COMPLEX-FORMATION

TITRATION
COMPLEXIMETRY
 Is a combination of metal ion with electron donating group or
nucleophile to form a complex.

M
Metal ion
+ nL
Ligand
⇋ [MLn]
Complex

Lewis acid Lewis base [ ], coordination sphere

Electron pair acceptor Electron pair donor n, coordination number
Vacant orbitals Neutral or negatively charged (controlled by metal ion)

 Ag+ + 2CN- [Ag(CN)2]-

 Cu2+ + 4NH3 [Cu(NH3)4]2+
 Fe2+ + 6SCN- [Fe(SCN)6]4-
 The metal ion acts as Lewis acid (electron acceptor) and complex
forming agent (Ligand) which acts as a Lewis base (electron pair
donor or a negatively charged group).
 Remember that
 The coordination number (n) of the metal ion represents the
number of coordinate bonds around the central metal which is
the number of monodentate ligands coordinated to the metal
ion.

 e.g. Ag+ + 2CN- [Ag(CN)2]- n= 2

 Cu2+ + 4NH3 [Cu(NH3)4]2+ n= 4
 Fe2+ + 6SCN- [Fe(SCN)6]4- n= 6

 Coordinate bond is the bond formed between electron

donating group (ligand) and an electron acceptor (metal ion).
 Primary
Coordinate bond or Dative bond Valence
from ligand to metal

SO42-

Coordination number of copper = 4

Copper tetraamine complex Copper can accommodate 4 lone

pairs of electrons as an extra-
valence in its vacant orbitals
Conditions for compleximetric titrations (Schwarzenbach
Concept)
Schwarzenbach concepts states that:
Although the reaction between a metal and a ligand can be
considered as an acid base interaction, but it was found that metal
ions cannot be titrated with simple ligands as ammonia or cyanide,
because the reaction by which the complex is formed lack a sharp
and definite end point and thus a titration curve cannot be easily
constructed.
Consider the following reactions,
H+ + NH3 NH4+ K= 109.3
Cu2+ + 4NH3 [Cu(NH3)4]2+ K= 1012.6
 The main difference between the two reactions is that hydrogen
ions and ammonia react usually in the ratio of 1:1, whereas
copper and ammonia react with a ratio 1:4 (stepwise formation).
 Thus the overall stability constant of the copper tetramine
complex is divided between four ligands and the value to be
obtained from addition of only one of them to the metal ion is
much less than that obtained by combination of the ligand with
the hydrogen ion.
 Cu2+ + NH3 Cu(NH3)2+ K1= 1.4x104
 Cu(NH3)2+ + NH3 Cu(NH3)22+ K2= 3.1x103
 Cu(NH3)22+ + NH3 Cu(NH3)32+ K3= 7.8x102
 Cu(NH3)32+ + NH3 Cu(NH3)42+ K4= 1.3x102
K= [Cu(NH3)4 2+] =K1K2K3K4 = 1012.6
[Cu2+] [NH3]4
 Notice that
 Compleximetric titrations are only possible if:

 The complex formation reaction occurs in one step with a high

stability constant.
OR
 If it proceeds stepwise, large stability constants of the
intermediate complexes are needed in order to obtain a good
jump of pM at the equivalence point.
 Chelate rings: heterocyclic rings formed by the interaction of a
metal ion with two or more functional groups in the same ligand.
 The complexes involving formation of rings have high stability
compared with those involving no ring formation.
 Chelating agents usually form 1:1 complexes with metal ions with
large stability constant, thus overcoming problems arising with
stepwise formation as in Cu(NH3)42+.
 The chelate effect become more pronounced as the number of rings
per complex increase and is most pronounced for five-membered
rings.
Example:
[Ni(NH3)6]2+ (no chelate ring) K= 5.5x108
[Ni(en)3]2+ (five-membered ring) K = 2 x 1018
 Types of ligands
 Molecules or ions which acts as ligands generally contain an
electroactive atom, such as nitrogen, oxygen or one of the
halogens.
 Monodentate ligands, are ligands which contain only one center of
donation e.g.: CN-, F-, :NH3, H2O: , Cl-
 Bidentate ligands, ligands which contain 2 centers of donation.
e.g. ethylene diamine (en) H2N:-CH2-CH2-:NH2, Both nitrogens
have unshared electrons.
 Multidentate ligands, Ligands which contain more than 2
centers of donnation as triethylene-tetramine (Trien) and
Ethylene diamine tetraacetic acid (EDTA).

