Energy Resources Physical Chemistry I

Chapter 3. The Second and Third Laws

Jin Soo Kang

Department of Energy Resources Engineering
Seoul National University

1
 The Direction of Spontaneous Change

❖ A ball bouncing on the floor

✓ The ball does not rise as high after each bounce because some of the energy associated
with its motion spreads out into the thermal motion of the particles in the ball and the floor
✓ A ball resting on a warm floor has never been observed to start bouncing as a result of
energy transferred to the ball from the floor

(Adopted from the textbook: Atkins’ Physical Chemistry)

❖ The signpost of spontaneous change

✓ Look for the direction of change that leads to the dispersal of energy

2
 The Direction of Spontaneous Change

❖ A statement by Kelvin
✓ “No process is possible in which the sole result is the absorption of heat from a reservoir
and its complete conversion into work”

❖ A statement by Clausius
✓ “Heat does not flow spontaneously from a cool body to a hotter body”

❖ Example: heat engine

✓ A heat engine consists of two reservoirs,
a hot source and a cold sink, connected
in such a way that some of the energy
flowing as heat between the two reservoirs
can be converted into work

❖ Example: refrigerator
✓ Conceptually opposite to a heat engine
✓ Work is done on a system to transfer heat
to a hotter body (cold source → hot sink)
(Adopted from the textbook: Atkins’ Physical Chemistry)

3
 Entropy

❖ Entropy (S)
✓ Definition by its infinitesimal change

𝑑𝑞𝑟𝑒𝑣
𝑑𝑆 = [J K–1] (extensive property)
𝑇
✓ From the definition, entropy is a state function

✓ For a measurable change between two states i and f,

𝑓
𝑑𝑞𝑟𝑒𝑣
∆𝑆 = න
𝑖 𝑇
✓ As entropy is a state function,
𝑓
𝑑𝑞𝑟𝑒𝑣
∆𝑆𝑟𝑒𝑣 = ∆𝑆𝑖𝑟𝑟𝑒𝑣 =න
𝑖 𝑇
❖ Molar entropy (Sm)
𝑆
𝑆𝑚 = [J K–1 mol–1] (intensive property)
𝑛

4
 The Second Law of Thermodynamics

❖ A system and its surrounding in an isolated system (‘the universe’)

✓ Energy can be transferred between the actual system and its surroundings
✓ None can enter or leave it

❖ The Second Law of thermodynamics

✓ The entropy of an isolated system increases in the course of a spontaneous change:

∆𝑆𝑡𝑜𝑡 > 0
(𝑆𝑡𝑜𝑡 = 𝑆 + 𝑆𝑠𝑢𝑟 , S is the entropy of the system of interest)

✓ It is a statement about the total entropy of the overall isolated system (the universe), not
just about the entropy of the system of interest

❖ Some useful remarks

✓ The First Law uses the internal energy to identify permissible changes
✓ The Second Law uses the entropy to identify which of these permissible changes are
spontaneous

5
 Entropy Change of the Surroundings

❖ Surroundings consist of a reservoir of constant volume and pressure

✓ Consider an infinitesimal transfer of heat dqsur from the system to the surroundings
✓ Then,
𝑑𝑞𝑠𝑢𝑟 = 𝑑𝑈𝑠𝑢𝑟 or 𝑑𝑞𝑠𝑢𝑟 = 𝑑𝐻𝑠𝑢𝑟

✓ Since U and H are state functions and dUsur and dHsur are exact differentials, they are
independent of whether the process is reversible or irreversible

𝑑𝑞𝑠𝑢𝑟
𝑑𝑆𝑠𝑢𝑟 =
𝑇𝑠𝑢𝑟
✓ Furthermore, because the temperature of the surrounding is constant, for a measurable
change,
𝑞𝑠𝑢𝑟
∆𝑆𝑠𝑢𝑟 =
𝑇𝑠𝑢𝑟
✓ 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 an adiabatic change,

∆𝑆𝑠𝑢𝑟 = 0 (as 𝑞𝑠𝑢𝑟 = 0)

6
 Statistical Definition of Entropy

❖ Boltzmann distribution
✓ Distribution over the available energy states

❖ Boltzmann formula of the entropy

✓ Link between the spread of molecules over the available energy states and the entropy

𝑆 = 𝑘 ln 𝑊
(where k is Boltzmann’s constant and W is the number of microstates)

✓ The concept of the number of microstates makes quantitative the ill-defined qualitative
concepts of ‘disorder’ and ‘the dispersal of matter and energy’ used to introduce the
concept of entropy
✓ A more disorderly distribution of matter and a greater dispersal of energy corresponds to a
greater number of microstates associated with the same total energy
✓ The entropy calculated from Boltzmann formula is called statistical entropy

❖ Some remarks
✓ If all the molecules are in one energy state (ground state) → W = 1 and S = 0
✓ Boltzmann formula cannot readily be applied to the surroundings (far too complex W)

7
 Molecular Interpretation of Entropy

❖ Comparison between heating a system at high and low temperatures

(Adopted from the textbook: Atkins’ Physical Chemistry)

✓ At high temperature, the molecules are spread out over a larger number of energy states
✓ When the energy of the system is increased by the transfer of heat, relative change in the
number of occupied energy states is larger when the initial temperature is lower
✓ Proportionate change of W is larger in the case of the low temperature (panel b in the figure)

❖ Entropy change depends inversely on the temperature (from the definition)

8
 Entropy as a State Function

❖ Proving that entropy is a state function

✓ Integral of dS between any two states is
independent of the path between them
✓ It is sufficient to prove that the integral of
dqrev/T round an arbitrary circle is zero
✓ This guarantees that the entropy is the same
at the initial and final states of the system
regardless of the path taken between them

❖ Strategy to prove that the entropy is (Adopted from the textbook: Atkins’ Physical Chemistry)
a state function
✓ Show that the following is true for a specific cycle involving an ideal gas (Carnot cycle)

𝑑𝑞𝑟𝑒𝑣
ර 𝑑𝑆 = ර =0
𝑇
(The symbol ‫ ׯ‬denotes integration around a closed path)

✓ Then, show that the result is true whatever the working substance (heat engine)
✓ Finally, show that the result is true for any cycle (approximation as a collection
of Carnot cycles)
9
 Carnot Cycle

❖ Carnot cycle
✓ Consists of four reversible stages in which a gas (the working substance) is either
expanded or compressed in various ways

qh

qc

(Adopted from the textbook: Atkins’ Physical Chemistry)

✓ Stage 1: Reversible isothermal expansion (ΔS = qh / Th)

✓ Stage 2: Reversible adiabatic expansion (Th → Tc, ΔS = 0)
✓ Stage 3: Reversible isothermal compression (ΔS = qc / Tc)
✓ Stage 4: Reversible adiabatic compression (Tc → Th, ΔS = 0)

