Chemistry lec.

Volumetric analysis

An important method for determining the amount of particular substance

which is based on measuring the volume of reactant solution.

Suppose substance ((A)) react in solution with substance ((B)). If you

know the volume and concentration of ((B)) that just react with substance
((A)) in a sample, you could determine the amount of ((A)).

*The reagent of exactly known composition (volume and concentration)

in a titration is called a ((Standard solution)).

Commonly, the concentration of standard solution is arrived at in either

of two ways:

1- From preparatory data obtained when a carefully weighed quantity

of the pure reagent is diluted to an exactly known volume.
2- Form data obtained by titration of a weighed quantity of a pure
compound with the reagent.

The first is named primary standard solution; the second is named

secondary standard solution.

A primary standard substance should satisfy the following requirements:

1- It must be of the highest purity.

2- It should be stable, not be attacked by constituents of the
atmosphere.
3- The compound should not be hygroscopic, otherwise drying and
weighing would be difficult
4- It should be available and not too expensive.
5- It should have a high equivalent weight.

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Titration:

It is a process for determining the amount of the substance by adding

to it a carefully measured volume of standard solution until the
reaction between them is just complete. The point at which this occurs
is called the equivalence point or the theoretical end point.

Equivalence point: is the point where the amount of titrating solution

added is chemically equivalent to the amount of substance being
titrated:

Number of milliequivalent of titrant=Number of milliequivalent of titrated

Volume × normality = volume × normality

The completion of the titration should be detectable by the addition of

a reagent, known as an indicator.

Indicator: is a substance that undergoes color change when a reaction

approaches completion.

After the reaction between the substance and the standard solution is
practically complete, the indicator should give a clear visual change in
the liquid being titrated. The point at which this occurs is called the
end point of titration.

End point: is the point where the indicator changes color. In the ideal
titration the visible end point will coincide with the equivalence point.
In practice, however, a very small difference usually occurs, this
represents the titration error.

Titration error: is the volume difference between the end point and
equivalence point, (it must be very small).

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Chemistry lec.5

Example:

Titration of HCl with NaOH solution.

Transfer an accurate volume of HCl solution to conical flask and add a

few drops of phenolphthalein indicator. Phenolphthalein indicator is
colorless in HCl solution but turns pink at the completion of the
reaction of the reaction of NaOH with HCl.

Sodium hydroxide is contained in a buret.

Buret: is a glass tube graduated to measure the volume of liquid

delivered from the stopcock.

The solution in the buret is added to HCl in the flask until the
indicator just change from colorless to pink. (This is the end point). At
this point the reaction is complete and the volume of NaOH that react
with HCl is read from the buret. This volume then used to obtain the
concentration of HCl in the original solution.

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Reactions used in volumetric analysis:

To be suitable for a volumetric analysis, a chemical reaction should

meet certain requirements:

1- The reaction must be simple which can be expressed by a chemical

equation; this requirement implies the absence of side reactions
between the reagent and the unknown or other constituents of the
solution.
2- The reaction should be rapid, and the substance to be determined
should react completely with the reagent in equivalent proportions.

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Chemistry lec.5

3- There must be available a method for detecting the equivalence

point in the reaction, that is a satisfactory end point is required.
4- An indicator should be available which should sharply define the
end point of the reaction.

Reaction Types:
Volumetric methods may be divided conveniently into four categories
based upon reaction type, these include:
1- Acid-base reactions or ( neutralization):

This titration reaction involves the determination of the volume of

solution of an acid (or base) of known concentration termed the
"standard solution" (titrant) required to be added to a base (or acid) of
unknown concentration. When the total number of milliequivalents of
reactant added are unknown (ml × N = milliequivalents) we will then
have a numerically exact and equal measure of the quantity of the
substance that it has neutralized.

