Class 11

Chemistry Thermodynamics
• Important Terms and Definitions
System: Refers to the portion of universe which is under observation.
Surroundings: Everything else in the universe except system is called surroundings. The Universe = The
System + The Surroundings.

Open System: In a system, when there is exchange of energy and matter taking place with
the surroundings, then it is called an open system.
For Example: Presence of reactants in an open beaker is an example of an open system. Closed System: A
system is said to be a closed system when there is no exchange of matter ‘ but exchange of energy is possible.
For example: The presence of reactants in a closed vessel made of conducting material.
Isolated System: In a system, when no exchange of energy or matter takes place with the surroundings, is
called isolated system.
For example: The presence of reactants in a thermoflask, or substance in an insulated closed vessel is an
example of isolated system.

Homogeneous System: A system is said to be homogeneous when all the constituents present is in the same
phase and is uniform throughout the system.
For example: A- mixture of two miscible liquids.
Heterogeneous system: A mixture is said to be heterogeneous when it consists of two or more phases and the
composition is not uniform.
For example: A mixture of insoluble solid in water. ’
The state of the system: The state of a thermodynamic system means its macroscopic or bulk properties which
can be described by state variables:
Pressure (P), volume (V), temperature (T) and amount (n) etc.
They are also known as state functions.
Isothermal process: When the operation is carried out at constant temperature, the process is said to be
isothermal. For isothermal process, dT = 0 Where dT is the change in temperature.
Adiabatic process: It is a process in which no transfer of heat between system and surroundings, takes place.
Isobaric process: When the process is carried out at constant pressure, it is said to be isobaric. i.e. dP = 0
Isochoric process: A process when carried out at constant volume, it is known as isochoric in nature.
Cyclic process: If a system undergoes a series of changes and finally returns to its initial state, it is said to be
cyclic process.
Reversible Process: When in a process, a change is brought in such a way that the process could, at any
moment, be reversed by an infinitesimal change. The change r is called reversible.
• Internal Energy
It is the sum of all the forms of energies that a system can possess.
In thermodynamics, it is denoted by AM which may change, when
— Heat passes into or out of the system
— Work is done on or by the system
— Matter enters or leaves the system.
Change in Internal Energy by Doing Work
Let us bring the change in the internal energy by doing work.
Let the initial state of the system is state A and Temp. TA Internal energy = uA
On doing’some mechanical work the new state is called state B and the temp. T B. It is found to be
TB > TA
∴ Δu = uB – uA
uB is the internal energy after change.

Change in Internal Energy by Transfer of Heat

Internal energy of a system can be changed by the transfer of heat from the surroundings to the system without
doing work.
Δu = q
Where q is the heat absorbed by the system. It can be measured in terms of temperature difference.
q is +ve when heat is transferred from the surroundings to the system. q is -ve when heat is transferred from
system to surroundings.
When change of state is done both by doing work and transfer of heat.
Δu = q + w
First law of thermodynamics (Law of Conservation of Energy). It states that, energy can neither be created nor
be destroyed. The energy of an isolated system is constant.
Δu = q + w.
• Work (Pressure-volume Work)
Let us consider a cylinder which contains one mole of an ideal gas in which a frictionless piston is fitted.
• Work Done in Isothermal and Reversible Expansion of Ideal Gas

