Context

• We can use calorimetry to calculate the heat

absorbed or released by a chemical reaction
• We know collision theory – we also know that
Thermochemistry not all chemical reactions necessarily happen in
5.2 - Hess’s Law one step
5.1 - Enthalpies of Formation • Do we need to worry all of the steps, or just the
final result?
• Can we apply this concept to determine other,
unknown quantities?

Enthalpy Hess’s Law

• .. is a state function • “In going from a particular set of reactants to a
• .. A function whose change depends on the initial particular set of products, the change in
and final states and not on how one got from the enthalpy is the same whether the reaction takes
initial to the final state. place in one step or a series of steps.”
• .. Is independent of the pathway of the reaction
• ..No matter what series of steps is involved, the
overall enthalpy change is the same for a given
set of reactants and products.

Example: NO2
• Nitrogen dioxide can be made:
N2(g) + 2O2(g)  2NO2(g) ΔH1 = 68 kJ
• The reaction can also have two steps:
N2(g) + O2(g)  2NO(g) ΔH2 = 180 kJ
2NO(g) + O2(g)  2NO2(g) ΔH3 = -112 kJ
• Note that the sum of the two gives the net
reaction
• ΔH1 = ΔH2 + ΔH3

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Energy Cycles
• This idea can also be represented as a cycle,
written clockwise, showing the steps and overall
enthalpy change:
Tips for Hess’s Law Problems
• See a reaction, but desire the reverse?
▫ If a reaction takes place in the opposite
direction, ΔH is reversed
• Need a step to happen more than once?
▫ The magnitude of ΔH is directly proportional
to the balanced chemical equation.
Helpful Reactions
• C(graphite) + O2(g)  CO2(g)
ΔH°rxn = -393.5 kJ
• H2(g) + ½ O2(g)  H2O(l)
ΔH°rxn = -285.8 kJ
• 2 C2H2(g) + 5 O2(g)  4 CO2(g) + 2 H2O(l)
ΔH°rxn = -2598.8 kJ
TARGET : 2 C(graphite) + H2(g)  C2H2(g) ΔH° = ???
Applications of Hess’s Law
• If we want to know the enthalpy change of a new
reaction, we can use the “pieces” or steps to
figure it out!
• Lots of thermochemical data is known and can
be looked up.
Example 2
2 C(graphite) + H2(g)  C2H2(g) ΔH° = ???
• You decide you want to avert the energy crisis
and save the world by converting pencils into
acetylene gas
• But, would this be energy efficient? What is the
enthalpy change here?
• (and you cannot access Google)
• But, other reactions have been well studied …
Flip Equations!
• C(graphite) + O2(g)  CO2(g)
ΔH°rxn = -393.5 kJ
• H2(g) + ½ O2(g)  H2O(l)
ΔH°rxn = -285.8 kJ
• 4 CO2(g) + 2 H2O(l)  2 C2H2(g) + 5O2(g)
ΔH°rxn = +2598.8 kJ
TARGET : 2 C(graphite) + H2(g)  C2H2(g) ΔH° = ???
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Make Sides Equal Result
• 4C(graphite) + 4O2(g)  4CO2(g) • Gives:
ΔH°rxn = -(4)393.5 kJ 4C(graphite) + 2H2(g)  2 C2H2(g)
• 2H2(g) + O2(g)  2H2O(l)
ΔH°rxn = -(2)285.8 kJ ΔH°rxn = -(4)393.5 kJ + -(2)285.8 kJ +
• 4 CO2(g) + 2 H2O(l)  2 C2H2(g) + 5O2(g) +2598.8 kJ
ΔH°rxn = +2598.8 kJ ΔH°rxn = +453.2 kJ
TARGET : 2 C(graphite) + H2(g)  C2H2(g) ΔH° = ??? TARGET : 2 C(graphite) + H2(g)  C2H2(g) ΔH° = ???

Final Answer Important Known Data

• Enthalpy of formation needs to be in kJ per mole • When we determine values indirectly by Hess’s
Therefore, law, we often look up known values
2C(graphite) + H2(g)  C2H2(g) • One important set of known values are called
ΔH°f = +226.6 kJ/mol Enthalpies of Formation

ΔH°f
Elements in Standard States
• Enthalpy of Formation
• Given the definition of enthalpy of formation,
• The change in enthalpy that accompanies the
the enthalpy of formation of elements in their
formation of one mole of a compound from
standard state is…
elements with all substances in their standard
• Zero!
states.
• ΔH°f for O2(g) = Zero!
• ° = standard conditions, 298 K, 100 kPa
• ΔH°f for Na(s) = Zero!
• e.g. Enthalpy of formation of NO2
• ΔH°f for Br2(l) = Zero!
½ N2(g) + O2(g)  NO2(g) ΔH°f = 34 kJ/mol
• ΔH°f for H2O(l) = Not Zero!
• But what about N2?
• ΔH°f for Na+(aq) = Not Zero!

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Consider this ...
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
 From Hess, we know that the actual path of
steps that may be involved is not important.
With no other data, we can calculate ΔH°rxn
usings ΔH°f for each species.
How? All other species will cancel out! Prove it
to yourself!
Symbols Galore
 ΔH°rxn = ∑ ΔH°f products - ∑ ΔH°f reactants
The enthalpy change for a given reaction
can be calculated by subtracting the
enthalpies of formation of the reactants
from that of the products
Apply the co-efficients from the balanced
chemical equation

But... Proof - Back to Methane

• Where can I find information on standard
enthalpies of formation?
• Data Booklet – always provided
• Your job to recognize elements in their standard
states
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
We can look up:
ΔH°f methane= -75 kJ/mol
ΔH°f oxygen gas= 0
ΔH°f carbon dioxide= -394 kJ/mol
ΔH°f liquid water= -286 kJ/mol

Given the heats of the following reactions:

∆H° (kJ)
So ...
P4(s) + 6Cl2(g) → 4PCl3(g) –1225.6
ΔH°rxn = ∑ ΔH°products - ∑ ΔH°reactants
P4(s) + 5O2(g) → P4O10(s) –2967.3
ΔH°rxn = [2(-286 kJ/mol) + (-394 kJ/mol)] – [-75 PCl3(g) + Cl2(g) → PCl5(g) –84.2
kJ/mol + 0] PCl3(g) + (1/2)O2(g) → Cl3PO(g) –285.7

ΔH°rxn = -891 kJ/mol

Calculate the value of ∆H° for the reaction below:

TIME TO PRACTICE! P4O10(s) + 6PCl5(g) → 10Cl3PO(g)

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Given the heats of the following reactions:
∆H° (kJ)
I. P4(s) + 6Cl2(g) → 4PCl3(g) –1225.6
II. P4(s) + 5O2(g) → P4O10(s) –2967.3
III. PCl3(g) + Cl2(g) → PCl5(g) –84.2
IV. PCl3(g) + (1/2)O2(g) → Cl3PO(g) –285.7

Calculate the value of ∆H° for the reaction below:

P4O10(s) + 6PCl5(g) → 10Cl3PO(g)