6. THE SOLVAY PROCESS This is the process used to manufacture sodium carbonate. A.

RAW MATERIALS AND PRODUCTS Raw Materials: Brine (sodium chloride solution) Ammonia (recycled) Limestone (calcium carbonate) Products: Sodium carbonate Calcium chloride B. USES OF SODIUM CARBONATE Glass-making: accounts for more than 50% of Na2CO3used. Water treatment: used to soften water by precipitating Ca2+ and Mg2+both in industry and domestically. Used in place of phosphates to make builders for detergents. Making Soaps & Detergents: used in place of NaOH as it is cheaper As a common base: in factories as it is cheaper than NaOH Removing SO2: from flue gases from power stations as it neutralises

C. FLOW CHART TO DESCRIBE THE STEPS IN THE SOLVAY PROCESS Outline of Steps: 1. 2. 3. 4. 5. 6. 7. 8. Purify the brine Saturate conc. brine with ammonia Decompose limestone to produce CO2 Bubble CO2 (from decomposing limestone) through this to give a sodium hydrogen carbonate precipitate Filter off the NaHCO3 and heat it to form Na2CO3 Convert the CaO from step 3 to Ca(OH)2 Regenerate the ammonia from the filtrate in step 4 using Ca(OH)2. Dispose of the CaCl2 produced in step 7.

Overall Equation:

CaCO3(s)

2NaCl(aq)

Na2CO3(aq)

CaCl2(aq)

CHEMISTRY OF THE MAIN PROCESSES

CARBON DIOXIDE FORMATION Crushed limestone is mixed with coke and decomposed in a kiln. (endothermic) CaCO3(s) CaO(s) + CO2(g) The CaO is added to water to make Ca(OH)2 suspension (milk of lime) CaO(s) + H2O(l) Ca(OH)2(s) Ca2+(aq) + 2OH-(aq) BRINE PURIFICATION Salt is obtained from sea water or underground deposits of salt water or rock salt. 30% NaCl solution is required 30g per 100g soln. Impurities are usually Ca2+, Mg2+, Fe3+and other heavy metal ions. These can lead to precipitates forming. They are removed using CO32- and OH- : Na2CO3 Mg2+ Fe3+ + +
+

Ca2+ 2OH3OH-

CaCO3(s) Mg(OH)2(s)

2Na+(aq)

Fe(OH)3(s)

Flocculation removes these solids

HYDROGEN CARBONATE FORMATION The brine is saturated with ammonia Carbon dioxide gas (from CaCO3) is bubbled through this brine Overall:

H2O + CO2

H2CO3

Then H2CO3 + NH3

HCO3- + NH4+

The solid is filtered off and the remaining solution is treated to recover the ammonia

SODIUM CARBONATE RECOVERY The sodium hydrogen carbonate filtered off is converted to sodium carbonate by heating

2NaHCO3(s)
The carbon dioxide is recycled AMMONIA RECOVERY

Na2CO3(s) + CO2(g)

H2O(g)

The reaction which produces the carbon dioxide is: CaCO3(s) CaO(s) CaO(s) + + CO2(g) H2O(l) Ca(OH)2(aq)

The calcium oxide is slaked:

The filtrate from the carbonator is reacted with this to recover the ammonia

Ca(OH)2(aq)

+ NH4Cl(aq) 2NH3(g) +

CaCl2(s)

+2H2O(l)

to carbonator

waste

6D Environmental Issues associated with Solvay Process

Mining of limestone: open cut mines do impact unsightly but limestone is just rock so there are no wastes from the mine which could contaminate the area Disposal of Wastes: CaCl2 solution is the only waste product and if the factory is on the coast this can be discharged into the ocean without causing problems Ca2+ is used by marine organisms and any excess is precipitated as CaCO3. Cl- is already present in relatively high concentration. If the factory has an inland location then disposal of the calcium chloride would present an issue as it cannot be discharged into lakes, rivers etc without having a significant impact on aquatic life and causing soil salinity and hardening of water. Thermal Pollution: the CaCl2 solution is quite hot and needs to be cooled before discharge. Ammonia: as this is efficiently recycled it is not released into the environment.

6E Laboratory Modelling of a Solvay Step Decomposition of Sodium Hydrogen Carbonate Risk Factors None significant. Wear safety goggles Method Weigh a side-arm test tube. Weigh 1g of NaHCO3 into the test tube and stopper. Clamp the test tube onto a retort stand and heat strongly using a Bunsen. Allow the evolved gases to pass through a rubber delivery tube into limewater in a test tube. Remove hose from limewater, turn off Bunsen and allow to cool. Reweigh. Calculate theoretical mass loss and compare with actual. Calculations:
2NaHCO3 Na2CO3 + CO2 + H2O n (NaHCO3) = 1 g/23 + 1 + 12 + 48 g = 0.012 n (Na2CO3) = 0.006 ( 2 : 1 ratio) m (Na2CO3) = 0.006 X 106 g = 0.636 g

Problems Encountered: melting test tubes, poor results due to ?

6F Quantity Calculations in the Solvay Process

See questions on p. 377-78 in Conquering Chemistry

6G Locating a Solvay Plant

Refer to the handout to make your own notes on this point.

6G Locating a Solvay Plant