Compleximetric Problems

Objectives:
 Quick overview on type of EDTA titrations.
 Solving EDTA problems.
Types of EDTA titrations
A. Direct titration:
 Many metal ions can be titrated using EDTA taking into account
choosing a suitable indicator and pH medium.

 This type has a very important application in the determination of:

hardness of water (hard water can’t form foam with soap)
B. Back titration:
1.Back titrations are useful for the determination of cations that form
stable EDTA complexes and for which no suitable indicator is
available as in case of determining Thallium.

2. The method is also useful for cations as Cr(III) and Co(III) that
react only slowly with EDTA. A measured excess is added and
after the reaction , the excess EDTA is titrated against standard zinc
or magnesium.

3. It can also be used when the analyte forms precipitates at the

required pH of its titration.
C. Displacement titration:
 In displacement titrations ,an unmeasured excess of a solution
containing the magnesium or zinc complex of EDTA is introduced
into the analyte solution.

 The analyte which forms more stable complex than that of

magnesium or zinc will undergo the following displacement reaction:
MgY2- + M2+ --- MY2- + Mg2+
Where M2+ can be Hg(II), Pd(II), Ti(II), Mn(II) and V(II).

 The liberated Mg2+ or Zn 2+ can be then titrated with standard EDTA

solution.

Displacement titrations are used on lacking sharp end point or

when no suitable indicator is available.
 Remember that
• Number of moles = MV = weight
molec.weight

• (MV)edta =(MV)metal ion

• Wt (g)= M x V(ml)x Mwt = No. of moles x Mwt

1000

• Strength (g/L)= M x Mwt

• Water Hardness (ppm) = Strength x 1000

 Questions
1- A 0.5 g sample containing Ca and Mg carbonates was dissolved in dil HCl and completed
with distilled water to 250 ml. 10 ml of the resulting solution were titrated with 0.01M EDTA
solution. Using EBT indicator, 19 ml of EDTA were consumed, while on using murexide
indicator, 8 ml of EDTA were consumed. Calculate the percentage of both Ca and Mg
carbonates in the sample.

Using EBT, Volume of EDTA is equivalent to Ca2+ + Mg2+ = 19 ml

Using Murexide, V EDTA is equivalent to Ca2+ only = 8ml
Volume of EDTA equivalent to Mg2+ = 19-8 = 11 ml

(MV)EDTA = (MV)Ca2+ , 0.01x8 = Mx10, MCa2+ = 0.008mol/l

(MV)EDTA = (MV)Mg2+, 0.01x11=Mx10, MMg2+ = 0.011 mol/l
wCaCO3 = 0.008x100x250/1000= 0.2 g
% CaCO3 =(0.2/0.5)x100 = 40%

wMgCO3 = 0.011x84x250/1000= 0.231g,

% MgCO3=(0.231/0.5)x100=46.2%
7
2- To 10 ml of Mn(II) solution, 25 ml of 0.1 M Mg-EDTA is added. The liberated Mg2+ ions were
titrated with 14.4 ml of 0.027 M EDTA solution. Calculate the molarity of the Mn(II) solution.

(MV)EDTA = (MV)Mg2+ = (MV)Mn2+

(14.4 x 0.027) = M x 10

MMn2+ = 0.038 mol /l

8
3- An EDTA solution was prepared by dissolving approximately 4g of disodium salt in
approximately 1 L of water. An average of 42.35 ml of this solution was required to
titrate 50 ml aliquots of a standard that contained 0.7682 g of MgCO3 per liter.
Titration of 25 ml sample of mineral water at pH 10.00 required 18.8 ml of the EDTA
solution.
A 50 ml aliquot of the mineral water was rendered strongly alkaline to precipitate the
magnesium as Mg(OH)2 .
Titration with a calcium specific indicator required 31.54 ml of the EDTA solution.
Calculate:
a- The Molarity of the EDTA solution.
b- The ppm of CaCO3 in the mineral water.
c- The ppm of MgCO3 in the mineral water.

9
 Answer
 Molarity of MgCO3=Strength/molecular mass
We can never add or
=0.7682/84 subtract concentrations,
=9.14×10-3 M and we can never calculate
(MV)EDTA= (MV) Mg total concentration of a
mixture.
M×42.35=9.14×10-3×50 We can only add or
MEDTA=0.01 M subtract number of moles.

 At pH 10:
(MV)Ca+ (MV) Mg= (MV) EDTA
MCa×25+MMg×25=0.01×18.81 (1)

 At strongly alkaline medium:

(MV)Ca= (MV) EDTA
MCa×50=0.01×31.54
MCa=6.81×10-3 M (2)
Substitute from (2) in (1)
10
MMg=1.31×10-3 M
For CaCO3:
Strength×1000=Molarity × molecular weight×1000
=6.81×10-3×100×1000
=681 ppm

For MgCO3:
Strength×1000=Molarity×molecular weight×1000
=1.31×10-3×84×1000
=110.04 ppm
4- The Tl in a 9.76 g sample of rodenticide was oxidized to the trivalent state and
treated with an unmeasured excess of Mg/EDTA solution. The reaction is

Tl3+ + MgY2- TlY- + Mg2+

Titration of the liberated required 13.34 ml of 0.03560 M EDTA.

