Determination of Calcium oxide and

Magnesium Oxide in Selected Cements

◙◙ Abubakar El-Ishaq , Ibrahim Ishaku and ☞☞Mohammed Alkali

◙◙ School of Science and Technology
Department of Science Laboratory Technology,
(Chemistry/Biochemistry unit)
Federal Polytechnic, P.M.B 1006.Damaturu.
☞☞ Department of Natural Science
Bukar Abba Ibrahim University, Damaturu.

ABSTRACT

Calcium and Magnesium oxides content in selected cement were determined. The selected cement samples revealed the
following: Ashaka Cement – CaO (66.75) and 3.97% (MgO); Sokoto Cement – CaO (63.7%) and MgO;
(3.789%)Dangote Cement – CaO (61.9%), MgO (3.69%) and Gboko Cement – CaO (57.45) and MgO (3.62%). Ashaka
Cement demonstrated the highest percentage of calcium oxide (CaO) and Magnessium oxide (MgO). The percentage of
calcium oxide (CaO) falls within the standard reference value for CaO in cement (i.e. 62.68%) except for Gboko Cement
which falls below the reference value. While the MgO content were found to be higher than the standard reference value.
The research proffered some recommendations to chemists and construction workers for the betterment of our country
now and the future.

INTRODUCTION
There is need for quality control of imported and home based cements, due to series of building collapse in Gwarinpa
housing estate in Abuja, Lagos, Abuja 2009, port Harcourt .e.t.c. The Nigeria Society of Engineers frown on the last
building collapse at Abuja, what of Chemical Society of Nigeria, our is empirical. Cements, in general can be described
as a material with adhesive and cohesive properties which make it capable of binding mineral fragment into a compact
whole (Neville, 1981).
The popular cement is Portland cement, which is essentially powdered calcium aluminosilicate (CaO.Al 2O3.SiO2) which
sets to a hard mass when treated with water. It is made by pulvering a mixture of limestone and clay, and roasting the
powder in rotary kiln heated by gas or powered coal to a temperature of about 1,500 0C. This treatment yield sintered
lumps called clinker about the size of a marble. The clinker is then cooled and ground with a little gypsum,
(CaSO4.2H2O) to a very fine powder. (Nerbergal and Schmist, 1968). The reaction taking place during the process
calcium aluminate hydrolysis, forming calcium aluminosilicate in the form of interlocking crystals. The named Portland
Cement can be said to be cement obtained by intimately mixing together calcareous and argillaceous or other silica,
alumina and iron oxide bearing materials, burning them at clinkering temperature and grinding the resulting clinker
(Shukula, 1977). Portland cement is a synthetic material of comparatively recent origin, which can well be compared to
the product of Aspandin.
Many reports have been established on cement analysis by prominent scientist. (Bogue, 1962) studied the physical and
chemical properties of cement when mixed with water and their function as a binding agent. The principal reactions are
those by which calcium oxide combined with acidic components. (David, 1978) reported that triple chemical action take
place, first fixation of water by all the constituents then combination of lime with silica whereby hardening takes place
and then free hydrated lime combine with carbondioxide of the air.
CaO + SiO2 CaO, SiO2
Ca(OH)2 + CO2 CaCO3 + H2O
Lee (1956) reported that the setting of cements was due to two distinct simultaneous reactions. The semi-hydrated
calcium sulphate when mixed with water dissolves and become hydrates forming a super saturated solution.

