Exercises for the complexometric titrations

Type 1: Calculate pM; error; and exact concentration.

Problem 1 (65): A 100 mL aliquot of 0.100 M MgSO4 is titrated with a 0.100 M EDTA solution at pH 8.0.
a) Calculate pMg ater the addition of 99.0; 100; and 101 mL the EDTA solution.
b) Calculate titration error when 50% indicator of Erio-T exits in the complex with metal ion.
Given the conditional formation constants of MgY2- and MgIn- are 4.4×106 and 2.8×103, respectively.

Problem 2 (68). A titration of 100 mL solution of CaCl2 requires 40.0 mL of 0.0100 M EDTA solution to the
end point of Erio-T at pH 10.0. Given that at the end point, 50% of indicator exits in the complex with metal
ion.
a) Write the reaction during the titration
b) Calculate the titration error
c) Calculate the concentration of CaCl2 with the consideration of titration error.
Given logβ(CaY2-)=5.0×1010; logβ(CaIn-) 2.5×105; pKa (H4Y): 2.00; 2.67; 6.16; 10.26.

Problem 3. To determine copper concentration in a solution: pipette 25.0 mL of copper ion solution in to a
flask; add amonia solution drop-wise until the light blur precipitate formed dissolves to form a clear blue
solution; add 3-4 drops of murexide indicator; titrate with 0.0010 M EDTA until the color changes from
yellow to purpule. The volume of the EDTA solution to reach the end point is 15.64 mL.
a) Write the reaction during the titration
b) Calculate the concentration of CaCl2 without the consideration of titration error
c) Calculate the titration error, given that at the end point 90% of indicator exits in the free-metal
complexed form and the analytical concentration of NH3 is 0.1 M.
Given logβ(CuY2-)=1018.8; logβ(CuIn-)=1017.9;logβ(Cu(NH3)4)=12.03; pKa(H4Y): 2.00; 2.67; 6.16; 10.26.

Type 2: Titration techniques.

Problem 4. A solution contains 1.569 mg of CoSO4 (155.0 g/mol) per milliliter. Calculate
a) The volume of 0.007840 M EDTA needed to titrate a 25.00-mL aliquot of this solution.
b) The volume of 0.009275 M Zn2+ needed to titrate the excess reagent after addition of 50.00 mL of
0.007840 M EDTA to a 25.00-mL aliquot of this solution.
c) The volume of 0.007849 M EDTA needed to titrate the Zn2+ displaced by Co2+ following addition of
an unmeasured excess of ZnY2- to a 25.00-mL aliquot of the CoSO4 solution.
Problem 5. The Cr plating on a surface that measured 3.00 × 4.00 cm was dissolved in HCl. The pH was
suitably adjusted, following which 15.00 mL of 0.01768 M EDTA were introduced. The excess reagent
required a 4.30-mL back-titration with 0.00812 M Cu2+. Calculate the average weight of Cr on each square
centimeter of surface.
Problem 6. The Tl in a 9.57-g sample of rodenticide was oxidized to the trivalent state and treated with an
unmeasured excess of MgY2- solution. Titration of the liberated Mg2+ required 12.77 mL of 0.03610 M EDTA
(Erio-T as an indicator). Write the reaction during the experiment and calculate the percent Tl2SO4 (504.8
g/mol) in the sample.

Type 3: Titration mixtures of metal ions.

Problem 7. Titration of Ca2+ and Mg2+ in a 50.00-mL sample of hard water required 23.65 mL of 0.01205 M
EDTA. A second 50.00-mL aliquot was made strongly basic with NaOH to precipitate Mg2+ as Mg(OH)2. The
supernatant liquid was titrated with 14.53 mL of the EDTA solution. Calculate
a) The total hardness of the water sample, expressed as ppm CaCO3
b) The concentration of CaCO3 and MgCO3 in the sample in ppm.

Problem 8. A 0.3304-g sample of brass (containing lead, zinc, copper, and tin) was dissolved in nitric acid.
The sparingly soluble SnO2.4H2O was removed by filtration, and the combined filtrate and washings were
then diluted to 500.0 mL. A 10.00-mL aliquot was suitably buffered; titration of the lead, zinc, and copper in
this aliquot required 34.78 mL of 0.002700 M EDTA. The copper in a 25.00-mL aliquot was masked with
thiosulfate; the lead and zinc were then titrated with 25.62 mL of the EDTA solution. Cyanide ion was used to
mask copper and zinc in a 100-mL aliquot; 10.00 mL of the EDTA solution was needed to titrated the lead
ion. Determine the composition of the brass sample; evaluate the percentage of zinc by difference.