Fundamentals of Analytical Chemistry.

Skoog et al., 8th ed, chapter 17

At the end of this lecture you should be able to:

 Define terms related to metal-chelate complexing agent

 Explain different types of EDTA titrations
 Understand and explain protonated and deprotonated form of EDTA
 Apply calculations to obtain pMn+ at , before and after equivalent
point
 Compare different forms of EDTA in relation to pH
 List and explain regions involved in EDTA titration curve.
 Design a clear titration procedure to obtain the expected endpoint
 Assess the titration procedure in relation to the endpoint
expected/obtained
1,2-bis(3-aminopropylamino)ethane (BAP)

EDTA: Ethylene Diamine Tetra Acetic acid

Ligand
- An atom or group of atoms bound to metal ions to form complexes

Monodentate Ligand
- Binds to metal ions through only one ligand atom [cyanide (CN-) binds
through only carbon]

Multidentate Ligand
- Binds to metal ions through more than one ligand atom

Chelating agent
- Is an organic molecule that has two or more groups capable of complexing
with metal ions e.g. EDTA.
Ethylenediaminetetraacetic acid, [CH2N(CH2CO2H)2]2
(C10H16N2O8, 292.24 g mol-1)
• EDTA is hexadentate (binds through two N and four O atoms)
• Strong metal binding agent (chelating agent)
• Forms 1:1 complexes with most metal ions which remain in solution with
diminished reactivity.

It is hexaprotic in the form H6Y2+

- Six pKa values

- Four are carboxyl protons (COOH)

- Two are amino protons (NH+)

pKa1 = 0.0 (CO2H) pKa2 = 1.5 (CO2H)

pKa3 = 2.00 (CO2H) pKa4 = 2.69 (CO2H)

pKa5 = 6.13 (NH+) pKa6 = 10.37 (NH+)

- Neutral EDTA is tetraprotic in the form H4Y

- Protonated below pH 10.24

- Fully protonated form H6Y2+ predominates at very low pH

- Fully deprotonated form Y4- predominates at very high pH

- Y4- is the ligand form that binds to metal ions

- Common reagent found in labs is the disodium salt

(Na2H2Y.2H2O)
 • The resulting metal–ligand complex, in
which EDTA forms a cage-like structure
around the metal ion is very stable.

• The actual number of coordination sites

depends on the size of the metal ion.

Metal-EDTA complex with

divalent metal ion
- Titration based on complex formation

Formation constant (stability constant) (Kf)

- The equilibrium constant for the reaction between a metal ion (M+n) and a
chelating agent (L-P).
Mn+ + Y4- ↔ MYn-4
[MY n 4 ]
Kf 
[Mn ][Y 4  ]

- EDTA complexes have large Kf values

- Higher for more positively charged metal ions
- Chelating agents with more than one electron pair to donate will form
stronger complexes with metal ions than chelating agents with only one
electron pair.
 n 4
[MY ]
KMY  n 4
[M ][Y ]
- Prevents metal ion from precipitating in the hydroxide form
- Forms weak complex with metal ion
- Displaced by EDTA during titration

Examples
•Ascorbate
•Citrate
•Tartrate
•Ammonia
•Triethanolamine
 Direct Titration

- Analyte is buffered to an appropriate pH and then directly titrated with

EDTA

- Auxiliary complexing agent may be required to prevent metal hydroxide

precipitation
 Back Titration

Necessary under three conditions

- If analyte blocks the indicator
- If analyte precipitates in the absence of EDTA
- If analyte reacts too slowly with EDTA

- A known excess EDTA is added to analyte solution

-When reaction is complete, excess EDTA is back titrated with a standard

Mg2+ or Zn2+solution
(Mg or Zn must form complex that is less stable than the analyte)
 Displacement Titration

- Analyte is treated with excess Zn or Mg(EDTA)2- to displace Zn2+ or Mg2+

Mn+ + MgY2- → MYn-4 + Mg2+

- The liberated Mg2+ or Zn2+ is then titrated with standard EDTA

An example is Hg2+ (as analyte)

