Analisa Titrimetri

Titrimetric Analysis
 Quantitative chemical analysis carried out by

determining the volume of a solution of
accurately known concentration which is
required to react quantitatively with a
measured volume of the substance to be
determined.
Classification
 Neutralisation Reactions
 Complex Formation Reactions
 Redox Reactions
 Precipitation Reactions
Basics
 Equivalence and end points
 Standards
Basics

 Precise and accurate titrations require the
reproducible determination of the end point which
either corresponds to the stoichiometric point of the
reaction or bears a fixed and measurable relation to
it.
Basics

 Monitor a property of the titrand which is
removed at the end point.
 Monitor a property which is readily
observed when excess titrant has been
added.
 Two main methods
 Coloured indicators
 Electrochemical techniques.
Basics
 Colour Change Indicators
 Common to a wide variety of titrations.
 In general terms a visual indicator is a compound that

changes from one colour to another as its chemical form
changes.
 InA = InB + nX where X may be H+, Mn+ or e-, and the

colour is sensitive to the presence of H+, Mn+, oxidants
or reductants.
Basics
 An indicator constant is defined as:
KIn = [InB][X]n / [InA]
[X]n = KIn ([InB] / [InA])
npX = pKIn + log10([InB] / [InA])
pH = pKa + log10 ([InB] / [InA])

Basics
 Potentiometric Measurements
 Measuring the change in potential

during the titration.
 Acid-base titrations.
 Precipitation titrations.
 Redox titrations.
Basics
 Monitor the change of Ecell during the
course of a titration where the indicator
electrode responds to one of the reactants or
the products.
 A plot of Ecell against the volume of titrant is

obtained.
 Precision of better than 0.2%.

Basics
Basics
 The Nernst Equation
aA + bB + …+ ne- = xX + yY + ...
RT [X] x
[Y] y
...
E=E -
0
ln
nF [A] a
[B]b
...
Basics
 RT/F ln 10 = 0.059158 V thus:
[X]x[Y]y...
E = E0 - (0.059 V/n) log10
[A]a[B]b...
 And E = E0 at unity concentrations

Basics
 Conductimetric Indication
 The electrical conductance of a solution is a measure
of its current carrying capacity and is determined by
its total ionic strength.
 It is a non-specific property.
 Conductance is defined as the reciprocal of resistance

(Siemans, -1).
Basics
 A conductance cell consists of two

platinum electrodes of large surface area.
 5-10 V at 50 -10,000 Hz is applied.
 Control of temperature is essential.

Basics
 Acid-base titrations especially at trace levels.
 Relative precision better than 1% at all levels.
 Rate of change of conductance as a function of added

titrant used to determine the equivalence point.
 High concentrations of other electrolytes can

interfere.
Basics
Basics
 Standards
 Certain chemicals which are used in defined
concentrations as reference materials.
 Primary standards.
 Secondary standards.
Basics
 Primary Standards
 Available in pure form, stable and easily dried
to a constant known composition.
 Stable in air.
 High molecular weight.
 Readily soluble.
 Undergoes stoichiometric and rapid reactions.

Basics
 Acid-base reactions.
 Na2CO3, Na2B4O7, KH(C8H4O4), HCl (cbpt.)
 Complex formation reactions.

 AgNO , NaCl
3
 Precipitation reactions.
 AgNO , KCl
3
 Redox reactions.
 K2Cr2O7, Na2C2O4, I2
Basics
 Secondary Standards
 A substance that can be used for
standardisations, and whose concentration of
active substance has been determined by
comparison to a primary standard.
Classification
 Neutralisation Reactions
 Complex Formation Reactions
 Redox Reactions
 Precipitation Reactions
Neutralisation Titrations
 The neutralisation reactions between acids

and bases used in chemical analysis.
 These reactions involve the combination of

hydrogen and hydroxide ions to form water.
 For any actual titration the correct end point
will be characterised by a definite value of
the hydrogen ion concentration.
 This value will depend upon the nature of the

