THERMODYNAMICS

Basic terms

Thermodynamics is that branch of chemistry which deals with study of different

form of energy and quantitative relationship.

1. Isothermal process: An isothermal process is a process that occurs under

constant temperature (ΔT = 0) but other parameters of the system can be
changed accordingly.

Ex 1. A refrigerator works isothermally. A set of changes take place in the

mechanism of a refrigerator but the temperature inside remains constant.

Ex 2. Boiling water is an isothermal process as the temperature of

the water stays at 100oC even though heat can be added to the system. The
extra heat escapes the system as steam.

2. Adiabatic Process: An adiabatic process is a thermodynamic process where

there is no transfer of heat (Δq = 0) between the system and the surroundings.
In this process, the temperature of the system is changed in order to keep the
heat constant. This process is known as Adiabatic Process.

Ex. Hot water flask is considered as adiabatic system

3. Isobaric process: An Isobaric process is a thermodynamic process taking place

at constant pressure (ΔP = 0). The term isobaric has been derived from the
Greek words “iso” and “baros” meaning equal pressure. The decrease or
increase in volume basically neutralizes any pressure change.

Ex. Boiling of water in a pan to steam or the freezing of water to ice. In

these processes, a gas either expands or contracts to maintain constant
pressure. In fact, most of daily processes are isobaric because we are in contact
with a very large container called atmosphere and the pressure of atmosphere
remains constant.

1|P ag e
4. Isochoric process: An isochoric processes is a thermodynamic process taking
place at constant volume (ΔV = 0).

Ex. Heating of a gas in a closed cylinder and cooking in pressure cooker.

5. System & Surroundings: The part of universe for study is called system and
remaining portion is surroundings. System and Surrounding together constitute
Universe.

Ex. Reaction in test tube represents the system.

Remaining portion outside the test tube like chemistry lab, science block
represents the surrounding.

6. Types of System:

a. Open System: In a system when there is exchange of matter and energy

taking place with the surrounding. Ex- Tea placed in a cup.

b. Closed System: In a system when there is exchange of energy only and not
the matter with the surrounding. Ex- Tea placed in a kettle.

c. Isolated System: In a system when there is no exchange of energy and

matter taking place with the surrounding. Ex- Tea placed in a thermos flask.

7. State of system: The State of a thermodynamic system is described by its

measurable or macroscopic properties.

Ex. The state of a gas is described in terms of temperature (T), pressure (P),
volume (V) etc.

8. State function or state variable: The property which depends only on state of
system not upon path (how it is reached) is called state function.

Ex. P, V, T, E, H, S etc.

9. Path functions: The property which depends on the route or path taken
between two states.

Ex. Heat and work.

10. Physical properties: They are of two types.

2|P ag e
a. Extensive Properties: The Properties which depends on quantity of matter
contained in the system are called extensive properties.

Ex. Mass, Volume, Heat capacity, Energy, Enthalpy etc.

b. Intensive Properties: The properties which depend only upon the nature of
matter and are independent of the amount of matter present in the system, are
called Intensive properties.

Ex. T, P, density, refractive index, viscosity, surface tension, specific heat, boiling
point, pH etc.

Extensive property becomes intensive property by specifying unit amount of

the substance/matter concerned.

Ex.

Internal Energy

It represents the total energy of system. It may be chemical, electrical, mechanical

or any other.
i.e.U = Eelectrical + Emechanical + Echemical + Epotential + Ekinetic + ------

It changes when
1. Heat passes into or out of the system
2. Work is done on or by the system
3. Matter enters or leaves the system

3|P ag e
Its absolute value cannot be find out because it involves translational, vibrational
and rotational kinetic energy, which cannot be measured. So
ΔU is always used instead of U.
ΔU = Ufinal – Uinitial
or ΔU = UProduct – UReactant
Internal energy is state function and extensive property.

First Law of Thermodynamics

It is also known as law of conservation energy.

“Energy can neither be created nor destroyed; it may be converted from one form
into another.”

“Whenever certain quantity of some form of energy disappears, an exactly

equivalent amount of some other form of energy is produced.”

Mathematically

Suppose initial internal energy (IE) = U1

IE can be increased by

i) absorption of heat = +q

ii) work on system = +w

Final IE would be (U2) = U1 + q + w

ΔU = U2 – U1
ΔU= q + w ………………equation no.1
If work is done by system w = - PΔV

Then ΔU = q – PΔV
q = ΔU + PΔV ……………………equation no. 2
Equation no. 1 & 2 is the mathematical formulation of first law of thermodynamics.

q and w are not state function, but ΔU is the state function.