10
 Carnot Cycle

❖ Total change in entropy around the cycle

✓ The sum of the changes in each four steps
𝑞ℎ 𝑞𝑐
ර 𝑑𝑆 = + =0
𝑇ℎ 𝑇𝑐
✓ For an ideal gas at constant temperature, ΔU = 0 (independent to the volume) and
wrev = –nRT ln(Vf/Vi) for expansion. Therefore, qrev = nRT ln(Vf/Vi)

𝑉𝐵 𝑉𝐷
(Stage 1) 𝑞ℎ = 𝑛𝑅𝑇ℎ ln 𝑞𝑐 = 𝑛𝑅𝑇𝑐 ln (Stage 3)
𝑉𝐴 𝑉𝐶

✓ For reversible adiabatic processes, VTc = constant

(Stage 2) 𝑉𝐶 𝑇𝑐𝑐 = 𝑉𝐵 𝑇ℎ𝑐 𝑉𝐴 𝑇ℎ𝑐 = 𝑉𝐷 𝑇𝑐𝑐 (Stage 4)

✓ Simplification and rearrangement leads to

𝑉𝐵 𝑉𝐶 𝑞ℎ 𝑞𝑐 𝑉𝐵 𝑉𝐷 𝑉𝐵 𝑉𝐴
= → ර 𝑑𝑆 = + = 𝑛𝑅 ln + 𝑛𝑅 ln = 𝑛𝑅 ln + 𝑛𝑅 ln = 0
𝑉𝐴 𝑉𝐷 𝑇ℎ 𝑇𝑐 𝑉𝐴 𝑉𝐶 𝑉𝐴 𝑉𝐵

11
 Heat Engine

❖ Efficiency (η) of a heat engine

✓ Definition

𝑤𝑜𝑟𝑘 𝑝𝑒𝑟𝑓𝑜𝑟𝑚𝑒𝑑 |𝑤|

𝜂= =
ℎ𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑓𝑟𝑜𝑚 ℎ𝑜𝑡 𝑠𝑜𝑢𝑟𝑐𝑒 |𝑞ℎ |

✓ Expression in terms of the heat transactions

𝑞ℎ − |𝑞𝑐 | |𝑞𝑐 |
𝜂= = 1−
|𝑞ℎ | |𝑞ℎ |

✓ As qh/Th + qc/Tc = 0 for Carnot cycle,

|𝑞𝑐 | 𝑇𝑐
=
|𝑞ℎ | 𝑇ℎ
✓ Therefore,
𝑇𝑐
𝜂 =1− (Adopted from the textbook: Atkins’ Physical Chemistry)
𝑇ℎ
Carnot efficiency

12
 Heat Engine

❖ Consider two reversible engines coupled together between the same hot
source and cold sink

(Adopted from the textbook: Atkins’ Physical Chemistry)

✓ If the efficiencies of the reversible engines A and B are different, the outcome goes against
the Kelvin statement of the Second Law, because some heat was directly converted to work
✓ Kelvin statement of the Second Law: “No process is possible in which the sole result is the
absorption of heat from a reservoir and its complete conversion into work”
✓ The two reversible engines cannot have different efficiencies
→ Efficiencies of reversible engines are the same, and this is true for any substance

13
 Approximation as a Collection of Carnot Cycles

❖ Any reversible cycle can be approximated as a collection of Carnot cycles

✓ The path shown by the purple line can
be approximated more closely by using
more Carnot cycles, each of which is
much smaller
✓ In the limit, they are infinitesimally small
so that the perimeters could match the
purple path exactly

❖ Entropy change of the overall cycle

✓ The entropy change around each
individual cycle is zero, so the sum of (Adopted from the textbook: Atkins’ Physical Chemistry)
entropy changes for all the cycles is zero
✓ In the sum, the entropy change along the path is cancelled by the entropy change along the
path it shares with the neighboring cycle
✓ Therefore, all the entropy changes cancel except for those along the perimeter of the
overall cycle, and the sum qrev/T around the perimeter is zero

❖ This result implies: dS is an exact differential and S is a state function

14
 Thermodynamic Temperature

❖ Thermodynamic temperature scale

✓ Suppose an engine working reversibly between a hot source at a temperature Th and a cold
sink at a temperature T
✓ Then, we can use the expression of Carnot efficiency

𝑇 = 1 − 𝜂 𝑇ℎ

✓ This expression enabled Kelvin to define the thermodynamic temperature scale in terms of
the efficiency of a heat engine:
✓ An engine in which the hot source is at a known temperature and the cold sink is the object
of interest
✓ The temperature of the cold sink can then be inferred from the measured efficiency of the
engine

❖ Kelvin scale (absolute temperature)

✓ A special case of the thermodynamic temperature scale
✓ Currently defined by using water at its triple point as the notional hot source and defining
that temperature as 273.16 K

15
 Clausius Inequality

❖ Linking the definition of entropy to the Second Law

✓ More work is done when a change is reversible than when it is irreversible

𝑑𝑤𝑟𝑒𝑣 ≥ 𝑑𝑤
✓ Since dw and dwrev are negative when energy leaves the system as work,

−𝑑𝑤𝑟𝑒𝑣 ≥ −𝑑𝑤
𝑑𝑤 − 𝑑𝑤𝑟𝑒𝑣 ≥ 0

✓ As U is a state function, its change is the same for reversible and irreversible paths

𝑑𝑈 = 𝑑𝑞 + 𝑑𝑤 = 𝑑𝑞𝑟𝑒𝑣 + 𝑑𝑤𝑟𝑒𝑣
𝑑𝑞𝑟𝑒𝑣 − 𝑑𝑞 = 𝑑𝑤 − 𝑑𝑤𝑟𝑒𝑣
✓ Then, as dw – dwrev ≥ 0,
𝑑𝑞𝑟𝑒𝑣 − 𝑑𝑞 ≥ 0 → 𝑑𝑞𝑟𝑒𝑣 ≥ 𝑑𝑞

✓ Division by T leads to
𝑑𝑞𝑟𝑒𝑣 𝑑𝑞 𝑑𝑞
≥ → 𝑑𝑆 ≥ Clausius inequality
𝑇 𝑇 𝑇
16
 Clausius Inequality

❖ What Clausius inequality tells us

✓ In an isolated system (i.e. dq = 0)

𝑑𝑆 ≥ 0
“In an isolated system the entropy cannot decrease when a spontaneous change occurs”

✓ Introduction of the inequality into the expression for the total entropy change that
accompanies a process
𝑑𝑆𝑡𝑜𝑡 = 𝑑𝑆 + 𝑑𝑆𝑠𝑢𝑟 ≥ 0
𝑑𝑆 ≥ 𝑑𝑞/𝑇 𝑑𝑆𝑠𝑢𝑟 = −𝑑𝑞/𝑇

