Study of Compounds

11 D. Sulphuric Acid

SYLLABUS
Large scale preparation, its behaviour as an acid when dilute, as an oxidizing agent when concentrated -oxidation of carbon and
Sulphur, as a dehydrating agent dehydration of sugar and copper (II) sulphate crystals; its non-volatile nature.

Manufacture by Contact process Equations with conditions where applicable

Its behaviour as an acid when dilute - reaction with metal, metal oxide, metal hydroxide, metal carbonate, metal bicarbonate,
metal sulphite, metal sulphide.
Concentrated sulphuric acid as an oxidizing agent the oxidation of carbon and sulphur.
Concentrated sulphuric acid as a dehydrating agent - (a) the dehydration of sugar (b) Copper (11) sulphate crystals.
Non-volatile nature of sulphuric acid - reaction with sodium or potassium chloride and sodium or potassiun nitrate.

SULPHURIC ACID 11.3 PREPARATION OF SULPHURIC ACID

Molecular formula H,SO4 (1) By oxidation of an aqueous solution of sulphur
Relative molecular mass: 98 dioxide with oxygen, chlorine or bromine.
250, + 2H0 + O, > 2H,S0
Structure: SO +2H,0 + Cl, H,SO +2HCL
H-0-S-0-H
SO, +2H0 +
Br, >
HSO, +2HBz.
The colour of Cl, and Br, fades.
11.1 INTRODUCTION
(2) Sulphur with conc. nitric acid
Sulphuric acid is rightly called the 'King of S+6HN0, H,$0, +6NO +2H,0.
Chemicals' because there is no other manufactured
compound which is used by such a large number (3) By dissolving sulphuryl chloride in water
of key industries. It has been known for a long time. SO,Cl,+2H,0H,SO, +2HCI.
In the later Middle Ages, it was obtained as an 11.4 MANUFACTURE OF SULPHURIC ACID
oily viscous liquid by heating crystals of green (CONTACT PROCESS)
vitriol, and was, therefore, known by the name of
The various steps in the Contact process are as
oil of vitriol.
follows
2FeSO,.7H,0-Fe,O, +S0, + S0g+ 14H,0. (1) Production ofsulphur dioxide: Sulphur dioxide
The sulphur trioxide evolved gets dissolved in is produced by roasting metallic sulphides in air
water forming sulphuric acid. Fes, Iron pyrites) + 110, 2Fe,0, +8S0.
OR
sO, +H,0H,SO
11.2 OcCURRENCE by burning Louisiana sulphur (99.5% pure) in
purified air.
In the free state, it is found in certain mineral
springs and is formed by the action of water on S+O,SO,.
(2) Purification of gases: The mixture of sulphur
certain sulphides. dioxide and air contains various impurities which
In the combined state, as Barytes [BaSO,l. must be removed, otherwise the catalyst loses
Gypsum [CasO, 2H,0] and Kieserite [MgsO4H,O} its efficiency.
etc.
181
 CONC. cONC. H,so
WATER
COOLER TESTING
STEAM H,SO BOX
(98 %)
SO2+AIR WASTE GASs
PYRITE
BURNERSs* |SSS|
SSS ABSORPTION
AIR SSS TOWER
SSS
(BLOWER) SSS
SSS OLEUM
(CONTACT
TOWER n
DUST CHAMBER DRYING CHAMBER)
F WATER
SCRUBBERA TOWER ARSENIC PURIFIER
Fig. 11.1Gehtact process
Parts of the Plant for the manufacture of H,SO, acid
Blower Function 3
For passage of
Sulphur or iron For
purified air or oxygen.
pyrite burners production of sulphur dioxide by burning
sulphur or iron pyrites.
Dusting chamber For removal of dust
Cooling pipes For cooling the
particles by downward blow of steam.
gases by passage through isolated
Scrubbing tower For further removal of pipes.
Drying tower For drying moist
impurities and dust particles by downward
spray of water.
Arsenic purifier gases by downward spray of conc.
For removing arsenic
oxide by passage over ferric
H,SO4
Testing box For testing the hydroxide.
Contact tower purity the gases by passage of light through a darkened box.
of
For catalytic oxidation of
SO, to SO, by passage of sulphur dioxide and
packed with vanadium pentoxide
catalyst initially heated to 450°C.
oxygen through iron tower
Absorption tower For absorption of
Dilution tank sulphur trioxide vapours by descending stream of conc.
For dilution of oleum
by flow of required amount of water H,SO,[98%].
The mixture is
passed through a purifier called Since the reaction is
electric precipitator, consisting of a chamber with highly exothermic, the
wires at high electric catalyst is heated only in the beginning
potential. The electric charge 450°C. This
to about
attracts solid
particles which are removed. The temperature is maintained by heat the
mixture is then led to
evolved during the reaction.
water scrubber where it is
a

