Unit II

Complexometric Titration - II

By
Dr. Mohd Nasir
Assistant professor
(Analytical division)
Department of chemistry
A.M.U., Aligarh
Metal-EDTA titration curve (Complexometric titration curve): The graphical representation of pM vs Volume
of EDTA added at a given pH Unit II

𝑲′𝒇 = 𝐾𝑓 ∝4

EDTA
pM = −𝒍𝒐𝒈𝟏𝟎 [𝑴𝟐+ ]

𝟏
[𝑴𝟐+ ] ∝
𝒑𝑴

𝑀2+
 Unit II

Figure 2: complexometric titration curve of

𝐶𝑎2+ , 𝐹𝑒 2+ , 𝑍𝑛2+ , 𝐻𝑔2+ 𝑎𝑛𝑑 𝐹𝑒 3+at a constant
pH
Figure 3: complexometric titration curve of 𝐶𝑎 2+ , at different
pH (6, 8, 10, and 12)
Question: Which of the following metal ions (Figure) has
(i) high value of formation constant Unit II
(II) very leas feasibility to form complex with titrant
Example: The formation constant for CaY2- is 5.0 × 1010. At pH 10, ∝4 is calculated to be 0.35 to give a conditional
constant of 1.80 × 1010 . Calculate pCa in 100 mL of a solution of 0.100 M Ca2+ at a pH 10 after addition of
(a) 0.0 mL of 0.100 M EDTA
Unit II
(b) 50.0 mL of 0.100 M EDTA
(c) 100.0 mL of 0.100 M EDTA
(d) 150.0 mL of 0.100 M EDTA

Draw complexometric titration curve for the above titrimetric analysis and calculate the equivalence point from the curve
Numerical
Example 2: The formation constant for CaY2- is 5.0 × 1010 . At pH 10, ∝4 is calculated (Example 1) to be 0.35 to give a Unit II
conditional constant of 1.80 × 1010 . Calculate pCa in 100 mL of a solution of 0.100 M Ca2+ at a pH 10 after addition of
(a) 0.0 mL of 0.100 M EDTA
(b) 50.0 mL of 0.100 M EDTA
(c) 100.0 mL of 0.100 M EDTA
(d) 150.0 mL of 0.100 M EDTA
Solution:
Given: 𝐾𝑓 = 5.0 × 1010 , pH = 10, ∝4 = 0.35, 𝑲′𝒇 = 1.8.0 × 1010 , initial concentration of Ca2+ = 0.100 M, Volume of Ca2+ = 100 mL, initial
concentration of EDTA = 0.100 M,

To be calculate: pCa When

(a) Volume of EDTA added = 0.0 mL (before addition)

pCa = −𝑙𝑜𝑔10 [𝐶𝑎2+ ] = −𝑙𝑜𝑔10 (0.100) = −𝑙𝑜𝑔10 (1.00 × 10−1 ) = −(−1) = 𝟏. 𝟎𝟎 (𝑙𝑜𝑔10 10𝑦 = 𝑦)

(b) Volume of EDTA added = 50.0 mL

Millimoles of 𝐶𝑎2+ and EDTA initially added

mmol 𝐶𝑎2+ = 0.100 M × 100.00 mL = 10.00 mmol 𝐾𝑓 = 5.0 × 1010

High values
𝑲′𝒇 = 1.8.0 × 1010
mmol 𝐸𝐷𝑇𝐴 = 0.100 M × 50.00 mL = 5.00 mmol
At equilibrium

5.00 mmol of EDTA will react with 5.00 mmol of 𝐶𝑎2+ (5.00 mmol 𝐶𝑎2+ in excess) to form 5.00 mmol of CaY2- complex.
 𝑚𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 CaY2− 10.00
[CaY2-] = = = 0.050 𝑀
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 200 Unit II
Suppose x M of 𝐶𝑎2+ dissociated then concentration of uncomplexed EDTA = x M

