Thermodynamics

• Industrial revolution in the late 1700s or early 1800s

• Up till then, heavy work was performed by horses: horsepower

• Fantastic new invention: Heat Engine,

• Thermodynamics: to gain the maximum efficiency from such

heat engines

• Thermodynamics deals with the science of “motion” (dynamics)

and/or the transformation of “heat” (thermo) and energy into various

other energy– containing forms.

 Thermodynamic Definitions
Thermodynamic System
• A thermodynamic system is defined as any part of the Universe under
consideration.

• It may be something as similar as a beaker of water, a chemical

reaction taking place in a test tube, oil refinery or as complicated as an
entire galaxy.
 Thermodynamic Definitions

Thermodynamic Surroundings
• Thermodynamics surroundings are defined as everything other than the
thermodynamic system.

• In other words, the entire rest of the universe.

The Universe

• The universe is therefore the system plus the surroundings.

Boundaries
• The boundary may be actual or notional.
• It controls transfer of work, heat, and matter from the system to the
surroundings and vice-versa.
• The boundary may or may not impose restrictions on such transfers.

A diathermic system allows heat flow into or An adiabatic system prevents heat flow
out of the system. into or out of the system.
 Thermodynamic Definitions

Open, Closed, and Isolated Systems

• Open System: An open system may exchange both energy and

matter with its surroundings. Changes in composition are therefore
possible.

• Closed System: A closed system may exchange energy but not

matter with its surroundings. Pressure build-up is a distinct
possibility.

• Isolated System: An isolated system may exchange neither

energy nor matter with its surroundings. Pressure build-up is a
possibility.
 Thermodynamic Definitions

Isothermal, Isobaric, and Isochoric Processes

• Isothermal implies constant temperature, T.

• Isobaric implies constant pressure, P.

• Isochoric implies constant volume, V.

 Thermodynamic Definitions

State Functions

• A state function describes the state of the system. How the system
came to be in that state is of no consequence.

• The following are all state functions:

Pressure, P;
Volume, V;
Temperature, T;
Mass, m;
Quantity, n
Internal Energy, U;
Enthalpy, H;
Entropy, S;
Gibbs Energy, G
 Thermodynamic Definitions
Random molecular motion
Path Functions

• Functions governing transition between

the states are called path functions.

• Heat, q & Work, w: are both forms of

energy.

• State of a system is changed by supply or

removal of energy in the form of heat or
work.

Uniform molecular motion

Thermodynamic Definitions
Heat and Work Conventions

• Path functions are positive when

energy enters the system.

• Path functions are negative when

energy leaves the system.

• They are often defined as:

Heat supplied to the system, qin

Mechanical work done on the

system, Won
 The Zeroth Law of Thermodynamics
• When two objects are separately in thermodynamic equilibrium with a third
object, they are in thermodynamic equilibrium with each other.

• Whenever two objects are in contact with one another, energy will flow between
them until they reach a state of thermodynamic equilibrium. Upon reaching this
state we say that the two objects are at the same temperature.
 The First Law of Thermodynamics and Enthalpy

• Law of Conservation of Energy: Energy can neither be created nor

destroyed, merely changed from one form to another.
 The First Law of Thermodynamics and Enthalpy

• Every thermodynamic system (even all matter) possesses an internal

energy, U.
𝚫𝑼 = 𝒒𝒊𝒏 + 𝒘𝒐𝒏

• Energy is conserved only for system + surroundings; system &

surroundings can exchange energy
 The First Law of Thermodynamics and Enthalpy

• Energy can be transported into a system resulting in an increase in

internal energy.
• The system absorbs heat from the surroundings: +q
• or the surroundings do work on the system: +w

Chemical work done during a chemical reaction

Emerging gas performs a chemical work

 The Work Done by an Expanding gas
𝑤 = 𝐹𝑑
𝐹
𝑝=
𝐴
𝐹 = 𝑝𝐴

𝑤 = 𝑝𝐴𝑑

𝑤𝑜𝑛 = −𝑝Δ𝑉
𝑤 = 𝑝Δ𝑉
 The First Law of Thermodynamics

Δ𝑈 = 𝑞𝑖𝑛 + 𝑤𝑜𝑛

𝑤𝑜𝑛 = −𝑝Δ𝑉

Δ𝑈 = 𝑞𝑖𝑛 − 𝑝Δ𝑉

• Expansion work clearly depends on 𝑝 and Δ𝑉.