completely freed from (4) Absorption of sulphur trioxide in

dust.particles. It is then dried acid. The sulphuric
by a spray of concentrated sulphuric acid in another is
gas cooled in a heat
chamber. It then goes into the arsenic isthen absorbed in exchanger and
purifier where absorption tower in
concentrated sulphuric acid
every trace of arsenic oxide is removed (98%)..
(Fig. 11.1).
(3) Catalytic oxidation of SO + H,SO, > H,SO, (oleu or
sulphur dioxide. The clean
dried gaseous mixture of
is
sulphur dioxide and air Vyrosulphuric acid)
passed through contact tower loosely packed (5) Dilution of oleum to obtain
with vanadium s diluted in dilution sulphuric acid. It
pentoxide or platinum on tank by adding calculated
perforated shelves. The catalyst is placed in amount of water to obtain sulphuric acid of the
vertical iron pipes inside a desired strength.
cylindrical iron tower
called the converter. Here, the
of sulphur dioxide and air
preheated mixture KS,0, +H,O 2H,SO,
(oxygen) on passing
through catalyst pipes forms sulphur trioxide. Since sulphur trioxide does not dissolve in
water
V,O satisfactorily and it gives a lot of heat and forms
90,+O 250 misty droplets of sulphuric acid, it is not directy
450°C absorbed by water
182
 tions for the conversion of
Favourabl

SO,(contact process)
SO, name the productformed. Give all the main reactions

to
of this process. ,n,to eH,
Lxothermic reactions are favoured at low (o) Name a gas that can be oxidized to sulphur.
temperature: The temperature should be as low 3 Why the impurity of arsenic oxide must be removed before
as
pOssible. The yield has been found to be passing the mixture of 8O, and air through the catalytic
lt
maximum at about 410-450°C. chamber ? thod he toddyt dra nol ley

High pressure favours

chamberelcin
High pressure :
the 4. Sulphur Sulphuríc acid
reaction because the product formed has less
B
volume than reactant. But the acid-resistant
towers which are able to withstand high Sulphur dioxide C Sulphur trionide
pressure are difficult to build. Hence the E VF
pressure of 1 2 atmosphere is used.
-

Sodium sulphite
Excess oj orygen: This increases the
(a) Name the catalyst which helps in the conversion°sof
production of sulphur trioxide. sulphur dioxide to sulphur trioxide in step C. 2

In the Contact process for the manufacture of

i A suitable catalyst: Platinum is more efficient (b)
as a catalyst than vanadium pentoxide (V,0), sulphuric acid, sulphur trioxide is not converted to
two
but platinum is more expensive and also it easily sulphuric acid by reacting it with water. Instead a
the
steps procedure is used. Write the equations for
gets poisoned by impurities like arsenic (11) two steps involved in D.
oxide.
liberate sulphur dioxide
(c))What type of substance will
Vanadium pentoxide is used as a catalyst. from sodium sulphite in step E?

(d)) Write the equation for the reaction by which sulphur

SUMMARY OF CONTACT PROCESS dioxide is converted to sodium sulphite in step F.
Formation of Sulphur dioxide:
S+0,SO; or 4FeS + 110, 2 Fe,0, +8S0 11.5 PROPERTIES OF SULPHURIC ACID
Conversion of purified SO, to SO, 11.5.1 Physical properiies
V,O/Pt 1. Colourr Colourless.
2s0, +0,400- 450°C2S03 2. Odour Odourless.
Conversion of sulphur trioxide into oleum 3. Taste Slightly sour in taste.

4. Nature Dense, oily, hygroscopic liquid. It

SO, +H,SO, H,S,0,/%h absorbs moisture, so H,SO, should
Dilution of oleum always be kept stoppered.
HS,O, +H,0 2 H,So 5. Density Pure acid: 1.85 g/ce.
6. Boiling point 338C
7. Melting point Pure sulphuric acid freezes to

{Intext Questions colourless crystals at 10.4°C.

