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Quantitative analytical chemistry

I- Acid-Base:
Aqueous solutions of substances differ in their behavior when submitted to an electric
current. Some of them allow the current to pass, i.e. they conduct the electric current,
these are termed "electrolytes"; while other do not allow the current to pass, i.e. they
yield nonconducting solutions, and are called "nonelectrolytes". The first class
includes mineral acid, caustic alkalies and salts, while the second class is exemplified by
cane sugar, glycerin and ethyl acetate.
Pure water is a bad conductor of electricity, but when acid like HCl, a base such as KOH
or a salt like Na2SO4 is dissolved in water its conductivity is greatly improved. At the
same time, it is noticed that the solute decomposes by the passage of the electric current
into its components at the cathode and the anode. These components of the electrolyte are
called "ions".
Acids and bases:
According to the classical theory of Arrhenius all acids when dissolved in water dissociate
giving rise to hydrogen ions as positive ions. Bases, on the other hands, undergo dissociation
with the formation of hydroxyl ions [OH] as the only negative ions. The old definition of
both acids and bases was laid, therefore, on that observation. The acidity of a solution or its
basicity, can also be determined by measuring the amount of either hydrogen ions or hydroxyl
ions it contains, respectively. The degree of dissociation of the dissolved acid or base can be
used to calculate the concentration of the ions present in the solution.
According to the degree of dissociation acids can be divided into two groups:
A) Strong acids, having a high degree of dissociation and
B) Weak acids, which are feebly dissociated.
Similarly strong bases have a high degree of ionisation. While weak bases dissociate feebly.
Apart from monobasic acids, which dissociate in one stage, polybasic acids dissociate in
consecutive stages. Sulphuric acid, for example, dissociate in two stages, in the first stage one
hydrogen is almost completely ionised, thus:
H2SO4 H+ + HSO4
In the second stage, the other hydrogen is only partially ionised.
Phosphoric acid dissociates in three stages:
H3PO4 H+ + H2PO4
1

H2PO4 H+ + HPO42
HPO42 H+ + PO43
These stages are called the primary, secondary and tertiary dissociations, respectively, the
first stage is the most complete while the others are smaller and smaller.
The equilibrium, which exists in a dilute solution of an acid like acetic acid (HAc) at
constant temperature, is
HAc H+ + Ac
Applying the law of mass action
K

[H ] x [Ac ]
[HAc]

Where K is called "dissociation" "ionisation" or "acidity constant"


The stronger the acid, the larger the acidity constant. For a completely ionised acid, the
acidity constant is assumed to be 1, and the mass action law does not help much in this case.
Buffers are mixtures of compounds which by their presence in solution, resist changes in pH
caused by addition of small amounts of acid or base; or upon dilution. The resistance to a
change in pH is known as buffer action.
The end point in neutralization reactions can be detected by including in the reaction medium
a third material which shows a definite change in some physical character when a given pH
value is reached. This third material is the indicator.
Two theories have been advanced to account for the change of the colour of neutralization
indicators according to the acidity or alkalinity of the medium.
1) Ostwald Theory or Ionisation Theory
Neutralization indicators are either weak acids or weak bases. when put in a solution, will
ionise to a limited extent and a state of equilibrium will exist between the undissociated
molecule and its ions as follows:
H In H+ + In (acid indicators)
In OH In+ + OH (basic indicators)
The colour of the undissociated molecule is different from that the ions, for example;
phenolphthalein is an acid indicator, which behaves in solution as follows:
H In H+ + In
(colourless)
(red)

Methyl orange is a basic indicator, which can be represented by the following


equilibrium in solution:
In OH In+ + OH
(yellow)
(red)
Generally the net colour of the indicator will depend upon the ratio of the
concentrations of the ionised and unionised indicator which is, in turn, decided by the
hydrogen ion concentration in the medium.
Certain objections have been raised against this simple theory of Ostwald. For example,
when a small quantity of alkali is added to phenolphthalein solution it turns red, but addition
of more alkali yields a colourless solution while, as expected from the theory; the colour
should increase.
Another objection to the ionisation theory is the observed slow colour change in certain
instances while ionic reactions are usually instantaneous. A number of acid base
indicators show their characteristic colour changes in nonaqueous media where
ionisation is markedly depressed.
2 ) The chromophoric theory:
Acid base indicators are dyes which contain one or more groups of atoms loosely bound to
each other forming an unsaturated group fundamentally responsible for the colour, called
chromophoric group. Examples of such colour confirming groups are the azo ( N=N),
nitro (NO2) or nitroso (N=O) groups or conjugated double bonds. These groups confer
on the molecule the ability to absorb certain radiations from those composing the visible light.
The colour of the compound depends upon the type of radiations it absorbs. On the other
hand, if the substance absorbs radiations in the ultraviolet region and does not absorb any of
the coloured radiations composing the visible light it will appear colourless.
In the most dyes there are also other groups, usually of the phenolic or amino types, which
increase the effect of the chromophores, and are called auxochromes. In explaining the effect
of such auxochromes, it was suggested that they are sufficiently polar to set the molecule in
resonance between two or more hybrids. This resonance confers greater mobility on the
electrons of the chromophoric system with consequent increase in the intensity of light
absorption and displacement of the absorption maxima to longer wavelengths.
3

