Applied Chemistry

CODE NO: 07
I B.TECH
CIVIL ENGINEERING
Unit No: VIII
Nos. of slides:
 Applied Chemistry
INORGANIC CEMENTING MATERIALS
Term: 2008-09

Unit-VIII Power Point Presentations

Text Books:
 A text book of Engineering Chemistry
by Jain & Jain,
 Chemistry of Engineering Materials by
C.P. Murthy, C.V. Agarwal and A.
Naidu
 INDEX
UNIT-VIII PPTS
Srl. Module as per Lecture
PPT
No. Session Planner No.
Slide No.
---------------------------------------------------------------------------------------------
----
4. Introduction L-1 L1-1 to
L1-19
2. Hardness & Units L-2 L2-1 to
L2-28
3. Estimation of Hardness by EDTA L-3 L3-1 to
L3-18
4. Problems on Hardness L-4 L4-1 to
L4-18
5. Analysis of water L-5 L5-1 to
L5-19
6. Methods for treatment of water (Domestic) L-6,7 L6,7-1
to L6,7-33
 The manufacture of
cement consists of the
following steps.
Mixing of raw materials
or slurry:
An intimate mixture of finely ground
limestone and clay (3:1) is made
into thin slurry with water by any of
the following methods.
Dry process
Wet process
 Dry process:
If the lime stone and clay are hard,
then the dry process is used. in this
process the lime stone is first broken
into small pieces. it is then mixed with
clay in the proper proportion (3:1) and
finally pulverized to such a finesse that
90-95% passes through a 100 mesh
sieve. Then the raw mix is fed to a
rotary kiln.
 Wet process:
If lime stone and clay are soft, the wet
process is preffered. In this process, the clay
is washed with water in wash mill to remove
the foreign materials, organic matters etc.
the powdered limestone is then mixed with
the clay paste in the proper proportion (3:1)
and the two ingredients are finely ground and
homogenized. in this process, the slurry
contains about 40% of water. Now the slurry
can be fed to rotary Kiln.
 Burning:
The dry pulverized raw mixture or slurry is
introduced into a rotary kiln which consists of
an inclined steel rotating cylinder. 150-200
feet long and 10 feet in diameter lined with
fire bricks. The water evaporates at the
upper ends of kiln by means of hot gases.
The Kiln rotates on its axis at the rate of ½ to
1 revolution per minute. As the Kiln rotates
the charge slowly moves down-wards due to
the rotary motion of the Kiln. Now the charge
is heated by blast of air charged with coal
dust is admitted. this produces a
temperature range of 1500 to 1700 0C in
step wise process as:
 • At 750 0C the moisture is completely
eliminated.
• b. At 10000C the limestone is completely
decomposed to CaO.
c. At 1500 to 17000C the mixture is partly
fused and sintered and chemical
combinations between lime, alumina,
ferric oxide and silica.
The charge takes 2 to 3 hrs. to covers the
journey in the Kiln.
Chemical reactions: in the rotary Kiln the
chemical reactions can be divided into the
following parts.
 a. Drying zone:
In this zone temperature raises to
maximum 750 0C so that entire
moisture in the slurry gets evaporated.
The clay is broken into Al2O3, SiO2 and
Fe2O3.
Al2O3 2SiO2 Fe2O3 2H2O  Al2O3
+ 2SiO2 + Fe2O3 + 2H2O
 Calcinations zone:
When the temperature raises at 1000
0C, the limestone is completely
decomposed into CaO.
CaCO3  CaO + CO2
 Reaction zone
(Clinkering zone):
when the temperature reaches about
16000C, the mixture is partly fused
and chemical combinations between
lime, alumina, ferric oxide and silica,
resulting in the formation of calcium
aluminates and silicates occur.
 2CaO + SiO2  2CaO.SiO2 (di
calcium silicate)
3CaO + SiO2  3CaO.SiO2 (Tri
calcium silicate)
2CaO + Al2O3  2CaO. Al2O3(di
calcium Aluminate)
3CaO + Al2O3  3CaO. Al2O3(tri
calcium Aluminate)
4CaO + Al2O3 + Fe2O3 4CaO.
Al2O3 Fe2O3(Tetra calcium
Aluminate)
 The resulting product is known as
cement clinkers and as it comes out
into the cooler. The clinkers are very
hot (10000C. The clinkers have the
appearance of small greenish black
or grey colored.
 3. Mixing of cement clinkers
with gypsum:

 The cooled clinker is ground and

almost 3% of gypsum is mixed with it
in order to reduce the rate of setting.
After the initial setting, Al2O3 which
is a fast setting constituent of clinker
reacts with gypsum to form the
crystals of calcium sulpho aluminate.
 3CaO. Al2O3 3(CaSO4.2H2O) +
2H2O  3CaO. Al2O3
3CaSO42H2O + 6H2O
 At the initial setting, gypsum
removes the fast setting elements
and hence the process of setting
cement gets retarded and the results
in better strength of the mass which
sets.
 Packing:

 The ground cement is stored in silos,

from which it is fed to automatic
packing machines. Each bag, usually,
contains 50 kg of cement.
 2CaO + SiO2  2CaO.SiO2 (di
calcium silicate)
 3CaO + SiO2  3CaO.SiO2 (Tri
calcium silicate)
 2CaO + Al2O3  2CaO. Al2O3(di
calcium Aluminate)
 3CaO + Al2O3  3CaO. Al2O3(tri
calcium Aluminate)
 4CaO + Al2O3 + Fe2O3 4CaO.
Al2O3 Fe2O3(Tetra calcium
Aluminate)
 The resulting product is known as
cement clinkers and as it comes out
into the cooler. The clinkers are very
hot (10000C. The clinkers have the
appearance of small greenish black
or grey colored.
 3. Mixing of cement clinkers
with gypsum:
 The cooled clinker is ground and
almost 3% of gypsum is mixed with it
in order to reduce the rate of setting.
After the initial setting, Al2O3 which
is a fast setting constituent of clinker
reacts with gypsum to form the
crystals of calcium sulpho aluminate.
3CaO. Al2O3 3(CaSO4.2H2O) + 2H2O

3CaO. Al2O3 3CaSO42H2O + 6H2O

 At the initial setting,
gypsum removes the fast
setting elements and
hence the process of
setting cement gets
retarded and the results
in better strength of the
mass which sets.
 Packing:

 The ground cement is stored in silos,

from which it is fed to automatic
packing machines. Each bag, usually,
contains 50 kg of cement.
Calcareous materials (Lime stone) Argillaceous materials (clay or Shale)

Crushing and powdering Washing

Proportioning

Grinding Water

Slurry

Rotary Kiln Pulverized coal

Cement clinkers

Cooler

Gypsum Clinkers grinding elevators

Cement soils
Ch emic al
composit ion
of
cem en t
Chem ical composi ti on of
cement:
• The essential constituents are
lime, silica and alumina. For a good
quality of cement the following
ratio should be maintained.
• %SiO2 = 2.5 to 4.0
• %Al2O3
• _____%CaO - %SO3____ = 1.9 to
2.
• %SiO2 + %Al2O3 + Fe2O3
• The ratio of silica to alumina lies
between 2.5 and 4.
• The ratio of calcium oxide to silica +
alumina + ferric oxide should be close
to 2.5 and 4.
• Total percentage of magnesia should
be < 6%
• Total sulphur content should not be
more than 2.75%
• The ratio of Alumina to Iron oxide
should be close to 0.65
• Total loss on ignition shall not exceed
4%.
Setti ng an d Har deni ng of
Cem en t:
• Cement has the property of setting to hard
mass after being mixed with water which is
called cement paste. After mixing with water,
hydration reaction starts and the mass
becomes hard and very resistant to pressure.
This is called as the setting of cement. The
first setting takes place within 24 hours. The
subsequent hardening requires about a
fortnight. Setting is defined as stiffening of the
original plastic mass and hardening is
development of strength due to crystallization.
Both these processes are due to hydration and
hydrolysis reactions.
 Initia l se ttin g:
• primarily the reactions involved are the hydration of
calcium aluminates and calcium silicates which
change into their colloidal gel. At the same time some
calcium hydroxide and aluminium hydroxide are formed
as precipitates due to hydrolysis.
• 3CaO Al2O3 + 6H 2O  3CaO . Al2O3 .6H2 O + 880
Kj/ kg
• 4CaO Al2O3 F e2O3 + 7H2O  3CaO . Al2O 3 .6H2O
+ 3Ca O F e2O3 H2O + 420 Kj/ kg
• 3CaO Al2O3 + 3( CaS O4 + 2H 2O  3CaO Al2O3
3CaS O4 2H2O
• Addition of gypsum removes the fast setting elements.
• Reaction takes place between 1 and 7 days:
• Hydrolysis reaction: 3Ca OS iO2 + H2O  Ca (OH )2
+ 2Ca OS iO2
Fin al se ttin g ( between
7 to 28 days):

• begins to hydrate and forms the

hydrated colloidal gel of the
composition.
• 2CaO SiO 2 + X H2O 
2CaO SiO 2 XH 2O + 500K j/kg
 Sequence of chemi cal
r eacti ons during setting and
har de ning of c ement :
• when water is added to cement, its
various constituents undergo
hydration and crystallization at
different rates.
• At first, hydration of tricalcium
aluminate and tetra calcium
aluminoferrite takes place.
• Next, the hydration of tricalcium
silicate begins within 24 hours and
gets completed in 7 days.
Sequence of chemi cal
r eacti ons during setting and
har de ning of c ement :

• The gel of aluminate begins to crystallize

and at the same time, dicalcium silicate
begins to hydrate in 7 to 28 days. Thus, the
initial set of cement is due to the hydration
of aluminate. The development of early-
strength, between 1 to 7 days, is due to the
hydration of tricalcium silicate and the
further hydration of aluminate. The increase
of strength, between 7 to 28 days, is due to
hydration of dicalcium silicate and
continued hydration of tricalcium silicates.