NITRIC ACID
Nitric Acid: A Powerful Chemical Nitric acid is a strong, corrosive,
and oxidizing mineral acid with the formula HNO3.
Structure:
Formation of nitric acid in atmosphere
1. Formation of NO during lightning discharge:
2. Oxidation of NO to nitrogen dioxide:
3. Dissolution of nitrogen dioxide in rain or moisture to form nitric acid:
Lab preparation of nitric acid Temp: below 200 ℃.
Why Yellow: because
HNO3 dissociates into
water, nitrogen dioxide
(yellow) and oxygen gas.
How to remove yellow
color??
1. By passing dry air or
CO2.
2. By adding excess
water so that NO2
dissolves in it.
Industrial manufacture of nitric acid (Ostwald’s Process)
Step 1: oxidation of ammonia in
presence of Pt at 800 ℃.
NH3 + O2 → NO + H2O + heat
Step 2: formation of nitrogen dioxide
NO + O2 → NO2, temp~ 50 ℃.
Step 3: Absorption of NO2
(Formation of HNO3)
NO2 + H2O + O2 → HNO3 + NO
The acid obtained is around 68 %
concentrated.
How to increase concentration of obtained nitric acid?
1. Distilling HNO3 over conc. H2SO4. Around 98% of conc. HNO3 can be
obtained.
2. Cooling ( -42 ℃) 98% HNO3 to obtain crystals (colorless).
Physical Properties of Nitric Acid
1. Color: Colorless in pure form but yellowish at about 68%.
2. Odour: Suffocating Smell
3. Taste: Acidic
4. Nature: Hygroscopic and fumes in air
5. Density: 1.54 g/cm3 for (98%) and 1.42 g/cm3 for (68%).
6. BP and MP: 86 ℃ and -42℃ respectively.
7. Solubility: Soluble in water
8. Physiological reaction: Non-poisonous. Stains skin yellow and form
xanthoproteic acid.
Chemical properties:
1. Stability: HNO3 decomposes to form nitrogen dioxide, water and oxygen.
Hence nitric acid is kept in amber or dark color bottles.
2. Reaction with oxides and hydroxides: forms nitrates and water.
Na2O + HNO3 → NaNO3 + H2O
ZnO + HNO3 → Zn(NO3)2 + H2O
Fe(OH)3 + HNO3 → Fe(NO3)3 + H2O
3. Reaction with carbonates and bicarbonates: forms nitrates + water + CO2
CaCO3 + HNO3 → Ca(NO3)2 + H2O + CO2
NaHCO3 + HNO3 → NaNO3 + H2O + CO2
4. Reaction with metallic sulphites and bisulphites: forms nitrates + water + SO2
Na2SO3 + HNO3 → NaNO3 + H2O + SO2
CaHSO3 + HNO3 → Ca(NO3)2 + H2O + SO2
5. Oxidising properties: is a good oxidising agent due to formation in nascent
oxygen [O].
HNO3 (conc.) → NO2 + H2O + [O]
HNO3 (dil.) → NO + H2O + [O]
ACTION ON METALS
1. Cold and dil. Nitric acid: Nitrates + water + nitrogen monoxide
2. Conc. or hot dil. Nitric acid: Nitrates + water + nitrogen dioxide
3. Very dil. Nitric acid (~ 1 %): nitrates + hydrogen gas
Mg + HNO3 → Mg(NO3)2 + H2
Mn + HNO3 → Mn(NO3)2 + H2
FORMATION OF PASSIVITY
❖ Metals such as Fe, Al, Co, Ni becomes inert when treated with
pure nitric acid. This is because nitric is a good oxidising agent
and can oxidise metal to oxides. Thus a layer of oxide is
developed over metals which further prevents the reactions,
making it passive.
❖ Passivity can be removed by cleaning the surface of metals with
sand paper or by treating with strong reducing agents.
FORMATION OF AQUA REGIA (ROYAL WATER)
❖ AQUA REGIA = CONC. HNO3 (1 PART) + CONC. HCl (3 PART)
❖ HNO3 + HCl → NOCl + H2O + [Cl]
Aqua regia produces nascent Cl which can react with inert metals such as gold
and silver converting them into soluble chlorides.
Pt + aqua-regia → PtCl4 (soluble)
Au + aqua-regia → AuCl3 (soluble)
Effects of heat on nitrates
1. Alkali metal nitrates to produce nitrites and oxygen:
a. NaNO3 → NaNO2 + O2 (glowing splinter burst into flames, due to formation of oxygen)
2. All other nitrates produces oxides, nitrogen dioxide and oxygen:
a. Ca(NO3)2 → CaO + NO2 + O2
b. Pb(NO3)2 → PbO + NO2 + O2
3. Silver and Mercury nitrates decomposes to respective metals, nitrogen
dioxide and oxygen.
a. AgNO3 → Ag + NO2 + O2
b. Hg(NO3)2 → Hg + NO2 + O2
Test for nitrates or nitric acid
1. Reddish-brown fumes of nitrogen dioxide are evolved on heating nitrates and
nitric acid.
2. Brown-ring test:
The brown ring test is a typical nitrate test that involves adding iron(II) sulphate to a nitrate
solution, then slowly adding strong sulfuric acid until the acid forms a layer below the
aqueous solution. The existence of the nitrate ion will be shown by the formation of a brown
ring at the junction of the two layers.
Steps:
1. Place the given sample, which may contain nitrate ions, in a test tube.
2. In a separate test tube, make a fresh ferrous sulphate solution.
3. When the ferrous sulphate solution is ready, combine it with the sample in the test
tube.
4. Add concentrated sulphuric acid along the test tube’s wall in the same test tube.
5. When adding concentrated sulphuric acid, tilt the test tube slightly. This allows the
acid to sink to the bottom of the test tube, resulting in the creation of a brown ring at
the intersection of the two layers.
6. Don’t jiggle the test tube once the brown ring has formed, since this may cause the
brown ring to dissolve into the solution.
Brown Ring Test with the Equation