Bernthsen and Friedlander explained the behavior of phenolphthalein in acid and in basic
solutions as follows:
The compound had different structures in each medium. In acid solutions phenolphthalein
possessed a lactone structure which is colourless, while the red salt formed by alkalies
contained a chromophore quinone group. Hence the colour transformation was accompanied
by change in structure.
Hantzsch proposed that indicators being either acids or bases would either donate or accept
protons, respectively. This is naturally accompanied by rearrangement of the bonding in the
molecule leading to some different structure having a different absorption maximum and
consequently a different colour.
The theory is really a completion to Ostwald theory. Hantzch regarded the colour change not
to be due to the ionisation alone, but also some tautomeric changes in the structure
participate in the process. He showed that an indicator is able to exist in two forms one of
them is a non electrolyte (pseudo acid and pseudo base) the other form is a true acid or a
true base which has a high conductivity and ionisation constant. He called then aci and
baso forms, respectively, and suggested that these true forms are alone able to ionise and
that the colour of the aci forms (or baso forms) is different from that of the pseudo ones.
The whole system can be represented by the following equilibrium:
Pseudo form True form

H+ + In

The following examples may be given to illustrate the above concepts:

The colour changes of some common indicators:


Phenolphthalein is an example of all phthalein indicators. This compound is prepared by
fusing phenol with phthalic anhydride in presence of a dehydrating agent.

HO

OH

Pseudo-form (I)
Colourless, pH Below 7

C O
CO

H
O

H2O

OH

pH 8 - 10

HO

O
C

COO

+H

OH

(II)
Aci-form

COO

O
C

H2O

O
+H

C
COO

COO

Quinonoid ph.ph, resonance hybride of the two


tautomeric forms.
Red in colour, pH 8 - 10

O
C OH
COO

Tribasic salt of ph.ph. devoid of quinonoid chromophore.


Colourless pH above 12

It has a pink colour in alkaline solutions of pH greater than 8.3 but becomes colourless in
acid solutions as well as in solutions, which contain a large excess of alkali hydroxide. It is a
tribasic acid, and it has been proved that its colourless forms are due to free phenolphthalein
and to the ion of tribasic salt.

Methyl orange is the free sulphonic acid of dimethylaminoazo benzene or its sodium or
ammonium salt. It is prepared by coupling diazotised sulphanilic acid with dimethylaniline
5

In the free state, the indicator is obtained in the form of reddish violet scales, soluble in
considerable amount of water.
The colour change which takes place between pH 3.1 4.4 can be explained as follows:
N

Benzenoid structure, yellow,


due to azo group - N=N-

SO3H

N
H3C

CH3

H
OH

OH

Methyl Orange
H

SO3

N
H3C

O2- S-O
CH3

N
H3C

Alkaline colour
Yellow, pH 4.4

CH3

Acidic colour
Red pH 3.3

The yellow substance has a benzenoid structure and the colour is due to the azogroup (
N=N). It has also a sulphonic acid group, which imparts acid properties to the molecule.
Addition of an alkali would remove the hydrogen ions and shift the balance of equilibrium to
the left (yellow benzenoid structure). On the other hand, addition of an acid depresses the
ionisation of the sulphonic acid group and favors the formation of an inner salt having a
different chromophoric center, the quinone group with different (red) colour.

Colorimetric
Colorimetricdetermination
determinationofofpH
pH
Two methods are generally used for the determination of pH of a solution; an
electrochemical method and a colorimetric one.
The colorimetric method usually uses a neutralisation colour indicators. Among the
different colorimetric methods commonly used for the determination of pH value are: buffer
solution, comparator and hydrogen ion colorimeter methods.
6

5.1. Buffer solution method:


In this method, an approximate determination of pH of the solution is first made by the use
of a universal indicator. This would give the pH of the solution within one or two units, and
would also indicate the range of pH of the buffer solutions required for comparison.

A series of buffer solutions is then chosen, differing successively in pH about 0.2. Equal
volumes of the buffer solutions are placed in a series of test tube of colourless glass having
approximately the same dimension. A small equal quantity of a suitable indicator, for the
particular pH range of the buffer solutions is added to each tube. A series of different colour
shades is obtained, each shade corresponding to a particular pH.

An equal volume of test solution, in a test tube similar to those used for the buffer solutions
series, is treating with a volume of the indicator. Equal to that added to each buffer solution
tube. The colour produced is compared with that of the coloured standard buffer solutions.
When a compete match is found, the test solution and the corresponding buffer solution have
the same pH.
For turbid or slightly coloured solutions the direct comparison method given above can no
longer applied. Interference due to the coloured substance can be eliminated in a simple way
by a device due to Walpole.

Walpole technique for matching turbid or coloured solution

A,B,C and D in the above figure are glass cylinders with plane bottoms standing in a box
which is painted dull black on the inside. A contains the coloured test solution, [i.e. test
solution + indicator], B contains an equal volume of water, C Contains a solution of
known strength for comparison, [i.e. buffer solution + indicator], D contains an equal
volume of the turbid or coloured test solution without any added indicator.
By this Walpole technique, the colour or turbidity of the unknown solution is compensated.

