HELMHOLTZ ENERGY

• Define which chemical reactions will occur spontaneously at constant 𝑉 and 𝑇.

Having introduced the entropy function and the second and third laws of thermodynamics 𝑨 ≡ 𝑼 − 𝑻𝑺
in the last chapter, we now have essentially all the tools we need for studying chemical and • For a reversible change, 𝑑𝑞rev = 𝑇𝑑𝑆 , so that the above equation becomes
physical processes. However, to help us focus on the system and on specific practical
𝑑𝐴 = 𝑑𝑈 − 𝑑𝑞rev
conditions in this chapter, we shall develop two functions that form the basis of chemical
• Applying the first law of thermodynamics,
thermodynamics: Gibbs energy and Helmholtz energy.
𝑑𝐴 = 𝑑𝑞rev + 𝑑𝑤rev − 𝑑𝑞rev = 𝑑𝑤rev
OBJECTIVES • For, for a finite process, 𝚫𝑨 = 𝒘𝐫𝐞𝐯

1. To gain an understanding of the relationship between spontaneity, free energy,

and temperature. GIBBS FREE ENERGY (𝐆)
2. Calculate changes in Gibbs free energy, Δ𝐺 , from values of Δ𝐻 and Δ𝑆 • A function that combines the system’s enthalpy and entropy
3. Know when to use each type of calculation from tabulated values of standard molar • Provides criterion for spontaneity of a reaction 𝑮 ≡ 𝑯 – 𝑻𝑺
free energies of formation • The free energy change (𝚫𝑮) is a measure of the spontaneity of a process and of
4. To be able to calculate the temperature at which a process is at equilibrium under the useful energy available from it.
standard conditions.
5. Derive some thermodynamic relations 𝚫𝑮𝐬𝐲𝐬 = 𝚫𝑯𝐬𝐲𝐬 − 𝐓𝚫𝑺𝐬𝐲𝐬

THIRD LAW OF THERMODYNAMICS Relationship Between 𝚫𝑮 and Spontaneity

• The third law of thermodynamics was first stated by Nernst: For certain isothermal 1. 𝚫𝑮 < 𝟎, spontaneous process in the forward direction; the process releases
chemical reactions between solids, the entropy changes approach zero as the energy.
thermodynamic temperature approaches zero. 2. 𝚫𝑮 > 𝟎, nonspontaneous process in the forward direction.
• In other words, the entropy of a perfect crystal is zero at 0 K. 3. 𝚫𝑮 = 𝟎, system is at equilibrium; no net change occurs.
− At 0 K there are no translational, vibrational or rotational motions.
− As a substance is heated, entropy increases due to increased molecular motion Note: If a process is nonspontaneous in one direction, it is spontaneous in the
and increased kinetic energy. opposite direction.
• Entropy of a substance is determined by measuring the specific heat of a substance
at different temperatures. Standard Free Energy Changes
• Another way to calculate Δ𝐺rxn o is with the values for standard free energy of
THE MEANING OF HELMHOLTZ AND GIBBS ENERGIES formation Δ𝐺𝑓 o of the components:
• Standard free energy of formation, Δ𝐺𝑓 o : the free energy change that occurs when
• The Gibbs and Helmholtz energies provide information about the maximum
amount of work that can be done by a system. 1 mole of a compound is formed from its elements in their standard states.
• These free energies are state functions which do not have measurable absolute − Δ𝐺𝑓 o = 0 for an element in its most stable form at 1 atm pressure and
values. 25°C.
• Gibbs free energy, Δ𝐺 , is the maximum amount of non–𝑃𝑉 work that can be • Standard free energy of reaction, Δ𝐺rxn o : the free energy change that results when
extracted from the reaction at constant 𝑃 and 𝑇, while Δ𝐴 is the maximum amount reactants in their standard states are converted to products in their standard states
of non–𝑃𝑉 work obtained from constant 𝑉 isothermal processes. 𝚫𝑮𝐨𝐫𝐱𝐧 = ∑ 𝒏 𝚫𝑮𝒇 𝐨 (𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬) − ∑ 𝒎 𝚫𝑮𝒇 𝐨 (𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬)

