3-Classical Analytical Methods

Chapter 3: Classical Analytical Methods Analytical Chemistry (Chem-2202)
CLASSICAL ANALYTICAL METHODS

There are four types of wet analytical protocols that we use to determine or estimate certain analyte in
any matrix, namely acid-base titration, redox titrations, complexometric titrations and gravimetric
analysis. In this chapter we will discuss following points.
Acid-Base titrations
 Concepts of acids and bases
 Different theories of acids and bases
 Stoichiometry of neutralization
 Potentiometric titrations, pKa value and titration curve
 Chemistry of indicators used in acid-base titrations
Redox titrations
 Introduction
 Oxidation-Reduction and Molecular Compounds
 Assigning oxidation numbers
 Types of chemical reactions
Complexometric titrations
 Introduction
 Warner’s coordination number
 Classification of ligands
 Principle of complexometric titration
 Mechanism of indicators
 Types of complexometric titration
 Selective titration using masking and demasking agent
Gravimetry analysis
 Classifications of Gravimetric methods
 Mechanism of Precipitate Formation
 Types of coprecipitation
Acid-Base Titrations
The chemistry of acids and bases has remained the core of chemistry from ancient times to the modern
era, and indeed, most of chemistry that was performed in laboratories in old times was the acid-base
chemistry. When chemistry began to strengthen its theoretical side at the end of the 19th century, the
first topic attacked by theoretical chemists was the acid-base chemistry. As a result of this theoretical
thrust, chemistry became remarkably quantified. We will discuss here some important concepts as
hydrogen ion concentration, the ionization constant, hydrolysis, titration curves, buffer solutions, and
indicators.
3rd Version, May 17 Page 1

Concept of acids and bases

Before the advent of modern chemistry, acids were defined as something soar, and alkalis were
something which could cancel, or rather, neutralize, the effect of acids. There had been some confusion
about the nature of acids. Oxygen had been regarded as the essential constituent of acids. In fact, the
word “oxygen” is Greek in origin, meaning “to make something sour”. The only acid known to the
alchemists of the ancient age was impure acetic acid, and the bases they could use were such as crude
potassium carbonate obtained from ashes of plants. In the middle age, Arabian alchemists developed
methods to produce mineral acids such as hydrochloric acid or nitric acid and used these. Much the
same was the case with bases. In fact, the word “alkali”, a common name of strong bases, is Arabic in
origin. In the modern age, the increase of population and the rise of living standard became gradually
remarkable, and demands for various materials were increased. For instance, soap, once luxurious and
expensive, became widely used. Consequently, demand for sodium carbonate, the raw material for
soap, rapidly increased. Demand for clothes also increased, which caused the increase of demand for a
variety of chemicals for bleaching and dying. In these days, it was already understood that acids and
bases had opposite properties which were cancelled each other.
Chemical equilibrium: When substances A, B and C change into substances X, Y and Z and
simultaneously substances X, Y and Z change into substances A, B and C, the combined processes are
called reversible reactions and are expressed by the following equation with a double arrows.
A + B + C +・・・ ⇄ X + Y + Z + ・・・
where the substances in the left side are called reactants, and substances in the right side are called
products. In the initial stage of the reaction, the concentrations of products are low, and consequently
the rate of the reverse reaction is slow. As the reaction proceeds, the rate of the reverse reaction will
increase, and to the contrary, the rate of the forward reaction will decrease. When finally the rate of
two reactions will be equal, no reaction seems to take place in appearance. Such a state is called the
chemical equilibrium. At equilibrium, the concentrations of components vary depending on the
temperature. The concentration (usually in mol dm-3) of each component, e.g., that of the component A,
is designated as [A]. Then the equilibrium constant K is defined as below.
K = ([X][Y][Z] )/([A][B][C])
Electrolytic dissociation equilibrium: A dissociation reaction in which an electrolyte AB dissolves in
water and dissociates into its component ions A- and B+ is called electrolytic dissociation or ionization.
This reaction is also a reversible reaction.
AB ⇄ A- + B+
Dissociation equilibrium of an electrolyte is called electrolytic dissociation equilibrium. The equilibrium
constant of this type of equilibrium is called electrolytic dissociation constant. It is defined as below.
K = [A-][B+]/[AB]
Where [AB], [A-] and [B+] are the concentration at equilibrium of electrolyte AB, anion A- and cation B+,
respectively. Water dissociates to a small extent. The electrolytic dissociation constant of water is
defined as below:

H2O ⇄ H+ + OH- ; K = [H+][OH-]/[H2O]

The ion-product constant Kw of water is defined as:
Kw = [H+][OH-] = 1.00 x 10-14 mol2 dm-6
This equation is applicable not only to pure water but also to aqueous solutions in general. Hence, in
acidic solutions, [H+] is larger and [OH-] is smaller. Hydrogen ion concentration [H+] of 1 molar
hydrochloric acid is [H+] = 1.0 mol dm-3 (a strong electrolyte) and that of 1 molar aqueous sodium
hydroxide is [H+] = 10-14/[OH-] = 10-14 mol dm-3. This indicates that [H+] of solutions varies in the order of
10-14 as they change from acidic to basic. Moreover, [H+] of an aqueous solution is typically quite small.
Thus, it is convenient to use the hydrogen ion exponent, pH scale, which is a log scale based on 10
where pH = -log [H+]
+ -3 -3
Sample exercise: Calculate [H ] and pH of 1.00 x 10 mol dm aqueous sodium hydroxide,
- -3 + -14 -3 -11
assuming a complete dissociation. (Answer [OH ] = 10 、[H ] = 10 /10 = 10 pH = 11)
Theory of acid-base
Arrhenius’s theory of electrolytic dissociation: In 1886, Arrhenius proposed the theory of electrolytic
dissociation in which he defined acids as substances which dissolve and ionize in water to yield protons
(H+) while bases as substances which dissolve and ionize in water to yield hydroxide ions (OH-).
Accordingly, the acidity of hydrochloric acid and the basicity of aqueous sodium hydroxide are explained
by the following equations:
HCl + aq → H+(aq) + Cl-(aq)
NaOH + aq → Na+(aq) + OH-(aq)
where (aq) indicates an aqueous solution. If a proton is bonded with one molecule of H2O to form a
hydronium ion H3O+, the equation for the electrolytic dissociation of hydrochloric acid will be as follows:
HCl + H2O → H3O+ + Cl-
Arrhenius’ theory failed to explain the fact that such compounds like gaseous ammonia, which do not
have a hydroxyl group and hence cannot give a hydroxide ion, exhibited basicity.
Brønsted and Lowry Theory: In 1923, the Danish chemist Johannes Nicolaus Brønsted (1879-1947) and
the English chemist Thomas Martin Lowry (1874-1936) proposed acids as substances which can yield
and donate protons (H+) to other substances while bases are the substances which can accept and
receive protons (H+) from other substances. According to this theory, the reaction between gaseous
hydrogen chloride and gaseous ammonia can be explained as an acid-base reaction. Thus,
HCl(g) + NH3(g) →NH4Cl(s)
where the symbols (g) and (s) indicate that the relevant substance is a gas or a solid, respectively.
Hydrogen chloride donated a proton to ammonia to act as an acid. According to the theory of Brønsted
and Lowry, a substance can behave either as an acid or as a base. If a substance in question can more
readily emit a proton, it will act as an acid and the counterpart will act as a base. To the contrary, if the

substance can more readily accept a proton, it will act as a base. In an aqueous solution of acid, water
behaves as a base.
HCl + H2O → Cl - + H3O+
acid1 base2 conjugate base1 conjugate acid 2
Among the chemical species in the above reaction, the difference between HCl and Cl- is whether there
is a proton or not, and the inter-conversion between them is reversible. This type of relation is called a
conjugate relation, and the pair HCl and Cl- is called conjugate acid-base pair. An aqueous carbonate ion
CO32- is basic. In the reaction between CO32- and H2O, the former behaves as a base and the latter as an
acid and they form a conjugate acid-base pair.
H2O + CO32- → OH- + HCO3
A substance is said to be amphoteric if it can behave either as an acid or as a base. Water is a typical
amphoteric substance. The reaction between two molecule of water to give a hydronium ion and a
hydroxide ion is a typical reaction of amphoteric substances.
H2O + H2O → OH- + H 3O+
Lewis acid-base theory:

In the year (1923) when Brønsted and Lowry proposed their acid-base theory, Lewis also proposed a
new acid-base theory. Lewis, who proposed the octet theory, proposed that acids are the substances
which can accept electron pairs whereas the bases are the substances which can donate electron pairs.
All substances defined as acids by the Arrhenius theory are also acids in the framework of the Lewis
theory since a proton is an acceptor of an electron pairs. In neutralization reactions, a proton forms a
coordinate bond with a hydroxide ion.
H+ + OH- ⇄ H2O
The situation is the same with the gas-phase reaction which was first accepted as an acid-base reaction
in the framework of the Brønsted and Lowry theory.
HCl(g) + NH3(g) ⇄ NH4Cl(s)
In this reaction, proton from HCl makes a coordinate bond with the lone pair of the nitrogen atom.
Several reactions which were not regarded as acid-base reactions in the framework of both the
Arrhenius theory and the Brønsted and Lowry theory proved acid-base reactions in the light of the Lewis
theory. An example is the reaction between boron trifluoride BF3 and fluoride ion F-.
BF3 + F- → BF4-
This reaction includes the coordination of boron trifluoride to the lone pair of fluoride ion. According to
the Lewis acid-base theory, BF3 is an acid. In order to differentiate such acids as BF3 from protic acids

