3.

7 The Fundamental Equation

• First Law of thermodynamics:
dU = dq + dw
• For a reversible change in a closed system of constant
composition, and in the absence of any additional (non-
expansion) work,
dwrev = −pdV
• and from the definition of entropy,
dqrev = TdS
where p is the pressure of the system and T its temperature.
• For a reversible change in a closed system,
dU = TdS – pdV (3.43)
• eqn 3.43 applies to any change—reversible or irreversible—of
a closed system that does no additional (non-expansion) work.
The fundamental equation combines the First and Second
Laws.
 Fundamental Equations and Maxwell Relations

dU = TdS – pdV
Enthalpy:
H = U + pV
dH = TdS + Vdp
Helmholtz energy:
A = U – TS
dA = -SdT – pdV
Gibbs energy:
G = H – TS
dG = -SdT + Vdp
 Criteria for Spontaneity
• Consider a system in thermal equilibrium with
its surroundings at a temperature T. When a
change in the system occurs and there is a
transfer of energy as heat between the system
and the surroundings, the Clausius inequality,
eqn 3.12,

• Consider heating at constant volume, in the

absence of non-expansion work, dqV = dU
 Criteria for spontaneity (cont’d)

• When energy is transferred as heat at

constant pressure, and there is no work other
than expansion work, dqp = dH
 Chemical Potential
• For a one-component system, ‘molar Gibbs
energy’ Gm and ‘chemical potential’ µ (mu)
are synonyms, µ = Gm, but chemical
potential has a broader significance and a
more general definition. The name
‘chemical potential’ is also instructive: µ is
a measure of the potential that a substance
has for undergoing (physical and chemical)
change in a system.
 The thermodynamic criterion of
equilibrium
• As a result of the Second Law: at
equilibrium, the chemical potential of a
substance is the same throughout a sample,
regardless of how many phases are present.
When the liquid
and solid phases
of a substance are
in equilibrium,
the chemical
potential of the
substance is the
same throughout
the system.
The thermodynamic criterion of equilibrium (cont’d)
• Consider a system in which the chemical potential of a
substance is µ 1 at one location and µ 2 at another location. The
locations may be in the same or in different phases.
• When an amount dn of the substance is transferred from one
location to the other, the Gibbs energy of the system changes by
−µ 1dn when material is removed from location 1, and it changes
by +µ 2dn when that material is added to location 2.
• The overall change is dG = (µ 2 − µ 1)dn.
• If the chemical potential at location 1 is higher than that at
location 2, the transfer is accompanied by a decrease in G, and
so has a spontaneous tendency to occur.
• Only if µ 1 = µ 2 is there no change in G, and only then is the
system at equilibrium.
• The transition temperature, Ttrs, is the temperature at which the
chemical potentials of two phases are equal.
The schematic temperature
dependence of the chemical
potential of the solid, liquid,
and gas phases of a substance
(in practice, the lines are
curved). The phase with the
lowest chemical potential at a
specified temperature is the
most stable one at that
temperature. The transition
temperatures, the melting and
boiling temperatures (Tf and
Tb, respectively), are the
temperatures at which the
chemical potentials of the two
phases are equal.
The pressure dependence of
the chemical potential of a
substance depends on the
molar volume of the phase.
The effect of increasing
pressure on µ of the solid
and liquid phases (in
practice, the lines are
curved), and on the
freezing temperatures.
(a) The molar volume of
the solid is smaller than
that of the liquid and µ(s)
increases less than µ(l).
The freezing temperature
rises.
(b) Here the molar
volume is greater for
the solid than the
liquid (as for water),
µ(s) increases more
strongly than µ(l), and
the freezing
temperature is
lowered.
 Partial molar quantities - Partial molar volume
• The partial molar volume, V J ,of a substance J at some general composition is defined:

• where the subscript n′ signifies that the amounts of all other substances present are constant.
• When the composition of the mixture is changed by the addition of dnA of A and dnB of B, then the total volume
of the mixture changes by

• Because the partial molar volumes are constant, provided the composition is held constant as the amounts of A
and B are increased,

