Experiment 7: CaCO3 Decomposition

Objective:
To study the decomposition of calcium carbonate in a furnace.

Aim:
To interpret decomposition-time data in terms of a suitable reaction model. To predict the rate determining step from experimental data obtained.

Theory:
Fluid solid reactions are numerous and of great industrial importance. Most common examples are roasting of ores, burning of carbon/coke, decomposition of calcium carbonate etc. Treatment of above type of reaction requires the consideration of two factors in addition to those normally encountered in homogeneous reactions. The modifications of kinetic expressions resulting from the mass transfer and the heat transfer limitations between phases and the contacting patterns of reacting phases. Purpose of this experiment is the development of rate expressions for the decomposition of calcium carbonate. There are two types of idealized simple models for the non-catalytic reaction of particles of unchanging size surrounded by fluid [1]. Progressive Conversion model : Here we visualize that the reactant gas enters and reacts throughout the particles at all times, most likely at uniform rates, at different locations within the particle. Thus, the solid reactant is converted continuously and progressively throughout the particles.

Unreacted Core Model : Here we visualize that the reaction occurs first at the outer skin of the particles. The zone of reaction then moves into the solid and may leave behind completely converted material and inert solid shell. We refer to these as ash. Thus at any time there exists an unreacted core of material which shrinks in size during reaction.

Decomposition of CaCO3, is reasonably represented by unreacted core model. Unreacted CaCO3 model for spherical particles of changing size visualizes five steps occurring in succession during reaction. A (fluid) + b.B (solid) Fluid and/or solid product. Step 1.: Diffusion of gaseous reactantA through the fluid film surrounding the particle to the surface of solid. Step 2. : Penetration and diffusion of A through the blanket of ash to the surface of unreacted core. Step 3. : Reaction of gases with solids at this reaction surface. Step 4. : Diffusion of gaseous product through the ash film back to the external surface of the solid. Step 5.: Diffusion of gaseous product through the fluid film back into the main body of fluid [1]. It is not necessary that at a time all the steps may have a controlling influence on the reaction. Depending on the type of reaction, some of them may control the overall rate of conversion. Following are the conversion-time relations for various models for solids of identical size[1]: 1. Diffusion through gas film controls: 2. Diffusion through ash film controls: 3. Chemical reaction controls: t/ = xB (1) t/ = 1 3(1 xB)2/3 + 2(1 xB) t/ = 1 (1 xB)1/3

(2) (3)

Wheret = time in min. xB = fractional conversion of solids. = time (in min) for complete conversion of solid.

Procedure:
1. We maintained the temperature in the muffle furnace at 750C by adjusting the controls. 2. 10 g of calcium carbonate was taken in each of 5 trays of known mass. 3. These 5 trays were kept in furnace for different time. 4. One tray after every 25 min was removed from the furnace. 5. Trays were kept in desiccators after removing so as to avoid absorption of moisture by material by cooling. 6. After cooling trays for approx. 60 min each tray were weighed for calculating loss in mass.

7. Conversion of solids by loss in weight of trays was calculated. Thus we have conversion vs. time data (100% conversion corresponds to 44% loss in mass of sample).

Calculations:
The standard deviation of a set of N data points is defined by the following relation; ( ( ) )

As is constant in all three models, so we have compared the standard deviation of 's calculated from these models. The values of t/ for all the three models have been calculated and these have been used for calculating for every experimental reading. Table 1: Calculations when diffusion through gas film is the controlling step X 0 0.177273 0.493182 0.747727 0.95 0.970455 t (min.) 0 30 60 90 120 150 t/ (1) 0 0.177273 0.493182 0.747727 0.95 0.970455 (1) (min) 0 169.2308 121.659 120.3647 126.3158 154.5667

For X=0.1772, using equation (1), t/ = xB=.1772 ( ) = 22.15545 min.

Table 2: Calculations when diffusion through ash film is the controlling step X 0 0.177273 0.493182 0.747727 0.95 0.970455 t (min.) 0 30 60 90 120 150 t/ (2) 0 0.011397 0.106613 0.30679 0.692837 0.772377 (2) (min) 0 2632.167 562.7839 293.3602 173.2008 194.2056

For X=0.3159, using equation (2), t/ = 1 3(1 xB)2/3 + 2(1 xB) t/ = 1 3(1 0.177273)2/3 + 2(1 0.177273) t/ = .011397 ( ) = 1051.843 min. Table 3: Calculations when chemical reaction is the controlling step X 0 0.177273 0.493182 0.747727 0.95 0.970455 t (min.) 0 30 60 90 120 150 t/ (3) 0 0.062973 0.202708 0.368136 0.631597 0.690854 (3) (min) 0 476.3924 295.9922 244.4747 189.9946 217.1226

For X=0.3159, using equation (3), t/ = 1 (1 xB)1/3 t/ = 1 (1 0.177273)1/3 t/ = 0.062973 ( )

= 114.0475 min.

t/ versus X for all three models

1 0.9 0.8 t/ (min/min) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.2 0.4 X 0.6 0.8 1 t/ (1) t/ (2) t/ (3)

Fig. 1: Variation of time taken upon time for complete conversion of solids versus fractional conversion of solids based on all three models and experimental readings.

X versus time
1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 50 100 Time (min.) 150 200 X X

Fig. 2: Variation of fractional conversion of solids based on all three models and experimental readings versus time taken.

Result:
After statistical analysis of the experimental data it has been found that diffusion through gas film is the rate controlling step in calcium carbonate decomposition as standard deviation for this case is minimum.

Conclusion:
The study has demonstrated that for the decomposition of calcium carbonate the diffusion through gas film is the most critical step in the process. The reaction temperature has a direct effect on the rate of reaction. The reaction rate can be enhanced through improved heat transfer systems.

Precautions:
1. Give the number to each steel tray to avoid discrepancy as steel trays might be of different mass. 2. Use the gloves and tongs for putting trays in furnace. 3. Dont put the door of furnace open for longer duration. 4. Put the trays in desiccators very carefully so that no loss of products occurs. 5. Measure the mass of trays using mass balance with care.