Examples
Tetradentat Ligand
NH2CH2CH2 NH CH2CH2 NH CH2CH2NH2
(Trien)
Hexadentat Ligands
 Multidentate ligands usually have Oxygen, Nitrogrn or both
i.e. they are highly effective in forming stables complexes
comprising a heterocyclic ring i.e., a chelate.

 Accordingly they are commonly known as chelating agents.

 Advantage of multidentate ligands

 They generally react more completely with cations and thus

provide sharper end point.

 They react with metal ions in a single step.

 Cu2+ + 4 NH3 = [Cu(NH3)4]2+

Cu2+ + 2 NH2CH2CH2NH2 = [Cu(en)2]2+

Cu2+ + trien = [Cu(trien)]2+

Cu2+ + EDTA = Cu-EDTA

 Only few metals ions such as Cu, Co, Ni, Zn, Cd and Hg2+
form stable complexes with nitrogen ligands such as ammonia
and trien.

 Al, Pb and Bi are better complexed with ligands containing

oxygen atoms.

 A wide variety of metals form stable complexes with

chelating agents containing both oxygen and nitrogen.
 Trien
 Trien, triethylenetetramine, is a
quadridentate ligand, it has
4 nitrogen atoms linked by three
ethylene bridges.

 The bonding between Cu and the first

nitrogen brings the other nitrogens of
the trien molecule into such proximity
to form more bonds with Copper,
ending up with the formation of a 1:1
and stable complex.

 The formed complex is stable because

it contains five membered rings (3
rings). It is called a chelates.
 EDTA (H4Y)
 EDTA is a tetrabasic acid that has six potential sites for
bonding with a metal ion, four carboxyl groups and two amino
groups, each of the latter with unshared pair of electrons. Thus
EDTA is a hexadentate ligand.

 The dissociation constants for the acidic groups in EDTA are

K1= 1.02x10-2, K2= 2.14x10-3, K3= 6.92x10-7 and K4 = 5.50x10-11.

 The various EDTA species are often abbreviated as H4Y, H3Y-,

H2Y2-, HY3- and Y4-.
 The fully protonated form H4Y is only a major component in
very acidic solutions (pH<2).
 Throughout the pH range of 3 to 10 the species H2Y2- and HY3-
are predominant.
 The fully unprotonated form Y4- is dominant only in very basic
solutions (pH>10).
H4Y ⇌ H3Y ⇌ H2Y2 ⇌ HY3 ⇌ Y4
pH <2 2-3 4-5 8-10 >12
 EDTA is a multidentate ligand, so it is capable of forming
complexes that contain cyclic rings.
 These complexes are known as chelates and thus EDTA can also
be called chelating agent.
 Nature of EDTA titrations with metal ions
1. EDTA is not a selective reagent (G.R.) as it can complex with all
metal ions with a ratio 1:1 regardless of the charge on the cation.
e.g. Ag+ + Y4- AgY3-
Al3+ + Y4- AlY-
Mx+ EDTA
1 mole 1 mole (MV)Mx+ = (MV)EDTA
MV MV

2. Mode of Chelation of EDTA with metal ions

3. The stability of the formed complexes is highly dependent on the
pH of the medium (G.R.):

a. Tri and tetravalent metal ions such as Bi3+, Fe3+, Cr3+, Th4+, V4+
form highly stable EDTA complexes having log K>20 . These
can be titrated with EDTA in acid medium pH 1-3 using 0.2 N
HNO3 to adjust pH.