5.2. Comparator or permanent colour standard method:


In this technique comparison is made with a series of permanent glass of certain colours,
which match with those of a universal indicator at different pH values. Certain numbers,
mostly 9, of glass colour standards are fitted into a disc, each one provides different colour at
certain varying pH values. The disc fits into a comparator which is furnished with
compartments to receive small test tube or cuvette and is also provided with an opal glass
screen. The disc moves in the comparator, where each colour standard passes in turn in front
of an aperture through which the solution in the cuvette containing a suitable amount of the
used universal indicator. The matching of the colours indicate the pH value.

5.3. Hydrogen ion colorimeter method:


Using the principle of the Hendersons equation of the indicator, Gillespie developed a
special colorimeter for measuring the pH values of solutions.
The colorimeter consists of the vessels A,B,C,D and E, made of good transparent glass
with plane bottoms.

pH Colorimeter

A and C are fixed vessels, while B is indicated on a scale, the zero point of which
corresponds to the position of B when B and C are in contact, and the 100 point
corresponds to the position when B is in contact with A. Vessels B and C have the
same amounts of a suitable indicator in the same concentration and amounts of an acid or a
base respectively. The position of B will determine the ratio of the two forms of the
indicator as the sum of the amounts taken in B and C. Vessels A and D are fixed and
having an auxilliary functions to compensate if the solution is turbid or slightly coloured as in
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the case of Walpole technique. B moves until the matching of the two fields, the combined
depth of the acidic and alkaline colours remains the same but their ratio is changed.
Determine the pH value from the Hendersons equation:
pH = pKind. + log

(basic colour)
(acid colour)

or
pH = pKw pKind. + log

(basic colour)
(acid colour)

The pKw and pKind. are constant values, while the ratio

(basic colour)
is the ratio obtained
(acid colour)

from the determination.


The pH value can be read from tables, or can be directly obtained by applying Hendersons
equation for either acidic or basic indicators.

Titration of sodium carbonate:


Sodium carbonate is typically a salt of strong base (sodium hydroxide) with a very weak acid
(carbonic acid, pKa = 6.38). the salt is hydrolysable and its aqueous solution reacts alkaline
(pH of 0.1 N solution is 11.7). Also, it can be estimated by displacement titration with a
mineral acid, like hydrochloric acid. In addition carbonic acid is a dibasic acid and both its
replaceable hydrogen atoms are so weakly ionised that both its normal and acid salts can be
titrated by displacement. Since the two ionisation constants of carbonic acid are sufficiently
far from one another, the titration of sodium carbonate takes place in two stages as follows:
Na2CO3 + HCl = NaHCO3 + NaCl
NaHCO3 + HCl = H2CO3 + NaCl
The pH at the first equivalence point is [(pK1 + Pk2)] 8.35, phenolphthalein or thymol blue
is a suitable indicator. However, the end point of this first titration stage is not at all sharp; a
solution of HCO3, ia a good buffer and the pH thus changes only gradually. This situation is in
general true of the titration of the di or trivalent anion of a very weak di- or tri- basic acid.
At the end point of the first stage sodium carbonate is formed and, being also a salt of the
strong base NaOH and the very weak acid HCO3, it hydrolyses giving an alkaline solution
with pH about 8.3. this new solution can also be titrated by displacement with hydrochloric
acid until, at the end point, there will be formed the neutral sodium chloride and the very
10

weak acid carbonic acid in the free state and the pH of the solution drops to about 3.8; in the
middle of methyl orange colour change interval.
Therefore, sodium carbonate may be titrated with standard acid;
a) To the bicarbonate stage (half neutralisation), thus consuming one equivalent of
acid, using phenolphthalein as indicator.
Na2CO3 + HCl = NaHCO3 + NaCl
b)

or

Until all the carbonic acid displaced (complete neutralisation), thus consuming two
equivalents of acid, using methyl orange as indicator.
Na2CO3 + 2HCl = 2NaCl + H2CO3

Suitable indicators for complete neutralisation are also congo red, methyl orange and
bromophenol blue.
Practical application of the above displacement titration using double indicator technique
are in the analysis of a mixtures containing sodium carbonate together with sodium
hydroxide, sodium bicarbonate and borax.
a) Mixture of sodium carbonate and sodium hydroxide:Titrations with standard acid, using phenolphthalein, would give a colour change of pink to
colourless only. When sodium hydroxide has been neutralised and the sodium carbonate has
been half neutralised (i.e. converted to NaHCO3). The use of creasol red plus thymol blue in
place of phenolphthalein also gives better accuracy.
Methyl orange, and better bromophenol blue, would give a yellow colour to the solution, and
the additional volume of acid required to change the colour to red would be that required to
complete the reaction with NaHCO3. in this case, the aditiononal volume of acids requried for
the methyl the methyl orange end point is less than the volume required for the
phenolphthalein end point.