✓ The inequality corresponds to an irreversible process and the equality to a reversible

process
✓ A spontaneous process is an irreversible process (dStot > 0)
✓ A reversible process is at equilibrium (dStot = 0)
✓ Spontaneous processes are necessarily irreversible processes

17
 Clausius Inequality

❖ Example: cooling an object to the temperature of its surroundings

✓ When |dq| leaves the hot source (dqh < 0),

𝑑𝑞ℎ
𝑑𝑆 ≥
𝑇ℎ
✓ When |dq| enters the cold sink (dqc > 0),
𝑑𝑞𝑐
𝑑𝑆 ≥
𝑇𝑐
✓ Therefore,
𝑑𝑞ℎ 𝑑𝑞𝑐
𝑑𝑆 ≥ +
𝑇ℎ 𝑇𝑐

✓ As dqh = –dqc,
(Adopted from the textbook: Atkins’ Physical Chemistry)

𝑑𝑞𝑐 𝑑𝑞𝑐 1 1
𝑑𝑆 ≥ − + = − 𝑑𝑞𝑐 > 0
𝑇ℎ 𝑇𝑐 𝑇𝑐 𝑇ℎ
✓ Hence, cooling (the transfer of heat from hot to cold) is spontaneous

18
 Entropy Changes

❖ Thermodynamic definition of entropy change

✓ As mentioned in the previous part,
𝑓
𝑑𝑞𝑟𝑒𝑣 𝑑𝑞𝑟𝑒𝑣
𝑑𝑆 = ∆𝑆 = න
𝑇 𝑖 𝑇
✓ Entropy change of surroundings was also explained in the previous part,

𝑑𝑞𝑠𝑢𝑟 𝑞𝑠𝑢𝑟
𝑑𝑆𝑠𝑢𝑟 = ∆𝑆𝑠𝑢𝑟 =
𝑇𝑠𝑢𝑟 𝑇𝑠𝑢𝑟

and this is the same whether or not the process is reversible or irreversible for the system

✓ The total change in entropy of an overall isolated system (the ‘universe’)

∆𝑆𝑡𝑜𝑡 = ∆𝑆 + ∆𝑆𝑠𝑢𝑟

❖ The entropy changes accompanying various physical changes will be

treated in the following slides

19
 Expansion

❖ Entropy change for the isothermal expansion of an ideal gas

✓ Change of the volume from Vi to Vf, T = constant

𝑓
𝑑𝑞𝑟𝑒𝑣 1 𝑓 𝑞𝑟𝑒𝑣
∆𝑆 = න = න 𝑑𝑞𝑟𝑒𝑣 =
𝑖 𝑇 𝑇 𝑖 𝑇

✓ As internal energy of an ideal gas is independent of its volume,

∆𝑈 = 𝑞 + 𝑤 = 0
𝑤𝑟𝑒𝑣 = −𝑛𝑅𝑇 ln 𝑉𝑓 /𝑉𝑖

✓ Therefore,
𝑞𝑟𝑒𝑣 = 𝑛𝑅𝑇 ln 𝑉𝑓 /𝑉𝑖
𝑞𝑟𝑒𝑣 𝑉𝑓
∆𝑆 = = 𝑛𝑅 ln
𝑇 𝑉𝑖
✓ As S is a state function, the value of ΔS of the system is independent of the path between
the initial and final states
✓ This expression applies whether the changes of state occurs reversibly or irreversibly

20
 Expansion

❖ The total change in entropy for the isothermal expansion of an ideal gas
✓ This does depend on how the expansion take place
✓ For any process the energy lost as heat from the system is acquired by the surroundings

𝑑𝑞𝑠𝑢𝑟 = −𝑑𝑞

✓ For the reversible isothermal expansion of an ideal gas,

𝑞𝑠𝑢𝑟 = −𝑞𝑟𝑒𝑣 = −𝑛𝑅𝑇 ln 𝑉𝑓 /𝑉𝑖

𝑞𝑟𝑒𝑣 𝑉𝑓
∆𝑆𝑠𝑢𝑟 = − = −𝑛𝑅 ln ∆𝑆𝑡𝑜𝑡 = ∆𝑆 + ∆𝑆𝑠𝑢𝑟 = 0
𝑇 𝑉𝑖
✓ For a free expansion (into a vacuum),

∆𝑈 = 0 and 𝑤 = 0 → 𝑞=0

✓ Therefore,
𝑞𝑠𝑢𝑟 = 0 → ∆𝑆𝑠𝑢𝑟 = 0
𝑉𝑓
∆𝑆𝑡𝑜𝑡 = 𝑛𝑅 ln > 0
𝑉𝑖

21
 Phase Transitions

❖ Entropy changes when phase transition occurs

✓ Solid → liquid (ΔS > 0)
✓ Liquid → gas (ΔS >> 0)

❖ Normal transition temperature (Ttrs)

✓ The temperature at which two phases are in equilibrium at 1 atm
✓ At the transition temperature, any transfer of energy as heat between the system and its
surroundings is reversible, because the two phases in the system are in equilibrium

❖ Entropy changes at constant pressure

✓ As q = ΔtrsH at constant pressure,
∆𝑡𝑟𝑠 𝐻
∆𝑡𝑟𝑠 𝑆 =
𝑇𝑡𝑟𝑠
✓ ΔtrsS < 0 when the phase transition is exothermic (ΔtrsH < 0)
✓ ΔtrsS > 0 when the phase transition is endothermic (ΔtrsH > 0)
✓ The change in entropy of the surroundings have opposite signs (and the same amount)
✓ At the transition temperature, ΔStot = 0 as the two phases are in equilibrium

22
 Phase Transitions

❖ Experimental entropies of phase transitions

✓ Standard entropies of phase transitions (ΔtrsSϴ, unit: J K–1 mol–1) at Ttrs

(Adopted from the textbook:

Atkins’ Physical Chemistry)

✓ The standard enthalpies and entropies of vaporization of liquids at the boiling temperatures

(Adopted from the textbook:

Atkins’ Physical Chemistry)

✓ A wide range of liquids give similar standard entropy of vaporization (~85 J K–1 mol–1)
✓ This empirical observation is called Trouton’s rule
→ A similar change in volume occurs when any liquid evaporates and becomes a gas

23
 Heating

❖ Entropy variation with temperature

✓ Based on the change of entropy, the entropy at a temperature Tf can be expressed by using
the entropy at another temperature Ti
𝑓 𝑇𝑓
𝑑𝑞𝑟𝑒𝑣 𝑑𝑞𝑟𝑒𝑣
∆𝑆 = න → 𝑆 𝑇𝑓 = 𝑆 𝑇𝑖 + න
𝑖 𝑇 𝑇𝑖 𝑇
✓ At constant pressure (the most common condition),
𝑑𝑞𝑟𝑒𝑣 = 𝑑𝐻 𝐶𝑃 = 𝜕𝐻/𝜕𝑇 𝑃