 The First Law of Thermodynamics

Free Expansion

Δ𝑈 = 𝑞𝑖𝑛 − 𝑝Δ𝑉; but in space 𝑝 = 0 and Δ𝑈 = 𝑞𝑖𝑛 . However,

relatively very few experiments are carried out in space.

Reactions at Constant Volume (Domain of Heavy Industries)

Δ𝑈 = 𝑞𝑖𝑛 − 𝑝Δ𝑉; but at constant volume Δ𝑉 = 0 and Δ𝑈 = 𝑞𝑣 .
Constant volume reactors must withstand massive pressure changes,
heavy chemical industries; very expensive.
 Reversible Isothermal Expansion of an Ideal Gas

❑ Leads to maximum amount of work performed by the gas.

Ideal Gas Equation: p𝑉 = 𝑛𝑅𝑇 : p = Pressure; V = Volume; T = Absolute

temperature measure in K; n = quantity; R = Ideal gas constant, 8.314 J K-1 mol-1

𝑛𝑅𝑇
⇒p=
𝑉
 won for Reversible Isothermal Expansion

𝑤𝑜𝑛 = −𝑝𝑑𝑉
But, p𝑉 = 𝑛𝑅𝑇

So, 𝑛𝑅𝑇
𝑝=
𝑣

𝑛𝑅𝑇
𝑤𝑜𝑛 = − 𝑑𝑉
𝑣

Now consider an expansion from Vi to Vf

𝑉𝑓
𝑑𝑉
𝑤𝑜𝑛 = −𝑛𝑅𝑇 න • Reversible change is a
𝑉
𝑉𝑖
theoretical construct.
𝑉𝑓 • Determines maximum possible
𝑤𝑜𝑛 = −𝑛𝑅𝑇 ln expansion work.
𝑉𝑖

𝑤𝑜𝑛 = - 1 mol × 8.314 J K-1 mol-1 × 298 K × ln(11)

 The First Law of Thermodynamics

Reactions at Constant Pressure

Δ𝑈 = 𝑞𝑖𝑛 − 𝑝Δ𝑉 Δ𝑈 + 𝑝Δ𝑉 = 𝑞𝑖𝑛 at constant pressure.
• Now we define a new state function, enthalpy:

𝐻 = 𝑈 + 𝑝𝑉

∴ ∆𝐻 = ∆𝑈 + ∆ 𝑝𝑉 , Use product rule

⇒ ∆𝐻 = ∆𝑈 + 𝑝∆𝑉 + 𝑉∆𝑝, but at constant pressure ∆𝑝 = 0, 𝑉∆𝑝 = 0

∴ ∆𝐻 = ∆𝑈 + 𝑝∆𝑉

∆𝑯 = 𝒒𝒑
 The First Law of Thermodynamics Does Not Predict
Spontaneous Change

Energy is conserved. It is neither created nor destroyed, but it is transferred

in the form of heat and/or work.

ΔE = q + w

The total energy of the universe is constant:

ΔEsys = -ΔEsurr or ΔEsys + ΔEsurr = ΔEuniv = 0

The law of conservation of energy applies to all changes, but it does not
allow us to predict the direction of a spontaneous change.
Spontaneous Processes
Processes that are spontaneous in one
direction are nonspontaneous in the reverse
direction.

Processes that are spontaneous at one temperature may

be nonspontaneous at other temperatures.
 H Does Not Predict Spontaneous Change

A spontaneous change may be exothermic or endothermic.

Spontaneous exothermic processes include:

• freezing and condensation at low temperatures,
• combustion reactions,
• oxidation of iron and other metals.

Spontaneous endothermic processes include:

• melting and vaporization at higher temperatures,
• dissolving of most soluble salts.

The sign of ΔH does not by itself predict the direction of a spontaneous change.
 Entropy
• Entropy (S) is a term coined by Rudolph Clausius in the 19th century.

• Entropy can be thought of as a measure of the randomness of a system.

• It is related to the various modes of motion in molecules.

qrev
S =
T
 The Second Law of Thermodynamics
The sign of ΔS for a reaction does not, by itself, predict the direction of a
spontaneous reaction.

If we consider both the system and the surroundings, we find that all real
processes occur spontaneously in the direction that increases the entropy of the
universe.

For a process to be spontaneous, a decrease in the entropy of the system must

be offset by a larger increase in the entropy of the surroundings.

Suniv = Ssys + Ssurr > 0

• For enthalpy there is no zero point; we can only measure changes in enthalpy.
• For entropy there is a zero point, and we can determine absolute entropy values.
 The Third Law of Thermodynamics

A perfect crystal has zero entropy at absolute zero.

