EDTA Titrations

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

Senyawa Koordinasi
Senyawa koordinasi umumnya terdiri atas ion kompleks dan ion lawan Ion kompleks adalah ion yang mengandung kation logam pusat yang berikatan dengan satu atau lebih ion atau molekul (ligan).
kation logam pusat

ligan

Senyawa Koordinasi
Atom dalam suatu ligan yang terikat langsung dengan atom logam disebut atom donor

Bilangan koordinasi dalam suatu senyawa koordinasi adalah banyaknya atom donor di seputar atom logam pusat dalam ion kompleks

Senyawa Koordinasi
Bergantung pada banyaknya atom donor, ligan digolongkan menjadi: Ligan monodentat (1 atom donor) H2O, NH3, Cl Ligan bidentat (2 atom donor) etilenadiamina Ligan polidentat (lebih dari 2 atom donor) EDTA

Ligan bidentat

Ligan polidentat

Geometri Senyawa Koordinasi

Bilangan koordinasi 2 4 Struktur Linear Tetrahedral atau

segi empat planar

Oktahedral

Some Complex Ion Equilibria

M + D = MD
where D is tetradentate ligand nitrilotriacetic acid (NTA)

[MD] K = ----------[M][D]

K = tetapan kestabilan kompleks

Some Complex Ion Equilibria

M + 2 B = MB2
where B is a bidentate ligand ethylene diamine

[MB2] K = ----------[M][B]2

Some Complex Ion Equilibria

M + B = MB [MB] K1 = --------[M][B] and MB + B = MB2

[MB2] K2 = -----------[MB][B]

Some Complex Ion Equilibria

[MB] K = K1 * K2 = ------[M][B]
[MB2] K = -------[M][B]2

[MB2] * ---------[MB][B]

Some Complex Ion Equilibria

M + 4 A = MA4
where A is a monodentate ligand water, ammonia, Cl- ion

[MA4] K = ----------[M][A]4

Some Complex Ion Equilibria

M + A = MA

[MA] K1 = ---------[M][A] and

MA + A = MA2

[MA2] K2 = -----------[MA][A]

Some Complex Ion Equilibria

MA2 + A = MA3

[MA3] K3 = ------------[MA2][A] and

MA3 + A = MA4

[MA4] K4 = ------------[MA3][A]

Some Complex Ion Equilibria

K = K1 * K2 * K3 * K4
[MA] [MA2] [MA3] [MA4] K = --------- * ----------- * ----------- * -----------[M][A] [MA][A] [MA2][A] [MA3][A]

[MA4] K = ----------[M][A]4

EDTA
ethylenediaminetetraacetic acid => H4EDTA => H4Y ethylenediaminetetraacetate anion => EDTA-4 => Y-4

EDTA
ethylenediaminetetraacetate anion => EDTA-4 => Y-4 +1 cation
Ag+ + Y-4 = AgY-3

EDTA
ethylenediaminetetraacetate anion => EDTA-4 => Y-4 +2 cation
Hg+2 + Y-4 = HgY-2

EDTA
ethylenediaminetetraacetate anion => EDTA-4 => Y-4 +3 cation Fe+3 + Y-4 = FeY-1

EDTA
ethylenediaminetetraacetate anion => EDTA-4 => Y-4 +n ion M+n + Y-4 = MY(n-4)+

EDTA
[MY(n-4)+] KMY = -------------[M][Y-4]
[Y-4] a4 = --------CT
where CT = [Y-4] + [HY-3] + [H2Y-2] + [H3Y-1] + [H4Y]
KMY (tetapan kestabilan mutlak)

EDTA
[MY(n-4)+] KMY = -------------[M][Y-4]
[Y-4] a4 = --------CT thus [Y-4] = a4 * CT

EDTA
[MY(n-4)+] KMY = -------------[M][Y-4]
[MY(n-4)+] KMY = ------------------[M+n] * a4 * CT

EDTA
[MY(n-4)+] KMY = ------------------[M+n] * a4 * CT
then [MY(n-4)+] K'MY = KMY * a4 = ------------------[M+n] * CT
K'MY = tetapan kestabilan efektif

EDTA
[MY(n-4)+] KMY = ------------------[M+n] * a4 * CT [MY(n-4)+] K'MY = KMY * a4 = ------------------[M+n] * CT and
K1 * K2 * K3 * K4 a4 = -------------------------------------------------------------------[H3O+]4+K1[H3O+]3+K1K2[H3O+]2+K1K2K3[H3O+]+K1K2K3K4

EDTA
[MY(n-4)+] K'MY = KMY * a4 = ------------------[M+n] * CT and
K1 * K2 * K3 * K4 a4 = -------------------------------------------------------------------[H3O+]4+K1[H3O+]3+K1K2[H3O+]2+K1K2K3[H3O+]+K1K2K3K4
where D = [H3O+]4 + K1[H3O+]3 + K1K2[H3O+]2 + K1K2K3[H3O+] + K1K2K3K4

K1 * K2 * K3 * K4 a4 = ----------------------D

Ca2+ was titrated with EDTA at a constant pH of 10.0. What is the effective formation constant? (log Kf = 10,69 and a4 = 0.3 at pH 10.0)

EXAMPLE: Derive a curve (pCa as a function of volume of EDTA) for the titration of 50 mL of 0.01 M Ca2+ with 0.01 M EDTA in a solution buffered to a constant pH of 10.0. (0 mL, 30 mL, 50 mL & 60 mL EDTA added). Kf = 1.76 x 1010

Theoretical titration curves

EDTA Titrations