Thermodynamics

Thermodynamics
(D) Heat of hydrogenation (DHHydrogenation) :
The heat evolved during the complete hydrogenation of one mole
unsaturated organic compound into its saturated compound is called as
heat of hydrogenation.
change
Unsaturated organic compound ⎯⎯→ saturated organic compound
(= or ≡ Bond) (– Bond)

C2H2 + 2H2 ⎯⎯→ C2H6 Dhhydro✓

C2H2 + H2 ⎯⎯→ C2H4 DHhydro
C2H4 + H2 ⎯⎯→ C2H6 DHhydro ✓

Note

Heat of hydrogenation is exothermic in nature.

 If enthalpy of combustion of
DHc (C2H4) = – 1409.5 kJ/mol
DHc (H2) = – 285.6 kJ/mol
DHc (C2H6) = – 1558.3 kJ/mol
Then calculate DH(Hydrogenation) of C2H4 ?
Solution
 Thermodynamics
(F) Heat of Transformation
Heat of fusion : The required amount of heat to convert 1 mole solid into
liquid at its melting point is called as heat of fusion.

1 H2O(s) ⎯→ H2O(l) ; DHfusion ✓

Note

Heat of fusion is always endothermic reaction i.e. (DH = + ve)

 Thermodynamics
Heat of vapourization (DHVapour) : The required amount of heat to convert
1 mole liquid into gas at its boiling point is called as heat of vapourization.

1 H2O(l) ⎯→ H2O(g) ; DHVapour ✓

Note

Heat of vapourization is always endothermic reaction i.e. (DH = +ve)

 Thermodynamics
Heat of sublimation (DHSub) : The required amount of heat to convert 1 mole
solid into gas at a certain temperature is called as heat of sublimation.

H2O(s) ⎯→ H2O(g), DHSub ✓

Note

Heat of sublimation is always endothermic reaction i.e. (DH = + ve)

 Thermodynamics
(E) Heat of Atomization (DHatom) :
The amount of heat required to dissociate 1 mole stable substance into
gaseous atoms is called as heat of atomization.
𝟏
H (g) ⎯→ 1 H(g) DHatom 
𝟐 2

H2(g) ⎯→ 2 H(g) DHatom ✓

𝟏
Cl (g) ⎯→ 1 Cl(g) DHatom 
𝟐 2

Cl2(g) ⎯→ 2 Cl(g) DHatom ✓

Na(s) ⎯→ Na(g) DHatom ✓

Note
Heat of atomization is always endothermic reaction i.e. (DH = + ve)
 Thermodynamics
Bond Energy/ Bond Dissociation Energy
The required amount of energy to dissociate one mole gaseous bond into
separate gaseous atoms is called as bond dissociation energy.

𝐄𝐱𝐚𝐦𝐩𝐥𝐞

1H – H(g) ⎯→ 2H(g) ; DHH – H ✓

1Cl – Cl(g) ⎯→ 2Cl(g) ; DHCl – Cl ✓
1H – Cl(g) ⎯→ H(g) + Cl(g) ; DHH – Cl ✓
1H – Cl(g) ⎯→ H+(g) + Cl–(g) ; DHH – Cl 
𝟏 𝟏
1H – Cl(g) ⎯→ 𝟐
H2(g) + Cl
𝟐 2(g)
; DHH – Cl 

1H2O(g) ⎯→ 2H(g) + O(g) ; DHH – O 

 Thermodynamics
Bond Energy/ Bond Dissociation Energy

➢ In case of poly atomic molecule, we calculate the average bond energy.

Total energy required to dissociate all bonds

(BE)av = Average bond energy =
Number of moles of bonds dissociated

𝐄𝐱𝐚𝐦𝐩𝐥𝐞

H – O – H(g) + X kJ ⎯→ H – O(g) + H(g)

H – O(g) + Y kJ ⎯→ H(g) + O(g)

1H2O(g) ⎯→ 2H(g) + O(g)

X+𝑌
(BE)av = Average bond energy = kJ​
2
 Thermodynamics
Bond Energy/ Bond Dissociation Energy

Special Points
➢ The bond energy may be defined as the average amount of energy
required to dissociate one mole gaseous bond into separate gaseous
atoms.

➢ Bond dissociation is endothermic.

➢ If bond energy of various bonds present in the reactants and products

are given then DH of that reaction can be calculated as following:

𝚫𝐇 = 𝚺(𝐁. 𝐄. )𝐑 − 𝚺(𝐁. 𝐄. )𝐏
If bond energy (C – C) = 83 kCal/mol
(H – H) = 104 kCal/mol
(C – H) = 99 kCal/mol
(C = C) = 147 kCal/mol
Then calculate enthalpy of hydrogenation of CH2 = CH2 .

Solution
 Thermodynamics
Heat of Hydration (DHhydra)
Amount of heat evolved when one mole of anhydrous salt combines with fixed numb
of water molecules to convert into its specific hydrated crystal is called as heat of
hydration.

1 CuSO4(s) + 5H2O(ℓ) → CuSO4 . 5H2O(s) ΔH = –ve

anhydrous salt

1 MgSO4(s) + 7H2O(ℓ) → MgSO4 . 7H2O(s) ΔH = –ve

anhydrous salt

1 CaCl2(s) + 6H2O(ℓ) → CaCl2 . 6H2O(s) ΔH = –ve

anhydrous salt

Note Heat of hydration is exothermic.

 Thermodynamics
Heat of Solution (DHsolution)
Amount of heat absorbed or evolved when one mole of substance is dissolved in suc
large volume of solvent such that further addition of solvent does not produce a
more heat change is called as heat of solution.

1 CuSO4(s) + aq → CuSO4 (aq) ΔHsolution ✓

1 CuSO4(s) + 5H2O (ℓ) → CuSO4 . 5H2O(s) ΔHhydration ✓

MgSO4(s) + 7H2O (ℓ) + aq → MgSO4(aq) ΔHsolution ✓

MgSO4 . 7H2O (s) + aq → MgSO4(aq) ΔHsolution ✓

Note Heat of solution may be endothermic or exothermic.

The heat of solution of anhydrous CuSO4 (s) is – 15.9 kcal/mol and that of
CuSO4 . 5H2O (s) is 2.8 kcal/mol .Calculate the heat of hydration of CuSO4 (s) .

Solution
 Thermodynamics
Resonance Energy
Resonance energy shows the difference in energies of most stable
resonating structure and resonating hybrid.

–ve
+ve
Resonance energy = Observed heat of formation – Calculated heat of formation
Calculate resonance energy of N2O from the following data
𝚫𝐟 𝐇 𝑵𝟐 𝑶 = 𝟖𝟐 𝒌𝒋/𝒎𝒐𝒍
BE of N ≡ N ⇒ 946 kj/mol
N = N ⇒ 418 kj/mol
N = O ⇒ 607 kj/mol
O = O ⇒ 498 kj/mol
Solution
The bond energy of A2 (g) , AB(g) & B2(g) are in the ratio of 1: 1: 0.5 . The heat
of formation of AB from A2 (g) and B2(g) is – 100 kJ/mol. Then calculate the
bond energy of A2 (g) and B2(g) .

Solution