Page | 1
Gibbs Free Energy and Temperature EXAMPLE PROBLEMS
• The sign of Δ𝐺 , which tells us whether a process is spontaneous, depends on the 1. Calculate the standard free-energy change for the formation of NO(g) from N2(g)
signs and magnitudes of Δ𝐻 and −𝑇Δ𝑆 . The various combinations of Δ𝐻 and and O2(g) at 298 K:
−𝑇Δ𝑆 signs are given in the Table below. N2(g) + O2(g) → NO(g)
given that Δ𝐻° = 180.7 kJ and Δ𝑆° = 24.7 J/K. Is the reaction spontaneous
TABLE 1. The Effect of Δ𝐻, Δ𝑆, and 𝑇 on Spontaneity under these conditions?
Plan: To calculate Δ𝐺°, we use Equation Δ𝐺° = Δ𝐻° ― 𝑇Δ𝑆°. To determine
whether the reaction is spontaneous under standard conditions, we look at the
sign of Δ𝐺°.
1 kJ
Solution: Δ𝐺° = Δ𝐻° ― 𝑇Δ𝑆° = 180.0 kJ − (298 K)(24.7 J/K) ( )
1000 J
= 𝟏𝟕𝟑. 𝟑 𝐤𝐉
• How do we determine the temperature at which a process goes from 2. The Haber process for the production of ammonia involves the equilibrium
nonspontaneous to spontaneous (or vice versa)? N2(g) + 3 H2(g) ⇋ 2 NH3(g)
Set Δ𝐺° = 0: 0 = Δ𝐻° − 𝑇Δ𝑆° Assume that Δ𝐻° and Δ𝑆° for this reaction do not change with temperature. (a)
− Note that this temperature is an approximation because we are assuming Predict the direction in which Δ𝐺 for the reaction changes with increasing
that Δ𝐻° and Δ𝑆° don’t change with temperature. temperature. (b) Calculate Δ𝐺 at 25 °C and at 500 °C.

Solution:
Phase Transitions Between Physical States
(a) The temperature dependence of Δ𝐺 comes from the entropy term, Δ𝐺 =
• A system undergoing a phase transition (melting, evaporation, condensation, etc.)
Δ𝐻 − 𝑇Δ𝑆. We expect Δ𝑆 for this reaction t o be negative because the
is at equilibrium so Δ𝐺 is always zero
number of molecules of gas is smaller in the products. Because Δ𝑆 is negative,
• The equation Δ𝐺 = Δ𝐻 − 𝑇Δ𝑆 then becomes Δ𝐻 = 𝑇Δ𝑆 or
𝚫𝑯 −𝑇Δ𝑆 is positive and increases with increasing temperature. As a result, Δ𝐺
𝚫𝑺 = becomes less negative (or more positive) with increasing temperature. Thus,
𝑻
− This equation simply shows that entropy (system) increases during an the driving force for the production of NH3 becomes smaller with increasing
endothermic phase transition and decreases during an exothermic phase temperature.
transition. J 1 kJ
(b) Δ𝐺° = Δ𝐻° ― 𝑇Δ𝑆° = −92.38 kJ − (298 K) (−198.3 ) ( ) = −𝟑𝟑. 𝟑 𝐤𝐉
K 1000 J
At 𝑇 = 500 ℃ = 773 K we have
1 kJ
Δ𝐺° = Δ𝐻° ― 𝑇Δ𝑆° = −92.38 kJ − (773 K)(−198.3J/K) ( ) = 𝟔𝟏 𝐤𝐉
1000 J

3. What is Δ𝑆 for the vaporization of liquid argon if Δ𝐻vap = 6.3 kJ/mol. Argon’s
normal boiling point is -186 ℃.
Solution: Δ𝑆 = Δ𝐻/𝑇 = (6.3 kJ/mol)/87 K · 1000 J/kJ = 𝟕𝟐 𝐉/𝐦𝐨𝐥 · 𝐊

Page | 2
EXERCISE 1 • The Gibbs-Helmholtz expression is most useful when applied to changes in 𝐺 at
1. Which of these statements is true? constant pressure, such as in the course of a chemical reaction, when it may be
a. All spontaneous reactions have a negative enthalpy change. written in the form:
b. All spontaneous reactions have a positive entropy change. 𝝏 𝚫𝑮 𝚫𝑯
[ ( )] = − 𝟐
c. All spontaneous reactions have a positive free-energy change. 𝝏𝑻 𝑻 𝑷 𝑻
d. All spontaneous reactions have a negative free-energy change. • The Gibbs-Helmholtz equation can also be express as
e. All spontaneous reactions have a negative entropy change.
𝚫𝑮
𝚫𝑮 = 𝚫𝑯 = 𝑻 𝒅 ( )
𝑻 𝑷
2. Use Δ𝐺𝑓 o values to calculate the free energy change at 25°C for each of the
following reactions: Variation of Gibbs Energy with Pressure
(a) 2 NO(g) + O2(g) → 2 NO2(g) • The pressure dependence of 𝐺 or Δ𝐺 for solids and liquids is different than for
1
(b) 2 C(graphite) + O2(g) → 2 CO(g) gases, as shown on the map.
2
➢ Solids or liquids: Δ𝐺 = 𝑉Δ𝑃
o
Given Δ𝐺𝑓 (kJ/mol): NO(g) = 86.60; C(graphite) = 0; NO2(g) = 51; O2(g) = 0; 𝑃2
➢ Gases: Δ𝐺 = 𝑛𝑅𝑇 ln
CO(g) = ―137.2 𝑃1

