ENTROPY

CHE121 Physical Chemistry for Chemical Engineers 2 | Abdul Azis Pandi | BSChE

TOPIC 1 FIRST EXAMINATION

BASIC CONCEPTS ● To achieve the transfer of heat to a hotter body, it is necessary to do

work on the system.
● Entropy is the concept which explains why some physical ● If transfer occurs from a cold body, there is an external

transformations and chemical reactions are spontaneous and others intervention.

are not. ● The Second Law is expressed in terms of a new state function, the

● The change in entropy of a system can be calculated from the heat entropy, S.
transferred to it reversibly. ● The entropy of an isolated system increases in the course of a
● A spontaneous process in an isolated system is accompanied by an spontaneous change (ΔStot > 0).
increase in entropy. ● The First Law uses the internal energy to identify permissible
changes; the Second Law uses the entropy to identify which of these
Determining the direction of spontaneity permissible changes are spontaneous.
● The tendency to achieve a lower energy does not determine the
direction of spontaneity. The Definition of Entropy
● This is because the First Law asserts that the total energy of the
universe does not change in any process. The thermodynamic definition of entropy
● The manner in which energy and matter are distributed ● The thermodynamic definition of entropy concentrates on the change
determines the direction of spontaneity. in entropy, dS, that occurs as a result of a physical or chemical
● This concept is made precise by the Second Law of change associated with a process.
thermodynamics and made quantitative by introducing the ● Transferred heat, not work, determines the dispersion of energy.
property known as entropy. ● Heat stimulates random motion of atoms whereas work
stimulates their uniform motion and so does not change the
The Second Law OF THERMODYNAMICS extent of their disorder.

● The signpost of spontaneous change has been identified: look for the Equation
direction of change that leads to the dispersal of energy. The thermodynamic definition of entropy is based on the expression:

DEFINITION
The Kelvin definition of the Second Law states: where
𝑞𝑟𝑒𝑣 is the energy transferred as heat reversibly to the system
No process is possible in which the sole result is the absorption of heat
from a reservoir and its complete conversion into work. 𝑇 is the absolute temperature

For a measurable change between two states i and f:

● Statements like this are commonly explored by thinking about an
idealized device called a heat engine.
● A heat engine consists of two reservoirs, one hot (the ‘hot source’)
and one cold (the ‘cold source’), connected in such a way that
some of the energy flowing as heat between the two reservoirs ● To calculate the difference in entropy between any two states of a
can be converted into work. system, find a reversible path between them, and integrate the
energy supplied as heat at each stage of the path divided by the
temperature at which that heat is transferred.
● Entropy is a state function and is an extensive property.
● Molar entropy is an intensive property.
● Regardless of how the change is brought about in the system,
reversibly or irreversibly, the change of entropy of the surroundings is
calculated simply by dividing the heat transferred by the temperature
at which the transfer takes place.

● For any adiabatic change, qsur = 0, and therefore:

● This statement is true if the surrounding is in equilibrium.

(a) A heat engine is a device in which energy is extracted from a hot reservoir (the hot
● If hot spots form, localized energy subsequently disperses
source) as heat and then some of that energy is converted into work and the rest
spontaneously and increases entropy.
discarded into a cold reservoir (the cold sink) as heat. (b) The Kelvin statement of the
Second Law denies the possibility of the process illustrated here, in which heat is ● From the Kelvin definition, the transfer of energy as work does not
changed completely into work, there being no other change. result in the production of entropy, so the overall result is that the
entropy of the (overall isolated) system decreases.
● The Kelvin statement implies that it is not possible to construct a ● According to the Second Law, this is not a spontaneous process.
heat engine in which all the heat drawn from the hot source is ● In the Clausius definition, the entropy of the cold source decreases
completely converted into work: all working heat engines must when energy leaves it as heat, but when that heat enters the hot sink,
have a cold sink. the rise in entropy is not as great.
● Heat does not flow spontaneously from a cool body to a hotter body.

Abdul Azis Pandi | BS Chemical Engineering | Entropy

 ● This is because at the hot sink, the temperature is higher.
● Overall, there will also be a decrease in entropy, hence, the
process is not spontaneous.

