Compleximetry
Complexation Titrimetry
Introduction
Historically, the quantitative analysis of inorganic pharmaceutical products containing metal ions such as
Al, Bi, Ca, Mg and Zn was performed using gravimetric methods.
With the introduction of the analytical reagent disodium ethylenediaminetetraacetate, commonly
referred to as EDTA, a new volumetric procedure evolved for metal determination employing metal-ion
indicators.
Complexation Reactions
When a metal ion combines with a molecule which can donate electrons, the resulting compound is
termed complex.
If the combining molecule contains two or more groups that donate electrons, this complex is called a
chelate.
EDTA will react with metal ions to form a water-soluble, stable complex, or chelate compound.
The reaction is rapid and quantitative with such polyvalent metal ions as Al, Bi, Ca, Cu, Hg, Mg, and Zn.
Monovalent metal ions yield relatively weak or unstable complexes.
Structure of EDTA
Physical Properties
Appearance: Colourless crystals
Density: 0.860 g cm−3 (at 20 °C)
Molar mass: 292.244 g·mol−1
Chemical Formula: C10H16N2O8
Taste: slightly salty taste
Melting point: 237 °C
Boiling point: 101 to 614.2
Solubility: Water, 1000 mg/L (25 deg C)
Odor: None
Polarity: very polar
Chemical Properties:
Acidity: 2.0, 2.7, 6.16, 10.26
Chemical bonding: polyprotic acid containing four carboxylic acid groups and two amine groups with
lone pair electrons
Flammability: non-flammable
Toxicity: cytotoxic and weakly genotoxic, but not carcinogenic
Oxidation state/number: 4
Coordination number: 6 (Octahedral structure)
Reagent
The disodium salt is preferred over the free acid (ethylenediaminetetraacetic acid) in preparing the
standard solution of EDTA.
The disodium salt is more water-soluble, nonhygroscopic, and very stable.
Disodium EDTA has a MW of 372.24g/mol
The water used should be metal-free; therefore glass-distilled water is preferred.
Pair of Standard Solutions
For Direct titrations – Standard EDTA
For Residual titrations – Standard ZnSO4
EDTA Titration
The equivalence point is indicated by an abrupt change in pH because EDTA is weakly acidic (acetic acid).
In certain instances an indirect or residual titration method is more practical. An excess of EDTA is added
to complex the metal ion to be determined, and the residual EDTA is titrated with a suitable metal-ion
standard.
Indicators
EDTA titration indicators are organic compounds which form colored complex ions with the metal ion in
high dilution.
Qualities of a good indicator
1. Sharpness of color change at end point
2. Specificity of the indicator for the metal ion
3. Stability constant smaller than that of the metal-EDTA complex
The end point may be sharpened by the addition of a nonchelating screening dye that is complementary
to the color observed (either just before or just after the end point is reached).
Metal Ion Indicator Color Change pH range Metals Detected
Mordant black II Red to blue 6-7 Ca, Ba, Mg, Zn, Cd, Mn,
Eriochrome black T Pb, Hg
Solochrome black T
Murexide Violet to blue 12 Ca, Cu, Co
(Ammonium
purpurate)
Catechol-violet Violet to red 8 to 10 Mn, Mg, Fe, Co, Pb
Methyl blue Blue to yellow 4 to 5 Pb, Zn, Cd, Hg
Thymol blue Blue to grey 10 to 12 Pb, Zn, Cd, Hg
Alizarin Red to yellow 4.3 Pb, Zn, Co, Mg, Cu
Sodium alizarin Blue to red 4 Al, Thorium
sulphonate
Xylenol orange Lemon to yellow 1 to 3 Bi, Thorium
4 to 5 Pb, Zn
5 to 6 Cd, Hg
Direct Titration Methods
The metal ions which are determined by direct titration with EDTA are Ca, Mg, and Zn.
Element – Indicator Pairs for Direct Titration
Metal Indicator
Mg Eriochrome Black
Calcium Hydroxynaphthol Blue
Zinc Eriochrome Black
Residual Titrations
The indirect or residual titration method is applied to the analysis of aluminum and bismuth compounds,
since conditions for direct titrations may introduce errors because of the precipitation of the metal as
hydroxides in alkaline media.
In such cases an excess of the standard solution of EDTA is added to the sample; then the pH is adjusted
for the back titration with a metal-ion solution, zinc sulfate, using an indicator that is sensitive to the
titrant.
Elements – Indicator Pairs for Residual Titration with Zinc sulfate
Element Indicator
Aluminum Dithizone
Bismuth Dithizone
Masking
Indicate the determination of a metal in the presence of another metal
The masking agent itself is a compound capable of entering a complexation reaction
The masking can be accomplished by adjusting the pH of the titration medium so that it will be favorable
for complexation of the metal being detected and not for the other metal.
Masking agent pH Ions masked Ions titrated with
EDTA
Cyanide 10 Cu, Co, Ni, Zn, Cd, Hg, Pb, Mn, Mg, Ca,
Pt, Pd, Ag, Fe alkaline earths, rare
earths
Triethanolamine 10 Sn, Al, Fe Zn, Cd, Pb, Mn, rare
earths
Aluminium Fluoride 10 Al, alkaline earths, rare Zn, Cd, Mn
6 earths Cu
Al, Ti
Ascorbic acid 2 Cu, Fe, Hg Bi, Th
Ammonia 10 Zn Cd
It shows the total number of electrons removed or
added to an element. Oxidation state
It determines the concentration of an unknown
solution that contains an oxidizing or reducing agent.
