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L13 Energy Enthalpy
L13 Energy Enthalpy
Conservation of Energy
∆E = q+w
1
Enthalpy
We define heat flow in a chemical reaction by whether heat moves
from the system to its surroundings, or from the surroundings to
the system:
Exothermic reactions release heat from the system into the sur-
roundings. By definition:
At constant pressure,
w = −P ∆V
2
which leads to
H = E + PV
Hess’s Law
There is a simple way to state Hess’s Law: enthalpy is a state
function. As a result:
1. The change in enthalpy for a reaction only depends on its
initial and final states (reactants and products), not on the
path taken.
2. If we have two reaction paths:
A −→ B −→ C
and
A −→ C
then
∆HA→C = ∆HA→B + ∆HB→C
3
3. Since ∆H = 0 for a reaction that does nothing:
A −→ A
A −→ B −→ A
it follows that
and so
∆HB→A = −∆HA→B
4
Now, if we want the enthalpy for the reaction
is just
∆Hrxn = ∆Hf (products) − ∆Hf (reactants)
5
We calculate standard enthalpies of reaction from standard en-
thalpies of formation, as we’ve already seen for the combustion of
methane. We can generalize for a reaction:
aA + bB −→ cC + dD
we have
◦
∆Hrxn = c∆Hf◦ (C) + d∆Hf◦ (D) − a∆Hf◦ (A) − b∆Hf◦ (B)
and this generalizes further if there are more products and more
reagents.
6
Enthalpies of Solution
This gives us
◦
∆Hsol = ∆Hf◦ (Na+ (aq)) + ∆Hf◦ (OH− (aq)) − ∆Hf◦ (NaOH(g))
= [(−240.1) + (−230.0) − (−425.93)] kJ mol− 1
= −44.17 kJ mol− 1
7
Bond Enthalpies
A sometimes-useful simplification is to describe molecules in terms
of bond enthalpies. The idea behind this is that a reaction that
involves a single bond might not depend on the rest of the molecule.
8
Heat Capacity and Specific Heat
When heat goes from the surroundings to the system, the tem-
perature of the system rises; when heat leaves the system, the
system temperature drops. How much the temperature rises or
drops depends on the heat capacity, C, an extensive property of
the material(s) of which the system is composed. We write
q
Tfinal − Tinitial =
C
In terms of units, we have
q(J)
(Tfinal − Tinitial ) (K) =
C(J K−1 )
q = nCp ∆T
q = mCs ∆T
The specific heat divided by the density will give the molar heat
capacity.