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DARRELL
H. BEACH
The Culver Academies
CuIver. Indiana 46511

Nitric Acid
Sardul S. Pannu
University of the District of Columbia
Washington, DC 20008
3HN02 - 2N0 + HN03 + Hz0
Ostwald's Method
Catalytic Oxidation of Ammonia. In this method NH3 is
Old Names: oxidized a t 700°C by air or oxygen gas to form NO in the
Latin: Aoua Fortis. Acidum Nitri, Aqua Dissolutiva presence of either platinum gauze or platinum-rhodium cat-
French: E&Lde Depart, Acide ~ i t r i q u k alyst. The reaction is rapid and goes almost to completion
German: Starkwasser, Salt Petersaure (959~98%).
Alchemist's Symbol:
7 +
4NH3 502 - 4N0 + 6H20 AH = -229.4 kcallmale

History
The earliest reference to nitric acid is in the writing of the
eighth century Arab scholar Geber, who prepared nitric acid
by "distilling a pound of Cyprus vitriol, a pound and half of
saltpeter and a quarter of a pound of alum." In 1658 Glauber
obtained concentrated fuming nitric acid by distilling niter
with oil of vitriol (sulfuric acid). In 1776 Lavoisier proved that
nitric acid contained oxygen. The complete chemical com-
position was established in 1816 by Gay-Lussac and Ber-
tholet.
Occurrence
A considerable amount of nitric acid is produced by light-
ning and in the combustion of fossil fuel causing "acid rains"
which contain mainly sulfuric acid and nitric acid. Oxides of
nitrogen are also formed when air is irradiated in a nuclear
reactor. In the combined state it occurs in form of sodium
nitrate (Chile saltpeter) and potassium nitrate.
Methods of Preparation
Until 1924, nitric acid was obtained from the reaction of
Chile saltpeter and concentrated sulfuric acid. Since then
Ostwald's method of catalytic oxidation of ammonia has been
used in the manufacture of nitric acid.
From Chile Saltpeter and Concentrated Sulfuric Acid
Physical Properties
Nitric acid is a colorless mobile liquid which fumes strongly
in moist air. It has a pungent, choking odor. Nitric acid melts
a t -41.6'C and boils at 82.6"C. Its density is 1.51 g cm-%at
25°C. I t is very soluble in water. I t forms a maximum con-
stant-boiling mixture which boils at 120.5% containing 68.5%
HN03, and the solution has a density of 1.41 g ~ m at- 20°C.~
"Fuming nitric acid" is the concentrated nitric containing
dissolved nitrogen dioxide. The color of fuming nitric acid
ranges from yellow to red depending upon the concentration
of NO? present. The following are some h p o r t a n t standard
electrode potentials of nitric acid solution.
Nitric acid is a planar molecule containing an sp2nitrogen
atom. The predominant resonating structures of the acid
are

Rirkeland-Eyde Arc Process

In this process air is passed through an electric arc at a The bond distance and angles in nitric acid are given in the
temperature of about 3000°C. structural formula:
N2(g) + O2(g) f 2NO(g) AH = +43.2 kcal
According to Le Chatelier's Principle, the amount of NO
formed will be greater at higher temperatures and will not be
affected by pressure. The equilibrium concentration of NO
is 0.4% at 1500°C and 5% at 3000°C. This process is not used
currently because of the high cost of electricity. Another
variation of the above method was developed at the University
of Wisconsin. It consists of passing air through a preheated
bed of magnesia and then heating by combustion of fuel gases. The structure, properties, and uses of a variety of chemicals are high-
After the gases containing NO have been chilled, nitric oxide lighted in this feature which is aimed at increasingthe use of descriptive
reacts with oxygen to form nitrogen dioxide which is suhse- chemistry.
quently absorbed in water.

174 Journal of Chemical Education

Chemical Properties
Decomposition -
+0.80V to +O.96V. Therefore, it can oxidize V2+ V3+, V3+
to VO2+, Cr2+ Cr3+, Ti3+ to Ti02+, Fez+ to Fe3+, and Nh3+
-
to NhO2+.
Nitric acid is fairly stable a t room temperature. However,
i t is decomposed by heat, especially ahove 68°C. 3Fezt + 4Ht + NOs- -
3Fe3++ 2H20 +NO
Fez++ NO -
Fe(N0)2+
brawn
T h e familiar yellow color of concentrated nitric acid in re-
agent bottles is due to its decomposition to NO*. The following These reactions form the basis of detecting nitric acid or ni-
seems to he the most plausible mechanism for the decompo- trate ion by the familiar ring-test method.
sition of nitric acid a t room temperature.
Reaction with Nitrogen ( I I ) Oxide
When gaseous nitric oxide is bubbled through an aqueous
nitric acid solution nitrous acid is formed.