b. Divalent metal ions such as Pb2+, Cd2+, Zn2+ can be titrated in

acidic medium using hexamine buffer (5-6) and xylenol orange
as indicator.
c. Ca2+can be titrated in highly alkaline medium pH>12 using
murexide as indicator. Also, Mg2+ and Ba2+(after special
treatment with tartarte salt) can be titrated.

d. Most of divalent metal ions as Mg2+, Ca2+, Ba2+, Pb2+, Zn2+ can
also be titrated in alkaline medium (pH 10) using ammoniacal
buffer and Eriochrome black T as indicator.
 The pH values shown in fig is the
minimum values for titration of the given
metal using EDTA.
 For each metal ion, there would be a
certain pH below which the titration of
this metal ion with EDTA will not be
possible.
 Titration at higher pH values is possible
using a suitable indicator.
 The main determining factor in the pH
dependence is the stability of the formed
complex in comparison to the free EDTA
in a given pH, the complexes should have
higher stability constants so that the
titration is possible.
 Indicators for EDTA titrations

These indicators can be divided into:

1- Colorless or weakly colored substances which form colored or
slightly soluble product with metal.
Example:
SCN- + Fe3+ = [Fe(SCN)6]3- (red complex)
2- Dyes which react with metal ion to form dye of different color
(Metallochromic indicator)
They are chelating agents which contain chromophoric group
(color forming)
 These indicators can form colored complexes with metal ions
in a pM range characteristic of the particular indicator and
metal cation.

M + In= MIn complex

MIn + EDTA = In + M-EDTA complex
 Properties of Metallochromic indicators
1. The free indicator must posses a different color from the metal
indicator complex.
2. The metal indicator complex must be formed in the same pH of
the metal EDTA complex.
3. The indicator must be very sensitive towards the metal ion so
that only a small amount of it is necessary for a titration.
4. The metal indicator complex must be less stable than metal
EDTA so as to dissociate easily in the vicinity of the end point.
5. The reaction between the indicator and the metal should be
rapidly reversible.
 Example of Metallochromic indicator Eriochrome black T
(EBT ) (H3In)
 This is one of the most widely used metallochromic indicators in
EDTA titrations.

 It is the sodium salt of 1-(1-hydroxy-2-naphthylazo)-2-naphthol-

6-nitro-4-sulphonic acid.
6

1 4
1

2
It ionizes in three steps:

 Therefore, the optimum pH for a color change from red to

blue is pH 10.
 The blue color is due to the blue anion HIn2-
 Mode of Chelation of EBT with metal ions
The indicator reacts with many divalent ions to form a metal
complex as shown in Figure. All the complexes are red, it
commonly reacts with Divalent metals as Mg2+, Ca2+, Ba2+, Zn2+
to form a complex MIn- (red).

Tetradentate ligand
 Principles underlying the use of EBT

1. At pH 8-10 , the predominant species is the blue HIn2- indicator

ion.

2. When a metal ion is added to a solution of EBT at pH 10, the

blue solution turns red due to the formation of the red metal-
indicator complex MIn- ions thus:
M2+ + HIn2- (blue) ⇌ H+ + MIn- (red)
3. As a general rule, the metal ion-EBT complex should be
weaker than the metal ion-EDTA complex. Thus on titrating
the red MIn- solution with EDTA, the stronger M-EDTA is
formed continuously, until the end point is detected by
complete formation of M-EDTA and liberation of the blue
HIn2- indicator ions.

HY3-(EDTA at pH10) + MIn-(red) MY2- + HIn2-(blue)

 Murexide Indicator

 Murexide is the ammonium salt of purpuric acid whose

monovalent anion H4In- as represented above.
 A solution of murexide is red violet below pH 9, violet from pH
9 to pH 11 and violet blue (purple) above pH 11, thus
H4In- H3In2- H2In3-
pH = 9 9-11 > 11
Its complexes are red with Ca, orange with Cu, yellow with Ni and
Co.
Thus on adding Ca ions to a solution of murexide at pH 12- 13, the
blue H2In3- species turns red and on titrating the red solution with
EDTA, the solution turns violet blue at the end point, thus:
Ca2+ + H2In3- (Blue) ⇌ CaH2In- (Red)
CaH2In- (Red) + Y4- CaY2- + H2In3- (Violet blue)

Tridentate ligand
 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.

