A student determines the change in oxidation number of nitrogen when a solution of magnesium nitrate, Mg(NO3)2 , is titrated with aqueous titanium(III) chloride.
Procedure
Step 1 | Using a volumetric flask, prepare 100.0 cm3 of an aqueous solution containing 0.750 g of solid Mg(NO3)2•6H2O. |
Step 2 | Pipette 10.0 cm3 of the solution from Step 1 into a conical flask and add a few drops of alizarin indicator. Add 2 cm3 of concentrated hydrochloric acid and heat the mixture. |
Step 3 | Fill a burette with 0.0850 mol dm–3 aqueous titanium(III) chloride and titrate the contents of the conical flask from Step 2 while continuing to heat the mixture. |
During the titration, Ti3+ ions are oxidised to TiO2+ ions
Ti3+ + H2O → TiO2+ + 2H++ e–
Alizarin indicator is green in the presence of aqueous Ti3+ and yellow in the presence of aqueous TiO2+. The end‐point of the titration is reached on the addition of 20.70 cm3 of aqueous titanium(III) chloride.
i) State the colour change that would be observed at the end‐point of the titration.
(1)
From .............................. to ..............................
ii) Use the results to determine the final oxidation state of nitrogen in the titration. You must show your working.
[Mr value: Mg(NO3)2∙6H2O = 256.3]
(5)
iii) Write the overall ionic equation for the titration reaction using your answer to (c)(ii) and the relevant half‐equations from the list below.
(2)
TiO2+ + 2H++ e– ⇌ Ti3+ + H2O Eθ = +0.10V
NO3– + 2H++ e– ⇌ NO2 + H2O Eθ = +0.80V
NO3– + 3H++ 2e– ⇌ HNO2 + H2O Eθ = +0.94V
NO3– + 4H++ 3e– ⇌ NO + 2H2O Eθ = +0.96V
iv) Use the electrode potential data provided to calculate Eθcell for the overall titration reaction.
(1)
v) Suggest why the contents of the conical flask are heated.
(1)
vi) The student’s teacher said, “As TiCl3 is blue and TiO2+ ions are colourless in aqueous solution, the titration can be carried out without an alizarin indicator.”
Assess the teacher’s statement. In your answer you should
identify, by name or formula, a coloured complex ion expected to be present when TiCl3 dissolves in water
explain how the colour of this complex ion arises
suggest why the titration may be more accurate with an alizarin indicator.
(6)