Thermodynamics

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What is Thermodynamics?
Thermodynamics is a branch of science which deals with energy interaction
and its effect on the system and surrounding.

• Thermodynamics can be defined as the study of energy i.e. energy transformations and
its relation to matter.
• The analysis of thermal systems is achieved through the application of the conservation
equations: namely, Conservation of Mass, Conservation of Energy.

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 Definitions

❖ System: A thermodynamic system is that portion of the Universe that we

have selected for investigation
❖ Surroundings: Everything (e.g. The mass or region) outside the system
❖ Boundary: The real or imaginary surface that separates the system from
its surroundings is called boundary.

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 Classification of Chemical Systems
The type of system depends on the characteristics of the boundary that divides it
from the surroundings
Open System: Mass and energy can be transferred through the boundary (e.g. an
open beaker to which we can add or extract water)
Closed System: Energy exchange with the surrounding but no mass transfer (you
can cool a closed water bottle in fridge)
Isolated System: Incapable of exchanging both energy and matter (e.g. a closed
thermo-flask (approximate) can be considered as isolated).

heat matter heat matter

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 Intensive and Extensive Properties
Any characteristic of a system is called a property. For example, mass,
volume, temperature, pressure, density, etc.

➢ Intensive properties: are those that are independent of the quantity (mass) of a
system, such as temperature, pressure, and density

➢ Extensive properties: values that are dependent on mass of the system such as
mass, volume, and total energy U

➢ Extensive properties per unit mass are called specific properties, e.g. specific
volume (v = V/m)

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 Processes and Cycles
➢ Any change that a system undergoes from one equilibrium state to
another is called a process and the series of states through which a
system passes during a process is called a path

To specify a process, initial and final states

and path must be specified

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 Classification of Processes
1) Reversible process: In a reversible process, the change of the system is
allowed to happen slowly in minute quantities. In an ideally reversible process,
the change must occur in successive stage of infinitesimal quantities.
• A reversible process must be such that the system changes back to the initial
condition along the same path, the magnitude of change of the thermodynamic
quantities in the different stage will be the same in the forward and backward
direction but with opposite sign.

2) Irreversible process: Such process occurs suddenly or spontaneously without

the restriction of the occurring in successive stage of infinitesimal quantities.

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 Types of Chemical Reactions
Chemical reaction

Exothermic Endothermic
Heat is liberated into the surroundings Heat is absorbed from the surroundings

Chemical reaction

Isochoric Isothermal process Adiabatic Process

process Isobaric process ΔT = 0 Δq = 0
ΔV = 0 Δp = 0
➢No change in ➢No heat leaves or enters
➢ No change in ➢No change in internal energy the system
volume pressure ➢No change in ➢Temperature of the
➢ Temperature ➢Temperature and Temperature system changes
and pressure volume will
will increase increase
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 Isobaric Process
Isochoric Process

Isothermal Process
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❖ Zeroth Law of Thermodynamics
“ If two bodies are in thermal equilibrium with a third body separately,
they are also in thermal equilibrium with each other.”

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 Mechanical work description

• Work = force required to move a body x distance that body is

moved x
w =  Fdx
x0

• Because F = PA, i.e. force = pressure x area

x
w =  Fdx = ( PA)( x − x0 ) = PdV
x0

• This describes a piston’s movement and potential ‘energy’

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 Internal Energy of the System
➢ The internal energy U of a system is the total of all kinds of energy possessed by
the particles that make up the system

➢ Internal energy is extensive property, and it is a state function

Two ways to increase the internal energy, U

work done on a gas (positive)

Apply heat into a system (positive)

Two ways to decrease the internal energy, U

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Work done in reversible process

Work done in irreversible process:

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 First Law of Thermodynamics
In all cases in which work is produced by the agency of heat, a quantity of heat is
consumed which is proportional to the work done; and conversely, by the
expenditure of an equal quantity of work an equal quantity of heat is produced.
(Clausius, 1850)

➢ The energy cannot be created nor destroyed

➢ The total energy of the universe is a constant
➢ Energy can, however, be converted from one form to another or
transferred from a system to the surroundings: q = ΔU+ W (Where q is an
amount of heat and ΔU is changes in internal energy; W is work done

dq = dU + dw and w = PdV
If V is constant, then ΔV = 0, and PdV = 0. This leaves ∆U = qv

➢ Measure of ΔU is measuring heat released or taken up at constant

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Exercise:
A gas is expanding against a constant pressure of 2 atm. from 10 to 20
liters absorbs 300 cal. of heat. What is the change of internal energy?

Work done during expansion, W = PdV = 2 (20 - 10) = 20 L atm = 484 cal.
From 1st law of thermodynacs
dq = dU+dW
300 = dU+ 484
So dU = - 184 cal.
Hence internal energy is decreased by 184 Cal.

