Heat (enthalpy) of Reaction

Key Concepts

Enthalpy of Reaction (Heat of Reaction) is the heat

liberated or the heat absorbed when a chemical
reaction takes place.
An exothermic reaction liberates heat,
temperature of the reaction mixture
increases.
An endothermic reaction absorbs
heat, temperature of the reaction
mixture decreases.

The units of enthalpy of reaction, or heat of reaction, are kJ mol-1 for a specified
reactant or product.
The enthalpy (heat) of reaction for a neutralisation reaction is known as the enthalpy
(heat) of neutralisation.
The enthalpy (heat) of reaction for a solute dissolving in a solvent is known as
theenthalpy (heat) of solution.
The enthalpy (heat) of reaction for a precipitation reaction is known as the enthalpy
(heat) of precipitation.
Enthalpy (heat) of reaction can be measured experimentally.

Measuring Heat of Reaction Experimentally

a. A known quantity of reactant is placed in a well insulated vessel (eg,
a polystyrene foam cup, that is, a styrofoam cup)
b. The initial temperature of this reactant is recorded, Ti.
c. A known quantity of the second reactant is added, the vessel is sealed with a lid and
the reaction mixture stirred.
d. The final temperature of the reaction mixture is recorded, Tf.
e. The the heat released or absorbed (the heat change) q, in joules (J), for the reaction is
calculated:
heat change = mass specific heat capacity temperature change
q = m cg T

f.

The enthalpy change, H, in kJ per mole of a given reactant for the reaction is
calculated:
H = heat change/1000 moles
H = q/1000 n
exothermic reactions: H is negative

endothermic reactions: H is positive

Common assumptions for reaction mixtures made up of aqueous solutions:

density of aqueous solution assumed to be the same as for water, 1 g mL-1 at 25C
eg, 100 mL of solution is said to have a mass of 100 g
additivity of volumes of reactants in solution is assumed
eg, 100 mL of "reactant a(aq)" + 200 mL of "reactant b(aq)" = 300 mL of "aqueous
solution"
specific heat capacity of the reaction mixture assumed to be the same as water,
ie, specific heat capacity = 4.184 JK-1g-1
Heat is not lost to, or absorbed by, the surroundings.

Typically, the calculation for heat released or absorbed, q, for the reaction of aqueous solutions
is measured in units of joules (J):
q = (mass in grams of "reactant a" + mass in grams of "reactant b") x 4.184 x (Tfinal - Tinitial)
Enthalpy (heat) of Reaction in kJ mol-1 = q/1000 moles of reactant
For a reaction that liberates heat, an exothermic reaction, H is negative.
For a reaction that absorbs heat, an endothermic reaction, H is positive.
Heat of Solution Example
In an experiment, 1.2 g of sodium hydroxide pellets, NaOH(s), were dissolved in 100 mL of
water at 25oC.
The temperature of the water rose to 27.5oC.
Calculate the enthalpy change (heat of solution) for the reaction in kJ mol-1 of solute.
a. Calculate the heat released, q, in joules (J), by the reaction:
q = mass(water) x specific heat capacity(water) x change in temperature(solution)
q = mH2O(l) x cg x (Tf - Ti)
q = 100 x 4.184 x (27.5 - 25) = 1046 J
b. Calculate the moles of solute (NaOH(s)):
moles = mass molar mass
moles (NaOH) = 1.2 (22.99 + 16.00 + 1.008) = 0.030 mol
c. Calculate the enthalpy change, H, in kJ mol-1 of solute:
H = -q/1000 n(solute) = -1046/1000 0.030 = -35 kJ mol-1
H is negative because the reaction is exothermic (energy is released causing the

temperature of the solution to increase).

Heat of Neutralisation Example

In an experiment to determine H for the neutralisation reaction:
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
The following results were obtained:
Mass of 100 mL of 0.50 mol L-1 HCl (ma)

= 100 g

Mass of 100 mL of 0.50 mol L-1 NaOH (mb)

= 100 g

Initial Temperature (Ti)

= 20.1oC

Final Temperature (Tf)

= 23.4oC

Specific heat capacity of solutions (cg)

= 4.184 JK-1g-1

Calculate H in kJ mol-1 of water formed for the reaction.

a.

Calculate the heat released, q, in Joules (J) by the neutralisation reaction:

q = mass(reaction mixture) x specific heat capacity(water) x change in
temperature(solution)
q = (ma + mb) x cg x (Tf - Ti)
q = (100 + 100) x 4.184 x (23.4 - 20.1) = 200 x 4.184 x 3.3 = 2761.44 J

b.

Calculate the moles of reactants:

moles = molarity x volume
moles (NaOH) = 0.50 mol L-1 x (100 x 10-3) L = 0.05 mol
moles (HCl) = 0.50 mol L-1 x (100 x 10-3) L = 0.05 mol
NaOH(aq) and HCl(aq) are in 1:1 mole ratio which is an exact stoichiometric ratio as
shown by the neutralisation equation.
0.05 mole of NaOH(aq) reacts with 0.05 mole HCl(aq) to produce 0.05 mole of water.

c.

Calculate the enthalpy (heat) of reaction, H, in kJ mol-1

Since the reactants are present in a 1:1 stoichiometric ratio, 0.05 mole of NaOH(aq)
reacts with 0.05 mole HCl(aq) to produce 0.05 mole of water, moles (n) = 0.05 mol
H = -q/1000 n = -2761.44/1000 0.05 = -55.2 kJ mol-1
H is negative because the reaction is exothermic.

Heat of Precipitation Example

50 mL of 0.20 mol L-1 lead(II) nitrate solution, Pb(NO3)2(aq), at 19.6oC was added to 30 mL of a
solution containing excess potassium iodide, KI(aq) also at 19.6oC.
The solutions reacted to form a yellow lead(II) iodide precipitate, PbI2(s), and the temperature
of the reaction mixture increased to 22.2oC.
Pb(NO3)2(aq) + 2KI(aq) PbI2(s) + 2KNO3(aq)
Calculate the enthalpy change per mole of lead(II) iodide precipitated for the reaction.
a. Calculate the heat released, q, in Joules (J), by the precipitation reaction:
q = mass x specific heat capacity x change in temperature
q = [mPb(NO3)2(aq) + mKI(aq)] x cg x (Tf - Ti)
q = [50 + 30] x 4.184 x (22.2 - 19.6) = 870.27 J
b. Calculate the moles of species specified, n(PbI2(s)):
From the equation, 1 mole Pb(NO3)2(aq) reacts with excess KI(aq) to produce 1 mol PbI2(s)
moles Pb(NO3)2(aq) = moles PbI2(s)
n(Pb(NO3)2(aq)) = n(PbI2(s))
n(Pb(NO3)2(aq)) = molarity x volume
n = moles(Pb(NO3)2(aq)) = moles(PbI2(s))= 0.20 x 50 x 10-3 = 0.010 mol
c. Calculate the enthalpy (heat) of precipitation, H, in kJ mol-1 of PbI2(s):
H = -q/1000 n
H = -0.870/1000 0.010 = -87 kJ mol-1
H is negative because the reaction is exothermic (energy was released causing the
temperature to increase).