PRICIPLES AND APPLICATIONS

OF CHEMICAL EQUILIBRIA
TITRIMETRIC METHODS OF
ANALYSIS
TITRATIONS: Taking Advantage of Stoichiometric Reactions
Principles of Neutralization Titrations
Complexation and Precipitation Titrations
TITRIMETRIC METHODS OF ANALYSIS
Titrimetry includes a group of
analytical methods based on
determining the quantity of a
reagent of known concentration
that is required to react
completely with the analyte.
Titration is a process in which a
standard reagent is added to a
solution of an analyte until the
reaction between the analyte and
reagent is judged to be complete.
Types of Titrimetry
• Volumetric titrimetry is a type of
titrimetry in which the standard
reagent is measured
volumetrically.
• Coulometric titrimetry is a type of
titrimetry in which the quantity
of charge in coulombs required to
complete a reaction with the
analyte is measured.
• Complex Formation Reactions
• Precipitation Reactions
Definition of Terms
• A standard solution/titrant is a reagent of known
concentration that is used in a titrimetric analysis.
• Back-titration is a process in which the excess of a
standard solution used to consume an analyte is
determined by titration with a second standard
solution. Back-titrations are often required when
the rate of reaction between the analyte and
reagent is slow or when the standard solution
lacks stability.
Equivalence Points and End Points
• The equivalence point of a titration • Indicators are often added to the
cannot be determined analyte solution to give an
experimentally. observable physical change (the
• The equivalence point/ end point) at or near the
stoichiometric point is the point in a equivalence point.
titration when the amount of added
standard reagent is equivalent to the • The end point is the point in a
amount of analyte. titration when a physical change
• The difference in volume or mass occurs that is associated with
between the equivalence point and the condition of chemical
the end point is the titration error. equivalence.
Primary Standards
• A primary standard is a highly Important requirements for a primary standard are:
purified compound that 1.High purity (established methods for confirming purity should
serves as a reference material be available)
in all volumetric and mass 2. Atmospheric stability
titrimetric methods. 3. Absence of hydrate water so that the composition of the solid
does not change with variations in relative humidity
• A secondary standard is a
compound whose purity has 4. Ready availability at modest cost
been established by chemical 5. Reasonable solubility in the titration medium
analysis and that serves as the 6. Reasonably large molar mass so that the relative error
reference material for a associated with weighing the standard is minimized
titrimetric method of analysis.
Desirable Properties of Standard Solutions
• The ideal standard solution for a titrimetric method will
− 1. Be sufficiently stable so that it is only necessary to determine its
concentration onced
− 2. React rapidly with the analyte so that the time required between additions
of reagent is minimized
− 3. React completely with the analyte so that satisfactory end points are
realized
− 4. Undergo a selective
reaction with the analyte
that can be described by a
balanced equation
Establishing the Concentration of Standard
Solutions
• The first is the direct method in • The second is by standardization
which a carefully weighed in which the titrant to be
quantity of a primary standard is standardized is used to titrate (1)
dissolved in a suitable solvent a weighed quantity of a primary
and diluted to a known volume standard, (2) a weighed quantity
in a volumetric flask. of a secondary standard, or (3) a
measured volume of another
standard solution.
Treating Titration Data