• For displacement to occur, Kf of HgY2- must be greater than Kf of MgY2-
 Masking Agents

- Masking agent protects some component of analyte from reaction with

EDTA
- Masks by forming complexes with the components
- F− masks Al3+, Fe3+, Ti4+, Be2+
- HF may form and is extremely hazardous
[Al3+ with F− forms AlF63- complex]
 Masking Agents

- CN− masks Hg2+, Zn2+, Ag+, Co2+, Cu+, Fe2+/3+, Ni2+

but not Pb2+, Mn2+, Mg2+, Ca2+
- Gaseous HCN may form at pH below 11 and is very toxic

- Triethanolamine masks Al3+, Fe3+, Mn2+

- 2,3-dimercaptopropanol masks Bi3+, Cu2+, Hg2+, Pb2+, Cd2+

Exercise 1
25.00 mL of an unknown Ni2+ solution was treated with 25.00 mL of
0.05283 M Na2EDTA. The pH of the solution was buffered to 5.5 and
than back-titrated with 17.61 mL of 0.02299 M Zn2+. What was the
concentration of unknown Ni2+?
Exercise 1 Solution

Zn2  Y 4-  ZnY 2-
mol EDTA  (0.02500 L)(0.05283 M)  0.001321mol

mol Zn2  (0.01761L)(0.02299 M)  0.0004049mol

Ni 2  Y 4-  NiY 2-
mol Ni 2  0.001321- 0.0004049 0.0009161mol

Conc. of Ni 2  (0.0009161mol)  (0.02500 L)  0.03664M

Eriochrome Black T is a typical metal-ion indicator used in the titration of
several common cations.

H2O + H2In- ⇌ HIn2- + H3O+ K1 = 5 X 10-7

red blue

H2O + HIn2- ⇌ In3- + H3O+ K2 = 2.8 X 10-12

blue orange

The acids and their conjugate bases have different colours.

• The metal complexes of Eriochrome Black T are generally red, as is H2In-
• 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.
• Until the equivalence point in a titration, the indicator complexes the
excess metal ion so that the solution is red.
• With the first slight excess of EDTA, the solution turns blue as a
consequence of the reaction:

MIn- + HY3- ⇌ HIn2- + MY2-

red blue
• If the MIn complex is too strong, the change in colour occurs after the
equivalence point and if the MEDTA complex is too weak, the end point occurs
before equivalence point
•

Must bind to the metal ion, but

Must release the metal ion to EDTA at the equiv. point
i.e. Metal-Indicator complex must be weaker (smaller K) than metal-EDTA
complex
Minimum pH for Titration
- Metal-EDTA complex becomes less stable as pH
decreases, Kf decreases
- In order to get a “complete” titration (Kf ≥106), EDTA
requires a certain minimum pH for the titration of each
metal ion

- By adjusting the pH of an EDTA titration:

one type of metal ion (e.g. Fe3+) can be titrated without
interference from others (e.g. Ca2+)

from "Fundamentals of Analytical Chemistry", Skoog et al., 8th ed.

Like a strong acid/strong base
titration, there are three points on
the titration curve of a metal with
EDTA: before, at, and after the
equivalence point.
Region 1: Before the equivalence point
• In this region, there is excess Mn+ left in solution after the EDTA has been
consumed.
• The concentration of free metal ion is equal to the concentration of excess,
unreacted Mn+.
•The dissociation of MYn−4 is negligible

Region 2: At the equivalence point

•There is exactly as much EDTA as metal in the solution. We can treat the
solution as if it had been made by dissolving pure MYn-4.
• Some free Mn+ is generated by the slight dissociation of MYn−4
Region 3: After the equivalence point
• Now there is excess EDTA, and virtually all the metal ion is in the form
MYn−4.
• The concentration of free EDTA can be equated to the concentration of
excess EDTA added after the equivalence point.
 The equivalence point is sharper for Ca2+vs. Mg2+.
- Kf for CaY2- is greater than Kf for MgY2-

