Thermodynamics

Thermo refers heat, dynamics refers flow of heat.

Thermodynamics an science and engineering tool used to

describe processes that involve changes in temperature and
transformation of energy.

It establishes a relationships between heat and work.

Combustion Heat Mechanical Work

Solar Heat Heat Engine
Electrical Energy
Nuclear Heat

Heat Waste
System and surrounding
• For the purposes of physical chemistry, the universe is
divided into two parts, the system and its surroundings.

• The system is the part of the world in which we have a

special interest. It may be a reaction vessel, an engine, an
electrochemical cell, a biological cell, and so on.

• The surroundings comprise the region outside the system

and are where we make our measurements.
 Different types of systems

Fig. 2.1
(a) An open system can exchange matter and energy with its surroundings.
(b) A closed system can exchange energy with its surroundings, but it cannot exchange
matter.
(c) An isolated system can exchange neither energy nor matter with its surroundings.
Diathermic And Adiabatic Wall

Diathermic wall Adiabatic wall

Passage of heat is Passage of heat is

permitted not permitted
Exothermic and endothermic process;
Endothermic – Gaining of heat during a process
Exothermic – Release of heat during a process

Adiabatic system;
Heat neither goes out or come in.
Temperature reading in thermometer falls
during endothermic process.
Temperature rises during exothermic process.

Isothermal Process; Heat is exchanged

between system and surrounding depending
upon the process as may be.
So, T of the system is maintained constant.
Objects in thermal equilibrium
The temperature, T, is the property that indicates
the direction of the flow of energy through a
thermally conducting rigid wall.

If energy flows from A to B when they are in

A B
contact, then we say that A has a higher
temperature than B

Vice versa, If energy flows from B to A when they

are in contact, then we say that B has a higher
temperature than A.

Thermal equilibrium is established if no change

A B
of state occurs when two objects A to B are in
contact through a diathermic boundary.
Zeroth Law of Thermodynamics
Suppose an object A (which we can think of as a
block of iron) is in thermal equilibrium with an
object B (a block of copper), and that B is also in
thermal equilibrium with another object C (a flask
of water). Then it has been found experimentally
that A and C will also be in thermal equilibrium
when they are put in contact.
This observation is summarized by the Zeroth Law
of thermodynamics:

“If A is in thermal equilibrium with B, and B is in thermal

equilibrium with C, then C is also in thermal equilibrium
with A”
 Zeroth Law of Thermodynamics

– Adiabatic wall

– Diathermal wall

If TA = Tc and TB = TC Zeroth Law Provides the Basis for the

thermometer function.
Then, TA = TB Where mercury and the liquid in contact
are separated by a diathermal wall
First Law; Basic concepts

• It is law of conservation of energy

• Energy cannot be created or destroyed, it can only be

transformed from one form to another form.

• The concept of internal energy (E or U), Heat (q), Work(w),

and enthalpy (H) follows from first law of thermodynamics.

Reference Book: Peter Atkins and Julio de Paula; Physical Chemistry, 7th Ed
Work
• The fundamental physical property in thermodynamics is work

• Work is motion against an opposing force. Doing work is

equivalent to raising a weight somewhere in the surroundings.
•
• An example of doing work is the expansion of a gas that pushes out
a piston and raises a weight (Expansion work or Pressure-Volume
Work). –Pressure-volume change occurs

• A chemical reaction that drives an electric current through a

resistance also does work, because the same current could be
driven through a motor and used to raise a weight (Non expansion
work). –Gibbs free energy change occurs
Energy
• The energy of a system is its capacity to do work.

• When work is done on an otherwise isolated system

(for instance, by compressing a gas or winding a spring),
the capacity of the system to do work is increased; in
other words, the energy of the system is increased.

• When the system does work (when the piston moves

out or the spring unwinds), the energy of the system is
reduced and it can do less work than before.
Heat
• Experiments have shown that the energy of a
system may be changed by means other than
work itself.

• When the energy of a system changes as a result of

a temperature difference between the system and
its surroundings we say that energy has been
transferred as heat.
Molecular/atomic motion during
energy transfer to or work done on
surrounding
 State Functions

A state function is a property whose value does not depend

on the path taken to reach that specific value.