If the process is carried out at constant volume i.e. ΔV = 0

4|P ag e
Then
ΔU = qv
Limitation of First Law of Thermodynamics
1. First law does not say anything about whether the process is possible or
not.
In the engines, the chemical energy of the fuel is converted into useful mechanical
work. But this mechanical energy cannot be converted back into fuel. (Or in other
words, engine cannot produce fuel back)

2. First law of thermodynamics does not say whether the process will occur
on its own or not.
Ice melt down after some time on its own but conversion of water into ice does not
occur on its own.

3. First law does not provide any sufficient condition for a certain process to
take place.
Heat always flows from higher temperature body to lower temperature body. But
the reverse process is not possible without doing anything.

5|P ag e
Enthalpy (ΔH)

From 1st law of thermodynamics q = ΔU + PΔV

Since all the reactions proceeds at constant pressure. So heat (q) can be written as

qp = ΔU + PΔV

qp = ΔH
Or ΔH = ΔU + PΔV

Enthalpy change is equal to the heat absorbed by the system at constant pressure.

Or

It is the sum of the change in internal energy of system and the pressure – volume
work done.

Or

The energy stored within the substance of the system that is available for
conversion into heat is called enthalpy.

Enthalpy is the state function and extensive property.(as U, P, V are extensive)

In standard state enthalpies of all elements is zero.

Standard state means pressure is 1 atm or 1 bar and temperature is 298.15 K
Exothermic and Endothermic reactions: ΔH = –ve for exothermic i.e. evolution
of heat and ΔH = +ve for endothermic reaction i.e. absorption of heat.

Ex. C+O2 = CO2 + 393.5 KJ ΔH = – 393.5 kJ, exothermic

N2 + O2 = 2NO – 180.7 KJ ΔH = + 180.7 kJ, endothermic

Relation between enthalpy (ΔH) and internal energy (ΔU)

It is well known that ΔH = ΔU + PΔV

From ideal gas equation PV= nRT

6|P ag e
PΔV = Δ ng RT

So ΔH = ΔU + Δ ng RT

Or
qp = qv + Δ ng RT

Where qp is heat evolved/absorbed at constant pressure.

And qv is heat evolved/absorbed at constant volume.

Heat Capacity

The heat capacity of a system is defined as the amount of heat required to raise the
temperature of the system through 1oC.

Specific Heat Capacity

The specific capacity of a system is defined as the amount of heat required to raise
the temperature of 1 gram of the substance/system through 1 oC.

Molar Heat Capacity

The molar heat capacity of a system is defined as the amount of heat required to
raise the temperature of 1 mole of the substance/system through 1 oC.

Types of Molar Heat Capacities

Since ‘q’ is not a state function and depends upon the path. Hence C is also not a
state function. Hence to define C, conditions like constant volume or constant
pressure should be specified which define the path. Thus there are two types of
heat capacities.

1. Molar heat capacity at constant volume (Cv)

The molar heat capacity at constant volume of a system is defined as the amount of

7|P ag e
heat required to raise the temperature of 1 mole of the substance/system through
1oC keeping the volume of the system constant.
2. Molar heat capacity at constant pressure (Cp)
The molar heat capacity at constant pressure of a system is defined as the amount
of heat required to raise the temperature of 1 mole of the substance/system through
1oC keeping the pressure of the system constant.

Relation between Cv and Cp

𝑞𝑣
Heat capacity at constant volume CV =
ΔT

𝑞𝑝
Heat capacity at constant pressure CP =
ΔT

ΔH = ΔU + PΔV

qp = qv + PΔ V

CP ΔT = CV ΔT + PΔ V

CP ΔT = CV ΔT + RΔ T

C P = CV + R

For 1 mole of gas

CP - CV = R

CP- CV= nR For n moles of gas

Thus, CP is greater than CV by the gas constant R.

Hess’s Law of constant heat summation

“The total amount of heat evolved or absorbed in a reaction is the same whether the
reaction takes place in one step or in several steps.” The heat change in a reaction
depends only upon the nature of the initial reactants and that of the final products,
and is independent of the path by which the change is brought about.
Ex.

8|P ag e
Thermodynamic basis of Hess law
As Enthalpy / heat content is a state function, it depends only on initial reactants
and final products.

Application- The thermo-chemical equation can be treated as algebraic equations

which can be added, subtracted, multiplied or divided.

