DETERMINING THE ENTHALPY OF FORMATION OF CaCO3

Standard Enthalpy Change

Standard Enthalpy Change for a reaction, symbolized as H0298 , is defined as

The enthalpy change when the molar quantities of reactants shown in a balanced
chemical equation completely react to from products under standard conditions.

Standard conditions are as follows:

- a pressure of 1 atmosphere
- a temperature of 298 K
- if solution is used, 1M is specified.
- Elements or compounds in their normal stable state

Example

H2(g) + 1/2 O2(g)  H2O(l) H0 = -285.9 kJ mol-1

When one mole of hydrogen and half mole of oxygen react to form one mole water,
285.9 kJ of heat are evolved under standard conditions. This is an exothermic reaction.

All the substance involved must be in their normal physical states under standard
conditions. The enthalpy of all elements in their most stable form and standard state is
conventionally taken as zero. For example,

H0298 [O2(g)] = 0
H0298[Na(s)]=0

Therefore, the standard enthalpy of formation of a compound represents the enthalpy content of
the compound.

Hess’s Law

The law of conservation of energy states that energy can be neither be created or destroyed, though
one form of energy can be converted to another form. This law therefore implies that the total energy
content ( in the system ) is constant. Based on it, Hess’s law arises.

Hess’s Law: The standard enthalpy change of reaction depends only on the difference
between the standard enthalpy of the reactants and the standard enthalpy of the products, and
not no the route by which the reaction occurs.

In other words, for processes involving several stages, the enthalpy change for the reaction is equal to
the algebraic sum of the enthalpy change for each intermediate stage.

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The enthalpy change for the oxidation of carbon (graphite) to carbon dioxide is the same
whether it is carried out Route A ( 1 stage ) or Route B ( 2 stages)

Route A: C(s) + O2(g)  CO2(g) Ha = -393.5 kJ mol-1

Route B: C(s) + 1/2 O2(g)  CO(g) Hb1 = -110.5 kJ mol-1

CO(g) + 1/2 O2(g)  CO2(g) Hb2 = -283.0 kJ mol-1

Hb1 + Hb2 = (-110.5) + (-283.0) = -393.5 kJ mol-1

The Use of Hess’s Law in determining Enthalpy Changes

Some reactions proceed very slowly or involve formation of side products. Hess’s Law can be
used to determine the enthalpy changes of such reactions which cannot be determined directly
by calorimetry experiments.

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The molar enthalpy of formation, Hf, is defined as the enthalpy change when 1 mole of a
compound is formed directly from its elements. Although some compounds (e.g., MgO) can
be formed by direct synthesis from the elements, many cannot. Calcium carbonate is one of
them. Below is the chemical equation representing the formation of 1 mole of CaCO3:-
Ca (s) + C (s) + 1½ O2 (g)  CaCO3 (s)
The enthalpy change for this reaction can be found indirectly from reactions which can
actually be carried out in the lab and then applying Hess’s Law.
Both calcium metal and calcium carbonate react with dilute hydrochloric acid to form a
solution of calcium chloride. In addition, calcium metal forms H2 gas and calcium carbonate
forms CO2 and H2O. The enthalpy changes for these two reactions can be measured
relatively easily in the lab. For the calculation of Hf for CaCO3, two more pieces of data are
needed, i.e., the enthalpies of formation of water and carbon dioxide.

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METHOD
1) H1 for Ca + HCl
 Weigh out accurately about 1g of calcium metal into a weighing bottle and record the
mass.
 Weigh a polystyrene calorimeter cup and record the mass.
 Use a measuring cylinder to add 100cm3 of 1M HCl.
 Reweigh the cup with the acid and record the mass.
 Place the polystyrene cup inside a beaker for support, as shown in the diagram opposite.
 Place the thermometer in the acid and start the stop-clock. Record the temperature every
minute for 3 minutes.
 On the 4th minute, quickly add all the calcium metal and stir to mix thoroughly, keeping
the lid on top of the cup.
 Record the temperature every minute from the 5th minute for a further 10 minutes. Stir
the solution before each reading.
 Empty and rinse the cup and thermometer and dry them with paper towel.

2) H2 for CaCO3 + HCl

 Weigh out accurately between 2 and 3g of calcium carbonate powder into a clean
weighing bottle and record the mass.
 Using the same polystyrene cup as before, add a fresh lot of 100cm3 of 1M HCl using the
measuring cylinder, weigh again and record the mass.
 Repeat the steps in experiment 1, recording the temperature every minute and adding the
solid on the 4th minute.
 Empty and rinse the cup and thermometer and place them on the wet tray. Clear away all
the apparatus and leave your bench clean and tidy.

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 EXPERIMENT 1 EXPERIMENT 2
Mass of calcium metal Mass of calcium carbonate
Mass of empty cup Mass of empty cup
Mass of cup plus acid Mass of cup plus acid
Mass of acid 1 (M1) Mass of acid 2 (M2)

TEMPERATURE (OC)
TIME (minutes)
EXPERIMENT 1 EXPERIMENT 2
1
2
3
4 ADD THE SOLID
5
6
7
8
9
10
11
12
13
14
15

FINDING THE TEMPERATURE CHANGES

Plot two separate graphs of temperature against time, one for each experiment. Extrapolate
the points find out the instantaneous temperature change at the 4th minute in each reaction.
Call these t1 and t2.

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CALCULATING THE ENERGY CHANGES
 Take the Specific Heat Capacity (c) for the solutions to be 4.18 J.g-1.OC-1
 Take the mass of the solutions to be the mass of acid used in each experiment
 Ignore the sign of the temperature change (rise or drop) – just use the numerical value

1) For Ca metal
Heat change = mass of solution 1  c  t1
= ……………………………………………………………………. J
= ……………………… kJ

Moles of Ca = mass of Ca  Atomic Wt. (At.Wt. for Ca = 40.1)

= ………………………

Energy per mole = Heat change  number of moles

= ………………………………………………………….… kJ.mol-1

Now decide whether the reaction was exothermic (temperature rise) or endothermic
(temperature drop). Use the correct sign convention to write your value for the enthalpy
change for this reaction below:-

H1 = ……………………………………….. kJ.mol-1

2) For CaCO3
Heat change = mass of solution 2  c  t2
= ……………………………………………………………………. J
= ……………………… kJ

Moles of CaCO3 = mass of CaCO3  Molar Mass (Molar Mass = 100.1)

= ………………………

Energy per mole = Heat change  number of moles

= ………………………………………………………….… kJ.mol-1

Now decide whether the reaction was exothermic or endothermic. Use the correct sign
convention to write your value for the enthalpy change for this reaction below:-

H2 = ……………………………………….. kJ.mol-1

3) Use Hess’ Law and your values for H1 and H2 and the enthalpies of formation for
water and carbon dioxide to calculate the enthalpy of formation for CaCO3.
H2 (g) + ½O2 (g)  H2O (l) Hf = -285.8 kJ.mol-1 (call this H3)
C (s) + O2 (g)  CO2 (g) Hf = -393.5 kJ.mol-1 (call this H4)

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