Dissociation of acids and bases: Sodium chloride dissolves into the water. This means that the
stabilization obtained by hydration of ions, i.e., interaction between ions and polar water molecules.
NaCl → Na+(aq) + Cl-(aq)
The system emits a substantial amount of energy (hydration energy) and obtains stabilization. In the
following equations, (aq) is omitted though in fact hydration takes place.
HCl → H+ + Cl-
HNO3 → H+ + NO3-
H2SO4 → 2H+ + HSO4-2
Such is the case with strong bases.
NaOH → Na+ + OH-
KOH → K+ + OH-
Weak acids and weak bases behave in a different manner. In aqueous solution, electrolytic dissociation
is not complete, and a part or almost all of these remain as neutral species. Thus, in the case of acetic
acid,
CH3COOH ⇄ H + + CH3COO-
The equilibrium constant for this dissociation, Ka, is called electric dissociation constant or acid
dissociation constant. In analogy with pH, pKa, electric dissociation exponent, is defined as below:
pKa = -logKa
Ka = ([H+][CH3COO-])/[ CH3COOH] = 1.75 x 10-5 mol dm-3, pKa = 4.56 (25°C)
By using pKa, extremely small values of Ka are converted to values easy to handle. Thus, the effect of
using pKa is the same as that of using pH. The strength of acids is defined by electric dissociation
constants or electric dissociation exponents. The larger electric dissociation constants or the smaller
electric dissociation exponents, means the stronger acid. In following table, electric dissociation
constants and electric dissociation exponents of some of the representative weak acids are given.
Acid dissociation constants dissociation

exponents (pKa)
Formic acid (HCOOH) 1.77 x 10–4 3.55
Acetic acid (CH3COOH) 1.75 x 10-5 4.56
Chloroacetic acid (ClCH2COOH) 1.40 x 10-3 2.68
Benzoic acid (C6H5COOH) 6.30 x 10-5 4.20
Carbonic acid (H2CO3) K1 4.3 x 10-7 6.35
K2 5.6 x 10-11 10.33
Hydrogen sulfide (H2S) K1 5.7 x 10-8 7.02
K2 1.2 x 10-15 13.9
Phosphoric acid (H3PO4) K1 7.5 x 10-6 2.15
K2 6.2 x 10-8 7.20
K3 4.8 x 10-13 12.35
-5 -3
Sample exercise: Ka of butanoic acid (butyric acid) CH3CH2CH2COOH is 1.51 x 10 mol dm .
-2 -3
Calculate the pH of a 1.00 x 10 mol dm solution of this acid.

Ammonia is a weak base, and when it dissolves in water, a part of it reacts with water to give hydroxide
ion OH-1.
NH3 + H2O ⇄ NH4+ + OH-
In this reaction water acts as a solvent and at the same time as a reagent. The equilibrium constant of
this equilibrium reaction is defined by the equation below:
K = [NH4+] [OH-]/[NH3] [H2O]
The concentration of water, [H2O], may be regarded almost constant (55.5 mol dm-3) at ambient
temperature and pressure, and the base dissociation constant is defined as below.
Kb = [NH4+] [OH-]/[NH3] = 1.76 x 10-5 mol dm-3
In aqueous solutions, Kb can be converted to Ka with the aid of ion product Kw. Thus,
Kb = Ka/Kw
This is equal to express the strength of a base by the strength (in fact the weakness) of its conjugate
acid. With this procedure, acids and bases are compared with a common standard.
Polyprotic acids: Sulfuric acid H2SO4 is a diprotic acid since it can release two protons in two steps. For
polyprotic acids, more than one dissociation constants are defined. The dissociation constant for the 1st
step is designated as K1, and that for the 2nd step is K2. As compared with the first ionization step in
which the first proton is released, the 2nd ionization, that is, the release of proton from HSO4-, is less
extensive. This tendency is more significant for phosphoric acid, which is considerably weaker than
sulfuric acid. Phosphoric acid is a trivalent acid and dissociates in three steps as shown below.
H3PO4 ⇄ H+ + H2PO4-, K1 = 7.5 x 10-3 mol dm-3
H2PO4- ⇄ H+ + HPO42-, K2 = 6.2 x 10-8 mol dm-3
HPO42- ⇄ H + + PO43-, K3 = 4.8 x 10-13 mol dm-3
These data indicate that the acid involved in each step of the dissociation is successively weaker.
Similarly, calcium hydroxide Ca(OH)2 is a divalent base since it can release two hydroxide ions.
Neutralization
The most fundamental and practical concept in acid-base chemistry is no doubt neutralization. The fact
that acids and bases cancel each other has been well known as the fundamental property of them
before the advent of modern chemistry. Neutralization can be defined as the reaction between proton
(or hydronium ion) and hydroxide ion along with formation of water.
H+ + OH- → H2O
H3O+ + OH- → 2 H2O
where the moles of the acid (i.e., proton) should be equal to that of the base (hydroxide ion).

Stoichiometry of neutralization
With the aid of the mole ratios in above equation, it is possible to determine the concentration of a
solution of a base (or an acid) whose concentration is unknown by the neutralization with a solution of
an acid (or a base) whose concentration is known.
Sample exercise: 0.500 g of impure ammonium chloride NH4Cl was heated with excess sodium
3 -3
hydroxide, and the generated ammonia NH3 was absorbed in 25.0 cm of 0.200 mol dm sulfuric
3 -3
acid. 5.64 cm of 0.200 mol dm sodium hydroxide was required to neutralize excess sulfuric
acid. Calculate the purity of ammonium chloride. (Answer purity is 93 %)
Acidic and Basic Salts: Each acid or salt has its own counter ion, and acid-base reactions involve all these
ions. In a typical neutralization reaction such as the one between HCl and NaOH,
HCl + NaOH → NaCl + H2O
NaCl is formed in addition to water from chloride ion, the counter ion of proton, and sodium ion, the
counter ion of the base. Such substances formed during neutralization are called salts. As far as the
reaction proceeds in water, both sodium ion and chloride ion exist independently as ions, not as a salt
NaCl. If water is evaporated, sodium chloride remains as such. One tends to believe that salts are neutral
since they are formed during neutralization. In fact aqueous sodium chloride is completely neutral.
However, aqueous solutions of some of the salts are sometimes acidic or basic. For instance, sodium
acetate, CH3COONa, a salt generated from the reaction between acetic acid and sodium hydroxide, is
weakly basic. On the other hand, ammonium chloride NH4Cl, a salt of a strong acid, hydrochloric acid,
and a weak base, ammonia, is acidic. This phenomenon is called hydrolysis (of salts). A schematic
scheme of hydrolysis is shown below. In aqueous solutions, the salt AB is in equilibrium with small
amounts of H+ and OH- generated from electrolysis of water to yield an acid HA and a base BOH. Since
HA is a weak acid, the equilibrium is shifted to the acid side, and consequently [H+] decreases. On the
other hand, BOH is a strong base, and dissociates nearly completely, and hence there is no decrease of
the concentration of OH-. By dissociation of water, an equal amount of H+ and OH- is formed.
Consequently [OH-] of the aqueous solution increases to make the solution basic. This explanation is
applicable to all salts of a weak acid and a strong base.
AB A+ + B-
+ + Hydrolysis (of salts)
H2O H+ + OH-
↕ ↕
HA BOH
To summarize, in hydrolysis of a salt from a weak acid and a strong base, a part of the anion of the salt
reacted with water to give hydroxide ion.
A- + H2O → HA + OH-
By treating this reaction as an equilibrium, hydrolysis of a salt can be expressed in a quantitative
manner. The equilibrium constant Kh for this equilibrium is called hydrolysis constant

Kh = [HA][OH-]/[A-]
A- is the conjugate base of the weak acid HA and Kh corresponds to its base dissociation constant.
Accordingly the following relation holds if the acid dissociation constant of HA is Ka. Thus,
Ka Kh = Kw
Then the concentration of [OH-] and [H+] is given by the following equations.
[H+] = Kw/[OH-]
Since a weak acid is involved, [H+] < √Kw = 10-7
Thus, a salt of a weak acid is basic. In a similar manner, [H+] of a salt of a weak base and a strong acid is
given below.
[H+] > √Kw = 10-7
Thus, a salt of a weak base is acidic.
(c) Titration curve during neutralization of an acid with a base, or, neutralization of a base with an acid,
how hydrogen ion concentration, [H+], or pH, of the solution varies? The calculation of [H+] during the
titration of a strong acid with a strong base, or reversibly, or the titration of a strong base with a strong
acid is not difficult at all. It can be obtained by dividing the mole of remaining acid (or base) by the
volume of the solution. The treatment is more complicated when the combination of a weak acid and a
strong base, or that of a strong acid and a weak base is involved. [H+] will depend, not only the remaining
acid or base, but also the hydrolysis of the salt formed. The plot of [H+] or pH vs. the amount of acid or
base added is called the titration curve. Let us draw titration curves where the initial volume of acid is VA,
the concentration of it is MA, and the volume of added base is VB and its concentration is MB.
Titration of a strong acid with a strong base (curve a):
Before the equivalent point: Since the dissociation of water can be neglected, the mole of H+ is equal to
the mole of the remaining acid. At the equivalent point: Dissociation of water cannot be neglected here.
[H+] = √Kw = 10-7
After the equivalent point: The mole of excess base is equal to the mole of hydroxide ion. The [OH-] can
be obtained by dividing the mole by the volume of the solution. The obtained [OH-] can be converted
into [H+]. The curve is symmetric near the equivalent point. The titration of 1 a strong acid such as 0.1
mol dm3 hydrochloric acid with a strong base such as 0.1 mol dm3 aqueous sodium hydroxide gives a
characteristic titration curve as shown in Fig. a. At the initial stage, the change of pH is slow. The change
of pH is very rapid near the equivalent point. Near the equivalent point, pH changes for a few units with
one drop of the base.

