UNIVERSITY OF THE PHILIPPINES MANILA

Complex-Formation Titrations
COMPLEX-FORMATION REACTIONS

Copper(II) ion forms a neutral complex with glycine, Cu(NH3CH2COO)2.

..
NH2 O Cu2+ O O Cu NH2 NH2 O O CH2

H H

.. ..
OH

H2 C

2H+

Most metal ions form stable complexes with EDTA.

O
O

Mn+

HO HO O

H2 .. .. C N C C N H2 H2 C H2

H2 O C OH C H2 OH O

O O O O M

N N

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA Complexometric titrimetry are titrimetric methods based on complex formation.
It is based upon a particular class of coordination compounds called chelates. A chelate is produced when a metal ion coordinates with two (or more) donor groups of a single ligand to form a five- or six-membered heterocyclic ring. Multidentate ligands, particularly those having four or six donor groups, have two advantages over the unidentate ones. 1) react more completely with cations and thus provide sharper end points 2) react with metal ions in a single-step process
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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA Curves for Complex Formation Titrations

20 1:1 2:1 4:1

pM

10

Much sharper end point is obtained with a reaction that takes place in a single step
EP 0 Volume of Titrant

Multidentate ligands are ordinarily preferred for complexometric titrations.

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA

TITRATIONS WITH AMINOCARBOXYLIC ACIDS

Ethylenediaminetetraacetic acid (EDTA)

EDTA is the most widely used complexometric titrant.

The EDTA molecule has six potential sites (i.e. hexadentate) for bonding a metal ion; the four -COOH groups and the two -NH2 groups.
1.0

0
H 4Y

EDTA species: H4Y, H3 H2Y2-, HY3-, and Y4-. Y-,

2
H2Y2-

3
HY3-

4
Y4-

0.5

0 0
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H3Y-

6 pH

10

12

14

Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA It is apparent that the H2Y2- predominates in moderately acidic media (pH 3 to 6). Only at a pH values greater than 10 does Y4- become a major component of solutions.
COMPLEXES OF EDTA AND METAL IONS

EDTA reagent combines with metal ions in a 1:1 ratio regardless of the charge on the cation.

Ag+ + Y4Al3+ + Y41:1

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AgY3AlYM : EDTA
Billones Lecture Notes

Structure of H4Y and its dissociation products

HOOC H N C C N H H2 H2 -OOC COOH
+ +

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COO-OOC COO-

H N C C N H H2 H2 -OOC COO-

H 4Y

H2Y-2

-OOC

H N C C N H H2 H2 -OOC COOH

COO-

-OOC

H N C C N H2 H2 -OOC

COOCOO-

H3Y-

-OOC -OOC ..
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..

N C C N H2 H2

..

..

..

HY-3

COOCOO..
Billones Lecture Notes

Y-4

UNIVERSITY OF THE PHILIPPINES MANILA The dissociation constants for the acidic constants for the acidic groups in EDTA are K1 = 1.02 x 10-2 K2 = 2.14 x 10-3 K3 = 6.92 x 10-7 K4 = 5.50 x 10-11 Formation constants KMY for common EDTA complexes
The constant refers to the equilibrium involving the deprotonated species Y4- with the metal ion:

Mn+ + Y4The Health Sciences Center

MY(n-4)

KMY = [MY(n-4)+] [Mn+][Y4-]

Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA

Cation KMY
2.1 x 107 4.9 x 108 5.0 x 1010 4.3 x 108 5.8 x107 6.2 x 1013 2.1 x 1014 2.0 x 1016 4.2 x 1018

logKMY

Cation

KMY
6.3 x 1018 3.2 x 1016 2.9 x 1016 6.3 x 1021 1.1 x 1018 1.3 x 1016 1.3 x 1025 7.9 x1025 1.6 x 1023

logKMY

Ag+ Mg2+ Ca2+ Sr2+ Ba2+ Mn2+ Fe2+ Co2+ Ni2+

7.32 8.69 10.70 8.63 7.76 13.79 14.33 16.31 18.62

Cu2+ Zn2+ Cd2+ Hg2+ Pb2+ Al3+ Fe3+ V3+ Th4+

18.80 16.50 16.46 21.80 18.04 16.13 25.1 25.9 23.2

Billones Lecture Notes

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UNIVERSITY OF THE PHILIPPINES MANILA Equilibrium Calculations Involving EDTA