Ssys = 0 at 0 K
A “perfect” crystal has flawless alignment of all its particles. At absolute zero, the
particles have minimum energy, so there is only one microstate.
 Standard Molar Entropies

S° is the standard molar entropy of a substance, measured for a substance in its

standard state in units of J/mol·K.

The conventions for defining a standard state include:

• 1 atm for gases
• 1 M for solutions, and
• the pure substance in its most stable form for solids
and liquids.
 Factors Affecting Entropy

• Entropy depends on temperature.

• For any substance, S°increases as temperature increases.

• Entropy depends on the physical state of a substance.

• S°increases as the phase changes from solid to liquid to gas.

• The formation of a solution affects entropy.

• Entropy is related to atomic size and molecular complexity.

• Remember to compare substances in the same physical state.
The increase in entropy during phase changes from solid to liquid to gas.
 The entropy change accompanying the dissolution of a salt.

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

pure solid

MIX

pure liquid
solution

The entropy of a salt solution is usually greater

than that of the solid and of water, but it is
affected by the organization of the water
molecules around each ion.
 Entropy and Structure

For allotropes, S°is higher in the form that allows the atoms more freedom of
motion.

S°of graphite is 5.69 J/mol·K, whereas S°of diamond is 2.44 J/mol·K.

 Entropy Changes in the System
The standard entropy of reaction, ΔS°rxn, is the entropy change that occurs
when all reactants and products are in their standard states.

S°rxn = mS°products - nS°reactants

where m and n are the amounts (mol) of products and reactants, given by the
coefficients in the balanced equation.
Calculating the Standard Entropy of Reaction, S°rxn

PROBLEM: Predict the sign of ΔS°rxn and calculate its value for the
combustion of 1 mol of propane at 25°C.
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)

PLAN: From the change in the number of moles of gas (6 mol yields 3 mol), the
entropy should decrease (ΔS°rxn < 0).

SOLUTION:
ΔS°rxn = [(3 mol CO2)(S° of CO2) + (4 mol H2O)(S° of H2O)]
- [(1 mol C3H8)(S° of C3H8) + (5 mol O2)(S° of O2)
= [(3mol)(213.7J/K·mol) + (4 mol)(69.9J/K·mol)]
– [(1mol)(269.9 J/K·mol) + (5 mol)(205.0 J/K·mol) = -374 J/K
 Entropy Changes in the Surroundings

A decrease in the entropy of the system is outweighed by an increase in the

entropy of the surroundings.

The surroundings function as a heat source or heat sink.

In an exothermic process, the surroundings absorbs the heat released by the system,
and Ssurr increases.

qsys < 0; qsurr > 0 and ΔSsurr > 0

In an endothermic process, the surroundings provides the heat absorbed by the

system, and Ssurr decreases.

qsys > 0; qsurr < 0 and ΔSsurr < 0

 Temperature at which Heat is Transferred

For any reaction, qsys = -qsurr, the heat transferred is specific for the reaction and is
the same regardless of the temperature of the surroundings.

Ssurr = - qsys
T

Ssurr = - Hsys for a process at constant P.

T
 Surroundings & system

= – Gibbs Free Energy

 = – Gibbs Free Energy
Make this equation nicer:
 Gibbs Free Energy
The Gibbs free energy (G) combines the enthalpy and entropy of a system;
G = H – TS.

The free energy change (ΔG) is a measure of the spontaneity of a process and of the
useful energy available from it.

Gsys = Hsys - T Ssys

G < 0 for a spontaneous process

G > 0 for a nonspontaneous process
G = 0 for a process at equilibrium
 Calculating G°

G°rxn can be calculated using the Gibbs equation:

G°sys = H°sys - T S°sys

G°rxn can also be calculated using values for the

standard free energy of formation of the components.

G°rxn = m G°products – n G°reactants

 Reaction Spontaneity and the Signs of H, S, and G

H S -TS G Description
– + – – Spontaneous at all T
+ – + + Nonspontaneous at all T
+ + – + or – Spontaneous at higher T;
nonspontaneous at lower T
– – + + or – Spontaneous at lower T;
nonspontaneous at higher T
 Free Energy and Equilibrium

G = RT ln Q = RT lnQ – RT lnK
K

If Q and K are very different, ΔG has a very large value (positive or negative). The
reaction releases or absorbs a large amount of free energy.

If Q and K are nearly the same, ΔG has a very small value (positive or negative).
The reaction releases or absorbs very little free energy.

For standard state conditions, Q = 1 and G° = -RT lnK

To calculate ΔG for any conditions:

ΔG = ΔG° + RT lnQ