• The two most widely used

end points involve (1)
changes in color due to
the reagent, the analyte,
or an indicator and (2) a
change in potential of an
electrode that responds to
the concentration of the
reagent or the analyte.
Types of Titration Curves
• Titration curves are plots of a
concentration-related variable as a
function of reagent volume.
• A sigmoidal curve,important
observations are confined to a small
region (typically ± 0.1 to ± 0.5 mL)
surrounding the equivalence point.
• Linear segment curve, measurements
are made on both sides of but well
away from the equivalence point.
Measurements near equivalence are
avoided.
Principles of Neutralization
Titrations:
Determining Acids, Bases, and the pH of Buffer Solution
Polyfunctional Acids
Reagents for Neutralization Titrations
Applications of Neutalization Titrations
Neutralization Titrations
• Neutralization Titrations are widely used to
determine the concentration of analytes
that are themselves acids or bases or that
are convertible to such species by suitable
treatment.
• These include the titration of bases with a
standard acid (alkalimetry) and the titration
of acids with a standard base (acidemetry).
• It involves the combination of hydronium
(H3O+) and hydroxyl ions (OH-) to form
water.
Reagents For Neutralization Titrations
• Strong acids and Strong bases
cause the most pronounced
change in pH at the equivalence
point.
• Standard solutions for
neutralization titrations are
always prepared from these
reagents.
Preparing Standard Acid Solutions
• Hydrochloric acid is widely used PRIMARY STANDARD FOR ACIDS
for titration of bases. • Tris-(hydroxymethyl)
• Perchloric acid and Sulfuric acid aminomethane, (HOCH₂)₃CNH₂ ,
are also stable and are useful for known also as TRIS or THAM, is
nitric acid are seldom available in primary-standard.
encountered because of their • It possesses the advantage of a
oxidizing properties. substantially greater mass per
mole of protons consumed
(121.1) than sodium carbonate.
Preparing Standard Base Solutions
• Sodium hydroxide is the most common base potassium hydroxide
and barium hydroxide are also encountered. None of these is
obtainable in primary-standard purity.
• Distilled water, should be boiled briefly to eliminate the gas. The
water is then allowed to cool because hot alkali solutions rapidly
absorb carbon dioxide.
• The concentration of a sodium hydroxide solution will decrease
slowly (0.1 to 0.3% per week) if the base is stored in glass bottles
Standardizing Solutions of Bases
• Potassium Hydrogen Phthalate, KHC₈H₄O₄
− nonhygroscopic crystalline
− high molar mass (204.2 g /mol)
• Other Primary Standards for Bases
− Benzoic acid is obtainable in primary-standard purity
− Potassium hydrogen iodate, KH(IO₃)₂
Acid/Base Indicators
• An acid/base indicator is a weak organic
acid or a weak organic base whose
undissociated form differs in color from
its conjugate form.
Variables that Influence the Behavior of
Indicators
• The pH interval over which a given
indicator exhibits a color change is
influenced by temperature, by the ionic
strength of the medium, and by the
presence of organic solvents and colloidal
particles.
BUFFER SOLUTIONS
• A buffer is a mixture of a weak acid and its conjugate base or a weak base and
its conjugate acid that resists changes in pH of a solution.
• By definition, a buffer solution is a solution of a conjugate acid / base pair
that resists changes in pH.
• Buffers do not maintain pH at an absolutely constant value, but changes in pH
are relatively small when small amounts of acid or base are added.
• The buffer capacity of a buffer is the number of moles of strong acid or strong
base that causes one liter of the buffer to change pH by one unit.
• We prepare buffers by making up a solution of approximately the desired pH
and then adjust by adding acid or conjugate base until the required pH is
indicated by a pH meter.
APPLICATIONS OF NEUTRALIZATION
TITRATION
• Neutralization titrations are used to determine the innumerable
inorganic, organic, and biological species that possess inherent acidic
or basic properties.
• Two major end points:
• Visual end point based on indicators
• Potentiometric end point- determination of a potential of a
glass/calomel electrode system using voltage-measuring
device.
 Elemental Analysis
• Nitrogen
• Kjeldahl method- most common method for determining organic nitrogen
that is based on neutralization titration. The procedure is straighforward,
requires no special equipment, and is readily adapted to the routine analysis
of large samples
• Dumas method-the sample is mixed with powdered copper(II) oxide and
ignited in a combustion tube to give carbon dioxide, water, nitrogen, and small
amounts of nitrogen oxides. A stream of carbon dioxide carries these products