✓ Therefore, 𝑑𝑞𝑟𝑒𝑣 = 𝐶𝑃 𝑑𝑇
𝑇𝑓
𝐶𝑃 𝑑𝑇
𝑆 𝑇𝑓 = 𝑆 𝑇𝑖 + න
𝑇𝑖 𝑇
✓ When CP is independent of temperature over the temperature range of interest,
𝑇𝑓 𝑇𝑓
𝑑𝑇
𝑆 𝑇𝑓 = 𝑆 𝑇𝑖 + 𝐶𝑃 න = 𝑆 𝑇𝑖 + 𝐶𝑃 ln
𝑇𝑖 𝑇 𝑇𝑖
✓ At constant volume, same expressions can be used by replacing CP with CV

24
 Entropy Measurement

❖ The measurement of entropy

✓ Calorimetric measurement of the heat required to raise the temperature of a sample from
T = 0 to the temperature of interest
✓ At constant pressure,

𝑇2
𝐶𝑃 𝑑𝑇 ∆𝑡𝑟𝑠 𝐻(𝑇𝑡𝑟𝑠 )
𝑆 𝑇2 = 𝑆 𝑇1 + න ∆𝑆(𝑇𝑡𝑟𝑠 ) =
𝑇1 𝑇 𝑇𝑡𝑟𝑠

✓ Calculation of molar entropy of a substance at a temperature T above its Tf and Tb,

𝑇𝑓
𝐶𝑃,𝑚 (𝑠, 𝑇 ′ ) ∆𝑓𝑢𝑠 𝐻
𝑆𝑚 𝑇 = 𝑆𝑚 0 + න 𝑑𝑇′ +
0 𝑇′ 𝑇𝑓
𝑇𝑏 𝑇
𝐶𝑃,𝑚 (𝑙, 𝑇 ′ ) ∆𝑣𝑎𝑝 𝐻 𝐶𝑃,𝑚 (𝑔, 𝑇 ′ )
+න 𝑑𝑇′ + +න 𝑑𝑇′
𝑇𝑓 𝑇′ 𝑇𝑏 𝑇𝑏 𝑇′

✓ All the properties can be measured calorimetrically, except Sm(0)

✓ If all measurements are made at 1 bar on a pure material, the final value is
→ standard entropy (Sϴ(T)) or standard molar entropy (Smϴ(T) = Sϴ(T)/n)

25
 Entropy Measurement

❖ Heat capacity near T = 0

✓ Heat capacity of a non-metallic solid is proportional to T3 when T is low (based on quantum
mechanical theory)

❖ Debye extrapolation (or the Debye T3 law)

✓ CP is measured down to as low a temperature as possible
✓ A curve of the form aT3 is fitted to the data
✓ The expression CP,m(T) = aT3 is then assumed
to be valid down to T = 0
✓ Therefore, without any phase transition,

𝑇
𝑎𝑇 ′3
𝑆𝑚 𝑇 = 𝑆𝑚 0 +න 𝑑𝑇′
0 𝑇′
𝑇
= 𝑆𝑚 0 + 𝑎 න 𝑇 ′2 𝑑𝑇′
0

1 3 1 (Adopted from the textbook: Atkins’ Physical Chemistry)

= 𝑆𝑚 0 + 𝑎𝑇 = 𝑆𝑚 0 + 𝐶𝑃,𝑚 (𝑇)
3 3

26
 The Third Law of Thermodynamics

❖ At T = 0
✓ All energy of thermal motion is quenched
✓ In a perfect crystal, all the atoms or ions are in a regular, uniform array
✓ The localization of matter and the absence of thermal motion suggest that such materials
have zero entropy
✓ This understanding is in line with the molecular interpretation of entropy (W = 1 for S = k lnW)

❖ Nernst heat theorem

✓ The entropy change accompanying any physical or chemical transformation approaches
zero as the temperature approaches zero

∆𝑆 → 0 𝑎𝑠 𝑇 → 0
when all the substances are perfectly ordered
✓ Then, all perfect crystalline compounds also have zero entropy at T = 0, because the
change in entropy that accompanies the formation of the compounds is zero at T = 0

❖ The Third Law of thermodynamics

✓ The entropy of all perfect crystalline substance is zero at T = 0

27
 The Third Law of Thermodynamics

❖ Residual entropy
✓ S(0) > 0 when W > 1 at T = 0
✓ Non-perfect crystalline substance has a residual entropy due to different atomic/molecular
arrangements
✓ Examples: diatomic molecules arranged in … AB AB AB … and … BA AB BA …,
ice crystals with different molecular arrangements (3.4 J K–1 mol–1)

(Adopted from the textbook: Atkins’ Physical Chemistry)

28
 Third-Law Entropies

❖ Third-Law entropies
✓ Entropies reported on the basis that S(0) = 0
✓ When the substance is in its standard state
at the temperature T, the standard (Third-Law)
entropy is denoted Sϴ(T)

❖ Standard reaction entropy (ΔrSϴ)

✓ The difference between the molar entropies
of the pure, separated products and reactants
at standard states and specified temperature

∆𝑟 𝑆 𝜃 = ෍ 𝜃 −
𝜈𝑆𝑚 ෍ 𝜃
𝜈𝑆𝑚
𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
or

∆𝑟 𝑆 𝜃 = ෍ 𝜈𝐽 𝑆𝑚
𝜃 (𝐽) (Adopted from the textbook: Atkins’ Physical Chemistry)

✓ ΔrSϴ is likely to be positive if there is a net formation of gas in a reaction (and vice versa)

29
 Third-Law Entropies

❖ Standard molar entropies of ions

✓ The standard entropy of the H+ ions in water is taken as zero at all temperatures

𝑆 𝜃 (𝐻 + , 𝑎𝑞) = 0

✓ A positive entropy means that an ion has a higher molar entropy than H+ in water
✓ A negative entropy means that an ion has a lower molar entropy than H+ in water

❖ Ion entropies and degree of hydration

✓ Hydration → ordering of water molecules around ions
✓ A larger degree of ordering takes place when the ionic charge is larger and the ionic radius
is smaller

B. Huang et al. JACS Au 1, 1674 (2021)

✓ The absolute, Third-Law Smϴ of H+ in water is estimated as –21 J K–1 mol–1 (induces order)

30
 Temperature Dependence of Reaction Entropy

❖ Temperature dependence
𝑇2
𝐶𝑃,𝑚 (𝑇)
𝑆𝑚 𝑇2 = 𝑆𝑚 𝑇1 + න 𝑑𝑇
𝑇1 𝑇
✓ This equation applies to each substance in the reaction
𝑇2𝜃
∆ 𝑟 𝐶𝑃
∆𝑟 𝑆 𝜃 𝑇2 = ∆𝑟 𝑆 𝜃 𝑇1 + න 𝑑𝑇
𝑇1 𝑇

