Chapter one

Chapter One

Introduction
1.1 Introduction

Nitric acid (HNO3), also known as aqua Fortis, azotic acid, hydrogen

nitrate, or nitryl hydroxide, is a chemical of major industrial importance.

In 1993, it ranked thirteenth in production volume for chemicals made in

the United States; production in Western Europe is estimated to be about

19 million t/yr. Nitric acid is a powerful oxidizing agent, as well as its

ability to nitrate organics, nitric acid is essential in the production of

many chemicals, but is used mostly in the production of ammonium

nitrate for the fertilizer industry. (1)

Nitric acid is a strong acid that occurs in nature only in the form of nitrate

salts. When large-scale production of nitric acid began, sodium nitrate

(soda saltpeter, Chile saltpeter) was used as the feedstock. At the

beginning of the 20th century the reserves of Chile saltpeter were thought

to be nearing exhaustion, so processes were developed for replacing

nitrogen from natural nitrates with atmospheric nitrogen. The direct

combustion of air in an electric arc, developed by Birkeland and Eyde,

was abandoned because of its poor energy efficiency, In Norway, where

electricity was inexpensive, electric arc furnaces were used to make

nitrogen oxides, and subsequently nitric acid, directly from air. The

commercial life of these furnaces was relatively brief and most were shut

down by 1930. At about the same time, a different production method

was being developed. Later direct processes, such as thermal nitrogen

monoxide synthesis with fossil fuels or nitrogen monoxide synthesis in

nuclear reactors, did not gain widespread acceptance. Ammonia

production from calcium cyanamide was of only transitory value.

Ammonia produced from nitrogen and hydrogen by the Haber – Bosch

process is, however, still used as feedstock for nitric acid production. (1, 2)

3D structure of nitric acid. (3)

1.2 History

The first reports of nitric acid have been credited to Arab alchemists of

the eighth century. By the middle Ages it was referred to as aqua Fortis

(strong water) or aqua valens (powerful water). From that time onward,

nitric acid was produced primarily from saltpeter (potassium nitrate) and

sulfuric acid. In the nineteenth century, Chilean saltpeter (sodium nitrate)

from South America largely replaced potassium nitrate. By the end of the

nineteenth century, nitric acid industrial importance had already become

established in the production of explosives and dyestuffs. In 1908, at

Bochum, Germany, Ostwald piloted a 3-t per day nitric acid process

based on the catalytic oxidation of ammonia with air. In 1913 the

synthesis of ammonia from coal, air, and water was successfully

demonstrated. With a secure and economical supply of ammonia,

ammonia oxidation became firmly established as an industrial route to

nitric acid manufacture. The first full-size plant to be built in the United

States was installed in 1917 by Chemical Construction Company (Muscle

Shoals, Alabama). Since those early days, ammonia oxidation has

become the basis of all commercial nitric acid production. After World

War II nitric acid production grew rapidly with the expanding use of

synthetic fertilizers, because of the increased popularity of urea as a

fertilizer, production has leveled off. Most growth in demand has come

from the production of polyurethanes, fibers, and ammonium nitrate-

based explosives. However, at the beginning of the twentieth century

newer manufacturing technologies were introduced. (1)

Table [1 – 1] shows the production volume of nitric acid in Japan

from 2012 to 2020. (4)

Year × 1000 tons

2012 433.85

2013 430.14

2014 433.97

2015 414.41

2016 363.31

2017 384.63

2018 339.68

2019 378.26

2020 297.39
1.3 Uses

1. The principal use of nitric acid is as a starting material in the

manufacture of nitrogen fertilizers; large amounts are reacted with

ammonia to yield ammonium. Weak acid (60% HNO3) is most

suitable for this purpose. Smaller amounts of weak acid are used to

digest crude phosphates. About 75 – 85% of the nitric acid produced is

used in the fertilizer sector. (2)

2. Considering its ability to nitrate organics, nitric acid is used as a

nitrating agent in the preparation of explosives such as: trinitrotoluene

and nitroglycerin. (1)

3. Nitric acid properties makes it behave as a very strong acid and a

powerful oxidizing agent. (1)

4. Nitric acid is used in the treatment of metals (eg, the pickling of

stainless steels and metal etching), as a rocket propellant, and for

nuclear fuel processing. (1)

5. Also it is essential in the production of many chemicals such as:

pharmaceuticals, dyes, synthetic fibers, insecticides, and fungicides. (1)

6. It is also used in the production of adipic acid. (2)

7. Other uses for nitric acid are in the manufacture of metal nitrates,

nitrocellulose and nitrochlorobenzene. (1)

1.4 Physical properties

Crystals of pure nitric acid are colorless and quite stable. Above the

melting point of —41.6° C, nitric acid is a colorless liquid that fumes in

moist air and has a tendency to decompose, forming oxides of nitrogen.