THE Statistical definition of entropy

● Atoms and molecules are distributed over the energy states
available to them in accord with the Boltzmann distribution.
● As the temperature is increased the molecules populate higher
energy states.

Equation
The Boltzmann equation for entropy is given by:

where 1. The gas is in thermal contact with the hot sink at Th and undergoes
𝑘 is the Boltzmann constant (1.381 × 10−23 JK−1) a reversible isothermal expansion from A to B. The entropy change
𝑊 is the number of microstates is qh/Th.
2. The contact is broken and then undergoes a reversible adiabatic
expansion from B to C at Tc. It expands until Th falls to Tc. Entropy
● Microstates is the number of ways in which molecules of a system
change is zero.
can be distributed over the energy states for a specific total energy.
3. The gas is in thermal contact with the cold sink at Tc and undergoes
● At the same total energy, the microstates increases if there is:
reversible isothermal compression from C to D at Tc where energy
1. more disorderly distribution of matter
is released to the cold sink. Entropy change is qc/Tc.
2. greater dispersal of energy
4. The contact is broken and then undergoes reversible adiabatic
3. separation of energy states decreases, since more states become
compression from D to A until Tc rises to Th. Entropy change is zero.
accessible
● As W increases, entropy also increases.
Total entropy for the carnot cycle
● Entropy change depends inversely on temperature.
● The total entropy change around the Carnot cycle is:
● Increasing the energy of a high temperature system makes more
states accessible but since many of them are already occupied,
the change in W is relatively small.
● Hence, ΔS is small too.
● If this is done on a low temperature system, the change in W and
ΔS will be greater.
Proving that entropy is a state function

Proving that ΔS for a perfect gas is zero

● Recall from the First Law of Thermodynamics the equation for
isothermal processes (stages 1 and 3).

● For the adiabatic processes (stages 4 and 2):

● Multiply the right and left hand sides from the first equation and
𝑐 𝑐
cancel the 𝑇ℎ𝑇𝑐 terms.
● The Boltzmann definition of entropy makes it possible to calculate for
the value of S, whereas the thermodynamic definition only allows the
calculation for ΔS.
● However, it cannot be applied to the surroundings since it will be ● On cancellation of the temperatures, we obtain:
too complex for W to have a meaningful quantity.

Entropy as a state function

● Write an expression for energy discarded as heat to the cold sink in
● Entropy is a state function. terms of VA and VB.

● To prove this, there are three steps:

● Since qh is simply the negative of qc (since the heat gained by qc is the
1. Show that the equation is true for a special cycle (Carnot cycle)
heat lost by qh), we obtain:
for a perfect gas (the working substance).
2. Show that the equation is true for any working substance.
3. Show that the equation is true for any cycle.

The Carnot Cycle ● Rearrange the expression:

● It consists of four reversible changes for a perfect gas.

Abdul Azis Pandi | BS Chemical Engineering | Entropy

 ● Because the total change in entropy around the cycle is qh/Th + qc/Tc, ● Remember that internal energy (U) is a state function.
it follows that for a perfect gas, this entropy change is zero.
● We introduce efficiency, defined as:
● This also means that:
Equation
The definition of efficiency is given by:

● Dividing both sides by T, we obtain the definition of entropy from

dqrev, and we obtain the Clausius inequality.

● All efficiencies are positive numbers.

Equation
The Clausius inequality is given by:
● The higher the work output, the greater the efficiency.
● It can be expressed in terms of heat transferred, q.
● We define work as the difference between the energy supplied as
heat by the hot source and that returned to the cold source.
● For a system isolated from its surroundings where dq = 0, it follows
that:

● And since qc/qh = Tc/Th, we can rewrite the expression as: ● It means that in an isolated system, the entropy cannot decrease
when a spontaneous change occurs.
● The Clausius inequality implies that spontaneous processes are
irreversible processes.
● The Second Law of Thermodynamics implies that all reversible
engines have the same efficiency regardless of their construction.
● This suggests that heat transfers and the temperatures are
independent of the working material. ● A reversible process for which dStot = 0 is at equilibrium.
● Therefore, the equation is true for any substance involved in a
Carnot cycle. Additional information
● ∆Sfus and ∆Svap always positive because in each of these transitions,
Proving that the equation is true for any reversible cycle attractive forces must be overcome.
● Any reversible cycle can be broken down into a collection of smaller ● The efficiency of a Carnot heat engine is the highest efficiency of a
Carnot cycles. heat engine because the maximum work that can be done on the
surroundings by the expansion of a gas is in a reversible process.
● All definitions of efficiency are applicable to real gases as well as
ideal gases.
● Efficiency’s definition is independent of the type of material
involved in a process.