• Although we have envisaged the two integrations as being linked (in order to preserve constant composition),
because V is a state function, the final result in above eqn is valid however the solution is in fact prepared.
 Partial molar Gibbs energies
• The concept of a partial molar quantity can be
extended to any extensive state function. For a
substance in a mixture, the chemical potential is
defined as the partial molar Gibbs energy:

• The chemical potential is the slope of a plot of Gibbs

energy against the amount of the component J, with
the pressure and temperature (and the amounts of the
other substances) held constant.
• For a pure substance, G = nJGJ,m, and µ J = GJ,m: in this
case, the chemical potential is simply the molar Gibbs
energy of the substance.
The chemical potential
of a substance is the
slope of the total Gibbs
energy of a mixture with
respect to the amount of
substance of interest. In
general, the chemical
potential varies with
composition, as shown
for the two values at a
and b. In this case, both
chemical potentials are
positive.
 Partial molar Gibbs energies
• The total Gibbs energy of a binary mixture is

• where µ A and µ B are the chemical potentials at

the composition of the mixture. That is, the
chemical potential of a substance in a mixture is
the contribution of that substance to the total
Gibbs energy of the mixture.
 Fundamental Equation of Chemical Thermodynamics
• Because the chemical potentials depend on composition (and the pressure
and temperature), the Gibbs energy of a mixture may change when these
variables change, and for a system of components A, B, etc., the equation
dG = Vdp − SdT becomes

• At constant pressure and temperature,

• Additional (non-expansion) work can arise from the changing composition

of a system. For instance, in an electrochemical cell, the chemical reaction
is arranged to take place in two distinct sites (at the two electrodes). The
electrical work the cell performs can be traced to its changing composition
as products are formed from reactants.
 The wider significance of the chemical potential
U = −pV + TS + G

• At constant volume and entropy,

• µ J shows how all the extensive thermodynamic properties U, H, A, and G

depend on the composition. The chemical potential is central to chemistry.
 The Gibbs–Duhem equation

• When the compositions are changed infinitesimally, G of a binary system changes by

• At constant pressure and temperature, a change in Gibbs energy is given by

• Because G is a state function, these two equations must be equal. At constant

temperature and pressure,

• Gibbs–Duhem equation

• The significance of the Gibbs–Duhem equation: the chemical potential of one

component of a mixture cannot change independently of the chemical potentials of
the other components.
 The thermodynamics of mixing

• The dependence of the Gibbs energy of a mixture

on its composition is given by above eqn
• At constant temperature and pressure systems tend
towards lower Gibbs energy. This is the link we
need in order to apply thermodynamics to the
discussion of spontaneous changes of composition,
as in the mixing of two substances
• One simple example of a spontaneous mixing
process is that of two gases introduced into the
same container. The mixing is spontaneous, so it
must correspond to a decrease in G.
mixing of two perfect gases
 The Gibbs energy of mixing of perfect gases
• Let the amounts of two perfect gases in the two
containers be n A and n B; both are at a temperature
T and a pressure p. The chemical potentials of the
two gases have their ‘pure’ values, which are
obtained by applying the definition µ = Gm to
eqn 3.57:

• where µ is the standard chemical potential, the

chemical potential of the pure gas at 1 bar. Let p
denote the pressure relative to p ; replace p/p by p,
 The Gibbs energy of mixing of perfect gases
• The Gibbs energy of the total system

• After mixing, the partial pressures of the gases are pA and pB,
with pA + pB = p. The total Gibbs energy changes to

• The difference Gf − Gi, the Gibbs energy of mixing, ∆ mixG,

• pJ/p = xJ for each component

 ∆mixG < 0
The Gibbs energy of
mixing of two perfect
gases and (as discussed
later) of two liquids that
form an ideal solution. The
Gibbs energy of mixing is
negative for all
compositions and
temperatures, so perfect
gases mix spontaneously in
all proportions.
 Other thermodynamic mixing functions
• Because (∂G/∂T)p,n = −S, for a mixture of perfect gases initially at the same
pressure, the entropy of mixing, ∆ mixS, is

• Because ln x < 0, ∆ mixS > 0 for all compositions.