✓ ΔrCPϴ is the difference of the molar heat capacities of products and reactants under
standard conditions weighted by the stoichiometric numbers that appear in the following
chemical equation

∆𝑟 𝐶𝑃𝜃 = ෍ 𝜈𝐽 𝐶𝑃,𝑚
𝜃
(𝑇)
𝐽

✓ If ΔrCPϴ is independent of temperature in the range T1 to T2,

𝑇2
∆𝑟 𝑆𝜃 𝑇2 = ∆𝑟 𝑆𝜃 𝑇1 + ∆𝑟 𝐶𝑃𝜃 ln
𝑇1

31
 Concentrating on the System

❖ Helmholtz energy (A)

✓ Consider a system in thermal equilibrium with its surrounding at a temperature T
✓ From the Clausius inequality
𝑑𝑞 𝑑𝑞
𝑑𝑆 ≥ → 𝑑𝑆 − ≥0
𝑇 𝑇
✓ As dqV = dU at constant volume,
𝑑𝑈
𝑑𝑆 − ≥0
𝑇
✓ The importance of this inequality in this form is that it expresses the criterion for
spontaneous change solely in terms of the state functions of the system

𝑇𝑑𝑆 ≥ 𝑑𝑈

✓ If the internal energy is constant (dU = 0), TdS ≥ 0 → dSU,V ≥ 0 (as T > 0)
→ In a system at constant V and U, the entropy increases in a spontaneous change

✓ Helmholtz energy (A)

𝐴 = 𝑈 − 𝑇𝑆

32
 Concentrating on the System

❖ Gibbs energy (G)

✓ Similarly, as dqP = dH at constant pressure,
𝑑𝐻
𝑑𝑆 − ≥0
𝑇
✓ The importance of this inequality in this form is that it expresses the criterion for
spontaneous change solely in terms of the state functions of the system

𝑇𝑑𝑆 ≥ 𝑑𝐻
✓ If the internal energy is constant (dH = 0), TdS ≥ 0 → dSH,P ≥ 0 (as T > 0)
→ In a system at constant P and H, the entropy increases in a spontaneous change

✓ Gibbs energy (G)

𝐺 = 𝐻 − 𝑇𝑆

❖ Helmholtz and Gibbs energies

✓ When the state of the system changes at constant temperature,

𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆

33
 Concentrating on the System

❖ Criteria of spontaneous change

✓ At constant volume,
𝑇𝑑𝑆 > 𝑑𝑈 → 𝑑𝐴 < 0

✓ At constant pressure,

𝑇𝑑𝑆 > 𝑑𝐻 → 𝑑𝐺 < 0

✓ Criteria of spontaneous change

𝑑𝐴 𝑇,𝑉 < 0 𝑑𝐺𝑇,𝑃 < 0

These criteria are central to chemical thermodynamics

✓ The criteria for equilibrium

𝑑𝐴 𝑇,𝑉 = 0 𝑑𝐺𝑇,𝑃 = 0

✓ Endothermic reactions are therefore driven by the increase of entropy of the system, which
overcomes the reduction of entropy brought about in the surroundings by the inflow of heat
into the system in an endothermic process
✓ dSsur = –dU/T at constant volume and dSsur = –dH/T at constant pressure

34
 Remarks on the Helmholtz Energy

❖ Maximum work
✓ From the Clausius inequality,
𝑑𝑞
𝑑𝑆 ≥ → 𝑇𝑑𝑆 ≥ 𝑑𝑞
𝑇
✓ Since dU = dq + dw,

𝑑𝑈 ≤ 𝑇𝑑𝑆 + 𝑑𝑤
✓ This expression rearranges to

𝑑𝑤 ≥ 𝑑𝑈 − 𝑇𝑑𝑆

✓ The equality applies for a reversible process, and thus a reversible process gives the
maximum amount of energy as work, which is given by

𝑑𝑤𝑚𝑎𝑥 = 𝑑𝑈 − 𝑇𝑑𝑆

✓ As dA = dU – TdS at constant temperature,

𝑑𝑤𝑚𝑎𝑥 = 𝑑𝐴

35
 Remarks on the Helmholtz Energy

❖ Relation between the Helmholtz energy and the work that a system can do
✓ For a measurable isothermal change, as Helmholtz energy is a state function,

𝑤𝑚𝑎𝑥 = ∆𝐴 ∆𝐴 = ∆𝑈 − 𝑇∆𝑆
✓ Depending on the sign of TΔS, not all the change in internal energy may be available for
doing work
✓ If the change occurs with a decrease in entropy of the system (TΔS < 0), ΔU – TΔS is not
as negative as ΔU itself → the magnitude of wmax is smaller than that of ΔU
✓ For the change to be spontaneous, some of the energy must escape as heat in order to
generate enough entropy in the surrounding to overcome the reduction in entropy in the
system

(Adopted from the textbook: Atkins’ Physical Chemistry)

36
 Remarks on the Helmholtz Energy

❖ Relation between the Helmholtz energy and the work that a system can do
✓ Work: energy transferred to the surroundings as the uniform motion of atoms
✓ A = U (total internal energy of the system) – TS (contribution that is stored as energy of
thermal motion)
✓ Energy stored in random thermal motion cannot be used to achieve uniform motion in the
surroundings → only the part of U (U – TS) is available for conversion into work
✓ If the change occurs with an increase in entropy of the system (TΔS > 0), ΔU – TΔS is more
negative than ΔU → the magnitude of wmax is larger than that of ΔU
✓ For the change to be spontaneous, some of the energy must flow into the system as heat
(contributing to the generated work) → The S increases in the expense of a reduction of Ssur

(Adopted from the textbook: Atkins’ Physical Chemistry)

37
 Remarks on the Gibbs Energy

❖ The ‘free energy’

✓ The Gibbs energy is more common in chemistry than the Helmholtz energy, as changes
occurring at constant pressure are more common than at constant volume
✓ At constant temperature and pressure, chemical reactions are spontaneous in the direction
of decreasing Gibbs energy

❖ Spontaneous endothermic reactions

✓ dH > 0 and dG < 0
→ Entropy of the system increases so much that TdS outweighs dH
✓ Endothermic reactions are therefore driven by the increase of entropy of the system
✓ This entropy change overcomes the reduction of entropy brought about in the surroundings
by the inflow of heat into the system (dSsur = –dH/T at constant pressure)