8. Solubility Soluble in water in all proportions.

Comment, sulphuric acid is referred to asa:s i t wa8 o i t a u n
9. Conductivity Pure acid: Almost a non-conductor
aKing of chemicals, Qil of vitriol.asa of electricity.
2. Sulphuric acid is manufactured by Contact'process. Good conductor of
Dilute acid
(aGive two balanced equations to obtain SO in this
electricity.
process, le , '. ]1o,2 , 0 3D2 It forms a constanu boiling
|10. Constant
Give the conditions for the oxidation of SOp mixture at 338°C containing 98.5%
boiling mixure
Why Hso, is not obtained by directly reacting SO of the acid.
with water? Concentrated acid is highly corrosive
11. Physiological
Name the chemical used to dissolve SOg and also in nature and chars the skin black.
nature

183
 11.5.2 Chemical properties (3) It liberates carbon
Pure (100% H,SO) hydrogen sulphate is not an carbonates and bicarbonates. dioxide from me
acid as it does not ionise. Carbonate/ + Acid
bicarbonate
Salt (2)
Sulphuric acid when dissolved in water form +Water
hydronium ion and so shows acidic properties. Na,CO3 H,S04
+
Na,So+ Catw
HOC
H
A,SO, +H,O H,O* +HSO4". 2NaHCO HSO4 +
Na,So, + 24
HSO, + H,O H,Ot+SO,2 2KHCO +HS04 KSo + 24
lt
ionises in two stages and
acid. The chemical properties thus
it is a dibasic (4) It evolves
of sulphuric acia
hydrogen sulphide fr
depend on whether the acid is dilute or concentrated.
sulphides. from mea
Metal + Acid
Dilution of H^SO4: Water is never Salt
acid to
dilute it as large amount of heat is poured on sulphide
Na,S +
HSO4
Hydrwg
sulphide
evolved which NaSO4 +
The steam so
changes poured water to steam. FeS HS
formed causes spurting of acid HSO4 FeSO4
which can cause burn ZnS + H,SO4 HS
by pouring acid on a
injuries, so dilution is done ZnSO +
HS
controlled
givenamount of water in a (5) It evolves sulphur dioxide from
hydrogen sulphites (bisulphites). sulphites
manner by continuous stirring, else
acid being heavier will and
settle down. The evolved
heat is
dissipated
the spurting of the
in the water itself and
hence
Sulphite + Acid Salt +Water +Sulphur
acid is minimized. bisulphites
dioxide
Na,SO +HSO4 Na,sO4 +
H,O + SO,1
a) Properties of dilute sulphuric acid 2NaHSO, H,SO4 Na,SO4 +
2H,0 + 280,1
Acidic property: Note: Sulphur dioxide is poisonous and, is
1) Dilute sulphuric acid reacts with therefore, responsible
are above hydrogen in the activity
metals, which for polluting environment.
series to form It adversely affects the human health
metallic sulphate and
hydrogen at ordinary vegetation.
temperature.
(b) Properties of concentrated sulphuric acid
Active metal Acid Metal + Hydrogen
sulphate (1) Non-volatile nature
Mg H,SO4 MgSO4 +
HT Concentrated sulphuric acid has a high bong
point (338°C) and so, it is considered
Zn +
HsO ZnS04+HT a non-volatile
to
acid. It is, therefore, used tor
Fe Hso FeSO H, 1 preparing volatile acids like hydrochloric acid
Note Noble metals like gold and platinum do
: itric acid and acetic acid from their salts o
react with H,s04 under any condition. double decomposition.
It neutralises bases (oxides and hydroxides) to Salt of Acid Acid salt +Volatile
form salts and water. volatile acid (conc.) acid

NaCl
Base/Alkali + Acid Salt Water KCI
HSO NaHSO + HCI

CuO HSO4 CuSO4+ HO

+H,sO KHSO4 + HCI

NaNO +H,so4 NaHSO, + HNO3

NaOH + HSO4 NaHSO4 + HO KNO HsO KHSO, + HNO
2NaOH + HSO4 Na,SO4 + 2H,0
eH,COONa +
HSO NaHSO, + CH,CO0
Acetic acid
FeO +H,SO FeSO4 + H,o Sodium acetate
 ridising agent
o r i d i s i n g
age

an (3) As a deh
As
xidising roperty of concentrated sulphuric aydrating agent
The is due to the fact that on thermal H,SO has a great affinity for water. It
decomp
acid
1position, it ields nascent oxygen [O]. removes elements of readily
water from other
ASO > HO.+SO, +[O] compounds i.e., it acts as a
(a) dehydrating agent.
Nascen oxygen oxidises non-metals, metals and Organic acids and organic
inorganic compounds.
dehydrated by conc. H,SO, as compounds
follows?
are