II- Redox:
Chemical reactions which involve oxidation reduction are more widely used in quantitative
analysis than precipitation, complexformation, acid base reactions. This attributed to fact
that a large number of elements can exist in more than one oxidation state. Oxidation
11

reduction (redox) reactions involve the loss and gain of electrons and frequently many
hydrogen ions are also involved.
Oxidation is the loss of electrons by an atom, molecule or ion; while reduction is the gain of
electrons by such particles. For a redox reaction to take place, there must be an oxidising
agent to accept the electrons given by the reducers. The oxidised form and the reduced form
of a substance (the redox conjugated pair), may be regarded as inter convertible is called a
half reduction:
Reduction form electrons = oxidized form
The sum of two half reactions constitutes the redox reaction, e.g. the oxidation of ferrous
ion by ceric ion:
Fe2+ e = Fe3+ (oxidation half reaction)
Ce4+ + e = Ce3+ (reduction half reaction)
Adding
Fe2+ + Ce4+ = Fe3+ + Ce3+ (redox reaction)
In this redox reaction (left to right), ferrous ion is the reducer (donor of electrons), it loses
an electron and becomes oxidised to ferric ion, while ceric ion is the oxidiser (acceptor of
electrons), it accepts an electrons and becomes reduced to cerous ion. This transfer of
electrons can be expected to continue until the concentrations of the ions involved achieves
corresponding to equilibrium for the redox reaction.

1.1 The oxidation number:


Oxidation numbers are arbitrary numbers assigned to atoms to indicate their states of
oxidation. Any change in these numbers can be attributed to a loss or gain of electrons.
Although it frequently happens that the oxidation number assigned to an atom corresponds to
its valence number, yet in several cases the oxidation numbers turn out to the entirely different
from known valences, they have plus or minus signs associated to them and are sometimes
fractional. The following rules are to be followed in assigning oxidation numbers.

1. Any uncombined atom (e.g. Na) or any atom in a molecule of an element (e.g. H2) is
assigned an oxidation number of zero.

12

2.

The oxidation number of a simple, monoatomic ion is the same as the charge on
the in (the electrovalence number). Thus the oxidation number of Zn2+ is 2+ and that
of Cl is 1.

3. The oxidation number of hydrogen ion is 1+ in all its compounds; except the metallic
hydrides (e.g., NaOH), in which hydrogen has an oxidation number of 1.
4. The oxidation number of oxygen is always 2, except in peroxides (e.g., Na2O2), in
which oxygen has an oxidation number of 1
5. In a complex ion, the algebraic sum of the oxidation numbers of the constituent
atoms must equal the charge on the ion. For example, ferrocyanide ion, Fe(CN)64
has a charge of 4 ; and since the oxidation number of ferrous ion is 2+, the
oxidation number of each cyanide radical is 1 (total of 4 for the four cyanide
radicals)
6. In a neutral molecule, the algebraic sum of oxidation number of the constituent
atoms must add up to zero (because the molecule is electrically neutral). Thus in a
molecule of NaCl, the oxidation number of sodium is 1+ and that of chloride is 1.
7. Oxidation numbers are sometimes fractionals. Thus, the oxidation number of sulphur
in sodium tetrathionate, Na2S4O6. is 2 + ; and the oxidation number of crbon in
butane , C4H10 is 2 .

Electrode potentials:
If a metal plate is dipped into water, processes occur at the metal surface resulting in the
formation of what is known as an electric double layer.
Under the action of the polar water molecules the metal ions are torn out of its crystal lattice
into the water. As a result, the metallic surface becomes negatively owing to the electrons
remaining in the metal, while the layer of water becomes positively charged due to the ions
which have passed into solution the metallic ions do not spread into the bulk of the liquid, but
concentrate around the surface of the metal, being hold there by its charge. An electric double
layer forms on the surface of the metal and a dynamic equilibrium is set up between the metal
and the solution, corresponding to the definite difference in potentials. As metals differ in
ability to lose ions to the solution, the difference of potentials thus caused will evidently vary
from metal to metal.
13

A similar phenomenon is observed when a metal plate is dipped into a solution of a salt of
that metal. The increased concentration of metallic ions in the solution reduces the ability of
metallic ions to pass from the plate into solution, equilibrium is reached at a smaller potential
difference between the metal and the solution. Metals having a low ability to lose their ions to
the solution for e.g. gold, silver, platinum etc. may take up ions from the solution thus
acquiring a +ve charge.
The equilibrium potential difference established at the boundary between a metal and
solution of its readily soluble salt is called electrode potential. There are two major factors
that determine the electrode potential. The first is the electrolytic solution pressure of the
element, which is the tendency of an active element to send its ions into solution. At a given
temperature and pressure this is a characteristic constant for an element. The second is the
ionic pressure, which is the activity of the dissolved ions of the element, ions which in turn
varies with their concentration at constant temperature.
The dependence of the equilibrium potential of an electrode on these two factors is expresses
by the Nernst equation.
The potential established between a metal and its ions can be calculated from the equation
formulated by Nernst in 1889 as follows:
A nM
RT
E t Eo
log e
nF
AM
This is called Nernst equation where:
the equation can be simplified by introducing the known values of R and F and converting the
natural logarithm to common logarithm it then becomes:
An
0.0001982 T
E t Eo
log M
n
AM
since the activity of massive metal or any solid phase is taken as unity, and the activity of
the metal ions equals its molar concentration being a dilute solution.
Et Eo