Second law of thermodynamics

It overcomes the limitation of 1st law. 1st law tells the exact equivalence between the
various forms of energies but it provides no idea about the feasibility of reaction.

“All spontaneous processes are thermodynamically irreversible.”

Ex. Diffusion of gas from high pressure to low pressure, flow of water down a hill
etc.

“The complete conversion of heat into work is impossible without leaving some
effect elsewhere.”
“Without the help of an external agency, a spontaneous process cannot be
reversed.”

9|P ag e
“All spontaneous processes are accompanied by a net increase of entropy.”
“The entropy of the universe is continuously increasing.”

Entropy (S)
It is measure of randomness or disorder ofsystem. It increases during the change in
physical state.
i.e. Solid ˂ Liquid ˂ Gas
It is defined as the heat absorbed or lost isothermally and reversibly divided by the
absolute temperature at which the heat is absorbed or lost is a constant quantity for
a particular system.
𝑞rev,isothermal
𝑆= = Constant
𝑇
Since S is state function.

𝑞rev,isothermal
Hence ∆𝑆 =
𝑇
= constant
Entropy is extensive property, but mostly expressed for 1 mole of substance.

Standard molar Entropy

The entropy per mole of the substance under standard conditions i.e 1 atm pressure
and 298K is called standard molar entropy (Sm0) or absolute entropy.
Spontaneity in term of entropy:
For spontaneous process ∆S = +ve
For non-spontaneous process ∆S = -ve
For cyclic process ∆S = 0
At equilibrium ∆S = 0
∆Ssystem˃ 0
∆Stotal= ∆Suniverse = ∆Ssystem + ∆Ssurrounding˃ 0

Spontaneous & Non Spontaneous Processes

A process which can take place by itself is called spontaneous process. A process
which can neither take place by itself or by initiation is called non Spontaneous.

Driving forces for spontaneous process

10 | P a g e
 a. Tendency for minimum energy state.

b. Tendency for maximum randomness.

3rd law of thermodynamics

Entropy depends upon temperature. It increases with rise in temperature. Nernst

in 1906 gave the following statement regarding the entropies of crystalline solids
known as 3rd law of thermodynamics.

“The entropy of all perfect crystalline solids may be taken as zero at the absolute
zero of temperature.”

Actually at 0oK, the constituents in a crystalline solid are not expected to have any
movement i.e. no randomness.

Gibbs Free Energy (∆ G)

J. Williard Gibbs introduced a term free energy to predict the direction of

spontaneity.

G = H – TS

Since G is state function So, ∆ G = ∆H – T∆S (1)

Equation 1 is the Gibbs Helmholtz equation.

Now it is well known that ΔH = ΔU + PΔV

Putting the value of ΔH in equation no.1

∆ G = ΔU + PΔV – T∆S (2)
From 1st law of thermodynamics ΔU = q + w
When work is done by the system then, ΔU = q rev-wmax
Putting the value of ΔU in equation no.2

∆ G = qrev - wmax + PΔV – T∆S (3)

Putting the value of ΔS in equation no.3 (ΔS = q rev/T)

∆ G = qrev - wmax + PΔV – qrev

∆ G = - wmax + PΔV

11 | P a g e
Or -∆G = wmax - PΔV
The decrease in Gibbs free energy is equal to “maximum net work” obtained from
the system i.e. the total work minus the pressure- volume work or work of
expansion.

It is a part of energy of the system which is free for conversion to useful work and
is therefore called free energy.

Change in G is a measure of the useful work done.

-∆ G = wnon expansion

-∆ G = wuseful

If the work involved is the electrical work as in the case of galvanic cells,

Then -∆ G = welectrical
-∆G = nFE

In case of standard conditions -∆Go = nFEo

Where n = number of electrons involved in the cell reaction

E = EMF of the cell
F = Faraday

Spontaneity in term of Gibbs free energy:

For spontaneous process ∆G = -ve
For non-spontaneous process ∆G = +ve
At equilibrium ∆G = 0

Spontaneity in term of Temperature:

It can be explained with the help of Gibbs Helmholtz equation, which includes both
term ∆H and ∆S. All these decide the feasibility of reaction or process in forward
reaction.
(i) For endothermic process
∆H = +ve, ∆S = +ve for -∆G (spontaneous), temperature should be high. It will
become non spontaneous at low temp.

12 | P a g e
(ii) For exothermic process

∆H = -ve, ∆S = +ve for -∆G (spontaneous), temperature doesn’t matter. It may be

either high or low.