❖ Maximum non-expansion work

✓ As H = U + PV and dU = dq + dw,

𝑑𝐻 = 𝑑𝑞 + 𝑑𝑤 + 𝑑(𝑃𝑉)
✓ As G = H – TS,
→ (G + dG) = (H + dH) – (T + dT)(S + dS) = H + dH – TS – TdS – SdT – dTdS

38
 Remarks on the Gibbs Energy

❖ Maximum non-expansion work

✓ Therefore, dG = dH – TdS – SdT

𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = 𝑑𝑞 + 𝑑𝑤 + 𝑑 𝑃𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

✓ When the change is isothermal (dT = 0),

𝑑𝐺 = 𝑑𝑞 + 𝑑𝑤 + 𝑑 𝑃𝑉 − 𝑇𝑑𝑆

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

𝑑𝐺 = 𝑑𝑞𝑟𝑒𝑣 + 𝑑𝑤𝑟𝑒𝑣 + 𝑑 𝑃𝑉 − 𝑇𝑑𝑆 = 𝑑𝑤𝑟𝑒𝑣 + 𝑑(𝑃𝑉)

✓ dwrev can be expressed as expansion work (–PdV) and other (additional) work (dwadd,rev)

𝑑𝐺 = −𝑃𝑑𝑉 + 𝑑𝑤𝑟𝑒𝑣.𝑎𝑑𝑑 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑑𝑤𝑟𝑒𝑣,𝑎𝑑𝑑 + 𝑉𝑑𝑃

✓ If the process occurs at constant pressure (dP = 0), dG = dwadd,rev ≥ dwadd

𝑑𝑤𝑎𝑑𝑑,𝑚𝑎𝑥 = 𝑑𝐺 and 𝑤𝑎𝑑𝑑,𝑚𝑎𝑥 = ∆𝐺

39
 Standard Molar Gibbs Energies

❖ Standard Gibbs energy of reaction (ΔrGϴ)

✓ Combination of standard entropies and enthalpies of reaction

∆𝑟 𝐺 𝜃 = ∆𝑟 𝐻𝜃 − 𝑇∆𝑟 𝑆 𝜃

❖ Standard Gibbs energy of formation (ΔfGϴ)

✓ Gibbs energy for the formation of a compound from its elements in their reference states
(ΔfGϴ of the elements in their reference states are zero)
✓ Expression of ΔrGϴ using ΔfGϴ

∆𝑟 𝐺 𝜃 = ෍ 𝜈∆𝑓 𝐺 𝜃 − ෍ 𝜈∆𝑓 𝐺 𝜃
𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
or

∆𝑟 𝐺 𝜃 = ෍ 𝜈𝐽 ∆𝑓 𝐺 𝜃 (𝐽)
𝐽

✓ The ΔfGϴ of H+(aq) is set equal to zero at all temperatures

∆𝑓 𝐺 𝜃 (𝐻+ , 𝑎𝑞) = 0

40
 Standard Molar Gibbs Energies

❖ Example: standard Gibbs energy of formation of Cl– in water

✓ The formation reaction: ½ H2(g) + ½ Cl2(g) → H+(aq) + Cl–(aq)

(Adopted from the textbook:

Atkins’ Physical Chemistry)

✓ The sum of the Gibbs energies for all the steps around a closed cycle is zero

∆𝑓 𝐺 𝜃 𝐶𝑙 − , 𝑎𝑞 = 1287 𝑘𝐽 𝑚𝑜𝑙 −1 + ∆𝑠𝑜𝑙𝑣 𝐺 𝜃 𝐻+ + ∆𝑠𝑜𝑙𝑣 𝐺 𝜃 𝐶𝑙 −

✓ ΔfGϴ of Cl– includes contributions from the dissociation, ionization, and hydration of hydrogen

41
 Standard Molar Gibbs Energies

❖ Gibbs energies of solvation of individual ions

✓ Gibbs energies of solvation of individual ions may be estimated on the basis of a model in
which solvation is expressed as an electrostatic property

✓ The ion is regarded as a charged sphere and the solvent is treated as a continuous medium
(a continuous dielectric)

✓ The key is to identify the Gibbs energy of solvation with the work of transferring an ion from
a vacuum into the solvent

✓ The work is calculated by taking the difference of the work of charging an ion when it is in
the solution and the work of charging the same ion when it is in a vacuum

42
 Standard Molar Gibbs Energies

❖ Gibbs energies of solvation of individual ions

✓ Coulomb potential energy of two point electric charges Q1 and Q2 separated by a distance r
in a medium with permittivity ε
𝑄1 𝑄2
𝑉 𝑟 =
4𝜋𝜀𝑟
✓ The energy of this interaction can be expressed in terms of the Coulomb potential (Φ) that
the point charge Q2 experiences at a distance r form the point charge Q1
✓ Then, V(r) = Q2Φ(r)
𝑄1
𝑉 𝑟 = 𝑄2 𝜙 𝑟 𝜙 𝑟 =
4𝜋𝜀𝑟
✓ The work of bringing up a charge dQ to the sphere is Φ(ri)dQ
✓ If the charge number of the ion is zi, the total work of charging the sphere from 0 to zie is

𝑧𝑖 𝑒
1 𝑧𝑖 𝑒
𝑧𝑖2 𝑒 2
𝑤=න 𝜙 𝑟𝑖 𝑑𝑄 = න 𝑄𝑑𝑄 =
0 4𝜋𝜀𝑟𝑖 0 8𝜋𝜀𝑟𝑖

✓ The electrical work of charging multiplied by NA is the molar Gibbs energy for charging the
ions

43
 Standard Molar Gibbs Energies

❖ Gibbs energies of solvation of individual ions

✓ The work of charging an ion in a vacuum is obtained by setting ε = ε0, the vacuum
permittivity
✓ When the permittivity is ε = εrε0, where εr is the relative permittivity of the medium

𝑧𝑖2 𝑒 2 𝑧𝑖2 𝑒 2
𝑤(vacuum) = 𝑤(medium) =
8𝜋𝜀0 𝑟𝑖 8𝜋𝜀𝑟 𝜀0 𝑟𝑖
✓ The change in molar Gibbs energy that accompanies the transfer of ions from vacuum to a
solvent is the difference of these two expression for the work of charging

𝑧𝑖2 𝑒 2 𝑁𝐴 𝑧𝑖2 𝑒 2 𝑁𝐴 𝑧𝑖2 𝑒 2 𝑁𝐴 𝑧𝑖2 𝑒 2 𝑁𝐴

∆𝑠𝑜𝑙𝑣 𝐺𝜃 = − = −
8𝜋𝜀𝑟𝑖 8𝜋𝜀0 𝑟𝑖 8𝜋𝜀𝑟 𝜀0 𝑟𝑖 8𝜋𝜀0 𝑟𝑖

✓ A minor rearrangement of the right-hand side gives

𝑧𝑖2 𝑒 2 𝑁𝐴 1
∆𝑠𝑜𝑙𝑣 𝐺𝜃 =− 1− Born equation
8𝜋𝜀0 𝑟𝑖 𝜀𝑟

✓ ΔsolvGϴ < 0
(strongly negative for small, highly charged ions in media of high relative permittivity)