Titration curve: (a) Titration of HCl with

NaOH. A rapid change of pH at the
equivalent point is characteristic. (b)
Titration curve: titration of CH3COOHl
with NaOH. The change of pH at the
equivalent point is not so rapid.
Titration of a weak acid with a strong base (curve b):

The result is different when a weak acid is titrated with a strong base. The titration of a 0.1 mol dm3
acetic acid with 0.1 mol dm3 aqueous sodium hydroxide will be an example.
At starting point the pH at the initial stage is larger than the previous case. Until the equivalent point,
the change of pH is rather slow. At the equivalent point only sodium acetate CH3COONa exists. [H+] can
be obtained in a manner similar to the one for hydrolysis of salts. After the equivalent point: [H+] of the
solution is determined by the concentration of NaOH rather than that of CH3COONa.
The slow change of pH value before the equivalent point is due to the buffer action. Before the
equivalent point, there exist in the solution sodium acetate (a salt of a weak acid and a strong base) and
acetic acid (a weak acid). Because of the presence of sodium acetate, the dissociation equilibrium of
sodium acetate
CH3COOH ⇄ H+ + CH3COO- shifts to the left side, and [H+] decreases.
If an acid is added to this solution, the equilibrium shifts to the left since there is plenty acetate ion so
that the added acid is neutralized.
CH3COOH ⇄ H + + CH3COO-
To the contrary, if a base is added, acetic acid in solution is going to neutralize it. Thus,
CH3COOH + OH- ⇄ H2O + CH3COO-
Hence [H+] does not scarcely change
Titration of a weak base with a strong acid:
The titration of a weak base such as a 0.1 mol dm3 aqueous ammonia with a strong acid such as a 0.1
mol dm3 hydrochloric acid will be considered. In this case, pH value at the equilibrium point is slightly
smaller than that of the titration of a strong acid and a strong base. The curve is steep, however, and its
change is rapid near the equilibrium point. Accordingly titration is possible if a proper indicator with a
narrow indicator range.

Titration of a weak base (a weak acid) with a weak acid (a weak base): In this type of titration, the
titration curve fails to be steep at the equilibrium point, and the change of pH is slow. Hence no
indicator can exhibit a clear color change. This means that such types of titration are not possible.
Titration curve: titration of NH3 with HCl.

Buffer action: The buffer action is defined as an action to the effect that the pH of a solution scarcely
changes upon addition of an acid or of a base. A solution that has the buffer action is called the buffer
solution. Most of buffer solutions are composed of a combination of a salt of a weak acid and a strong
base, and a weak acid. The body fluid of living organism is a buffer solution, which will suppress a rapid
change of pH, which is harmful for living organism. The pH values of a buffer solution made of a weak
acid and its salt can be calculated by the following equation.
pH = pKa + log([salt]/[acid])
Following table gives some buffer solutions.
components range of pH
Phthalic acid + Potassium Phthalate 2.2--3.8
CH3COOH + CH3COONa 3.7--5.6
NaH2PO4 + Na2HPO4 5.8--8.0
H3BO3 + Na2B4O7 6.8--9.2
-3
Sample exercise: Three solutions (a), (b) and (c) contain a 0.10 mol dm propanoic acid
-5 -3 -3 -3
(propionic acid; pKa = 1.80 x 10 mol dm ) and (a) a 0.10 mol dm , (b) a 0.20 mol dm and
-3
(c) a 0.50 mol dm sodium propanoate, respectively. Calculate pH of three solutions.
(Answer (a) pH = 4.75 (b) pH = 5.05 (c) pH = 5.45)

Indicators
Such pigments as phenolphthalein and methyl orange used as an indicator for titration are themselves
weak acids (hereafter designated as HIn) and their colors are determined by [H+] of the solution. Thus,
HIn ⇄ H+ + In-
The concentration ratio of the indicator and its conjugate base which determines the color of the
solution is given below:
KI = [H+][In-]/[HIn], ∴ [In-]/[HIn] = KI/[H+]
where KI is the dissociation constant of the indicator. The range of pH where a remarkable change in
color of the indicator occurs is called the transition interval. The reason why there are so many
indicators available is due to the fact that pH values at the equivalent point vary depending on the
combination of an acid and a base. The key point of selecting an indicator should depend on whether a
remarkable change of color will take place near the equivalent point. In following table, some important
indicators and their transition intervals are listed.
Indicator transition interval(pH) color change
(acidic→basic)
thymol blue 1.2-2.8 red → yellow
methyl orange 3.1-4.4 red → yellow
methyl red 4.2-6.3 red → yellow
bromothymol blue 6.0-7.6 yellow → blue
cresol red 7.2-8.8 yellow → red
phenolphthalein 8.3-10.0 colorless → red
alizarin yellow 10.2-12.0 yellow → red
3
Sample exercise: A 25 dm solution containing sodium hydroxide NaOH and sodium carbonate
-3
Na2CO3 was titrated with a 0.100 mol dm hydrochloric acid with phenolphthalein as an
3
indicator. The color of the indicator disappeared when 30.0 dm of hydrochloric acid was added.
3
Methyl orange was added and the titration was continued. 12.5 dm of hydrochloric acid was
necessary before the color of methyl orange changed. Calculate the concentration of NaOH and
-3 -3 3 -3
Na2CO3 in the solution. (Answer [Na2CO3] = 1.25 x 10 mol/25.0 x 10 dm = 0.050 mol dm
-3 -3 3 -3
[NaOH] = 1.75 x 10 mol/25.0 x 10 dm = 0.070 mol dm )

Redox Titrations
Introduction:
In many important chemical reactions, electrons are transferred from atom to atom. We are surrounded
by these reactions, commonly called oxidation-reduction (or redox) reactions. The electric currents from
the batteries that power the computer, blasting a tunnel that trigger explosions, and the combustion of
natural gas in the heater all are due to some kind of redox reactions.
Zinc oxide is a white substance used as a pigment in rubber, sun-blocking ointments, and paint. It is
added to plastics to make them less likely to be damaged by ultraviolet radiation and is also used as a
dietary supplement. It can be made from the reaction of pure zinc and oxygen:
2 Zn (s) + O2 (g) → 2 ZnO (s)
In a similar reaction that occurs every time you drive your car around the block, nitrogen monoxide is
formed from some of the nitrogen and oxygen that are drawn into your car’s engine:
N2 (g) + O2 (g) → 2 NO (g)
This nitrogen monoxide in turn produces other substances that lead to acid rain and help create the
brown haze above our cities. When an element, such as zinc or nitrogen, combines with oxygen,
chemists say it is oxidized (or undergoes oxidation).
We also use the term oxidation to describe many similar reactions that do not have oxygen as a
reactant. This section explains the meaning of oxidation and shows why oxidation is coupled with a
corresponding chemical change called reduction. Oxidation, Reduction, and the Formation of Binary
Ionic Compounds ”Zinc oxide” is an ionic compound made up of zinc cations, Zn2+, and oxide anions, O2‒.
When uncharged zinc and oxygen atoms react to form zinc oxide, electrons are transferred from the zinc
atoms to the oxygen atoms to form these ions. Each zinc atom loses two electrons, and each oxygen
atom gains two electrons.
Overall reaction: 2 Zn(s) + O2 (g) → 2 ZnO (s)
What happens to Zn: Zn → Zn2+ + 2e‒ or 2 Zn → 2 Zn2+ + 4 e‒
What happens to O: O + 2e‒ → O2‒ or O2 + 4e‒ → 2 O2‒
As we know the transfer of electrons from metal atoms to nonmetal atoms is the general process for the
formation of any binary ionic compound from its elements. For example, when sodium chloride is
formed from the reaction of metallic sodium with gaseous chlorine, each sodium atom loses an electron,
and each chlorine atom gains one.
Overall reaction: 2Na (s) + Cl2 (g) → 2NaCl (s)
Na → Na+ + e‒ or 2 Na → 2 Na+ + 2e‒
Cl + e‒ → Cl‒ or Cl2 + 2e‒ → 2Cl‒
The reactions that form sodium chloride and zinc oxide from their elements are so similar that chemists
find it useful to describe them using the same terms. Zinc atoms that lose electrons in the reaction with

oxygen are said to be oxidized; therefore, when sodium atoms undergo a similar change in their reaction
with chlorine, chemists say they too are oxidized, even though no oxygen is present. According to the
modern convention, any chemical change in which an element loses electrons is called an oxidation.
The concept of reduction has undergone a similar evolution. At high temperature, zinc oxide, ZnO,
reacts with carbon, C, to form molten zinc and carbon monoxide gas.
ZnO (s) + C (s) → Zn (l) + CO (g) ∆
Bonds between zinc atoms and oxygen atoms are lost in this reaction, so chemists say the zinc has been
reduced. Like the term oxidation, the term reduction has been expanded to include similar reactions,
even when oxygen is not a participant. The zinc ions in zinc oxide have a +2 charge, and the atoms in
metallic zinc are uncharged. Thus, in the conversion of zinc oxide to metallic zinc, each zinc ion must
gain two electrons. According to the modern definition, any chemical change in which an element gains
electrons is called a reduction. Some people use a memory aid to remember what oxidation and
reduction mean in terms of the electron transfer. One device is the phrase oil rig which stands for
oxidation is loss (of electrons) and reduction is gain (of electrons). When an electric current passes
through molten sodium chloride, the sodium ions, Na+, are converted to uncharged sodium atoms, and
the chloride ions, Cl‒, are converted to uncharged chlorine molecules, Cl2. Because sodium ions gain one
electron each, we say they are reduced. Chloride ions lose one electron each, so they are oxidized.
2 NaCl (l) → 2Na (l) + Cl2(g) (Electric current)
oxidation: 2 Cl‒ → Cl2 + 2e‒
reduction: 2 Na+ + 2e‒ → 2Na
Electrons are rarely found unattached to atoms. Thus, for one element or compound to lose electrons
and be oxidized, another element or compound must be there to gain the electrons and be reduced. In
other words, oxidation (loss of electrons) must be accompanied by reduction (gain of electrons). In the
reaction that forms ZnO from Zn and O2, the uncharged zinc atoms cannot easily lose electrons and be
oxidized unless something such as oxygen is there to gain the electrons and be reduced. In the reaction
that converts NaCl to Na and Cl2, the chloride ions can lose electrons and be oxidized because the
sodium ions are available to gain the electrons and be reduced. By similar reasoning, we can say that
reduction requires oxidation. Because electrons are not likely to be found separated from an element
or compound, a substance cannot gain electrons and be reduced unless there is another substance that
is able to transfer the electrons and be oxidized. Oxidation and reduction take place together. Reactions,
in which electrons are transferred, resulting in oxidation and reduction, are called oxidation-reduction
reactions. Because the term oxidation-reduction is a bit cumbersome, we usually call these reactions
redox reactions. Even though the oxidation and reduction of a redox reaction take place simultaneously,
each making the other possible, chemists often have reason to describe the reactions separately. The
separate oxidation and reduction equations are called half-reactions. For example, in the reaction:
2Zn(s) + O2(g) → 2 ZnO (s) the oxidation half-reaction is 2 Zn → 2 Zn2+ + 4e‒ and the reduction
half-reaction is O2 + 4e‒ → 2 O2‒. Because the zinc atoms lose the electrons that make it possible for the
oxygen atoms to gain electrons and be reduced, the zinc is called the reducing agent. A reducing agent
is a substance that loses electrons, making it possible for another substance to gain electrons and be