● The entropy change in each individual Carnot cycle is zero (as

proven), therefore, the total entropy change must also be zero.
● The more Carnot cycle used, the more accurate the approximation
is.
● This implies that entropy is a state function and is an exact
differential.

Equation
The thermodynamic temperature is given by the equation:

The Clausius inequality

● To show that Clausius’ definition of entropy is consistent with the
Second Law, remember that more work is done when a change is
reversible than when it is irreversible.

Abdul Azis Pandi | BS Chemical Engineering | Entropy

 ENTROPY CHANGES ACCOMPANYING PROCESSES
CHE121 Physical Chemistry for Chemical Engineers 2 | Abdul Azis Pandi | BSChE

TOPIC 2 FIRST EXAMINATION

BASIC CONCEPTS ● The opposite is true for endothermic processes.

● At the transition temperature, ΔStot is zero between the two phases
● The ΔS for the surrounding is the same regardless of reversibility. since they are in equilibrium.
● The ΔStot of an (overall) isolated system (the universe) is: ● An interesting feature of the data is that a wide range of liquids give
approximately the same standard entropy of vaporization (about 85
JK−1mol−1).
● This empirical observation is called Trouton’s rule.
● It states that a similar change in volume occurs when any liquid
Expansion evaporates and becomes a gas.
● All liquids can be expected to have similar standard entropies of
● The entropy of a perfect gas increases when it expands
vaporization.
isothermally.
● It is established that the change in entropy of a perfect gas when it
expands isothermally from Vi to Vf is:

● Since ΔS is a state function, this expression also applies regardless

of reversibility.
● The ΔStot, however, depends on how the expansion takes place.
● For any process the energy lost as heat from the system is acquired
by the surroundings.
The standard enthalpies and entropies of vaporization
of liquids at their boiling temperatures.
● For the reversible isothermal expansion of a perfect gas:
● Deviations from this rule are due to strong molecular interactions
that result in partial order of their molecules.
● Therefore, we obtain the expression for the entropy of the ● Therefore, there is greater change in disorder when the liquid

surroundings. turns into a vapor than for a fully disordered liquid.

● Fewer translational and rotational states are accessible at room
temperature.
● For molecules with low mass and moments of inertia, the molar
● This change is negative of the change in the system, so we expect entropy is slightly lower than for molecules with relatively high
ΔStot to be equal to zero. mass and moments of inertia.
● If isothermal expansion occurs freely (if the expansion is into a
vacuum), no work is done (w = 0). Heating
● Since expansion is isothermal, ΔU = 0, therefore, according to the ● The increase in entropy when a substance is heated is calculated
First Law, q = 0. from its heat capacity.
● For the expansion doing no work, the ΔStot is given by: ● The thermodynamic definition of entropy change is used to calculate
the entropy of a system at a temperature Tf from a knowledge of its
entropy at another temperature Ti and the heat supplied.

● In this case, ΔS > 0 is expected for an irreversible process because

it is spontaneous.

● Constant pressure heating is given by:

Phase transitions
● A transition is expected to be accompanied by a change in entropy.
● From the definition of constant-pressure heat capacity, it follows that
● For instance, when solid ice (higher entropy) melts into liquid
dH = CpdT, and hence dqrev = CpdT. Substitution gives us:
water (lower entropy), there is an associated entropy change.
● The change in entropy of a substance accompanying a change of
state at its transition temperature is calculated from its enthalpy of
transition.
● The normal transition temperature (Ttrs) is the temperature at ● The same expression applies at constant volume, but with Cp
which two phases are in equilibrium at 1 atm. replaced by CV.
● At the Ttrs, any transfer of heat between the system and its
surroundings is reversible (since they are at equilibrium). Composite Processes
● Since, at constant pressure q = ΔtrsH, the change in molar entropy of
a system is: ● In many processes, more than one parameter changes.
● These are called composite processes.
● For instance, it might be the case that both the volume and the
temperature of a gas are different in the initial and final states.
● If the phase transition is exothermic (ΔtrsH < 0), then the entropy ● It might be convenient to split the path into steps.
change of the system is negative.