Now
[𝑀𝑌 2− ]
𝐾𝑓 ∝4 = 𝑲′𝒇 = (𝐴𝑡 𝑔𝑖𝑣𝑒𝑛 𝑝𝐻)
[𝑀2+ ] 𝐶𝐻4𝑌

10
0.050 2
0.050
1.80 × 10 = 𝑜𝑟 𝑥 = 10
= 0.0277 × 10−10 𝑜𝑟 𝑥 2 = 2.77 × 10−12 𝑜𝑟 𝑥 = 1.66 × 10−6
(x)(x) 1.80 × 10

𝑥 = [𝐶𝑎2+ ] = 1.66 × 10−6

pCa = −𝑙𝑜𝑔10 [𝐶𝑎2+] = −𝑙𝑜𝑔10 (1.66 × 10−6) = −𝑙𝑜𝑔10 166 × 10−8 = −(−8) 𝑙𝑜𝑔10 (166) = −{(−8) + 2.220} = 𝟓. 𝟕𝟖
(d) Volume of EDTA added = 150.0 mL
Unit II
Millimoles of 𝐶𝑎2+ and EDTA initially added

mmol 𝐶𝑎2+ = 0.100 M × 100.00 mL = 10.00 mmol

mmol 𝐸𝐷𝑇𝐴 = 0.100 M × 150.00 mL = 15.00 mmol

At equilibrium

10.00 mmol of EDTA (5.00 mmol EDTA in excess) will react with 10.00 mmol of 𝐶𝑎2+ to form 10.00 mmol of CaY2- complex.

𝑚𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 CaY2− 10.00

[CaY2-] = = = 0.040 𝑀
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 250

5
Concentration of uncomplexed EDTA [𝐶𝐻4𝑌 ] = = 0.020 𝑀
250

Suppose x M of 𝐶𝑎2+ dissociated

Now
[𝑀𝑌 2− ]
𝐾𝑓 ∝4 = 𝑲′𝒇 = (𝐴𝑡 𝑔𝑖𝑣𝑒𝑛 𝑝𝐻)
[𝐶𝑎2+ ] 𝐶𝐻4𝑌

0.040 0.040 0.040

1.80 × 1010 = 𝑜𝑟 𝑥 = = = 1.11 × 10−10 𝑜𝑟 𝑥 = [𝐶𝑎2+ ] = 1.11 × 10−10
(x)(0.020) (1.80 × 1010 ) (0.020) 0.036 × 1010

pCa = −𝑙𝑜𝑔10 [𝐶𝑎2+ ] = −𝑙𝑜𝑔10 (1.11 × 10−10 ) = −𝑙𝑜𝑔10 111 × 10−12 = −(−12) 𝑙𝑜𝑔10 (111) = −{(−12) + 2.045} = 𝟗. 𝟗𝟓𝟒
Table: Titration of 100 mL of 0.100 M Ca2+
with 0.100 M EDTA at pH 10 Unit II
Table: Titration of 50 mL of 0.010 M Ca2+ with
Volume of EDTA added (mL) [Ca2+] pCa 0.010 M EDTA at pH 10
00.00 0.100 1.00

50.00 0.030 1.522

100.00 1.66 × 10−6 5.78

150.00 1.11× 10−10 9.954

200.00 10.32

250.00 10.41

10
12 9
10 8
7 Equivalence point (50 mL )
8 Equivalence point (100 mL )

pCa
6
pCa

6 5
4 4
3
2
2
0 0 10 20 30 40 50 60 70
0 50 100 150 200 250 300 350 EDTA (mL)
Volume of EDTA added
INDICATOR Unit II
 Unit II

At initial stage of titration

+7
+7
KMnO4 (purple) +7
KMnO4 (purple)

Excess Mn+7 (purple)

Oxalate ion Mn+2 (colorless)
Indicators used in complexometric titration (Metallochromic indicators)
Unit II

Calmagite
Eriochrome Black T

Murexide
Eriochrome Black T (EBT)
Ionizable protons Unit II
Effect of pH

Eriochrome Black T (H3In)

(pH < 6)
(Black solid)

−𝑯+ −𝑯+

𝑯𝑰𝒏𝟐− 𝑰𝒏𝟑−
𝑯𝟐 𝑰𝒏−
pH = 7-11 pH >11
pH = 6-7
(Blue liquid) (Yellowish orange)
(Red liquid)
The use of Eriochrome Black T (EBT) as indicator for EDTA titration
Unit II
(a) Before titration