• Isothermal and Free Expansion of an Ideal Gas

For isothermal expansion of an ideal gas into vacuum W = 0

• Enthalpy (H)
It is defined as total heat content of the system. It is equal to the sum of internal energy and pressure-volume
work.
Mathematically, H = U + PV
Change in enthalpy: Change in enthalpy is the heat absorbed or evolved by the system at constant pressure.
ΔH = qp
For exothermic reaction (System loses energy to Surroundings),
ΔH and qp both are -Ve.
For endothermic reaction (System absorbs energy from the Surroundings).
ΔH and qp both are +Ve.
Relation between ΔH and Δu.
• Extensive property
An extensive property is a property whose value depends on the quantity or size of matter present in the system.
For example: Mass, volume, enthalpy etc. are known as extensive property.
• Intensive property
Intensive properties do not depend upon the size of the matter or quantity of the matter present in the system.
For example: temperature, density, pressure etc. are called intensive properties.
• Heat capacity
The increase in temperature is proportional to the heat transferred.
q = coeff. x ΔT
q = CΔT
Where, coefficient C is called the heat capacity.
C is directly proportional to the amount of substance.
Cm = C/n
It is the heat capacity for 1 mole of the substance.
• Molar heat capacity
It is defined as the quantity of heat required to raise the temperature of a substance by 1° (kelvin or Celsius).
• Specific Heat Capacity
It is defined as the heat required to raise the temperature of one unit mass of a substance by 1° (kelvin or
Celsius).
q = C x m x ΔT
where m = mass of the substance
ΔT = rise in temperature.
• Relation Between Cp and Cv for an Ideal Gas
At constant volume heat capacity = Cv
At constant pressure heat capacity = Cp
At constant volume qv= CvΔT = ΔU
At constant pressure qp = Cp ΔT = ΔH
For one mole of an ideal gas
ΔH = ΔU + Δ (PV) = ΔU + Δ (RT)
ΔH = ΔU + RΔT
On substituting the values of ΔH and Δu, the equation is modified as
Cp ΔT = CvΔT + RΔT
or Cp-Cv = R
• Measurement of ΔU and ΔH—Calorimetry
Determination of ΔU: ΔU is measured in a special type of calorimeter, called bomb calorimeter.

Working with calorimeter. The calorimeter consists of a strong vessel called (bomb) which can withstand very
high pressure. It is surrounded by a water bath to ensure that no heat is lost to the surroundings.
Procedure: A known mass of the combustible substance is burnt in the pressure of pure dioxygen in the steel
bomb. Heat evolved during the reaction is transferred to the water and its temperature is monitored.
• Enthalpy Changes During Phase Transformation
Enthalpy of fusion: Enthalpy of fusion is the heat energy or change in enthalpy when one mole of a solid at its
melting point is converted into liquid state.

Enthalpy of vaporisation: It is defined as the heat energy or change in enthalpy when one mole of a liquid at
its boiling point changes to gaseous state.

Enthalpy of Sublimation: Enthalpy of sublimation is defined as the change in heat energy or change in
enthalpy when one mole of solid directly changes into gaseous state at a temperature below its melting point.

• Standard Enthalpy of Formation

Enthalpy of formation is defined as the change in enthalpy in the formation of 1 mole of a substance from its
constituting elements under standard conditions of temperature at 298K and 1 atm pressure.

Enthalpy of Combustion: It is defined as the heat energy or change in enthalpy that accompanies the
combustion of 1 mole of a substance in excess of air or oxygen.

• Thermochemical Equation
A balanced chemical equation together with the value of ΔrH and the physical state of reactants and products is
known as thermochemical equation.
Conventions regarding thermochemical equations
1. The coefficients in a balanced thermochemical equation refer to the number of moles of reactants and
products involved in the reaction.

• Hess’s Law of Constant Heat Summation

The total amount of heat evolved or absorbed in a reaction is same whether the reaction takes place in one step
or in number of steps.

• Born-Haber Cycle
It is not possible to determine the Lattice enthalpy of ionic compound by direct experiment. Thus, it can be
calculated by following steps. The diagrams which show these steps is known as Born-Haber Cycle.
• Spontaneity
Spontaneous Process: A process which can take place by itself or has a tendency to take place is called
spontaneous process.
Spontaneous process need not be instantaneous. Its actual speed can vary from very slow to quite fast.
A few examples of spontaneous process are:
(i) Common salt dissolves in water of its own.
(ii) Carbon monoxide is oxidised to carbon dioxide of its own.
• Entropy (S)
The entropy is a measure of degree of randomness or disorder of a system. Entropy of a substance is minimum
in solid state while it is maximum in gaseous state.
The change in entropy in a spontaneous process is expressed as ΔS