From first law of thermodynamics

Internal Energy (E),
Enthalpy (H),

From second law of thermodynamics

Entropy (S),
and Free Energy (G)
Internal Energy (E)
 Internal energy: A
The total energy of a system is called its internal energy, U.
The internal energy is the total kinetic and potential energy of the
molecules in the system.
∆U = Uf − Ui,

Where, ∆U - change in internal energy ;

Ui - internal energy of initial state;
Uf internal energy of final state

Changing state variable such as Pressure (P), Temperature(T),

Volume (V) will alter the internal energy of a system.

w = - pdv (doing work on the system changes the

internal energy of a system)
Internal energy
It has been found experimentally that the internal energy of a
system may be changed either by doing work on the system or by
heating it.
q = heat change
∆U = q + w w = work
If the system absorbs heat q > 0
If systems looses heat q < 0
If system does work on surrounding w < 0
If work is done on the system w > 0

q + w = ∆U
The sign convention of q and w
 Units of Internal Energy, Heat, and Work

• U, q, and w are all measured in the same units, the

joule (J).

• The joule, named after the nineteenth-century scientist

J.P. Joule, is defined as 1 J = 1 kg m2 s−2

• Changes in molar internal energy, ∆Um, are typically

expressed in kilojoules per mole (kJ mol−1 ).
Units of Internal Energy, Heat, and Work

• Calories (cal) and kilocalories (kcal) are still

encountered.

• 1 cal = 4.184 J

• An energy of 1 cal is enough to raise the temperature of

1 g of water by 1°C
Expansion work
For infinitesimal change of state
dU = dq + dw

dw = −Fdz (Force x distance moved)

dV = Adz

F = PexA

dw = −PexdV

For general case, total work done when volume goes from Vi to Vf

For expansion w is negative, as Vf > Vi

For compression w is positive, as Vf < Vi
Different types of expansion

• Free expansion, expansion against zero opposing force,

Pex = 0, w = 0

• That is, no work is done when a system expands freely.

Expansion of this kind occurs when a system expands
into a vacuum.
Expansion against constant
pressure
• Now suppose that the external pressure
is constant throughout the expansion.
• For example, the piston may be pressed
on by the atmosphere, which exerts the
same pressure throughout the
expansion.
Reversible expansion
• A reversible change in thermodynamics is a change
that can be reversed by an infinitesimal
modification of a variable.

• The key word ‘infinitesimal’ sharpens the everyday

meaning of the word ‘reversible’ as something that
can change direction (reverse).
Reversible expansion
• To achieve reversible expansion we set pex equal to
internal pressure (p) at each stage of the expansion.

• In practice, this equalization could be achieved by

gradually removing weights from the piston so that
the downward force due to the weights always
matched the changing upward force due to the
pressure of the gas.

• When we set pex = p, we can write as

Isothermal reversible expansion
Consider a perfect gas is expanding under
constant temperature (Isothermal),
We can replace p with p = nRT/V using the
equation of state, pV = nRT.

As T, n, and R are constants, those can be taken

out of the integral
Work done under reversible and irreversible
process
Whole area under the PV curve =
work done under reversible process

The dark rectangular area under

PV curve = work done under
irreversible process
In irreversible process
compression or expansion is
drastic/quick. So more energy is
lost as heat.
Summary for expansion work
• The work of free expansion is w = 0.

• The work of expansion against a constant external

pressure is w = −pex∆V.

• The work of isothermal reversible expansion of a

perfect gas is w = −nRT ln(Vf/Vi)
or w = nRT ln(Vi/Vf).
 Fe (s) + 2 HCl (aq) H2 (g) + FeCl2 (aq)

Method to solve this problem

We need to judge the magnitude of the volume change and then to decide how the
process occurs.

If there is no change in volume, there is no expansion work however the process takes
place.

If the system expands against a constant external pressure, the work can be calculated
from eqn w = −pex∆V.

A general feature of processes in which a condensed phase changes into a gas is that
the volume of the former may usually be neglected relative to that of the gas it
forms.
Initial and final PV Relationship

The curves of pressure versus volume for

adiabatic change are known as adiabats,
and one for a reversible path is illustrated in
in the given figure.