50 mL (95 % ethyl alcohol)

Eriochrome Black T
Solution Preparation
H3In 𝐻𝐼𝑛2− 𝑀𝑛+ 𝑀𝐼𝑛−(𝑛+)
Put on gloves and
protective eyewear
and weigh out
approximately 0.5 g
of solid Eriochrome
Black T, (EBT) on a
𝑀𝑛+ balance and transfer it
to a small beaker or
flask. Add about 50
mL of 95 percent
ethyl alcohol and
𝐻𝐼𝑛2− 𝑀𝐼𝑛2−(𝑛+) swirl the mixture until
Complexed EBT (Wine red color) the EBT has fully
Uncomplexed EBT(Blue color) (1:1 Complex) dissolved
(b) During titration Stability
𝑀𝑛+ − Y4− > 𝑀𝑛+ − 𝐻𝐼𝑛2− Unit II

EDTA
(Colorless)

𝑀𝐼𝑛 −(𝑛+) +Y4− Y4− −− −𝑀𝑛+ … … . 𝐻𝐼𝑛2−

𝑀𝐼𝑛 −(𝑛+)
(blues red )
(Wine red)
(c) At the equivalence point
Unit II

𝐻𝐼𝑛2−
𝑀𝑌 4−(𝑛+) (1: 1 𝑐𝑜𝑚𝑝𝑙𝑒𝑥)
(Stable: colorless) (Stable: Blue color)
𝑀𝐼𝑛2−(𝑛+) +Y4− Y4− −− −𝑀𝑛+ … … . 𝐻𝐼𝑛2− End point: Blue
(unstable: blues red )
Calmagite
Unit II

Effect of pH

H2O pH > 8
pH > 12

H3In H2In- HIn2-

In3-
(Black Solid) (Red liquid) (Blue liquid)
(Reddish orange liquid)
pH<6 pH = 6-8 pH = 8-12
pH >12
The use of Calmagite as indicator for EDTA titration
(a) Before titration Unit II

0.5 g (1 L of DMW )
pH> 8 +

H2O + HIn2- M2+ H2O + HIn2− + M2+ = 𝑀𝐼𝑛−

H3In
Blue Colorless Red Calamagite Solution
Preparation

Dissolve 0.5 g of
Calmagite in 1 L of
distilled water at pH > 8.
M2+ + Stir the solution for one
hour and let sit overnight.
In spite of its long shelf
life, the indicator should
be prepared fresh every
month
HIn2-
H3In (Blue) 𝑴𝑰𝒏−
pH = 8-12 (Red)
(b) During titration Stability
𝑀2+ − Y4− > 𝑀2+ − 𝐻𝐼𝑛2− Unit II

EDTA
(Colorless)

𝑀𝐼𝑛− +Y4− Y4− −− −𝑀2+ … … . 𝐻𝐼𝑛2−

𝑀𝐼𝑛−
(Wine red)
(blues red )
(c) At the equivalence point
Unit II

𝐻𝐼𝑛2−
𝑀𝑌 2− (1: 1 𝑐𝑜𝑚𝑝𝑙𝑒𝑥)
(Stable: colorless) (Stable: Blue color)
𝑀𝐼𝑛2− +Y4− Y4− −− −𝑀2+ … … . 𝐻𝐼𝑛2− End point: Blue
(unstable: blues red )
Application of EDTA titration
Direct titration
Simplest and most
convenient method used in
complexometric titration and
in this method
EDTA titration
Back titration
 Used when the reaction between
cation and EDTA is slow
 When a suitable indicator is not
available
 Method is also useful for cations as
Cr (III), Mn (III) and Co(II) that
react slowly with EDTA
Unit II
Replacement titration
 When direct and back titration don't
give sharp end point
 When a suitable indicator is not
available
 Exact Concentration of calcium ion can not be easily determined in absence of magnesium ion spatially when we use
EBT as indicator by the direct titration
Unit II
But why ?????????????????