Calculate the % of Tl2SO4 (504.8 g/mol) in the sample.

12
 Answer
 (MV)Mg= (MV) EDTA= (MV) Tl=No. of Tl moles
No. of Tl mmoles=0.0356×13.34=0.474904 mmoles

No of Moles equal ½ that of Tl ions as each mole of molecule has 2

atoms of Tl

 No. of Tl2SO4 moles=No. of Tl moles/2=0.474904/2 X 1000

=0.237452 x 10-3 moles

 Mass of Tl2SO4=No. of moles × mass of one mole

=0.237452×10-3×504.8
=0.119 grams
 Percentage of Tl2SO4= (0.119/9.76)×100=1.228%

13
5- A 0.3284 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 rest of the solution was then diluted to 500.0 ml. A 10
ml aliquot was suitably buffered, titration of the lead , zinc and copper in
this aliquot required 37.56 ml of 0.00250M EDTA. The copper in a 25 ml
aliquot was masked with thiosulphate; the lead and zinc were then
titrated with 27.67 ml of The EDTA solution. Cyanide ion was used to
mask Copper and Zinc in a 100 ml Aliquot; 10.80 ml of EDTA solution was
needed to titrate Lead ion. Determine the composition of the brass
sample and evaluate percentage of tin by difference.
Strategy of answer:
The main idea of the problem is that, we have aliquots of
samples of different volumes, 10, 25, 100 ml, and we have
to put this into consideration, we can’t subtract volumes
used by EDTA, unless the samples we are working on have
the same volumes.
Also, The percentage of the last element will be obtained by
subtraction and this is not done in all cases EXCEPT it is
CLEARLY REQUESTED or the sample is indicated TO BE
PURE.
In the first titration: (1)
 (MV)Pb+ (MV) Zn+ (MV) Cu= (MV) EDTA
MPb×10+MZn×10+MCu×10=0.0025×37.56
In the second titration: (2)
 (MV)Pb+ (MV) Zn= (MV) EDTA
MPb×25+MZn×25=0.0025×27.67
In the third titration:
 (MV)Pb= (MV) EDTA
MPb×100=0.0025×10.8
MPb=2.7×10-4 M (3)

Substitute from (3) in (2)

 MZn=2.497×10-3 M
Substitute from (2) in (1)
 MCu=6.623×10-3 M
 Weight% of Lead=
[(2.7×10-4×0.5×207.2)/0.3284]×100=8.52%

 Weight% of Zinc=
[(2.497×10-3×0.5×65.39)/0.3284]×100=24.86%

 Weight% of copper=
[(6.623×10-3×0.5×63.546)/0.3284]×100=64.08%

 Weight% of tin=100-(8.52+24.86+64.08) =2.54%

( WE CANT DO THIS ALL THE TIME UNLESS IT IS

STATED THAT THE SAMPLE IS 100% PURE)
Extra problems
 1-Calamine, used for the relief of skin irritation, is a mixture of zinc and iron oxides.
A 1.022 g sample of dried calamine was dissolved in acid and diluted to 250.0 ml.
Potassium fluoride was added to a 10.0 ml aliquot of the diluted solution to mask the
iron; after suitable adjustment of the pH, Zn2+ consumed 38.710ml of 0.01294 M EDTA.
A second 50.0 ml aliquot was suitably buffered and titrated with 2.40 ml of
0.002727M ZnY2- solution :

Fe3+ + ZnY2- FeY- + Zn2+

Calculate the % of ZnO and Fe2O3 in the sample.

19
 Answer
(MV)Zn= (MV) EDTA (MV)Fe= (MV) ZnY
M×10=0.01294×38.71 M×50=0.002727×2.4
MZn=0.05 M MFe=1.3×10-4 M

No of Moles equal ½ that of Fe ions as

each mole of molecule has 2 atoms of Fe

Weight of ZnO= No. of Fe2O3 moles= No. of Fe moles/2

0.05×250x81.39 /1000 = (1.3×10-4×250)/ (2)
=1.017375 g =0.01675 mmoles
Weight of Fe2O3= 0.01675 x
159.69/1000
=2.61×10-3 g
% of ZnO= % of Fe2O3=
(1.017375/1.022)×100=99.73% [(2.61×10-3)/1.022]×100= 0.256%
20
2-A 50 ml sample containing 0.45g of MgSO4 (Mwt 120.37 g/mole) in 0.5 L required 37.6
ml of EDTA for titration. How many milligrams of CaCO3 (100.09 g/mole) will react with
1.00 ml of this EDTA solution?

 First calculate the concentration of MgSO4 as molar concentration

Strength=M x molec.wt.
0.9 g/l=Mx120.37
M= 0.0074M
 Calculate the Molarity of EDTA
(MV)EDTA=(MV)Mg++
M x 37.6 = 0.0074 x 50
M= 0.0098 M
 Find out the weight Of CaCO3 reacting with 1 ml of this EDTA
(MV)EDTA= wt
mol.wt
0.0098 x 1 = wt
100.09
Wt of CaCO3 = 0.98 mg