Abdul Azis Pandi | BS Chemical Engineering | Entropy Changes Accompanying Processes

 ENTROPY MEAsurements
CHE121 Physical Chemistry for Chemical Engineers 2 | Abdul Azis Pandi | BSChE

TOPIC 3 FIRST EXAMINATION

BASIC CONCEPTS ● The change in entropy that accompanies the formation of

compounds is also zero.
● The entropy of a substance can be determined by calorimetric
measurements of the heat required to raise the temperature of a
Residual entropies
sample from T = 0 to the temperature of interest.
● In certain cases ,W > 1 at T = 0, and therefore S(0) > 0.
● There are then two equations to use.
● In this case, if S(0) > 0 the substance is said to have a residual
● One is the dependence of entropy on temperature.
entropy.
● The residual entropy of a solid is the entropy arising from disorder
that persists at T = 0.
−1 −1
● For example, ice has a residual entropy of 3.4 JK mol stemming

● The second is the contribution of a phase change to the entropy: from the arrangement of the hydrogen bonds.

Third law entropies

● Entropies reported on the basis that S(0) = 0 are called Third Law
entropies.
The calorimetric measurement of entropy ● When the substance is in its standard state at the temperature T,
the standard entropy is denoted S⦵(T).
● When a process involves heating from a base temperature to a final
● It is defined as the difference between the molar entropies of the
temperature, the total entropy is the sum of the individual entropies
pure, separated products and reactants, being in their standard
of each process, including phase transitions.
states at the specified temperature.
● Provided all measurements are made at 1 bar on a pure material, the
final value is the standard entropy, S⦵(T).
● Division by the amount of substance, n, gives the standard molar
entropy, Sm⦵(T).
● One problem with the determination of entropy is the difficulty of ● Standard reaction entropies are likely to be positive if there is a net
measuring heat capacities near T = 0. formation of gas in a reaction.
● There are theoretical grounds for assuming that the heat capacity ● They are likely to be negative if there is a net consumption of gas.
of a non-metallic solid is proportional to T3 when T is low.
● This dependence is the basis of the Debye extrapolation. SOLUTION ENTROPIES
● In this method, Cp is measured down to as low a temperature as ● Solutions of cations cannot be prepared in the absence of anions.
possible and a curve of the form aT3 is fitted to the data. ● The standard molar entropies of ions in solution are reported on a
scale in which the standard entropy of the H+ ions in water is taken as
The third law of thermodynamics zero at all temperatures:

DEFINITION
The Third Law of Thermodynamics states: ● A positive entropy means that an ion has a higher molar entropy
than H+ in water.
All perfect crystalline compounds have zero entropy at T = 0. ● A negative entropy means that the ion has a lower molar entropy
than H+ in water.
● At T = 0, all energy of thermal motion has been quenched, and in a ● Small, highly charged ions induce local structure and decrease the
perfect crystal all the atoms or ions are in a regular, uniform array. disorder of the solution, hence, decreases entropy.
● This decrease is greater than in the case of large, singly charged
● The absence of thermal motion suggests that such materials also
have zero entropy. ions.
● This is consistent with the Boltzmann equation for entropy because
there is only one way of arranging the molecules when they are all in The temperature dependence of reaction entropy
the ground state, which is the case at T = 0.
● Thus, at T = 0, W = 1 and from S = klnW it follows that S = 0. ● The temperature dependence of entropy is given by:

The Nernst Heat theorem

● The Nernst heat theorem summarizes a series of experimental ● This equation applies to each substance in the reaction.
observations consistent with the view that the entropy of a regular ● The temperature dependence of the standard reaction entropy is:
array of molecules is zero at T = 0.

DEFINITION
The Nernst heat theorem states: ● ΔrCp⦵ is the difference of the molar heat capacities of products and
reactants under standard conditions weighted by stoichiometry.
The entropy change accompanying any physical or chemical ● If ΔrCp⦵ is independent of temperature in the range T1 to T2, use:
transformation approaches zero as the temperature approaches zero
provided all the substances involved are perfectly ordered.