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 CaSO4.H2O + H2O CaSO4.2H2O
The super saturated solution deposits, a crystal of hydrated calcium sulphates which gradually increase in volume and
unite with one another. The final hardness or strength of the set mass according to (Lee, 1956) will depend upon the
cohesion of the crystal and upon their mutual adhesion. (Atkins and Walkinson, 1983) reported that due to the both
chemical and physical force hardness occurred. (Alina, 1997), wrote a report that hydraulicity of a cement is due to the
formation of a orthosilicate lime, 2CaO.SiO 2. (Dalil,1999), determined the effect of Pb s and Cr6+ ions on the hydration of
slag alkaline cement and the immobilization of these heavy metals ions. (Duda and Walter, 1979) determined the
influence of sulfuric acid based admixture on interactive force between cement and particles and fluidity of cement paste.
(Lee, 1991) examined the effect of sulphate in cement clinker on the concrete durability. (Bhalty, 1997) wrote a report on
the thermal analysis studies on cement pest treated with organic solvents. (Belcher and Nuhen, 1970) gave a report on
the single point imaging method for the determination of the influence of shrinkage and cracking on the drying behaviour
of white Portland cement.
RAW MATERIAL OF CEMENT
The raw material of cement may be classified into three groups: Calcereous, orgillocalcerous and argillaceous. It is
evident that the essential constituents of cement are lime, silica and alumina (Orchard, 1980). Lime does not occur in
nature but is found in a suitable form in a carbonate while silica and alumina are found free in nature in the form of clay,
shale or slate.
CEMENT HISTORY
Throughout history, cementing materials have played a vital role. They were used widely in the ancient world. The
Egyptians used calcined gypsum as cement. The Greeks and Romans used lime made by heating limestone and added
sand to make mortar, with coarser stones for concrete.
The Romans found that cement could be made which set under water and this was used for construction of harbours. The
cement was made by adding crushed volcanic ash to lime and was later called a pozzolanic cement, named after the
village of Pozzuoli.
In places such as Britain, where volcanic ash was scarse, crushed brick or tile was used instead. The Romans were
therefore the first to manipulate the properties of cementitious materials for specific application and situation. There is
also kind of powder from which natural causes produce astonishing result. This substance, when mixed with lime and
rubble, not only lends strength to building of other kind, but even when piers are constructed of it in the Sea, they set
hard under water. (Dover, 1960).
CALCIUM OXIDE
When calcium carbonate is heated sufficiently, it undergoes a decomposition which yields the calcium oxide and
carbondioxide.
Pure calcium oxide is a white amorphous substance that emits an intense light called limelight, when heated to a high
temperature. Calcium oxide reacts readily with water, and therefore, it is often employed as a drying agent. Calcium
oxide is known by various names such as lime, quicklime and slaked lime for the product formed from its reaction with
water. Because of the high heat of reaction of quicklime with water, it should always be stored where it can not come in
contact with water, for the slacking reaction generates enough heat to ignite paper or wood.
CaO + H2O Ca(OH)2,
Ca(OH)2 Ca2+ + 2OH-

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Calcium hydroxide is classified as strong base and because of its activity and cheapness; it is only sparingly soluble in
water, 1.7 grams dissolving in one litre of water at room temperature. A saturated solution of calcium hydroxide is often
called lime water.
Prominent scientists have reported different methods of analyzing calcium oxide. Lee (1956) determined the percentage
of free calcium oxide in ground clinker sample. A 0.75g of the sample was diluted with 30ml of the methylated ethylene
glycol, and the solution was titrated with dilute Heland ethylene 3.39% of CaO was obtained. (Kamitomi, 1997) wrote a
report on lime classification, carried out by chemical agent principally by lime in combination with sulphur dioxide gas
(lime-sulphortation) in the treatment tank of sugar processing industry. The organic acids in the juice are neutralized by
this process and the temperature is raised to 90 0C. Knee (1971) examined the effect of minor compound on the strength
of calcium oxide silicate 2CaO.SiO2- quartz moisture under high temperature and high pressure cementing condition.
The hardened specimens were studied for reaction product by x-ray diffraction method. Lee (1991) determined Mg and
Ca in aluminiun chloride by atomic absorption spectroscopy method. Another report came in 1979 by Duda on the
determination of calcium fluoride in the presence of high concentration of Na and Al fluoride by atomic absorption
spectroscopy (AAS) method.
CLASSIFICATION OF CEMENTS
a) High Alumina Cements d) Iron Ore Cement
b) Super Sulphated Cement e) Special Cement
C) White Cement f) Pozzolan Cement
CHEMISTRY OF CEMENT MANUFACTURE

