Chalk Chalk is a soft, white, porous sedimentary rock, a form of limestone composed of the mineral calcite.

Calcite is calcium carbonate or CaCO3. It forms under reasonably deep marine conditions from the gradual accumulation of minute calcite plates (coccoliths) shed from micro-organisms called coccolithophores. It is common to find chert or flint nodules embedded in chalk. Calcium Calcium is a silvery white metal belonging to group 2 of the periodic table known as the alkaline earth metals. Calcium ranks fifth in abundance by weight among the elements in the earths crust, atmosphere and surface waters. It is widely distributed over the earths surface in many rock and mineral forms. The best known of these minerals forms is calcium carbonate. Calcium carbonate Calcium carbonate is an abundant found in a number of different forms. It is used in preparation of carbon dioxide in the lab and also in the preparation of calcium oxide which is one of the largest tonnage chemicals in the industry. Calcium carbonate occurs principly as limestone, calcite and marble.

MOLE CONCEPT
Mole, Molecular weight, equivalent weight ,numberrmality and molarity.
Mole- It is defined as the amount of substance that contains the same number of particles as the number of atoms present in C12. Thus a mole is a collection of 6.023*1023 particles and this corresponds to gram molecular mass. In the case of gases in mole corresponds to 22.4 litres of the gas at stp and in the case of a solution of 1 molar conc it means 1 gram molecular mass of the solute is dissolved in 1litre of solution. Molecular Weight- It is the weight of the compound that contains the same number of particles of the compound as the number of atoms present in C12. Equivalent Weight-The equivalent weight of a element is the number of parts by weight of the elemnt which can combine with or displace 1.008 parts by weight of hydrogen, 8 parts by weight of O2, 35.46parts of chlorine, or the equivalent weight of any other element. Molarity- moles of solute present in 1litre of solution. numberrmality-the number of gram equivalence present in 1litre of solution. Redox titrations They involve reactions in which a change in oxidation number takes place and are used in volumetric analysis either to estimate the amount of an oxidizing agent or that of a reducing agent in their solutions. The reagent that gains electrons is called as oxidizing agent. Example - KMnO4,K2Cr2O7. The reagent that looses electrons is called as reducing agent. Example-Sncl2, Fe2+.

PERMANGANOMETRIC TITRATIONS The permanganometric method is based on reactions of oxidation by permanganate ions.Oxidation may proceed in acidic or alkaline or neutral solutions. When potassium permanganate acts as an oxidising agent in acidic solutions the hepta valent manganese is reduced to bivalent Mn2+ and the manganese salt of the acid used is formed. For example- if ferrous sulphate is the reducing agent and it is oxidized in the presence of sulphuric acid and then the reaction is represented by FeSO4 + 2KMnO4 + 8H2SO4 --> 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + 8H20 During oxidation, in alkaline or natural solution, the heptavalent Mn7+ is reduced to quadrivalent Mn4+ with the formation of manganese dioxide. For example, Cr2(SO4)3 + 2KMnO4 + 8 KOH --> 2K2CrO4 + 2MnO2 + 2K2SO4 +4H20 In the former cases, the equivalent weight of KMnO4, is given by equivalent weight=molecular weight/5=158/5=31.6 In the latter case, the equicalent weight is given by Equivalent weight=molecular weight/3=52.66 In the case of titrations involving KMnO4, number indicator is used since KMnO4 itself is coloured. When the kMnO4 is completely reduced to Mn2+ the pink colour vanishes and the solutions thus becomes colourless. Thus KMnO4 acts as a self indicator. Preparation of standard KMnO4 solution KMnO4 solution cannumbert be prepared by exact weighing as the permanganate is numbert pure. It contains some reduction products. Such as MnO2. Moreover, it is easily decomposable by ammonia,