Abdul Azis Pandi | BS Chemical Engineering | Entropy Measurements

 Concentrating on system entropies
CHE121 Physical Chemistry for Chemical Engineers 2 | Abdul Azis Pandi | BSChE

TOPIC 4 FIRST EXAMINATION

Basic Concepts Remarks on the Helmholtz energy

● At constant temperature and volume, a change is spontaneous if it
● Entropy is the basic concept for discussing the direction of natural corresponds to a decrease in the Helmholtz energy.
change. ● The criterion of equilibrium, when neither the forward nor reverse
● The Clausius inequality implies a number of criteria for spontaneous process has a tendency to occur is dAT,V = 0.
change under a variety of conditions which may be expressed in ● Systems change spontaneously if in doing so the total entropy of the
terms of the properties of the system alone. system and its surroundings increases, not because they tend to
lower internal energy.
The Helmholtz and Gibbs energies
Maximum work
● When a change in the system occurs and there is a transfer of
energy as heat between the system and the surroundings, the ● The change in the Helmholtz energy is equal to the maximum work
Clausius inequality is: obtainable from a system at constant temperature.

Proving maximum work

● We combine the Clausius inequality in the form TdS ≥ dq with the
Criteria for spontaneity
First Law, dU = dq + dw, and obtain:
● Consider heating at constant volume.
● Under these conditions and in the absence of additional
(non-expansion) work, dqV = dU, and therefore: ● The term dU is smaller than the sum of the two terms on the right
because TdS in general is larger than dq.
● This expression rearranges to:

● This inequality expresses the criterion for spontaneous change solely

in terms of the state functions of the system. ● It follows that the most negative value of dw is obtained when the
equality applies, which is for a reversible process.

● When energy is transferred as heat at constant pressure and there

is no work other than expansion work, dqP = dH, and the equation ● Because at constant temperature dA = dU − TdS, this is now
becomes: equivalent to dwmax.
● A is sometimes called the maximum work function.
● When a measurable isothermal change takes place in the system, the
● If the enthalpy is constant as well as the pressure, this relation equation becomes wmax = ΔA where ΔA = ΔU − TΔS.
becomes TdS ≥ 0 and therefore dS ≥ 0 (dSH,P ≥ 0). ● For change to be spontaneous, some energy must escape as heat in
● The criteria of spontaneity at constant volume and pressure can be order to generate enough entropy in the surroundings to overcome
expressed more simply by introducing two more thermodynamic the reduction in entropy in the system.
quantities. ● ΔA is that part of the change in internal energy free to do work.

● One is the Helmholtz energy (A) which is defined as:

Remarks on the Gibbs energy
● At constant temperature and pressure, chemical reactions are
● The other is the Gibbs energy (G). spontaneous in the direction of decreasing Gibbs energy.
● To decide whether a reaction is spontaneous, the pressure and
temperature being constant, it is necessary to assess the change in
● All the symbols in these two definitions refer to the system. the Gibbs energy.
● When the state of the system changes at constant temperature, the ● If G decreases as the reaction proceeds, then the reaction has a

two properties change as follows: spontaneous tendency to convert the reactants into products.
● If G increases, the reverse reaction is spontaneous.
● The criterion for equilibrium under conditions of constant
● The criteria of spontaneous change in terms of dA and dG are: temperature and pressure is dGT,P = 0.

Maximum non-expansion work

● Endothermic reactions are driven by the increase of entropy of the ● At constant temperature and pressure, the change in Gibbs energy
system, which overcomes the reduction of entropy brought about in is equal to the maximum additional (non-expansion) work.
the surroundings.
● Exothermic reactions are commonly spontaneous because dH < 0
and then dG < 0, provided TdS is not so negative that it outweighs the
decrease in enthalpy.

Abdul Azis Pandi | BS Chemical Engineering | Concentrating on System Entropies

Proving maximum non-expansion work
● Because H = U + pV and dU = dq + dw, the change in enthalpy for a
general change in conditions is:

● The corresponding change in Gibbs energy (G = H − TS) is:

● When the change is isothermal (dT = 0), then:

● When the change is reversible, dw = dwrev and dq = dqrev = TdS.