Before titration before equivalence point

+ EDTA

Ca-EBT complex (very week complex) Ca-EDTA complex (very strong complex)

blues red not a perfect wine red color

 EBT-Magnesium complex is more stable than EBT-calcium complex and EDTA-magnesium Unit II
complex is less stable than EDTA-calcium complex

Step I: Preparation of magnesium blank Step II: Add 5 mL, freshly prepare magnesium blank in aqueous solution of
calcium ion

After addition of
+ EDTA Mg-EBT

Ca-EDTA complex (very strong complex complex)

Mg-EBT complex (very strong complex)

Mg2++ EBT (pH 10.3)
Mg-EDTA complex Ca-EBT complex (very week) Ca- EBT complex (very weak complex Magnesium)
(Magnesium blank)
Step III: Titrate the mixture obtained in the second step with EDTA

b) Just before the equivalence point Unit II

c) At the equivalence point

a) During titration

 All Ca-EBT Ca-EDTA complex

(Ca-EDTA + Mg-EBT + EBT)

(Ca-EDTA + Mg-EDTA + EBT)

 EDTA will start replacing calcium ion from Ca-EBT Ca-EDTA
End Point
How the concentration of EDTA consumed during this process will be chemically equivalent
to the concentration of calcium
Unit II

Before titration

Mg-EDTA + Ca-EBT Ca-EDTA + Mg-EBT + Ca-EBT

X mmol X mmol 1-X mmol
(Small amount) (Small amount) (Excess)

Just before the equivalence point

Ca-EDTA + Mg-EBT + Ca-EDTA + EBT

X mmol X mmol 1-X mmol
(Small amount) (Excess)
(Small amount)

At the equivalence point

At the end point
M1V1 = M2V2
𝑀1 𝑉1
Ca-EDTA + Mg-EDTA + Ca-EDTA + EBT 𝑀2 =
𝑉2
X mmol X mmol 1-X mmol
(Small amount) (Small amount) (Excess)
M1= concentration of EDTA (known)
V1= Volume of EDTA (known from the burette)
X + 1-X = 1
M2= concentration of Calcium ion (unknown)
V2= Volume of calcium ion taken in conical flask (known)
Example 1: Titration of 100 mL of a water sample at pH 11 in the presence of a calcium specific indicator
such as Eriochrome Black T required 14.0 mL of 0.02M EDTA solution. Calculate the hardness of the water
Unit II
sample as CaCO3 in mg/L .

Solution:
Given: Concentration of EDTA = 0.02M, Volume of EDTA Added = 14.0 mL
Volume of aqueous solution of CaCO3 = 100 mL, Molecular weight of CaCO3 = 100 g/mole
To be calculate: hardness of water sample as CaCO3 in mg/L

0.02 𝑚𝑜𝑙𝑒𝑠
Moles of EDTA consumed = × 14 𝑚𝐿 = 0.02 × 14 × 10−3 = 𝟐. 𝟖 × 𝟏𝟎−𝟒 𝐦𝐨𝐥𝐞𝐬
1000𝑚𝐿

So, 2.8 × 10−4 moles of Ca2+ will be present in 100 mL of water as CaCO3 (1:1 complex)

Amount of CaCO3 present in 100 mL of water = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 CaCO3 × 𝑀. 𝑊𝑡 𝑜𝑓CaCO3

= 2.8 × 10−4 × 100 = 2.8 × 10−2 g/ 100 mL

2.8×10−2 ×103 𝑚𝑔
= 1
100 ×
1000𝐿

2.8×10−2 ×103 𝑚𝑔
=
10−1 𝐿

2.8×102 𝑚𝑔
= = 𝟐𝟖𝟎𝒎𝒈/𝑳 hardness
𝐿
So, hardness of water = 280 mg/L
Example 2: A 200 mL of sample of well water sample at pH 12 in the presence of a calcium specific indicator
such as Eriochrome Black T required 17.940 mL of 0.025M EDTA solution. Calculate the hardness of the
Unit II
water sample as CaCO3 in ppm.