3. Calculate the standard free-energy change (Δ𝐺°) at 25°C for the reaction EXAMPLE PROBLEMS
2 H2(g) + N2(g) ⇌ N2H4(l)
1
At 25 °C, the standard enthalpy change (Δ𝐻°) is 50.6 kJ/mol, and the absolute 1. For the reaction: H2(g) + O2(g) → H2O(l). The values of enthalpy change and
2
entropies of the products and reactants are Δ𝑆𝑓 o (N2H4) = 121.2 J/(mol.K), Δ𝑆𝑓 o free energy change are –68.32 and –56.69 kcals respectively. Calculate the value
(N2) = 191.6 J/(mol.K), and Δ𝑆𝑓 o (H2) = 130.7 J/(mol.K). Is the reaction of free energy change at 25ºC.
spontaneous as written?
Solution: Using the Gibb’s Helmholtz equation we get
4. Calculate the temperature (in kelvin) at which the sign of Δ𝐺° changes from Δ𝐺
positive to negative. This corresponds to the temperature at which 𝐾 < 1 changes −56.69 = −68.32 + 298 𝑑 ( )
𝑇 𝑃
to 𝐾 > 1. Assume that Δ𝐻° and ΔS° are constant and do not change with Δ𝐺
temperature. 𝑑 ( ) = 0.0390 kcal
CO2(g) + H2(g) → CO(g) + H2O(g) Δ𝐻° = 41.2 kJ and Δ𝑆° = 42.1 J/K 𝑇 𝑃
Δ𝐺
Assuming that 𝑑 ( ) remains constant over this temperature
𝑇 𝑃
DEPENDENCE OF GIBBS ENERGY ON TEMPERATURE AND PRESSURE range. At 30ºC we can write

Because Gibbs energy plays such a central role in chemical thermodynamics, understanding Δ𝐺 = −68.32 + 303 × 0.0390 = −𝟓𝟔. 𝟓𝟎𝟑 𝐤𝐜𝐚𝐥
its properties is important. The Equation, 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 shows that it is a function of 2. A 0.590-mol sample of an ideal gas initially at 300 K and 1.50 bar is compressed
both pressure and temperature. isothermally to a final pressure of 6.90 bar. Calculate the change in Gibbs energy
for this process.
Variation of Gibbs Energy with Temperature Solution:
𝑃
Δ𝐺 = 𝑛𝑅𝑇 ln 2 = (0.590 mol)(8.314)(300 K) ln
6.90 bar
= 𝟐. 𝟐𝟓 𝐤𝐉
𝑃1 1.50 bar
• These is an equation derived by J.W. Gibbs and [Link] Helmholtz and are known
as Gibbs–Helmholtz equations.
• Gibb's Helmholtz equation can be expressed as
𝜕 𝐺 𝐻
[ ( )] = − 2
𝜕𝑇 𝑇 𝑃 𝑇

