Chemical Technology

Subject Code: CH2001

Lecture 5

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 Sodium carbonate – Na2CO3
Properties
Chemical formula Na2CO3
Molar mass 105.9888 g/mol (anhydrous), 286.1416 g/mol
(decahydrate)
Appearance White solid, hygroscopic
Odor Odorless
3 3
Density 2.54 g/cm (25 °C, anhydrous), 1.92 g/cm (856 °C)
Melting point 851 °C (1,564 °F; 1,124 K) (Anhydrous)
100 °C (212 °F; 373 K), decomposes (monohydrate)
Thermochemistry
33.5 °C (92.3 °F; 306.6 K), decomposes
(heptahydrate) Heat capacity (C) 112.3 J/mol·K
34 °C (93 °F; 307 K). (decahydrate) Std molar 135 J/mol·K
o
Solubility in water •Anhydrous, g/100 mL:7 (0 °C) entropy (S 298)
•16.4 (15 °C) Std enthalpy of −1130.7 kJ/mol
•34.07 (27.8 °C) ⦵
formation (ΔfH 298)
•48.69 (34.8 °C)
Gibbs free energy (ΔfG˚) −1044.4 kJ/mol

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 SODA ASH: GRADES AND USES
• Soda ash is an odorless, white powder. It is stable, not toxic or explosive or
flammable. There are basically three grades of soda ash that are
produced, namely:
• Dense soda ash, which is an anhydrous substance. It forms an important
industrial chemical, and is widely used in the manufacture of different
products.
• Light soda ash, which is widely used as a pH regulator/ buffering agent in
multiple industrial processes.
• Washing soda, which is also an anhydrous substance that’s produced by
combining light soda ash along with additional molecules of water. It’s
mostly used in soaps and washing detergents to improve their cleaning
properties.

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• Sodium carbonate (Na2CO3) is found naturally or is
manufactured from natural salt i.e., sodium chloride
(common salt).
• https://www.youtube.com/watch?v=anl0xqSnRGM
• It has many uses but, one of the major notable
applications is in making of glass.
• Soda ash is a key chemical for producing soap, paper
making, baking soda production, and bleaching fabrics
and paper.

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 ORIGIN OF SODA ASH TERM

• The name "soda ash" is based on the principal historical

method of obtaining alkali, which was by using water to
extract it from ashes.
• The word "soda" (from the Middle Latin) originally
referred to certain plants that grow in salt marshes; it was
discovered that the ashes of these plants yielded the
useful alkali "soda ash."

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WHY IS SODIUM CARBONATE CALLED AS WASHING SODA?

• CO32- from dissolved Na2CO3 can precipitate Mg2+ and Ca2+ ions
from hard water as the insoluble carbonates, preventing them from
forming a precipitate with soap resulting in scum.
• For this reason, sodium carbonate is also known as washing soda.
• Soda ash is used to produce the NaHSO3 necessary for the sulfite
method of separating lignin from cellulose.
• Sodium carbonate removes grease from wool and neutralizes acidic
solutions.
• Na2CO3 is used to remove SO2(g) from flue gases in power stations.

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 Methods of production
• Classification of Processes
✓ Solvay or ammonia soda
✓ Dual process (Na2CO3 + NH4Cl)
✓ Natural soda ash from deposits

➢ The Solvay Process (also known as the ammonia-soda process),

developed in 1861, is the world's major industrial process for the
production of sodium carbonate (NaCO3), or soda ash.
➢ The ingredients for this are readily available and inexpensive:
salt brine (from inland sources or from the sea) and limestone (from
quarries).
➢ https://www.youtube.com/watch?v=VS4_wwDmoMc