44
 Combining the First and Second Laws

❖ The fundamental equation

✓ Combination of the First and Second Laws
✓ For a reversible change in a closed system of constant composition, and in the absence of
any additional (non-expansion) work,

𝑑𝑤𝑟𝑒𝑣 = −𝑃𝑑𝑉 𝑑𝑞𝑟𝑒𝑣 = 𝑇𝑑𝑆

from the definition of entropy

✓ Therefore, for a reversible change in a closed system,

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

✓ As dU is an exact differential, its value is independent of path

→ This equation applies to any change (reversible or irreversible) of a closed system that
does no additional (non-expansion) work

✓ When a change is irreversible, TdS > dq (the Clausius inequality) and –PdV < dw
→ dw + dq remains equal to TdS – PdV, if the composition is constant

45
 Combining the First and Second Laws

❖ Exact differentials
✓ When f is a function of x and y, suppose that df can be expressed as follows,

𝑑𝑓 = 𝑔 𝑥, 𝑦 𝑑𝑥 + ℎ 𝑥, 𝑦 𝑑𝑦

✓ If df is an exact differential, it can be expressed that

𝜕𝑓 𝜕𝑓
𝑑𝑓 = 𝑑𝑥 + 𝑑𝑦
𝜕𝑥 𝑦
𝜕𝑦 𝑥

✓ Then, g(x,y) and h(x,y) can be written as,

𝜕𝑓 𝜕𝑓
= 𝑔(𝑥, 𝑦) = ℎ(𝑥, 𝑦)
𝜕𝑥 𝑦
𝜕𝑦 𝑥

✓ Successive derivatives may be taken in any order (a property of partial derivatives)

𝜕 𝜕𝑓 𝜕 𝜕𝑓
=
𝜕𝑦 𝜕𝑥 𝑦
𝜕𝑥 𝜕𝑦 𝑥 𝑦
𝑥

46
 Combining the First and Second Laws

❖ Exact differentials
✓ Taking the partial derivative with respect to x of the first equation, and with respect to y of
the second gives

𝜕 𝜕𝑓 𝜕𝑔 𝑥, 𝑦 𝜕 𝜕𝑓 𝜕ℎ 𝑥, 𝑦
= =
𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦 𝑥 𝑦
𝜕𝑥 𝑦
𝑦 𝑥
𝑥
✓ By the property of partial derivatives, these two successive derivatives of f with respect to x
and y must be the same

𝜕𝑔 𝑥, 𝑦 𝜕ℎ 𝑥, 𝑦
=
𝜕𝑦 𝑥
𝜕𝑥 𝑦

✓ If this equality is satisfied, df = g(x,y) dx + h(x,y) dy is an exact differential

✓ This equality is the mathematical criterion for df(x,y) = gdx + hdy being an exact differential

47
 Properties of the Internal Energy

❖ U as a function of S and V
✓ U can be expressed as a function of the two variables among P, V, T, S, as these are all
interrelated
✓ From the fundamental equation, it is simple to express U as U(S, V)

𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑆 + 𝑑𝑉
𝜕𝑆 𝑉
𝜕𝑉 𝑆

✓ When this expression is compared term by term to the thermodynamic relation,

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

✓ For systems of constant composition,

𝜕𝑈 𝜕𝑈
=𝑇 = −𝑃
𝜕𝑆 𝑉
𝜕𝑉 𝑆

✓ (∂U/∂S)V = T is a purely thermodynamic definition of temperature as the ratio of changes in

the internal energy (a First-Law concept) and entropy (a Second-Law concept)

48
 Maxwell Relations

❖ U as a function of S and V
✓ As dU = TdS – PdV is an exact differential,

𝜕𝑇 𝜕𝑃
=− a Maxwell relation
𝜕𝑉 𝑆
𝜕𝑆 𝑉
❖ Maxwell relations
✓ U, H, A, and G are all state functions and can be used to derive the following relations
(Maxwell relations)

(Adopted from the textbook:

Atkins’ Physical Chemistry)

49
 Maxwell Relations

❖ Using the Maxwell relations

✓ To show: entropy of an ideal gas is linearly dependent on ln V (S = a + b ln V)
✓ The starting point would be,

𝜕𝑆 𝜕𝑃
=
𝜕𝑉 𝑇
𝜕𝑇 𝑉
✓ Since P = nRT/V,
𝜕𝑆 𝜕 𝑛𝑅𝑇/𝑉 𝑛𝑅
= =
𝜕𝑉 𝑇
𝜕𝑇 𝑉
𝑉

✓ At a constant temperature,

𝑑𝑉
න 𝑑𝑆 = 𝑛𝑅 න = 𝑛𝑅 ln 𝑉 + constant
𝑉

✓ For a van der Waals gas,

න 𝑑𝑆 = 𝑛𝑅 ln(𝑉 − 𝑛𝑏)

50
 Variation of Internal Energy

❖ Derivation of a thermodynamic equation of state

✓ Starting from the fundamental equation

𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑆 + 𝑑𝑉
𝜕𝑆 𝑉
𝜕𝑉 𝑆

✓ Division of both sides by dV with a constraint of constant temperature

𝜕𝑈 𝜕𝑈 𝜕𝑆 𝜕𝑈
= +
𝜕𝑉 𝑇
𝜕𝑆 𝑉
𝜕𝑉 𝑇
𝜕𝑉 𝑆
πT T –P

✓ From the definition of internal pressure (πT) and the Maxwell relation,

𝜕𝑆 𝜕𝑃
𝜋𝑇 = 𝑇 −𝑃 → 𝜋𝑇 = 𝑇 −𝑃
𝜕𝑉 𝑇
𝜕𝑇 𝑉

𝜕𝑃
𝑃=𝑇 − 𝜋𝑇 Thermodynamic
𝜕𝑇 𝑉 equation of state

51
 Variation of Internal Energy

❖ Internal pressure of an ideal gas

✓ For an ideal gas,
𝜕𝑃 𝜕 𝑛𝑅𝑇/𝑉 𝑛𝑅
= =
𝜕𝑇 𝑉
𝜕𝑇 𝑉
𝑉
✓ Therefore,
𝜕𝑃 𝑛𝑅𝑇
𝜋𝑇 = 𝑇 −𝑃 = −𝑃 =0
𝜕𝑇 𝑉
𝑉

❖ Internal pressure of a van der Waals gas

✓ For a van der Waals gas,
𝑛𝑅𝑇 𝑛2
𝑃= −𝑎 2
𝑉 − 𝑛𝑏 𝑉
✓ As a and b are independent of temperature