acid and the base, the concentration of the
solution and the nature of the indicator.
 A large number of substances called neutra-

lisation indicators change colour according to the
hydrogen ion concentration of the solution.
 The end point can also be determined

electrochemically by either potentiometric or
conductimetric methods.
Theory of Indicator Behaviour
 An acid/base indicator is a weak organic acid or

a weak organic base whose undissociated form
differs in colour from its conjugate base or
conjugate acid form.
 The behaviour of an acid type indicator is

described by the equilibrium;
 HIn + H2O In- + H3O+
 The behaviour of an base type indicator

is described by the equilibrium;
 In + H2O InH+ + OH-

 The equilibrium constant takes the form:
[H3O+][In-]
= Ka
[HIn]
 Rearranging:
[HIn -
]
[H3O ] = Ka
+
[In-]
 pH (acid colour) = -log(Ka . 10) = pKa +1
 pH (base colour) = -log(Ka / 10) = pKa -1
 Therefore; indicator range = pKa ± 1

 The human eye is not very sensitive to colour
change in a solution containing In- and HIn.
 Especially when the ratio [In-] / [HIn] is greater

than 10 or less than 0.1.
 Hence the colour change is only rapid within the

limited concentration ratio of 10 to 0.1.
 Strong acids and bases
 Weak acids
 Weak bases
 Polyfunctional acids
 Applications
 Strong acids and bases.

 When both reagent and analyte are strong
electrolytes, the neutralisation reaction can
be described by the equation:
H3O+ + OH- 2H2O

 The H3O+ concentration in aqueous solution
comprises of two components.
 The reaction of the solute with water.
 The dissociation of water.
 [H3O+] = CHCl + [OH-] = CHCl
 [OH-] = CNaOH + [H3O+] = CNaOH

 Using these assumptions you can calculate the
pH of a titration solution directly from
stoichiometric calculations and therefore
simulate the titration curves.
 This is useful in determining the correct

indicator for a new titration.
 Examples:
 HCl, HNO3
 NaOH, KOH, Na2CO3
 Standards:anhydrous Na2CO3 and constant

boiling HCl.
 Weak acids and bases
 Examples
 Ethanoic acid
 Sodium cyanide
 Four types of calculation are required to derive

a titration curve for a weak acid or base.
 Solution contains only weak acid. pH is calculated from
the concentration and the dissociation constant.
 After additions of the titrant the solution behaves as a

buffer. The pH of each buffer can be calculated from
there analytical concentrations.
 At the equivilence point only salt is present and the pH is

calculated from the concentration of this product.
 Beyond the equivilence point the pH is governed largely

by the concentration of the excess titrant.
 Effect of Concentration
 Effect of reaction completeness
 Indicator choice; Feasibility of

titration
 Polyfunctional acids and bases
 Typified by more than one

dissociation reaction.
 Phosphoric acid
 Yield multiple end points in a titration.

 Sulphuric Acid
 Unusual because one proton behaves as a strong

acid and the other as a weak acid (K2 = 1.20 x
10-2).
 Applications:
 Determination of the concentration of
analytes which are either acid or bases.
 Determination of analytes which can be
converted to acids or bases.
Complexometric Titrations
 Titrations between cations and complex

forming reagents.
 The most useful of these complexing agents

are organic compounds with several
electron donor groups that can form
multiple covalent bonds with metal ions.
 Most metal ions react with electron-pair

donors to form coordination compounds or
complex ions.
 The donor species, or LIGAND, must have

at least one pair of unshared electrons
available.
 Inorganic Ligands
 Water
 Ammonia
 Halides
 Organic Ligands
 Cyanide
 Acetate
 The number of bonds a cation forms with

an electron donor is called the
COORDINATION NUMBER.
 Typical values are 2, 4 and 6.
 The species formed as a result of

coordination can be electrically positive,
neutral or negative.
 Complexometric methods have been

around for more than a century.
 Rapid expansion in the 1940’s based on

a class of coordination compounds
called CHELATES.
 A chelate is produced when a metal ion

coordinates to two or more donor groups
within a single ligand.
 For example the copper complex of glycine.