organic substances, etc. entering the water in the form of dust. It therefore has to be standardized. The permanganate solution made is kept in a dark place because, light accelerates the decomposition of KMnO4 by the reaction: 4KMnO4 + 2H2O --> 4MnO2 + 4KOH + 302. Taking these into account, KMnO4 solution is prepared as follows: for producing a 0.1 solution, 0.1* 31.6 or 3.16 grams of KMnO4 crystals are measured using a balance and dissolved in 1 litre of water or 0.79 grams of kMnO4 is dissolved in 250 ml of water. Since KMnO4 dissolves slowly, a part of the water is heated and the KMnO4 is dissolved in this with constant stirring. Thus a small portion of KMnO4 is dissolved and the solution is thus made up. Standardization of potassium permanganate 100ml of standard solution of oxalic acid prepared by weighing 0.63 grams of A.R. oxalic acid crystals. A standard flask and a funnel are taken. The crystals are carefully washed with distilled water. The funnel and its tip are repeatedly washed with water and the solution is washed down into the flask and the crystals are dissolved by shaking. care is taken to make up the solution in the standard flask. 20 ml of this solution is pipette out and one to one and a half test tubes of dilute H2SO4 is added. The mixture Is heated to bearable warmth and titrated with KMnO4. The end point is indicated by the appearance of a pale pink colour. Titrations are repeated for the obtainment of concordant values. Estimation of percentage purity of calcium carbonate This can be done by permanganumbermetric titrations where the calcium in the calcium carbonate is converted into calcium oxalate and the oxalic acid generated by dissolving it in a dilute acid is estimated, Titrating it against standardized KMnO4 solution. In this project permanaganometric method is employed.

Experiment Determination of calcium by precipitation with oxalate followed by titration with permanganate AIM To determine the amount of calcium present in given amount of chalk. APPARATUS REQUIRED
y y y y y y y

Burette Pipette 200 &250 ml beakers Conical flask Balance with weight box etc Funnel Porcelain dish

CHEMICALS REQUIRED 1. 1:1 Hcl: it is prepared by mixing 1 volume of concentrated Hcl with 1 volume of water. 2. A.R.Oxalic acid crystals: This is used to prepare 0.1N Oxalic acid. 3. chalk(2.5g) 4. 2% ammonium oxalate solution : it is prepared by dissolving 2g of ammonium oxalate in water. 5. Ammonium hydroxide solution (bench reagent) 6. Dilute Sulphuric acid (bench reagent)

Theory: The calcium carbonate is first converted into soluble calcium chloride by dissolving it in Hcl. The Cacl2 solution is treated with ammonium oxalate and calcium oxalate is precipitated out. The precipitate is dissolved in dilute sulphuric acid to give oxalic acid. The obtained oxalic acid is heated. It is titrated with potassium permanganate solution (0.1N).

EQUATION CaCO3+2Hcl --> CaCl2+H2O+CO2 Cacl2 + (NH4)2C2O4 --> CaC2O4 + 2NH4Cl CaC2O4 + H2SO4 --> CaSO4 + (COOH)2

IONIC EQUATION MnO42- + 5e- + 8H+ --> Mn2+ + 4H2O C2O42- --> 2CO2 + 2e-

NET EQUATION 2MnO42- + 5C2O4 + 16H+ --> 2Mn2+ + 8H2O + 10CO2

EXPERIMENT FOR DETERMINING THE PERCENTAGE PURITY Chalk is numberthing but a form of Calcium carbonate. The Calcium Chloride solution is prepared by accurately weighing 2.5g of Calcium Carbonate and dissolving it in 1:1 HCl completely (minimum amount is taken). This is numberw boiled to expel all the Carbon di oxide. The solution is cooled to room temperature and is made up to 250ml in a standard flask. After this the following steps are taken. PRECIPITATION AND STANDARDIZATION OF CALCIUM SALT SOLUTION The Calcium Chloride solution is transferred to a 250 ml standard flask and exactly made upto the mark. 20ml of the made up solution is pipette out into a 250ml beaker and a drop of methyl orange is added to it. Ammonium hydroxide is then added drop by drop till the acid is neutralized and the solution is diluted to about 150ml. The beaker is covered with cover glass and the solution is heated to boiling point. To the boiling solution about 10ml of freshly preapared 2% solution of ammonium oxalate solution(prepared by dissolving 2g of ammonium oxalate in 100ml of water). Ammonium hydroxide is then added drop by drop to the mixture till the solution strongly smells of ammonia. The mixture is boiled for a few minutes to make the precipitate granular. The precipitate is complete a few drops of ammonium oxalate is added to the supernatant liquid along the sides of the beaker. If precipitation is incomplete turbidity will be seen in the supernatant liquid and the drops of the reagent come in contact with it. The precipitate of Calcium Oxalate is numberw filtered by decantation with the help of a quantitative filter paper. The precipitate is washed with water containing ammonia till the washings give number opalescence with HNO3 & AgNO3. The precipitate is almost completely transferred to the filter paper. The beaker in which precipitation is done is then placed under the funnel containing the precipitate. The apex of the filter paper is then pierced with a pointed glass rod and the precipitate is washed into the beaker

with a jet of hot water. About 25ml of hot dilute sulphuric acid is poured into the filter paper in small portions at a time taking care that the acid comes in contatct with every part of the filter paper. The acid is also poured into the double folds of the filter paper to dissolve any precipitate that may be sticking there. The filter paper is again thoroughly washed with hot water. The sides of the beaker is slao washed with dilute sulphuric acid. The liquid in the beaker containing oxalic acid is heated to about 70 degree centigrade and titrated with standard potassium permanganate. The end point is the appearance of a permanent pale pink colour. The experiment is repeated till concordant values are obtained.