reduced. The oxidized substance is always the reducing agent. Because the oxygen atoms gain electrons
and make it possible for the zinc atoms to lose electrons and be oxidized, the oxygen is called the
oxidizing agent. An oxidizing agent is a substance that gains electrons, making it possible for another
substance to lose electrons and be oxidized. The reduced substance is always the oxidizing agent. In the
reaction that forms sodium chloride from the elements sodium and chlorine, sodium is oxidized, and
chlorine is reduced. Because sodium makes it possible for chlorine to be reduced, sodium is the reducing
agent in this reaction. Because chlorine makes it possible for sodium to be oxidized, chlorine is the
oxidizing agent.
2 Na (s) + Cl2 (g) → 2 NaCl (s)
(reducing agent) (oxidizing agent)
Oxidation Half-reaction: 2Na → 2Na+ + 2e‒ Reduction Half-reaction: Cl2 + 2e‒ → 2Cl‒
Oxidation-Reduction and Molecular Compounds:

The oxidation of nitrogen to form nitrogen monoxide is very similar to the oxidation of zinc to form zinc
oxide.
N2 (g) + O2 (g) → 2 NO (g)
2 Zn (s) + O2 (g) → 2 ZnO (s)
The main difference between these reactions is that as the nitrogen monoxide forms, electrons are not
transferred completely, as occurs in the formation of zinc oxide, and no ions are formed. Nitrogen
monoxide is a molecular compound, and the bonds between the nitrogen and the oxygen are covalent
bonds, in which electrons are shared. Because the oxygen atoms attract electrons more strongly than
nitrogen atoms, there is a partial transfer of electrons from the nitrogen atoms to the oxygen atoms in
the formation of NO molecules, leading to polar bonds with a partial negative charge on each oxygen
atom and a partial positive charge on each nitrogen atom.
Because the reactions are otherwise so much alike, chemists have expanded the definition of
oxidation-reduction reactions and included partial as well as complete transfer of electrons. Thus
oxidation is defined as the complete or partial loss of electrons, reduction as the complete or partial
gain of electrons. The nitrogen in the reaction that forms NO from nitrogen and oxygen is oxidized, and
the oxygen is reduced. Because the nitrogen makes it possible for the oxygen to be reduced, the
nitrogen is the reducing agent. The oxygen is the oxidizing agent
N2 (g) + O2 (g) → 2 NO (g)
Oxidized; Reduced;
the reducing agent the oxidizing agent
Oxidizing agents might play a role in aging and a good healthy diet might slow the aging process.
Substances called antioxidants that are found in food react with oxidizing agents (such as hydrogen
peroxide) and thus remove them from our system. Vitamins C and E are antioxidants, and foods that
contain relatively high amounts of them are considered important in slowing aging problems

Oxidation number:
Phosphates, like ammonium phosphate, are important components of fertilizers used to stimulate the
growth of agricultural crops and to make our gardens green. Their commercial synthesis requires
elemental phosphorus, which can be acquired by heating phosphate rock (containing calcium
phosphate) with sand (containing silicon dioxide) and coke (a carbon-rich mixture produced by heating
coal). This method for isolating phosphorus, called the furnace process, is summarized in the first
equation below. The other equations show how phosphorus can be converted into ammonium
phosphate.
2 Ca3(PO4)2 + 6 SiO2 + 10 C → P4 + 10 CO + 6 CaSiO3
P4 + 5 O2 + 6 H2O → 4 H3PO4
H3PO4 + NH3 → (NH4)3PO4
Are these reactions oxidation-reduction reactions? Are electrons transferred?
Simply reading a chemical equation does not always tell us whether oxidation and reduction have
occurred, so chemists have developed a numerical system to help identify a reaction as redox. For redox
reactions, this system also shows us which element is oxidized, which is reduced, what the oxidizing
agent is, and what the reducing agent is. The first step in this system is to assign an oxidation number to
each atom in the reaction equation. As you become better acquainted with the procedure, you will gain
a better understanding of what the numbers signify, but for now, just think of them as tools for keeping
track of the flow of electrons in redox reactions. Oxidation numbers are also called oxidation states. If
any element undergoes a change of oxidation number in the course of a reaction, the reaction is a redox
reaction. If an element’s oxidation number increases in a reaction, that element is oxidized. If an
element’s oxidation number decreases in a reaction, that element is reduced. The reactant containing
the element that is oxidized is the reducing agent. The reactant containing the element that is reduced is
the oxidizing agent.
Assignment of Oxidation numbers:
To determine the oxidation number of an atom, use the following guidelines to assign oxidation
numbers to as many atoms as you can. (Following table provides a summary of these guidelines with
examples).
 The oxidation number for each atom in a pure element is zero.

 The oxidation number of a monatomic ion is equal to its charge.
 When fluorine atoms are combined with atoms of other elements, their oxidation number is ‒1.
 When oxygen atoms are combined with atoms of other elements, their oxidation number is ‒2,
with exception like in peroxides, H2O2, where their oxidation number is ‒1.
 The oxidation number for each hydrogen atom in a molecular compound or a polyatomic ion is +1.
If a compound’s formula contains one element for which you cannot assign an oxidation number using
the guidelines listed above, calculate the oxidation number according to the following rules.
 The sum of the oxidation numbers for the atoms in an uncharged formula is equal to zero.

 The sum of the oxidation numbers for the atoms in a polyatomic ion is equal to the overall
charge on the ion
Guidelines for Assigning Oxidation Numbers
Oxidation number Examples Exceptions
Pure element 0 The oxidation number None
for each atom in Zn,
H2, and S8 is zero
Monatomic ions charge on ion Cd in CdCl2 is +2. None
Cl in CdCl2 is ‒1.
H in LiH is ‒1.
Fluorine in the -1 F in AlF3 is ‒1. None
combined form
F in CF4 is ‒1
Oxygen in the -2 O in ZnO is ‒2. O in O is ‒1 in peroxides,
combined form H2O is ‒2. such as H2O2
Hydrogen in the +1 H in H2O is +1 H is ‒1 when
combined form combined with a
metal
Oxidation Numbers and Redox Reactions:

The following equations represent the reactions that lead to the formation of ammonium phosphate for
fertilizers. Determine the oxidation number for each atom in the formulas. Decide whether each
reaction is a redox reaction, and if it is, identify what element is oxidized, what is reduced, what the
oxidizing agent is, and what the reducing agent is.
a. 2 Ca3(PO4)2 + 6 SiO2 + 10 C → P4 + 10 CO + 6 CaSiO3
b. P4 + 5 O2 + 6 H2O → 4 H3PO4
c. H3PO4 + NH3 → (NH4)3PO4
Solution: The first step is to determine the oxidation number for each atom in the reaction. Let’s
consider the first equation above:
 Monatomic ion (Ca), oxidation number equal to its charge (+2)

 Combined oxygen, oxidation number −2 for pure elements (O),
 oxidation number zero for monatomic ion (C & P),
Because the sum of the oxidation numbers for the atoms in an uncharged molecule is zero, the
oxidation number of the carbon atom in CO is +2:
 (ox # C) + (ox # O) = 0
 (ox # C) + −2 = 0
 (ox # C) = +2

Using a similar process, we can assign a +4 oxidation number to the silicon atom in SiO2:
 (ox # Si) + 2(ox # O) = 0

 (ox # Si) + 2(−2) = 0
 (ox # Si) = +4
Calcium phosphate, Ca3(PO4)2, is an ionic compound that contains monatomic calcium ions, Ca2+, and
polyatomic phosphate ions, PO4 3‒. The oxidation number of each phosphorus atom can be determined
in two ways. The following shows how it can be done considering the whole formula.
 3(ox # Ca) + 2(ox # P) + 8(ox # O) = 0
 3(+2) + 2(ox # P) + 8(−2) = 0
 (ox # P) = +5
The oxidation number for the phosphorus atom in PO43‒ is always the same, no matter what the cation is
that balances its charge. Thus we could also have determined the oxidation number of each phosphorus
atom by considering the phosphate ion separately from the calcium ion.
 (ox # P) + 4(ox # O) = −3
 (ox # P) + 4(−2) = −3
 (ox # P) = +5
The silicon atoms in CaSiO3 must have an oxidation number of +4.
 (ox # Ca) + (ox # Si) + 3(ox # O) = 0
 (+2) + (ox # Si) + 3(−2) = 0
 (ox # Si) = +4
The oxidation numbers for the individual atoms in the first reaction are below.
2 Ca+23(P+5O-24)2 + 6 Si+4O-22 + 10C0 → P04 + 10 C+2O-2 + 6 Ca+2Si+4O-23
Phosphorus atoms and carbon atoms change their oxidation numbers, so the reaction is redox. Each
phosphorus atom changes its oxidation number from +5 to zero, so the phosphorus atom is reduced,
and Ca3(PO4)2 is the oxidizing agent. Each carbon atom changes its oxidation number from zero to +2, so
the carbon atoms are oxidized, and carbon is the reducing agent.
Now, let’s consider the second reaction:
P4 + 5 O2 + 6 H2O → 4H3PO4.
Pure elements (P & O) have oxidation number 0 while hydrogen and oxygen in a molecular compound
bearing oxidation number +1 and -2 respectively.
The following shows how we can determine the oxidation number of the phosphorus atom in H3PO4:
 3(ox # H) + (ox # P) + 4(ox # O) = 0
 3(+1) + (ox # P) + 4(−2) = 0
 (ox # P) = +5
The oxidation numbers for the individual atoms in the second reaction are below.