A titration curve for the reaction of a cation Mn+ with EDTA consists of a plot of pM versus reagent volume. Values for pM are readily computed in the early stage of a titration by assuming that the [Mn+] is equal to cM. Calculating [Mn+] in a buffered solution containing EDTA is a relatively straightforward procedure provided the pH is known. The 4 for H4Y would be defined as

4 = [Y4-] cT

[Y4-] = 4cT

where cT is the total molar concentration of uncomplexed EDTA:

cT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA Conditional Formation Constants, K (pH dependent K)

Conditional or effective formation constants are pH dependent equilibrium constants that apply at a single pH only.
To obtain K for the equilibrium shown in the equation, we substitute 4cT for [Y4-] in the formation-constant expression:

Mn+

+ Y4KMY = [MY(n-4)+] [Mn+][Y4-]

MY(n-4)

but [Y4-] = 4cT KMY = [MY(n-4)+] [Mn+]4cT

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA Combining the two constants yields a new constant KMY
KMY = [MY(n-4)+] = 4KMY [Mn+]cT KMY = 4KMY
KMY describes equilibrium relationships only at the pH for which 4 is applicable.

Computation of 4 Values for EDTA Solutions

4 =

___K1K2K3K4_____________ __ [H+]4 + K1[H+]3 + K1K2[H+]2 + K1K2K3[H+] + K1K2K3K4

or

HY3-

4 = K1K2K3K4 D = K1K2K3[H+] H2Y2- = K1K2[H+]2 D D

Billones Lecture Notes

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UNIVERSITY 3OF THE PHILIPPINES MANILA H3Y- = K1[H+] H4Y = [H+]4 D D

where K1, K2, K3 and K4 are the four dissociation constants for H4Y and D is the denominator.

4 at Selected pH Values
pH 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0
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4
3.7 x 10-14 2.5 x 10-11 3.6 x 10-9 3.5 x 10-7 2.2 x 10-5 4.8 x 10-4 5.4 x 10-3 5.2 x 10-2 3.5 x 10-1 8.5 x 10-1 9.8 x `10-1

Only about 4 x 10-12 percent of the EDTA exists as Y4- at pH 2.00.

Billones Lecture Notes

Example

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Calculate 4 and the mole percent of Y4- in a solution of EDTA that is buffered to pH 10.20. [H+] = antilog (-10.20) = 6.31 x 10-11

From the values for the dissociation constants for H4Y, we obtain
K1 = 1.02 x 10-2 K1K2 = 2.18 x 10-5 K1K2K3 = 1.51 x 10-11

K1K2K3K4 = 8.31 x 10-22

Numerical values for the several terms in the denominator:

[H+]4 = (6.31 x 10-11)4 = 1.58 x 10-41

K1[H+]3 = (1.02 x 10-2)(6.31 x 10-11)3 = 2.56 x 10-33

K1K2[H+]2 = (2.18 x 10-5)(6.31 x 10-11)2 = 8.68 x 10-26

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Billones Lecture Notes

K1K2K3[H+] = (1.51 x 10-11)(6.31 x 10-11) = 9.53 x 10-22 K1K2K3K4

UNIVERSITY OF THE PHILIPPINES MANILA

= 8.31 x 10-22 D = 1.78 x 10-21

signicant conguration

The equation 4 = K1K2K3K4 becomes D

4 = K1K2K3K4 = 8.31 x 10-22 = 0.466 D 1.78 x 10-21

mol % Y4- = 0.47 x 100% = 47%

Only the last two terms in the denominator contribute significantly to the sum D at pH 10.20.

At low pH values, in contrast, only the first two or three terms are important
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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA Calculation of the Cation Concentration in EDTA Solutions
Calculate the equilibrium concentration of Ni2+ in a solution with an analytical NiY2- concentration of 0.0150 M at a pH (a) 3.0 and (b) 8.0.

Ni2+ + Y4-

NiY2-

KMY = [NiY2-] = 4.2 x 1018 [Ni2+][Y4-]

The equilibrium concentration of NiY2- is equal to the analytical concentration of the complex minus the concentration lost by dissociation.