OBSERVATIONS AND CALCULATIONS:

STANDARDIZATION OF KMnO4 SOLUTION: MOLECULAR WEIGHT OF KMnO4 = 158 g EQUIVALENT WEIGHT OF KMnO4 = 31.6 G MnO4- + 5e- + 8H+ --> Mn2+ + 4H2O MOLECULAR WEIGHT OF H2C2O4 = 126 g EQUIVALENT WEIGHT OF H2C2O4 = 63 g C2O42- --> 2CO2 + 2e-

FIVE POINT PROCEDURE: Burette Solution: Standardized KMnO4 solution(0.1N); Pipette Solution: H2C2O4; Indicator: self Indicator(H2C2O4); Medium: Acidic; (i)Condition: Bearable warmth; End Point: Colourless to pale pink;

EQUATION: MnO4- + 5e- + 8H+ --> Mn2+ + 4H2O C2O42- --> 2CO2 + 2e-

NET EQUATION: 2MnO4- + 5C2O4 + 16H+ --> 2Mn2+ + 8H2O + 10CO2

STANDARD H2C2O4 VS GIVEN KMnO4

SL. NO 1 2) 3) 4)

Volume of oxalic acid (ml) 20 20 20 20

Burette reading Initial(ml) Final(ml) 0 0 0 0 20 19.9 19.9 19.9

Volume of KMnO4 solution (ml) 20 19.9 19.9 19.9

Volume of Oxalic acid(V1)=20 ml Normality of Oxalic acid(N1)=0.1 Volume of KMnO4 solution(V1)=19.9ml

V1N1=V2N2 Therefore N2=V1NI/V2

N2=V1N1/V2

Therefore N2=20*0.1/19.9 =0.1005N

Normality of KMnO4 solution(N2)=0.1005N

ESTIMATION OF CALCIUM

FIVE POINT PROCEDURE: Burette Solution: Standardized KMnO4 solution(0.1N); Pipette Solution: H2C2O4; Indicator: self Indicator(KMnO4); Medium: Acidic; (i)Condition: Bearable warmth; End Point: Colourless to pale pink;

STANDARD H2C2O4 VS GIVEN KMnO4

SL. NO 1 2) 3) 4)

Volume of oxalic acid (ml) 20 20 20 20

Burette reading Initial(ml) Final(ml) 0 0 0 0 3 3 3 3

Volume of KMnO4 solution (ml) 3

Volume of KMnO4 Solution(V1)=3ml Volume of Calcium Solution(V2)=20ml Normality of KMnO4 solution (N1)=0.1N Normality of Calcium solution (N2)=?

V1N1=V2N2 N2=V1N1/V2 3 x 0.1/20 =0.015N

Therefore, Normality of Calcium Solution (N2)=0.015N

Weight of Calcium in 1g of CaCo3N2 = Weight * 1000 Equivalent Weight V

Weight =Equivalent Weight * N2 * V/1000

Weight =20*0.015* 250/100 =0.075

40 g of Calcium ~ 100g of CaCO3 0.075 g of Ca ~ 0.075 * 40 40

~ 0.1875g Weight of Seas shells taken =2.5g Therefore, Percentage Purity-0.1875 *100 2.5

=7.5%

Results

1. The amount of Ca present in 2.5 grams of chalk was found to be

0.1875 grams
2. The percentage purity of Ca in 2.5 grams of chalk was found to be

7.5%

SUMMARY

In this project the percentage purity of the given chalk was estimated by permanganometric titration. The KmnO4 solution was standardized using standard Oxalic Acid solution. The given Calcium Carbonate was dissolved in dilute Hydrochloric Ammonium Oxalate and from it Oxalic acid was generatedby addition of dilute acid. This was titrated with the Potassium Permaganate solution and the Calciujm present in it was estimated. By calculating, the amount of Calcium Carbonate present the percentage purity of the sample of chalk was calculated.

The percentage purity of the sample of 2.5 grams of chalk was found to be 7.5%