P04 + 5O02 + 6 H+12O-2 → 4 H+13P+5O-24

Phosphorus atoms and oxygen atoms change their oxidation numbers, so the reaction is redox. Each
phosphorus atom changes its oxidation number from zero to +5, so the phosphorus atoms in P4 are
oxidized thus P4 is the reducing agent. Each oxygen atom in O2 changes its oxidation number from zero
to −2, so the oxygen atoms in O2 are reduced thus O2 is the oxidizing agent.
Finally, let’s consider the third reaction.
H3PO4 + NH3 → (NH4)3PO4
The oxidation number of the nitrogen atom in NH3 is calculated below.
 (ox # N) + 3(ox # H) = 0
 (ox # N) + 3(+1) = 0
 (ox # N) = −3
We can determine the oxidation number of each nitrogen atom in (NH4)3PO4 in two ways, either from
the whole formula or from the formula for the ammonium ion alone (from previous reaction we found
that oxidation number of the phosphorus atoms in H3PO4 is +5).
 3(ox # N) + 12(ox # H) + (ox # P) + 4(ox # O) = 0
 3(ox # N) + 12(+1) + (+5) + 4(−2) = 0
 (ox # N) = −3
or
 (ox # N) + 4(ox # H) = +1
 (ox # N) + 4(+1) = +1
 (ox # N) = −3
The oxidation numbers for the individual atoms in this reaction are below.
H+13P+5O-24 + N-3H+13 → (N-3H+14)3P+5O-24
None of the atoms change their oxidation number, so the reaction is not redox
Exercise: In one part of the steel manufacturing process, carbon is combined with iron to form pig iron.
Pig iron is easier to work with than pure iron because it has a lower melting point (about 1130 °C
compared to 1539 °C for pure iron) and is more pliable. The following equations describe its formation.
Determine the oxidation number for each atom in the formulas. Decide whether each reaction is a redox
reaction, and if it is, identify what is oxidized, what is reduced, what the oxidizing agent is, and what the
reducing agent is.
2 C (s) + O2 (g) → 2 CO (g)
Fe2O3 (s) + CO (g) → 2Fe (l) + 3 CO2 (g)
2 CO (g) → C (in iron) + CO2 (g)

Types of Chemical Reactions

Combination Reactions: In combination reactions, two or more elements or compounds combine to
form one compound. Combination reactions are also called synthesis reactions. The following are
examples of combination reactions.
 2 Na (s) + Cl2 (g) → 2 NaCl (s)
 C (s) + O2 (g) → CO2 (g)
 MgO (s) + H2O (l) → Mg(OH)2 (s)
Two of the above combination reactions are also redox reactions. Guess which one is not.
Decomposition Reactions: In decomposition reactions, one compound is converted into two or more
simpler substances. The products can be either elements or compounds. For example, when an electric
current is passed through liquid water or molten sodium chloride, these compounds decompose to form
their elements.
Electric current 2 NaCl (l) → 2 Na (l) + Cl2 (g)
Electric current 2 H2O (l) → 2 H2 (g) + O2 (g)
Another example is the decomposition of nitroglycerin. When this compound decomposes, it produces
large amounts of gas and heat, making nitroglycerin a dangerous explosive.
4 C3H5N3O9 (l) → 12 CO2 (g) + 6 N2 (g) + 10 H2O (g) + O2 (g)
As is true of combination reactions, not all decomposition reactions are redox reactions. The following
equation represents a decomposition reaction that is not a redox reaction.
CaCO3 (s) → CaO (s) + CO2 (g)
Combustion Reactions: A log burns in the fireplace as a result of a combustion reaction, a redox reaction
in which oxidation is very rapid and is accompanied by heat and usually light. The combustion reactions
that you will be expected to recognize have oxygen, O2, as one of the reactants. For example, the
elements carbon, hydrogen, and sulfur react with oxygen in combustion reactions.
C (s) + O2 (g) → CO2 (g)
2 H2 (g) + O2 (g) → 2 H2O (l)
S8 (s) + 8 O2 (g) → 8 SO2 (g)
When any substance that contains carbon is combusted (or burned) completely, the carbon forms
carbon dioxide. When a substance that contains hydrogen is burned completely, the hydrogen forms
water. Therefore, when hydrocarbons found in natural gas, gasoline, and other petroleum products
burn completely, the only products are CO2 and H2O. The equations below represent the combustion
reactions for methane, the primary component of natural gas, and hexane, which is found in gasoline.
CH4 (g) + 2 O2 (g) → CO2 (g) + 2 H2O (l)
2 C6H14 (l) + 19 O2 (g) → 12 CO2 (g) + 14 H2O (l)

The complete combustion of a substance, such as ethanol, C2H5OH, that contains carbon, hydrogen, and
oxygen also yields carbon dioxide and water.
C2H5OH (l) + 3 O2 (g) → 2 CO2 (g) + 3 H2O (l)
When any substance that contains sulfur burns completely, the sulfur forms sulfur dioxide. For example,
when methanethiol, CH3SH, burns completely, it forms carbon dioxide, water, and sulfur dioxide. Small
amounts of this strong‑smelling substance are added to natural gas to give the otherwise odorless gas a
smell that can be detected in case of leaks
CH3SH(g) + 3 O2 (g) → CO2 (g) + 2 H2O (l) + SO2 (g)
Single-Displacement Reactions: In single‑displacement reactions, atoms of one element in a compound
are displaced (or replaced) by atoms from a pure element. These reactions are also called
single‑replacement reactions. All of the following are single‑displacement reactions.
Pure element displaces element in compound
Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
Cd (s) + H2SO4 (aq) → CdSO4 (aq) + H2 (g)
Cl2 (g) + 2 NaI (aq) → 2 NaCl (aq) + I2 (s)
Our model of particle behavior enables us to visualize the movements of atoms and ions participating in
single‑displacement reactions. For example, consider the first equation above, a reaction in which atoms
of zinc replace ions of copper in a copper sulfate solution. Because copper(II) sulfate is a water‑soluble
ionic compound, the CuSO4 solution consists of free Cu2+ ions surrounded by the negatively charged
oxygen ends of water molecules and free SO42‒ ions surrounded by the positively charged hydrogen ends
of water molecules. These ions move throughout the solution, colliding with each other, with water
molecules, and with the walls of their container. Now imagine that a lump of solid zinc is added to the
solution. Copper ions begin to collide with the surface of the zinc. When the Cu2+ ions collide with the
uncharged zinc atoms, two electrons are transferred from the zinc atoms to the copper (II) ions. The
resulting zinc ions move into solution, where they become surrounded by the negatively charged ends
of water molecules, and the uncharged copper solid forms on the surface of the zinc. Because the zinc
atoms lose electrons in this reaction and change their oxidation number from 0 to +2, they are oxidized,
and zinc is the reducing agent. The Cu2+ ions gain electrons and decrease their oxidation number from +2
to 0, so they are reduced and act as the oxidizing agent. The half reaction equations and the net ionic
equation for this reaction are below.
oxidation: Zn(s) → Zn2+(aq) + 2e‒
reduction: Cu2+ (aq) + 2 e‒ → Cu (s)
Net Ionic Equation: Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)

Complexometric Titrations
Introduction: The technique involves titrating metal ions with a complexing agent or chelating agent
(Ligand) and is commonly referred to as complexometric titration. This method represents the analytical
application of a complexation reaction. In this method, a simple ion is transformed into a complex ion
and the equivalence point is determined by using metal indicators or electrometrically. Various other
names such as chilometric titrations, chilometry, chilatometric titrations and EDTA titrations have been
used to describe this method. All these terms refer to same analytical method and they have resulted
from the use of EDTA (Ethylene diamine tetra acetic acid) and other chilons. These chilons react with
metal ions to form a special type of complex known as chelate.
Chilon Chelate
Metal ion + Complexing agent Metal-ion Indicators Complex ion
(analyte; Ligand
Metal co-ordination compound
Cation) Chelating agent
pM Indicators Metal complex
Sequestering agent
Chelate compound
Metal ions in solution are always solvated, i.e. a definite number of solvent molecules (usually 2, 4 or 6)
are firmly bound to the metal ion. However, these bound solvent molecules are replaced by other
solvent molecules or ions during the formation of a metal complex or metal coordination compound.
The molecules or ions which displace the solvent molecules are called Ligands. Ligands or complexing
agents or chelating agents can be any electron donating entity, which has the ability to bind to the metal
ion and produce a complex ion. An example of a complexation reaction between Cu (II) ion and four
ammonium molecules in an aqueous solution may be expressed by the following equation:
+2 +2
H2O OH2 4 NH3 H3N NH3
Cu Cu
H2O OH2 H3N NH3
Bonding in Complexes: The bonds are either ordinary covalent bonds in which the metal and the ligand
contribute one electron each, or co-ordinate bonds in which both electrons are contributed by the
ligand. Thus, the hexacyanoferrate ion may be considered to consist of three ordinary covalent bonds
and three co-ordinate bonds, although in the complex the bonds are identical hybrid bonds which have
been shown to be directed towards the apices of a regular octahedron.
CN-1 CN -3
CN
CN-1 CN-1 CN CN CN CN
Fe Fe Fe
CN CN CN CN CN CN
CN CN CN
(a) (b) (c)