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 SOLVAY PROCESS HISTORY
• In 1861, after realizing the polluting impacts of the Leblanc Process,
Belgian industrial chemist Ernest Solvay rediscovered and perfected
Augustin Fresnel's reaction. This process recovered the ammonia in
the reaction for re-use, therefore making it less detrimental to the
environment.
• In 1874, other companies had bought the right to use the Solvay
process in their own plants. Now the sodium carbonate production
market became a booming industry with several plants opening
worldwide.
• In 1890s, Solvay-based process plants produced the majority of the
world's soda ash.
• The materials needed in the Solvay process are nearly all readily
available and inexpensive:
• https://www.youtube.com/watch?v=5quHknBSgKs
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 Chemistry/Chemical reactions
Ernest Solvay developed a method to make sodium
carbonate by first reacting sodium chloride, ammonia,
water, and carbon dioxide to generate sodium
bicarbonate and ammonium chloride

Overall Reaction
➢ 2 NaCl + CaCO3 → Na2CO3 + CaCl2

This reaction takes place in a number of steps:

NaCl + CO2 + NH3 + H2O → NaHCO3 + NH4Cl (I)

CaCO3 → CO2 + CaO (II)
Chemistry of the Solvay Process. Each closed
2 NH4Cl + CaO → 2 NH3 + CaCl2 + H2O (III) loop represents a reaction.
2 NaHCO3 → Na2CO3 + H2O + CO2 (IV)
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 Manufacturing of soda ash by Solvay process
SOLVAY PROCESS FEEDSTOCKS

Salt Brine – Salt brine as one of the

feedstock provides salt and water
and it can be easily sourced from
both inland and the ocean.
Limestone
Ammonia

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• The following steps are involved in Solvay
process and in this process some amount
of ammonia recycled back as feedstock to
start the new round of Solvay process.

• Brine purification
• Ammoniation of brine
• Reactions in Solvay Tower
• Reactions in Klin / Separation of solid
sodium hydrocarbon
• Formation of sodium carbonate
• Ammonia Recovery

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 Brine Purification
The Solvay process will commence with brine purification.
• The brine solution is concentrated by evaporation to at least 30 percent
• Calcium, magnesium, and iron are collected as precipitants in this
reaction

• Ca2+(aq) + CO32-(aq) → CaCO3(s)

• Mg2+(aq) + 2OH-(aq) → Mg(OH)2(s)
• Fe3+(aq) + 3OH-(aq) → Fe(OH)3(s)

• Following the precipitation reaction, the brine solution is then filtered and
passed through an ammonia tower to dissolve ammonia.
• Through this process energy is released because of its exothermic
nature, thereby, the ammonia tower will get cooled by this energy.

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 AMMONIATION OF BRINE

• In the second step, Ammonia gas is absorbed in

concentrated brine to give a solution containing both
sodium chloride and ammonia.
REACTIONS IN KLIN / SEPARATION OF SOLID SODIUM
HYDROCARBONATE
• LIME KILN
• A lime kiln is used to produce quicklime through the
calcination of limestone. This reaction takes place at
900°C.

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 TYPES OF KILNS
• Shaft kilns
• Countercurrent shaft kilns
• Regenerative kilns
• Annular kilns
• Rotary Kilns
• Kilns are fed with a limestone/coke mixture (13:1 by mass). The coke burns in a
counter-current of pre-heated air
• C(s) + O2(g) → CO2(g)
• The heat of combustion raises the temperature of the kiln and the limestone
decomposes
• CaCO3(s) ↔ CaO(s) + CO2(g)
• The gas, containing approximately 40 percent carbon dioxide, is freed of lime dust
and sent to the carbonating (Solvay) towers. The residue, calcium oxide, is used in
ammonia recovery.

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 REACTIONS IN SOLVAY TOWER
• The Solvay Tower is tall and contains a set of mushroom-shaped
baffles to slow down and break up the liquid flow so that the carbon
dioxide can be efficiently absorbed by the solution. Carbon dioxide,
on dissolving, reacts with the dissolved ammonia to form ammonium
hydrogen carbonate
• NH3(aq) + H2O(l) + CO2(g) → NaHCO3(s)
• The solution now contains ions Na+(aq), Cl-(aq), NH4+(aq) and HCO3-
(aq).
• Of the four substances which could be formed by different
combinations of these ions, sodium hydrogen carbonate (NaHCO3)
is the least soluble. It precipitates as a solid in the lower part of the
tower, which is cooled.
• NaCl(aq) + NH3(aq) +H2O(I) +CO2(g) → NaHCO3(s) + NaCl (aq)