NiY2-

Ni2+ + Y4-

Kinstab =
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1 KMY

very small
Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA [NiY2-] = 0.0150 [Ni2+] 0.0150 because Kinstab is small
Since the complex is the only source of both Ni2+ and the EDTA species,

[Ni2+] = cT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y] Substitution of this equality gives KMY = 4KMY = [NiY2-] = [NiY2-] [Ni2+]cT [Ni2+]2 (a) 4 is 2.5 x 10-11 at pH 3.0. Substitution of this value and the concentration of NiY2- into the equation for KMY gives KMY = 0.0150 = 4KMY = 2.5 x 10-11 x 4.2 x 1018 = 1.05 x 108 [Ni2+]2
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Billones Lecture Notes

UNIVERSITY OF THE8PHILIPPINES MANILA [Ni2+] = sqrt(0.0150/1.05 x 10 ) = 1.2 x 10-5 M

[Ni2+] << 0.0150, as assumed b) At pH 8.0, the conditional constant is much larger. Thus, KMY = 5.4 x 10-3 x 4.2 x 1018 = 2.27 x 1016 Substitution into the equation for KMY followed by rearrangement gives
[Ni2+] = sqrt(0.0150 / 2.27 x 1016) = 8.1 x 10-10 M

large KMY, small 1/KMY , low [ion]

Example

Calculate the concentration of Ni2+ in a solution that is prepared by mixing 50.0 mL of 0.0300 M Ni2+ with 50.0 mL of 0.500 M EDTA. The mixture was buffered to a pH of 3.00.
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Billones Lecture Notes

Here, the solution has an excess of EDTA, and the analytical concentration of the complex is determined by the amount of Ni2+ (limiting reagent) originally present. Thus,

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cNiY2- = 50.0 x 0.03000 = 0.0150 M 100

cEDTA = 50.0 x 0.0500 50 x 0.0300 = 0.0100M 100
Again assume that [Ni2+] << [NiY2-] so that [NiY2-] = 0.0150 [Ni2+] 0.0150 M
At this point, the total concentration of uncomplexed EDTA is given by its analytical molarity:

cT = 0.0100 M
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Billones Lecture Notes

Substitution into the equation gives

UNIVERSITY OF THE PHILIPPINES MANILA

KMY = [NiY2-] = 0.0150 = 4KMY [Ni2+] cT [Ni2+] 0.0100

= 2.5 x 10-11 x 4.2 x 1018 = 1.05 x 108

[Ni2+] = 0.0150 0.0100 x 1.05 x 108 = 1.4 x 10-8

EDTA Titration Curves

Example

Derive a curve (pCa as a function of volume of EDTA) for the titration of 50.0 mL of 0.00500 M Ca2+ with 0.0100 M EDTA in a solution buffered to a constant pH of 10.0.
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Billones Lecture Notes

Calculation of Conditional Formation Constant

UNIVERSITY OF THE PHILIPPINES MANILA KCaY = [CaY2-] = 4KCaY [Ca2+] cT

From Table, 4 = 0.35 and KCaY = 5.0 x 1010 Substitution gives

KCaY = 0.35 x (5.0 x 1010) = 1.75 x 1010

Preequivalence Point Values for pCa Before the EP is reached, the [Ca2+] is equal to the sum of the contributions from the untitrated excess of the cation and from the dissociation of the complex, which is equal to cT, and assumed to be small. For example, after addition of 10.00 mL reagent: [Ca2+] = 50.0 x 0.00500 10.0 x 0.0100 + cT 2.50 x 10-3 60.0
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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA pCa = -log (2.50 x 10-3) = 2.60

Other pre-EP data are derived in this way.

The Equivalence-Point pCa

Compute first the analytical concentration of CaY2-. cCaY2- = 50.0 x 0.00500 = 3.33 x 10-3 50.0 + 25.0
The only source of Ca2+ ions is the dissociation of the CaY2- complex.

At EP,

[Ca2+] = cT

[CaY2-] = 3.33 x 10-3 [Ca2+] 3.33 x 10-3 M

Substituting into the conditional formation constant expression gives

KMY = [CaY2-] = 0.00333 = 1.75 x 1010 [Ca2+]cT [Ca2+]2

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA [Ca2+] = sqrt(0.00333 / 1.75 x 1010) = 4.36 x 10-7 M
pCa = -log (4.36 x 10-7) = 6.36 Postequivalence-Point pCa
Beyond the equivalence point, analytical concentrations of CaY2and EDTA are obtained directly from the stoichiometric data.