• For equal amounts of gas, e.g., set xA = xB = 1/2 , ∆ mixS = nR ln 2, with n the
total amount of gas molecules.
• Increase in entropy: when one gas disperses into the other and the disorder
increases.
• Isothermal, isobaric (constant p) enthalpy of mixing, ∆ mixH, the enthalpy
change accompanying mixing, of two perfect gases from ∆G = ∆H − T∆S.

• The enthalpy of mixing is zero, as we should expect for a system in which

there are no interactions between the molecules forming the gaseous mixture.
It follows that the whole of the driving force for mixing comes from the
increase in entropy of the system, because the entropy of the surroundings is
unchanged.
The entropy of mixing of two
perfect gases and (as discussed
later) of two liquids that form
an ideal solution. The entropy
increases for all compositions
and temperatures, so perfect
gases mix spontaneously in all
proportions. Because there is
no transfer of heat to the
surroundings when perfect
gases mix, the entropy of the
surroundings is unchanged.
Hence, the graph also shows
the total entropy of the system
plus the surroundings when
perfect gases mix.
 The chemical potentials of liquids
• To discuss the equilibrium properties of liquid mixtures we
need to know how the Gibbs energy of a liquid varies with
composition. At equilibrium, the chemical potential of a
substance present as a vapor must be equal to its chemical
potential in the liquid.
• (a) Ideal solutions
• Denote quantities relating to pure substances by a superscript *,
so the chemical potential of pure A is written µ A*, and as µ A*(l)
when we need to emphasize that A is a liquid. Because the
vapor pressure of the pure liquid is p A*, the chemical potential
of A in the vapor (treated as a perfect gas) is µ A + RT ln p A*
(with pA to be interpreted as the relative pressure pA/p ). These
two chemical potentials are equal at equilibrium,
At equilibrium, the chemical
potential of the gaseous form
of a substance A is equal to
the chemical potential of its
condensed phase. The
equality is preserved if a
solute is also present.
Because the chemical
potential of A in the vapor
depends on its partial vapor
pressure, it follows that the
chemical potential of liquid
A can be related to its partial
vapor pressure.
 Ideal solutions
• If another substance, a solute, is also present in the liquid, the chemical potential
of A in the liquid is changed to µ A and its vapor pressure is changed to pA. The
vapor and solvent are still in equilibrium, so

• Combine two equations to eliminate the standard chemical potential of the gas.
Write µ A = µ A* – RT ln pA* and substitute into above eqn

• Raoult’s law: the ratio of the partial vapor pressure of each component to its
vapor pressure as a pure liquid, pA/pA*, is approximately equal to the mole
fraction of A in the liquid mixture.

• For an ideal solution (definition of an ideal solution),

The total vapor pressure
and the two partial vapor
pressures of an ideal
binary mixture are
proportional to the mole
fractions of the
components.
Some mixtures obey
Raoult’s law very well,
especially when the
components are
structurally similar.
Mixtures that obey the law
throughout the
composition range from
pure A to pure B are called
ideal solutions.
 The solvent activity
• µ A = µ A * + RT ln xA -- The form of the this relation can be preserved
when the solution does not obey Raoult’s law by writing

• The quantity aA is the activity of A, a kind of ‘effective’ mole fraction,

just as the fugacity is an effective pressure.
A convenient way of expressing this convergence is to introduce the activity coefficient,
γ, by the definition

at all temperatures and pressures. The chemical potential of the solvent is then

The standard state of the solvent, the pure liquid solvent at 1 bar, is established when xA = 1
 The reaction Gibbs energy
• Consider the equilibrium A B (isomerization)
• Suppose an infinitesimal amount dξ of A turns into B, then the
change in the amount of A present is dnA = −dξ and the
change in the amount of B present is dnB = +dξ. The quantity
ξ (xi) is called the extent of reaction; it has the dimensions of
amount of substance and is reported in moles. When the extent
of reaction changes by a finite amount ∆ξ, the amount of A
present changes from nA,0 to nA,0 − ∆ξ and the amount of B
changes from nB,0 to n B,0 + ∆ξ.
• So, if initially 2.0 mol A is present and we wait until ∆ξ =
+1.5 mol, then the amount of A remaining will be 0.5 mol.
• The reaction Gibbs energy, ∆rG, is defined as the slope of the
graph of the Gibbs energy plotted against the extent of reaction:
 The reaction Gibbs energy
• Although ∆ normally signifies a difference in values, here ∆r
signifies a derivative, the slope of G with respect to ξ.
However, to see that there is a close relationship with the
normal usage, suppose the reaction advances by dξ. The
corresponding change in Gibbs energy is