Page | 3
THERMODYNAMIC RELATIONS EXAMPLE PROBLEM
One of the most powerful applications of thermodynamics is to find relations between 1. Show that the equation; 𝑑𝐹 = 3𝑥 2 𝑦 2 𝑑𝑥 + 2𝑥 3 𝑦 𝑑𝑦 is exact and determine
properties that, at first glance, look like they are not related. 𝐹(𝑥, 𝑦).
Solution: 𝑀(𝑥, 𝑦) = 3𝑥 2 𝑦 2 and 𝑁(𝑥, 𝑦) = 2𝑥 3 𝑦
Exact and Inexact Differentials
𝝏𝑴 𝝏𝑵
• A part of the richness of thermodynamics is that it uses the mathematical = 6𝑥 2 𝑦 and = 6𝑥 2 𝑦
𝝏𝒚 𝝏𝒙
properties of state functions to draw far-reaching conclusions about the relations 𝜕𝑀 𝜕𝑁
=
between physical properties and thereby establish connections that may be 𝜕𝑦 𝜕𝑥
completely unexpected. Euler’s test is satisfied and the differential 𝑑𝐹 is exact. Now,
1. An exact differential is an infinitesimal quantity that, when integrated, gives a ∫ 𝑀(𝑥, 𝑦) 𝑑𝑥 = ∫ 3𝑥2 𝑦2 𝑑𝑥 = 𝑥3 𝑦2
result that is independent of the path between the initial and final states
and
2. An inexact differential is an infinitesimal quantity that, when integrated, gives
𝜕
a result that depends on the path between the initial and final states. ∫ 𝑀(𝑥, 𝑦) 𝑑𝑥 = 2𝑥3 𝑦
𝜕𝑦
• The expression 𝑀(𝑥, 𝑦)𝑑𝑥 + 𝑁(𝑥, 𝑦)𝑑𝑦 is said to be an exact differential if there Therefore,
exists a function 𝐹(𝑥, 𝑦) for which 𝜕
𝐾(𝑦) = ∫ [𝑁(𝑥, 𝑦) − ∫ 𝑀(𝑥, 𝑦) 𝑑𝑥] 𝑑𝑦
𝜕𝐹 𝜕𝐹 𝜕𝑦
𝑑𝐹 = ( ) 𝑑𝑥 + ( ) 𝑑𝑦 = 𝑀(𝑥, 𝑦)𝑑𝑥 + 𝑁(𝑥, 𝑦)𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥 𝐾(𝑦) = ∫(2𝑥3 𝑦 + 2𝑥3 𝑦) 𝑑𝑦 = 𝐶
If 𝐹(𝑥, 𝑦) does not exist, 𝑀(𝑥, 𝑦)𝑑𝑥 + 𝑁(𝑥, 𝑦)𝑑𝑦 is NOT EXACT and is called Which gives 𝐹(𝑥, 𝑦) = 𝑥 3 𝑦 2 + 𝐶
inexact differential.
EXERCISE 2
Euler’s Test for Exactness. If 𝑀(𝑥, 𝑦)𝑑𝑥 + 𝑁(𝑥, 𝑦)𝑑𝑦 is exact, then
𝜕𝐹 𝜕𝐹
1. Test the following differentials for exactness.
( ) = 𝑀(𝑥, 𝑦) and ( ) = 𝑁(𝑥, 𝑦) a.
1
𝑑𝐹 = 𝑑𝑥 −
𝑥
𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
𝑦 𝑦2
𝑛𝑅 𝑛𝑅𝑇
Taking the mixed second derivatives gives b. 𝑑𝑃 = 𝑑𝑇 − 𝑑𝑉 ; 𝑛 and 𝑅 are constants.
𝑉 𝑉2
𝜕2 𝐹 𝜕𝑀 𝜕2 𝐹 𝜕𝑁 𝑛𝑅𝑇
(𝜕𝑦𝜕𝑥) = ( 𝜕𝑦 ) and (𝜕𝑥𝜕𝑦) = ( 𝜕𝑥 ) c. 𝑑𝑞 = 𝑛𝐶𝑉 𝑑𝑇 +
𝑉
𝑑𝑉 ; 𝑛, 𝐶𝑉 , and 𝑅 are constants.
𝑥 𝑦
However, since
Cyclic Chain Rule
𝜕2𝐹 𝜕2𝐹
= • The triple product rule, known variously as the Euler's chain rule, is a formula
𝜕𝑦𝜕𝑥 𝜕𝑥𝜕𝑦
which relates partial derivatives of three interdependent variables.
Then
• The rule finds application in thermodynamics, where frequently three variables can
𝝏𝑴 𝝏𝑵 be related by a function of the form 𝑓(𝑥, 𝑦, 𝑧) = 0, so each variable is given as an
( ) =( )
𝝏𝒚 𝒙 𝝏𝒙 𝒚 implicit function of the other two variables.
Is a necessary condition for exactness. The equation (
𝜕𝑀 𝜕𝑁
) = ( ) is known as • For example, an equation of state for a fluid relates temperature, pressure, and
𝜕𝑦 𝑥 𝜕𝑥 𝑦
volume in this manner. The triple product rule for such interrelated variables 𝑥 , 𝑦,
Euler’s test for exactness.