We know that γ > 1, as Cp > Cv

So, an adiabat falls more steeply (p ∝ 1/Vγ)

than the corresponding isotherm (p ∝ 1/V).
For example
Vi = 50 dm3
Vf = 100 dm3

Vi/Vf = 50/100 = 1/2

Limitation of 1st Law of
Thermodynamics

• First law of thermodynamic is the law of

“conservation of energy”

• It tell us the possibility of converting one form of

energy into other form.

• But it does tell about the thermodynamically

allowed direction of the conversion (or change).
Second law of thermodynamics
• “Some things happen naturally; some things don’t”

• The thing that occurs in a specific direction are called

spontaneous change.

• For example cooling of your hot coffee to its surrounding

temperature.

• The “spontaneous changes are always accompanied by a

dispersal of energy” (specifically thermal energy = heat).
Kelvin Planck and Clausius
Statements
• The second law of thermodynamics “describes the
spontaneity of a specific thermodynamic process with
the help of various equivalent statements”

• Kelvin Planck’s and Clausius statements provide the

formwork to understand the dispersal of thermal
energy as essential criteria of spontaneous events.
Kelvin Plank’s and Clausius’s Statements

Heat source

Heat Sink
 Second Law and Entropy
• The Second Law of thermodynamics analyses these
statements in terms of the entropy (disorder/randomness)

• Entropy is a state function denoted by S

• The entropy of an isolated system increases in the course

of a spontaneous change:
∆S tot > 0 ,
where Stot is the total entropy of the system and its
surroundings.
Thermodynamic irreversibility
“Spontaneous process are thermodynamically irreversible
process”

Examples
1. Transfer of heat from the hot coffee to it’s cold surrounding

2. The free expansion of gases into the vacuum

These process must be accompanied by an increase in total

entropy.
∆Stot = ∆Ssys + ∆Ssur >> 0
Thermodynamic definition of
entropy
Calculating entropy change for
isothermal process

If the change is isothermal, T is constant, then change in internal energy is zero

One mole of gas has volume X = 50 cm3),
Upon isothermal reversible expansion the volume becomes doubled, that means 2X
Entropy change for adiabatic
process
The easiest pathway for which to calculate entropy
changes is an adiabatic pathway.

Since dq=0 for an adiabatic change,

then dS=0 as well.

Entropy change and heat (qrev)
• The entropy change (ΔS) is related to heat flow (qrev) by
ΔS = qrev/T.

• At constant pressure
qrev = nCpΔT = Enthalpy change (∆H)

• At constant volume
qrev = nCvΔT = Internal energy change (∆U)
where n is the number of moles of substance present,
Solution to the integrals
• The change in entropy for a substance whose
temperature changes from T1 to T2 is as follows:
Entropy change in the surrounding:
Upon heat transfer and work

Upon release of heat from system, entropy of surrounding increases.

Upon system does work, the entropy of surrounding decreases.
Heat engines and the second law
of thermodynamics
“A heat engine is a device that converts internal energy to
mechanical energy”
Kelvin Planck's Statement
No process is possible in which the sole result is the
absorption of heat from a reservoir and its complete
conversion into work.

“Work cant be extracted from a single heat reservoir”

A heat engine needs two reservoirs,

a heat reservoir and a heat sink
Thermal efficiency of a heat engine

A heat engine has 100% efficiency ( e=1), if and only if Qc= 0.

It is impossible extract work from a heat source without

transferring heat to sink (Kelvin Planck’s statement), hence, thermal
efficiency of a engine is always < 100 %

For example, a good automobile engine has an efficiency of about

20%, and diesel engines have efficiencies ranging from 35% to 40%.
THE CARNOT ENGINE
• In 1824 a French engineer named Sadi Carnot
described a theoretical engine, now called a Carnot
engine, that is of great importance from both
practical and theoretical viewpoints.
• Carnot theorem
“No real heat engine operating between two
energy reservoirs can be more efficient than a
Carnot engine operating between the same
two reservoirs”
Cyclic Process –Carnot Engine
During isothermal expansion Qh
enters the engine (from source)

During isothermal compression Qc

enters the sink (from engine)

During adiabatic expansion,

Temperature drops from Th to Tc

During adiabatic compression,

temperature of the system
A to B – Isothermal expansion rise from Tc to Th
B to C – Adiabatic expansion
C to D – Isothermal compression
D to A – Adiabatic compression
For a cyclic reversible path-Carnot Cycle

0 0
∆S = dSadia (expansion) + dSadia (compression) + dSiso (expansion)
+ dSiso (compression)

dQ for two adiabatic change in the cycle is zero, so dS = 0

For two isothermal process (expansion and compression) in the cycle

For Carnot engine , Equivalently, Qc/Tc = Qh/Th

∆S = 0
Entropy change for Carnot cycle

The change in entropy for a Carnot cycle is zero

∆S = 0 for any reversible cycle

 Carnot engine Vs real heat engine
• Practically, the efficiency of real heat engine cycle is less than that of
an ideal engine cycle (Carnot cycle).