• ∆rG can also be interpreted as the difference between the

chemical potentials (the partial molar Gibbs energies) of the
reactants and products at the composition of the reaction
mixture.
As the reaction
advances
(represented by
motion from left
to right along the
horizontal axis)
the slope of the
Gibbs energy
changes.
Equilibrium
corresponds to
zero slope, at the
foot of the valley.
 Exergonic and endergonic reactions
• Spontaneity of a reaction at constant temperature and pressure:
• If ∆rG < 0,the forward reaction is spontaneous.
• If ∆rG > 0, the reverse reaction is spontaneous.
• If ∆rG = 0, the reaction is at equilibrium.
• A reaction for which ∆rG < 0 is called exergonic (釋出能的 from the
Greek words for work producing). The name signifies that, because
the process is spontaneous, it can be used to drive another process,
such as another reaction, or used to do non-expansion work.
• In biological cells, the oxidation of carbohydrates drives other
reactions forward and results in the formation of proteins from amino
acids, muscle contraction, and brain activity.
• A reaction for which ∆rG > 0 is called endergonic (吸能的 signifying
work consuming). The reaction can be made to occur only by doing
work on it, such as electrolysing water to reverse its spontaneous
formation reaction.
• Reactions at equilibrium are spontaneous in neither direction: they are
neither exergonic nor endergonic.
If two weights are
coupled as shown
here, then the heavier
weight will move the
lighter weight in its
non-spontaneous
direction: overall, the
process is still
spontaneous. The
weights are the
analogues of two
chemical reactions: a
reaction with a large
negative ΔG can
force another
reaction with a less
ΔG to run in its non-
spontaneous
direction.
 Perfect gas equilibria

• Note that in the definition of ΔrG ,the Δr has its normal

meaning as a difference whereas in the definition of ΔrG the
Δr signifies a derivative.
• The ratio Q is an example of a reaction quotient. It ranges
from 0 when pB = 0 (corresponding to pure A) to infinity when
pA = 0 (corresponding to pure B). The standard reaction
Gibbs energy,∆rG , is defined (like the standard reaction
enthalpy) as the difference in the standard molar Gibbs energies
of the reactants and products.
 Perfect gas equilibria
• For our reaction
The general case of a reaction
 The dependence of the reaction Gibbs energy on the reaction quotient
• The reaction with stoichiometric numbers νJ. When the reaction advances by
dξ, the amounts of reactants and products change by dnJ = νJdξ. The
resulting infinitesimal change in the Gibbs energy at constant T and p is

• µ of a species J is related to its activity by µ J = µ J + RT ln aJ

• An equilibrium constant K expressed in terms of activities (or fugacities) is

called a thermodynamic equilibrium constant.
 The response of equilibria to the conditions
• How equilibria respond to pressure
The equilibrium constant depends on the value of ∆rG , which is defined
at a single, standard pressure. The value of ∆ rG , and hence of K, is
therefore independent of the pressure at which the equilibrium is actually
established

• The response of equilibria to temperature

• Le Chatelier’s principle predicts that a system at equilibrium will tend to
shift in the endothermic direction if the temperature is raised, for then
energy is absorbed as heat and the rise in temperature is opposed.
Conversely, an equilibrium can be expected to shift in the exothermic
direction if the temperature is lowered, for then energy is released and
the reduction in temperature is opposed. These conclusions can be
summarized as follows:
• Exothermic reactions: increased temperature favors the reactants.
• Endothermic reactions: increased temperature favors the products.
The van ’t Hoff equation