Chapter – 6 : Thermodynamics

The branch of which deals with the quantitative relationship between heat and other forms of energies is called
thermodynamics.

Basic terms involved in thermodynamics

Term Explanation
System Part of the universe under investigation.
Open System A system which can exchange both energy and matter with its surroundings.
Closed System A system which permits passage of energy but not mass, across its boundary.
Isolated system A system which can neither exchange energy nor matter with its surrounding.
Surroundings Part of the universe other than system, which can interact with it.
Boundary Anything which separates system from surrounding.
State variables The variables which are required to be defined in order to define state of any
system i.e. pressure, volume, mass, temperature, surface area, etc.
State Functions Properties of system which depend only on the state of the system and not on the
path.
Example: Pressure, volume, temperature, internal energy, enthalpy, entropy etc.
Path Functions Properties of system which depend on the path of the process which the system
undergoes.
Example: Heat, work.
Intensive properties Properties of a system which do not depend on mass of the system i.e. temperature,
pressure, density, concentration,
Extensive properties Properties of a system which depend on mass of the system i.e. volume, energy,
enthalpy, entropy etc.
Process Path along which state of a system changes.
Isothermal process Process which takes place at constant temperature
Isobaric process Process which takes place at constant pressure
Isochoric process Process which takes place at constant volume.
Adiabatic process Process during which transfer of heat cannot take place between system and
surrounding.
Cyclic process Process in which system comes back to its initial state after undergoing series of
changes.
Reversible process Process during which the system always departs infinitesimally from the state of
equilibrium i.e. its direction can be reversed at any moment.
Irreversible Process This type of process is fast and gets completed in a single step. This process cannot
be reversed. All the natural processes are of this type.

Internal Energy (E or U) of a system:

• Sum of all the possible types of energy present in the system.

• ΔE or ΔU = heat change for a reaction taking place at constant temperature and volume.
• It is a state function.
• It is an extensive property.
ΔU = Ufinal– Uinitial
 Heat (Q):

• Energy is exchanged between system and surround in the form of heat when they are at different temperatures.
• Heat added to a system is positive, whereas heat extracted from a system is negative.
• It is an extensive property.
• It is a path function.

Work (W):
• Work = Force × Displacement i.e. dW = Fdx
• Work done on the system is given by positive sigh while work done by the system is given negative sign.
• Mechanical Work or Pressure-Volume Work: work associated with change in volume of a system against an external
pressure.
• Work done in reversible process: W=

W = – 2.303 nRT log V2/V1 = –2.303 nRT log P1/P2

• Unit: Joule.

First Law of Thermodynamics:

Energy can neither be created nor destroyed although it can be converted from one form to another.
OR
Energy of an isolated system is constant.

Mathematical Expression
Heat observed by the system = change in internal energy + work done by the system.
i.e. q = ΔU + w
For an infinitesimal process
dq = dE + dw
Where, q is the heat supplied to the system and w is the work done on the system.
• For an isolated system,
q=0
so, ΔU = –w
• For system involving mechanical work only
ΔU = q – pΔV
• At constant volume i.e. isochoric process
ΔU = qv
• For Isothermal Process
ΔU = 0
so, q = – pΔV = –W
• For adiabatic process
q=0
so, ΔU = W

Enthalpy (H):
• H = E+PV
• At constant pressure:
dH = dE + pdV
• For system involving mechanical work only
dH = QP (at constant pressure)
• For exothermic reactions:
dH = –ve
• For endothermic reactions:
dH = +ve
Relation between dH and dE:
dH = dE + dng RT
where, dng = (number of moles of gaseous products – number of moles of gaseous reactants).
Heat capacity:
• Amount of heat required to rise temperature of the system by one degree.
C = q / dT
• Specific heat capacity: Heat required to raise the temperature of 1 g of a substance by one degree.
Cs = Heat capacity / Mass in grams
• Molar heat capacity: Heat required to raise the temperature of 1 g of a substance by one degree.
Cm = Heat capacity / Molar mass.
• Heat capacity of system at constant volume:
Cv = (dU/dT)v
• Heat capacity of system at constant pressure:
Cp = (dH/dT)p
•Relation between Cp and Cv
Cp – Cv = R (for 1 mole of an ideal gas).

