METTLER TOLEDO

Basics of Titration

Definition

■ Quantitative chemical determination

of a compound in a sample….

….by the controlled addition of a

reagent (titrant) of known
concentration

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Conditions for Reaction (1)

■ Simple and instantaneous

■ The endpoint (equivalence point) must be clear
„ stoichiometric

Conditions for Reaction (2)

■ Known titrant concentration - titer value

■ Observable end point

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Titration Techniques (1)

■ Manual

Titration Techniques (2)

■ Automatic

Indicator
Burette (sensor)

Titrant

Sample

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Major Measurement Techniques

Electrochemical
Potentiometric
Voltametric
Amperometric

Photometric
Turbidimetric
Colorimetric

Conductometric

Measurement Techniques (1)

■ Electrochemical Measurement
„ Electrode behaviour in Galvanic cell
„ Nernst Equation U = Potential difference

E = Eo + 2.3 RT/nF x ln aH+ glass

electrode

reference
electrode

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Measurement Techniques (2)

■ Electrochemical Measurement Techniques

„ Potentiometric
■ Nernst equation
■ Electrodes in chemical and electrical equilibrium
■ Acid/base, precipitation, redox
„ Voltametric
■ Potential difference with constant current
■ E - V curve
■ KF
„ Amperometric
■ Current difference with constant voltage (potential)
■ I - V curve
■ Vit C

Measurement Techniques (3)

■ Electrochemical sensors
„ combined glass electrodes (DGxxx)
„ aqueous and non-aqueous acid/base
„ half-cell reference electrode (DX200)
„ metal electrodes (DMxxx)
„ platinum and silver ring
„ redox and precipitation titrations
„ ion selective electrodes (DXxxx)
„ surfactant sensitive electrode (DS500)

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Measurement Techniques (4)
■ Photometric Measuring Principle
„ Turbidimetric
„ decrease in light intensity
„ Colorimetric
Detector
„ change in light transmission
„ Bouguer- Beer- Lambert Law
Photodiode
„ Applications
„ metal determinations
Light guide
„ surfactants

Concave
mirror
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Measurement Techniques (5)

■ Photometric sensors – DP550/660

Phototrode DP550/660

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Measurement Techniques (6)

■ Principle of Measurement
„ migration of ions
- Current +
„ Faraday’s Law
- +
- +
- - +
+
+
- +
χ = G.Z -
G = conductance, µS or mS Ionic Mobility in a Solution
Z = cell constant, cm-1

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Measurement Techniques (7)

■ Conductometric Sensor
„ 4 ring platinum rings

Induced current by outer rings

is measured by inner rings
Removable
plastic sheath
Main sensor body

Voltage applied to outer

Platinum rings rings generating a current

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Major Titration Reactions

Titrimetric Analyses

Acid-Base Oxidation-Reduction
Aqueous (Redox)
Non-aqueous Diazotizations
Manganometry
Complexometric Precipitation Iodometry
Turbidimetry Dichromate
Cerimetry

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Types of Titrimetric Analyses (1)

■ Acid/Base Titration - Aqueous

„ DG111,101,114,115
„ Titration of an acid HA with a strong base
(eg NaOH)

HA + H2O H3O+ + A-
H3O+ + OH- 2 H2O

„ fast reaction, rapid equilibrium

„ weak acids difficult to titrate
„ for not too dulute solutions, titration curve depends on Ka (Kb)
„ titrate separate protons : at least 2 pK units difference
„ Applications : Acid content in wine, ketchup, milk
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Types of Titrimetric Analyses (2)

■ Acid/Base Titration - Non- Aqueous

„ DG113 – movable sleeve diaphragm
„ analyte is only sparingly soluble in water
„ analyte or titrant enter into an undesired reaction with water
„ pKa values of analytes are too close together
„ analyte is too weak an acid or base in water
„ alcoholic titrants : check titer frequently (eg KOH in ethanol)
„ Applications : TAN/TBN

Solvent HS acts both as an acid and a base

Acid : HS H+ + S-
Base : HS + H+ SH2+
Sum : 2 HS SH2+ + S-
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Types of Titrimetric Analyses (3)

■ Redox Titration (DM140)

„ gain or loss of electrons
„ conjugate redox couple
„ reduction → entity gains electrons
„ oxidation → entity gives up electrons
„ eg Titration of copper with sodium thiosulphate in excess KI

2Cu2+ + 4I- <===> 2CuI↓ + I2

I2 + I- <===> I3- (reactive species)
2S2O32- + I3- <===> S4O62- + 3I-
2Cu2+ ≡ I2 ≡ 2S2O32-
Applications : Copper, chromium and nickel content in electroplating baths
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Types of Titrimetric Analyses (4)

■ Precipitation Titration (DM141)

„ formation of a sparingly soluble precipitate between
titrant and analyte
„ classic example : determination of halogens with silver
nitrate

Ag+ + X- AgX (solid) X = Cl-, Br-, I-

„ reaction may be quite slow under certain conditions

„ solution becomes supersaturated before precipitation takes place
„ coprecipitation in mixed halides
„ too concentrated solutions → inclusion of sample and titrant in
precipitation → errors, counter with rapid stirring
„ Applications : NaCl in chips, silver content of coins
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Types of Titrimetric Analyses (5)

■ Turbidimetric Titration
„ similar to precipitation
„ colloidal formations
„ phototrode
„ DP550/660 : for precipitation during titration
„ Applications : anionic content of metal coolants and
lubricants used in metal cutting processes

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Types of Titrimetric Analyses (6)

■ Complexometric Titration (DP550/660)

„ colorimetric
„ metal-indicator complex → metal-titrant complex MY
„ most important - EDTA (Na2H2Y.2H20)
„ others : DCTA, EGTA, etc
CO
„ metal to ligand ratio - 1 : 1
O CH2
CO CH2
O N
M2+ + H2Y2- MY2- + 2H+ CH2

M3+ + H2Y2- MY- + 2H+

M
CH2
N
O
CO CH2
CH2
„ Applications : Total hardness in water O CO

Calcium content in cheese

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Types of Titrimetric Analyses (7)

■ 2-phase Titration
„ colorimetric, DP550, special beaker with lateral port
„ mixed anionic- cationic dye in chloroform

dye
H2O H2O
H2O
CHCl3 CHCl3 CHCl3
Surfactant-dye Titrant-dye
Surfactant-Titrant
Before EQP At EQP After EQP
Pink titrant-anionic dye Blue titrant-cationic dye
complex in chloroform complex in chloroform

Applications : Liquid detergents and shower foam

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Types of Titrimetric Analyses (8)

■ 2-phase titration setup with DP550

„ Application brochure 22

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Types of Titrimetric Analyses (9)

■ Conductometeric
„ Water analyses - conductivity, pH, alkalinity
„ α-acids in hobs
„ Acid mixtures (segmented curve)

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Who Titrates?

„ Pharmaceuticals
„ Food
„ Plastics
„ Cosmetics
„ Beverages
„ Toiletries
„ Petrochemical
„ Chemicals
„ Etc

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