Page | 4
 and 𝑧 comes from using a reciprocity relation on the result of the implicit function Fundamental Equations of Thermodynamics
theorem, and is given by • In addition to the mechanical properties 𝑃 and 𝑉, a system has three fundamental
𝝏𝒙 𝝏𝒚 𝝏𝒛 properties 𝑇, 𝑈, and 𝑆, defined by the laws of thermodynamics, and three
( ) ( ) ( ) = −𝟏
𝝏𝒚 𝒛 𝝏𝒛 𝒙 𝝏𝒙 𝒚 composite properties 𝐻 , 𝐴, and 𝐺, which are important.
− where each factor is a partial derivative of the variable in the • To demonstrate this, we can start with combining the First and Second Laws into
numerator, considered to be a function of the other two. the Fundamental Law; if 𝑑𝑈 = 𝑑𝑞 + 𝑑𝑤 , 𝑑𝑤rev = −𝑃𝑑𝑉 and 𝑑𝑞rev = 𝑇𝑑𝑆 , then
• The advantage of the triple product rule is that by rearranging terms, one can 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 (1)
derive a number of substitution identities which allow one to replace partial The same value of 𝑑𝑈 should be obtained whether the change is reversible or
derivatives which are difficult to analytically evaluate, experimentally measure, or irreversible because 𝑑𝑈 is a state function and is path-dependent.
integrate with quotients of partial derivatives which are easier to work with.
• Using the definitions of the composite functions,
𝐻 = 𝑈 + 𝑃𝑑𝑉 , 𝐴 = 𝑈 − 𝑇𝑆, 𝐺 = 𝐻 − 𝑇𝑆 = 𝑈 + 𝑃𝑉 − 𝑇𝑆
EXAMPLE
and differentiating each one, we obtain
1. The ideal gas law relates the state variables of pressure (𝑃 ), volume (𝑉), and
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
temperature (𝑇) via 𝑃𝑉 = 𝑛𝑅𝑇 which can be written as 𝑓(𝑃, 𝑉, 𝑇) = 𝑃𝑉 − 𝑛𝑅𝑇 =
𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
0 so each state variable can be written as an implicit function of the other state
variables: 𝑑𝐺 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑛𝑅𝑇 In each of these three equations, 𝑑𝑈 is replaced by its value from Eq. (1); after
𝑃 = 𝑃(𝑉, 𝑇) = collecting terms, the equations becomes
𝑉
𝑛𝑅𝑇 𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽 (1)
𝑉 = 𝑉(𝑃, 𝑇) =
𝑃 𝒅𝑯 = 𝑻𝒅𝑺 + 𝑽𝒅𝑷 (2)
𝑃𝑉
𝑇 = 𝑇(𝑃, 𝑉) = 𝒅𝑨 = −𝑺𝒅𝑻 − 𝑷𝒅𝑽 (3)
𝑛𝑅
From the above expressions, we have 𝒅𝑮 = −𝑺𝒅𝑻 + 𝑽𝒅𝑷 (4)
𝜕𝑃 𝜕𝑉 𝜕𝑇
( ) ( ) ( ) = −1 • From Equation 1, we see that U is a function of V and S, so we can write the exact
𝜕𝑉 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑉
𝑛𝑅𝑇 𝑛𝑅 𝑉 differential
(− 2 ) ( ) ( ) = −1 𝜕𝑈 𝜕𝑈
𝑉 𝑃 𝑃 𝑛𝑅 𝑑𝑈 = ( ) 𝑑𝑆 + ( ) 𝑑𝑉 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝜕𝑆 𝑉 𝜕𝑉 𝑆
𝑛𝑅𝑇 𝑃
− = − = −1 • Comparing the coefficients for 𝑑𝑆 and 𝑑𝑉 in both Equations above we arrive at the
𝑃𝑉 𝑃
results,
𝜕𝑈 𝜕𝑈
( ) =𝑇 and ( ) = −𝑃
𝜕𝑆 𝑉 𝜕𝑉 𝑆

• By a similar procedure, we proceed as follows for 𝑑𝐻 :

