Thermal Dissociation of Calcium Carbonate

Summary
The aim of this experiment is to observe the variation of partial pressure of CO2 against
absolute temperature and to determine the value of equilibrium constant and calculate the
reaction heat of dissociation.

Theoretical aspects
Thermal dissociation of CaCO3 is a solid-gas heterogeneous reaction and the equilibrium
constant will depend on CO2 because it is the only gaseous substance. The dissociation
occurs following the equation:
CaCO3( s ) CaO( s ) CO2 ( g )
(1)
The expression of the equilibrium constant corresponding to this reaction is:
a CaO aCO2
ka
, a represents the activity of a particular substance (2)
aCaCO3
The activity of any substance in solid pure phase is considered equal to 1.
Then : k a aCO2 .More, a CO2 can be replaced by the corresponding partial pressure of
CO2 according to the equation:
V

RT ln a RT ln p (V
0

RT
)dp
p

(3)

,where V is the molar volume of the gas. Since the variation of the tension of dissociation
is a few atmospheres the integral term from eq (3) becomes naught. Consequently:
aCO pCO
(4)
The dissociation constant Ka becomes equal to the corresponding tension of dissociation:
k a pCO2
(5)
The variation of the equilibrium constant against the absolute temperature is given by eq
(6):
r H
ln k a

(6)
2
T p R T
If one considers rH as a constant and separate the variables it results:
2

r H

d
ln
k

R T 2

dT

(7)

By indefinite integration it yields:

ln( K a )

r H
I ,
R T

I=constant of integration

(8)

rH can be determined by plotting ln(Ka) against the reciprocal of absolute temperature.a

straight line is obtained with the slope:
tg

r H
R

(9)

Thus: r H R tg

(10)

In eq.7 one integrates definitely, it results:

ln( K a , 2 ) ln( K a ,1 )

r H
R

1
1

T1 T2

(11)

Which means that the value of rH can be also calculated analytically according to
eq.11:
r H R

ln( K a , 2 ) ln( K a ,1 )
1
1

T1 T2

(12)

Or by replacing R with its value( 1.987 cal/mol K):

r H 4.575

ln( K a , 2 ) ln( K a ,1 )
1
1

T1 T2

(13)

Method
In a hard fusible tube (fig1), made by quartz or enameled porcelain, connected with one
of the extremity to a vacuum pump an a manometer, a sample of CaCO3 is introduced.
The tube may be heated to a constant temperature. Before the oven heating, the pump is
connected a few minutes until the vacuum is obtained inside. Turn off the pump tap and
then heat gradually.CO2 will be released inside of the tube and will press on the
manometric liquid.
If vacuum is made in tube again, one will see that the pressure will rise gradually till the
corresponding characteristic value is reached. This operation can be repeated many other
times till the entire amount of CaCO3 is decomposed. CaO remains in the tube.
If the tube gets cool, the pressure gradually decreases passing through the same
characteristic values of the temperature(as during heating).CaO2 will partially react with
CaO recovering CaCO3 .When the tube gets to the ordinary temperature the pressure is
practically null.
For a certain pressure, the thermal dissociation is limited. The dissociation occurs till the
CaO2 resulted from the reaction reaches a maximum pressure called tension of
dissociation similar with vapor tension of a liquid. This tension depends on temperature;
the tension of dissociation increases with the temperature and is dependant on tube
volume and also on amount of CaCO3.

Laboratory equipment
A hard fusible tube containing a sample of CaCO3 is situated inside the electric oven. The
tub is obturated at one extremity and connected through a three ways tap to a manometer
and a vacuum pump at the other extremity. A thermoelectric couple touching the
porcelain tube is fixed in the middle of the oven; the electric wires are connected to a

milivoltmeter with a scale in centidegrees. The oven can be gradually heated till 780C
by varying the current intensity with a rheostat.

manometer
oven
Hard fusible tube

milivoltmeter

Procedure
Obtain the vacuum inside the tube. The two columns of the manometric liqid must be at
the same level. The oven is heated with a constant heating rate. Determinations will be
accomplished between 620 and 820C reading simultaneously the pressure ( the
difference of Hg level between the 2 columns) and the temperature( on milivoltmeter).