97 154.94
4B.17 The Clapeyron equation does not apply to second-order phase
p/Pa 13.07 18.49 25.99 36.76 50.86 59.56 transitions, but there are two analogous equations, the Ehrenfest equations,
that do. They are:
Estimate the standard enthalpy of sublimation of chloromethane at 150 K.
(Take the molar volume of the vapour to be that of a perfect gas, and that of
dp α 2 − α1 dp C p, m;2 − C p, m;1
the solid to be negligible.) (a) = (b) =
dT κ T ;2 −κ T ;1 dT TVm (α 2 −α1 )
4B.11 Show that, for a transition between two incompressible solid phases,
ΔG is independent of the pressure. where α is the expansion coefficient, κT the isothermal compressibility,
4B.12 The change in enthalpy is given by dH = CpdT + Vdp. The Clapeyron and the subscripts 1 and 2 refer to two different phases. Derive these two
equation relates dp and dT at equilibrium, and so in combination the two equations. Why does the Clapeyron equation not apply to second-order
equations can be used to find how the enthalpy changes along a phase transitions?
boundary as the temperature changes and the two phases remain in 4B.18 For a first-order phase transition, to which the Clapeyron equation does
equilibrium. Show that d(ΔH/T) = ΔCp d ln T. apply, prove the relation
4B.13 In the ‘gas saturation method’ for the measurement of vapour pressure, a
volume V of gas (as measured at a temperature T and a pressure p) is bubbled αV ∆ trs H
CS = C p −
slowly through the liquid that is maintained at the temperature T, and a mass ∆ trsV
loss m is measured. Show that the vapour pressure, p, of the liquid is related
to its molar mass, M, by p = AmP/(1 + Am), where A = RT/MPV. The vapour where CS = (∂q/∂T)S is the heat capacity along the coexistence curve of two
pressure of geraniol (M = 154.2 g mol−1), which is a component of oil of roses, phases.
was measured at 110 °C. It was found that, when 5.00 dm3 of nitrogen at 760
Integrated activities
4.1 Construct the phase diagram for benzene near its triple point at 36 Torr ln(p / bar) = −10.418/y + 21.157 − 15.996y + 14.015y 2
and 5.50 °C using the following data: ΔfusH = 10.6 kJ mol−1, ΔvapH = 30.8 kJ mol−1,
− 5.0120 y 3 + 4.7334(1 − y )1.70
ρ(s) = 0.891 g cm−3, ρ(l) = 0.879 g cm−3.
4.2‡ In an investigation of thermophysical properties of toluene, R.D. where y = T/Tc = T/(593.95 K). (a) Plot the solid–liquid and liquid–vapour
Goodwin (J. Phys. Chem. Ref. Data 18, 1565 (1989)) presented expressions for phase boundaries. (b) Estimate the standard melting point of toluene. (c)
two phase boundaries. The solid–liquid boundary is given by Estimate the standard boiling point of toluene. (d) Compute the standard
enthalpy of vaporization of toluene, given that the molar volumes of the liquid
p / bar = p3/bar + 1000(5.60 + 11.727x )x and vapour at the normal boiling point are 0.12 dm3 mol−1 and 30.3 dm3 mol−1,
respectively.
where x = T/T3 – 1 and the triple point pressure and temperature are 4.3 Proteins are polymers of amino acids that can exist in ordered structures
p3 = 0.4362 µbar and T3 = 178.15 K. The liquid–vapour curve is given by: stabilized by a variety of molecular interactions. However, when certain
conditions are changed, the compact structure of a polypeptide chain may
collapse into a random coil. This structural change may be regarded as a
phase transition occurring at a characteristic transition temperature, the
‡ These problems were supplied by Charles Trapp and Carmen Giunta. melting temperature, Tm, which increases with the strength and number
Exercises and problems 177
of intermolecular interactions in the chain. A thermodynamic treatment methane (D.G. Friend, J.F. Ely, and H. Ingham, J. Phys. Chem. Ref. Data 18,
allows predictions to be made of the temperature Tm for the unfolding of a 583 (1989)), which included the following data describing the liquid–vapour
helical polypeptide held together by hydrogen bonds into a random coil. If a phase boundary.
polypeptide has N amino acids, N − 4 hydrogen bonds are formed to form an
α-helix, the most common type of helix in naturally occurring proteins (see T/K 100 108 110 112 114 120 130 140 150 160 170 190
Topic 17A). Because the first and last residues in the chain are free to move, p/MPa 0.034 0.074 0.088 0.104 0.122 0.192 0.368 0.642 1.041 1.593 2.329 4.521
N − 2 residues form the compact helix and have restricted motion. Based on
these ideas, the molar Gibbs energy of unfolding of a polypeptide with N ≥ 5
(a) Plot the liquid–vapour phase boundary. (b) Estimate the standard boiling
may be written as
point of methane. (c) Compute the standard enthalpy of vaporization of
methane, given that the molar volumes of the liquid and vapour at the
∆ unfoldG = (N − 4)∆ hb H − (N − 2)T ∆ hb S standard boiling point are 3.80 × 10−2 and 8.89 dm3 mol−1, respectively.
where ΔhbH and ΔhbS are, respectively, the molar enthalpy and entropy of 4.5‡ Diamond is the hardest substance and the best conductor of heat yet
dissociation of hydrogen bonds in the polypeptide. (a) Justify the form of the characterized. For these reasons, it is used widely in industrial applications
equation for the Gibbs energy of unfolding. That is, why are the enthalpy and that require a strong abrasive. Unfortunately, it is difficult to synthesize
entropy terms written as (N − 4)ΔhbH and (N − 2)ΔhbS, respectively? (b) Show diamond from the more readily available allotropes of carbon, such as
that Tm may be written as graphite. To illustrate this point, calculate the pressure required to convert
graphite into diamond at 25 °C. The following data apply to 25 °C and 100 kPa.
Assume the specific volume, Vs, and κT are constant with respect to pressure
(N − 4)∆ hb H
Tm = changes.
(N − 2)∆ hb S
(c) Plot Tm/(ΔhbHm/ΔhbSm) for 5 ≤ N ≤ 20. At what value of N does Tm change by Graphite Diamond
less than 1 per cent when N increases by 1? 0 +2.8678
ΔrG</(kJ mol−1)
4.4‡ A substance as well-known as methane still receives research attention Vs/(cm3 g−1) 0.444 0.284
because it is an important component of natural gas, a commonly used fossil
fuel. Friend et al. have published a review of thermophysical properties of κT/kPa 3.04 × 10−8 0.187 × 10−8