𝜕𝐻 𝜕𝐻
( ) =𝑇 and ( ) =𝑉
𝜕𝑆 𝑃 𝜕𝑃 𝑆

• For 𝑑𝐴
𝜕𝐴 𝜕𝐴
( ) = −𝑆 and ( ) = −𝑃
𝜕𝑇 𝑉 𝜕𝑉 𝑇

Page | 5
 • Lastly for 𝑑𝐺 Koenig-Born Diagram
𝜕𝐺
( ) = −𝑆 and
𝜕𝐺
( ) =𝑉 • A Koenig Born diagram is a diagram used to remember the Maxwell's relations.
𝜕𝑇 𝑃 𝜕𝑃 𝑇
These are arranged as follows:
• The diagram is read as follows. For
Maxwell Relations example, the top row of the square
• Maxwell's relations are a set of equations in thermodynamics which are derivable would be read as 𝑑𝐴 is a function of
from the symmetry of second derivatives and from the definitions of the 𝑑𝑉 and 𝑑𝑇 and 𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 .
thermodynamic potentials. • The coefficient of 𝑑𝑉 is −𝑃 because
• In the 1870s, James Clerk Maxwell derived a set of equations that relate 𝑆 to 𝑃 , the arrow links 𝑉 to 𝑃 and the
𝑉 , and 𝑇. Starting with Equation 1 and realizing that 𝑑𝑈 is an exact differential, connection goes against the arrow.
applying Euler’s Theorem Similarly, the coefficient of 𝑑𝑇 is 𝑆
𝝏𝑻 𝝏𝑷 𝝏𝑻 𝝏𝑽 because the arrow links 𝑇 to 𝑆 and the
From 𝑈: ( ) = −( ) From 𝐻: ( ) =( )
𝝏𝑽 𝑺 𝝏𝑺 𝑽 𝝏𝑷 𝑺 𝝏𝑺 𝑷 the minus sign is because the
connection goes against the arrow.
𝝏𝑷 𝝏𝑺 𝝏𝑽 𝝏𝑺
From 𝐴: ( ) =( ) From 𝐺: ( ) = −( )
𝝏𝑻 𝑽 𝝏𝑽 𝑻 𝝏𝑻 𝑷 𝝏𝑷 𝑻
THERMODYNAMIC EQUATIONS OF STATE
• We can also derive equations that give 𝑈 and 𝐻 in terms of 𝑃, 𝑉, and 𝑇 and that
Proof: are therefore, called thermodynamic equations of state.
• From the definition of 𝐴, which equals 𝑈— 𝑇𝑆, we have
The internal energy is function of entropy and volume, 𝑈 = 𝑈(𝑆, 𝑉). Thus,
𝜕𝑈 𝜕𝑈 𝜕𝑈 𝜕(𝐴 + 𝑇𝑆) 𝜕𝐴 𝜕𝑆
𝑑𝑈 = ( ) 𝑑𝑆 + ( ) 𝑑𝑉 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 ( ) = −𝑃 [ ] = ( ) +𝑇( )
𝜕𝑆 𝑉 𝜕𝑉 𝑆 𝜕𝑉 𝑇 𝜕𝑉 𝑇
𝜕𝑉 𝑇 𝜕𝑉 𝑇

If 𝑑𝑈 = 𝑀𝑑𝑆 + 𝑁𝑑𝑉 and is an exact differential, then −

𝜕𝐴
Then from ( ) = −𝑆, ( ) = −𝑃
𝜕𝐴
𝜕𝑇 𝑉 𝜕𝑉 𝑇
𝝏𝑴 𝝏𝑵 𝜕𝑆 𝜕𝑃
( ) =( ) so − From the Maxwell relation ( ) = ( ) the thermodynamic equation of
𝝏𝑽 𝑺 𝝏𝑺 𝑽 𝜕𝑉 𝑇 𝜕𝑇 𝑉

𝝏𝑻 𝝏𝑷 state for 𝑈
( ) = −( ) 𝜕𝑈 𝜕𝑃
𝝏𝑽 𝑺 𝝏𝑺 𝑽 ( ) = 𝑇( ) −𝑃
𝜕𝑉 𝑇 𝜕𝑇 𝑉
• The corresponding thermodynamic equation of state for 𝐻 is obtained as follows:
𝜕𝐻 𝜕(𝐺 + 𝑇𝑆) 𝜕𝐺 𝜕𝑆
( ) = −𝑃 [ ] = ( ) +𝑇( )
𝜕𝑃 𝑇 𝜕𝑃 𝑇
𝜕𝑃 𝑇 𝜕𝑃 𝑇

𝜕𝐺 𝜕𝐺
and by use of Equations ( ) = −𝑆 and ( ) = 𝑉 and from the Maxwell
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑉 𝜕𝑆
relation ( ) = − ( ) , we have the thermodynamic equation of state for 𝐻
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝐻 𝜕𝑉
( ) = 𝑉 −𝑇( )
𝜕𝑃 𝑇 𝜕𝑇 𝑃

