Stoichiometry of Bicarbonate Decomposition MONASH UNIVERSITY School of Engineering - Sunway

CHE2162/Lab/2011

CHE2162: Material and Energy Balances Experiment: Stoichiometry of Bicarbonate Decomposition INTRODUCTION Material and energy balances are fundamental to any chemical process. They are important as they form the basis for control of processing and control of the yield of the process. A small scale experimental process has been developed so that mass and energy balances can be carried out for a reactive process and measurement and calculation errors can be identified in satisfying mass and energy balances. The process to be studied is the thermal decomposition of sodium bicarbonate. In this process, sodium bicarbonate decomposes to form sodium carbonate upon the application of heat: 2 Na HCO3 Na2CO3 + CO2 + H2O Material quantities, as they pass through processing operations, can be described by material balances. Such balances are statements of the law of conservation of mass. Similarly, energy quantities can be described by energy balances, which are statements of the conservation of energy. For a continuous operation over any chosen time interval if there is no accumulation, what goes into a process must come out, and operation is at steady state. Figure 1 shows the process instrumentation diagram of the decomposition rig situated in the Chemical Engineering Lab. Description of the process and equipment The feed tank is first filled with aqueous sodium bicarbonate solution. The feed is then pumped into the reactor by a peristaltic pump. The reactor is kept at a constant temperature by circulating heated oil in the reactor jacket. An overhead stirrer driven by a small motor ensures that the temperature distribution around the reactor is even. At temperatures above 70C, the sodium bicarbonate in the reactor will begin to decompose into sodium carbonate, carbon dioxide and water. The gaseous CO2 product saturated with water will travel upwards into a condenser, where most of the water is condensed and separated. The dry CO2 will then enter the calibrated cylinder where its volume is measured. As the system is continuous, the hot liquid products will exit the reactor via the adjustable overflow port. A second condenser is located below the reactor to cool down the temperature of the liquid products before they enter the product tank.

Figure 1: LS-32001-28 DECOMPOSITION REACTOR UNIT THEORY Mass Balance In order to calculate all the terms and carry out mass balance for all the species, the compositions and mass flowrates for all the streams must be known. The total mass balance inside the reactor at steady-state would be:

Accumulation = Input output + Generation Consumption The following flow rate can be measured: Flow rate of bicarbonate feed can be measured via measuring cylinder placed in the collection tank, prior to the experiment. Flow rate of carbon di oxide from the syringe measurement Flow rate of liquid come out of the reactor via measuring cylinder placed in the collection tank.

Energy Balance The energy balance written for a chemically reacting steady-flow system can be expressed per unit mole of reactants as:

Where NP = no of moles, h = specific enthalpy; the superscript O denotes at 25 oC, the subscript f denotes formation, p denotes product and r denotes reactant. The heat in the reactor is equal to the change in energy due to the decomposition reaction taking place inside the reactor. At steady-state, the left hand side of the equation is represented by the amount of heat input to the system, which can be written as:

The heat loss from the reactor jacket may be approximated by calculating the heat transfer of a vertical cylinder by free convection. The right hand side of the equation is the energy change due to the reaction taking place in the reactor:

Energy Balance for Condenser/Cooler The Graham coil condenser/cooler found above and below the reactor are used to transfer heat from the hot top/bottom products to the cold water circulating through them. Cold water is circulated through the coil in a counter-current direction to the hot products travelling through the shell as shown in Figure 4. The temperature of the hot products may be taken as the temperature of the reactor, while the temperature of the hot liquid products may be measured from the product tank. Since there is no temperature sensor for the hot gas products, a thermometer may be used. For the condenser/cooler above the reactor, the energy balance may be written as:

The heat from the cooling of carbon dioxide and condensation of water vapor must be equal to the heat absorbed by the cooling water circulating through the coils and the heat lost to the surroundings. If the reactor is operating at temperatures of below 80C, we may simplify the equation by assuming that no water vapor is present, thus the equation may be simplified to:

The heat loss to the surroundings, Qloss, may be approximated by calculating the convective heat transfer across a cylinder with surface temperature of (Th,in + Th,out)/2. The flowrate of the hot gas is obtained by measuring the volume of gas collected by the gas syringe over a period of time, whilst the flowrate of cold water is directly read off from the digital display meter. For the condenser/cooler below the reactor, the energy balance may be written as:

The heat from the cooling of the liquid products must be equal to the heat absorbed by the cooling water circulating through the coils and the heat lost to the surroundings. Once again, the heat loss to the

surroundings, Qloss, may be approximated by calculating the convective heat transfer across a cylinder with surface temperature of (Th,in + Th,out)/2. Specific heat capacity of different compounds present in the liquid can be determined from the prescribed text book (Elementary Principles of Chemical Processes) and additional reference provided in the Blackboard. Suitable assumption can also be done. The flow rate of the hot liquid products is obtained by measuring the volume of liquid collected in a measuring cylinder over a period of time. The mass flow rate may be obtained by measuring the density of the liquid by using a hydrometer/densitometer. SETUP

LEGEND A - Gas syringe B - Condenser C - Stirrer D - Reactor E - Cold water inlet F - Cooler G - Product tank

H - Thermal bath pump I - Bypass valve J - Thermal bath K - Feed tank L - Main switch M - Stirrer ON/OFF switch N - Feed pump ON/OFF switch O - Thermal bath pump ON/OFF switch P - Heater ON/OFF switch Q - Temperature controller R - Flow meter S - Feed pump

SAFETY / PRECAUTION 1. Please put on personal protective equipment such as: hand gloves, lab coat and safety goggles when operating the system. 2. Do not touch the hot surfaces of the jacketed vessel and thermal bath piping when conducting the experiment. 3. Ensure that the thermal bath is at least 3/4 filled before switching on the heater. 4. Do not attempt to change the settings of the digital meters. 5. Ensure that the main switch is switched off and the power supply plug is removed before carrying out any electrical works. 6. All electrical works should be carried out only by suitably qualified personnel.

SETUP 1. Lock the castor wheels of Decomposition reactor. 2. Connect the water inlet (E) and outlet to a laboratory water supply and drain respectively. 3. Open the cold water supply and allow water to circulate through the coolers/condensers (B, F). 4. Plug the 3 pin plug to a 240 VAC single phase 50 Hz power supply. Switch ON the power supply. 5. Fill the thermal bath (J) with heating oil to at least 3/4 full. 6. Ensure that the bypass valve (I) for the thermal bath is fully open. 7. Ensure that all tanks (G, K) are empty before filling in the desired chemicals. 8. Adjust the overflow port inside the reactor to the desired level. 9. Switch ON the main switch (L) in front of the control panel. The stirrer for the feed tank should operate immediately. 10. Switch ON the heater (P) for the thermal bath and set the temperature to 100C. Observe the temperature of the thermal bath. The temperature of the bath should gradually rise to the set temperature. 11. Switch ON the thermal bath pump (O). The pump should now begin to circulate heating oil through the reactors jacket. 12. Switch ON the feed pump (N) and set the speed to maximum. Observe the transparent feed tube and reactor. The feed pump should now begin to dose chemicals into the reactor. 13. Switch ON the overhead stirrer (M) and gradually increase the speed to maximum. 14. Ensure that both the digital flow indicators (R) are displaying values. 15. The equipment is ready for use if all parts are in working order. SHUTDOWN 1. After using, switch off the heater, feed pump, thermal bath pump and stirrer. 2. Switch OFF the main switch and the power supply. USEFUL INFORMATION Stirrer Maximum speed; 330 rpm Reactor internal diameter: 120 mmm Reactor outer diameter: 160 mm Reactor maximum height: 150 mm Specific heat capacity of heating oil: 1.67 Kj/Kg.K CHEMICAL PREPARATION 2 M sodium bicarbonate aqueous solution Analytical grade sodium bicarbonate x 168 g Distilled water x 1 L 1 L Volumetric flask x 1 Weighing scale & beaker x 1 Glass rod x 1