The negative charge on the complex ion is equal to the total number of the negative groups minus the
valency of the metal ion. When neutral groups only are involved, the charge on the complex is positive
and is equal to the metal ion, e.g. [Cu (NH3)4]2+.
Werner’s Co-ordination Number: Werner (1891) first noticed that for each atom there were an
observed maximum number of small groups which can be accommodated around it. This number, which
is called Werner’s coordination number, depends purely upon steric factors and is in no way related to
the valency of the ion. Thus, although the valence shell of the elements of the third period is
theoretically capable of expanding up to 18 electrons, and that of the fourth to 32 electrons, there is, in
practice, a limit to the number of small groups which can be accommodated owing to limitations of
space around the ion. For example, in the [BF4]- ion, the octet is completed and the maximum co-
ordination number is reached, but in the [AlF6]- ion the outer shell contains 12 electrons and cannot
expand to the maximum number of 18 electrons since the maximum co-ordination number has been
reached. Within the limits imposed by Werner’s co-ordination number, there is a tendency for the
metal to attain or approach inert gas structure, and this is probably the driving force for complex
formation.
Classification of Ligands
1. Unidentate Ligands: Ligands that are bound to metal ion only at one place are called unidentate
ligands (one toothed). NH3, for example, is a unidentate ligand capable of complexing with cupric ions.
Halide ions, cyanide ions and NH3 are common examples of unidentate ligands. The formation of
complex Cu (NH3)42+ proceeds in the following steps:
Step 1 Cu2+ + NH3 Cu (NH3)2+
Step 2 Cu (NH3)2+ + NH3 Cu (NH3)22+
Step 3 Cu (NH3)22+ + NH3 Cu (NH3)32+
Step 4 Cu (NH3)32+ + NH3 Cu (NH3)42+
Considering the overall reaction:
Cu2+ + 4NH3 Cu (NH3)42+
2. Bidentate and Multidentate Ligands: Many ligands are known that contain more than one group,
capable of binding with metal ions. Such ligands are known as multidentate ligands or chelating agents.
They include bidentate ligands (2 donar atoms), tridentate ligands (3 donar atoms), quadridentate
ligands, etc.
Thus, ethylene diamine is an example of bidentate ligand. H2N-CH2-CH2-NH2. Ethylene diamine tetra
acetic acid (EDTA) is an example of multidentate ligand.
Chelate Compound or Chelate Complexes involving simple ligands, i.e., those forming only one bond are
described as coordination compound. A complex of a metal ion with 2 or more groups on a multidentate
ligand is called a chelate or a chelate compound. There is no fundamental difference between co-
ordination compound and a chelate compound except that in a chelate compound, ring influence the
stability of compound. Thus, a chelate can be described as a heterocyclic ring structure in which a metal

atom is a member of ring. The stability of a chelate is usually much greater than that of corresponding
unidentate metal complex.
Chelating agent: Ligands having more than one electron donating groups are called chelating agents.
The most effective complexing agent in ligands are amino and carboxylate ions. All the multidentate
ligands important in analytical chemistry contain the structure component as follows:
CH2COOH
N
CH2COOH
The solubility of metal chelates in water depends upon the presence of hydrophilic groups such as
COOH, SO3H, NH2 and OH. When both acidic and basic groups are present, the complex will be soluble
over a wide range of pH. When hydrophilic groups are absent, the solubilities of both the chelating
agent and the metal chelate will be low, but they will be soluble in organic solvents. The term
sequestering agent is generally applied to chelating agents that form water-soluble complexes with bi-
or poly-valent metal ions. Thus, although the metals remain in solution, they fail to give normal ionic
reactions. Ethylenediamine tetra acetic acid is a typical sequestering agent, whereas, dimethylglyoxime
and salicylaldoxime are chelating agents, forming insoluble complexes and used in gravimetric assays.
HOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COOH
EDTA
CH NOH
CH3 NOH
Salicylaldoxime
CH3 NOH Dimethylglyoxime
OH
Reagent EDTA: Disodium salt of EDTA is a water soluble chelating agent and is always preferred. It is
non-hygroscopic and a very stable sequestering agent (Ligands which form water soluble chelates are
called sequestering agents). EDTA has the widest general application in analyses because of the
following important properties:
1) It has low price. 2) The special structure of its anion which has 6 ligand atoms. 3) It forms strainless
five-membered rings.
Factors influencing EDTA reactions:
1) The nature and activity of metal ion. ‘
2) The pH at which the titration is carried out.
3) The presence of interfering ions such as CN-, Citrate, Tartrate, F- and other complex forming agents. ‘
4) Organic solvents also increase the stability of complex.

Nature and stability of metal complexes of Ethylene diamine tetra-acetic acid: Ethylene diamine tetra-
acetic acid forms complexes with complexes with most cations in a 1:1 ratio, irrespective of the valency
of the ion:
M2+ + [H2X]2- [MX]2- + 2H+
M3+ + [H2X]2- [MX]- + 2H+
M4+ + [H2X]2- [MX] + 2H+
where M is a metal and [H2X]2- is the anion of the disodium salt (disodium EDTA) which is most
frequently used. The structures of these complexes with di-, tri- and tetravalent metals contain three,
four and five rings respectively:
Effect of pH on complex formation: Ethylenediamine tetra-acetic acid ionizes in four stages (pK1=2.0,
pK2=2.67, pK3=6.16 and pK4=10.26) and, since the actual complexing species is Y4-, complexes will form
more efficiently and be more stable in alkaline solution. If, however, the solubility product of the metal
hydroxide is low, it may be precipitated if the hydroxyl ion concentration is increased too much. On the
other hand, at lower pH values when the concentration of Y4- is lower, the stability constant of the
complexes will not be so high. Complexes of most divalent metals are stable in ammonical solution.
Those of the alkaline earth metals, such as copper, lead and nickel, are stable down to pH 3 and hence
can be titrated selectively in the presence of alkaline earth metals. Trivalent metal complexes are usually
still more firmly bound and stable in strongly acid solutions; for example, the cobalt(III) edetate complex
is stable in concentrated hydrochloric acid. Although most complexes are stable over a fair range of pH,
solutions are usually buffered at a pH at which the complex is stable and at which the colour change of
the indicator is most distinct.
Colour of complexes: There is always a change in the absorption spectrum when complexes are formed
and this forms the basis of many colorimetric assays.
Stability of Complexes : The general equation for the formation of a 1:1 chelate complex, MX, is
M + X MX
where M is the metal ion and X the chelating agent.
Stability Constant (K) = [MX]/[M][X]
where [ ] represents activities. Increase in temperature causes a slight increase in the ionization of the
complex and a slight lowering of K. the presence of electrolytes having no ion in common with the

complex decreases K, whilst the presence of ethanol increases K, probably due to the suppression of
ionization.
Principle of Complexometric Titration: Many principles of acid-base titrations are used in
complexometric titration. In complexometric titration, the free metal ions disappear as they are
changed into complex ions. In acid-base titrations, the end point is marked by sudden change in pH.
Similarly, in EDTA titration, if we plot pM (negative log of metal ion concentration) v/s volume of titrant,
we will find that at the end point, the pM rapidly increases (Fig. 1). This sudden pM raise results from
removal of traces of metal ions from solution by EDTA.
Any method, which can determine this disappearance of free metal ions, can be used to detect end
point in complexometric titrations. End point can be detected usually with an indicator or instrumentally
by potentiometric or conductometric (electrometric) method.
There are three factors that are important in determining the magnitude of break in titration curve at
end point.
1. The stability of complex formed: The greater the stability constant for complex formed, larger
the charge in free metal concentration (pM) at equivalent point and more clear would be the
end point.
2. The number of steps involved in complex formation: Fewer the number of steps required in the
formation of complex, greater would be the break in titration curve at equivalent point and
clear would be the end point.
3. Effect of pH: During a complexometric titration, the pH must be constant by use of a buffer
solution. Control of pH is important since the H+ ion plays an important role in chelation. Most
ligands are basic and bind to H+ ions throughout a wide range of pH. Some of these H+ ions are
frequently displaced from the ligands (chelating agents) by the metal during chelate formation.
Equation below shows complexation between metal ion and H+ ion for ligand:
M2+ + H2-EDTA2- M-EDTA2- + 2H+
Thus, stability of metal complex is pH dependent. Lower the pH of the solution, lesser would be
the stability of complex (because more H+ ions are available to compete with the metal ions for
ligand). Only metals that form very stable complexes can be titrated in acidic solution, and
metals forming weak complexes can only be effectively titrated in alkaline solution.

