Inorganic Commodity Chemicals

HYDROCHLORIC ACID
ChE 313 Industrial Chemistry Lecture
Engr. May V. Tampus

Hydrochloric Acid: interesting facts

Found naturally from volcanoes Present in the planet Venus Present in the most mammals Listed as one substance in the gases evolved atmosphere of the digestive system of of the prohibited

Hydrochloric Acid Production

*Data source: Kirk-Othmer Encyclopedia of Chemical Technology

Today worldwide usage of HCl exceeds 20 M tons annually.

Industrial Uses of HCl

Descaling agent Catalyst in food processing Pickling liquor to dissolve mill scales in steel industry Dissolve pulverized stone during petroleum operation oil-well acidiIng CaCl2 manufacture Oil & gas well acidizing Production of high-fructose corn syrup (HFCS)
Manufacture of dyes, phenols, & plastics

pH control and neutralization

Regenerant of ion-exchange resins Gelatin manufacture Soy sauce production Magnesia and metal production Manufacture of chemical intermediates, e.g., FeCl3, ZnCl2, Al2Cl3, etc. Ore reduction (Mn, Ra, V, Ta, Sn, W) Leather processing

Hydrochloric Acid

Forms of Hydrochloric Acid

Hydrogen chloride: gas at ordinary temperature Hydrochloric acid: aqueous solution of hydrogen chloride Muriatic acid: commercial grade of HCl solution; clear colorless to slightly yellow liquid with a strong pungent and irritating odor; strong and highly corrosive; soluble in water and alcohol but insoluble in hydrocarbon

Common Grades of Muriatic Acid

Mass % HCl Density

Specific gravity 1.1417

1.1600 1.1789

Be

27.92
31.45 35.21

18
20 22

Industrial Grades of HCl

1) Concentrated grade 38-40% 2) Bulk-industrial grade 30-34% (optimized for transport & limit product loss) 3) Household grade 10-12% (intended for cleaning)

Physical Properties of Hydrochloric Acid

Properties Molar mass Melting point Boiling point Specific gravity Solubility in water Vapor pressure 36.46 g/mol -114.8o C -84.9oC 1.84 720 g/L (at 20o C) 423 kPa Value

pKa
pKb NFPA ratings Stability

-7
21.0 Health: 3 Flammability: 0 Reactivity: 1 Other: ACID Stable under ordinary conditions

Thermochemistry of HCl
Thermodynamic Properties Std enthalpy of formation 92.31 kJ mol-1 fHo298 Std enthalpy of combustion 95.31 kJ mol-1 cHo298 Standard molar entropy 186.902 J K-1 mol-1 So298 Specific heat capacity, C 0.7981 J K-1 g-

Chemical Properties of Hydrochloric Acid

Hydrochloric acid readily ionizes in water: HCl (g) + H2O(l) Cl-(aq) + H3O+(aq)

Even in the absence of water it still reacts as an acid to form: HCl (g) + CH3OH (l) Cl-(aq) + CH3O+H2(aq)

Industrial Production of Hydrochloric Acid

Direct Synthesis from hydrogen and chlorine Decomposition of metal chlorides by acids As by-product from chemical

processes
Recovery by incineration of waste organics Recovery from hydrochloric acid solutions

Synthesis from Hydrogen and Chlorine

Less than 10% of HCl in U.S. is made via this reaction Reaction is adiabatic and takes place in an HCl burner or HCl oven Acid produced is called BURNER ACID

H 2 ( g ) Cl2 ( g )

2 HCl ( g ) 184 kJ (44 kcal)

Synthesis from Hydrogen and Chlorine

PROCESS CONDITIONS
Temperature: 2490o C Pressure: 14 kPa Rapid cooling of free H2 & Cl2 to 200o C Equilibrium mixture contains 4.2% v/v free Cl2 Use a stoichiometric amount of feed gas mixture in order to produce 99% HCl 30-32% HCl (burner acid) is produced by absorption

Decomposition of Metal Chlorides by Acids

1. Salt-Sulfuric Acid (Saltcake) Process
NaCl + H2SO4 HCl + NaHSO4 at 150oC (1) NaCl + NaHSO4 HCl + Na2SO4 at 550-660o C (2) Both reactions are endothermic. Reactions occur in a Mannheim mechanical furnace. Produces 30-60% HCl

Decomposition of Metal Chlorides by Acids

2. Hargreaves Process & Leblanc Process
2SO2 + O2 + 2H2O + 4NaCl 4HCl + 2Na2SO4

Reaction is at 4000-5500o C Reaction is self-sustaining. Reaction is exothermic. Produces 10-12% HCl

Hydrogen chloride as By-products from Chemical Processes

1. As a by-product in chlorination of both aromatic and aliphatic hydrocarbons
integration of organic and inorganic chemicals industry

RH + Cl2 RCl + HCl RCl + HF RF + HCl

Hydrogen chloride as By-products from Chemical Processes

2. As a by-product of the Leblanc Process

NaCl + H2SO4 NaHSO4 + HCl NaHSO4 + NaCl Na2SO4 + HCl

4HCl + MnO2 2Cl2 + MnCl2 + H2O Na2SO4 + C + CaCO3 Na2CO3 + CaSO4 Na2CO3 + Ca(OH)2 2NaOH + CaCO3

Hydrogen chloride as By-products from Chemical Processes

3. As a by-product of the Manufacture of Isocyanate

RNH2 + COCl2 RNCO + 2HCl

But HCl cannot be recycled other than the regeneration of chlorine!

Group Assignment
INSTRUCTION:S Write your answer on a short bondpaper. Cite references used. Submit assignment on July 13, WED, not later than 5:00 PM. Group members must affix their signature.

1.

Enumerate at least five industries which use hydrochloric acid and describe how HCl is used or applied in each industry. 2. List down at least seven chemical reactions of HCl with other compounds. Literature source: Kirk-Othmer Encyclopedia. 3. Identify the sources of raw materials for each production method presented. 4. Tabulate the operating temperature, operating pressure, enthalpy of reaction, yield, and other process conditions for the following:
a. b. c. d. e. Production of HCl via the Saltcake process Productio of HCl via the Hargreaves process Production of HCl as by-product of chlorination of benzene Production of HCl as by-product of the Leblanc process Production of HCl as by-product of the Isocyanate manufacture