CHCOOH Conc. H,S04 CO

(a) N o n - m e t a l s
+
HO
. Carbon COOH), Conc. H,SO4 C0+CO+ H,O
C+24,504 CO + 21H,0 + 2s0,1 Conc. H2504
2. Sulphur
HOH -

170°C CHT +HO

Ethylene
S+2H,SO4 3SO, +2H,0. (6) All carbohydrates such as glucose, sugar, and
(b) Metals cellulose (paper, cotton, wood, etc.) react
immediately to give a black spongy mass of
1. Copper
carbon which rises up. Steam is given off and
Cu + 2H,S04 CuSO, + 2H,0 + SOT the whole mass gets heated due to an exothermic
2. Zinc reaction. They are said to get charred.

+2H,SO4 Conc. HSO4 6C + 6H,O

Zn >
ZnSO4 +
2H,0 +
SOT
Glucose
(c) Inorganic compounds CpH ()Conc.HSO 12C(s) + 11H,0
1. Hydrogen bromide kane Sugar Sugar Charcoal

2HBr+HSO4 Brz + 2H,0 + SO,T Carbon obtained in this reaction is very pure
2. Hydrogen sulphide and is called sugar charcoal.

HS + H,sO4 > S + 2H,0 + SO2T

cONC. H,S0
Note oxidising as well
Sulphur dioxide gas is
as reducing agent. It also shows temporary bleaching -STEAM

in presence of BLACK
property due to its reducing nature
moisture. YSTALSCRYSTALs * SPONGY
CARBON
OF SUGAR MASS
So+2H,0 >
H,SO4 + 2[H] Fig. 11.2. Addition of conc. HSO, to sugar
Nascent hydrogen
Colourless
Coloured + [H]
product
Note Conc. H,SO4 reacts with skin to give
material Nascent blisters, because of removal of water, and chars the
hydrogen skin black.
This colourless material, if
remains in air, of
(c) Conc. sulphuric acid removes water
regains its original colour. crystallisation from salts.
Coloured (original)
Colourless + Oxygen (air) material For example, blue copper (11) sulphate
material
as chlorine. CuSO.5H,O taken in a test tube becomes white
strong bleaching agent
Tt is not a
materials
anhydrous copper sulphate, when a few drops of
ience, it is used to bleach only delicate conc. sulphuric acid are added.
as coloured clothes, coloured wet flower petals
or fresh green grass.
euso, SH,0 HSO CuSO (s) + 5H,O
(Removed
Blue Dirty
white by acid)

185
 of insoluble
sulphates
acla
4) Preparation
(4) acid precipitates the
conpr sulphuric Sulphuric
Dtference between dilute and
Concentrated of lead, barium and calcium nsoluk
Dilute acid
sulphates
of their salts. from
1. It ionises to great 1. tis a weak solutions
extent so behaves as
strong acid.
2. Weak electrolyte.
Soluble Acid
Insoluble Ac
2. Strong electrolyte. as salt salt
acts
3. lt cannot act as an 3. Conc. H,SO
an oxidising agent. Pb(NO,), + H,SO4 Pbso, L +2
oxidising agent. 2HN
Dilute sulphuric acid 4. It is used to dry gases
cannot be used as a like HCl and even
BaCl +HSO > Baso, 2 H
dehydrate substances
drying or dehydrating
agent. like CuSO4 5H,O

11.6 USES OF SULPHURIC ACID

1. It is used in the preparation of:
(a) Halogens, (b) Carbon monoxide, (c) Carbon dioxide, (d)
Hydrogen, (e) Sulphur dioxide.
2. Metallurgy
) Extraction Its reaction with metallic compounds gives sulphates which
electrolysis give the metal in the pure form.
(i) Pickling metals Removes metallic impurities like oxides and carbonates from
surface of metals before galvanizing.
3. In lead accumulators It undergoes electrolysis in the aqueous state.
4. Oil refining Sulphuric acid is used to remove harmful impurities in purifica
of oil products, e.g., petrol, kerosene and lubricants.
5.Industrial uses: in the manufacture of:
Fertilizers like (a) Ammonium sulphate
[(NH,),SO,].
(b) Superphosphate of lime
[Ca(H,PO,)2 +
CaSO,1.
(ii) Dyes, drugs (a) Artificial fibres
Rayon, [] Nylon.
(b) Dyes, drugs [from coal tar
(ii) Explosives like
derivatives].
(a) Tri-nitro toluene [T.N.T.].
b) Picric acid,
(c) Tri-nitro glycerine [CgH,O,(NO,),].
iv) Acids like (a) Nitric acid [HNOl.
(b) Hydrochloric acid [HCI),
(c) Phosphorie acid
(d) Acetic acid
H,PO.
(v Coppounds like
[CH,COOH].
(a) Sodium sulphate
Iglass
(b) Ferrous sulphate [ink industry],
industry].