 Water hardness is represented in terms of the presence of

Ca2+ and Mg2+ salts.
 Total Ca2+ and Mg2+ are determined by direct titration with
EDTA at pH 10 using ammoniacal buffer and EBT as
indicator.

 Ca2+ alone can be determined at pH 12 using 0.4 g. eq L-1

NaOH and murexide as indicator.

M + In = M-In
M-In + EDTA = M-EDTA + In
 B. Back titration

M(analyte) + EDTAexcess = M-EDTA

EDTA + In +M* (titrant)= M*-EDTA +M*-In

 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 or
when the metal blocks the indicator (If a metal and the
indicator complex is too strong, the metal is said to block the
indicator).
 The method is also useful for cations as Cr(III) and
Co(II) 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.

 It can also be used when the analyte forms precipitates at

the required pH of its titration.
 In a back titration, an excess known
volume (Vt) of standard EDTA is added
V2 mL of titrant
to the metal ion solution (M1, analyte). is needed to
reach the E.P.
 The excess EDTA is titrated with a
standard second metal ion (M2, titrant).
Std. M2
 The second metal ion (M2) must form a
weaker complex with EDTA than the
analyte ion (M1) so it does not displace
V1 mL of M1 +
the analyte ion from its complex with
Excess EDTA
EDTA. (Vt)

 In this case, the analyte concentration

Adjust pH
can be calculated as follows:
add suitable
indicator
  ?
(MVt)EDTA – (MV2)M2 = (MV1)M1
unreacted EDTA reacted
total EDTA excess EDTA with M1
 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 Zn2+ can be then titrated with

standard EDTA solution.

 Displacement titrations are used on lacking sharp end

point or when no suitable indicator is available.
 Titration of mixtures
How to increase selectivity of EDTA

1- Control of pH.
2- Precipitation of interfering cations.
3- By reduction of interfering cations by lowering its
valency so it becomes non interfering (eg. Fe3+ to Fe2+)
4- Complexation.
 One of the chief problems associates with the use of EDTA it is
lack of selectivity since it forms 1:1 complexes with all cations.

 This problem is overcome by using of masking and demasking

agents.

 A masking agent is a complexing agent that reacts selectively

with a component in a solution to prevent that component from
interfering in a determination.

 So it becomes available to determine a cation in presence of

others masked ones.
 By using stronger complexing agent than EDTA which is
either inorganic such as cyanide, fluoride (used to Mask
Al, Ca, Mg, Th, La), iodide that forms very stable
complex with Hg…etc or organic as triethanolamine
(used to mask Fe, Al, Mn), In this case the metal ions are
said to be masked from EDTA.

 The most important of such type is masking by

complexation with cyanide and it has a wide range of
applications.
 Masking with cyanide
 The cyanide ion can form very stable complexes with
cations of Ag(I), Cr(III), Cu(II), Hg(II), Cd(II), Zn(II),
Co(II), Ni(II), Fe(II) and Fe(III).

 So it is possible to determine any two metal ions from the

above groups with one of the following metals, Ca, Sr, Ba,
Mg, In, Pb and Mn that do not form any complexes with
cyanide. (Mn is exceptinally included in this class though it
forms complexes with CN- as its cyanide complex is less
stable than Mn-EDTA, accordingly, it can’t be used as a
masking agents.)
 Triethanolamine

 Triethanolamine is used as masking agent for iron, Al, traces of

Mn.

 With iron it forms yellow to brown complex which is discharged

by adding NaOH.

 Mn forms green color with it but because of the intense color of

the resulted complex, cause the use of this masking agent only
for traces of Mn.
 Other masking agents

 The F- is used as masking agent for Al, Ca, La, Th, Mg,
the ionization of the formed ppt is suppressed by the
common ion effect of excess F-

 The I- ion masks Hg(II) of HgI42- .