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FORMATION OF SODIUM CARBONATE
• Suspended sodium hydrogen carbonate is removed from the carbonating
tower and heated at 300oC to produce sodium carbonate:
• 2NaHCO3(s) → Na2CO3(s) + H2O (g) + CO2 (g)

AMMONIA RECOVERY
• CaO is formed as a by-product of the thermal decomposition of limestone in
the lime kiln.
• This CaO enters a lime slaker to react with water to form calcium hydroxide:
• CaO(s) + H2O (l) → Ca(OH)2(aq)
• The calcium hydroxide produced here is reacted with the ammonium chloride
separated out of the carbonating tower by filtration:
• Ca (OH)2(aq) + 2NH4Cl(aq) → CaCl2(aq) + 2H2O(l) + 2NH3(g)

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 Major Engg problem

• Development of suitable calcining equipment

• Economic balance on tower design
• Ammonia recovery
• Plant modernization
• Waste disposal

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• https://www.worldofchemicals.com/440/chemistry-
articles/manufacturing-of-sodium-carbonate-by-solvay-
process.html

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 Applications of Soda Ash
• Industrial applications – Being a highly soluble substance, It’s mostly used as an ingredient in the
manufacture of dyes and coloring agents, synthetic detergents and fertilizers. It’s also an important
chemical agent used in enameling and petroleum industries.
• Environmental applications – Sodium carbonate is used to improve and treat the alkalinity of lakes
that have been affected by rain. It is also used to reduce the acidity of emissions being generated
from a power plant.
• Detergent manufacture – Soda ash is replacing phosphates that were earlier being used in a
number of household detergents. Many other cleaning products such as dishwashing soaps also
contain varying amounts of soda ash in their formulations.
• Metallurgy – Sodium carbonate is used to remove or de-clarify phosphates and sulfurs from a
number of non-ferrous and ferrous ores. It’s also used in recycling of aluminum and zinc.
• Glass manufacture – Soda ash is an important ingredient in the manufacture of glass, since it helps
reduce silica’s melting point.
• Other applications – Soda ash is also a common addition to spa and pool treatment chemicals
helping in reducing the acidity in water. It is also used in manufacture and sealants and glues,
preparing pulp in paper manufacture, and sometimes in soil preparation as well.

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 APPLICATIONS OF BRINE
• Brine is an extremely useful substance used in domestic household tasks as well as commercial applications.
• Brine is used for the production of salts. The brine is generally evaporated and then processed to get the common salt or table salt.
• Brine is widely used for food preservation. The brine can be mixed with a wide variety of herbs and spices for flavor.
• Brine is often used for marinating meat. It makes the flesh juicier, and tender. Apart from feed that, Brine kills the microorganisms that
harbor in meat. The process of marinating the meat with brine, prior to cooking reduces the cooking time.
• The brine solution is an excellent prewetting agent and commercially used to treat the roads. The solution is non-corrosive,
biodegradable, and environmentally friendly.
• Brine is used to transferring heat from one place to another place and is largely used for refrigeration.
• Brine has a lower freezing point than water and can be cooled to below zero Celsius. Hence it is effectively used as a coolant other
than plain water. Brine freezes at -21ºC (-6ºF). It is used for cooling steels and other metals.
• Brine is often used for Pickling.
• Brine is an important source of chlorides, sulphates of magnesium and potassium apart from natural salt. These salts are extracted
through electrolysis.
• Brine solution cures Psoriasis, Osteoporosis, Arthritis, Gout and Herpes sores.
• Brine steam inhalation cures asthma, bronchitis, acute and chronic sinus, and ear infections.
• Brushing teeth with concentrated Brine solution helps to protect tooth enamel.
• Brine poultice is used to sterilize open wounds.
• Brine baths improve circulatory system and control high temperature during viral fever.
• Brine acts an excellent detoxification solution and improves metabolism. It maintains the body’s pH Factor and eliminates heavy
metals.

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