Bomb Calorimeter:
Enthalpies of Reactions:
Enthalpies
Enthalpy of Formation
Enthalpy of Combustion
Enthalpy of Neutralization
Enthalpy of Hydration
Enthalpy of Transition
Enthalpy of Sublimation
Enthalpy of Fusion
Hess’s Law of constant heat summation:
The total enthalpy change of a reaction is the same, regardless of whether the reaction is completed in one step or in several
steps.
E.g.
According to Hess’s law: ΔH = ΔH1 + ΔH2
Born–Haber Cycle:
Applying Hess’s law we get
ΔH1 + 1/2 ΔH2 + ΔH3 + ΔH4 + ΔH5 = ΔHf (MX) (ΔH5=Lattice enthalpy)
Definitions
Enthalpy change when one mole of a
given compound is formed from its
elements
Enthalpy change when one mole of a
substance is burnt in oxygen.
Enthalpy change when one equivalent
of an acid is neutralized by a base in
dilute solution.
Enthalpy change when a salt
combines with the required number of
moles of water to form
specific hydrate.
Enthalpy change when one mole of a
substance is transformed from one
allotropic form to another allotropic
form.
Enthalpy change when one mole of a
solid substance sublime at constant
temp. and 1 bar pressure
Enthalpy change when one mole of a
solid melts
Example
H2(g) + 1/2O2(g) → 2H2O(l),
ΔfH = –890.36 kJ / mol
CH4 + 2O2(g) →CO2 + 2H2O(l),
ΔcombH = –890.36 kJ / mol
H+ (aq) + OH– (aq) → H2O(l)
ΔneutH = –13.7 kcal
CuSO4(s) + 5H2O (l) → CuSO45H2O,
ΔhydH° = –18.69 kcal
C(graphite) → C(diamond),
ΔtransH° = 1.9 kJ/mol
CO2(S) → CO2(g)
ΔsubH° = 6.00 kJ/mol
H2O(S) → H2O (l)
ΔfusH° = 73.00 kJ/mol
Lattice enthalpy: The change in enthalpy that occurs when 1 mole of a solid crystalline substance is formed from its
gaseous ions.

Thermochemical equation

When a balanced chemical equation not only indicates the quantities of the different reactants and products but
also indicates the amount of heat evolved or absorbed, it is called thermochemical equation.

Entropy
• It is the measure of the degree of randomness of a system.
• It is an extensive property of a system.
• It is a state function.

It is difficult to determine the absolute entropy of a system. We are mainly concerned with the change in entropy of a
system (ΔS).

Mathematically:
• ΔS = qrev/T (for a reversible process)
where, ΔS is entropy change.
• Entropy increases with increase in randomness of particles of the system i.e. ΔS is positive for melting of ice.
• At equilibrium, ΔS = 0
• For a spontaneous process (irreversible process), ΔS > 0
• Entropy change in an isothermal reversible expansion of a gas

Second Law of Thermodynamics (in terms of entropy)

If a reversible process occurs, there is no net change in entropy. In an irreversible process, the total entropy always
increases. The total entropy of the universe is continuously increasing.

Gibbs free energy(ΔG):

• ΔG = ΔH - TΔS
• ΔG = nRTlnK eq
• ΔG = nFE cell
• At equilibrium, ΔG = 0
• For spontaneous process, ΔG < 0

Bond Enthalpy:
Average amount of energy required to break one mole bonds of a particular type in gaseous molecules.
E.g. H–OH(g) → 2H(g) + ½O(g) ΔH = 498 kJmol-1
O–H(g) → H2(g) + ½O2 (g) ΔH = 430 kJmol-1
ΔHO–H = (498 + 430)/2 = 464 kJ mol–1

The main difference between bond enthalpy and bond dissociation energy is that bond enthalpy refers to the average
amount of energy needed to break down all bonds between the same two types of atoms in a compound whereas bond
dissociation energy is the amount of energyneeded to break down a particular bond in homolysis.
 EXERCISE