 Demasking

 It was found that, for Zn and Cd cyano complexes that

the metal ions can be released (demasked) from the
complex using formaldehyde, acetone or chloral hydrate
as follows:

Zn(CN)42- + 4HCHO + 4H2O Zn2+ + 4H2C-CN-OH + 4OH-

Demasked
Masked Zn Free Zn
Formaldehyde cyanohydrin
 Suggest a suitable method to determine each metal
in the following mixture:

1. Fe2+ + Zn2+ + Ca2+

1- Back titration to find the equivalent volume for total

metals.

2- On a new portion, add CN-, Fe2+ and Zn2+ will be masked,

therefore by direct titration, the volume of EDTA will be
equivalent to Ca2+.
3- On the same flask, add acetone, Zn2+ will be de-masked,
therefore by direct titration, the volume of EDTA will be
equivalent to Zn2+.

4- By subtraction, you can obtain the equivalent volume to

Fe2+.
 2. Cd2+ + Fe2+ + Fe3+ + Ca2+

1. Back titration to find the equivalent volume for total

metals.

2. On a new portion, adjust the medium at highly acidic

pH. By direct titration, the volume of EDTA will be
equivalent to Fe3+ (selective control of pH).
3. On a new portion, add CN-, Fe3+, Fe2+and Cd2+ will be
masked, therefore by direct titration, the volume of EDTA
will be equivalent to Ca2+.

4. On the same flask, add acetone, Cd2+ will be de-masked,

therefore by direct titration, the volume of EDTA will be
equivalent to Cd2+.

5. By subtraction, you can obtain the equivalent volume to

Fe2+.
 3. Cd2+, Ca2+, Ni2+, Mn2+

1- Back titration to find the equivalent volume for total

metals.

2- On a new portion, adjust the pH to be highly alkaline

(pH>12) using NaOH. By direct titration, the volume of
EDTA will be equivalent to Ca2+ using murexide as an
indicator.
3- On a new portion, add CN-, Cd2+ and Ni2+ will be masked,
therefore by direct titration, the volume of EDTA will be
equivalent to Ca2+ and Mn2+
 By subtraction: volume of 3-2, you can obtain the
equivalent volume to Mn2+.

4- On the same flask, add acetone, Cd2+ will be de-masked,

therefore by direct titration, the volume of EDTA will be
equivalent to Cd2+.
5- By subtraction, you can obtain the equivalent volume to
Ni2+.
7.5 g of EDTA (disod. Salt , Mwt = 372.25) was dissolved into 500
mL of water. On standardizing with std Zn(II) solution (1.6274 g/l),
10 mL of the Zn2+ solution required 10.05 mL EDTA using EBT
indicator. What is the percent purity of EDTA?
Molarity of std Zn2+ solution can be calculated from the strength as
follows: Strength = M x At. Wt.
M= 1.6274 / 65.3 = 0.0249 mol/L
(MV)Zn2+ = (MV)EDTA, 0.0249x10 = Mx10.05
MEDTA = 0.0248 mol/L
WtEDTA = M V Mwt / 1000 = 0.0248 x 500 x 372.25 / 1000 = 4.61 g
% purity = (Wt of EDTA/ Total wt) x 100
= (4.61 / 7.5) x 100 = 61.5%
A powdered milk sample weighing 0.986 g is added to 10 mL of water.
Then 20 mL of 0.0421 M EDTA is added. The solution was adjusted to
pH 12 and titrated with 0.0242 M Ca2+. 21.09 mL were required to
reach the end point, calculate the percentage of Ca in the milk sample.
(MV) Ca2+ = (MV) Excess EDTA
(0.0242 x 21.09) Ca2+ = (0.0421 x V) Excess EDTA
Volume of excess EDTA = 12.12 mL
Volume of EDTA reacted with Ca2+ present in milk = 20 -12.12 = 7.88 mL
(MV) EDTA = (MV) Ca2+ in Milk
(0.0421 x 7.88) EDTA = (M x 10) Ca2+ in milk
Wt Ca2+ in milk = (MV) X At. Wt. Ca2+ / 1000 = 0.3316 x 40 / 1000 = 0.0133 g
% Ca2+ in milk = (wt of Ca2+ in milk / wt of milk sample) x 100
= (0.0133 / 0.986) x 100 = 1.37%
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
M Mn2+ = 0.038 mol /L
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 0.01 M 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 = 8 mL
Volume of EDTA equivalent to Mg2+ = 19 - 8 = 11 mL
(MV) EDTA = (MV) Ca2+ , 0.01 x 8 = M x 10, M Ca2+ = 0.008 mol/L
(MV) EDTA = (MV) Mg2+, 0.01 x 11 = M x 10, M Mg2+ = 0.011 mol/L
Wt CaCO3 = 0.008 x 100 x 250 / 1000 = 0.2 g
% CaCO3 = (0.2/0.5)x100 = 40%
Wt MgCO3 = 0.011 x 84 x 250 / 1000 = 0.231g,
% MgCO3= (0.231 / 0.5) x 100 = 46.2%
Titrating a 50.0 mL water sample for total hardness requires 4.08
mL 0.01 M EDTA. Calculate the hardness of the water as mg/L
(ppm) calcium carbonate.