Cement is a hydrophilic binder adhesive used in construction. Cement is commonly grey in colour, it can be of various
colours (for special purposes). Grinding of a mixture of limestone and clay generally produces cement, gypsum could be
added so as control the setting time of the cement.
Limestone consist chiefly of two oxides, CaO and CO 2 while clay is composed of various mineral containing basically
three oxides: SiO2, Al2O3 and Fe2O3. The CO2 is removed (by burning the mixture) from remaining oxide – CaO, SiO 2,
Al2O3, Fe2O3 to form the cement clinker. The contents of these oxides in the cement (commonly) are approximately as
follows:
Calcium Oxide (CaO) = 62 – 68%
Silica (SiO2) = 20 - 24%
Alumina (Al2O3) = 14 – 16%
Iron oxide (Fe2O3) = 2 – 5%
Magenessium Oxide (MgO) = 1.5 – 2.15%
These chief oxides are free in the clinker but combine in the process of burning into four principal minerals namely:
Tricalcium silicate (3CaO.SiO2) 45 – 65%
Dicalcium silicate (2CaO.SiO2) 15 – 35%
Tricalcium Aluminate (3CaO.AlO2) 4 – 14%
Tetracalcium Alumferrite (4CaO.Al2O2Fe2O3) 10 – 6%

Cement clinker may contain oxides such as magnesium oxide (MgO), potassium oxide (K 2O), sodium oxide (Na2O) etc.
their presence affects the quality of the cement (Bogue, 1962).

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METHODOLOGY/EXPERIMENTAL
Cement Sample were collected from various cement depots in Yobe State. This comprises of Ashaka, Sokoto, Gboko
and Dangote cements. The samples were randomly obtained for a fair representation of the samples under study.
DIGESTION: A mixture of exactly 10g of each sample and 1.0g of ammonium chloride was dissolved in 10ml of
concentrated hydrochloric acid; the solution was gently heated for 20 minutes. Boiled water was carefully poured down
to the solution; subsequently the solution was filtered into a 500ml volumetric flask and the residue was washed several
times with hot water, the filtrate was made up to the mark with distilled water and was allowed to cool.
50ml of the cooled solution above was pipetted into a 250ml beaker, 10ml of 50% triethanolamine and 20ml of ammonia
solution were added. The resulting solution was titrated against 0.025M disodium ethylene diamine tetra acetic solution.
Methylthymol blue was used as indicator.
The procedure was repeated for MgO. Hence, 20% potassium hydroxide was used instead of 50% ammonia solution, and
calcein powder was used as indicator. From the titration data, The CaO and MgO contents of the cement samples were
calculated using the following expressions:
% CaO = axb x 100
W
Where a = CaO Titre value
b = CaO Factor(1.4287)
W = Weight of the sample
And
% MgO = cxb
W
Where a = MgO Titre value – CaO Titre value
b = MgO Factor(2.951)
W = Weight of the sample
RESULTS
The tables below shows the percentage contents of calcium oxide (CaO) and Magnesium Oxide (MgO) in different
cement samples under study.
Table I: Average Titre Value for Calcium Oxide (CaO) and Magnesium Oxide (MgO) CM3

Sample CaO MgO

Ashaka 4.660 18.10
Sokoto 4.460 17.20
Dangote 4.430 16.90

Gboko 4.200 16.50

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Table 2 : Percentage of Calcium Oxide (CaO) and Magnesium oxide (MgO) in the Cement Samples
Samples % CaO % MgO
Ashaka 66.7 3.970
Sokoto 63.7 3.798
Dangote 61.9 3.670
Gboko 52.4 3.629