Page | 6
Some Applications of the Thermodynamic Relationships EXAMPLE PROBLEM
1. Internal pressure, 𝝅𝑻 1. Determine an expression for the entropy change of an ideal gas when temperature
• We can now derive internal pressure, 𝜋 𝑇 , using the relations we have and pressure data are known and the specific heats are constant.
𝐶P 𝜕𝑉
come up with. Dividing equation 𝑑𝑈 = (
𝜕𝑈 𝜕𝑈
) 𝑑𝑆 + ( ) 𝑑𝑉 by 𝑑𝑉 at Solution: 𝑆 = 𝑆(𝑇, 𝑃) ↔ 𝑆=
𝑇
𝑑𝑇 − ( ) 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑆 𝑉 𝜕𝑉 𝑆
constant temperature, we get 𝑇2
𝐶P 𝑃2
𝜕𝑉
𝜕𝑈 𝜕𝑈 𝜕𝑆 𝜕𝑈 𝜕𝑉 Δ𝑆 = ∫ 𝑑𝑇 − ∫ ( ) 𝑑𝑃
( ) = ( ) ( ) +( ) ( ) 𝑇1 𝑇 𝑃1 𝜕𝑇 𝑃
𝜕𝑉 𝑇 𝜕𝑆 𝑉 𝜕𝑉 𝑇 𝜕𝑉 𝑆 𝜕𝑉 𝑇
𝑅𝑇 𝜕𝑉 𝑅
Substituting the relations above For an ideal gas; 𝑉= ↔ ( ) =
𝑃 𝜕𝑇 𝑃 𝑃
𝜕𝑈 𝜕𝑆
( ) = 𝑇( ) −𝑃 For constant specific heat this becomes
𝜕𝑉 𝑇 𝜕𝑉 𝑇
𝑇2 𝑃2
𝜕𝑆 𝜕𝑃
𝑑𝑇 𝑑𝑃
From the Maxwell relation, ( ) = ( ) and, Δ𝑆 = 𝐶P ∫
𝑇
−𝑅∫
𝜕𝑉 𝑇 𝜕𝑇 𝑉 𝑇1 𝑃1 𝑃
𝝏𝑼 𝝏𝑷 𝑻𝟐 𝑷𝟐
( ) = 𝑻 ( ) − 𝑷 = 𝝅𝑻 Δ𝑺 = 𝑪𝐏 𝐥𝐧 ( ) − 𝑹 𝐥𝐧 ( )
𝝏𝑽 𝑻 𝝏𝑻 𝑽 𝑻𝟏 𝑷𝟏
2. Joule-Thomson coefficient, 𝝁 𝜕𝑈 𝜕𝑉
2. Prove 𝐶V = − ( ) ( )
𝜕𝑇 𝜕𝑉 𝑇 𝜕𝑇 𝑈
𝜕𝐻
𝜇 ≡ (𝜕𝑃) and 𝐶𝑃 ≡ ( )
𝐻 𝜕𝑇 𝑃 𝜕𝑈 𝜕𝑈
Solution: 𝑑𝑈 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉
𝜕𝑇 𝜕𝐻 𝜕𝑇 𝜕𝑇 𝑉 𝜕𝑉 𝑇
From the theory of partial derivatives ( ) = − ( ) ( ) so that
𝜕𝑃 𝐻 𝜕𝑃 𝑇 𝜕𝐻 𝑃 𝜕𝑈 𝜕𝑇 𝜕𝑉 𝜕𝑈
From cyclic rule, ( ) ( ) ( ) = −1 where ( ) = 𝐶V
𝟏 𝝏𝑯 𝜕𝑇 𝑉 𝜕𝑉 𝑈 𝜕𝑈 𝑇 𝜕𝑇 𝑉
𝝁=− ( ) 𝜕𝑇 𝜕𝑈
𝑪𝑷 𝝏𝑷 𝑻 𝐶V ( ) = − ( ) Thus,
𝜕𝑉 𝑈 𝜕𝑉 𝑇
3. Expansion coefficient 𝜕𝑈
𝐶V = − ( ) ( )
𝜕𝑉

• The cubic expansion coefficient (formerly called the thermal expansivity) 𝜕𝑉 𝑇 𝜕𝑇 𝑈

of a substance is defined as 𝜕𝐺
𝟏 𝝏𝑽 3. Prove ( ) = −𝑆
𝜕𝑇 𝑃
𝛂= ( )
𝑽 𝝏𝑻 𝑷 𝜕𝐺 𝜕𝐺
Solution: 𝐺 = 𝐺(𝑃, 𝑇); 𝑑𝐺 = ( ) 𝑑𝑃 + ( ) 𝑑𝑇
𝜕𝑃 𝑇 𝜕𝑇 𝑃
4. Isothermal compressibility
𝜕𝐺 𝜕𝐺
• The isothermal compressibility is defined by the fractional differential We knew that ( ) = 𝑉 and ( ) = −𝑆
𝜕𝑃 𝑇 𝜕𝑇 𝑃
change in volume due to a change in pressure
𝟏 𝝏𝑽 If we divide the equation 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 by 𝑑𝑉 at constant 𝐺, we’ll
𝒌𝑻 = − ( )
𝑽 𝝏𝑷 𝑻 𝜕𝑃
get 0 = 𝑉 (𝜕𝑇) − 𝑆
− The negative sign is important in order to keep the value of 𝑘 𝑇 𝐺
positive, since an increase in pressure will lead to a decrease in Applying the chain rule ( ) ( ) ( ) = −1
𝜕𝑃 𝜕𝑇 𝜕𝐺
volume. The 1/𝑉 term is needed to make the property intensive so 𝜕𝑇 𝐺 𝜕𝐺 𝑃 𝜕𝑃 𝑇