The rate of decomposition is accelerated by exposure to light and

increases in temperature. (1)

Table [1 – 2]. Physical properties of nitric acid. (1, 2)

Property Value

Formula HNO3

Molecular weight (kg/kmol) 63.013

Boiling point ℃ 82.6 ± 0.2

Freezing point ℃ –41.59

Density at 20 ℃ (kg/m3) 1512.8

Viscosity of liquid at 20 ℃ (mPa.s) 0.746

Refractive index n24D 1.3970

Surface tension at 20 ℃ (N/m) 0.04115

Thermal conductivity (W/m.K) 0.343

Heat of formation (kJ/mol) –174.10

Heat of vaporization at 20 ◦C (J/g) 626.3

Specific heat at 20 ◦C (J/g.K) 1.7481

Heat of fusion kJ/mol 10.48

1.5 Chemical properties

1. Acidic Properties. As a typical acid, it reacts readily with alkalis,

basic oxides, and carbonates to form salts. The largest industrial

application of nitric acid is the reaction with ammonia to produce

ammonium nitrate. however, because of its oxidizing nature, nitric

acid does not always behave as a typical acid. Bases having

metallic radicals in a reduced state (eg, ferrous and stannous

hydroxide becoming ferric and stannic salts) are oxidized by nitric

acid. Except for magnesium and manganese in very dilute acid,

nitric acid does not liberate hydrogen upon reaction with metals. (1)

2. Oxidizing Properties. Nitric acid is an oxidizing agent (electron

acceptor) that reacts violently with many organic materials such as:

turpentine, charcoal, and charred sawdust. The concentrated acid

may react explosively with ethanol. Such oxidizing properties have

had military application: nitric acid is used with certain organics,

eg, furfuryl alcohol and aniline, as rocket propellant. Depending on

acid concentration, temperature, and the reducing agent involved,

any of the following oxidations may occur: (1)

3. Organic Reactions. Nitric acid is used extensively in industry to

nitrate aliphatic and aromatic compounds. In many instances

nitration requires the use of sulfuric acid as a dehydrating agent or

catalyst; the extent of nitration achieved depends on the

concentration of nitric and sulfuric acids used. (1)

4. Alcohols and glycerols are nitrated by esterification in a mixture of

concentrated nitric and sulfuric acids. This reaction is of

importance in the production of nitroglycerin from glycerol and

nitrocellulose from cellulose. (1)

 5. Dilute nitric acid can be used to oxidize an aliphatic hydrocarbon.

For example, a significant use for nitric acid is the oxidation of

cyclohexanol and e cyclohexanone to produce adipic acid. Most

adipic acid is used for the production of nylon-6,6. (1)

C6H11OH + 3 C6H10O + 14 HNO3

⟹ 6 HOOC(CH2)4COOH + 14 NO + 10 H2O

6. Hot concentrated nitric acid and carbon reaction: Carbon (C) and

hot concentrated nitric acid react to give carbon dioxide (CO 2),

nitrogen dioxide (NO2) and water. Here, carbon is oxidized to its

+4 oxidation state and nitrogen's oxidation state is changed from

+5 to

+4.
(5)

7. Nitric acid and silver metal reaction: Silver reacts with nitric acid

to give silver nitrate (AgNO3), NO2 and H2O. Silver is oxidized to

+1 oxidation state. (5)

8. Lead and nitric acid reaction: Lead(Pb) and dilute nitric acid react

to form Lead nitrate (Pb(NO3)2), NO2 and water. Here lead is

oxidized to its +2 oxidation state. Lead nitrate is soluble in water.

(5)
References

1. Kirk-Othmer, (1998), Encyclopedia of Chemical Technology, 4 th

Edition Vol.17, John Wiley, New York.

2. Ullman, (2005), Encyclopedia of Industrial Chemistry, 2nd Edition,

John Wiley, New York.

3. https://pubchem.ncbi.nlm.nih.gov/compound/Nitric-acid

4. https://www.statista.com/statistics/731566/japan-nitric-acid-

production-volume/

5. https://www.chemistryscl.com/reactions/nitric-acid-reactions/

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