• Gibbs Energy and Spontaneity

A new thermodynamic function, the Gibbs energy or Gibbs function G, can be defined as G = H-TS
ΔG = ΔH – TΔS
Gibbs energy change = enthalpy change – temperature x entropy change ΔG gives a criteria for spontaneity at
constant pressure and temperature, (i) If ΔG is negative (< 0) the process is spontaneous.
(ii) If ΔG is positive (> 0) the process is non-spontaneous.
• Free Energy Change in Reversible Reaction

7 In a process, 701 J of heat is absorbed by a system and 394 J of work is done by the system.
. What is the change in internal energy for the process?
Sol.
We know that,
ΔU = ΔH + W
Where ΔU is changed in internal energy
Δ H changes in enthalpy
And W is work done on the system.
Given, 701 J of heat is taken by the system
Thus ΔH = 701 J
And 394 J of work is done by the system

∴∴ ΔU = 701 – 394
Thus W = - 394

= 307 J

8 Calculate the number of kJ of heat necessary to raise the temperature of 60 g of aluminium

. from 35 to 55° C. Molar heat capacity of Al is 24 J mol -1 K-1.
Sol.
No. of moles of Al (m) = (60 g)(27g mol−1)= 2.22 mol
Molar heat capacity (C) = 24 J mol-1 K-1
Rise in temperature (ΔT) = 55 - 35 = 20°C = 20K
Heat evolved (q) = C ×m×T = (24 J mol-1 K-1) ×(2.22 mol) × (20K)
= 1065.6 J = 1.067 kJ

9 Calculate the enthalpy change on freezing of 1.0 mol of water at 10.0 oC to ice at -10.00C. Δfus H
. = 6.03 kJ mol-1 at Cn[H2O(1)]=75.3 Jmol−1K−1 , Cp[H2O(s)]=36.8Jmol−1K−1.
Sol.
The change may be represented as:

According to Hess's Law:

ΔH = ΔH1 + ΔH2 + ΔH3
ΔH1 = 75.3 J mol-1 K-1 (10 K) = 753 mol-1
ΔH2(solidification) = -6.03 kJ mol-1 = -6030 J mol-1 (sign changed)
ΔH3 = 36.8 J mol-1 K-1 (-10 K) = - 36.8 J mol-1
ΔH = (753 - 6030 - 368) J mol-1 = - 5645 J mol-1
= - 5.645 kJ mol-1

11 Enthalpy of combustion of carbon to carbon dioxide is - 393.5 kJ mol -1. Calculate the heat
. released upon the formation of 35.2 g of CO 2 from carbon and oxygen gas.
Sol.

C(s) + O2(g) ⟶ CO2(g)(44g); ΔcH = - 393.5 kJ mol-1

The combustion equation is:

Heat released in the formation of 44 g of CO 2 = 393.5 kJ

Heat released in the formation of 35.2 g of CO 2 = [(393.5kJ)×(35.2g)]/(44g)= 314.8 kJ

12 Enthalpies of formation of CO(g),CO2(g),N2O(g) and N2O4(g) are -110 kJmol−1, -393 kJmol−1 ,
. 81 kJmol−1 and 9.7 kJmol−1 respectively. Find the value of ΔrH for the reaction.
N2O4(g)+3CO(g)⟶N2O(g)+3CO2(g)
Sol.
According to the question, enthalpy of formation of CO(g),CO2(g),N2O(g) and N2O4(g) are -110
kJmol−1 , -393 kJmol−1kJmol−1, 81 kJmol−1kJmol−1 and 9.7 kJmol−1kJmol−1 respectively.
Reaction:
N2O4(g)+3CO(g)⟶N2O(g)+3CO2(g)
We know that, Heat of reaction,
ΔrH∘=ΣΔfH0 products −ΣΔfH0 reactants
=[ΔfH∘(N2O)+3ΔfH∘(CO2)]= −[ΔfH∘(N2O4)+3ΔfH∘(CO)]
=[81+(3×−393)]−[9.7+(3×−110)]
=−777.7kJ ≈ −778kJ