For example, after the addition of 35.0 mL of reagent,

cCaY2- = 50.0 x 0.00500 = 2.94 x 10-3 M 50.0 + 35.0 the complex is diluted cEDTA = 35.0 x 0.0100 50.0 x 0.00500 = 1.18 x 10-3 85.0 As an approximation, we can write [CaY2-] = 2.94 x 10-3 [Ca2+] 2.94 x 10-3
from ionization
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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA cT = 1.18 x 10-3 + [Ca2+] 1.18 x 10-3 M

from ionization

Substitution into the KCaY expression gives

KCaY = [Ca2+] =

2.94 x 10-3 = 1.75 x 1010 [Ca2+] x 1.18 x 10-3 2.94 x 10-3 = 1.42 x 10-10 1.18 x 10-3 x 1.75 x 1010

pCa = -log (1.42 x 10-10) = 9.85 The approximation that [Ca2+] is small is clearly valid.
Curve A (red) in the following figure is a plot of the data for the Ca titration in the example.
Curve B is the titration curve for a solution of magnesium ion under identical conditions.
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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA

EDTA titration curves for 5.0 mL of 0.00500 M Ca2+ (K for CaY2- = 1.75 x 1010) and Mg2+ (K for MgY2- = 1.72 x 108) at pH 10.0.
10

pCa

pM

8 6

pMg

The shaded areas show the transition range for Eriochrome Black T (EBT).

CaIn- + HY3red

HIn2- + CaY2-

MgIn- + HY3red EP

HIn2- + MgY2blue

4 2

blue

25.0 mL

EP

35.0 mL

0 Volume of 0.0100 M EDTA

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Billones Lecture Notes

Titration curves for Ca

UNIVERSITY OF THE PHILIPPINES MANILA +2

solutions buffered to various pH levels

Recall that 4, and hence KCaY, becomes smaller as the pH decreases.

Influence of pH on the titration 50.0 mL of 0.0100 M Ca2+ with 0.0100 M EDTA

10 8

pH 12 pH 10

pH 8

pCa

6
pH 6

4 2 0 50.00 mL Volume of 0.0100 M EDTA

Smaller pM at e.p End points for EDTA titrations become less sharp as pH decreases because the complex formation reaction is less complete under these circumstances. Lower pH, smaller 4 Smaller 4, smaller KMY

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA

Titration curves for 50.0 mL of 0.0100 M cation solutions at pH 6.0 20 16 12

KFeY- = 1.3 x 1025 KHgY2- = 6.3 x 1021

pM 10
8 4 0 50.00 mL Volume of 0.0100 M EDTA
smaller KMY, smaller pM
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KZnY2- = 3.2 x 1014 KFeY2- = 2.1 x 1014 KCaY2- = 5.0 x 1012

Cations with larger formation constants provide good end points even in acidic media.
Billones Lecture Notes

Minimum permissible pH for a satisfactory end point in the titration

26 24 In3+ Sc3+ 22 20 18 16 14 12 10 8 0 2 4 Mg2+, 6 Sr2+ 8 10 12 La3+ Ni2+ Pb2+,Y3+ Cd2+ Al3+ La3+ Fe3+ Th4+ Hg2+ Ga3+ VO2+ Cu2+ Sm3+ Zn2+ Co2+ Fe2+ Mn2+ Ca2+
moderately acidic environment is satisfactory for many divalent heavy-metal cations

UNIVERSITY OF THE PHILIPPINES MANILA

Consider a mixture of Ca2+ and Zn2+.

log KMY

Titration w/ EDTA at pH 10 (both Ca2+ and Zn2+)

Titration w/ EDTA at pH 6 (only Zn2+ will titrate)

mmol Zn2+ = mL EDTA x M EDTA @ pH 6 mmol Ca2+ = (mL x M EDTA @ pH 10) mmol Zn

pH
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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA

THE EFFECT OF OTHER COMPLEXING AGENTS ON EDTA TITRATION CURVES

Many cations form hydroxide precipitates when the pH is raised to the level required for their successful titration with EDTA.

When this problem is encountered, an auxiliary complexing agent is needed to keep the cation in solution.
For example, zinc(II) is ordinarily titrated in a medium that has fairly high concentrations of ammonia and ammonium chloride. These species buffer the solution to a pH that ensures complete reaction between cation and titrant In addition, ammonia forms ammine complexes with zinc(II) and prevents formation of the sparingly soluble zinc hydroxide.