0.0001982 T
log (M n )
n

For a temperature of 25oC (T = 298o);


E

25 o C

Eo

0.0591
log (M n )
n

For a non metal, which yields negative ions. The equation becomes:

14

E t the oxidation potential of the redox electrode at T

o
E a constant value, characteristic for every redox system

called "standard electrode potential"

R gas constant 8.314

o
T absolute temperature of the system which at 25 C

25 273 298 o C

F Farady 96500 coulombs

log natural logarithm, that is to the base 2.718, and is

convertable to common logarithms, that is to the

base 10, by multiplying by 2.303

n valency of the ions.

A M activity of the metal ions in solution.

A activity of the metal.

25 o C

Eo

0.0591
log (M n )
n

if (Mn+) and (Mn) are equal to one molar then its logarithm will be zero and the second part
of the equation will be equal to zero and E is equal to Eo that is equal to the standard (or
normal) electrode potential of the metal system.

Detection
Detectionofofend
endpoint
pointininredox
redoxtitrations
titrations
1- No indicator :
In some cases, it is possible to do the titration without the use of any indicator, if the
colour of the titrating solution undergoes a sharp enough change at the equivalence point.
Such titration are possible when various reducing agents are oxidised by permanganate in
acid solution. We known that the purple violet colour of permanganate disappears owing
to reduction to the almost colourless Mn2+. When all the reducing agent has been oxidised
single excess drop of permanganate colourless the whole solution a distinct pink.
Similarly, titrations with iodine solution may be performed without the use of indicators
as a result of its reduction to iodine ions. However, since the colour of iodine solutions is
not very deep, titrations with iodine solution are beast done in presence of an indicator
starch that gives an intense blue colour even with very small amounts of free iodine. The
use of starch is based on its ability to form a blue adsorption compound with iodine
(unrelated to the oxidising properties of iodine)
15

2. External indicator:
The best known example is the spot test method for the titration of ferrous iron with
potassium dichromate. Near the equivalence point, drops of solution are removed and
brought into contact with dilute freshly prepared potassium ferricyanide solution on a
spot plate. The end point is reached when the drop first fails to give a blue coloration.
Another example is provided by the titration of zinc ions with standard potassium
ferrocyanide solution; here a solution of urnayl acetate or nitrate is the external indicator,
and titration is continued until a drop of the solution just imparts a brown colour to the
indicator. External indicators are gradually being superseded by the more satisfactory
internal oxidation reduction indicators.
3. Inetrnal redox indicator:
An oxidation reduction indicator should mark the sudden change in the oxidation potential
that occurs in the neighbor hood of the equivalence point in an oxidation reduction
titration (see titration curves). Redox indicator change colour when the oxidation potential
of the titrated solution reaches adefinite value. Redox indicator is a compound which has
different colours in the oxidised and reduced forms.
Inox + n e

Inred.

The oxidation and reduction of the indicator should be reversible, the leucocompounds
obtained on reduction are usually colourless, and are converting by oxidation into the
coloured dyes
Inox + n e

Inred.

Applying Nernst equation:

E Eo

0.0591
n

log

[In ox ]
[In red ]

Here, Eo is the standard oxidation potential of the indicator system i.e. potential where
[Inox] = [Inred]
Upon addition of 1 2 drops of a redox indicator to a solution of reducing or oxidising
agent, the concentration of the oxidised and reduced forms of the indicator will be in a
ratio corresponding to the oxidation potential of the solution. The solution acquire the
colour corresponding to the that ratio. If the solution is now titrated with an oxidizing or
reducing agent, the oxidation potential E changes. The [Inox] / [Inred] ratio alters

16

accordingly. However, not every change in this ratio corresponds to a colour change
perceived by the eye. As in acid base indicators colour change may be detected when:

[In ox ] 1 10
or
[In red ] 10 1
hence;
E Eo

E Eo

0.0591
n

log

1
10
or
10
1

0.0591
n

Redox
Redoxreaction
reactioninvolving
involvingiodine
iodine
3.1 Iodine iodide system
The redox system I2/ 2I has a standard oxidation potential of + 0.535 volt. This
intermediate position makes the system open to oxidation by stronger oxidizing agents at the
top of list such as MnO4 (Eo = 1.5). Cr2O72 (Eo = + 1.3), ClO3 (Eo + 1.45), IO3 4 (Eo = +
1.2) etc; the iodide ion being converted into iodine element:
Thus:
2 MnO4 + 16 H+ + 10 I = 2 Mn2+ + 8 H2O + 5 I2
Cr2O72 + 14H+ + 6 I = 2 Cr3+ + 7 H2O + 3 I2
ClO3 + 6H+ + 6I = Cl + 3H2O + 3 I2
H2O2 + 2 H+ + 2 I = 2 H2O + I2
NO2 + 2H+ + 2 I = NO + H2O + I2
Cl2 + 2I = 2 Cl + I2
And so on,
On the other hand, systems with low oxidation potentials like Sn4+/Sn2+, SO42 / SO32,
S4O62 /2S2O32 are easily oxidized with iodine:
SO32 + I2 +H2O = SO42 + 2 H+ + 2 I
2S2O32 + I2 = S4O62 + 2 I
Sn2+ + I2 = Sn4++ 2 I
Iodine is a weak oxidizing agent, and iodide ion a fairly strong reducing against since the
half cell e.m.f. For the reaction:
2 I I2 + 2 e

