1. Complexometric Titration
SMK Negeri 13 Bandung

2. Complexometric Titration
Reaction result is complex substance
Common standard solution : EDTA (Ethylene Diamine Tetra acetic Acid )

3. What is complex substance?
A substance formed by covalent
coordination bond;
A bonding formed by pair electrons sharing, while the source of pair electrons is only one atom/group.

4. The covalent coordinate in a complex substance
Between the center atom (metal ion) and the ligand (ion/atom/group that give the pair electrons).
Center atom give the orbital.
Ligand give the pair electrons.

5. Complex stability If Mn+ + Lx-  [ML]n-x
While [ML]n-x is complex substance then
[ML]
K = is Kstab
[M] [L]
Kstab= stability constant

6. The more stable the substance will has bigger Kstab
The complex is difficult to dissociated to be its ions
(Compare with weak acid or base)

7. EDTA (Ethylene Diamine Tetra acetic Acid)
Ligand that have 6 pairs of electron.
Other name : trilon B, complexon III, sequestrene, versene dan chelaton 3.
Release 2 H+ from 2 carboxylic.
Most available in disodium salt form.
Wrote as H2Y=

8. EDTA concentration always termed in Molar, because
EDTA has 6 electrons pair which could be used in covalent coordinate bond one-by-one.
EDTA reacts with any metal with mole ratio 1 : 1.

9. Mn+ + H2Y=  MY(n-4) + 2H+ REACTIONS M2+ + H2Y=  MY= + 2H+

10. pH influence to metal-EDTA complex stability
Every reaction of metal ion with EDTA resulted H+
As Le Chatelier, if [H+] increased, the equilibrium goes to the left (ions)
means
At low pH or high [H+] , the stability of metal-EDTA is decreased.

11. Some of Kstab of metal-EDTA
2+ Ions Ions
Mg Al 16.3
Ca Fe 25.1
Sr Y 18.2
Ba Cr 24.0
Mn Ce 15.9
Fe La 15.7
Co Lu 20.0
Ni Se 23.1

12. The Equivalence Point Detection
Instrumental : spectrophotometric, amperometric, conductimetric or potentiometric
Conventional : Using indicator
Indicator available: metal ion indicator (metalochromic indicator)
This indicator is sensitive to very low concentration of metal ion (pM)

13. Metal ion Indicator
Ligand in the form of organic ion which its free ion colour differ from its complex.
Could also function as indicator pH.
Its Colour change depend on the pH ( owning typical pH job).
Complex metal-indicator own the Kstab expressed by Kin.

14. Criterion of Choosing Indicator
For Choosing the metal ion indicator, we have to know:
1. pH work indicator.
2. pH titration ( barbed with the nature of metal ion and metal complex stability – EDTA.
Metal stability – EDTA must > Metal ̶ Indicator

15. Some of metal ion indicators.
EBT (Eriochrome Black T)/Solochrome Black T/WDFA
Murexid
Xylenol Orange
Pyrocathecol Violet
Bromopyrogalol Red
Variamin Blue B

16. EBT (Eriochrome Black T) Solochrome Black T / WDFA
At pH < 5.5 red (H2D-).
At pH blue (HD=).
At pH > 11.5 yellowish-orange (D3-).
At pH 7-11 reacting with the metal ion. M++ + HD=(blue)  MD- (red)+ H+

17. Preparation of EBT Solution.
0.2 gram EBT dissolved in 15 ml three ethanol amine and 5 ml alcohol absolute.
This solution is stable for a few months.
0.4 gram EBT dissolved in 100 ml methanol, stable at least 1 month.
1 gram of EBT attenuated with gram of KCL or NaCl or K2So4 or Na2So4 . Most stable during carried through to run dry in bottle call a meeting to order.

18. Murexide Until pH 9 reddish violet (H4D-) pH 9 -11 Violet (H3D=)
Above pH 11 blue-violet or blue (H2D3-)
At pH base
Ni-murexide, Co-murexide yellow
Cu-murexide orange
Ca-murexide red

19. Preparation of murexide Solution.
0.5 g of the powdered dyestuff in water, shaking thoroughly, and allowing the undissolved portion to settle. This solution can only be used on making of. Everyday the old supernatant liquid is decanted and the residue treated with water as before, to provide a fresh solution of the indicator.
1 g murexide attenuated with 500 gram pure NaCl, most stable.

20. Xylenol Orange
The indicator at acid pH (1 – 5) is coloured lemon – yellow.
XO Metal at acid pH is intensely red.
Titration is generally conducted at pH 1-3, titration at pH 5 conditioned by hexamine.
0.5 % XO solution in water, most stable.

21. Types of Complexometric Titrations
1. Direct Titration.
The solution containing the metal ion to be determined is buffered to the desired pH (e.g. to pH = 10 with NH:-aq. NH,) and titrated directly with the standard EDTA solution. It may be necessary to prevent precipitation of the hydroxide of the metal (or a basic salt) by the addition of some auxiliary complexion agent, such as tartrate or citrate or triethanolamine.

22. 2. Back Titration.
Metal ion reacted by excessive EDTA, then at certain pH, the excess of EDTA titrated with the standard metal ion solution such as Mgso4 or Znso4.
At equivalence point obtained mmol of the rest of EDTA = mmol metal std, so that countable.
mmol metal ion = mmol (EDTA –metal std).

23. Why these Types of titrations are selected.
1. Metal ion precipitated at pH titration.
2. Its Complex forming is too slow.
3. There are not appropriate metal ion indicators ( complex stability of metal indicators are ineligible).
End Point determined with the sensitive metal ion indicator to metal standard.

24. 3. Substitution Titration.
Metal ion titrated by EDTA with the other metal ion attendance as an aid of determination of the end point ( For example, determination of Ca2+ with aid of Mg2+).
The titration is conducted if:
1. Metal ion does not react ( or its reaction dissatisfactory) with indicator, or
2. Complexion of metal EDTA more stable than other.

25. Examples:
Stability of Ca EDTA>Mg EDTA
Stability of Ca EBT>Ca EDTA
Hence titration Ca by EBT have to entangle the Mg, so that the end point can be reached.

26. 4. Alkalimetric Titration.
When metal ion reacted by EDTA will be formed by a number of ion H+. This ion H+ titrated by NaoH solution uses acid-base indicator.
Its condition, metal ion solution have to really neutral before is reacted by EDTA.