Estimation of Alkalinity in Water

Qualitative and Quantitative estimation of alkalinity

Aim

To determine the type (quality) and amount (quantity) of alkalinity present in the given water sample.

Principle Alkalinity of water may be mainly due to the presence of anions such as OH, CO32 or / and HCO3 . Both OH and CO32 have a pH value > 8, while the weak HCO3 has a pH >7 < 8 (7 To 8). The choice of indicator depends on the pH of the water, in other words the alkaline impurity present in water The working range of phenolphthalein lies between pH 8 to 10 and that of methyl orange is pH 3.4 to 11.3 ( in acidic medium it is pink and in alkaline medium it is yellow) OH can be detected using phenolphthalein only. While both CO32& HCO3 cannot be completely detected by phenolphthalein. CO32 + H+ HCO3 + H+ CO2 + H2O Hence for effective determination of both CO32& HCO3 the choice of indicator should be Methyl Orange.

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The determination of alkalinity is based on the following reactions: i) [OH ] + [H+] H2O (Phenolphthalein pink to colourless / Methyl orange yellow to pink) ii) a. [CO32] + [H+] [HCO3] (Partial neutralization Phenolphthalein pink to colourless) b. [HCO3 ] + [H+] H2O + CO2 (Methyl orange yellow to pink) iii) [HCO3 ] + [H+] H2O + CO2 (Methyl orange yellow to pink) The titration of the water sample against a standard acid up to phenolphthalein end point marks the (i) complete neutralization of OH (ii) partial neutralization of CO32 Titration of the water sample upto methyl orange end point marks the complete neutralization of all the ions as shown by reactions (i), (ii) & (iii). The possibility of OH and HCO3 ions existing together is ruled out as they combine immediately to form CO32 ions. OH+ HCO3 NaOH + NaHCO3 exist together. Requirements Standard alkali solution Link Acid Water sample ( unknown alkali) Indicators Phenolphthalein and Methyl Orange
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CO32 + H2O Na2CO3 + H2O

On the basis of same reasoning, all the three OH, CO32 and HCO3 ions cannot

Procedure

Titration 1 : Standardisation of the acid A known volume of standard alkali (say20 ml) is pipetted out into a clean conical flask and 2-3 drops of methyl orange indicator is added. The above solution is titrated against the acid solution till the pale yellow coloured solution turns pink in colour. The titration is repeated for concordancy. Titration 2 : Estimation of type and amount of alkalinity A known volume of water (say20 ml) sample is pipetted out into a clean conical flask and 2-3 drops of phenolphthalein indicator is added. The above solution is titrated against the acid solution till the pink colour disappears. This indicates the complete neutralization of hydroxide and partial neutralisation of carbonate to bicarbonate. Then to the same solution, 2-3 drops of methyl orange indicator is added and the titration is continued till the pink colour reappears. At this point all the alkaline substances would have been neutralized and the water sample becomes weakly acidic.

Calculations:

Titration 1: The strength of link acid is calculated using the volumetric law V1N1 = V2N2 Titration 2: Let the volume of acid consumed up to phenolphthalein end point be V1 ml and the total volume of acid consumed up to methyl orange end point be V2 ml

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Phenolphthalein alkalinity in terms of calcium carbonate equivalence

P = V1 X Strength of acid (N) X Equivalent Wt.of CaCO3 (50)X 1000 = ___ ppm Volume of water sample

Methyl Orange alkalinity in terms of calcium carbonate equivalence

M = V2 X Strength of acid (N) X Equivalent Wt. of CaCO3 (50)X 1000 =-___ ppm Volume of water sample

Relation between P & M Case I: If Alkalinity is due to HCO3 only P=0 ( ie on adding phenolphthalein the water sample is colourless) The titration is carried out with methyl orange indicator HCO3 + H+ CO2 + H2O Amount of HCO3 = M Case II: If Alkalinity is due to CO32 only
M

CO32 + H+ HCO3 + H+ CO2 + H2O

P P

M = 2P Amount of CO32 is 2P

(or)

P = M/2

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Case III: Alkalinity is due to OH only [OH ] + [H+]

H2O

P=M

On adding phenolphthalein the water sample is pink After phenolphthalein end point if MO is added the solution immediately becomes pink indicating that the water sample is already weakly acidic The titration is carried out with phenolphthalein indicator Amount of OH is = P Case IV: Alkalinity is due to OH and CO32 M OH, CO32 + H+ H2O + HCO3 + H+ CO2 + H2O pH > 8 pH < 8 MO

<P

When P > M/2 (or) 2P > M Let the acid consumed for partial neutralization that is phenolphthalein end point be P And the acid consumed for complete neutralization be M ( P + MO indicator) Acid consumed by HCO3 only = Total Phenolphthalein end point = M P Amount of CO32 = twice that consumed for bicarbonate = 2 (M P)

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We Know that total alkalinity M =,CO32 alkalinity + OH alkalinity Substituting the value of CO32 = 2 (M P ) M = 2 (M P) + OH alkalinity OH alkalinity = M [2 (M P )] = M [ 2M 2P] = M 2M + 2P = M + 2P Amount of OH = 2P M Case V: Alkalinity is due to CO32 and HCO3 M CO32, HCO3 + H+ HCO3 + H+ CO2 + H2O pH > 8 P pH < 8 MO

CO32 HCO3 = P Amount of CO32 = 2P Total alkalinity M = CO32 + HCO3 M = 2P + HCO3 Amount of HCO3 = M 2P

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Relation between the P and M values and the quality and quantity of ions present is summarized in the following table:

Case 1

Case 2

Case 3

Case 4

Case 5

Alkalinity (ppm) P=0 P=M/2 P=M P>M/2 P<M/2

OH

2PM

CO32

2P

2(MP)

2P

HCO3

M2P

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