Redox titration
This is the reactant which contains a constituent
atom/s which is/are converted to a lower state of
oxidation. Oxidizing agent
This is the reactant which contains a constituent
atom/s which is/are converted to a higher state of
oxidation. Reducing agent
Oxidation – Reduction Methods
What is Redox Reaction?
• Redox = Reduction + Oxidation
• Occur simultaneously
• Electrons are being transferred from one element to another
Theory
o The simplest type of oxidation-reduction reaction is the direct combination of elements.
o Mg + O2 MgO
o Oxidation – gain oxygen, loss hydrogen, lose electrons, higher oxidation number, reducing
agent. Increase oxidation number is oxidize or oxidation
o Reduction – gain hydrogen, loss oxygen, gain electrons, lower oxidation number, oxidizing
agent. Decrease oxidation number is reduced or reduction
o Oxidation state – also known as oxidation number, the number that we assign to an element can
to represent an electron lost or gained. Pure element has 0 oxidation state/number.
o +2, -2 oxidation state/number
o 2+, 2- charge number
Mnemonic
o LEORA
Lose Electron / gains a positive charge
Oxidation half reaction
Reducing Agent
Mnemonic
o GEROA
Gain Electron / gains a negative charge
Reduction half reaction
Oxidizing Agent
Example
o For example: Assay of ferrous sulfate by reacting it with ceric sulfate
o Fe2+ + Ce4+ Fe3+ + Ce3+
Equivalent weight of Reducing Agent
o For example, the equivalent weight of ferrous sulfate, Fe 2+ Fe3+
o In short
Equivalent weight of RA = MW/# electrons lost
Equivalent weight of Oxidizing Agent
o For example, the equivalent weight of ceric sulfate, Ce 4+ Ce3+
o In short
Equivalent weight of OA = MW/# of electrons gained
Standard Solutions Used in redox titrations
Oxidizing Agents
o Ferric ammonium sulfate
o Potassium permanganate
o Potassium dichromate
o Potassium bromate
o Potassium iodate
o Potassium ferricyanide
o Ceric sulfate
o Iodine
o Bromine
Reducing Agents
o Ferrous ammonium sulfate
o Oxalic acid
o Potassium arsenite
o Titanium chloride
o Sodium thiosulfate
Permanganate Methods
o The reactions of permanganate in solution are rapid.
o Indicator distinct pink color
o Potassium permanganate acts as a titrant and indicator
Permanganometry
o Titrant: KMnO4 (violet)
o Standard: Na Oxalate (Na2C2O4)
o Indicator: No indicator is used
o Endpoint: disappearance of violet color pink
o Analytes:
Direct = H2O2 Topical Solution
Indirect = Assay of cherry juice for malic acid content
Residual = Sodium nitrite (NaNo2): additive to prevent botulism (clostridium botulinum, food-borne)
Cerimetry
o Titrant: (CeSO4)2 (OA) Ceric Sulfate
o Solvent in preparing (CeSO4)2 : Perchloric acid
o Primary standard: Arsenic trioxide (AsO3)
o Analyte: Ferrous sulfate tablets, Menadione (vitamin K3)
o Indicator: Orthophenanthroline
Ferrous ion forms complex with indicator
Ferroin (red) Ferritin (blue)
Oxidation – Reduction:
Iodimetric and Iodometric Methods
Introduction
o Iodimetry
Direct titration
Reducing agents
o Iodometry
Indirect titration
Oxidizing agents
Deep reddish brown color
Thiosulfate in burette
Iodimetry Iodometry
Analyte Reducing Agent Oxidizing Agent
Titrant Iodine VS Na Thiosulfate VS
Titration Direct Indirect
Primary Standard Arsenic Trioxide Potassium dichromate
Indicator Starch: added at the beginning Starch: added before the end
point
Endpoint Blue color Disappearance of blue color
Samples Ascorbic acid, Sodium Sulfate Copper Sulfate, Selenium
Sulfide, Phenol
The reason why starch is added before end point in iodometry because at the beginning there is already
high concentration of iodine and if it is added at the beginning it will form a starch-iodine complex
stable, the release or liberation of iodine will be difficult and it will be hard to make a colorless end
point.
EXERCISE FOR BALANCING REDOX REACTIONS
1.) Show the 2 half reactions then answer the following questions. There will be no need to
explain your answers.
Mg + Fe2+ Mg2+ + Fe
Which is the reducing agent?
o Answer: Mg
Which is the oxidizing agent?
o Answer: Fe2+
What is the equivalent weight of the oxidizing agent?
o Answer: 27.92g
2.) Show the 2 half reactions then answer the following questions. There will be no need to
explain your answers. ACIDIC CONDITION
BrO3- + Zn Br- + Zn2+
Which underwent oxidation?
o Answer: Zn
Which underwent reduction?
o Answer: BrO3-
What is the equivalent weight of the reducing agent?
o Answer: 32.70g
3.) Show the 2 half reactions then answer the following questions. There will be no need to
explain your answers. BASIC CONDITION
Fe + ClO- Fe(OH)2 + Cl-
Which was required for oxidation to occur?
o Answer: Fe
Which was required for reduction to occur?
o Answer: ClO-
What is the equivalent weight of the one which underwent reduction?
o Answer: 25.73g
GENERAL STEPS WHEN BALANCING REDOX REACTIONS:
Balance the number of atoms on both sides (reactant and product sides) first
Balance the charges on both sides (reactant and product sides)
Balance the number of electrons, then cancel
When applicable, cancel out other ions present