• The difference between the two cycle is that the expansion and
compression process in Carnot engine is assumed to be reversible
Whereas in real engine these process occur in irreversible manner

Work done under any irreversible process is less than that of the
work done under a reversible process, because less energy is lost as
heat in a reversible process
Carnot engine Vs real heat engine
Assume that the Carnot engine and real heat engine draw
the same amount of heat (QH) from the same heat source

Tc = TL
In reversible process, In irreversible process,
change of variable is infinitesimal change in variable is abrupt(quick)
The heat lose (QL) to the sink is smaller The heat lose (QL) to sink is larger

OL, irrev > QL, rev

 Clausius Inequality
For Carnot Cycle For real engine cycle

QL,irrev> QL,rev
Qdiff = QL,irrev- QL,rev
QL,irrev
TL =

For reversible case

dq/T = 0 = ds
For irreversible case dq/T <0 = refers reversible process
dssys < 0 < refers irreversible process

Alternatively, Clausius inequality is dS ≥ dQ/T (entropy change in sys + sur)

Total entropy change is positive for a spontaneous (irreversible change)

Carnot engine Vs Real heat engine
For reversible cycles For irreversible cycles
(Carnot) (Real heat engine)
 Qc/Qh = Tc/Th

The temperature must be used in Kelvin scale to solve this kind of

problems, if Tc and Th are given.
Rank the engines in terms of theoretically possible efficiencies, from lowest to highest.

While lower Tc provides higher theoretical efficiency, higher Th is practically achievable.

HEAT PUMPS AND REFRIGERATORS
• Heat pump is a mechanical device that moves thermal
energy from a region at lower temperature to a
region at higher temperature.
• Heat pumps have long been used for cooling homes
and buildings, and they are now becoming
increasingly popular for heating them as well.
• According to the Clausius statement, the pumping of
heat from cold reservoir to hot reservoir requires
external work (example electrical work)
HEAT PUMPS AND REFRIGERATORS
Heating and cooling mode utilizes same principle

Theoretically, a Carnot-cycle heat

engine run in reverse cycle constitutes
the most effective heat pump possible.
Effectiveness of heat pump
The effectiveness of a heat pump is described in terms of a number
called the coefficient of performance (COP). In the heating mode,
the COP is defined as the ratio of the energy transferred to the hot
reservoir to the work required to transfer that energy:
Heat pump –Cooling mode

W = Qh - Qc

A good refrigerator must have a high COP of 5 or 6

The greatest possible COP for a heat pump in the cooling mode is
that of a heat pump whose working substance is carried through a
Carnot cycle in reverse:
Th/Tc = Qh/Qc 300/270

Qh = (Th/Tc ) * Qc
 Third law of thermodynamics
Nernst theorem: The entropy change accompanying any physical or
chemical transformation approaches zero as the temperature
approaches absolute zero: ∆S → 0 as T → 0 (−273.15 °C, or −459.67
°F) provided all the substances involved are perfectly crystalline.

In practical terms, this theorem implies the impossibility of attaining

absolute zero, since as a system approaches absolute zero, the
further extraction of energy from that system becomes more and
more difficult (more work is required to extract heat from a cold
body).

Modern science has attained temperatures less than a billionth of a

degree above absolute zero, but absolute zero itself can never be
reached.

https://www.britannica.com/biography/Walther-Nernst#ref102911
 Relative Entropy of Physical States

Disorder (randomness) of a system decreases, as we continue to extract heat from it.

This result in decreasing molecular kinetic energy as go from gas → liquid → solid

Third law states that at absolute zero (0K), the disorder in a solid
must be zero.
But, practically, reaching absolute zero is not possible.
Calculating the standard entropy
change for chemical changes
 Third law of thermodynamics
–Microscopic Interpretation
Third law

Quantum statistical mechanics provides the microscopic interpretation of zero

entropy for a perfect crystal as well as quantitative corrections for those few errant
substances exhibiting small positive entropy values at zero absolute temperature.