1 L atm = 24.21 cal

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 Enthalpy
Total kinetic energy and potential energy of system at constant pressure.
2 2 2

dq = dU + dw  dU
1
=  dq − P  dV
1 1

qp is measurable – by measuring temperature changes resulting from energy

changes (i.e. from a chemical reaction Total differential for Enthalpy is:
H = U + PV
dH = dU + PdV + VdP
If the change occurs at constant pressure dP = 0, so VdP = 0
dH = dU + PdV
From the first law of thermodynamics dq = dU + PdV (only mechanical work
involved)
So dH = dqp
So qp = ΔH This is the physical significance of qp

➢ So, change in enthalpy is nothing but heat of the process of constant

pressure

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 Enthalpy
1. It is an extensive property.
2. It is a state function

H = U + PV, where p is the pressure of the system and V is its volume.

Because U, p, and V are all state functions, the enthalpy is a state function
too.

➢ As it is true of any state function, the change in enthalpy, dH, between any
pair of initial and final states is independent of the path between them.

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 Incompleteness in the First Law
➢ First law does not indicate whether a transformation of energy would at all occur.
➢ If it occurs, to what extent or in which direction the transformation would take place.

To Illustrate:
(a) Fluid always flows from higher to lower elevation spontaneously.
(b) Heat always flows from high to low temperature spontaneously.
(c) Material always diffuse from high to low concentration spontaneously.
And reverse of these never happen naturally (without aided by any external agency)

The recognition of two classes of process, spontaneous and non-spontaneous, is

summarized by the Second Law of thermodynamics

The second law of thermodynamics is formulated to record our experiences

about direction of change, stated as

➢ All spontaneous processes are irreversible.

➢ All spontaneous processes tend to attain equilibrium.

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 The Second Law of Thermodynamics
This law may be expressed in a variety of equivalent ways
1. It is not possible to construct a device that operates in a cycle and whose sole
effect is to transfer heat from a colder body to a hotter body. –Clausius Statement

➢ That is, heat transfer can only occur

spontaneously in the direction of tempr.
decrease. For example, we cannot construct
a refrigerator that operates without any work
input.

2. It is impossible to take heat from a hotter reservoir and convert it completely into
work by a cyclic process without transferring a part of heat to the cooler reservoir.
Kelvin-Planck Statement

➢ No heat engine can have a thermal efficiency 100 percent.

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 Spontaneous Processes
✓ Spontaneous processes are those that can proceed without any outside
intervention
✓ The gas in vessel B will spontaneously effuse into vessel A
✓ 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

Water
Ice

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 Entropy
Entropy (S) is a state function
➢ 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
➢ It is an extensive property and state function

Physical concept of entropy

❖ Entropy can be viewed as a measure of molecular disorder or molecular
randomness
❖ As a system becomes more disordered, the position of molecules becomes less
predictable and the entropy increases
❖ The entropy of the system is lowest in the solid phase and highest in the gas
phase

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 Entropy and Spontaneity
1. When a system absorbs heat from surroundings or releases heat to
surroundings, both the system and surroundings undergo change in entropy.
Heat change of surroundings is the negative of the heat change of the system

Suniverse= Ssys+ Ssurr = 0

• Entropy change in reversible process for universe is zero

2. For an irreversible (spontaneous) process:

• For an irreversible process for universe the net entropy increases, or

• Entropy of the universe is increasing since spontaneous reactions are always
taking place in universe.

Ssys +Ssurr = 0 for reversible process

Ssys + Ssurr > 0 for irreversible process (spontaneous)

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Many processes results in an increase in a system’s entropy ΔS > 0:
• Increasing the volume that a gas can occupy will increase the disorder of a gas
• Dissolving a solute into a solution will increase the entropy of the solute - typically resulting
in an increase in the entropy of the system. (Note: the solvation of a solute can sometimes
result in a significant decrease in the solvent entropy - leading to a net decrease in entropy
of the system)
• Phase changes from solid to liquid, or liquid to gas, lead to an increase in the entropy of the
system.

Some processes result in a decrease in the entropy of a system ΔS < 0:

• A gas molecule dissolved in a liquid is much more confined by neighboring molecules than
when its in the gaseous state. Thus, the entropy of the gas molecule will decrease when it is
dissolved in a liquid
• A phase change from a liquid to a solid (i.e. freezing), or from a gas to a liquid (i.e.
condensation) results in an decrease in the disorder of the substance, and a decrease in the
entropy
• A chemical reaction between gas molecules that results in a net decrease in the
overall number of gas molecules will decrease the disorder of the system, and result in
a decrease in the entropy
2NO(g) + O2(g) → 2NO2(g) ΔS < 0

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 The Third Law of Thermodynamics
The entropy of a pure crystalline substance is zero at absolute zero (i.e. 0 K).