through a packing of hot copper, which reduces any oxides of nitrogen to
elemental nitrogen. The mixture then is passed into a gas buret filled with
concentrated potassium hydroxide. The only component not absorbed by the
base is nitrogen, and its volume is measured directly.
• The newest method for determining organic nitrogen involves combusting the
sample at 1100°C for a few minutes to convert the nitrogen to nitric oxide, NO.
Ozone is then introduced into the gaseous mixture, which oxidizes the nitric
oxide to nitrogen dioxide. This reaction gives off visible radiation
(chemiluminescence), the intensity of which is measured.
Elemental Analysis
• Sulfur
• Sulfur in organic and biological materials
is conveniently determined by burning
the sample in a stream of oxygen. The
sulfur dioxide formed during the
oxidation is collected by ditillation into a
dilute solution of hydrogen peroxide.
The sulfuric acid is then titrated with
standard base.
Determining Inorganic Substances
• Ammonium salts
• Ammonium salts are conveniently determined by
conversion to ammonia. The ammonia is collected
and titrated as in the Kjeldahl method.
• Nitrate or nitrite
• The method just described for ammonium salts
can be extended to the determination of
inorganic nitrate or nitrite.
• Carbonate and Carbonate Mixtures
• The analysis of such mixtures requires two
titrations, one with an alkaline-range indicator, the
other with an acid-range indicator.
COMPLEXED FORMATION
TITRATION
Complex Formation Reagents
Forming Complexes
Complexed-Formation Titration
• These depend upon the
combination of ions, other than
hydronium and hydroxyl ions, to
form soluble, slightly dissociated
ions or compound, as in the
titration of metal ions with an
organic complexion agent such
as ethylene diaminetetraacetic
acid (EDTA).
Complex Formation Reagents
• Complex-formation reagents are
widely used for titrating cations.
• Many complexes are colored or
absorb ultraviolet radiation. The
formation of these complexes is
often the basis for spectroscopic
determinations.
Complex Formation Reagents
• Most often in complexometric titrations,
the ligand is the titrant and the metal ion
is the analyte.
• Ligand is an ion or a molecule that forms a
covalent bond with a cation or a neutral
metal atom by donating a pair of electrons
that are then shared by two.
• A ligand that has a single donor group,
called unidentate, one such as glycine,
which has two groups available for
covalent bonding, is called bidentate.
Tridentate, tetradentate, pentadentate,
and hexadentate chelating agents are also
known.
Forming Complexes
• Most metal ions react with electron-pair
donors to form coordination compounds or
complexes. The donor species, or ligand,
must have at least one pair of unshared
electrons.
• A chelate is produced when a metal ion
coordinates with two or more donor groups
of a single ligand to form a five- or six-
membered heterocyclic ring.
Titrations with Inorganic Complexing Agents
• Titration of Cyanide with
Silver Nitrate
• Method is introduced by
Justus von Liebig that is
the most widely used
complexometric titration
employing a unidentate
ligand. This method
involves the formation of
soluble Ag (CN)2
Titrations with Inorganic Complexing Agents
• Precipitation Titrimetry
• It is based on the reactions that yield
ionic compounds of limited solubility.
• One of the oldest analytical techniques
dating to the mid-1800’s
• Silver Nitrate
• It is the most widely used and important
precipitating reagent used for the
determination of the halogens, the
halogen-like anions, mercaptans, fatty
acids, and several divalent inorganic anions.
• Titrations with Silver Nitrate is often called
as Argentometric Titrations.
Argentometric Titrations
• 3 types of end points are encountered in titrations with silver nitrate:
• Chemical- consists of a color change or appearance or disappearance of
turbidity in the solution being titrated.
• Potentiometric- obtained by measuring the potential between a silver
electrode and a reference electrode whose potential is constant and
independent of the added reagent.
• Amperometric- the current generated between a pair of silver
microelectrodes in the solution of the analyte is measured and plotted as a
function of reagent volume.
 Argentometric Titrations
• Formation of Colored
Precipitate: The Mohr Method
• Adsorption Indicators: The
Fajan’s Method
• Forming a Colored Complex: The
Volhard Method
MOHR’S METHOD
• It uses AgNO3 as the titrant
(burette) and a small quantity of
potassium chromate (K2CrO4) as
the indicator to determine the
concentration of chloride in a
given sample.
• For Mohr's method, the titrant is
titrated against a supply of
chloride ions such that silver
chloride and silver chromate
precipitate
MOHR’S METHOD
MOHR’S METHOD