(MV) EDTA = (MV) metal ions in water sample

0.01 x 4.08 = 50 x M
M Metal ions = 8.16 x 10-4 mol/L
Hardness of water = M x MWt CaCO3 x 1000
= 8.16 x 10-4 x 100 x 1000
= 81.6 mg/L (ppm) CaCO3
The Ni(II) and Zn(II) ions in a 25.0 mL sample were complexed by
adding 50 mL of 0.025 M EDTA. The excess EDTA was back
titrated with 7.5 mL of 0.01 M MgCl2. At this point, an excess of
2,3-dimercapto propanol (BAL) was added, which displaces only
Zn(II) ions from its EDTA complex:
ZnY2- + BAL ZnBAL + H2Y2-
Titration of the liberated H2Y2- required an additional 21.5 mL of
MgCl2 solution. Calculate the concentration of Zn(II) and Ni(II)
ions in the original solution.

Strategy of answer:
we can get from the 1st titration the volume of excess Unreacted
EDTA and by subtracting it from 50 mL, we can get the reacted
EDTA. And from the second titration, we can get the volume of EDTA
equivalent to Zn(II) and by subtraction from the volume of reacted
EDTA we can get EDTA equivalent to Ni(II).
(MV) EDTA Excess = (MV1) MgCl2
(0.025 X V) EDTA Excess = (0.01 x 7.5) MgCl2
V of excess EDTA = 3 mL,
V EDTA reacted with Ni & Zn = 50 – 3= 47 mL
(MV) EDTA equivalent to Zn = (MV2) MgCl2
(0.025 x V) EDTA equivalent to Zn = (0.01 x 21.5) MgCl2
V of EDTA equivalent to Zn = 8.6 mL
V of EDTA Equivalent to Ni = 47 – 8.6 = 38.4 mL
(MV) EDTA = (MV) Zn
(0.025 x 8.6) EDTA = (M x 25)Zn, MZn = 8.6x10-3 mol/L
(MV) EDTA = (MV) Ni
(0.025 x 38.4) EDTA = (Mx25) Ni MNi = 0.384 mol/L
A 50.0 mL Aliquot of a solution containing iron(II) and iron (III)
required 13.73 mL of 0.0120 M EDTA when titrated at pH 2.0 and
29.62 mL when titrated at pH 6.0, Express the concentration of the
solution in terms of the parts per million.
Strategy of answer:
The main idea of the problem is that in highly acidic pH only Fe(III)
can be determined, while in pH =6.0, Both Fe(II) and Fe(III) can be
determined, i.e. what reacts in lower pH will react in higher pHs.
 At pH=2
(MV) iron (III) = (MV) EDTA
M × 50 = 0.012×13.73 M iron (III) = 3.2952×10-3 mol/L
 At pH=6
(MV) iron (II) + (MV) iron (III) = (MV) EDTA
(M iron (II) × 50) + (3.2952×10-3×50) = (0.012 × 29.62)
M iron (II) = 3.8136×10-3 mol/L
For iron (II):
Strength × 1000 = Molarity × Atomic weight × 1000
= 3.8136×10-3× 56 × 1000 = 213.5 ppm
For iron (III):
Strength × 1000 = Molarity × Atomic weight × 1000
= 3.2952 × 10-3× 56 × 1000 = 184.5 ppm
Example 8 (solve it) Chromel is an alloy composed of nickel, iron and
chromium. A 0.6472 g sample was dissolved and diluted to 250 mL.
When a 50 mL aliquot of 0.05182 M EDTA was mixed with an equal
volume of the diluted sample and all the three ions were chelated and a
