COMPLEXOMETRY

Aliya Nur Hasanah ANALYTICAL CHEMISTRY LABORATORY 2012

DEFINITION
A TITRATION IN WHICH THE REACTION BETWEEN THE ANALYTE AND TITRANT IS A COMPLEXATION REACTION

Application
1) Calcium determination in food using EDTA titration AOAC Method 968.31 2) Water hardness (Ca, Mg) 3) Ca or Al content of drugs such as calcium pantothenate or alumina.

Typical kit for testing for water hardness in household water.

Terms in Complex-Formation Reaction

Ligand : an ion or molecule that forms a covalent bond with a cation by donating a pair of electron, which are then shared by the ligand and the cation Coordination number : number of covalent bonds it tends to form with electron donor species Complex : compound formed when metal ion combines with a molecule which can donate electron Chelate : cyclic complex formed when a cation is bonded by two or more donor groups contained in single ligand

CHEMISTRY AND PROPERTIES OF EDTA

Ethylenediaminetetraacetic acid, or EDTA is an aminocarboxylic acid EDTA is a lewis base Has six binding sites (the four carboxylate groups and the two amino groups) The resulting metal-ligand complex, in which EDTA forms a cage-like structure around the metal ion is very stable All metal-EDTA complexes have a 1:1 stoichiometrically

Structure of the EDTA (as Y4-)

Six coordinate metal-EDTA complex

Reaction of EDTA with metal ion :

Example :
Formation of the silver and aluminium complexes

The constant value refers to the equilibrium involving the spesi Y4- with the metal ion :

EQUILIBRIUM CALCULATION INVOLVING EDTA

A titration curve for the reaction of a cation with EDTA consists of a plot a pM as a function of reagent volume Values for pM computed by assuming that the equilibrium concentration of M is equal to its analytical concentration For calculating [Y4-] we need 4 (Y4- fraction)

CT is the molar concentration of uncomplexed EDTA To get [Y4-] in equilibrium and beyond, we used equation involving constant KMY and 4 :

KMY is the conditional formation constant, describes equilibrium relationship only at the pH for which 4 is aplicable

 Conditional formation constant (KMY) depends on pH, it becomes smaller at lower pH level and the complex becomes less stable to maintain a constant pH, we must add a buffering agent If one of the buffers components forms a metal -ligand complex,

then EDTA must compete with the ligand for the metal

Titrations
EDTA solution

Sample + indicator+buffer

Detection of the end point

Using indicator

Example indicator : EBT (eriochrome black T)

contains three ionizable protons.

can be used for the titration of Mg 2+ with EDTA.

a small amount of indicator is added to the sample solution and it forms a red

complex with part of the Mg 2+; the color of the uncomplexed indicator is blue.
as soon as all the free Mg 2+ is titrated, the EDTA displaces the indicator from

magnesium, causing a change in the color from red to blue.

MgIn+ H2Y2MgY 2+ HIn 2+ H+

red

colorless

colorless

blue

The metal indicator complex must be less stable than that of the metal-EDTA complex, or else the EDTA will

not displace it from the metal The metal indicator complex must not be too weak, or
the EDTA will start replacing it at the beginning of the titration The metal-indicator complex should be 10-100 times

less -stable than the metal-titrant complex

Metal Ion Indicators

Metal ion indicators are compounds whose color changes when they bind to a metal ion. Useful indicators must bind metal less strongly than EDTA does. A typical titration is illustrated by the reaction of Mg2+ with EDTA, using

Eriochrome black T as the indicator.

MgIn + EDTA MgEDTA + In (red) (colorless) (colorless) (blue)

Structure and molecular model of Eriochrome Black T(left) and Calmagite (right).

most indicator for complexation titration are organic dyes, form stable complexes with metal ions Most of these dyes (metalochromic indicators) are weak acids or weak bases Conditional formation constant for metal-indicator depends on pH

EDTA Titration Techniques

Direct titration: analyte is titrated with standard EDTA. Back titration: a known excess of EDTA is added to the analyte. Displacement titration: For metal ions that do not have a satisfactory indicator.

Techniques of EDTA Titration

Direct titration

the solution containing the metal ion to be determined is buffered

to the desired pH and titrated directly with the standard EDTA

solution. It may be necessary to prevent precipitation of the

hydroxide of the metal by addition of some auxiliary complexing

agent, such as tartrate or citrate or triethanolamine

 Back titration many metals cannot be titrated directly; thus they may precipitate from the solution in the pH range necessary for the titration or they

may form inert complexes, or a suitable metal indicator is not

available. In such cases an excess of standard EDTA solution is

added, the resulting solution is buffered to the desired pH and the

excess of the EDTA is back titrated with a standard metal ion solution; a solution of zinc chloride or sulphate or of magnesium chloride or sulphate is often used for this purpose. The end point is detected with the aid of the metal indicator which responds to the zinc or magnesium ions introduced in the back titration

 Replacement or substitution titration

May be used for metal that do not react (react unsatisfactory) with metal indicator, or for metal ion which form EDTA complexes that are more stable than those of other metals such as magnesium and calcium.

Example : In titration of calcium. In the direct titration of calcium ions, solochrome black gives

poor end poin; if magnesium is present, it is displaces from its EDTA complex by
calcium and improved end point results

There is excess EDTA, and vitually all the metal ion is in the form Myn-4

There is exactly as much EDTA as metal in the solution. [Mn+ ] = [EDTA] In this region, there is excess Mn+

left in solution after the EDTA has

been consumed.

Three regions in an EDTA titration illustrated for reaction of 50.0mL of 0.050

0M Mn+ with 0.050 0M EDTA, assuming Kf = 1.15 1016.

Laboratory Modul

Ion Pb2+ = Pb-asetat . C4H6O4 .Pb.3H2O 400 mg zat tambahkan 100 mL aquadest, 3 mL asam asetat Pekat (32%), setelah larut tambahkan 1 gram heksamin, 0,4 mL indikator jingga xylenol, titrasi dengan komplekson III 0,05 M sampai warna kuning. HgCl2 300 400 mg zat, larutkan dalam 100 mL aquadest tambahkan 40 mL komplekson III 0,05 M tambahkan 5 mL buffer salmiak, indikator EBT titrasi dengan ZnSO4/ZnCl2 0,05 M. (Becket)

Home Works

1. Derive the titration curve for 30 mL of 0,015 M Fe2+ with 0,03 M EDTA in a solution buffered to pH 7,0. Calculate pFe values after the addition of 0 ; 10 ; 15 and 25 mL of titrant. KMY value for Fe-EDTA 2,1 x 1012 and Y4- for pH 7 = 4,8 x 10-4

Home Works
2. Calculate the concentration of Mg 2+ in a solution prepared by mixing 100 mL of 0,03 M Mg 2+ with 100 mL of 0,05 M EDTA. The mixture is buffer to a pH of 3. 4 at pH 3 = 2,5 x 10-4. KMg-Y4- = 4,9x 108