Zn(NH3)42+

+ HY3-

ZnY2- + 3NH3 + NH4+

The solution also contains such other zinc/ammonia species as Zn(NH3)32+, Zn(NH3)22+, and Zn(NH3)2+.
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Billones Lecture Notes

Complexation of a cation by an auxiliary-complexing reagent causes preequivalence pM values to be larger than in a comparable solution with no such reagent.

UNIVERSITY OF THE PHILIPPINES MANILA

14 12 Influence of ammonia concentration on the end point for the titration of 50.0 mL of 0.00500 M Zn2+.

pZn

10 8 6 4 0

cNH3 = 0.100

cNH3 = 0.010
25.0 mL

Volume of 0.0100 M EDTA

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Billones Lecture Notes

Titration Curves When a Complexing Agent is Present

UNIVERSITY OF THE PHILIPPINES MANILA

A quantitative description of the effects of an auxiliary complexing agent (ACA) can be derived by a procedure similar to that used to determine the influence of pH on EDTA titration curves.

A quantity M is defined that is analogous to 4:

M = [Mn+] cM

[Mn+] = McM

where cM is the sum of the concentrations of species containing the metal ion exclusive of that combined with EDTA. cM = [Zn2+] + [Zn(NH3)2+] + [Zn(NH3)22+] + [Zn(NH3)32+] + [Zn(NH3)42+]

The value of M can be expressed readily in terms of the ammonia concentration and the formation constants for the various ammine complexes.
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Billones Lecture Notes

UNIVERSITY OF THE] PHILIPPINES MANILA K = [Zn(NH )2+

1 3

[Zn2+][NH3] [Zn(NH3)2+] = K1[Zn2+][NH3]

Similarly, it is readily shown that [Zn(NH3)22+] = K2[Zn2+][NH3]2 [Zn(NH3)32+] = K3[Zn2+][NH3]3 [Zn(NH3)42+] = K4[Zn2+][NH3]4 Substitution of these expressions into the cM equation gives
cM = [Zn2+](1 + K1[NH3] + K2[NH3]2 + K3[NH3]3 + K4[NH3]4)

Substituting this expression for cM (here, [Mn+] = [Zn2+]), leads to M = 1 1 + K1 [NH3] + K2[NH3]2 + K3[NH3]3 + K4[NH3]4
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Billones Lecture Notes

Finally, a conditional constant for the equilibrium between EDTA and zinc(II) in an ammonia/ammonium chloride buffer is

UNIVERSITY OF THE PHILIPPINES MANILA

KZnY = [ZnY2-] = 4MKZnY cMcT

where KZnY is a new conditional constant that applies at a single pH as well as a single concentration of ammonia.
Example

Calculate the pZn for solutions prepared by adding 20.0, 25.0, and 30.0 mL of 0.0100 M EDTA to 50.0 mL of 0.00500 M Zn2+. Assume that both the Zn2+ and EDTA solutions are 0.100 M in NH3 and 0.175 M in NH4Cl to provide a constant pH of 9.0. The logarithms of the stepwise formation constants for the four zinc complexes with ammonia are 2.21, 2.29, 2.36, and 2.03. Thus,
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Billones Lecture Notes

K1 = antilog 2.21 = 1.62 x 102

UNIVERSITY OF THE PHILIPPINES MANILA

K2 = antilog (2.21 + 2.29) = 3.16 x 104 K3 = antilog (2.21 + 2.29 + 2.36) = 7.24 x 106 K4 = antilog (2.21 + 2.29 + 2.36 + 2.03) = 7.76 x 108
Calculation of Conditional Constant, K

A value of the M can be obtained by assuming that the equilibrium molar and the analytical concentrations of ammonia are essentially the same; thus, for [NH3] = 0.100,

M =

1 = 1.17 x 10-5 1 + 16 + 316 + 7.24 x 103 + 7.76 x 104

KZnY = 4 x M x KZnY
= 5.2 x 10-2 x 1.17 x 10-5 x 3.2 x 1016

KZnY = 1.9 x 1010

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Billones Lecture Notes

Calculation of pZn after Addition of 20.0 mL of EDTA

UNIVERSITY OF THE PHILIPPINES MANILA

At this point, only part of the zinc has been complexed by EDTA. The remainder is present as Zn2+ and the four ammine complexes. cM = 50.0 x 0.00500 20.0 x 0.0100 = 7.14 x 10-4 M 70.0