DISCUSSION
The result obtained for calcium oxide (CaO) content in all the selected cements were found to fall within the standard
reference value for CaO content in cement (i.e. 62 – 68%). Only Gboko cement sample showed the least percent of CaO
which was below the reference value for CaO (Table 2). The Magnesium Oxide (MgO) content for all the selected
cement samples were found to be slightly higher than the reference value for MgO content in cement (Table 2 ).
Among all the selected cement samples, Ashaka cement was found to contain the highest percent content of CaO and
MgO while Gboko cement showed the least percent content of both Calcium Oxide (CaO) and Magnesium Oxide
(MgO). The main chemical compositions of Portland cement are found to be;Tri calcium silicate 3CaO.SiO 2 C2S,
Dicalcium silicate 2CaO.SiO2 C2S, Tricalcium Aluminate 3Cal.Al2O3 C3A, Tetra calcium Alumino Ferrite
4CaO.Al2O3Fe2O3O4AF.
The importance of CaO and SiO 2 stand out clearly. Similarly, the alumina (Al 2O3) and iron oxide (Fe2O3) are seen to be
lesser important but still of significance. The chemical change takes place when water is added to the dry cement initially
in the process of hydration. The early reactions are controlled by the gypsum present and the later rates of reaction of the
four main chemicals compared differ greatly (Bogue, 1955).
CONCLUSION
From the result obtained in this research work, it can be deduced that the level of calcium oxide (CaO) and Magnesium
oxides (MgO) in the selected cement samples i.e. Ashaka , Sokoto , Dangote and Gboko gave a positive result,
especially when compared with the standard reference value and with oxides analysis of different cement samples
(Bogue, 1955).
RECOMMENDATIONS
From the result obtained in this research work, the following recommendations are made;
☞ Since all the selected cement samples found to give a positive result for both the calcium and magnesium oxides
contents, the cements were recommended for general constructions (i.e. construction of all types).
☞ It is also recommended that further research should be carried out on the same cement sample for the level of
CaO and MgO, and for Al2O, SiO2, Fe2O3 and insoluble residue since they are of great significance to the quality of
cement.
☞ Standards Organization of Nigeria (SON) should bring out a modality of analysis as well as the percentage
composition of what to make cement, and publish same for public consumption. This will curtail the issues of
collapsed buildings in Nigeria; any company that violates these specifications should be prosecuted.
☞ Nigeria Institute of Builders and civil Engineers should bring our a modality of what our homeland cement
should look like, to meet the topographical demand as well as the nature of our land, the cases of collapsed buildings
has become the order of the day in Nigeria, in both government and civic areas.

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REFERENCES
Alina G. Maria. (1997), “High-Resistance Portland cement without Gypsum” (c. A. Vol. 131 No. 7 Aug. 16 91446-
91441.
Atkins P. W. and Walkinson. (1983). “Basic Inorganic Chemistry”. John wiley and sons. Pp. 231 – 236.
Belcher R. and Nuhen. A. J. (1970). Quantitative Inorganic Analysis. Bitter Worths and Co. Publishers. Pp. 26-32.
Bhalty J. I. (1997). “Cement Manufacturing and Composition”. Skokie 1-28 (C. A. Vol. 130 no. 8, Feb. 22 261421.
Bogue R. H. (1955). “Oxide Analysis of Cement”. Rhaihold publication. Pp. 171-176.
David (1978). High Reistance Portland Cement without gypsum. C. A. Vol. 131 No. 7 Aug. 16 91440-91441.
Duda and Walter H. (1979). “Cement Book” 2nd edition McDonald and Evans Co. London. Pp. 1 – 6.
Dover W. (1960). “The Ten Book of Architecture” Publication, Pp. 1 -3.
Kamitomo and Makoto (1997). “Inorganic Powders and cement Composition for rapid Setting and Handling, Kokaizzo.
180 (C. A. Vol. 130. No. 1 Feb. 15, 84992 – 84993.
Knee W. R. (19710. “Chemistry Facts, Pattern and principle”, Pp. 167 – 171.
Lee F. M. (1956). The chemistry of Cement and concrete” Edward Arnold Ltd., London. Pp. 165.
Marayi P. (1997). “Portland Cement Silica-based Composition for cementing oils wells” 01,397 (CA Vol. 130 No. 8
Feb. 22, 99423).
Nebergal W. H. and Schmidt. (1968). General Chemistry” D. C. Health and Company, Pp. 456-496.
Neville A. M. (1981). “Properties of Concrete” 3rd edition. Rhainhold Publishing Cooperation. Pp.36-42.
Orchard D. F. (1980). “Concrete Technology” Vol. 2 Applied Science Publication Ltd. Pp.112 -116.
Shukula A.(1977). Encyclopedia of Chemical Technology. 2nd edition. Vol. 4, Applied Science publication, Pp. 26-31.