Energy and Enthalpy

Conservation of Energy

Mechanical work is defined as

work = force × distance

work = mass × acceleration × distance

∆E = q+w

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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:

q < 0 for an exothermic reaction

Endothermic reactions require heat from the surroundings to

flow into the system.

q > 0 for an endothermic reaction

The change in enthalpy is equal to the heat transferred to a system

during a reaction (broadly defined) at constant external pressure.

qP (heat at constant pressure) = ∆H

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

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 3. Since ∆H = 0 for a reaction that does nothing:

A −→ A

and this is independent of path:

A −→ B −→ A

it follows that

0 = ∆HA→A = ∆HA→B + ∆HB→A

and so
∆HB→A = −∆HA→B

We can manipulate and add up reaction enthalpies in useful

ways:
∆H= −74.8 kJ/mol C(s) + 2H2 (g)−→CH4 (g)
1
∆H=−285.8 kJ/mol 2 O2 (g) + H2 (g)−→H2 O(g)
∆H=−373.5 kJ/mol C(s) + O2 (g)−→CO2 (g)

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Now, if we want the enthalpy for the reaction

CH4 (g) + 2O2 (g) −→ CO2 (g) + 2H2 O(g)

We can instead add up the energies for a multi-step reaction (which

would never actually happen this way).

∆H = 74.8 − 373.5 − 2 · 285.8 = −870.3 kJ mol−1

This is an enthalpy of combustion: the reaction with oxygen to
form carbon dioxide and water.

Standard Enthalpies of Formation

The process above is the one used for enthalpies of formation:
The enthalpy for any chemical reaction can be calcu-
lated if we know the enthalpies for forming (and thus
for breaking down) any compound from its component
elements.

The enthalpy for the two-step reaction:

reactants −→ component elements −→ products

is just
∆Hrxn = ∆Hf (products) − ∆Hf (reactants)

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 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.

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Enthalpies of Solution

We define the enthalpy of solution to be the heat released or re-

quired for:
solute(s) + solvent(l) −→ solution(l)
Solvation can be an exothermic process (it’s −44.2 kJ/mol for
NaOH) or it can be endothermic (+3.9 kJ/mol for NaCl).

You can also get enthalpies of solution using enthalpies of for-

mation, provided you have these for the aqueous species. We take
H O
2
NaOH(s) −→ Na+ (aq) + OH− (aq)

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

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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.

A few example values

C–H 410 kJ/mol
C–Cl 331 kJ/mol
H–Cl 431 kJ/mol
Cl–Cl 243 kJ/mol

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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 )

We define the molar heat capacity where for n moles of a substance,

q = nCp ∆T

We also use the specific heat, where for m grams of a substance,

q = mCs ∆T

The specific heat divided by the density will give the molar heat
capacity.