Procedure 1. Using a laboratory weighing scale and beaker, weigh 168 g of analytical grade sodium bicarbonate 2. Add distilled water to the beaker and gently stir using a glass rod. 3. Transfer the contents into the volumetric flask. 4. Repeat steps 2 and 3 to ensure that all the sodium bicarbonate has been transferred into the volumetric flask. 5. Add distilled water into the volumetric flask until the volume reaches exactly 1 L. 6. Transfer the contents into the feed tank. 7. Repeat steps 1 to 6 until there is 5 L of sodium bicarbonate solution in the feed tank. TITRATION The product (and the feed, if baking soda is used) must be titrated to determine the composition of carbonate and bicarbonate. 1 M HCl solution Phenolphtalein Methyl orange 500 ml conical flask Pipette Procedure 1. Collect 200 ml of the product or feed using a conical flask. 2. Use a clean pipette to transfer exactly 10 ml of the liquid into a conical flask. Add a few drops of methyl orange indicator. 3. Titrate the liquid with 1 M HCl solution; the endpoint is detected when the color changes from orange to red. 4. Repeat steps 2 and 3 until two sets of cohesive results are obtained. 5. Pipette a fresh 10 ml of liquid into a conical flask. Add a few drops of phenolptalein indicator. 6. Titrate the liquid with 1 M HCl solution; the endpoint is detected when the color changes from colorless to pink. 7. Repeat steps 5 and 6 until two sets of cohesive results are obtained. The following reactions is what occurs during the titrations: Na2CO3 + HCl NaCl + NaHCO3 NaHCO3 + HCl H2O + CO2 Methyl orange can detect the completion of HCl with either two carbonates while phenolphthalein can only detect the completion of HCl with Na2CO3. Phenolphtalein can not detect the completion of reaction of HCl with NaHCO3.

EXPERIMENT PROCEDURE 1. Ensure that all tanks are empty before filling in the desired chemicals. 2. Fill the feed tank with 5 L of sodium bicarbonate solution. 3. Disconnect the tube from the overhead condenser to the glass syringe. 4. Open the cold water supply at 2 LPM (The hose may leak above this flow) and allow water to circulate through the coolers/condensers. 5. Switch ON the main switch in front of the control panel.

6. Ensure that the thermal bath is at least 3/4 filled with heating oil before switching on the heater. 7. Switch ON the heater for the thermal bath and set the temperature to 100C. Allow the thermal bath to gradually heat up to the set temperature. 8. Meanwhile, start the feed pump to fill the reactor with sodium bicarbonate solution. Make sure that the liquid overflows through the overflow port. Record the flow rate at a very minimum flow rate (flow rate of the feed pump can be controlled by the valve in the feed line which is just above the reactor). It is advisable to record the flow rate at least five times. 9. Stop the feed pump. Empty out the product tank but keep the liquid in the measuring cylinder. 10. Ensure that the bypass valve for the thermal bath is fully open. Once the thermal bath has reached the set temperature, switch ON the thermal bath pump. The heating oil should circulate through the reactors jacket. WARNING: Do not touch the hot surfaces of the jacketed vessel and thermal bath piping when conducting the experiment. 11. Start the stirrer motor. Set the stirrer speed to 50%. 12. Allow the reactor temperature (T4) to reach at least 60C. 13. Start the feed pump and wait for 15 minutes. Record all the necessary temperatures and flow rates. 14. To measure the product flow rate, Connect the tube from the overhead condenser to the glass syringe and record the time taken to fill the 100 mL of gas into the syringe 15. Take at least 5 readings at the near stable condition. 16. If temperature fluctuates during repeated measurement, follow Step 9, 12, 13 and 14. 17. Collect a 200 ml sample of the product for titration. 18. Switch off the heater, thermal bath pump, feed pump and stirrer motor. 19. Drain all the liquid in feed tank, reactor and product tank 20. Fill 7L of distilled water to feed tank and flush the system through overflow in reactor. 21. Switch off the mains switch. 22. Tabulate the results obtained.

RESULTS

DISCUSSION Mass balances required The following overall mass balance equations should be set up: Total mass Water Na+ CO2 (or C) All the terms of these equations are known; hence the closure of the balance equations can be verified. Results should be tabulated, analyzed and errors should be calculated. Energy Balances required The energy balances should be written for The reactor The vapor products cooler/condenser Overall system Results should be tabulated, analyzed and errors should be calculated. REPORT The report should also include i. An estimate of heat loss from the reactor based on the reactor geometry ii. All raw data in an appropriately designed data sheet. iii. All your calculations (Note: Tabulate results obtained in Results Section and detailed calculations should be shown in Appendix section).