Complexometric titrations

Complexometric titrations
Many analytical methods rely on formation of complexes. Gravimetry Spectrophotometry Titrations Ni-dimethylglyoxime Fe-phenanthroline Metal- EDTA

Complexometric titrations
Determinations of metals Titrate metal ions with titrant which is a complexing agent EDTA very useful complexing agent
EDTA titration for determination of water hardness (how much Ca and Mg?)

Lewis acid-base concept

Lewis acid => electron pair acceptor metal Lewis base = electron pair donor ligand coordinate covalent bond ligand donates both electrons of the electron pair bond
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Formation of soluble complex between metal ion and a complexing agent

Metal ion acts as a Lewis acid (accepts electron pairs) base (donates electron pairs)

Complexing agent (ligand) acts a Lewis

Covalent bond between metal and ligand.

Ligands

UJIAN 2
Date Time Venue Topics: POLYPROTIC ACID COMPLEXOMETRY

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11

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15

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Chelate Effect
the ability of multidentate ligands to form more stable metal complexes than those formed by similar monodentate ligands results from the formation of 5membered "ring" with metal and two atoms on the ligand
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Chelating agent
Has two/more groups that complex with metal ion Chelate complex formed EDTA most widely used chelating agent in titrations

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Co-EDTA Complex

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Metal-ligand complex

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Pt(en)2 Complex

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Formation constant, Kf
Ag+ + NH3 Ag(NH3)+

Kf1= [Ag(NH3)+] = 103.3

[Ag+][NH3] Ag(NH3)+ + NH3 Ag(NH3)2+

Kf2 = [Ag(NH3)2+]

= 103.8 [Ag(NH3)+][NH3]
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Overall formation constant

Ag+ + 2NH3 Ag(NH3)2+

Kf = Kf1 . Kf2
= [Ag(NH3)2+ ] = 107.1 [Ag+][NH3]2

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Overall formation constant

Zinc ion forms the complex, Zn(NH3)4 2+ in a stepwise fashion. M + nL MLn Kf1= Kf Kf1Kf2 = Kf Kf1Kf2Kf3 = Kf Kf1Kf2Kf3Kf4 = Kf MLn Kf1Kf2Kf3Kf4..Kfn = Kf
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Complexometric titrations
Monodentate ligands rarely used as titrants
Sharp end point generally difficult to achieve Stepwise formation constants are frequently close together, not very large, single stoichiometric complex cannot be observed)

Most generally useful titrating agents

Aminocarboxylic acids nitrogen and carboxylate groups as ligands 1:1 metal-complex formed
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EDTA
H4Y has v.low solubility in water Disodium salt, Na2H2Y.2H2O is used to prepare EDTA standard solutions; dissociates to give predominantly H2Y2pH EDTA will influence distribution of H4Y, H3Y-, H2Y2-, Y4- .
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EDTA, H4Y
H4Y H3YH2Y2HY3H+ H+ H+ H+ + + + + H3YH2Y2HY3Y4-

Ka1 = 1.0 X 10-2 Ka2 = 2.2 X 10-3 Ka3 = 6.9 X 10-7 Ka4 = 5.5 X 10-11
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Fraction that exists as Y4-, 4

CH4Y = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]
Y4- = [Y 4-] = 4

CH4Y Ka1Ka2Ka3Ka4 Y4-= [H+]4 +Ka1[H+]3 + Ka1Ka2[H+]2 + Ka1Ka2Ka3[H+] + Ka1Ka2Ka3Ka4

Y4- predominant at pH > 11.0
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Metal ion complex with EDTA.

Ca2+ + Y4CaY2Kf = [CaY2-] [Y4-] influenced by pH. [Ca2+][ Y4-] K f = [CaY2-] [Ca2+] 4CH4Y Kf4 = Kf = [CaY2-]__ [Ca2+]CH4Y Kf - conditional formation constant, dependent on pH
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35

TEST 2
Date: Time: Venue: Topics: Acid-Base Equilibria

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Titration of 50.0 mL 0.100 M Ca2+ with 0.100 M EDTA standard solution

Ca
2+

+ Y4- CaY2- Kf = 5.0 x 1010

Ca2+ solution is buffered at pH 10.0. Use K because CH4Y can be easily determined compared to [Y4-]. K = 4 Kf = 5.0 x 1010 x 0.35 = 1.8 x 1010
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Before equivalence point

0.00 mL EDTA pCa = - log [Ca2+] = - log (0.100) = 1.000

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Before equivalence point

25.00 mL EDTA Amount of Ca2+ = uncomplexed Ca2+ + Ca2+ from dissociation of CaY2-. Ca2+ + Y4- CaY2Initial 5.00 2.50 m 2.50 2.50 [Ca2+] = 2.50 mmol = 0.0333 M pCa = ? 75.00 mL

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Equivalence point, 50.00 mL EDTA

Initial m Ca2+ + Y45.00 5.00 xM xM CaY2-

[CaY 2-] [Ca2+]CH4Y

{(5.00/100.00) x}M 0.0500 M (K v.large) = (0.0500) = 1.8 x 1010 (x)(x) pCa = ?

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x= [Ca2+] = ?