Indicator Methods of End Point Detection: The end point in complexometric titrations is shown by
means of pM indicators. The concept of pM arises as follows:
If K is the stability constant,
K = [MX]/[M][X]
then, [M] = [MX]/[X]K
or log [M] = log [MX]/[X] – log K
and pM = log [X]/[MX] – pK
Therefore, if a solution is made such that [X] = [MX], pM = -pK (or pM = pK’, where K’ = dissociation
constant). This means that, in a solution containing equal activities of metal complex and free chelating
agent, the concentration of metal ions will remain roughly constant and will be buffered in the same
way as hydrogen ions in a pH buffer. Since, however, chelating agents are also bases; equilibrium in a
metal-buffer solution is often greatly affected by a change in pH. In general, for chelating agents of the
amino acid type (e.g., edetic acid and ammonia triacetic acid), it may be said that when [X] = [MX], pM
increases with pH until about pH 10, when it attains a constant value. This pH is, therefore, usually
chosen for carrying out titrations of metals with chelating agents in buffered solutions.
The pM indicator is a dye which is capable of acting as a chelating agent to give a dye-metal complex.
The latter is different in colour from the dye itself and also has a low stability constant than the chelate-
metal complex. The colour of the solution, therefore, remains that of the dye complex until the end
point, when an equivalent amount of sodium EDTA has been added. As soon as there is the slightest
excess of EDTA, the metal-dye complex decomposes to produce free dye; this is accomplished by a
change in colour. Metal indicators must comply with the following requirements-
 Compound must be chemically stable throughout the titration.
 It should form 1:1 complex which must be weaker than the metal chelate complex
 Colour of the indicator and the metal complexed indicator must be sufficiently different.
 Colour reaction should be selective for the metal being titrated.
 The indicator should not compete with the EDTA.
Mechanism of action of indicator: Let the metal be denoted by M, indicator by I and chelate by EDTA.
At the onset of the titration, the reaction medium contains the metal-indicator complex (MI) and excess
of metal ion. When EDTA titrant is added to the system, a competitive reaction takes place between the
free metal ions and EDTA. Since the metal-indicator complex (MI) is weaker than the metal-EDTA
chelate, the EDTA which is being added during the course of the titration is chelating the free metal ions
in solution at the expense of the MI complex. Finally, at the end point, EDTA removes the last traces of
the metal from the indicator and the indicator changes from its complexed colour to its metal free
colour. The overall reaction is given by:
MI + EDTA M-EDTA + I
(Colour of metal- (original color
indicator complex) of indicator)
Many compounds have been used as indicators (as shown Table-1):

Types of Complexometric Titrations

Complexometric titrations are of 4 types:
1. Direct Titration: It is the simplest and the most convenient method used in chelometry. In this
method, the standard chelon solution is added to the metal ion solution until the end point is detected.
This method is analogous to simple acid-base titrations. e.g.-calcium gluconate injection, calcium lactate
tablets and compound sodium lactate injection for the assay of calcium chloride (CaCl2.6H2O). However
it is slow complexation reaction and encounter interference due to presence of other ions. Analysis of
Cu, Mn, Ca, Ba, Br, Zn, Cd, Hg, Al, Thallium, Sn, Pb, Bi, Vanadium, Cr, Mo, Gallium, Fe, Co, Ni, and Pd is
possible with direct titration.
2. Back Titration: In this method, excess of a standard EDTA solution is added to the metal solution,
which is to be analyzed, and the excess is back titrated with a standard solution of a second metal ion.
e.g. - Determination of Mn. This metal cannot be directly titrated with EDTA because of precipitation of
Mn(OH)2. An excess of known volume of EDTA is added to an acidic solution of Mn salt and then

ammonia buffer is used to adjust the pH to 10 and the excess EDTA remaining after chelation, is back
titrated with a standard Zn solution kept in burette using Eriochrome blackT as indicator.
3. Replacement Titration: In this method the metal, which is to be analyzed, displaces quantitatively the
metal from the complex. When direct or back titrations do not give sharp end points, the metal may be
determined by the displacement of an equivalent amount of Mg or Zn from a less stable EDTA complex.
Mn+2 + Mg-EDTA-2 Mg+2 + Mn-EDTA-2
Mn displaces Mg from Mn EDTA solution. The freed Mg metal is then directly titrated with a standard
EDTA solution. In this method, excess quantity of Mg EDTA chelate is added to Mn solution. Mn
quantitatively displaces Mg from Mg EDTA chelate. This displacement takes place because Mn forms a
more stable complex with EDTA. By this method Ca, Pb, Hg may be determined using Eriochrome blackT
indicator.
4. Indirect Titration: This is also known as Alkalimetric titration. It is used for the determination of ions
such as anions, which do not react with EDTA chelate. Protons from disodium EDTA are displaced by a
heavy metal and titrated with sodium alkali.
Mn+ + H2X-2 MX (n-4) + 2H+
e.g. - Barbiturates do not react with EDTA but are quantitatively precipitated from alkaline solution by
mercuric ions as 1:1 complex. Elements like Na, K, Ag, Au, As, C, N, P, S, Cl, Br, I and F can be analysed by
this method
Method: Barbiturate to be analyzed is taken in a flask and heated with excess of mercury in alkaline
solution. When precipitated Hg-barbiturate complex is formed, it is filtered and dissolved in excess of
standard EDTA solution. The unreacted EDTA solution is then back titrated with a standard Zn solution.
Use of masking and demasking agents: Masking agents act either by precipitation or by formation of
complexes more stable than the interfering ion-EDTA complex.
a) Masking by Precipitation: Many heavy metals e.g. Co, Cu and Pb, can be separated either in the form
of insoluble sulphides using Sodium sulphide, or as insoluble complexes using thioacetamide. These are
filtered, decomposed and titrated with disodium EDTA. Other common precipitating agents are sulphate
for Pb and Ba, oxalate for Ca and Pb, fluoride for Ca, Mg and Pb, ferrocyanide for Zn and Cu, and 8-
hydroxy quinoline for many heavy metals. Thioglycerol (CH2SH.CHOH.CH2OH) is used to mask Cu by
precipitation in the assay of lotions containing Cu and Zn.
b) Masking by Complex formation: Masking agents form more stable complexes with the interfering
metal ions. The most important aspect is that the masking agent must not form complexes with the
metal ion under analysis. The different masking agents used are enlisted below:
 Ammonium fluoride will mask aluminium, iron and titanium by complex formation.
 Ascorbic acid is a convenient reducing agent for iron(III) which is then masked by complexing as the very
stable hexacyanoferrate(II) complex.
 Potassium cyanide reacts with silver, copper, mercury, iron, zinc, cadmium, cobalt and nickel ions to form
complexes in alkaline solution which are more stable than the corresponding edetate complexes, so that

other ions, such as lead, magnesium, manganese and the alkaline earth metals can be determined in their
presence.
 Potassium iodide is used to mask the mercury(II) ion as (HgI 4) for mercury. It can be used in the assay of
mercury(II) chloride.
Demasking:
It is the process in which the masked substance regains its ability to enter in a particular reaction. This
enables to determine a series of metal ions in one solution containing many cations.
Titration Selectivity, Masking and Demasking Agents
By using masking and demasking agents in complexometry, analysis of 3 metals, Cu, Cd and Ca can be
done by following method:
1. Direct titration of the mixture with the EDTA gives the sum of the 3 metals.
2. Cu and Cd may be masked with the addition of cyanide to the solution, leaving only Ca ion.
3. When formaldehyde or chloral hydrate is added to the cyanide containing mixture, only Cd is
demasked and the EDTA titrates the sum of Ca and Cd. In this manner, the concentration of
three ions is determined by 3 individual titrations.
Step 1: All three metals are titrated.
Ca Ca-EDTA
Cd + EDTA Cd-EDTA
Cu Cu-EDTA
Step 2: Only Ca is titrated.
Cu + Cyanide ion Cu-Cyanide complex
Cd + Cyanide ion Cd-Cyanide complex
Ca + Cyanide ion No reaction EDTA Ca-EDTA
Step 3: Cd and Ca are titrated.
Cd-Cyanide complex + HCHO Cd+
Demasking agent Free
Cu-Cyanide complex + HCHO No reaction
Cd Cd-EDTA
+ EDTA
Ca Ca-EDTA

Gravimetric methods of analysis

Gravimetric methods are quantitative methods that are based on determining the mass of a pure
compound to which the analyte is chemically related.
Classifications of Gravimetric methods
1-Precipitation gravimetry, the analyte is separated from a solution of the sample as a precipitate and is
converted to a compound of known composition that can be weighed.
2-Volatilization gravimetry, the analyte is separated from other constituents of a sample by conversion
to a gas of known chemical composition. The weight of this gas then serves as a measure of the analyte
concentration.
3-Electrogravimetry, the analyte is separated by deposition on an electrode by an electrical current. The
mass of this product then provides a measure of the analyte concentration.
Features or properties of Gravimetric Analysis
 Traditional Method.
 Cheap, easily available apparatus, simple to carry out.
 Slow, especially when accurate results are required.
 Wide range of sample concentrations (ng - kg).
 No calibration required (except for the balance).
 Accurate.
Precipitation Gravimetry
In precipitation gravimetry, the analyte is converted to a sparingly soluble precipitate. This precipitate is
then filtered, washed free of impurities, converted to a product of known composition by suitable heat
treatment, and weighed. For example, a precipitation method for determining calcium in natural waters.
The reactions are: 2NH3 + H2C2O4 2NH4+ + C2O4-2
Ca+2 (aq) + C2O4-2 (aq) CaC2O4 (s)
The precipitate is filtered using a weighed filtering crucible, then dried and ignited. The process converts
the precipitate entirely to calcium oxide. The reaction is:
CaC2O4 (s) Δ CaO (s) + CO (g) + CO2
After cooling, the crucible and precipitate are weighed, and the mass of calcium oxide is determined by
subtracting the known mass of the crucible. The calcium content of the sample is then computed.
Procedure for gravimetric analysis (Precipitation gravimetry)
The steps required in gravimetric analysis, after the sample has been dissolved, can be summarized as
follows:
1. Preparation of the solution
2. Precipitation
3. Digestion

4. Filtration
5. Washing
6. Drying or igniting
7. Weighing
8. Calculation
Properties of precipitates and precipitating reagents
Ideally, a gravimetric precipitating agent should react specifically or at least selectively with the analyte.
Specific reagents, which are rare, react only with a single chemical species. Selective reagents, which are
more common, react with a limited number of species.
Properties of good precipitates
1. Easily filtered and washed free of contaminants.
2. Very low solubility so that no significant loss of the analyte occurs during filtration / washing.
3. Unreactive with constituents of the atmosphere
4. Of known chemical composition after it is dried or, if necessary, ignited.
Particle size and filterability of precipitates
Why we prefer precipitates of large particles: Precipitates consisting of large particles are generally
desirable for gravimetric work because these particles are easy to filter and wash free of impurities. In
addition, precipitates of this type are usually purer than are precipitates made up of fine particles.
Factors that determine the particle size of precipitates: The particle size of solids formed by
precipitation varies enormously.
1-Colloidal suspensions
 whose tiny particles are invisible to the naked eye (10-7 _ 10-4 cm in diameter).
 Colloidal particles show no tendency to settle from solution
 not easily filtered.
2-Crystalline suspension
 particles with dimensions on the order of tenths of a millimeter or greater.

