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Lec 9 Thermo Pc-Invert

The document discusses various thermodynamic concepts including heat of neutralization, hydrogenation, transformation, atomization, bond energy, hydration, and solution. It defines key terms, provides examples, and explains the exothermic or endothermic nature of these processes. Specific values and reactions are presented to illustrate the principles involved.

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10 views25 pages

Lec 9 Thermo Pc-Invert

The document discusses various thermodynamic concepts including heat of neutralization, hydrogenation, transformation, atomization, bond energy, hydration, and solution. It defines key terms, provides examples, and explains the exothermic or endothermic nature of these processes. Specific values and reactions are presented to illustrate the principles involved.

Uploaded by

shaurya2004x
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Heat of Neutralisation

The heat evolved when one equivalent of an acid is completely


neutralised by one equivalent of a base in dilute solution is called
as heat of neutralisation.

SA + SB ⎯→ Salt + Water

HCl (aq) + NaOH (aq) ⎯→ NaCl + H2O

H+ + Cl– + Na+ + OH– ⎯→ Na+ + Cl– + H2O

H + + OH − → H2 O
When one equivalent of SA is neutralised by one equivalent of SB
then evolved heat remain constant and its value is – 13.7 kcal/eq or –
57.2 kJ/eq.

EXAMPLE

SA SB
HCl (aq) + NaOH (aq) ⎯→ NaCl + H2O + 13.7 Kcal
NV = 1 eq. NV = 1 eq. ⎯→ DH = – 13.7 KCal
NV = 2 eq. NV = 2 eq. ⎯→ DH = 2 (–13.7) Kcal
NV = 3 eq. NV = 3 eq. ⎯→ DH = 3 (–13.7) Kcal
NV = 4 eq. NV=5 eq. ⎯→ DH = 4 (–13.7) Kcal
NV = 5 eq. NV = 3 eq. ⎯→ DH = 3 (–13.7) Kcal
If one of the acid or base or both are weak then heat of
neutralisation is usually less than –13.7 KCal eq–1 or –57.3 KJ eq–1
because some part of the heat released in neutralisation is
absorbed to dissociate the weak electrolyte completely.

EXAMPLE

CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O; ΔH = –13.4 kCal eq–1


WA SB

Exception:

For a reaction HF + NaOH ⎯→ NaF + H2O; DH = –16.7 Kcal; this is


because of hydration of fluoride ion.
Heat of hydrogenation (∆HHydrogenation)

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.


EXAMPLE
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
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. (∆H = + ve)


Heat of Transformation

Heat of vapourization (∆HVapour) : 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. (∆H = +ve)


Heat of Transformation

Heat of sublimation (∆HSub) : 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. (∆H = + ve)


Heat of Atomization (∆Hatom)

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. (∆H = + ve)


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

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) ⎯→ H2(g) + Cl ; DHH – Cl 
2 2 2(g)

1H2O(g) ⎯→ 2H(g) + O(g) ; DHH – O 


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)

(BE)av = Average bond energy = X+𝑌


kJ
2
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 ∆H of that reaction can be calculated as
following:
ΔH = Σ(B. E. )R − Σ(B. E. )P
EXAMPLE
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
Heat of Hydration (∆Hhydra)

Amount of heat evolved when one mole of anhydrous salt combines


with fixed number 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
Heat of Hydration (∆Hhydra)

NOTE

Heat of hydration is exothermic.


Heat of SOLUTION (∆HSolution)

Amount of heat absorbed or evolved when one mole of substance is


dissolved in such a large volume of solvent such that further
addition of solvent does not produce any 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 ✓


Heat of SOLUTION (∆HSolution)

NOTE

Heat of solution may be endothermic or exothermic.


Resonance Energy

Resonance energy shows the difference in energies of most stable


resonating structure and resonating hybrid.

–ve
+ve

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