The ahove reaction is catalyzed by hydrochloric acid and small

amounts (10-8 to 10-9M) of silver (I) and mercury (I) ions.
Acidic Properties Reactions with Inorganic Compounds
Nitric acid is hizhlv ionized (93% in 0.10 M ) in water solu- Nitric acid converts SO2 to H2SO4, H a s to S, HCI to Clz,
tions and, therefore,;t is a strong monoprotic acid. It reacts H3P03 to H3P04. and H3As03 to H3As04
with bases, metallic oxides, and carbonates to form salts and
water unless the metallic ion concerned is a reducing agent.
CdO + 2HN03 - Cd(N03h + Hz0 Reaction with Gaseous Fluorine
3Fe0 + lOHN03 - +
3Fe(NOh 5H20 + NO Dilute solution of nitric acid (1.3 N ) are oxidized a t low
temperature by gaseous fluorine to pungent pernitric acid
Oxidation of Metals (HN04), which decomposes to give oxygen gas:
Nitric acid solutions are strong oxidizing agents. Nearly all
metals are attacked by nitric acid except Au, Pt, Ir, Ta, and
Rh. Metals like Fe, Cr, and Al readily dissolve in dilute nitric
acid hut are rendered passive by concentrated nitric acid so-
lution due to the formation of an oxide layer on the metallic
surface. This feature makes it possible to store and ship con-
centrated nitric in steel containers. The metalloids Si, Ge, Sn,
2H202 - 2H20 + 0 2

As, and S b along with the transition metals Mo and W are Ox~dationsof Organic Compounds
converted to oxides by hot concentrated nitric acid. The re- Many organic compounds undergo oxidation with dilute
maining metals are attacked by nitric acid to form nitrates. or concentrated nitric acid. Sawdust reacts vigorously and
The other reaction products depend upon the nature of the turpentine oil explodes to produce black smoke. Warm and
metal, temperature, and concentration of the acid. The re- dilute nitric acid oxidizes the primary alcohol function of an
action product may contain one or more of the following aldose or aldonic acid to a carhoxylic acid. Under these con-
substances: NzO, NO, NO*, Hz, NH20H, Np, and NH3. In ditions, an aldose is converted into a dicarhoxylic acid, aldaric
general, metals which are ahove hydrogen on the electromotive acid (the diacid formed from D-glucose is called glucaric
series yield H2, N2, NH3, NH20H, or NO when treated with acid):
nitric acid. Metals which are below hydrogen in the electro-
motive series tend to give NO or NO*.
HOCH,-(CHOH),--c& HNO, HO,C-(CHOH),CO~H
Zn+ 2H+ + ZnZ++ Hz?
Aldose H' Aldaric Acid
(<25%)
-
3Zn + 8HC+ 2N03- 3Zn2++ 4Hz0 + 2NO
(dilute)
Concentrated nitric acid converts surruse to onalir acid and
-
4Zn + NO3- + 10H+ 4Zn2+ + 3H20 NHdt
(dilute)
+
alkyl hrnzene t o henzoic acid derivat~\.eon heating.

-
6Zn + 2N08- + 16Ht 6Zn2++ 4H20 + 2NHjOHt
(concentrated)
-
3Cu + 8H+ + 2N03- 3Cu2++ 4HzO + 2NO Nitrating Property
-. -
. of HNOg is due to formation of
(dilute)
Cu + 4Ht + 2N03- - Cu2++ 2H20 + 2N02
The nitratine nronertv
NO2+ in presence of concentrated sulfuric acid:
(concentrated)
+
Sn + 4Ht 4NOs-
(concentrated)
- SnOn+ 4N02 + 2H20 Solutions containing N02+ are of considerable importance in
the aromatic nitration reaction:
Oxidation of Nonmetals
Hot concentrated nitric acid oxidizes 12 to HI03, Pa to
H3P04, and C to H2C03.