Therefore, for a reversible, isothermal process:

● The work consists of expansion work, which for a reversible change is

given by −pdV, and possibly some other kind of work.
● This additional work is denoted as dwadd.
● Therefore, with d(pV) = pdV + Vdp, we obtain:

● If the change occurs at constant pressure and temperature, dp = 0

and hence dG = dwadd,rev.
● However, because the process is reversible, the work done must now
have its maximum value, so it follows that dwadd,max = dG.
● For a measurable change, the expression is wadd,max = ΔG.

Standard molar gibbs energies

● Standard entropies and enthalpies of reaction can be combined to
obtain the standard Gibbs energy of reaction (ΔrG⦵):

● The standard Gibbs energy of reaction is the difference in standard

molar Gibbs energies of the products and reactants in their
standard states for the reaction at the temperature specified.

The Gibbs energies of formation

● It is convenient to define the standard Gibbs energies of formation,

ΔfG⦵, for the formation of a compound from its elements in their
reference states.
● Standard Gibbs energies of formation of the elements in their
reference states are zero.
● This is because their formation is a null reaction.

● Similarly in the last topic, the standard enthalpy of formation of H+ in

water by convention is taken to be zero.

Abdul Azis Pandi | BS Chemical Engineering | Concentrating on System Entropies

 Combining the First and Second Laws
CHE121 Physical Chemistry for Chemical Engineers 2 | Abdul Azis Pandi | BSChE

TOPIC 5 FIRST EXAMINATION

Basic concepts The variation of internal energy with volume

● The First Law of thermodynamics may be written dU = dq + dw. ● The internal pressure (πT) is defined as πT = (∂U/∂V)T and represents
● For a reversible change in a closed system of constant composition how the internal energy changes as the volume of a system is
in the absence of any additional (non-expansion) work, dwrev = −pdV changed isothermally.
and dqrev = TdS. ● Using Maxwell relations, it can be expressed as a function of
pressure and temperature.
Equation
The fundamental equation is given by: Internal pressure as a function of pressure and temperature
● To construct the partial differential (∂U/∂V)T we divide both sides by
dV, and impose the constraint of constant temperature.

● This combination of the First and Second Laws is called the

fundamental equation.
● Because dU is an exact differential, its value is independent of
path. ● Introduce the two Maxwell relations for T and P.
● Therefore, the same value of dU is obtained whether the change is
brought about irreversibly or reversibly.
● The fundamental equation applies to any change—reversible or
irreversible—of a closed system that does no additional
(non-expansion) work. ● The Maxwell relation in the previous table turns (∂S/∂V)T into
(∂p/∂T)V. We then obtain:

Properties of the internal energy

● U is best regarded as a function of S and V.
● The simplicity of the fundamental equation suggests that U(S,V) is ● Expressing it as pressure:
the best function.

● This is called a thermodynamic equation of state, an expression for

● The two partial derivatives are the slopes of the plots of U against S pressure in terms of a variety of thermodynamic properties of the
at constant V, and U against V at constant S. system.
● When this expression is compared term-by-term to the
thermodynamic relation, it follows that for systems of constant
Properties of the Gibbs energy
composition:
● The Gibbs energy of a substance decreases with temperature and
increases with pressure.
● When the system undergoes a change of state, G may change
● The first of these two equations is a purely thermodynamic definition because H, T, and S all change.
of temperature as the ratio of the changes in the internal energy (a
First-Law concept) and entropy (a Second-Law concept) of a
constant-volume, closed, constant-composition system. ● Because H = U + pV, we get:

The Maxwell relations

● The Maxwell relations are a series of relations between partial
derivatives of thermodynamic properties based on criteria for ● For a closed system doing no non-expansion work, dU can be
changes in the properties being exact differentials. replaced by the fundamental equation (dU = TdS − pdV) to give:

● Four terms now cancel on the right, and so for a closed system in the
absence of non-expansion work and at constant composition, we
obtain:

Equation
The fundamental equation of chemical thermodynamics is given by:

● This expression, which shows that a change in G is proportional to a

change in p or T, suggests that G may be best regarded as a function
The Maxwell relations of p and T.