NH2 O
Cu2+ + 2 H C C
H OH
O O
C O O C
Cu + 2H +
C N N C
H2 H2 H2 H2
 A ligand with a single donor group is

called unidentate.
 Glycine is bidentate.
 Tri, tetra, penta and hexadentate

chelating agents are also known.
 Multidentate ligands have two advantages

over unidentate ligands.
 They react more completely with cations to

provide a sharper endpoint.
 The reaction is a single step process.

 Tertiary amines that also contain carboxylic acid
groups form remarkably stable chelates with many
metal ions.
 Ethylenediaminetetraacetic Acid EDTA
HOOCCH2 CH 2CO O H
N CH2 CH2 N
HOOCCH2 CH 2CO O H
 EDTA can complex a large number of metal ions.
 Approximately 40 cations can be determined by

direct titration.
 EDTA is usually used as the disodium salt,

Na2H2EDTA
H2EDTA2- + M2+ [M(EDTA)]2- + 2H+

 Because EDTA complexes most cations, the

reagent might appear at first glance to be totally
lacking in selectivity.
 However, great control can be acheived by pH

regulation and the selection of suitable indicators.
 Indicators are generally complexing agents which

undergo a colour change when bonded to a metal
ion.
H2EDTA2- + [M(Ind)] [M(EDTA)]2- + Ind2- + 2H+

 Typical indicators are:

 Murexide
 Solochrome black
 Calmagite
 Bromopyrogallol red
 Xylenol orange
 Typical applications:
 Determination of cations
 Hardness of water
Redox Titrations
 Basics
 Potassium Permanganate
 Potassium Dichromate
 Cerium IV
 Iodine
Redox Titrations
 Basics
 Electrode Potentials
 Indicators
Redox Titrations
 Electrode Potentials
 Derived from Nernst equation.
 Calculations of cell potentials leads to
theoretical titration curves.
 EOX = ERED = Esystem
Redox Titrations
Redox Titrations
 Indicators
 Potentiometric
 Coloured indicators
 EIn = EOX = ERED = Esystem
 Specific: Starch
 Oxidation / Reduction Indicators

Redox Titrations
Redox Titrations
 Potassium Permanganate
MnO4- + 8H+ + 5e-  Mn2+ + 4H2O
 Standardisation
 Sodium oxalate or arsenic (III) oxide
 Many Analyses
Redox Titrations
 Hydrogen Peroxide:
 2MnO4- + 5H2O2 + 6H+  2Mn2+ + 5O2 + 8H2O
 Nitrites:
 2MnO4- + 5NO2- + 6H+  2Mn2+ + 5NO3- + 3H2O
Redox Titrations
 Persulphates:
 Add an excess of iron (II)
 S2O82- + 2Fe2+ + 2H+  2Fe3+ + 2HSO4-
 The excess iron (II) is determined by back titration against

standardised permangenate.
 MnO4- + 8H+ + 5Fe2+  Mn2+ + 5Fe2+ + 4H2O
Redox Titrations
 Potassium Dichromate
CrO72- + 14H+ + 6e-  2Cr3+ + 7H2O
 Standardisation
 Against metallic iron
 1 mole K2CrO7 = 6 moles Fe
Redox Titrations
 Iron (II):
CrO72- + 14H+ + 6Fe2+  2Cr3+ + 6Fe3+ 7H2O

 Indicators include N-phenylanthranilic acid and
sodium diphenylamine sulphonate.
 Chlorates:
 Reduced with an excess of iron (II)
 The excess iron (II) is determined by back titration