14 Calculate the standard enthalpy of formation of CH 3OH(l) from the

. following data:

i. CH3OH(l)+3/2O2(g)⟶CO2(g)+2H2O(l);ΔrH∘= - 726 kJmol-1

ii. C( graphite )+O2(g)⟶CO2(g);ΔcH∘= - 393 kJmol-1
iii. H2(g)+12O2(g)⟶H2O(l);ΔfH∘= - 286 kJmol-1

Sol.
Given,
CH3OH(l)+3/2 O2(g)⟶CO2(g)+2H2O(l);ΔrH∘= - 726 kJmol-1....(i)
C( graphite )+O2(g)⟶CO2(g);ΔcH∘= - 393 kJmol-1....(ii)
H2(g)+12O2(g)⟶H2O(l);ΔfH∘= - 286 kJmol-1....(iii)
Multiplying Eq. (iii) by 2, we get
2H2(g)+O2(g)⟶2H2O(l);ΔfH∘= - 572 kJmol-1....(iv)
Adding Eqs. (ii) and (iv), we get
C(s)+2H2(g)+2O2(g)⟶CO2(g)+2H2O(l);ΔfH∘= - 965 kJmol-1....(v)
Reversing Eq. (i), we get
CO2(g)+2H2O(g)⟶CH3OH(l)+3/2 O2(g);ΔrH∘= + 726 kJ mol-1....(vi)
Adding Eqs. (v) and (vi) we get the required equation
C(s)+2H2(g)+12 O2(g)⟶CH3OH(l); ΔfH∘ = − 965+726
= − 239 kJmol-1

15 Calculate the enthalpy change for the process CCl4(g)⟶C(g)+4Cl(g) and calculate the bond
. enthalpy of C-CI in CCI4 (g)
ΔvapH∘(CCl4)=30.5kJmol−1
ΔfH∘(CCl4)=−135.5kJmol−1
 ΔaH∘(C)=715.0kJmol−1
where, ΔaH is enthalpy is atomisation, ΔaH∘(Cl2) = 242 kJmol-1.
Sol.
According to the question, ΔvapH∘(CCl4) =30.5kJmol−1, ΔfH∘(CCl4) =−135.5kJmol−1 , ΔaH∘(C)
=715.0kJmol−1, ΔaH∘(Cl2) = 242 kJmol-1.
CCl4(l)⟶CCl4(g); ΔvapH∘= + 30.5 kJ mol-1....(i)
C(s)+2Cl2(g)⟶CCl4(l); ΔfH∘ = - 135.5 kJ mol-1....(ii)
C(s)⟶C(g);ΔaH∘ = 715.0 kJ mol-1....(iii)
Cl2(g)⟶2Cl(g);ΔaH∘ = 242 kJ mol-1....(iv)
Multipling Eq. (iv) by 2, we get
2Cl2(g)⟶4Cl(g);ΔaH∘ = 484.0 kJ mol-1.....(v)
Adding Eqs. (iii) and (v), we get
C(s)+2Cl2(g)⟶C(g)+4Cl(g);;ΔH = 1199 kJ mol-1....(vi)
Reversing Eqs. (i) and (ii), we get
CCl4(g)⟶CCl4(l);ΔH = - 30.5 kJ mol-1....(vii)
CCl4(l)⟶C(s)+2Cl2(g);ΔH = + 135.5 kJ mol-1....(viii)
Adding Eqs. (vi), (vii) and (viii), we get
CCl4(g)⟶C(g)+4Cl(g);ΔH = 1304 kJ mol-1
Now, Bond enthalpy of C-CI bond is CCl4 =1304/4 = 326 kJ mol-1.