Abdul Azis Pandi | BS Chemical Engineering | Combining the First and Second Laws
 ● When applied to the exact differential dG = Vdp − SdT, it gives us:

● These relations show how the Gibbs energy varies with

temperature and pressure.
● The Gibbs energy of the gaseous phase of a substance, which has a
high molar entropy, is more sensitive to temperature than its liquid
and solid phases.
● Because the molar volume of the gaseous phase of a substance
is greater than that of its condensed phases, the molar Gibbs
energy of a gas is more sensitive to pressure than its liquid and
solid phases.

The variation of the Gibbs energy with temperature

● (∂G/∂T)p = −S can be expressed in terms of the enthalpy by using

the definition of G to write S = (H − G)/T.

● The equilibrium constant of a reaction is related to G/T rather than

to G itself.

The Gibbs-Helmholtz equation

● The Gibbs–Helmholtz equation is most useful when it is applied to
changes, including changes of physical state, and chemical reactions
at constant pressure.

● This equation shows that if the change in enthalpy of a system that

is undergoing some kind of transformation (such as vaporization or
reaction) is known, then how the corresponding change in Gibbs
energy varies with temperature is also known.
● The Gibbs energies of solids and liquids are almost independent of
pressure.
● The Gibbs energies of gases vary linearly with the logarithm of
the pressure.

Abdul Azis Pandi | BS Chemical Engineering | Combining the First and Second Laws
 Thermodynamic Diagrams and transitions
CHE121 Physical Chemistry for Chemical Engineers 2 | Abdul Azis Pandi | BSChE

TOPIC 6 FIRST EXAMINATION

The stabilities of phases Thermodynamic criteria for phase stability

● Thermodynamics provides a powerful framework for describing and ● All the following considerations are based on the Gibbs energy of a
understanding the stabilities and transformations of phases. substance.
● A phase is a form of matter that is uniform throughout in chemical ● For a system that consists of a single substance, the molar Gibbs
composition and physical state. energy and the chemical potential are exactly the same: μ = Gm.
● Thus, there are the solid, liquid, and gas phases of a substance ● The chemical potential of a substance (μ), is defined as the change
● The number of phases in a system is denoted P. in the Gibbs energy with respect to an amount at constant
● For example, two metals form a two-phase system (P = 2) if they temperature and pressure.
are immiscible, but a single-phase system (P = 1) if they are ● At equilibrium, the chemical potential of a substance is the same
miscible (and actually mixed) such as alloys. in and throughout every phase present in the system.

When two or more phases are in equilibrium, the chemical potential of a substance
(and, in a mixture, a component) is the same in each phase, and is the same at all
points in each phase.
The difference between (a) a single-phase solution, in which the composition is
uniform on a molecular scale, and (b) a dispersion, in which regions of one
Phase boundaries
component are embedded in a matrix of a second component.
● The phase diagram of a pure substance shows the regions of
pressure and temperature at which its various phases are
Phase transitions thermodynamically stable.

● A phase transition, the spontaneous conversion of one phase into

another phase, occurs at a characteristic transition temperature, Ttrs,
for a given pressure.
● At Ttrs, the two phases are in equilibrium and the Gibbs energy of the
system is a minimum at the prevailing pressure.
● Thermal analysis, which takes advantage of the heat that is evolved
or absorbed during a transition, can be used to identify the phases in
almost uniform mixtures.
● If the phase transition is exothermic and the temperature of a
sample is monitored as it cools, the presence of the transition can
be recognized by a pause in the otherwise steady fall of the
temperature.
● The lines separating the regions, which are called phase boundaries,
show the values of p and T at which two phases coexist in
equilibrium and their chemical potentials are equal.
● A single phase is represented by an area on a phase diagram.

Characteristic properties related to phase transitions

● The pressure of a vapor in equilibrium with the liquid is its vapor

pressure.
● The vapor pressure of a substance increases with temperature
because at higher temperatures more molecules have sufficient
energy to escape from their neighbors.
● This condition of free vaporization throughout the liquid in which

A cooling curve at constant pressure. The flat section corresponds to the pause in the the vapor pressure is equal to the external pressure is called
fall of temperature while an exothermic transition (freezing) occurs. This pause boiling.
enables Tf to be located even if the transition cannot be observed visually. ● Normal properties are measured at 1 atm, whereas standard
properties are measured at 1 bar.
● Thermodynamically unstable phases that persist because the ● The temperature at which a phase surface disappears is the critical
transition is kinetically hindered are called metastable phases. temperature (Tc) of the substance.
● For example, diamond is a metastable but persistent phase of ● The vapor pressure at the critical temperature is called the critical
carbon under normal conditions. pressure (pc).

