Experiment#2

Determination of heat of neutralization of an acid with a base.

Theory:

In chemical reactions, energy change is observed. This energy change is usually in the form of
heat and at constant pressure it is defined as heat of reaction or enthalpy change (ΔH). To form 1 mole
of compound from its constituent elements, necessary amount of enthalpy change occurs and this
change is defined as enthalpy of formation. If heat is released during the reaction, ΔH is shown with
negative sign and the reaction is called exothermic reaction. If heat is absorbed during the reaction, ΔH
is shown with positive sign and the reaction is called endothermic reaction.

Direct measurement of enthalpies of formation is difficult experimentally, so indirect methods

involving enthalpies of reaction are used. Hess’s Law states that the change in a thermodynamic
property such as enthalpy depends on the initial and final states and is independent of path followed.
An example for Hess’s Law is given below.

½ N2 (g) + 3/2 H2 → NH3 (g) ΔHformation (NH3(g)) = ΔH1

NH3 (g) → NH3 (aq) ΔH dissolving = ΔH2

Assume that ΔH1 and ΔH2 are known. If first and second reactions are added, net reaction
becomes;

½ N2(g) + 3/2 H2 → NH3(aq) ΔHformation (NH3(aq)) = ΔH1 + ΔH2

which is also formation reaction of NH3(aq).

Given that ΔH1 = - 45.8 kJ/mol and ΔH2 = - 35.4 kJ/mol, we can calculate the ΔH formation of
NH3(aq) as -81.2 kJ/mol.

The heat is measured experimentally by allowing the reaction to take place in a thermally
insulated vessel called as calorimeter. If the calorimeter is perfectly insulated, no heat change occurs
between system and surrounding and the system is defined as adiabatic (Q=0). Consequently, at
constant pressure, ΔHsystem is also equal to zero. The formulation of enthalpy change of the system,
ΔHsystem, is shown as in Equation (1).

ΔHsystem = ΔT (heat capacity of calorimeter + heat capacity of contents

For endothermic reaction in adiabatic system, Equation (1) can be written as below.

ΔHsystem = nΔHreaction + CpΔT

0 = nΔHreaction + CpΔT

nΔHreaction = - CpΔT

In a similar manner, for exothermic reaction in an adiabatic system, Equation (1) can be
simplified as:

ΔHsystem = - nΔHreaction + CpΔT

 0 = -nΔHreaction + CpΔT

nΔHreaction = CpΔT

In this experiment, you will determine the heat of formation of various ammonium salts NH4X(s)
where X is Cl, NO3 or SO4 by combining measurements of the heat for the neutralization reaction;

NH3(aq) + HX(s) → NH4X(aq) ΔHneut

And the heat of the dissolution reaction;

NH4X(s) + H2O → NH4X(aq) ΔHdiss

with known heats of formation of NH3(aq) and HX(aq).

Chemicals:

1.5 M Ammonia solution, 1.5 M Nitric acid solution, Ammonium nitrate salt

Apparatus:

Calorimeter, thermometer, beaker, Graduated cylinder, electric balance

Procedure:

1. Obtain a Styrofoam cup. In the first cup, place 50 mL of 1.5 M NH3.

2. Place a thermometer in the cup containing the NH3 and record temperature at 30
seconds intervals.
3. Add the acid solution to the NH3 and swirl to mix. Continue taking temperature data at 30
seconds intervals while swirling the solution occasionally.
4. Place a volume of distilled water equal to the final volume of solution from part (A) in a
Styrofoam cup and record temperature data at 30 seconds intervals.
5. Weigh out that mass of NH4NO3 salt into a clean, dry beaker.
6. Immediately, add the weighed amount of salt, swirl to dissolve (use stirring rod if
necessary), and continue taking temperature data at 30 seconds intervals.
7.