17

Eo = 0.54

In the development of analytical chemistry several factors led to an early utilization of


iodine methods. They are
1- a sensitive indicator, starch, has long been known, and
2- a reagent, sodium thiosulphate, is available for quantitative titration of free iodine,
because of these conditions a large number of analytical methods has been developed
about the iodine iodide ion equilibrium.
There are two types of iodine methods, direct and indirect. In the first, known as the
iodimetric method, iodine solutions are used for titration of reducing agents, which can be
quantitatively oxidized at the equivalence point. The number of such reactions is limited
because iodine is itself a weak oxidising agent; further, most of these determinations can
today be better done by some other method than the use of iodine. Thiosulphate alone, of the
common reducing agents must be determined by oxidation with iodine. It happens that the
stronger oxidizing agents give side reactions with thiosulphate, whereas iodine oxidises it
quantitatively to tetrathionate ion S4O62. Some of the oxidations which can be well done by
iodine are represented in the following equations:
H2S + I2 = 2 H+ + S + 2 I
H2SO3 + I2 + H2O = SO42 + 2 I + 4 H+
H2AsO3 + I2 + H2O = H2AsO4 + 2 I + 2H+
2S2O32 + I2 = S4O62 + 2 I
Sn2+ + I2 = Sn4++ 2 I
In indirect or iodometric methods the oxidising agent which is to be analyte is treated with
an excess of iodide ion under suitable conditions. Iodine is liberated quantitatively, and it is
titrated by a standard solution of sodium thiosulphate or arsenious acid. These methods can be
used for the analysis of almost any strong oxidising agent, consequently, there are many more
applications than there are few iodimetric methods.
2 MnO4 + 16 H+ + 10 I = 2 Mn2+ + 8 H2O + 5 I2
Cr2O72 + 14H+ + 6 I = 2 Cr3+ + 7 H2O + 3 I2
BrO3 + 6H+ + 6I = Br + 3H2O + 3 I2
lO3 + 6H+ + 5I = 3H2O + 3 I2
ClO3 + 6H+ + 6I = Cl + 3H2O + 3 I2
2HNO2 + 2H+ + 2 I = 2NO + 2H2O + I2
2Cu2+ + 4I = CuI + I
18

Indicators:
In both iodimetric and iodometric methods the end point is based on the presence of iodine.
This can be detected by starch or by extraction of iodine from water by immiscible solvent.
1. Starch:
Starch does not dissolve as a true solution, but it is readily dispersed as a colloid. With iodine
it give a deep blue colour which is formed on the surface of the colloid particles when iodine
is adsorbed and is discharged when iodine is reduced to iodide ion. The colour change is
reversible and the presence of iodide ion is necessary for development of a good colour.
Two milliliters of a 1% solution is added to 100 ml of the solution to be titrated, taking the
following precaution into consideration:
[a ]

The sensitivity of the colour decreases with increasing temperature of the solution;
thus at 50oC it is about 10 times less sensitive than at 25oC.

[b ]

In the titration of iodine, starch must not be added until just before the end point. If
added when the iodine in high concentration some iodine may remain adsorbed and it
becomes difficult to discharge the deep blue colour of the iodine starch adsorbate.

[c ]

It cannot be employed in alcoholic solution; the alcohol hinders the formation of


adsorbate, nor it can be used in strongly acid medium; strong acids hydrolyse the starch
and destroy the adsorption compound.

2- Chloroform or carbon tertrachloride:


In alcoholic or strongly acidic solutions the end point is detected by the use of either
chloroform or carbon tetrachloride. The solubility of iodine in chloroform is about 90 times as
in water. So, if chloroform is added to iodine solution and well shaken, the great part of iodine
will dissolve in the organic layer, which settles down in the bottom and is coloured deep
violet. Titration with, for example, sodium thiosulphate will gradually remove iodine that is in
the aqueous layer and on gentle shaking another part of the iodine in the organic layer passes
to the aqueous layer, and so on. Near the end point, when the organic layer contains only a
faint violet colour, vigorous shaking is necessary to bring the aqueous thiosulphate solution
and the organic layer in contact with each other. The end point is reached when the violet
colour in the organic layer just disappears.

