Chemical Composition of Portland Cement

The raw materials used to manufacture portland cement are lime, silica, alumina, and iron oxide. These
raw materials interact in the kiln, forming complex chemical compounds. Calcination in the kiln
restructures the molecular composition, producing four main compounds, as shown in Table 6.1.

C3S and C2S when hydrated, provide the desired characteristics of the concrete. Alumina and iron, which
produce and are included with the other raw materials to reduce the temperature required to produce
from 2000°C to 1350°C (3500°F to 2500°F). This saves energy and reduces the cost of producing the
portland cement.

In addition to these main compounds, there are minor compounds, such as magnesium oxide, titanium
oxide, manganese oxide, sodium oxide, and potassium oxide. These minor compounds represent a few
percent by weight of cement. The term minor compounds refers to their quantity and not to their
importance. In fact, two of the minor compounds, sodium oxide and potassium oxide are known as alkalis.
These alkalis react with the silica in some aggregates causing the disintegration of concrete (see Figures
5.19 and 6.2) and affecting the rate of strength development, as discussed in Chapter 5. 1Na 1K2O2, 2O2
C3S C C4AF, 3A C

Constituents of Ordinary Portland Cement

The principal raw materials used in the manufacture of Ordinary Portland Cement are:
1. Argillaceous or silicates of alumina in the form of clays and shales.

2. Calcareous or calcium carbonate, in the form of limestone, chalk and marl which is a
mixture of clay and calcium carbonate.
The ingredients are mixed in the proportion of about two parts of calcareous materials to
one part of argillaceous materials and then crushed and ground in ball mills in a dry state
or mixed in wet state.
The dry powder or the wet slurry is then burnt in a rotary kiln at a temperature between
1400 degree C to 1500 degree C. the clinker obtained from the kiln is first cooled and then
passed on to ball mills where gypsum is added and it is ground to the requisite fineness
according to the class of product.

The chief chemical constituents of Portland cement are as follows:

Lime (CaO) 60 to 67%

Silica (SiO2) 17 to 25%

Alumina (Al2O3) 3 to 8%

Iron oxide (Fe2O3)

0.5 to 6%

The above constituents forming the raw materials undergo chemical reactions during
burning and fusion, and combine to form the following compounds called BOGUE
COMPOUNDS.
Compound Abbreviated Designation
Lime (CaO) C3S

Silica (SiO2) C2S

Alumina (Al2O3)
C3A

Iron oxide (Fe2O3) C4AF

The proportions of the above four compounds vary in the various Portland cements.
Tricalcium silicate and dicalcium silicates contribute most to the eventual strength. Initial
setting of Portland cement is due to tricalcium aluminate. Tricalcium silicate hydrates
quickly and contributes more to the early strength.
The contribution of dicalcium silicate takes place after 7 days and may continue for up to
1 year. Tricalcium aluminate hydrates quickly, generates much heat and makes only a
small contribution to the strength within the first 24 hours. Tetracalcium alumino-ferrite
is comparatively inactive.

All the four compounds generate heat when mixed with water, the aluminate generating
the maximum heat and the dicalcium silicate generating the minimum. Due to this,
tricalcium aluminate is responsible for the most of the undesirable properties of concrete.

Cement having less C3A will have higher ultimate strength, less generation of heat and
less cracking. Table below gives the composition and percentage of found compounds for
normal and rapid hardening and low heat Portland cement.

BOGUE EQUATIONS

The Bogue equations widely used in cement quality control are mathematically based
estimates of the quantities of the four main clinker minerals under equilibrium
conditions. It is assumed that these four clinker minerals are pure minerals and have
the following chemical formulae

It is assumed that all of the Fe2O3 is present as C4AF. Each of these pure minerals
contains fixed amounts of the major clinker oxides. These molecular weight of oxides
and phases are
Therefore, the total SiO2 ,Al2O3 ,Fe2O3 and CaO content in any mixture of the four
minerals can be calculated as

The above four equations reduces to

SiO2 = 0.2631 x C3S + 0.3488 x C2S

Al2O3 = 0.3774 x C3A + 0.2098 x C4AF
Fe2O3 = 0.3285 x C4AF
CaO = 0.7369 x C3S + 0.6512 x C2S + 0.6226 x C3A + 0.4616 x C4AF

Solving one of the above equation

SiO2 = 0.2631 x C3S + 0.3488 x C2S
C2S = (SiO2 – 0.2631 x C3S ) / 0. 3488
C2S = 2.867 x SiO2 – 0.7544 x C3S Which is the bogue’s equation for C2S

Solving another equation from above

Fe2O3 = 0.3285 x C4AF
C4AF = Fe2O3/ 0.3285
C4AF = 1 / (0.3285 x Fe2O3)
C4AF = 3.044 x Fe2O3 Which is the Bogue’s equation for C4AF
Now, substituting the expression for C4AF in one of the above equations
Al2O3 = 0.3774 x C3A + 0.2098 x C4AF
Al2O3 = 0.3774 x C3A + 0.2098 x (3.044 x Fe2O3)
Al2O3 = 0.3774 x C3A + 0.6386 x Fe2O3

Rearranging this equation we get;-

C3A = (Al2O3 – 0.6386 x Fe2O3) / 0.3774

C3A = 2.650 x Al2O3 – 1.692 x Fe2O3 Which is the Bogue equation for C3A

Substituting the values of C2S ,C3A and C4AF in CaO equation

CaO = (0.7369 x C3S) + (0.6512 x C2S) + (0.6226 x (2.650 x Al2O3 – 1.692 x Fe2O3)) +
(0.4616 x 3.044 x Fe2O3 )

CaO = (0.7369 x C3S) + (0.6512 x C2S) + (1.650 x Al2O3 ) – (1.053 x Fe2O3) + (1.405 x
Fe2O3)

CaO = (0.7369 x C3S) + (0.6512 x C2S) + (1.650 x Al2O3) + (0.3520 x Fe2O3)

C3S = [CaO – (0.6512 x C2S) – (1.650 x Al2O3) – (0.352 x Fe2O3)] / 0.7369

C3S = (1.357 x CaO) – (0.8837 x C2S) – (2.239 x Al2O3) – (0.4777 x Fe2O3)

Putting the value of C2S = (2.867 x SiO2) – (0.754 x C3S)

C3S = (1.357 x CaO) – {0.8837 x (2.867 x SiO2) – (0.754 x C3S)} – (2.239 x Al2O3) –
(0.4777 x Fe2O3)

C3S – (0.8837 x 0.754 x C3S) = (1.357 x CaO) – {0.8837 x (2.867 x SiO2)} – (2.239 x
Al2O3) – (0.4777 x Fe2O3)

0.3337C3S = 1.357 x CaO – 2.53 x SiO2 – 2.239 x Al2O3 – 0.4777 x Fe2O3

C3S = [1.357 x CaO – 2.53 x SiO2 – 2.239 x Al2O3 – 0.4777 x Fe2O3]/0.3337

C3S = 4.07 x CaO – 7.6 x SiO2 – 6.70 x Al2O3 – 1.42 x Fe2O3 Which is the Bogue
equation for C3S

Calcination as "heating to high temperatures in air or oxygen". However, calcination is also used
to mean a thermal treatment process in the absence or limited supply of air or oxygen applied to
ores and other solid materials to bring about a thermal decomposition.
a hydration reaction is a chemicalreaction in which a substance combines with water.