186
 11.7 TESTS FOR SULPHURIC ACID AND chloride, with a glass rod dipped in ammonium
SULPHATES hydroxide.
(1) Conc. sulphuric acid on heating with copper
evolves sulphur dioxide. HCI+NH,OH NH,CI +H,O
(dense white fumes)
Co + 2H,SO, > CuSO, + 2H,0+ SO, T (3 When barium chloride solution is added to
(Cone.) sulphuric acid or any soluble metal sulphate,
Sulphur dioxide turns acidified potassium white precipitate of barium sulphate is formed.
dichromate solution green (Reducing property BaC1, + H,SO, >BaSO, + 2HCI
of SO,).
BaCl +MgSO, > BaSO4+ MgCl,
K,Cr,0, H,SO
+ +
3SO, >
Cr,(SO)3 + K2SO +
H,O The white precipitate of barium sulphate is
(Orange) (Green) insoluble in any mineral acid like hydrochloric
Cone. sulphuric acid on heating with NaCl acid or nitric acid.
evolves pungent fumes of HCl gas.
NaCl+
Note Precipitates of both barium sulphate and
HSO,A + HCI NaHSO T barium sulphite are white in colour but barium
(Conc.)
sulphite precipitate dissolves in mineral acids
HCl gas gives dense white fumes of ammonium while barium sulphate precipitate does not.

EXERCISE-11
JWhy is water not added to concentrated H,SO, in order ) a s a source of hydrogen by diluting it and adding a
to dilute it ? aarause in that case, atd n may puit
Y Spart stripof magnesium, a clale
e E hAt m,
G v e two hal
2 iGive balanced reactions of each type to show the d)in the preparation of sulphur dioxide by warming a
following properties of sulphuric acid mixture of conc. sulphuric acid and copper-turnings.
(a Acidic nature, (bY Oxidising agent, ehydrogen sulphide gas is passed through
concentrated sulphuric acid. o c l i r
Dehydrating nature, (d Non-volatile nature. 29er

.Give a chemical test to distinguish between What is the name given to the salts of
itute sulphuric acid and dilute hydrochloric acid, (asulphurous acid, (bsulphuric acid ? 9arara
Sprte/bigwlpr
(by dilute sulphuric acid and conc. sulphuric acid. 8. Give reasons for the following
4. Name the products formed when hot and concentrated SSulphuric acid forms two types of salts with NaOH.
sulphuric acid reacts with the following (bY Red brown vapours are produced when concentrated
(a) Sulphur, (b) NaOH, (c) Sugar, sulphuric acid is added to hydrogen bromide.
d) Carbon, (e) Copper. A piece of wood becomes black when concentrated
5. Why is sulphuric acid is poured on 1,o 6cér
a ) Brisk effervescence is seen when oil of vitriol is
( a concentrated sulphuric acid kept in air tight
bottles?a i t s
bottles ?
bre hydrorepic, absorbe
L tomu A
added to sodium carbonate. duu to kes matian
oC
Copy and complete the following table:
b) H,SO4 is not used as a drying agent for H,S ?
(sulphurie acid used in the preparation of HCI and Column 1 Column 2 Column 3
HNO, ? Give equations in both cases. xi12Ou d HCe Substance reacted | Dilute or Gas
5. What property of conc. H,sO, is made use of in each of with acid concentrated
the following cases? Give an equation for the reaction acid
ineach case
Mg dilvde Hydrogen
(in production of
the HCl gas when it reacts with a
ilude Carbon dioxide
chloride, dga agent, kcl + ,1Oa Ja t1
Only chlorine
6ROAOAPudu_olrlede |
i n the preparation of CO from HCOOH,ielratiy |
COn.HS 187 Ca dCl
HCOOu