Substitution of this value gives

[Zn2+] = cMM = (7.14 x 10-4)(1.17 x 10-5) = 8.35 x 10-9 M

pZn = 8.08
Calculation of pZn after Addition of 25.0 mL of EDTA

At the equivalence point, the analytical concentration of ZnY2- is cZnY2- = 50.0 x 0.00500 = 3.33 x 10-3 M 50.0 + 25.0
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Billones Lecture Notes

The sum of the concentrations of the various zinc species not combined with EDTA equals the sum of the concentrations of the uncomplexed EDTA species:

UNIVERSITY OF THE PHILIPPINES MANILA

cM = cT
and

[ZnY2-] = 3.33 x 10-3 cM 3.33 x 10-3 M

Substituting, we have

[ZnY2-] = KZnY cM2

3.33 x 10-3 = 1.9 x 1010 cM2

cM = 4.18 x 10-7 M

Employing [Zn2+] = cMM , we obtain

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Billones Lecture Notes

UNIVERSITY OF THE PHILIPPINES MANILA

Zn2+] = cMM = (4.18 x 10-7)(1.17 x 10-5) = 4. 90 x 10-12

pZn = 11.31
Calculation of pZn after Addition of 30.0 mL of EDTA

The solution now contains an excess of EDTA; thus,

cEDTA = cT = EDTA sample VT = 6.25 x 10-4 M and since essentially all of the original Zn2+ is now complexed, cZnY2- = [ZnY2-] = 50.0 x 0.00500 = 3.12 x 10-3 M 80.0 Rearranging KZnY = [ZnY2-] = 4MKZnY cMcT gives,
Billones Lecture Notes

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UNIVERSITY OF THE PHILIPPINES MANILA

cM = [ZnY2-] cTKZnY = 3.12 x 10-3 = 2.63 x 10-10 M (6.25 x 10-4)(1.9 x 1010)

From the equation [Mn+] = McM, [Zn2+] = cMM = (2.63 x 10-10)(1.17 x 10-5) = 3.07 x 10-15

pZn = 14.51
INDICATORS FOR EDTA TITRATION

Eriochrome Black T (EBT) is a typical metal-ion indicator that is used in the titration of several common cations. Its behavior as a weak acid is described by the equations:
H 2O + H2InRed HIn2blue + H3O+ K1 = 5 x 10-7

H 2O

HIn2blue

In3- + H3O+ orange

K2 = 2.8 x 10-12
Billones Lecture Notes

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The metal complexes of Eriochrome Black T are generally red as in H2In-. Thus, for metal ion detection, it is necessary to adjust the pH to 7 or above so that the blue form of the species, HIn2-, predominates in the absence of a metal ion.

UNIVERSITY OF THE PHILIPPINES MANILA

Until the equivalence point in a titration, the indicator complexes the excess metal ion, so the solution is red.
When the EDTA becomes present in slight excess, the solution turns blue as a consequence of the reaction

MInred

+ HY3-

HIn2- + MY2blue

TITRATION METHODS EMPLOYING EDTA Direct Titration

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Billones Lecture Notes

Methods Based on Indicators for the Analyte Ion

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Mn+ + EDTA color 1 M(EDTA) color 2

Over 40 elements can be determined by direct titration with EDTA using metal ion indicators.

Methods Based on Indicators for an Added Metal Ion

A small amount of a cation is introduced that forms an EDTA complex that is less stable than the analyte complex and for which a good indicator exists.

MgY-2 + Ca+2
(less stable)

CaY-2 + Mg+2
Mg(EBT) red MgY-2 + EBT
blue
Billones Lecture Notes

Mg+2 + EBT Mg(EBT) + Y4red

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Back-Titration Methods

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Back-titration is useful for the determination of the cations that form stable EDTA complexes and for which a satisfactory indicator is not available. The method is also useful for cations that react only slowly with EDTA.
A measured excess of standard EDTA solution is added to the analyte solution.

After the reaction is judged complete, the excess EDTA is back-titrated with a standard magnesium or zinc ion solution to an Eriochrome Black T or Calmagite end point.

M + Y(xs)
Y(unreacted) + Mg

MY + Y(unreacted)
MgY (should be less stable than MY)

Displacement Methods
An unmeasured excess of a solution containing the magnesium or zinc complex of EDTA is introduced into the analyte solution.
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Billones Lecture Notes

If the analyte forms a more stable complex than that of magnesium or zinc, the following displacement reaction occurs: analyte The liberated cation is then titrated with the standard EDTA.

