Thermodynamics

Thermo refers heat, dynamics refers to flow of heat.

Thermodynamics a science and engineering tool used to describe

processes that involve changes in temperature and transformation of
energy.

It establishes an 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 under

consideration. 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
Various Thermodynamic Processes
Exothermic and Endothermic Process
Endothermic – Gaining of heat during a process
Exothermic – Release of heat during a process

Adiabatic Process
Heat neither goes out or comes 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.
 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

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

of state occurs when two objects A to B are in
A B contact through a diathermic boundary.
 The 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”
 The Zeroth Law of Thermodynamics

– Adiabatic wall

– Diathermal wall

Zeroth Law Provides the Basis for the

If TA = Tc and TB = TC thermometer function. Where mercury and
Then, TA = TB the liquid in contact are separated by a
diathermal wall
 The First Law of Thermodynamics
Basic Concept
• 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.
 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)
 Path Functions
A path function is a property whose value depends on the path
taken to reach that specific value.

Heat exchange (q), work done (w)

Intensive properties: Physical quantity/property of a substance

whose value does not depend on the amount of substance.
Example: pressure, temperature, refractive index, mass density,
color, chemical potential etc.

Extensive properties: Physical quantity/property of a substance

whose value depends on the amount of substance. Example:
volume, mass, enthalpy, entropy, free energy, heat capacity etc.
Internal Energy (E)
 Internal energy: U
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

• 1 lit-atm = 101.325 J = 0.24 cal (unit of energy)

 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 of the 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.
 Enthalpy

Enthalpy is an extensive thermodynamic property which is refers to the sum of internal

energy and P-V work done; In the following derivation we have shown how enthalpy can be
related to internal energy and the corresponding differential forms for infinitesimal
changes; Change in enthalpy equals to the change in internal energy and P-V work done

H- enthalpy, U-internal energy, p-pressure

V-volume, qp heat transfer at constant p
 Internal energy, Enthalpy, Heat capacity

Heat capacity: Amount of heat required to increase the temperature of a substance by unity; C
= q/ΔT , q-heat transferred (joules), ΔT –change in temperature (in Kelvin)
CV heat capacity at constant volume, Cp heat capacity at constant pressure, heat
capacities for isothermal processes (ΔT=0) is infinite or undefined, phase change heat
capacity is also infinite (as temperature is constant during a phase change)

Relationship between internal energy (U) and CV Relationship between enthalpy (H) and Cp
 Adiabatic changes

∆U = q + w

For adiabatic process, q = 0; as adiabatic wall

does not allow the heat exchange.
∆U = wad

∆U = CV(Tf − Ti ) = CV∆T

Cv Heat capacity of the gas at constant volume

wad = CV∆T , work done under adiabatic condition

 Heat capacities
• heat capacity: amount of required to change the
temperature of particular amount of a substance by
one kelvin.

• Unit: Joule mol-1 K-1 (Molar heat capacity: Cv,m)

• Unit: Joule K-1 (Heat capacity, Cv)

• If molar heat capacity is provided, don’t forget to

multiply it with number of moles to convert the unit to
Joules K-1; e.g. ΔU = nCv,m ΔT, n-number of moles
 Molecular Connection

The work done during an adiabatic expansion of a perfect gas

wad  ∆T = Tf − Ti

That is exactly what we expect on molecular grounds, because the

mean kinetic energy is proportional to T, so a change in internal
energy arising from temperature alone is also expected to be
proportional to ∆T
The initial and final temperature

• where c = CV,m/R, γ-1 = R/CV,m , where γ = CP/CV

Cv,m = constant molar volume hear capacity of the gas

• or equivalently
Vi Tic = Vf Tf c

• This result is often summarized in the form

VTc = constant
 Adiabatic equations of state

equation-1: pVγ = constant, or p1 V1γ = p1 V2γ

equation-2: TVγ-1 = constant, or T1V1γ-1 = T2V2γ-1

equation-3: Tγpγ-1 = constant, or T1p1γ-1 = T2p2γ-1

where γ = Cp/CV, Cp-CV = R

TV1/c = constant, o T1V11/c=T2V21/c

where (1/c) = γ-1 = R/CV
 Adiabatic equation of state
Adiabatic processes are undergo without exchanging heat (q),

The relationship between temperature (T), pressure (p) and volume (V) of an ideal
gas undergoing adiabatic transformation can be derived as the following:

thus adiabatic expansion of a gas will always result in decrease in

temperature: due to the relation between T and V, where γ > 0.
 Adiabatic vs isothermal processes

Adiabatic process and its slope Isothermal process and its slope

As γ > 1, the slope of PV curve will always be larger for

adiabatic process than that of isothermal process; This is
Why? the reason why the blue curve (smaller slope) refers to an
isothermal process and red curve (larger slope) refers to an
adiabatic process

work done in adiabatic process = (p2V2 – p1V1)/(1-γ) work done in isothermal process = RT ln(V2/V1)
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).
 First Law- Directionality of changes ?

▪ When an ice cube melts in your hand, the first law tells that energy from your
hand was transferred to the ice to change it to a liquid. If you could measure the
work and heat involved in each case, you would find that energy is conserved as it
is converted from one form to another.
▪ However, the first law does not help us make sense of the direction of the change.
▪ Why doesn’t the pool of water in your cupped hand transfer the heat back to your
hand and refreeze? Neither of these events would violate the first law—energy
would still be conserved—but they never happen
▪ The first law by itself tells nothing about the direction of a spontaneous change,
so we must look elsewhere for a way to predict that direction.
 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 (S)
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

Efficiency of a Carnot engine
• 𝞰 = 1 – Qc/Qh = 1 – Tc/Th
 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).
• All reversible engines (Carnot) have the same efficiency regardless of
their construction
• Reversible Carnot engine is the most efficient engine

• The difference between the two cycle is that the expansion and
compression process in Carnot engine is assumed to be reversible
Whereas
Work done in under
real engine these process
any irreversible occurisinless
process irreversible
than thatmanner
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

 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 is carried through a Carnot cycle
in reverse:
also we can use COP = Tc / (Th-Tc) = Qc/W, first find COP = 270/(300-270)=9, and then
equate with COP=9=1/W, i.e. W = 0.11 Joules
 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.

[Link]
 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.
 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
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)

92
93
Relative Importance of ∆H and ∆S in Spontaneity

Enthalpy and entropy compensation effect

94
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.