𝜕𝑃 𝜕𝑛𝑅𝑇/(𝑉 − 𝑛𝑏) 𝑛𝑅
= =
𝜕𝑇 𝑉
𝜕𝑇 𝑉
𝑉 − 𝑛𝑏

𝑛𝑅𝑇 𝑛𝑅𝑇 𝑛2 𝑛2
𝜋𝑇 = − −𝑎 2 =𝑎 2
𝑉 − 𝑛𝑏 𝑉 − 𝑛𝑏 𝑉 𝑉

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 Properties of the Gibbs Energy

❖ General considerations
✓ When the system undergoes a change of state,

𝑑𝐺 = 𝑑𝐻 − 𝑑 𝑇𝑆 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
✓ As H = U + PV,

𝑑𝐻 = 𝑑𝑈 + 𝑑 𝑃𝑉 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝐺 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

✓ For a closed system doing no non-expansion work (dU = TdS – PdV),

𝑑𝐺 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇
Fundamental equation of chemical thermodynamics

✓ Gibbs energy carries around the combined consequences of the First and Second Laws in
a way that makes it particularly suitable for chemical applications

53
 Properties of the Gibbs Energy

❖ General considerations
✓ As Gibbs energy can be expressed as a function of P and T,

𝜕𝐺 𝜕𝐺
𝑑𝐺 = 𝑑𝑃 + 𝑑𝑇
𝜕𝑃 𝑇
𝜕𝑇 𝑃
✓ Then, as dG = VdP – SdT,
𝜕𝐺 𝜕𝐺
=𝑉 = −𝑆
𝜕𝑃 𝑇
𝜕𝑇 𝑃

(Adopted from the textbook: Atkins’ Physical Chemistry)

54
 Properties of the Gibbs Energy

❖ Physical interpretations of (∂G/∂T)P = –S

✓ Because S > 0 for all substances, G always decreases when the temperature is raised
(at constant pressure and composition)
✓ Because (∂G/∂T)P becomes more negative as S increases, G decreases most sharply with
increasing temperature when the entropy of the system is large
✓ Therefore, G of the gaseous phase of a substance (which has a high molar entropy) is
more sensitive to temperature than its liquid and solid phases

(Adopted from the textbook: Atkins’ Physical Chemistry)

55
 Properties of the Gibbs Energy

❖ Physical interpretations of (∂G/∂P)T = V

✓ Because V > 0 for all substances, G always increases when the pressure of the system is
increased (at constant temperature and composition)
✓ Because (∂G/∂P)T increases with V, G is more sensitive to pressure when the volume of the
system is large
✓ Therefore, as the molar volume of the gaseous phase of a substance is greater than its
condensed phases, the molar G of a gas is more sensitive to pressure than its liquid and
solid phases

(Adopted from the textbook: Atkins’ Physical Chemistry)

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 Variation of the Gibbs Energy

❖ Variation with temperature

✓ The starting point is
𝜕𝐺
= −𝑆
𝜕𝑇 𝑃
✓ As G = H – TS, S = (H – G)/T
𝜕𝐺 𝐺−𝐻
=
𝜕𝑇 𝑃
𝑇

✓ How G/T varies with temperature will be of our interest as the equilibrium constant of a
reaction is related to G/T rather than to G (will be discussed in Chapter 6)

✓ As d(fg)/dx = f(dg/dx) + g(df/dx),

𝜕𝐺/𝑇 1 𝜕𝐺 𝑑(1/𝑇) 1 𝜕𝐺 𝐺 1 𝜕𝐺 𝐺
= +𝐺 = − 2= −
𝜕𝑇 𝑃
𝑇 𝜕𝑇 𝑃
𝑑𝑇 𝑇 𝜕𝑇 𝑃
𝑇 𝑇 𝜕𝑇 𝑃
𝑇

1 𝐺−𝐻 𝐺 1 −𝐻 𝐻 Gibbs-Helmholtz
= − = =− 2
𝑇 𝑇 𝑇 𝑇 𝑇 𝑇 equation

57
 Variation of the Gibbs Energy

❖ Variation with temperature

✓ The Gibbs-Helmholtz equation is most useful when it is applied to physicochemical changes
at constant pressure
✓ As G is a state function (ΔG = Gf – Gi),

𝜕∆𝐺/𝑇 ∆𝐻
=− 2
𝜕𝑇 𝑃
𝑇

❖ Variation with pressure

✓ At constant temperature, dG = VdP
𝑃𝑓 𝑃𝑓
𝐺 𝑃𝑓 = 𝐺 𝑃𝑖 + න 𝑉𝑑𝑃 𝐺𝑚 𝑃𝑓 = 𝐺𝑚 𝑃𝑖 + න 𝑉𝑚 𝑑𝑃
𝑃𝑖 𝑃𝑖

✓ It is necessary to know how Vm depends on the pressure, but for a condensed phase, Vm
changes only slightly (can be thereby treated as a constant)
𝑃𝑓
𝐺𝑚 𝑃𝑓 = 𝐺𝑚 𝑃𝑖 + 𝑉𝑚 න 𝑑𝑃
𝑃𝑖

58
 Variation of the Gibbs Energy

❖ Variation with pressure

✓ Molar Gibbs energy of an incompressible substance

𝐺𝑚 𝑃𝑓 = 𝐺𝑚 𝑃𝑖 + 𝑃𝑓 − 𝑃𝑖 𝑉𝑚

(Adopted from the textbook: Atkins’ Physical Chemistry)

✓ Under normal laboratory conditions, (Pf – Pi)Vm is very small and may be neglected
→ Gibbs energies of solids and liquids are largely independent of pressure
✓ However, in geophysical problems, because pressures in the Earth’s interior are huge,
effect of pressure on the Gibbs energy cannot be ignored

59
 Variation of the Gibbs Energy

❖ Variation with pressure

✓ The Gibbs energy of a gas depends strongly on the pressure, and the volume cannot be
treated as a constant
✓ For an ideal gas, as Vm = RT/P
𝑃𝑓 𝑃𝑓
1
𝐺𝑚 𝑃𝑓 = 𝐺𝑚 𝑃𝑖 + 𝑅𝑇 න 𝑑𝑃 = 𝐺𝑚 𝑃𝑖 + 𝑅𝑇 ln
𝑃𝑖 𝑃 𝑃𝑖

✓ If Pi = Pϴ (the standard pressure of 1 bar), then Gm of an ideal gas at a pressure P is

𝜃
𝑃
𝐺𝑚 𝑃 = 𝐺𝑚 + 𝑅𝑇 ln 𝜃
𝑃

(Adopted from the textbook: Atkins’ Physical Chemistry)

60
Department of Mechanical Engineering, Seoul National University May 21, 2020

Thank you for your attention!

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