16 For an isolated system Δ U = 0 what will

. be Δ S?
Sol.
Change in internal energy (Δ U) for an isolated system is zero for it does not exchange any
energy with the surroundings. But entropy tends to increase in case of spontaneous reaction.
Therefore, ΔS > 0 or positive.

17 For a reaction at 298 K , 2A + B ⟶ C , ΔH = 400 kJ mol-1 and ΔS = 0.2 kJ k-1 mol-1

. At what temperature will the reaction become spontaneous considering ΔH and ΔS to
constant over the temperature range?
Sol.
As per the Gibbs Helmholtz equation:
ΔG = ΔH - TΔS
For ΔG = 0 , ΔH = TΔS or
T = (400kJmol−1)/(0.2kJK−1mol−1) = 2000 K
Thus, reaction will be in a state of equilibrium at 2000 K and will be spontaneous above this
temperature.

18 For the reaction 2 Cl (g) ⟶ Cl2 (g) what will be the signs of ΔH
. and ΔS?
Sol.
ΔH: negative (-ve) because energy is released in bond formation
ΔS: negative (-ve) because entropy decreases when atoms combine to form molecules.

19 For the reaction, 2A(g)+B(g)⟶2D(g); ΔU∘=−10.5kJ and ΔS∘=−44.1JK and ΔS∘=−44.1JK−1.

. Calculate ΔG∘ for the reaction and predict whether the reaction may occur spontaneously. (R
= 8.314 ×× 10-3 kJ mol-1, T = 298 K)
Sol.
According to the question, ΔU∘=−10.5kJ and ΔS∘=−44.1JK−1 , R = 8.314 ×× 10-3 kJ mol-1, T =
298 K.
Reaction:
2A(g)+B(g)⟶2D(g)2A(g)+B(g)⟶2D(g)
Δng=np−nr=2−3=−1
We know that, ΔH∘=ΔU∘+ΔngRT
ΔH∘=−10.5ΔH∘=−10.5 + (- 1 × 8.314 × 10-3 × 298 )
= - 12.977 kJ mol-1
Now, ΔG∘=ΔH∘−TΔS∘
ΔG∘=−12.977ΔG∘=−12.977 - ( 298 × - 44.1 × 10-3)
= 0.165 kJ mol-1
The reaction will not occur spontaneously because ΔG∘ is positive.

20 The equilibrium constant for a reaction is 10. What will be the value of ΔG°? R = 8.314JK-
. 1mol-1, T = 300 K.
Sol.
According to the question, equilibrium constant = K c = 10, R = 8.314J K-1 mol-1, T = 300 K.

ΔG∘=−2.303×8.314JK−1mol−1×300K×log10 ⇒ΔG∘= - 5744.14 J mol-1.

We know that, ΔG∘=−2.303RTlogKc

21 Comment on the thermodynamic stability of

. NO(g), given
 12N2(g)+12O2(g)→NO(g);ΔrH0 = 90 kJ mol-1
NO(g)+12O2(g)→NO2(g):ΔrH0 = –74 kJ mol-1
Sol.
The positive value of ΔnH indicates that heat is absorbed during the formation of NO(g). This
means that NO(g) has higher energy than the reactants (N 2 and O2) Hence, NO(g) is unstable.
The negative value of ΔrH indicates that heat is evolved during the formation of NO 2(g) from
NO(g) and O2(g). The product, NO2(g) is stabilized with minimum energy. Hence, NO(g) is
unstable.

22 Calculate the entropy change in surroundings when 1.00 mole of H 2O(l) is formed under
. standard conditions and ΔfH0 = - 286 kJ mol-1.
Sol.
Reaction:
H2(g)+12 O2(g)⟶H2O(l) ΔfH∘=−286kJmol−1
The energy released in the above reaction is absorbed by the surroundings.
So, qsurr = + 286 kJ mol-1
We know that, ΔS= q surr T
= +286kJmol−1298K
= 0.9597 kJ K-1 mol-1
= 959.9 JK-1 mol-1.