 The temporary dispersion of such particles of a tend to settle spontaneously,
 easily filtered.
Scientists have studied precipitate formation for many years, but the mechanist of the process is still not
fully understood. It is certain, however, that the particle size of a precipitate is influenced by such
experimental variables as precipitate solubility, temperature, reactant concentrations, and rate at which
reactants are mixed. The net effect of these variables can be accounted for, at least qualitatively, by
assuming that the particle size is related to a single property of the system called the relative super
saturations, where: relative super saturations = (Q – S) / S
in this equation, Q is the concentration of the solute at any instant and S is its equilibrium solubility.

Generally, precipitation reactions are slow, so that even when a precipitating reagent is added drop by
drop to a solution of an analyte, some s supersaturation is likely. Experimental evidence indicated that
the particle size of a precipitate varies inversely with the average relative supersaturation during the
time when the reagent is being introduced.
Thus, when (Q - S)/S is large, the precipitate tends to be colloidal, when (Q - S)/S is small, a crystalline
solid is more likely.
 High relative supersaturation means many small crystals (high surface area)
 Low relative supersaturation fewer, means larger crystals (low surface area)
Obviously, then, we want to keep Q low and S high during precipitation. Several steps are commonly
taken to maintain favorable conditions for precipitation or the experimental control of particle size:
1. Precipitate from dilute solution. This keeps Q low.
2. Add dilute precipitating reagents slowly, with effective stirring, this also keeps Q low. Stirring
prevents local excesses of the reagent.
3. Precipitate from hot solution. This increase S. the solubility should not be too great or the
precipitation will not be quantitative (with less than 1 part per thousand remaining). The bulk of
the precipitation may be performed in the hot solution, and then the solution may be cooled to
make the precipitation quantitative.
4. Precipitate at as low a pH as is possible to maintain quantitative precipitation. As we have seen,
many precipitates are more soluble in acid medium, and this slows the rate of precipitation.
They are more soluble because the anion of the precipitate combines with protons in the solution.
Colloidal Precipitates
Individual colloidal particles are so small that they are not retained by ordinary filters. Moreover,
Brownian motion prevents their settling out of solution under the influence of gravity. Fortunately,
however, we can coagulate, or agglomerate, the individual particles of most colloids to give a filterable,
amorphous mass that will settle out of solution.
Structure of Colloids
Colloidal suspensions are stable because all of the particles of the colloid are either positively or
negatively charged. Colloidal particles are very small and have a very large surface-to-mass ratio, which
promotes surface adsorption. (The process by which ions are retained on the surface of a solid is known
as adsorption).
As a precipitate forms, the ions are arranged in a fixed pattern. In AgCl, for example, there will be
alternating Ag+ and Cl- ions on the surface. While there are localized (+) and (-) charges on the surface,
the net surface charge is zero.
However, the surface does tend to adsorb the ion of the precipitate particle that is in excess in the
solution, for example, Cl- if precipitating Cl- with Ag+; this imparts a charge. (With crystalline
precipitates, the degree of such adsorption will generally be small in comparison with

particles that tend to form colloids.) The adsorption creates a primary layer that is strongly adsorbed
and is an integral part of the crystal. It will attract ions
of the opposite charge in a counter layer(counter-ion
layer) or secondary layer so the particle will have an
overall neutral charge. There will be solvent molecules
interspersed between the layers. Normally, the counter
layer completely neutralizes the primary layer and is
close to it, so the particles will collect together to form
larger sized particles; that is, they will coagulate.
However, if the secondary layer is loosely bound, the
primary surface charge will tend to repel like particles,
maintaining a colloidal state.
Coagulation of Colloids: Coagulation of a
colloidal suspension can often be
brought
1. by short period of heating to
decreases the number of
adsorbed ions and thus the
thickness, of the double layer.
2. Increase the electrolyte
concentration of the solution.
If we add ionic compound to a colloidal
suspension. The concentration of counter
– ions increases in the vicinity of each A colloidal silver chloride particle suspended in a solution of silver nitrate.
particle. The net effect of adding an
electrolyte is thus a shrinkage of the counter-ion layer.
Peptization of Colloids
Peptization is the process by which a coagulated colloid reverts to its original dispersed state.
Peptization is the reverse of coagulation (the precipitate reverts to a colloidal state and is lost). It is
avoided by washing with an electrolyte that can be volatized by heating.
Practical Treatment of Colloidal Precipitates
Colloids are best precipitated from hot. stirred solutions containing sufficient electrolyte to ensure
coagulation. The filterability of a coagulated colloid frequently improves if it is allowed to stand for an
hour or more in contact with the hot solution from which it was formed. This process is known as
digestion. Digestion is a process in which a precipitate is heated for an hour or more in the solution from
which it was formed (the mother liquor).
Crystalline Precipitates

Crystalline precipitates are generally more easily filtered and purified than are coagulated colloids. In
addition, the size of individual crystalline particles, and thus their filterability, can be controlled to a
degree.
Mechanism of Precipitate Formation
The effect of relative supersaturation on particle size can be explained if we assume that precipitates
form in two ways, by nucleation and by particle growth. The particles size of a freshly formed
precipitate is determined by the mechanism of predominates.
After the addition of the precipitating agent to the solution of the ion under analysis there is an initial
induction period before nucleation occurs. This induction period may range from a very short time
period to one which is relatively long, ranging from almost instantaneous to several minutes.
In nucleation, a few ions, atoms, or molecules (perhaps as few as four or five) come together to form a
stable solid. Often, these nuclei form on the surface of suspended solid contaminants, such as dust
particles. Further precipitation then involves a competition between additional nucleation and growth
on existing nuclei (particle growth).
 If nucleation predominates, a precipitate containing a large number of small particles results,

 If growth predominated, a smaller number of larger particles is produced.
We can summarized the precipitation mechanism
1) Induction period.
2) Nucleation.
3) Particle growth to form larger crystal
4) Adsorption.
5) Electrostatic.
Impurities in Precipitates
Precipitates tend to carry down from the solution other constituents that are normally soluble, causing
the precipitate to become contaminated. This process is called coprecipitation. In other wards,
coprecipitation is a phenomenon in which otherwise soluble compounds are removed from solution
during precipitate formation.
There are four types of coprecipitation:
1) surface adsorption,
2) mixed-crystal formation,
3) occlusion,
3. mechanical entrapment.
1- Surface adsorption
Adsorption is a common source of coprecipitation and is likely to cause significant contamination of
precipitates with large specific surface areas, that is, coagulated colloids.

Although adsorption does occur in crystalline solids, its

effects on purity are usually in-detectable because of
the relatively small specific surface area of these solids.
The net effect of surface adsorption is therefore the
carrying down of an otherwise soluble compound as a
surface contaminant. In order to minimizing adsorbed
impurities on colloids:
 Using digestion process to improve the purity.

 Washing a coagulated colloid with a solution containing a volatile electrolyte. The adsorbed
layers can often be removed by washing.
 Reprecipitation is effective way to minimize the effects of adsorption.
2- Mixed-crystal formation
Mixed-crystal formation ,one of the ions in the crystal lattice of a solid is replaced by an ion of another
element. For this exchange to occur, it is necessary that the two ions have the same charge and that
their sizes differ by no more than about 5%. This problem occur with both colloidal suspensions and
crystalline precipitates. Ex (Pb ion replace some of the barium ion). In order to minimizing this type of
coprecipitation:
 the interfering ion may have to be separated before the final precipitation step.
 a different precipitating reagent that does not give mixed crystals with the ions interested may
be used.
3- Occlusion
Occlusion is a type of coprecipitation in which a compound is trapped within a pocket formed during
rapid crystal growth. , material that is not part of the crystal structure is trapped within a crystal. For
example, water may be trapped in pockets when AgNO3 crystals are formed.
Occluded impurities are difficult to remove. Digestion may help some but is not completely effective.
The impurities cannot be removed by washing. Re-precipitation that go on at the elevated temperature
of digestion open up the pockets and allow the impurities to escape into the solution.
4- Mechanical entrapment
Mechanical entrapment occurs when crystals lie close together during growth. Here, several crystals
grow together and in so doing trap a portion of the solution in a tiny pocket.
Mechanical entrapment can be minimized when the rate of precipitate formation is low—that is under
conditions of low supersaturation. In addition, digestion is often remarkably helpful in reducing this
types of coprecipitation.

3-Classical Analytical Methods

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Chapter 3: Classical Analytical Methods Analytical Chemistry (Chem-2202)

CLASSICAL ANALYTICAL METHODS

3rd Version, May 17 Page 1

Concept of acids and bases

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H2O ⇄ H+ + OH- ; K = [H+][OH-]/[H2O]

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Lewis acid-base theory:

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Acid dissociation constants dissociation

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Titration curve: (a) Titration of HCl with

Titration of a weak acid with a strong base (curve b):

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Titration curve: titration of NH3 with HCl.

(Answer (a) pH = 4.75 (b) pH = 5.05 (c) pH = 5.45)

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Oxidation-Reduction and Molecular Compounds:

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 The oxidation number for each atom in a pure element is zero.

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Oxidation Numbers and Redox Reactions:

 Monatomic ion (Ca), oxidation number equal to its charge (+2)

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 (ox # Si) + 2(ox # O) = 0

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P04 + 5O02 + 6 H+12O-2 → 4 H+13P+5O-24

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Types of Chemical Reactions

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Types of Complexometric Titrations

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Cu-Cyanide complex + HCHO No reaction

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Gravimetric methods of analysis

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 particles with dimensions on the order of tenths of a millimeter or greater.

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 If nucleation predominates, a precipitate containing a large number of small particles results,

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Although adsorption does occur in crystalline solids, its

 Using digestion process to improve the purity.

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