Solution:
Given: Concentration of EDTA = 0.025M, Volume of EDTA Added = 17.940 mL
Volume of aqueous solution of CaCO3 = 200 mL, Molecular weight of CaCO3 = 100 g/mole
To be calculate: hardness of water sample as CaCO3 in ppm

0.025 𝑚𝑜𝑙𝑒𝑠
Moles of EDTA consumed = × 17.94 𝑚𝐿 = 0.025 × 17.94 × 10−3 = 𝟒. 𝟒𝟗 × 𝟏𝟎−𝟒 𝐦𝐨𝐥𝐞𝐬
1000𝑚𝐿

So, 4.49 × 10−4 moles of Ca2+ will be present in 200 mL of well water as CaCO3 (1:1 complex)

Amount of CaCO3 present in 200 mL of water = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 CaCO3 × 𝑀. 𝑊𝑡 𝑜𝑓CaCO3

= 4.49 × 10−4 × 100 = 4.49 × 10−2 g/ 200 mL

4.49×10−2 ×103 𝑚𝑔
= 1
200 ×
1000𝐿

4.49×10−2 ×103 𝑚𝑔
=
20×10−2 𝐿

4.49×103 𝑚𝑔
= = 𝟐𝟐𝟒. 𝟓𝒎𝒈/𝑳 hardness
20 𝐿
So, hardness of water = 224.5 mg/L = 224.5 ppm
Back titration
For the determination of the concentration of Mn 2+ Al+3 , CO+2 Cr+3, Ni+2
Unit II
Procedure:

Step I: An excess known amount of a standard EDTA solution is added to the solution of the analyte

(known volume)

Buffer solution

EBT

MnY2- + EDTA (remaining)

MnY2- + EDTA (remaining)
Mn2+ + EBT (free form)
(unknown concentration)

EDTA Blue color solution

(Known concentration)
Step II: Prepare a standard solution of metal ion (Shows very high formation constant with EDTA like Mg (II). Zn (II) etc) and fill it in
burette, Now titrate the analyte with this titrant (known concentration of salts of Zn+2 or Mg +2 )
Unit II

b) Just before the end point

a) Before titration (equivalence point) c) At the end point

MnY2- + EDTA (remaining)

+ EBT (free form) MnY2- + ZnY2- + EBT (free form) MnY2- + ZnY2- + Zn-EBT (complex form)

Blue color solution Blue color solution wine red color solution
Example: A 3208 g sample of nickel ore was processed to remove interferences and 50.00 ml of 0.1200 mol L
EDTA was added in excess to react with Ni ions in solution. The excess EDTA was titrated with 24.17 mL of Unit II
0.0755 mol/L standard Mg . Calculate the %Ni in the ore

Solution:
Given: weight of the sample = 3208 g, Concentration of EDTA 0.120M, Volume of EDTA added = 50.00 mL
Concentration of standard Mg2+ (titrant) = 0.0755M, Volume of Mg add to titrate excess of EDTA = 24.17 mL

To be calculate = %Ni in the ore

0.120 𝑚𝑜𝑙𝑒𝑠
Total number of moles of EDTA initially available in the 50.00 mL solution of 0.1200 M EDTA = × 50 𝑚𝐿 = 𝟔. 𝟎 × 𝟏𝟎−𝟑 𝐦𝐨𝐥𝐞𝐬
1000𝑚𝐿

0.0755 𝑚𝑜𝑙𝑒𝑠
Moles of Mg2+ consumed for the titration of excess EDTA = × 24.17 𝑚𝐿 = 𝟏. 𝟖𝟐𝟓 × 𝟏𝟎−𝟑 𝐦𝐨𝐥𝐞𝐬
1000𝑚𝐿

So, Moles of EDTA form complex with Nickel in ore= 6.0 × 10−3 moles - 1.825 × 10−3 moles = 4.175 × 𝟏𝟎−𝟑 moles

Therefore, moles of Nickel in the ore = Moles of EDTA form complex = 4.175 × 𝟏𝟎−𝟑 moles (1:1 complex)

𝑾𝒕
Amount of the Nickle present in the 3208 g of sample = 4.175 × 10−3 mole × 58.7 g/mole = 0.245. g 𝒏=
𝑴.𝒘𝒕 𝒐𝒓 𝒂𝒕𝒐𝒎𝒊𝒄 𝒘𝒕

So,
3208 g sample of nickel ore contain 254.07 × 10−3 g Nickle
254.07
1g ……………………………..
3208
0.254
100g …………………………….. ×100 = 0.00764%
3208