Enthalpy Changes During Phase Transformations:
Melting /
Fusion Vapourization
Freezing Condensation
Sublimation
Enthalpy of fusion (∆fusH ):
➢ The enthalpy change that is accompanied during the fusion of 1 mole of a
solid without change in temperature at constant pressure is called as enthalpy
of fusion.
➢ Its endothermic reaction
Example:
H2O (s) H2O (l)
∆fusHΘ = + 6.00 kJ/mole
Enthalpy of freezing (∆freezH) :
➢ Definition: The enthalpy change that is accompanied during the
freezing/solidification of 1 mole of a liquid without change in temperature at
constant pressure is called as enthalpy of freezing/solidification.
➢ Its exothermic reaction
Example:
H2O (l) H2O (s)
∆freezHΘ = – 6.00 kJ/mole
Enthalpy of Vapourization (∆vapH ) :
➢ The enthalpy change that is accompanied during the vapourization of 1 mole
of liquid to gas without change in temperature at constant pressure is called as
enthalpy of vapourization.
➢ Its endothermic reaction
Example:
H2O (l) H2O (g)
∆VapHΘ = + 40.79 kJ/mole
Enthalpy of Condensation (∆ConH ) :
➢ The enthalpy change that is accompanied during the condensation of 1 mole
of gas to liquid without change in temperature at constant pressure is called
as enthalpy of condensation.
➢ Its exothermic reaction
Example:
H2O (g) H2O (l)
∆ConHΘ = – 40.79 kJ/mole
Enthalpy of sublimation (∆SubH ):
➢ The enthalpy change that is accompanied during conversion of 1 mole of a
solid directly into its vapour at constant temperature and pressure is called
as enthalpy of sublimation.
➢ Its endothermic reaction
Example:
Solid CO2 (dry ice) sublimes at 195K with
∆subHΘ = + 25.2 kJ /mole
Standard Enthalpy Changes of Fusion and Vaporisation
Substance Tf/K fusH/(kJmol–1) Tb/K vapH/(kJmol–1)
N2 63.15 0.72 77.35 5.59
NH3 195.40 5.65 239.73 23.35
HCl 159.0 1.992 188.0 16.15
CO 68.0 6.836 82.0 6.04
CH3COCH3 177.8 5.72 329.4 29.1
CCl4 250.16 2.5 349.69 30.0
H2 O 273.15 6.01 373.15 40.79
NaCl 1081.0 28.8 1665.0 170.0
C 6 H6 278.65 9.83 353.25 30.8
The sublimation energy of I2(s) is 57.3 kJ/mol and the enthalpy of fusion is 15.5
kJ/mol. The enthalpy of vaporisation of I2 is
(a) 41.8 kJ/mol (b) –41.8 kJ/mol (c) 72.8 kJ/mol (d) –72.8 kJ/mol
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Consider the following data
H2O(s) → H2O(l) ΔH = 6.05 kJ
H2O(l) → H2O(g) ΔH = 43.7 kJ
At 273 K, the sublimation energy of H2O(s) → H2O(g) will be
(a) 56.75 (b) 75.20 (c) 49.75 (d) 100.20
9
What is the internal energy (kJ) change occurring when 36 g of H2O(l) at 100°C
converted to H2O(g)?
ΔH°(vapourisation) = 40.79 kJ/mol
(a) 75.38 (b) 80.98 (c) 70.98 (d) 45.89
10
Standard enthalpy of vapourisation ΔvapH° for water at 100°C is 40.66 kJ mol–1. The
change in internal energy of vaporisation of water at 100°C (in kJ mol–1) is :
(a) + 37.56 (b) – 43.76 (c) + 43.76 (d) + 40.66
(Assume water vapour to behave like an ideal gas)
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Bond Enthalpy:
➢ Chemical reactions involve the breaking and making chemical bonds.
Energy is required to break a bond and energy is released when a bond is
formed. It is always positive.
∆rHΘ =∑ bond enthalpiesreactants –∑ bond enthalpiesproducts
Two types of bond enthalpies are:
➢ Bond dissociation enthalpy
➢ Mean bond enthalpy
Bond dissociation enthalpy:
Change in enthalpy when 1 mole of covalent bond of a gaseous
covalent compound is broken to form products in the gas phase.
Example
For diatomic molecules
Cl2 (g) → 2Cl (g); C-ClH = 242 kJ mol–1
O2 (g) → 2O (g); O-OH = 428 kJ mol–1
Mean bond enthalpy:
CH4 (g) → C (g) + 4H (g);
It is the mean value of bond enthalpies. aH = 1665 kJ mol–1
Example For polyatomic molecules
CH4 (g) → CH3 (g) + H (g); bondH = +427 kJ mol–1
CH3 (g) → CH2 (g) + H (g); bondH = +439 kJ mol–1
CH2 (g) → CH (g) + H (g); bondH = +452 kJ mol–1
CH (g) → C (g) + H (g); bondH = +347 kJ mol–1
CH4 (g) → C (g) + 4H (g); bondH = 1665 kJ mol–1
Mean bond enthalpy:
CH4 (g) → C (g) + 4H (g);
It is the mean value of bond enthalpies. aH = 1665 kJ mol–1
Example For polyatomic molecules
To calculate C-H H ,we use mean bond enthalpy of C-H bond
𝟏
C-H H =
H
𝟒 a
= 𝟏
×1665 kJ mol–1
𝟒
=
416 kJ mol–1
Calculation of enthalpy of reaction from B.E data
16
The B.E of gaseous H2, Cl2, and HCl are 104, 58, and 103 kcal/mol respectively. Calculate
the enthalpy of formation of HCl(g)?
17
The B.E of C=C, C-C, C-H and H-H are 147, 83, 99, and 104 kcal/mol. Calculate the heat
of hydrogenation of ethene?
18
The dissociation energy of CH4 is 360 kcal/mol and dissociation energy of ethane is 620
kcal/mol. Calculate the B.E of C-C.
19
Calculate the enthalpy of formation of ammonia from the following bond energy data.
N-H bond = 389 kJ/mol; H-H bond = 435 kJ/mol; N=N bond = 945.36 kJ/mol.
20
Calculate the standard enthalpy change (in kJ mol–1) for the reaction
H2(g) + O2(g) → H2O2(g),
given that bond enthalpy of H–H, O=O, O–H and O–O (in kJ mol–1) are respectively
438, 498, 464 and 138.
(a) –130 (b) –65 (c) +130 (d) –334
21
Given that bond energies of H–H and Cl–Cl are 430 kJ mol–1 and 240 kJ mol–1
respectively and ∆Hf HCl is – 90 kJ mol–1, bond enthalpy of HCl is
(a) 380 kJ mol–1 (b) 425 kJ mol–1 (c) 245 kJ mol–1 (d) 290 kJ mol–1
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