- End point is more distinct at high pH

- pH should not be too high for metal hydroxides to precipitate

pM = -log(Mn+) Ca2+
Equivalent point Mg2+
of Ca2+’
pM

Equivalent point
of Mg2+

Volume of EDTA added (mL)

T7
Fraction of EDTA in the form Y4-

[Y 4  ]
α Y 4 
[EDTA]

[EDTA] = total concentration of all free EDTA species

(EDTA not bound to metal ions)

[EDTA] = [H6Y2+] + [H5Y+] + [H4Y] + [H3Y-] + [H2Y2-] + [HY3-] + [Y4-]

 [H6Y2+] = [H+]6

[H5Y+] = [H+]5K1

[H4Y] = [H+]4K1K2

[H3Y-] = [H+]3K1K2K3

[H2Y2-] = [H+]2K1K2K3K4

[HY3-] = [H+]K1K2K3K4K5

[Y4-] = K1K2K3K4K5K6
- EDTA exists in up to 7 different acid-base forms depending on the solution pH.
- The most basic form (Y4-) is the one which primarily reacts with metal ions
For EDTA titration curves, it is convenient to base calculations on the Y4- form
of EDTA and derive a new, pH-dependent formation constant K'f

[MY n4 ]
Mn  Y 4  MY n4 Kf 
[Mn ][Y 4  ]

CT = all forms of EDTA (Y4-, HY3- etc)

[Y 4 ]
αY4  and therefore αY4 C T  [Y 4  ]
CT
 [MY n4 ] [MY n4 ]
substituting into K f  
[M ][Y ] [Mn ]αY4 C T
n 4

[MY n4 ] [MY n4 ]

and finally K f  n
or K f αY4 
[M ]αY4 C T [Mn ]C T

[MY n4 ]
the conditional formation constant K 'f  K f αY4 
[Mn ]C T
All EDTA equilibrium
calculations will use K'f at the
pH of the titration. The value of
Y4- at this pH is taken from the
table
 Exercise 2
Consider a titration of 50.00 mL of 0.04000 M Ca2+ (buffered at pH=10)
with 0.08000 M EDTA. Kf (Ca2+)= 5 x 1010

Calculate the pCa2+ after the following volumes of EDTA are added:
a) 5.00 mL
b) 25.00 mL
c) 26.00 mL

T5
 Exercise 2 Solution
a) When we have added 5.00 mL of EDTA, it is before the equivalence point

Moles Ca2+ = 0.05000 L x 0.04000 M = 2.000 x 10-3 mol

Moles EDTA = 0.005000 L x 0.08000 M = 4.000 x 10-4 mol

Moles Ca2+ in excess = 1.600 x 10-3 mol

[Ca2+] = 1.600 x 10-3 mol ÷ 0.05500 L = 0.02909 M

pCa2+ = -log[Ca2+] = 1.54

 Exercise 2 Solution
b) When we have added 25.00 mL of EDTA, it is at the equivalence point

 At the equivalence point almost all the metal is in the form CaY2-
 Free Calcium is small and can be found with algebra

CaY 2-

0.08000M  0.02500L
0.07500L
 0.02667M

Kf 
CaY   0.02667 x
2

Ca  EDTA 
2
x 2

 Assume x is small and solve:

x  [Ca2 ]  7.300 107 M

pCa2  log(7.300 107 )  6.14

 Exercise 2 Solution
c) When we have added 26.00 mL of EDTA, it is after the equivalence
point and we have excess EDTA

EDTA   (0.08000 M)(0.02600 L)  2.737 102 M

0.07600L

CaY 2-

(0.04000 M)(0.05000 L)
0.07600L
 2.632 102 M

K 'f 
CaY   2.63210
2 2

Ca  EDTA  Ca (2.73710

2 2 2
)

[Ca2 ]  1.923 1011 M

pCa2  10.72