Enthalpy of a

Reaction
Learning Objectives
a. Define enthalpy.
b. Properly express the enthalpy
change of chemical reactions.
c. Explain how enthalpy changes are
measured experimentally.
In the study of gases and work indicate that
conditions like pressure, volume, and
temperature affect the energy content of a
system.
What we need is a definition of energy that
holds when some of these conditions are
specified (somewhat similar to our definition of
standard temperature and pressure in the study
of gases).
We define the enthalpy change (ΔH)
as the heat of a process when
pressure
ΔH =isq held constant. pressure
at constant
• The letter H stands for “enthalpy,” a kind of
energy, while the Δ implies a change in the quantity.
• We will always be interested in the change in H, rather than
the absolute value of H itself.
• When a chemical reaction occurs, there is a characteristic
change in enthalpy.
• The enthalpy change for a reaction is typically written after a
balanced chemical equation and on the same line.
For example:
When two moles of hydrogen react with one
mole of oxygen to make two moles of water,
the characteristic enthalpy change is 570 kJ.

We write the equation as:

2 H2(g) + O2(g) → 2 H2O(ℓ) ΔH = −570 kJ

A chemical equation that includes an enthalpy
change is called a thermochemical equation.

A thermochemical equation is assumed to refer

to the equation in molar quantities, which
means it must be interpreted in terms of
moles, not individual molecules.
Write the thermochemical equation for the
reaction of PCl3(g) with Cl2(g) to make
PCl5(g), which has an enthalpy
change of −88 kJ.
Solution:
The thermochemical equation is:
PCl3(g) + Cl2(g) → PCl5(g) ΔH = −88 kJ
PCl3(g) + Cl2(g) → PCl5(g) ΔH =
−88may
You kJ have noticed that the
ΔH for a chemical reaction may be
positive or negative. The number is
assumed to be positive if it has no sign;
a + sign can be added explicitly to avoid
confusion.
PCl3(g) + Cl2(g) → PCl5(g) ΔH =
−88 kJ
A chemical reaction that has a
positive ΔH is said to be endothermic,
while a chemical reaction that has a
negative ΔH is said to be exothermic.
What does it mean if the ΔH of a
process is positive?
It means that the system in which the chemical
reaction is occurring is gaining energy. If one
considers the energy of a system as being
represented as a height on a vertical energy
plot, the enthalpy change that accompanies the
reaction can be diagrammed as in part (a) in
Figure 1. “Reaction Energy”: the energy of
the reactants has some energy, and the system
increases its energy as it goes to products.
The products are higher on the vertical scale
than the reactants. Endothermic, then,
implies that the system gains, or absorbs,
energy.
• An opposite situation exists for an
exothermic process.
• If the enthalpy change of a
reaction is negative, the
system is losing energy, so the
products have less energy than
the reactants, and the products
are lower on the vertical energy
scale than the reactants are.
• Exothermic, then, implies that the
system loses, or gives off, energy.
 In an endothermic reaction, the energy
of the system increases (i.e., moves
higher on the vertical scale of
energy).
 In an exothermic reaction, the energy of
the system decreases (i.e., moves lower
on the vertical
scale of energy).
Example
Consider this thermochemical equation:
2 CO(g) + O2(g) → 2 CO2(g) ΔH =
−565 kJ
Is it exothermic or endothermic? How
much energy is given off or absorbed?
Solution:
By definition, a chemical
reaction that has a negative
ΔH is exothermic, in this case,:
565 kJ—is given off by the reaction.
How are ΔH values measured experimentally?

Actually, ΔH is not measured; q is

measured. But the measurements are
performed under conditions of constant
pressure, so ΔH is equal to the q
measured.
How are ΔH values measured
experimentally?
Actually, ΔH is not measured; q is measured.
But the measurements are performed under
conditions of constant pressure, so ΔH is
equal to the q measured.
Experimentally, q is measured by taking
advantage of the equation
q = mcΔT
We premeasure the mass of the chemicals in a
system. Then we let the chemical reaction occur
and measure the change in temperature (ΔT)
of the system. If we know the specific heat of the
materials in the system (typically, we do), we can
calculate q. That value of q is numerically equal
to the ΔH of the process, which we can scale up
to a molar scale. The container in which the system
resides is typically insulated, so any energy change
goes into changing the temperature of the
system, rather than being leaked from the
system. The container is referred to as a calorimeter,
and the process of measuring changes in enthalpy is
called calorimetry.
Example
Suppose 4.0 g of NaOH, or 0.10 mol of NaOH, are dissolved to
make 100.0 mL of aqueous solution, while 3.65 g of HCl, or
0.10 mol of HCl, are dissolved to make another 100.0 mL of
aqueous solution. The two solutions are mixed in an insulated
calorimeter, a thermometer is inserted, and the calorimeter is
covered like the example setup.
The thermometer measures the temperature change as the
following chemical reaction occurs:
NaOH (aq) + HCl(aq) → NaCl(aq) + H2O(ℓ)
An observer notes that the temperature increases from 22.4°C to 29.1°C. Assuming
that the heat capacities and densities of the solutions are the same as those of pure
water, we now have the information we need to determine the enthalpy change of
the chemical reaction.
The total amount of solution is 200.0 mL, and with a density of 1.00 g/mL, we thus
have 200.0 g of solution. Using the equation for q, we substitute for our
experimental measurements and the specific heat of water.

Solving for q, we get:

q = 5,600 J ≡ ΔH for the reaction
The heat q is equal to the ΔH for the
reaction because the chemical reaction
occurs at constant pressure.
However, the reaction is giving off this
amount of energy, so the actual sign on
ΔH is negative:
ΔH = −5,600 J for the reaction
Example
A 100 mL solution of 0.25 mol of
Ca2+(aq) was mixed with 0.50
mol of F−(aq) ions, and CaF2 was
precipitated:

Ca2+(aq) + 2 F−(aq) → CaF2(s)

The temperature of the solution increased
by 10.5°C. What was the enthalpy change
for the chemical reaction? Assume that the
solution has the same density and specific
heat as water.
Solution:
Because we are given ΔT directly, we can
determine the heat of the reaction, which is
equal to ΔH:
Solving for q, we get:
q = 4,400 J
Therefore, ΔH = −4,400 J
KEYPOINTS:
Every chemical reaction occurs with a
concurrent change in energy.
The change in enthalpy equals heat at
constant pressure.
Enthalpy changes can be expressed by using
thermochemical equations.
Enthalpy changes are measured by using
calorimetry.