Gibbs free energy and equilibrium constant

During the reaction, the free energy decreases. It varies with the composition of the
equilibrium mixture. On plotting free energy against changing composition of
equilibrium mixture, there is a point in curve where the free energy is minimum. This
corresponds to equilibrium point for reaction.

At equilibrium ∆G = 0
∆G = ∆Go + RT ln K
0 = ∆Go + RT ln K
∆Go = - RT ln K

∆Go = - 2.303RT log K

Where K is equilibrium constant

SOLVED NUMERICAL PROBLEMS

1. Calculate the internal energy change in following cases
(i) A system absorbs 15kJ of heat and does 5kJ of work.
(ii) 5kJ of work is done on the system and 15kJ of heat is given out by the
system.
Note- when the work is done by the system, it is always negative
When the work is done on the system, it is always positive
Solution: (i) q = +15kJ w = -5kJ
∆U = q + w
= 15 + (-5)
= +10 kJ internal energy of the system increases by 10kJ.
(ii) q = -15kJ w = +5kJ
∆U = q + w
= -15 + (+5)

13 | P a g e
= -10kJ internal energy of the system decreases by 10kJ.

2. For vaporization of water

the molar enthalpy change at 1 bar and 100 oC is 41kJ mol-1. Calculate the internal
energy change.
Solution: ∆ng = nProduct -nReactant
=1–0
=1
R = 8.314 x 10-3kJ K-1mol-1
T = 100 + 273 = 373oK
ΔU = ΔH - Δ ng RT
= 41 – (1 x 8.314 x 10-3 x 373)
= 41 – 3.10
= 37.90kJ mol-1

3. The molar heat capacity of a gas at constant volume is 12.50 Jmol -1.
Calculate the molar heat capacity at constant pressure.
Solution: Cv = 12.50 Jmol-1
Cp= Cv + R
= 12.50 + 8.314
= 20.834 Jmol-1

4. The enthalpy change for the following reaction is -92.38 Kj at 298K

Calculate ∆U at 298K.
Solution: Δng = no. of gaseous product – no. of gaseous reactant

= 2 – (1 +3)

= -2

ΔH = ΔU + PΔV

ΔH = ΔU + ΔngRT

- 92.38 = ΔU + (-2) x 8.314 x 10-3 x 298

= -87.42 kJ

14 | P a g e
5. Calculate the standard enthalpy of following reaction(ΔH orxn)

Standard enthalpies of formation at 25 oC for NH3, H2O and NO are - 46.2, -241.8
and + 90.4kJ/mole respectively.
Solution: ΔHorxn = sum of ΔHof of products - sum of ΔHof of products
= [6 x ΔHof H2O + 4 x ΔHof NO] – [4 x ΔHof NH3 + 5 x ΔHof O2]
= [6 x (-241.8) + 4 x (+90.4)] – [4 x (-46.2) + (0)]
= [-1450.8 + 361.6] – [-184.8]
= -1089.2 + 184.8
= -904.4kJ/mole
6. Calculate ΔGo at 300K for the following reaction and predict the feasibility.

Data given: ΔHo= +26kj , ΔSo = .083kJK-1

Solution: ΔGo = ΔHo - TΔSo
= 26 – 300 x .083
= 26 – 24.9
= 1.1kJ
7. For this reaction
the given data is
𝐺𝐼𝑜2 = 0J 𝑜
𝐺H2S = 33.8J 𝑜
𝐺𝐻𝐼 = 1.8J 𝐺𝑆𝑜 = 0J

Calculate free energy change for the above reaction.

ΔGoreaction = ƩΔG𝑓𝑜 product - ƩΔG𝑓𝑜 reactant

= [𝐺𝑆𝑜 + (2 x 𝐺𝐻𝐼
𝑜
)] - [𝐺𝐼𝑜2 + GoH2S]

= [0 + (2 x 1.8)] – [0 + 33.8]

= 3.6 – 33.8

= -30.2J

8. Calculate the standard entropy change for following reaction.

15 | P a g e
Given that the standard entropies of H2, Cl2 and HCl are 130.6, 223.0 and
186.7Jmol-1K-1 respectively.
𝑜 𝑜
Solution: ΔSoReaction = Ʃ𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 - Ʃ𝑆𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
= 2 x 186.7 – {(1 x 130.6) + (223.0 x 1)}
= 373.4-353.6
= +19.87Jmol-1K-1
9. Calculate the enthalpy of formation of methane
from the following data.

