Energy cycles in reactions
Reactivity 1.2(SL/HL)
PART 2: Calculating ΔH via Bond Enthalpies & Hess’s Law
BOND ENTHALPIES
⚫ Enthalpy change (ΔH) can also be calculated directly from
bond enthalpies.
⚫ Specifically, in the case of a bond that is breaking, energy
must be absorbed.If breaking a bond requires energy,
then forming a bond must release energy to the
surroundings.
Example:
● Everyday experiences can help in
understanding chemistry concepts.
● Bond formation can be compared to two
magnets attracting each other.
● Holding the magnets apart and then letting
them ‘snap’ together represents bond
formation.
● The sound of the magnets hitting is like the
energy released when bonds form.
● Each chemical reaction involves the breaking and
forming of bonds, with an overall change in energy
● Figure 2 where those chemical species with higher
energy are less stable than those with lower
energy. So, for an exothermic reaction, the
products have less energy than the reactants and
therefore the products are more stable (and vice
versa for an endothermic reaction).
● Figure 2. Endothermic and exothermic enthalpy
diagrams comparing the stability of reactants and
products.
BOND ENTHALPIES
⚫ Breaking bonds: ΔH = positive (endothermic)
⚫ Forming bonds: ΔH = negative (exothermic)
⚫ Calculating ΔH from bond enthalpies:
ΔHreaction = Σ(bonds broken) - Σ(bonds formed)
Bond enthalpies are averages
• A hydrogen-to-hydrogen bond only exists within a hydrogen
molecule.
• Most covalent bonds, like C–H bonds, are present in many
molecules (e.g., hydrocarbons, sugars, amino acids).
• Bond enthalpies vary slightly for the same bond type in different
compounds.
• Breaking the first C–H bond in methane requires **439 kJ/mol**.
• For ethane and methanol, it requires **423 kJ/mol** and **402
kJ/mol**, respectively.
Each subsequent C–H bond in methane requires a different
energy to break.
• Listing bond strengths for every C–H bond in all compounds is
impractical.
• The average C–H bond enthalpy in methane is **415 kJ/mol**
(calculated as 1661 kJ/mol ÷ 4).
• Average values differ for other compounds.
Table of bond enthalpies
Example: Calculate ΔH for the
hydrogenation of ethane
(g) + H−H (g) (g)
Energy absorbed to break bonds: Energy released as bonds form:
C=C 612 C-C 348
4 C-H 4 x 412 2696 kJ 6 C-H 6 x 412 2820 kJ
H-H 436
There is more energy released than absorbed,
so the rxn is exothermic.
ΔH = 2696 – 2820 = -124 kJ mol-1
Example: Calculate ΔH for the
combustion of hydrazine in oxygen.
This reaction has been used to
power spacecraft.
(g) + O=O (g) N≡N (g) + 2 (g)
Energy absorbed to break bonds: Energy released as bonds form:
N-N 163 N≡N 944
4 N-H 4 x 388 2211 kJ 4 O-H 4 x 463 2796 kJ
O=O 496
There is more energy released than absorbed,
so the rxn is exothermic.
ΔH = 2211 – 2796 = -585 kJ mol-1
Limitations of Using
Average Bond Enthalpies
● Can only be used if all reactants and products are gases
● If H₂O is a liquid, ΔH must also be included
vap
● Average bond enthalpies are based on similar compounds
● Bond energy varies slightly due to neighboring atoms
● ΔH values from average bond enthalpies are not highly
accurate
HESS’ LAW
Published by Germain Henri Hess (1840)
Key Concept:
● Enthalpy change (ΔH) is determined by the final and initial
conditions, not the reaction steps.
Comparison to Climbing a Mountain:
● Different paths may lead to the top, but the total change in height
(enthalpy) is the same.
Relation to the Law of Conservation of Energy:
● Both state that energy is conserved during the reaction.
Practical Use:
● Helps calculate enthalpy changes using intermediate reactions
when direct measurement is difficult.
HESS’ LAW
The value of ΔH for a reaction is the same whether it
occurs in one step or in a series of steps.
ΔH for the overall equation is the sum of the ΔH’s for
the individual equations.
ΔHreaction = ΔH1 + ΔH2 + …
Example: Calculate the enthalpy of reaction, ΔHrxn, for
the formation of nitrogen monoxide from its elements
N2 + O2 → 2NO ΔHrxn = ?
Using these equations:
4NH3 + 3O2 → 2N2 + 6H2O ΔH = -1530 kJ flip
4NH3 + 5O2 → 4NO + 6H2O ΔH = -1170 kJ
2N2 + 6H2O → 4NH3 + 3O2 ΔH = +1530 kJ
2N2 + 2O2 → 4NO ΔH = +360 kJ ÷2
N2 + O2 → 2NO ΔH =+180 kJ
HESS’ LAW
● Another way of thinking about Hess’ Law is
graphically in terms of “energy cycles.”
● The enthalpy change for a reaction depends only
on the difference between the enthalpy of the
products and the enthalpy of the reactants. It is
independent of the reaction pathway.
HESS’ LAW
The enthalpy change going from A to B is the same
whether the reaction proceeds directly to A or
whether it goes via an intermediate.
ΔH1= ΔH2 + ΔH3
HESS’ LAW
For example, the enthalpy of combustion of both carbon and carbon
monoxide to form carbon dioxide can easily be measured directly, but
the combustion of carbon to carbon monoxide cannot. This can be
represented by an energy cycle.
ΔHx
C(s) + ½O2(g) CO(g)
-393 O2(g)
kJ mol-1 ½O2(g)
-283 kJ mol-1
CO2(g)
-393 = ΔHx + (-283)
ΔHx = -393 + 283 = -110 kJ mol-1
Example: Calculate the standard enthalpy change when one mole
of methane is formed from its elements in their standard states.
The standard enthalpies of combustion ( ) of carbon, hydrogen
and methane are -393, -286 and -890 kJ mol-1 respectively.
● Step 1: Write the equation for enthalpy change with
the unknown ΔH value. Call this value ΔHx.
ΔHx
C(s) + 2H2(g) CH4(g)
Example: Calculate the standard enthalpy change when one mole
of methane is formed from its elements in their standard states.
The standard enthalpies of combustion ( ) of carbon, hydrogen
and methane are -393, -286 and -890 kJ mol-1 respectively.
● Step 2: Construct an energy cycle showing the
different routes to the products (in this case the
products of combustion).
ΔHx
C(s) + 2H2(g) CH4(g)
O2(g) O2(g)
2O2(g)
CO2(g) + 2H2O(g)
Example: Calculate the standard enthalpy change when one mole
of methane is formed from its elements in their standard states.
The standard enthalpies of combustion ( ) of carbon, hydrogen
and methane are -393, -286 and -890 kJ mol-1 respectively.
● Step 3: Use Hess’ Law to equate the energy changes
for the two different routes.
ΔHx
C(s) + 2H2(g) CH4(g)
O2(g) O2(g)
2O2(g)
CO2(g) + 2H2O(g)
direct route route via methane
Example: Calculate the standard enthalpy change when one mole of
methane is formed from its elements in their standard states. The standard
enthalpies of combustion ( ) of carbon, hydrogen and methane are -393,
-286 and -890 kJ mol-1 respectively.
● Step 4: Rearrange the equation and substitute values to
solve for the unknown ΔH value.