Short questions:

1. Define acid and base.

Answer:
There are three main theories that defines acids and bases in different manners. These theories
include the Arrhenius theory, the Bronsted-Lowry theory, and the Lewis theory of acids and bases.
Acids and bases can be defined via three different theories.
 The Arrhenius theory of acids and bases states that “an acid generates H+ ions in a solution
whereas a base produces an OH– ion in its solution”.
 The Bronsted-Lowry theory defines “an acid as a proton donor and a base as a
proton acceptor”.
 Finally, the Lewis definition of acids and bases describes “acids as electron-pair acceptors and
bases as electron-pair donors”.
2. Define neutralization reaction and heat of neutralization.
Answer:
A neutralization reaction is when an acid and a base react to form water and a salt as the products
of the reaction along with generation of heat. Neutralization reactions actually take place between
the acidic proton from the acid and the hydroxyl group of the base to generate water (H + and OH-
react to form H2O). The concentrations of the acid and base are the determining factors for the
volumes of the individual to be taken.
Acid + Base →→ Salt + Water
For example,
HCl + NaOH →→ NaCl + H2O

Types of Neutralization Reactions

Now, there are four types of neutralization reactions:

1. Strong acid and strong base

2. Strong acid and weak base
3. Weak acid and strong base
4. Weak acid and weak base

Heat of neutralization:
Enthalpy of neutralization is the heat evolved when one gram equivalent of the acid is completely
neutralized by a base in dilute solution.

When an acid reacts with a base a chemical reaction take place, called neutralization reaction, and heat
is evolved which is known as heat of neutralization.

Heat of Neutralization is expressed in kJ/mol of water. Neutralization reactions are generally exothermic
and thus ∆H is negative.

3. What is calorimeter?
Answer:

A calorimeter is a device used for heat measurements evolved or absorbed during a chemical reaction.
And the process is known as calorimetry.

Calorimeter mainly consists of a metallic vessel made of materials which are good conductors of
electricity such as copper and aluminium etc. There is also a facility for stirring the contents of the
vessel. This metallic vessel with a stirrer is kept in an insulating jacket to prevent heat loss to the
environment. There is just one opening through which a thermometer can be inserted to measure the
change in thermal properties inside.

Problem: A reaction of 100mL of 1.35M HCl and 100mL of 1.76M NaOH is monitored and the
following temperatures were recorded: starting temperature = 24.6 oC; and final temperature =
38.8 oC. Calculate the ΔH of this reaction.
Given that:
Cp of solution (J/K) = 4.13 J/( g . K)*Volume of solution in mL (1 mL ≈ 1 g for aqueous solution)
 Cp of calorimeter (J/K) = 50
Q = (-total Cp* ΔT) ΔT = Tf - Ti
ΔH = Q/n n = # of moles reacted
Soluton:

1. Determine the change in temperature for the system.

ΔT = Tf – Ti = 38.8 oC – 24.6 oC = 14.2 oC
Since we calculated ΔT,
So 14.2 oC = 14.2 K
2. Determine the Cp of the solution (J/K).
Cp (soln) = 4.13 x 200 ml
Cp (soln) = 826 J/K
3. Determine the total Cp of the system.
Cp (sys) = Cp (soln) + Cp (cal)
Cp (soln) = (826 +50)
= 876 J/K
4. Determine the number of moles of the acid and the base. Which is the limiting
reagent? Moles of HCL in 100ml
1.35 M = 1.35 mole / L = (1.35 mole/ 1000 ml)*100ml
= 0.135 mole
Moles of NaOH in 100ml
1.76 M = 1.76 mole / L = 1.76 mole/ 1000 ml = (1.76 mole/ 1000 ml)*100ml
= 0.176 mole
Since HCl is the limiting reagent, the moles of solution is 0.135 mole.
5. Determine the Heat Transfer, Q, for the reaction.
Q = (-876) (14.2)
Q = -12,439.2 joule
6. Determine the change in enthalpy, ΔH, for the reaction.
ΔH = -12,439.2 / 0.135
ΔH = -92,142 joule / mole