The statement that the lowest energy state of the crystal is nondegenerate (only a
single quantum state is available to it) is easily visualized as a perfectly ordered
crystal where only a single arrangement of atoms, molecules, or ions on the crystal
lattice is possible. Thus, in terms of Boltzmann's famous equation

W – number of possible microstates

kB - Boltmann’s constant
Boltzmann formula for the entropy
From a microscopic viewpoint, entropy is defined as

where kB is Boltzmann’s constant and W is the number of microstates available to

the system for the existing macrostate.

macroscopic properties are observable at larger scale: pressure and temperature

microscopic properties are observable at atomic/molecular scale: translational,

vibrational, rotational.

Translational, vibrational, rotational

states have quantized energy levels,
(Lower energy to higher energy)
Translational, vibrational, rotational motions

CO2

C
O O

As T approaches Zero, these motions are also approaches Zero

 Boltzmann formula for the entropy
From a microscopic viewpoint, entropy is defined as

If all the molecules are in one energy state there is only one way of
achieving this distribution, so W = 1 and, because ln 1 = 0, it follows
that S = 0.

As the molecules spread out over the available energy states, W

increases and therefore so too does the entropy.
Entropy for any substance increases
with temperature
“As temperature increase the average kinetic energy of molecules
increases”. Thermal energy is spread and dispersed.

At T1 At T2
Assume that there 36 molecules in a gas container.
 Summary
• First law of thermodynamics:
• Isothermal process: temperature is constant.
• Adiabatic process: no heat is exchanged.
• Work done by gas at constant pressure:

• Heat engine changes heat into

useful work; needs temperature
difference.
• Efficiency of a heat
engine:
© 2014 Pearson Education,
Inc.
Summary
 Summary
• Upper limit on efficiency:

(15-5)

• Refrigerators and air conditioners do work to extract heat from

a cooler region and send it to a warmer region:

(15-6a)
• A heat pump is similar:

(15-7)
© 2014 Pearson Education,
Inc.
 Summary
• Second law of thermodynamics:
• heat flows spontaneously from a hot object to a cold one,
but not the reverse
• a given amount of heat cannot be changed entirely to work
• natural processes tend to increase entropy.
• Change in entropy:

• Entropy is a measure of disorder.

© 2014 Pearson Education,

Inc.
 Third law of thermodynamics

• Entropy of a perfectly ordered crystalline solid is zero

at T = 0 K.

• Nernst heat theorem:

The entropy change accompanying any physical or
chemical transformation approaches zero as the
temperature approaches zero: ∆S → 0 as T → 0 provided
all the substances involved are perfectly crystalline
 The Third Law

At T = 0, all energy of thermal motion has been quenched, and in a perfect crystal all the
atoms or ions are in a regular, uniform array .

then there is only one way of arranging the molecules when they are all in the ground
state, which is the case at T = 0. Thus, at T = 0, W = 1 and from S = k ln W it follows that
S = 0.

The entropy of all perfect crystalline

(Third Law of thermodynamics)
substances is zero at T = 0
Further Reading
 Entropy and randomness
Entropy (S) has units of J K-1 mol-1 , same unit as gas constant R

On a macroscopic scale, we "quantify" entropy by measuring heat flow. The

change in entropy is defined as the "reversible" heat divided by the kelvin
temperature (K).

ΔS= qrev/T
Finally, entropy change is related to the "amount" of thermal energy (q) in a sample
(system).

As the energy "leaves" (q < 0), then the entropy of the system will decrease.

As the energy "comes in" (q > 0), the entropy of the system will increase.

“More the energy content in a system (q > 0), more will be disorder”
▪ Atomic size
Standard molar entropy increases down the group.
It is due to the increase of atomic size or molecular size.

92
Molecular complexity
As the molecular complexity increases, standard molar entropy
increases. It is due to the efficient dispersal of energy in molecular
vibrations.