• Since S = 0 corresponds to perfect order. The position of the atoms or molecules in the
crystal would be perfectly defined
• As the temperature increases, the entropy of the atoms in the lattice increase
• Vibrational motions cause the atoms and molecules in the lattice to be less well ordered

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 Entropy Changes in Chemical Reactions
Entropy change in a chemical reaction
is given by:

Haber Process

➢ It would appear that the process results in a decrease in entropy - i.e. a decrease in disorder. This is
expected because we are decreasing the number of gas molecules. In other words the N2(g) used to
float around independently of the H2 gas molecules. After the reaction, the two are bonded together
and can't float around freely from one another.
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Free energy : The thermodynamic functions which consider both energy and
randomness together are known as free energy functions.
There are two types
i) Gibb’s Free Energy
ii) Helmholtz free energy

Free energy (G) or Gibb’s function

G = H – TS
Gibb’s free energy is extensive property and it is a state function

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 Gibbs–Helmholtz equation
G = H – TS ………….. (1) Gibbs
H = U + PV ………….. (2) Helmholtz

So, G = U + PV - TS ………….. (3)

So, dG = dU + PdV + VdP – TdS – SdT ………………….. (4)

Now from first law, we know dU = dq - pdv and applying dq = Tds

We get, dU = TdS – PdV ……………….. (5)

So replacing this value of dU in eq. (4) we get,

dG = TdS – PdV + PdV + VdP – TdS – SdT
dG = VdP – SdT

At constant pressure dP = 0, we can write dGP = – SdT

[d(G)/dT]P = −S ……………. (6)

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 Contd….

[d(G)/dT]P = −S ……………. (6)

We know that, ΔG = ΔH – T ΔS …………………….. (ref: eq. 1)

So, - ΔS = (ΔG – ΔH) / T ……………………. (7)
Combining eq. (6) and (7),
[d(G)/dT]P = (ΔG – ΔH) / T ………………. (8)

Gibb’s – Helmholtz
G = H + T [d(G)/dT]P Equation

Rate of change of free energy with temperature

at constant presseure.
= Temperatute coefficient of free energy change

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Applications of the Gibbs-Helmholtz equation

1. Calculate ΔHrxn from ΔG and its variation with temperature at constant

pressure
This application is useful particularly in relation to reversible reactions in
electrochemical cells, where ΔG identifies with the electrical work done –nFE.

2. Calculate ΔGrxn for a reaction at a temperature other than 298K.

3. Calculate the effect of a temperature change on the equilibrium constant Kp

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Standard Free-Energy Change in Chemical Reactions
• There is no way to measure absolute enthalpies, although we can measure
changes in enthalpy (ΔH) during a chemical reaction.
• Because enthalpy is one of the components of Gibbs free energy, we are
consequently unable to measure absolute free energies; we can measure only
changes in free energy.
• The standard free-energy change (ΔG°) is the change in free energy when one
substance or a set of substances in their standard states is converted to one or
more other substances, also in their standard states.
• The standard free-energy change can be calculated from the definition of free
energy, if the standard enthalpy and entropy changes are known.

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 Standard Free-Energy Change in Chemical Reactions

Steps:
1. Calculate ΔS° from the absolute molar entropy values given.
2. Use the calculated value of ΔS°, and other data given to calculate ΔG° for the reaction.
3. Use the value of ΔG° to determine whether the reaction is spontaneous as written.

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Solution

➢ As we might expect for a reaction in which 2 mol of gas is converted to 1 mol of a much
more ordered liquid, ΔSo is very negative for this reaction.

➢ The negative value of ΔGo indicates that the reaction is spontaneous as written.
➢ Because ΔSo and ΔHo for this reaction have the same sign, the sign of ΔGo depends on the
relative magnitudes of the ΔHo and TΔSo terms.
➢ In this particular case, the enthalpy term dominates, indicating that the strength of the
bonds formed in the product is more that compensates for the unfavorable ΔSo term, and
for the energy needed to break bonds in the reactants.
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 ΔG° = standard change of
Gibb’s free energy.

K = e‒ΔG°/RT

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➢ The temperature dependence of free energy comes from the
entropy term.
➢ By knowing the sign (+ve or -ve) of Δ S and Δ H, we can get the
sign of ΔG and determine if a reaction is spontaneous or not

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Questions:
1. Define intensive properties. Explain with an example.
2. What is an extensive property? Explain with an example.
3. What in entropy? How it is related to the spontaneity of a process?
4. State second law of thermodynamics (two statements). What is efficiency of a
heat engine? Explain why the efficiency of a heat engine cannot be 1 (100%).
5. Define Gibb’s free energy function (equation). Is it a state or path function? Is
it an intensive or extensive property?
6. Derive Gibb’s –Helmholtz equation in terms of ΔG, ΔH and T.
7. In terms of Gibb’s free energy, explain the condition of an equilibrium and a
spontaneous process.
8. What is the relationship between the Gibb’s free energy change (ΔG) and
equilibrium constant (K).

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Thank you for your
attention

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