•MCQs

1. Which of the following is an intensive property?

(i) temperature (ii) surface tension (iii) viscosity (iv) all of these
2. The temperature of the system decreases in an
(i) adiabatic compression (ii) isothermal expansion (iii) isothermal compression (iv) adiabatic expansion
3. Based on the first law of thermodynamics, which one of the following is correct?
(i) For an isothermal process, q = +w (ii) For a cyclic process, q = -w, ΔU = -q (iii) For an adiabatic process, ΔU = -w
(iv) For an isochoric process
4. If one mole of ammonia and one mole of hydrogen chloride are mixed in a closed container to form ammonium chloride
gas, then
(i) H>U (ii) H= U (iii) H<U (iv) there is no relationship
5. For a spontaneous process, which of the following is always true?
(i) G<0 (ii) Stotal<0 (iii) -TS>0 (iv) G>0
6. For which of the following processes S is negative?
(i) H2(g) → 2H(g) (ii) N2(g, 1 atm) → N2(g, 5 atm) (iii) 2SO3(g) → 2SO2(g) + O2(g) (iv) C(diamond) → C(graphite)
7. In an adiabatic process, no transfer of heat takes place between system and surroundings. Choose the correct option for
free expansion of an ideal gas under adiabatic condition from the following:
(i) q = 0, ∆T ≠ 0, w = 0 (ii) q ≠ 0, ∆T = 0, w = 0 (iii) q = 0, ∆T = 0, w = 0 (iv) q = 0, ∆T < 0, w ≠ 0
8. The enthalpies of elements in their standard states are taken as zero. The enthalpy of formation of a compound
(i) is always negative (ii) is always positive (iii) may be positive or negative (iv) is never negative
9. During complete combustion of one mole of butane, 2658 kJ of heat is released. The thermochemical reaction for above
change is
(i) 2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l) ∆cH = –2658.0 kJ mol–1
13
(ii) C4H10(g) + O2 (g) → 4CO2 (g) + 5H2O(g) ∆cH = –1329.0 kJ mol–1
2
13
(iii) C4H10(g) + 2 O2(g) → 4CO2 (g) + 5H2O (l) ∆cH = –2658.0 kJ mol–1
13
(iv) C4H10 (g) + 2 O2(g) → 4CO2 (g) + 5H2O(l) ∆cH = +2658.0 kJ mol–1
10. Enthalpy of sublimation of a substance is equal to
(i) enthalpy of fusion + enthalpy of vapourisation (ii) enthalpy of fusion (iii) enthalpy of vapourisation
(iv) twice the enthalpy of vapourisation

•VSA Questions

1. Classify as extensive and intensive properties: molar heat capacity, temperature, enthalpy and volume.
2. When 580J of work was done on a system, it lost 150J of energy as heat. Calculate the change in internal energy (ΔU)
for this process.
3. Predict the sign of ΔS° for the reaction: 2H2S(g) + 3O2(g) → 2H2O(g) + 2SO2(g)
4. What is the limitation of first law of thermodynamics?
5. State a chemical reaction in which ΔH and ΔU are equal.
6. Will entropy increase or decrease in the following processes?
(i) Sugar dissolved in water.
(ii) Normal egg to hard boiled egg.
(iii) Two gases are mixed together.
(iv) Formation of dry ice.
7. If ΔG° for a reversible reaction is found to be zero, determine the value of its equilibrium constant?
8. The energy released in the neutralization of H2SO4 and KOH is 57.1 kJmol-1. Calculate the value of ΔH for the reaction:
H2SO4 + 2 KOH → K2SO4 + 2H2O
9. Why is the entropy of a solution higher than that of a pure liquid?
10. When ΔH>0 and ΔS<0, a reaction is never spontaneous. Explain.

•SA Questions

1. Define the following terms:

(i) Enthalpy of combustion; (ii) Hess’s law of constant heat summation; (iii) Lattice enthalpy.
2. Derive the relationship between Cp and Cv for an ideal gas.
3. Calculate the heat of reaction of the following reaction:
CO2(g) + H2(g) → CO(g) + H2O(g)
Given that the ΔfH° CO(g) = –110.5 kJmol-1, ΔfH° CO2(g) = –393.8 kJmol-1 and ΔfH° H2O(g) = –241.8 kJmol-1
respectively.
4. Find the temperature above which the reduction of lead oxide in the following reaction becomes spontaneous: PbO(s)
+ C(s) → Pb(s) + CO(g). Given ΔH =108.4 kJmol-1; ΔS=190 JK-1mol-1.
5. (a) Hess's law is a corollary of the first law of thermodynamics. Comment.
(b) Why is standard heat of formation of diamond not zero although it is an element?
6. (a) Explain why the entropy of a pure crystalline substance is zero at 0K?
(b)An exothermic reaction A→B is spontaneous in the backward direction. What will be the sign of ΔS for the forward
reaction?
7. The standard heat of combustion of benzene is −3271 kJmol-1, for CO2 it is −394 kJmol-1, and for H2O, it is −286 kJmol-
1
. Calculate the standard heat of formation of benzene.
8.Hydrogenation of double and triple bonds is an important industrial process. Calculate (in kJ) the standard enthalpy change
ΔH for the hydrogenation of ethyne (acetylene) to ethane:
H−C≡C−H(g) + 2H2(g) → H3C−CH3(g)
Bond enthalpies (in kJ/mol): C−C (347); C≡C (839); C−H (413); H−H (432).

•LA Questions

1. (a) State the significance of Born-Haber cycle.