Ox~dntionof Louw 0 ~ 1 d u l i o n.Vumbrr .\lr~rollrr i m ~ \

The stiindard putrntid of nitric arid sulutions range from

Volume 61 Number 2 February 1984 175

Uses was 1.1million tons in 1947,g.O million tons in 1980, and 9.4
~h~ largest use of nitric acid is still the production of am. million tons in 1981. The 1980 prices were $0.10 to $0.14/kg
monium nitrate, 90% of which is used as a fertilizer and the for 58-6896acid and $0.26/kg for 95%acid.
rest for explosives and as a source of nitrous oxide (NzO).
Nitric acid is used fur prrparation of s ~ l v r nitrate,
r trinitro-
toluene, nitroglycerine, nitrocellulose, and nitnrhenzene which General References
in turn is used to produce aniline for use in the manufacture
of dye intermediates, isocyanates, rubber chemicals and hy-
droquinone, and nitrochlorobenzene to produce insecticides,
such as parathions. A growing use of nitric acid is the manu-
."-.,
(1) Chem En8 Nous, 59. (37). 21 (September 14, 1981); 59. (51). 34 (December 21,
LrnOL,.

(21 Cotton, F. Albert, and Wilkinson, G., "Advanced Inorganic chemistry," 3rd ed., 1"-
facture of "luene diisocyanate (TD1) which is the raw mate- terscience.New York, 1972,pp. 179,130.
(31 Davenport, Robert E.,"ChemicalEconomicsHandbaok."SRI International, Menlo
rial for polyurethane plastics, and adipic acid from a cyclo- p a 7 k . c ~ .1977,pp. 'l56.3005~.7 5 6 . 3 0 0 ~ ~ , 7 5 6 . 3 ~ ~ 1 .
hexanol/cyclohexanone mixture to produce nylon-66. (41 D ~J O ~~" ~ ~. , , - ~ ~ ~ gchemistry: ~ ' ~ I~~ ~~ ~ ~~ ~d . b, M~ ~ ~ C ~~ ~ ~W -r H ~ I I B ~ ~
NewYork. 1979,pp. 6-13.
Small amounts of nitric acid are employed in stainless steel (5) "Great Soviet Encyclnpedia."Brd ed.,MaeMillan, Inc.. New York, 1973,Vol. l,pp.M7,
pickling, metal etching, rocket propellant, nuclear fuel pro- 648.
(61 Kemp,DsnielS..andVellaecia,Fmnk,"OraanicChemist'y."WarthPublishers.Ine.,
cessing, the separation of gold from silver, the manufacture New York. 1980.p~.740-741.873.
of sulfuric acid by the lead chamber process, and production (7) ~ ~ ~J. J., ~%dem ~ kinorganic
i ,~ h ~ ~ nekker,
i ~ N*W
hc., t Y ~W ~197.3.
,: ~ ~ ~ ~
Of nitrophosphates from phosphate rocks' especially in Eu- p p 407,408.
(6) Mel1ur.J. W.,"AComprehensiveTrestireon Inorgsni~andTheoreti~alChemistr~,"
rope. Aqua regia is a mixture of concentrated nitric acid and L ~ , creen ~ and
~ C~ O.,L~ O ~~ 1928,v01.
~ ~,D , VIII,pp.555,557.
concentrated hydrochloric acid (1:3) which can dissolve gold (9) ~ e w m a n ,ani id J., "~irk.othmer~ncyc~opedia of chemical T ~ F ~ ~ O I O 3rd
~ ~ ed.,
. "
John Wilev and Sona. New York. 19.81,Val. 15, pp. 864,866,869,
and platinum. (10) Partingtan, J. R.. "A Text-Rook oilnorgsnicChemistry." 6th ed., MscMillan andco.,
London. 1953,pp.536,539.
Production and Price (11) w,$ht. M. G. B., and Evans. P., " s ~to M ~~I I comprehensive
O~~ ~ I ~ ti^^ ~ ~ ~ ~
on Inorganic and Th~oreticalChemistry." John Wiley and Sons, New York, 1967,
The amount of nitric acid produced in the United States Val. VIII.SU~PI.2 . p ~ 3. 1 ~ 1 7 . 3 1 9 .

176 Journal of Chemical Education