5.11 mL back titration with 0.06241 M copper (II) was required. The
chromium in a second 50 mL aliquot was masked through the addition
of hexamethylenetetramine, titration of the Fe and Ni required 36.28
mL of 0.05182M EDTA. Iron and chromium were masked with
pyrophosphate in a third 50 mL aliquot and the nickel was titrated with
25.91 mL of the EDTA solution. Calculate the percentage of nickel,
chromium and iron in the alloy.
Answer: 15.75% Cr, 60.88%Ni, 23.18% Fe
1. A solution was prepared by dissolving about 3.0 g of NaH2Y2.2H2O (372.24
g/mol) in approximately 1 L of water and standardizing against 50.00-mL
aliquots of 0.004423 M Mg2+. An average titration of 30.27 mL of EDTA
was required. Calculate the molar concentration of the EDTA.
[Standardization: 7.30610-3 mol/L, Preparation (approximately):
8.05910-3 mol/L]

2. 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. [32.28 mL]
(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. [14.98 mL]
(c) the volume of 0.007840 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. The reaction is:
Co2+ + ZnY2 ⟶ CoY2 + Zn2+
[32.28 mL]
3. The Zn (65.39 g/mol) in a 0.7457-g sample of foot powder was titrated with
22.57 mL of 0.01639 M EDTA. Calculate the percent Zn in this sample.
[3.244%]

4. The Tl in a 9.57-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 Mg2+ required 12.77 mL of 0.03610 M EDTA.
Calculate the percent Tl2SO4 (504.8 g/mol) in the sample. [1.216%]

5. A 1.509-g sample of a Pb/Cd alloy was dissolved in acid and diluted to exactly
250.0 mL in a volumetric flask. A 50.00-mL aliquot of the diluted solution was
brought to a pH of 10.0 with a NH4+/NH3 buffer; the subsequent titration
involved both cations and required 28.89 mL of 0.06950 M EDTA. A second
50.00-mL aliquot was brought to a pH of 10.0 with an HCN/NaCN buffer,
which also served to mask the Cd2+; 11.56 mL of the EDTA solution were
needed to titrate the Pb2+. Calculate the percent Pb (207.2 g/mol) and Cd
112.41 g/mol) in the sample. [55.16% Pb, 44.86% Cd]
6. Calamine, which is used for relief of skin irritations, is a mixture of
zinc and iron oxides. A 1.056-g sample of dried calamine was
dissolved in acid and diluted to 250.0 mL. Potassium fluoride was
added to a 10.00-mL aliquot of the diluted solution to mask the iron;
after suitable adjustment of the pH, Zn2+ consumed 38.37 mL of
0.01133 M EDTA. A second 50.00-mL aliquot was suitably buffered
and titrated with 2.30 mL of 0.002647 M ZnY2– solution:
Fe3+ + ZnY2 ⟶ FeY + Zn2+
Calculate the percentages of ZnO and Fe2O3 in the sample. [83.75%
ZnO, 0.230% Fe2O3]
Prepared by Dr. Sally E. A. Elashery