III- Complexometry:
19

Complex formation titration are those titrations involving the formation of substances
known as complexes which are only slightly ionizing in solution, releasing ions to the solution
in minute amounts as does an insoluble electrolyte.
Most metal ions react with electron pair donors to form coordination compounds or
complex ions. The donor species, or ligand, must have at least one pair of unshared electrons
available for bond formation.
The complex formation reaction is a type of acid base reaction according to Lewis concept
where the metal ion is the Lewis acid (electron acceptor), while the ligand is the Lewis base
(electron donor).
Chelation
Ligands, which possess two or more donor groups, combine with metal to form ring structure
called chelate. The ligands in this case, are called chelating agents, and the products are called
chelates.
The chelate forming ligand must possess at least an acidic group or more and a
corresponding group or more as shown in the following tables:
Acidic groups
COOH

Coordinating groups

Carboxylic

C=O

Carbonyl

Phenolic

OH

Hydroxyl

SO3H

Sulphonic

Ethers

=NH

Imino

NH2

Amino

RSH

Mercaptyl

=N

Cyclic nitrogen

NO

Nitroso

OH

The presence of acidic or coorddination groups in an organic compound is not alone


sufficient to ensure capability of chelate formation. The groups must be located in the
molecule in such position that will involve the metal ion in stable ring.
Ethylenediamine tetraacetic acid disodium salt dihydrate (EDTA) is widely used as ligand
(titrant).

20

CH2COONa
CH2COOH
CH2COOH

. 2 H2O

CH2COONa

Detection of the end point:


The end point can be detected by may methods include: potentiometric, conductometric,
spectrophotometric techniques in addition to the use of metal indicators.
Metal indicators: (Metallochromic or pM indicators)
These are dyestuffs, which form coloured complex with specific metal cations. They are
cheleting agent i.e. the dye stuff molecule possesses several ligand atoms suitably disposed
for coordination with a metal atom. They are considered as lewis base and the metal as lewis
acid. Metal indicators are at the same time acid base indicators, i.e. they change their colour
according to the pH of the medium. So, in order to restrict the colour change to the metal
reaction, these indicator are usually used in buffered solutions. Metallochromic indicators
produce one colour in the free form and a different colour in the metallized form.

General requirements for a good metal indicators:


1) Its colour reaction with the metal ion should be specific or at least selective.
2) The metal indicator complex must be weaker than the metal EDTA complex.
3) The metal indicator complex must posses sufficient stability, otherwise, because of
dissociation, a sharp colour change is not obtained.
4) The colour of the metallized indicator and free indicator must be sufficiently different and
intense enough to allow visual detection of the end point with a minimum amount of
indicator.
The sample containing the metal ion is buffered to the suitable pH and titrated directly with
EDTA using suitable indicator. If the pH is high, metal hydroxides (or basic salts) are
sometimes precipitated and their reaction with EDTA becomes slow. The addition of auxiliary
complexing agents helps retain the metal ions in solution e.g. tartaric acid is used for direct
titration of lead. The buffer itself may act sometimes as auxiliary complexing agent as in the
case of ammonia buffer,.
21

If direct titration is not sufficiently rapid, a catalyst may be included or the titration liquid is
heated to accelerate the reaction.
Determination of some metal ions by direct titration with EDTA
Metal ion

Medium

Indicator

Colour change

Bi3+

pH 2 3 nitric

Xylenol orange

Pink yellow

Cd2+

pH 5 hexamine

Xylenol orange

Red yellow

Ca2+

pH 12 NaOH

Murexide

Pink purple

Murexide

Yellow purple

Ammonia buffer

EBT

Wine red blue

pH 10 ammonia

EBT

Red blue

Cu
Zn
**

2+

2+

Enough NH3
or Mg

2+

2+

Ca & Mg

2+

buffer
* to give blue Cu(NH3)42+
**

Total hardness of water

The presence of traces of other metals as impurities, may compete with ion to be estimated
and block the indicator as in the case of direct titration of Ca and Mg with EDTA, traces of
Cu, Co, Ni, Fe are frequently present and produce similar difficulties. In this case the
impurities is masked before adding the indicator by reducing it (using ascorbic acid), then
complexing with cyanide ion forming more stable complexes than their edetates.
Back titration:
Back titrations are useful for complexometric determination of metal ions in the following
cases:
1.

If the metal ion precipitates at the pH suitable for titration.

2. If the medium contains precipitating agent that precipitates the metal ion at the pH
suitable for titration e.g. Ca++ in the presence of oxalate.
3. If the reaction between the metal ion and EDTA is too slow as in the case of Al and
Cr.
4. If a suitable metal indicator is not available.

22

Back titration is also suitable for determining insoluble substance such as Ba and PbSO4,
magnesium phosphates, etc.
The procedure involves addition of known excess of standard EDTA to the metal being
determined. The medium is then suitably buffered and the excess EDTA is back titrated with
standard metal solution (e.g. ZnCl2 orMgCl2) in presence of suitable indicator.

Aluminum can be determined by adding known excess of EDTA and then adjusting the pH
of the solution to pH 7.8 using ammonia solution. the solution is then boiled for few minutes
to insure complete complexation. The excess EDTA is back titrated with standard Zn solution
using eriochrome back T as indicator, the change of colour is from blue to win red.

Chromium can be also determine by back titration at pH 6 using acetate buffer and pb(NO3)2
as atitrant for the excess EDTA. Xylenol orange is used for detecting the end point. Boiling
for 10 15 minutes is also necessary.