(b) Calculate the lattice enthalpy of MgBr2, given that:
Enthalpy of formation of MgBr2 = –524 kJmol-1; sublimation energy of Mg = 148 kJmol-1; ionization energy of Mg =
2187 kJmol-1; vapourisation energy of Br2(l) = 31 kJmol-1; dissociation energy of Br2(g) = 193 kJmol-1 and electron gain
enthalpy of Br2(g) = –331 kJmol-1.
2. (a) q and w are not state functions but their sum is a state function. Why?
(b) The molar enthalpy of vapourisation of acetone is less than that of water. Why?
(c) Why for predicting the spontaneity of a reaction, free energy is a better criterion than that of entropy?
(d) An exothermic reaction may not be always spontaneous. Explain.
(e) Why an ideal gas expands in vacuum though there is neither absorption nor evolution of heat?
3. Derive an expression for the work done during isothermal expansion of an ideal gas.

ANSWERS AND HINTS

•MCQs
1. (iv) 2. (iv) 3. (ii) 4. (iii) 5. (i) 6. (ii) 7. (iii) 8. (iii) 9. (iii) 10. (i)
•VSA Questions
1. Extensive properties – enthalpy and volume.
Intensive properties – molar heat capacity and temperature.
2. 430J
 3.negative.
4. It does not tell us the direction of feasibility of a process.
5. H2(g) + Cl2(g) 2HCl(g) or any other reaction where Δn = 0.
6. (i) increases, (ii) increases, (iii) increases and (iv) decreases.
7. ΔG°=2.303×R×T×logK =0
or, logK=0
or, K=1
8.–57.1×2= –114.2 kJmol-1
9.In solution, the randomness of solvent particles is higher than that in pure solvent.
10.ΔG= ΔH – TΔS.
When ΔS<0, TΔS<0 and – TΔS>0
∴ ΔG>0

•SA Questions

1.Refer to the book or the above synopsis.

2.We know that for one mole (n=1) of an ideal gas,
∆H = ∆U + ∆(pV) = ∆U + ∆(RT) = ∆U + R∆T
Therefore, ∆H = ∆U + R∆T ---- (i)
Now, by definition ∆H =CP∆T and ∆U=CV∆T.
Substituting the values of ∆H and ∆U in equation (i), we get:
CP∆T = CV∆T + R ∆T
or, CP = CV + R
or, CP – CV = R
3.41.5 kJ (Hint: Use Hess’s law).
4.570.5 kJ (Hint: Use ΔG= ΔH – TΔS ; ΔG<0 for reaction to be spontaneous).
5. (a)According to Hess's law, the change in heat energy remains the same during a process, whether carried directly in one
step or indirectly in multiple steps. Hence it implies that energy is not created or destroyed. It remains conserved which
is the same conclusion of the first law of thermodynamics.
(b) Diamond is one of the allotropes of carbon. The allotrope of carbon which is most stable (graphite) at room
temperature and 1 atm pressure is regarded as the standard form of carbon and is given the value of zero for heat of
formation.
6. (a) At 0K, there is a perfectly ordered arrangement of the constituent particles of a pure crystalline substance and there is
no disorder at all. Hence, its entropy is taken as zero.
(b) Since backward reaction is spontaneous, so forward reaction is non-spontaneous. Hence the sign of ΔS for the forward
reaction is negative.
15
7. 49 kJmol-1 (Hint: Formation of benzene: 6C + 3H2 → C6H6; Combustion of benzene: C6H6 + O2 → 6CO2 +3H2O; use
2
Hess’s law).
8.−296 kJmol-1 [Hint:ΔrH= (ΔHH3C−CH3) – (ΔHH−C≡C−H + 2ΔH H2)].

•LA Questions

1. (a) The Born-Haber cycle allows us to understand the different enthalpy changes possible for a particular chemical
process and also helps us to determine the lattice enthalpy of ionic solids.
(b) –2752 kJmol-1 (Hint: Use Born-Haber cycle).
2. (a) q and w are path functions and not state functions as they both depend upon the path followed by the reaction or
process, whereas their sum gives internal energy which doesn't depend upon the path but depends on the initial and final
states of the system undergoing a process.
(b) Acetone has weaker van der Waals’ forces of attraction whereas in water intermolecular H-bonding is present which
is stronger. Hence the molar enthalpy of vapourisation of acetone is less than that of water.
(c)Entropy only considers the increase of randomness as the criteria for spontaneity of a process whereas free energy
includes both the factor of enthalpy and entropy to determine spontaneity of a process.
(d) If during an exothermic reaction, entropy increases, then it is always spontaneous. However, if the exothermic
reaction has a decrease in entropy, then the reaction may or may not be spontaneous; it would depend on the temperature
of the system.
(e) In an ideal gas, there is no inter-molecular force of attraction. Hence, no energy is required to overcome the forces.
Moreover, when a gas expands in vacuum, work done is zero as Pext=0.
3.Work done during isothermal expansion of an ideal gas is given by:

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