Solution Aim:

(i) x 1 + (ii) x 2 – (iii)

= -393.7 + 2(-285.8) – (-890.4)

= -393.7 -571.6 + 890.4

= -74.9kJmol-1

10. The standard enthalpy of formation of Fe 2O3(s) is -824.5kJmol-1. Calculate

the enthalpy change for the reaction.

Solution: standard enthalpy of formation means “The enthalpy change

accompanying the formation of one mole of compound in standard state from its
constituent elements.”

According to definition

16 | P a g e
Now Hess’s law says that the thermo chemical equation can be treated as algebraic
equations, so the desired equation is obtained by multiplying 2 to equation (i)

= ∆HReaction = 1649.0 kJmol-1

PROBLEMS

Long Questions

1. State the first law of thermodynamics and derive it mathematically. Write its
limitation also.
2. Explain the term enthalpy. How is it related to the internal energy of the
system?
3. Explain the Gibb’s free energy change. “The sign of the free energy is very
important”. Justify the statement.
4. Starting with the thermodynamic relationship ∆U = q + w, derive the following
relationship: ∆G = wnon-expansion
5. Define the following: Entropy, internal energy, 2 nd law of thermodynamics,
Hess’s law of constant heat summation.
Short Questions

1. What are spontaneous and non- spontaneous changes? Give one example
of each.
2. Predict the entropy change in
(i) Milk converts into curd
(ii) Temperature of a crystallize solid raised from 0 oK to 115oK

3. Under what condition, the heat evolved/absorbed in a reaction is equal to

its free energy change?

4. Calculate the entropy change for the following process

Given that the heat change is 6.0kJmol -1 at 0oC.

17 | P a g e
 5. “A real crystal has more entropy than ideal crystal.” Why?

6. Why standard entropy of an elementary substance is not zero but

standard enthalpy of formation is taken as zero?

7. The equilibrium constant for a reaction is one or more if ∆G° for it is less
than zero. Explain.

8. Separate out the following into extensive and intensive property:

Volume, temperature, pressure, boiling point, free energy, enthalpy, path, work,
internal energy, entropy
9. Why standard heat of formation of diamond is not zero though it is an
element.

10. Calculate the ∆G and ∆Go for the reaction

at 25oC. Equilibrium constant for this reaction is 10 2. [hint : log 100=2]
11. Write the condition for following processes
a. Isothermal process
b. Adiabatic process
c. Isobaric process
d. Isochoric process

12. For the following reaction ∆HReaction = 100.0 kJmol-1

What is the standard enthalpy of formation of NH3(g)

13. A sample of gas expands isothermally from 10L to 20L against pressure of 2
atm. Calculate the work done.

Multiple choice questions

1. The __________ law of thermodynamics states that entropy is always
increasing.
a. first
b. second
c. third
d. zeroth

18 | P a g e
 2. The Law of _______________ states that energy cannot be created nor
destroyed only transferred.
a. Specific Heat
b. Conservation of Energy
c. Exothermic Reaction
d. Potential Energy

3. Identify the state function among the following:

a. q
b. q–w
c. q/w
d. q+w

4. If K ˂ 1.0, What will be the value of ∆Go of the following

a. 1.0
b. 0.0
c. Negative
d. Positive

5. In which of the following entropy does not increase

a. Rusting of iron
b. Melting of ice
c. Crystallization of sugar from solution
d. Vaporization of camphor

6. What will be the work done by 3 moles of an ideal gas when it expands
spontaneously in a vacuum?
a. zero
b. infinite
c. 3 joules
d. 9 joules

7. Which is true for the entropy of a spontaneous reaction?

a. ΔS(system) – ΔS(surroundings) > 0
b. ΔS(system) + ΔS(surroundings) > 0
c. ΔS(surroundings) > 0 only
d. ΔS(system) > 0 only

8. ΔH for the reaction N2 + 3H2 ⇋ 2NH3

a. ΔU – 2RT

19 | P a g e
 b. ΔU + 2RT
c. ΔU – RT
d. ΔU= RT

9. Which one of the following statement is true about a gas undergoing isothermal
change
a. The temperature of the gas is constant
b. The pressure of the gas remains constant
c. the volume of the gas remains constant
d. The gas is completely insulated from the surroundings

10. A system goes from state A to B via path I and II

ΔU1 is Change in internal energy via Path I
ΔU2 is Change in internal energy via Path II

Which of the following is true?

a. ΔU1>ΔU2
b. ΔU1<ΔU2
c. ΔU1=ΔU2
d. Relation between ΔU1 and ΔU2 cannot be determined

20 | P a g e