IV-

Theory
TheoryofofPrecipitimetry
Precipitimetry

Precipitation titrations are volumetric methods based on the formation of a slightly soluble
precipitate. They are in many ways simpler than gravimetric methods. Their precipitate needs
not be separated; and needs not be pure as long as the impurity does not consume titrant. The
unknown substance is determined simply by converting it into an insoluble form of known
composition by adding a standard solution of the titrant. The equivalence point is reached
when an equivalent amount of the titrant has been added. From the volume of the latter, the
amount of the unknown substance is calculated.
The reaction to be used in precipitimetry must satisfy a number of conditions.
a) The precipitate must be practically insoluble.
b) Precipitation should be rapid.
c) End point must easily detected.
d)
23

Formation of a second precipitate: The Mohr method


The formation of a second precipitate of distinctive colour can be used to indicate the
completion of a precipitation titration. The best known example of such a case is the Mohr
titration of chloride ion or bromide ion with standard silver nitrate, in which chromate ion is
used as the indicator. The first permanent appearance of the reddish silver chromate
precipitate is taken as the end point of the titration.
The method may be summarized as follows:
Cl

Ag+

Unknown
+

2 Ag +
Excess

titrant
2

CrO4

AgCl
white ppt.

indicator reagent

Ag2CrO4
red indicator ppt.

It is necessary, of course, that the precipitation of the indicator occurs at, or near, the
equivalence point of the titration. Silver chromate is more soluble, so that it cannot form
permanently in the mixture until precipitation has been lowered to a very small value. Any
silver chromate which form a localized excess of silver ion where the titrant is added to the
mixture, is transposed by untitrated chloride in the solution:
Ag2CrO4 + 2Cl CrO42 + 2 AgCl
The titration consists in adding silver ions to a solution containing a large concentration of
chloride ions, and a small concentration of chromate ions; silver chloride will first precipitate,
while silver chromate will not form until the silver ion concentration increases to a large
enough value to exceed the Ks of silver chromate. Remember that the concentration of silver
ion at the equivalence point in this titration is fixed at 1 x 105 M, it is possible to compute the
chromate ion concentration required to initiate precipitation of silver chromate in this
medium.
(Ag+)2 (CrO42) = 2 x 1012
Ks
2 x 10 -12
2
(CrO4 ) =
=
= 0.02 M
(Ag ) 2
(1 x 10 - 5 ) 2
But such a high concentration of chromate ion cannot be used in practice, because its deep
yellow colour effectively masks the reddish colour of the silver chromate (which indicates the
end point). Normally, a concentration of 0.005M chromate ion is employed. But the lowering
of the chromate ion concentration, from 0.02 M to 0.005 M, requires excess silver ion to keep
the Ks of silver chromate at its value:
24

(Ag+)2 x (0.005) = 2 x 1012 mole / liter3


i.e., (Ag+) = 2 x 105 M; or 2 x 105 m.mole/ml.
if the volume of the titrated solution is 100 ml., then, the m.mole Ag+ in the solution is
100 ml. x 2 x 105 = 0.002 m.mole Ag+
Since for no error in the titration,
m.mole Ag+ = m.mole Cl
or
m.mole Ag+ m.mole Cl = zero
The chloride ion concentration is given by:
(Cl) =

1.0 x10 10
2 x10

5 x 106

And m.mole Cl = 5 x 106 x 100 = 0.0005


Thus the error = m.mole Ag+ m.mole Cl
= 0.002 0.0005 = 0.0015
this amount is contained in 0.015 ml of a 0.01 N solution; and if 5.00 m.mole of chloride were
titrated, then:
the error =

0.0015
5.00

x100 0.03 %

This error, however, is negligible; but with very dilute solutions, a correction should be made
by determining an indicator blank, i.e. by determining the silver ion consumption for a
suspension of chloride free calcium carbonate in about the same volume and with the same
quantity of indicator as the sample.

V- Gravimetric analysis:
Solution reaction between analyte (sample) and reagent (precipitating agent) to give sparingly
soluble product; filtration; drying or ignition of precipitate; weighing then calculation.
Flaskes, beakers, filter funnels, pipettes, filter papers or crucibles, oven, muffele furnace,
chemical balance and desicators are needed for good gravimetric analysis. The main
disadvantage of gravimetric analysis is the presence of contaminations (co-precipitation) so it
is important to have large particles of precipitate to decrease the total surface area and hence
decrease adsorption of contaminations.
Gravimetry differs from preciptimetry in that in it weighing is main step while in
preceptimetry no weighing takes place.
25

Example:
Determination of chloride as AgCl:
- Sample is Cl-

- Precipitating agent is AgNO3

- Precipitated form is AgCl


- Weighed form is AgCl (after drying of precipitated form)
- Ag+ + Cl- . AgCl (white crudy PPT)
- The ppt is collected in a filtering crucible, washed with very dil. HNO3 to prevent
peptization of ppt, dried at 130- 150C, finally weighed as AgCl then finally calculation as
follow:
Cl-

AgCl

MW1

MW2

W1 (unknown)

W2 (known from weighing of ppt)

So W1 = W2 x MW1/ MW2
And % of Cl- in sample = W1 / W3 x 100
W3 is weight of sample

26