HESS’S LAW AND BOND ENTHALPY
Concept and calculation
HESS’S LAW
Hess’s law is an application of the
conservation energy law: “Regardless
of the route by which a chemical
reaction proceeds, the enthalpy
change will always be the same
providing the initial and final states of
the system are the same”
HESS' LAW STATES THAT : “THE HEAT EVOLVED OR ABSORBED IN A
CHEMICAL PROCESS IS THE SAME WHETHER THE PROCESS TAKES
PLACE IN ONE OR IN SEVERAL STEPS”.
THIS IS ALSO KNOWN AS THE LAW OF CONSTANT HEAT
SUMMATION.
WORKED EXAMPLE
Calculate the enthalpy for this reaction:
2C(s) + H2(g) ---> C2H2(g) ΔH° = ??? kJ
Given the following thermochemical equations:
C2H2(g) + (5/2)O2(g) ---> 2CO2(g) + H2O(ℓ) ΔH° = -1299.5 kJ
C(s) + O2(g) ---> CO2(g)
ΔH° = -393.5 kJ
H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -
285.8 kJ
WORKED EXAMPLE
Solution:
1) Determine what we must do to the three given equations to get our target equation:
a) first eq: flip it so as to put C2H2 on the product side
b) second eq: multiply it by two to get 2C
c) third eq: do nothing. We need one H2 on the reactant side and that's what we have.
2) Rewrite all three equations with changes applied:
2CO2(g) + H2O(ℓ) ---> C2H2(g) + (5/2)O2(g) ΔH° = +1299.5 kJ
2C(s) + 2O2(g) ---> 2CO2(g) ΔH° = -787 kJ
H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -285.8 kJ
Notice that the ΔH values changed as well.
3) Examine what cancels:
2CO2 ⇒ first & second equation
H2O ⇒ first & third equation
(5/2)O2 ⇒ first & sum of second and third equation
4) Add up ΔH values for our answer: +1299.5 kJ + (-787 kJ) + (-285.8 kJ) = +226.7 kJ
QUESTION
Calculate the enthalpy of the following chemical reaction:
CS2(ℓ) + 3O2(g) ---> CO2(g) + 2SO2(g)
Given:
C(s) + O2(g) ---> CO2(g) ΔH = -393.5 kJ/mol
S(s) + O2(g) ---> SO2(g) ΔH = -296.8 kJ/mol
C(s) + 2S(s) ---> CS2(ℓ) ΔH = +87.9 kJ/mol
THE BORN-HABER CYCLE
➤ Definition:
The lattice energy is the energy required to break apart
an ionic solid and convert its component atoms into
gaseous ions.
This definition causes the value for the lattice energy to
always be positive, since this will always be an
endothermic reaction. The other definition says that
lattice energy is the reverse process, meaning it is the
energy released when gaseous ions bind to form an ionic
solid. As implied in the definition, this process will always
be exothermic, and thus the value for lattice energy will
be negative. Its values are usually expressed with the
units kJ/mol.
THE BORN-HABER CYCLE
Heat of formation= Heat of atomization+ Dissociation energy+
(sum of Ionization energies)+ (sum of Electron
affinities)+ Lattice energy
THE BORN-HABER CYCLE
➤ Born-Haber Cycle can be reduced to a single equation:
Heat of formation= Heat of atomization+ Dissociation energy+ (sum
of Ionization energies)+ (sum of Electron affinities)+
Lattice energy
*Note: In this general equation, the electron affinity is
added. However, when plugging in a value, determine
whether energy is released (exothermic reaction) or
absorbed (endothermic reaction) for each electron affinity.
If energy is released, put a negative sign in front of the
value; if energy is absorbed, the value should be positive.
➤ Rearrangement to solve for lattice energy gives the
equation:
Lattice energy= Heat of formation- Heat of atomization- Dissociation
energy- (sum of Ionization energies)- (sum of Electron Affinities)
Heat of formation= Heat of atomization+ Dissociation energy+
(sum of Ionization energies)+ (sum of Electron
affinities)+ Lattice energy
Or
Lattice energy= Heat of formation- Heat of atomization-
Dissociation energy- (sum of Ionization energies)- (sum of
Electron Affinities)
BOND ENTHALPY
concept and calculation
BOND ENTHALPY
➤ Definition: energy required to break one mol of bonds
on gaseous covalent molecules under standard
conditions.
➤ Bond enthalpy is also referred to as bond dissociation
enthalpy (values are provided in section 11 of
Chemistry Data Booklet)
➤ These data are average values and are therefore only
an approximation. They are derived from experimental
data involving the breaking of the same bond found in
a wide variety of compounds.
WORKED EXAMPLE
WORKED EXAMPLE
➤Bond energies refer to breaking
(endothermic) or making
(exothermic) one mole of bonds.
➤Each bond has a typical value
➤During a chemical reaction,
energy must be supplied to
break chemical bonds in the
molecules, this the endothermic
➤When the new molecules are
formed, new bonds must be
made in the process, this is the
exothermic
➤The overall energy change for a
reaction (ΔH) is the overall
energy net change from the
bond making and bond forming
processes.
WORKED EXAMPLE