Abdul Azis Pandi | BS Chemical Engineering | Thermodynamic Diagrams and Transitions

 ● At and above the critical temperature, a single uniform phase
called a supercritical fluid fills the container and an interface no The dependence of stability on conditions
longer exists.
● There is a set of conditions under which three different phases of a ● At sufficiently low temperatures, the solid phase of a substance has
substance (typically solid, liquid, and vapor) all simultaneously the lowest chemical potential and is therefore the most stable
coexist in equilibrium. phase.
● These conditions are represented by the triple point, a point at ● The chemical potentials of different phases depend on
which the three phase boundaries meet. temperature because the molar entropy of each phase is
● The triple point of a pure substance cannot be changed. different.
● It occurs at a single definite pressure and temperature
characteristic of the substance. The temperature dependence of phase stability
● The chemical potential of a pure substance decreases as the
The phase rule temperature is raised.
● It also implies that because Sm(g) > Sm(l). The slope is steeper for
● The phase rule gives the number of parameters that can be varied gases than for liquids.
independently while the number of phases in equilibrium is ● It is also almost always the case that Sm(l) > Sm(s). The slope is also
preserved. steeper for a liquid than the corresponding solid.
● The variance (or number of degrees of freedom), F, of a system is ● The phase with the lowest chemical potential at a specified
the number of intensive variables that can be changed temperature is the most stable one at that temperature.
independently without disturbing the number of phases in
equilibrium. The response of melting to applied pressure
● A constituent of a system is any chemical species that is present. ● In most cases, Vm(l) > Vm(s), so an increase in pressure increases the
● A component is a chemically independent constituent of a chemical potential of the liquid phase of a substance more than that
system. of its solid phase.
● The number of components, C, in a system is the minimum number ● The pressure dependence of the chemical potential of a substance
of types of independent species (ions or molecules) necessary to depends on the molar volume of the phase.
define the composition of all the phases present in the system.
The vapor pressure of a liquid subjected to pressure
Equation ● Pressure can be exerted on the condensed phase mechanically or by
The phase rule is given by: subjecting it to the applied pressure of an inert gas.
● In the latter case, the partial vapor pressure is the partial pressure
of the vapor in equilibrium with the condensed phase.
where ● When pressure is applied to a condensed phase, its vapor
𝐶 is the number of components pressure rises.
𝐹 is the degrees of freedom ● In effect, molecules are squeezed out of the phase and escape as
𝑃 is number of phases a gas.
● Gas solvation is the attachment of molecules to gas-phase species.

● A system having two degrees of freedom is said to be bivariant. Pressure may be applied to a condensed phase either (a) by compressing it or (b) by
subjecting it to an inert pressurizing gas. When pressure is applied, the vapor
● In other words, a single phase is represented by an area on a
pressure of the condensed phase increases.
phase diagram.
● When two phases are in equilibrium (F = 1), it follows that the
The location of phase boundaries
equilibrium of two phases is represented by a line in the phase
● The precise locations of the phase boundaries—the pressures and
diagram.
temperatures at which two phases can coexist—can be found by the
● When three phases are in equilibrium (F = 0), the system is said to
fact that when two phases are in equilibrium their chemical
be invariant and is therefore represented by a point.
potentials must be equal.
● The triple point on a phase diagram represents an invariant
system.
● Four phases cannot be in equilibrium in a one-component system
The slopes of phase boundaries
because F cannot be negative.
● When T and P are changed infinitesimally, the phases remain in
equilibrium but their chemical potentials change.
Thermodynamic aspects of phase transition ● The change in chemical potential of phase α is the same as the
change in chemical potential of phase β.
● By using the notation of partial derivatives, the variation of chemical ● The Clapeyron equation is an exact expression for the slope of a
potential with temperature and pressure is: phase boundary.
● The Clausius–Clapeyron equation is an approximate expression for
the boundary between a condensed phase and its vapor.

Abdul Azis Pandi | BS Chemical Engineering | Thermodynamic Diagrams and Transitions