After equivalence point

75.00 mL EDTA Ca2+ + Y4- CaY2Initial 5.00 7.50 m x (2.50 + x) 5.00 x 125.00 125.00 [CaY2-] = (0.0400) = 1.8 x 1010 [Ca2+]CH4Y (x)0.0200
neglect x, K v. large

x = [Ca2+] = ?

pCa =

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After equivalence point

100.00 mL EDTA Millimoles EDTA added = 100.00 x 0.100 = 10.00 mmol Millimoles EDTA in excess = 5.00 mmol [CaY2- ] = 5.00/150.00 M = 0.033 M CH4Y = 5.00/150.00 = 0.033 M Amount of CaY2- which dissociates is negligible. [CaY 2- ] = (0.033) = 1.8 x 1010 [Ca 2+ ]CH4Y (x)0.033 x = [Ca2+] =? pCa =?
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43

Minimum pH for effective titration of various metal ions

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Detection of end point

Organic dye Eriochrome Black T, triprotic acid, H3In H2InH+ H+ + + HIn2-

Ka2 = 5.0 X 10-7 Ka3 = 2.8 X 10-12

red
HIn2-

blue
In3-

blue

orange

EDTA titrations at pH 8 and 10 HIn2- anion (blue) is predominant.

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Detection of end point

Mn+ + HIn2MIn(n-3) + H+

blue

red

Use a small amount of indicator Indicator forms red complex with metal ion
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Titration of zinc(II) with EDTA

Before equivalence point, red color is due to formation of zinc-indicator complex. Addition of EDTA titrant will complex free zinc ions. After free zinc ions has been titrated, EDTA will react with zinc from zinc-indicator complex ZnIn+ HY3- ZnY2+ HIn2-

red

blue
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Color of solution will gradually change from red to blue. Equivalence point reached when all ZnInhas been changed to ZnY2- and the solution is a pure blue color.

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Distribution of metal species in polyligand complexes

CAg = [Ag+] + [Ag(NH3)+] + [Ag(NH3)2+]
Rewrite as :

CAg = [Ag+] +Kf1[Ag+][NH3] + Kf1Kf2[Ag+][NH3]2

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Ag+ = [Ag+]

CAg

Ag(NH3)+

= [Ag(NH3)+] = Kf1[Ag+][NH3]

CAg
Ag(NH3)2+

CAg

= [Ag(NH3)2+]

CAg =Kf1Kf2[Ag+][NH3]2 CAg

The sum of all must be 1.
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1_________________ 1 +Kf1[NH3] + Kf1Kf2[NH3]2 Ag(NH3)+ = Kf1[NH3]_______________ 1 +Kf1[NH3] + Kf1Kf2[NH3]2 Ag(NH3)2+ = Kf1Kf2[NH3]2__________ 1 +Kf1[NH3] + Kf1Kf2[NH3]2
Ag+

Fraction of each species depends on ammonia concentration.

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Application of EDTA titrations

EDTA does not have high selectivity For samples with mixture of metal ions, require separation of ions, e.g. by pH control precipitation or extraction
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Minimum pH for effective titration of various metal ions

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Analytical Applications
Determination of water hardness titration of magnesium and calcium in the presence of cadmium, cobalt, copper, nickel, zinc ions use masking agents such as cyanide ion. Cyanide ions complexes interfering ions.

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55 Fig 1-f2, p.15

Analytical applications
As masking agent form complexes with unwanted/interfering metal ions. As spectrophotometric reagent, e.g., determination of iron by 1,10-phenanthroline, copper by dithizone.

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Water Test Kit from Hach

Semiquantitative determination of metal ions in water samples based on complexometry

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Crown ethers complexing agents of high selectivity

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Food Industry
Use in products such as mayonnaise to extend the shelf-life EDTA will complex with cations, preventing them from acting as catalyst in oxidation process.

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Medical applications..
Detoxification in heavy metal poisoning cases. Na2CaY is administered. Heavy metals (e.g. Pb) form more stable EDTA complex than calcium, and will displace calcium from EDTA. The chelated lead is excreted via the kidneys.
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CHELATION THERAPY AND THALASSEMIA

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Drugs Used for Iron Therapy

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Structure of desferrioxamine B

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Oxygen is carried in the circulatory system by the iron-containing protein, hemoglobin, When there is not enough hemoglobin in the red blood cells, oxygen cannot get to all parts of the body. Organs then become starved for oxygen and are unable to function properly. Hemoglobin consists of two pairs of subunits, designated as or .
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 -thalassemia major is a genetic disease in which the subunits of hemoglobin are not synthesised in sufficient amount.

Children afflicted with this disease can survive only with frequent transfusion of normal red blood cells.

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People with Thalassemia disease are not able to make enough hemoglobin, which causes severe anemia.

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The problem with transfusions is that the patient accumulates 4-8 g of iron per year. The body has no mechanism for excreting large quantities of iron, so iron builds up in all tissues. Most victims die by the age of 20 from the toxic effects of iron overload.

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Chelation therapy
Chelators are small molecules that can bind selectively with iron and make it soluble. The chelated iron is readily excreted from the body.

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Drugs Used for Iron Therapy

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Structure of desferrioxamine B

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CHELATION THERAPY AND THALASSEMIA

Deferoxamine is poorly absorbed if taken orally. It is also so rapidly eliminated from the body that it must be administered by a slow infusion to have the appropriate therapeutic effect. A needle is attached to a small subcutaneous pump five to seven times a week for up to 12 hours. It is a difficult and painful procedure.
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IDEAL DRUG FOR TOMORROW

Water soluble High specificity Cheap

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END

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