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MgY2- + M2+

MY2-

+ Mg2+

Interference from a particular cation can sometimes be eliminated by adding a suitable masking agent, an auxiliary ligand that preferentially forms highly stable complexes with the potential interference. For example, cyanide ion is often employed as a masking agent to permit the titration of magnesium and calcium ions in the presence of ions such as cadmium, cobalt, copper, nickel, zinc, and palladium.
All of the latter form sufficiently stable cyanide complexes to prevent reaction with EDTA.
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Illustration Showing How Masking and Demasking Agents Can Be Used to Improve The Selectivity of EDTA Titrations

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Lead, magnesium, and zinc can be determined on a single sample by two titrations with standard EDTA and one titration with standard Mg2+. The sample is first treated with an excess of NaCN, which masks Zn2+ and prevents it from reacting with EDTA.

Zn2+

+ 4CN-

Zn(CN)42-

Zn is masked, no reaction with EDTA

1.

The Pb2+ and Mg2+ are then titrated with standard EDTA.

After the equivalence point has been reached, a solution of the complexing agent BAL (2-3-dimercapto-1-propanol, CH2SHCHSHCH2OH), which we will formulate R(SH)2, is added to the solution.

This bidentate ligand reacts selectively to form a complex with Pb2+ that is much more stable than PbY2-:

PbY2-

+ 2R(SH)2 Pb(RS2)22-

+ Y4Billones Lecture Notes

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UNIVERSITY OF THE PHILIPPINES MANILA

2. Y4- is related to Pb2+. It is determined by titration with Mg2+

The liberated Y4- is then titrated with a standard solution of Mg2+. Finally, the zinc is demasked by adding formaldehyde.
Zn(CN)42- + 4HCHO + H2O Zn2+ + 4HOCH2CN + 4OH-

3.

Zn2+ is titrated with EDTA.

The liberated Zn2+ is then titrated with the standard EDTA solution.

Example
Suppose the initial titration of Mg2+ and Pb2+ required 42.22 mL of 0.02064 M EDTA. Titration of the Y4- liberated by the BAL consumed 19.35 mL of 0.007657 M Mg2+. Finally, after addition of formaldehyde, the liberated Zn2+ was titrated with 28.63 mL of the EDTA. Calculate the percentages of the three elements in a 0.4085 g sample.
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The initial titration reveals the number of millimoles of Pb2+ and Mg2+ present.
no. mmol (Pb2+ + Mg2+) = 42.22 x 0.02064 = 0.87142 The second titration gives the number of millimoles of Pb2+. Thus, no. mmol Pb2+ = 19.35 x 0.007657 = 0.14816 no. mmol Mg2+ = 0.87142 0.14816 = 0.72326

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Finally, from the third titration we obtain

no. mmol Zn2+ = 28.63 x 0.02064 = 0.59092

To obtain the percentage, we write 0.14816 mmol Pb x 0.2072 g Pb / mmol x 100% = 7.515% Pb 0.4085 g sample
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0.72326 mmol Mg x 0.024305 g Mg / mmol x 100% = 4.303% Mg 0.4085 g sample

0.59092 mmol Zn x 0.06539 g Zn / mmol x 100% = 9.459% Zn 0.4085 g sample

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Exercise

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A 1.3174-g sample containing the chloride salts of magnesium, mercury(II), and zinc was dissolved in 250.0 mL of solution. A 50.00-mL aliquot was treated with 10 mL of an NH3/NH4Cl buffer at pH 10 followed by 25.00 mL of 0.05331 M EDTA. After a few minutes of mixing, the excess EDTA was back-titrated with 11.43 mL of 0.01816 M MgCl2. A second 50.00-mL aliquot was made basic and treated with excess NaCN, complexing both the mercury and the zinc. The magnesium in this sample required 16.83 mL of 0.005583 M EDTA for titration. The solution remaining at the end of this titration was treated with excess formaldehyde, which reacts with the free CN- and with Zn(CN)42-: CN- + HCHO +H2O H2C(OH)(CN) + OH-

The liberated Zn+2 required 28.47 mL of the EDTA for titration. Calculate the percentage of each metal in the sample.

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Solution

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mmol xs EDTA = 25.00 mL x 0.05331 M = 1.3328 mmol mmol unreacted EDTA = 11.43 mL x 0.01816 M = 0.20757 mmol mmol M+2 = 1.3328 mmol - 0.20757 mmol = 1.12523 mmol ABANGAN ...

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Billones Lecture Notes