93
▪ Dissolving a solid or liquid
The entropy of a dissolved molecular solid
or liquid is greater than the entropy of the pure solute,
some exceptions may be found (e.g. AlCl3)

Solid Liquid
NaCl (s) Na+ (aq) + Cl- (aq)
One molecule Two ions
94
▪ Dissolving a gas
The particles in a gas already have so much freedom of motion—
and, thus, such highly dispersed energy—that they lose some
when they dissolve in a liquid or solid. Therefore, the entropy of a
solution of a gas in a liquid or in a solid is always less than the
entropy of the gas itself.
O2 (g) + H2O (l) O2….H2O (l)

For dissolving a gas in liquid

∆S = Sfinal-Sinitial
∆S = Sliq-Sgas

Sliq << Sgas

So ∆S < 0 95
Predicting the sign of the entropy
change of system
Predict the sign of the entropy change for the following processes. Indicate the
reason for each of your predictions.

1. One mole liquid water at room temperature ⟶ one mole liquid water at 50 °C
2. Ag+(aq)+Cl−(aq) ⟶ AgCl(s)
3. C6H6(l) + 15/2 O2(g) ⟶ 6CO2(g)+ 3H2O(l)
4. NH3(s) ⟶ NH3(l)
∆Ssys = Sfinal-Sinitial

Solution
1. Positive, as the temperature increases molecular motions raises.

2. Negative, reduction in the number of ions (particles) in solution, decreased dispersal

of matter

3. Negative, net decrease in the amount of gaseous species

4. Positive, phase transition from solid to liquid, net increase in dispersal of matter
Which of the following processes will lead to an increase in the
entropy of the system?

(a) N2(g) + 3H2 (g) → 2 NH3(g) (decrease)

(b) H2O(l) → H2O(g) (increase)

(c) CaCO3(s) → CaO(s) + CO2(g) (increase)

(d) NH4NO3(s) + H2O(l) → NH4+ (aq) + NO3- (aq) (entropy will

increase)
 Factors affecting entropy
1. Temperature changes. For a given substance, So increases as the
temperature rises.

2. Physical states and phase changes. entropy increases for a substance

as it changes from a solid to a liquid to a gas

3. Dissolving a solid or liquid. The entropy of a dissolved molecular solid

or liquid is greater than the entropy of the pure solute.

4. Dissolving a gas. The entropy of a solution of a gas in a liquid

or in a solid is always less than the entropy of the gas itself.

5. Molecular complexity. For compounds, entropy increases with

chemical complexity, that is, with the number of atoms in a formula
unit or molecule of the compound.

6. Atomic size. Within a periodic group, molar entropy increases down

the group:
Free energy change-Non-expansion work
 Change in Entropy and Spontaneity
ΔSuniv = +Ve (Spontaneous)
ΔSuniv = ΔSsys+ ΔSsurr> 0
However, the change in entropy of surrounding is difficult to
measure experimentally.
Therefore we need to introduce a quantity/function called, Gibbs
free energy or free energy (G) that combines systems enthalpy and
entropy:

At constant T, the change in free energy is

∆G = ∆H - T∆S
▪ Derivation of ∆G = ∆Hsys - T∆Ssys

It begins with our original hypothesis.

-T (-T)

103
104
Relative Importance of ∆H and ∆S in Spontaneity

Enthalpy and entropy compensation effect

105
If something (reaction or process) lowers the
free energy, we say such a process is
"spontaneous." That simply means it will tend to
happen - much like a ball tends to roll downhill.
The reverse of this situation is also evident - if a process is "not spontaneous," then it
will tend to not happen.

This is not to say that non-spontaneous processes/reactions never happen, it is just that if
they are to happen, some external amount of work must be applied to make the process
happen - much like physically taking the ball up the hill to a higher position
 ΔG and non-expansion work
Apart from predicting spontaneity, a second feature of the Gibbs
energy is that the value of ΔG for a process gives the maximum non-
expansion work that can be extracted from the process at constant
temperature and pressure.

By non-expansion work, w, we mean any work other than that

arising from the expansion of the system.
At constant temperature and pressure:

ΔG = wmax

Example;
Electrochemical cells, ΔG = -nFEo = wmax
 Summary of Free energy and Entropy

The only criterion of spontaneous change is the total entropy of the

system and its surroundings must be positive;

The Gibbs energy just provides a way to express the total entropy
change in terms of the properties of the system alone, and is valid
only for processes that occur at constant temperature and pressure.