that it can be tabulated in a useful manner. 𝜕𝐺 𝜕𝐺 𝜕𝑃 𝜕𝐺

So 0 = ( ) [− ( ) ( ) ] − 𝑆 Therefore ( ) = −𝑆
𝜕𝑃 𝑇 𝜕𝑇 𝑃 𝜕𝐺 𝑇 𝜕𝑇 𝑃

Page | 7
ADDITIONAL EXERCISES 9. The values of Δ𝐻 and Δ𝑆 for a chemical reaction are –85.2 kJ mol–1 and –170.2 J
K–1 mol–1, respectively, and the values can be taken to be independent of
1. For each of the following processes, state which (if any) of the variables, Δ𝑈 , Δ𝐻 ,
temperature.
Δ𝑆, or Δ𝐺 , is equal to zero: a. Calculate Δ𝐺 for the reaction at (a) 300 K, (b) 600 K, and (c) 1000 K.
a) Isothermal reversible expansion of an ideal gas. b. At what temperature would Δ𝐺 be zero?
b) Adiabatic reversible expansion of a non-ideal gas.
c) Vaporization of liquid water at 80°C and 1 bar pressure. 10. Derive expressions for (a) 𝛼 and (b) 𝜅 𝑇 for an ideal gas.
d) Vaporization of liquid water at 100°C and 1 bar pressure. 𝛼 2 𝑉𝑇
11. Prove 𝐶P − 𝐶V =
e) Reaction between H2 and O2 in a thermally insulated bomb calorimeter. 𝑘𝑇

f) Reaction between H2SO4 and NaOH in dilute aqueous solution at constant 𝜕𝑈

12. Show that for a perfect gas, if ( ) = 0 then
temperature and pressure. 𝜕𝑉 𝑇

𝜕𝑈 𝜕𝑉
2. Calculate standard free energy change using Δ𝐻𝑓 o and 𝑆 o values when carbon (a) 𝐶P − 𝐶V = 𝑛𝑅 Hint: Use 𝐶P − 𝐶V = [𝑃 + ( ) ] ( )
𝜕𝑉 𝑇 𝜕𝑇 𝑃
monoxide and oxygen gas react to form carbon dioxide. 𝜕𝐻
(b) ( ) =0
CO(g) + ½ O2(g) → CO2(g) 𝜕𝑉 𝑇

Calculate the standard free energy change for this reaction at 25 ℃ from Δ𝐻 o rxn (c) (
𝜕𝐶𝑉
) =0
𝜕𝑉
and Δ𝑆 o rxn . 𝑇

13. Derive an equation of state from

3. Using standard thermodynamic data to calculate Δ𝐺 at 298.15 K for the reaction
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
below, assuming that all gases have a pressure of 22.51 mm Hg.
by taking the partial derivative with respect to 𝑃 at constant temperature. Then
4 HCl(g) + O2(g) → 2 H2O(g) + 2 Cl2(g)
use the appropriate Maxwell relation and the definition of α to express the partial
1
4. For the reaction, H2(g) + O2(g) → 2 H2O(l). The values of enthalpy change in terms of easily measured quantities.
2
and free energy change are –68.32 and –56.69 kcals respectively. Calculate the
value of free energy change at 25 °C. 14. Taking 𝑈 as a function of 𝑃 and 𝑉, determine the following
𝜕𝑈 𝜕𝑈
(a) 𝑑𝑞 = ( ) 𝑑𝑃 + [( ) + 𝑃] 𝑑𝑉
𝜕𝑃 𝑉 𝜕𝑉 𝑃
5. For the following reaction: N2(g) + 3 H2(g) → 2 NH3(g)
The free energy changes at 25ºC and 35ºC are –33.089 and –28.018 kJ (b) (
𝜕𝑈
) = 𝐶𝑉
𝑘𝑇
𝜕𝑃 𝑉 𝛼
respectively. Calculate the heat of reaction, Δ𝐻.
𝜕𝑈 𝐶𝑃
6. The latent heat of vaporization of water at 100°C is 40.6 kJ mol–1 and when 1 mol (c) ( ) = −𝑃
𝜕𝑉 𝑃 𝑉𝛼
of water is vaporized at 100°C and 1 atm pressure, the volume increase is 30.19
dm3. Calculate the work done by the system, the change in internal energy Δ𝑈 ,
the change in Gibbs energy Δ𝐺 and the entropy change Δ𝑆.
7. At 25 °C 1 mol of an ideal gas is expanded isothermally from 2 to 20 dm3. Calculate
Δ𝑈, Δ𝐻 , Δ𝑆, Δ𝐴, and Δ𝐺 . Do the values depend on whether the process is
reversible or irreversible?
8. A quantity of 0.35 mole of an ideal gas initially at 15.6°C is expanded from 1.2 L
to 7.4 L. Calculate the values of 𝑤, 𝑞, Δ𝑈, Δ𝑆, and Δ𝐺 if the process is carried out
(a) isothermally and reversibly, and (b) isothermally and irreversibly against an
external pressure of 1.0 atm.

Page | 8