against standardised dichromate.
Redox Titrations
 Iodine
 Iodometric Titrations
I2 + 2e- 2I-
 Standardisation
 Standardised sodium thiosulphate or
arsenic (III) oxide
 Many Analyses
Redox Titrations
 Hydrogen Peroxide:
 H2O2 + 2I- + 2H+ I2 + 2H2O
 Thiosulphates:
 2S2O32- + I2  S4O62- + 2I-
 Hydroxyl Groups:
 2OH- + I2  IO- + H2O + 2I-
Redox Titrations
 Others:
 Copper
 Dissolved oxygen
 Chlorine
 Arsenic (V)
 Sulphides
 etc..........
Redox Titrations
 Cerium (IV) Sulphate
 Very strong oxidising agent (1.43V)
Ce4+ + e- Ce3+
 Standardisation
 Sodium oxalate or arsenic (III) oxide
 Many Analyses
Precipitation Titrations
 Titrations between analytes and reagents
resulting in the formation of a precipitate.
 The most useful of these precipitating

reagents is silver nitrate.
 Titrimetric methods based upon the use of

silver nitrate are sometimes called
Argentometric titrations.
 Used for the determination of many

anions including:
 halides
 divalent anions
 mercaptans
 certain fatty acids
 Precipitation titrations are based on

the SOLUBILITY PRODUCT of the
salt, KSP.
 The smaller KSP, the less soluble the

silver salt and the easier it is to
determine the endpoint
 Endpoint determination is by
coloured indicators (usually back
titrations) or turbidity methods.
 The most accurate is the

VOLHARD METHOD.
 VOLHARD METHOD
 A back titration of thiocyanate ions

against the excess silver ions using an
iron (II) salt as the indicator.
Ag+ + SCN- AgSCN
Fe3+ + SCN- FeSCN2+
Blood Red

Analisa Titrimetri

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Analisa Titrimetri

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Titrimetric Analysis

 Quantitative chemical analysis carried out by

 Complex Formation Reactions

 Equivalence and end points

 Equivalence and end points

 Equivalence and end points

 In general terms a visual indicator is a compound that

 InA = InB + nX where X may be H+, Mn+ or e-, and the

KIn = [InB][X]n / [InA]

[X]n = KIn ([InB] / [InA])

npX = pKIn + log10([InB] / [InA])

pH = pKa + log10 ([InB] / [InA])

 Measuring the change in potential

 A plot of Ecell against the volume of titrant is

 Precision of better than 0.2%.

 The Nernst Equation

 RT/F ln 10 = 0.059158 V thus:

 And E = E0 at unity concentrations

 Conductance is defined as the reciprocal of resistance

 A conductance cell consists of two

 5-10 V at 50 -10,000 Hz is applied.

 Control of temperature is essential.

 Relative precision better than 1% at all levels.

 Rate of change of conductance as a function of added

 High concentrations of other electrolytes can

 High molecular weight.

 Undergoes stoichiometric and rapid reactions.

 Complex formation reactions.

 Complex Formation Reactions

 The neutralisation reactions between acids

 These reactions involve the combination of

 This value will depend upon the nature of the

 A large number of substances called neutra-

 The end point can also be determined

 An acid/base indicator is a weak organic acid or

 The behaviour of an acid type indicator is

 HIn + H2O In- + H3O+

 The behaviour of an base type indicator

 In + H2O InH+ + OH-

 pH (acid colour) = -log(Ka . 10) = pKa +1

 pH (base colour) = -log(Ka / 10) = pKa -1

 Therefore; indicator range = pKa ± 1

 Especially when the ratio [In-] / [HIn] is greater

 Hence the colour change is only rapid within the

 Strong acids and bases.

H3O+ + OH- 2H2O

 The dissociation of water.

 [H3O+] = CHCl + [OH-] = CHCl

 [OH-] = CNaOH + [H3O+] = CNaOH

 This is useful in determining the correct

 NaOH, KOH, Na2CO3

 Standards:anhydrous Na2CO3 and constant

 Four types of calculation are required to derive

 After additions of the titrant the solution behaves as a

 At the equivilence point only salt is present and the pH is

 Beyond the equivilence point the pH is governed largely

 Effect of reaction completeness

 Indicator choice; Feasibility of

 Polyfunctional acids and bases

 Typified by more than one

 Yield multiple end points in a titration.

 Unusual because one proton behaves as a strong

 Titrations between cations and complex