• Disadvantage of Mohr’s method:

can only be carried out between pH
of 7 and 10. In acidic environments,
chromate (CrO42–) is converted to
chromic acid which does not react
with excess silver ions. Furthermore,
the low concentration of chromate
ions in solution is not sufficient to
precipitate with silver.
FAJAN’S METHOD
• This method uses the reaction between
the precipitate formed and indicator. The
indicator used is dichlorofluorescein
which acts as an anion in solution. In
chloride solution, due to excess chloride
ions, they form the primary layer of the
precipitate. The second layer is formed by
the cations of sodium. The reaction ends
with the silver ion in excess. Therefore the
positively charged silver ion becomes the
primary layer and attracts indicator to
form a second layer. The color of the
indicator signals the end of the reaction.
Volhard’s Method
• It uses titrants other than AgNO3g.
NH4SCN, and Fe(NO3)3 as the indicator
to determine the concentration of
chloride in a given sample.
• Known excess quantity of AgNO3 is first
mixed with the chloride solution e.g.
NaCl. This is placed in the conical flask.
• Volhard’s method is used if the pH of
the solution in the conical flask is acidic.
If the solution is neutral or basic, Mohr’s Volhard’s method is a variant of back titration.
method should be used. The endpoint indicated by the formation of
iron(III) thiocyanate first determines the
amount of excess unreacted Ag+.
Organic Complexing Agents
• Many organic reagents are useful in
converting metal ions into forms that can be
readily extracted from water into an
immiscible organic phase.
• Organic complexing agents:
– 8-Hydroxyquinoline
– Ammonium pyrrolidine
– Diphenylthiocarbazone
– Acetyleacetone
– Tenoyltrifluoroacetoine
– Dibenzo-18-crown-6
TITRATIONS WITH AMINOCARBOXYLIC ACIDS

• Versatile Ethylenediaminetetraacetic Acid(EDTA)

• EDTA, is the most widely used complexometric titrant.

• EDTA is a hexadentate ligand.

10-39
The Nature of EDTA Complexes with Metal Ions

• Solutions of EDTA are particularly valuable as

titrants because the reagent combines with
metal ions in a 1 : 1 ratio regardless of the
charge on the cation.

Structure of a metal /EDTA complex. Note that EDTA behaves here

as a hexadentate ligand in that six donor atoms are involved in
bonding the divalent metal cation.
Indicators for EDTA Titrations
• Eriochrome Black T is a typical metal-ion indicator

• The metal complexes of Eriochrome Black T are generally red.

• it is necessary to adjust the pH to 7 or above so that the blue form of
the species, HIn²¯, predominates
Titration Methods Employing EDTA
• Direct Method
• Potentiometric Methods
• Spectroscopic Methods
• Back-Titration Methods
• Displacement Methods
Titration Methods Employing EDTA
• Direct Titration
− Many of the metals in the periodic table
can be determined by titration with
standard EDTA solutions.

− METHODS BASED ON INDICATORS FOR

THE ANALYTE
− METHODS BASED ON INDICATORS FOR
AN ADDED METAL ION
Titration Methods Employing EDTA
• Potentiometric Methods • Spectrophotometric Methods
• Potential Measurements can be used • Measurement of UV/visible absorption
for end-point detection in the EDTA can also be used to determine the end
titration of those metal ions for points of titrations. In these cases, an
which specific ion electrodes are instrument responds to the color change
availale. In addition, a mercury in the titration rather than relying on
electrode can be made sensitive to visual determination of the end point.
EDTA ions and used in titrations with
this reagent.
Titration Methods Employing EDTA
• Back Titration Methods • Displacement Methods
• These are useful for the • An unmeasured excess of solution
determination of cations that form containing the magnesium or zinc
stable EDTA complexes and for which complex of EDTA is introduced into the
a satisfactory indicator is not analyte solution.
available. • Displacement methods are used when
• Example: Determination of Thallium no indicator for an analyte is available.
Determining Water Hardness
• Water hardness is ordinarily determined
by an EDTA titration after the sample has
been buffered to pH 10. Magnesium,
which forms the least stable EDTA
complex of all the common multivalent
cations in typical water samples, does not
form a stable EDTA complex until enough
EDTA has been added to complex all the
other cations in the sample.
• A magnesium ion indicator can serve as
indicator in water-hardness titrations.
 END
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