NaOH +HCl NaCl +H2O

A number of indicators are used in this titration such as:

Methyl orange Phenolphthalein Methyl red

pH range 3.1-4.4 8-9.6 4.2-6.2
Acid color red colorless Red
Base color yellow pink Yellow
Approximate pH range for color change

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 Chemistry lec.5

2- Precipitation reactons:

Based on the formation of a slightly soluble precipitate.

For example: Ag+ + Cl- AgCl(s)

A chemical indicator produces in solution readily observable change –

usually of color or of turbidity- that serves to signal a state of chemical
equivalence between the participants of a titration.

3- Oxidation –reduction reactions:

Potassium permanganate in the most widely used in this reaction. It is
powerful oxidant. The intense color of permanganate ion is sufficient to
signal the end point titrations:
MnO4- + 5 Fe++ +8 H+ 5 Fe+++ +Mn++ +4H2O

4-Complex formation reactions:

Twenty five (25) metals that can be determined by direct titration with
organic material as a titrant is that it combines with metal ions in a 1:1
ratio regardless of the charge on the cation in order to produce complex
compound such as EDTA (Ethylene di- amine tetra acetic acid).
CH2COOH CH2COOH
N-CH2-CH2-N
CH2COOH CH2COOH
(EDTA)
A number of metal- ion indicators have been developed for use in
complexometric titrations with EDTA. In general, these indicators are
organic dyes that form colored chelates with several metal ions.

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 Chemistry lec.5

Volumetric Calculations:
Equivalent weight:
1- Acid-base titration:
The gram- equivalent weight of an acid, or simply the gram- equivalent,
is that weight of the acid which contains 1 gram-equivalent, (1.008 gm)
of replaceable hydrogen.
The gram- equivalent weight of a base is that weight of the base which
contains 1 gm-equivalent (17.008 gm) of replaceable hydroxyl ion,
(OH).

EX.

Eq.wt of HCl = eq.wt of NaOH =

Eq.wt of H2 SO4 = eq.wt of Ba(OH)2 =

Eq.wt of CH3COOH = eq.wt of Al(OH)3 =

Eq.wt of H3PO4 = eq.wt of NH3 =

2- Precipitation or complex formation titration:

The equivalent weight of a salt in which a change of oxidation state does
not occur during the reaction is equal to its molecular weight divided by

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 Chemistry lec.5

the total charge of all positive ions (or the equal total charge of all
negative ions).

Equivalent weight of salt =

Eq.wt of KCL =

Eq.wt of Na2CO3 =

Eq.wt of BaCl2 =

Eq.wt of FeCl3 =

Eq.wt of Ca3(PO4)2 =

3- Oxidation – reduction titration:

The equivalent weight of an oxidizing or reducing agent for a particular
reaction is equal to its molecular weight divided by the total number of
electrons gained or lost when the reaction occurs (or divided by the total
change in oxidation state).

Equivalent weight of oxidizing or reducing agent =

Ex. H+
KMnO4 MnO + --------
+5e-
Eq.wt of KMnO4 =

H+
K2Cr2O7 2Cr+++
+6e-

Cr2O7-- +3 Sn++ + 14H+ 3Sn++++ + 2Cr+++ + 7H2O

Eq.wt of Cr2O7 -- =

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 Chemistry lec.5

Eq.wt of Sn =
6e
KIO3 + 6H+ I- + H2O

eq.wt for KIO3 =

H2C2O4 2CO2
Eq.wt for H2C2O4 =
HNO3 + 3H+ NO + H2O
Eq.wt for HNO3 =

This reaction is named oxidation- reduction reaction.

Calculation of normality of results from titration data:

The fundamental reaction of acidimetry and alkalimetry is as follows:
H+ + OH- H2O
Since a gram- milliequivalent weight of an acid will just neutralize a gram-
milliequivalent weight of base and since the number of milliequivalent in
each case is found by multiplying the number of milliliters of solution by its
normality, we have the following simple relationship between tow reacting
solutions:
VA × NA = VB × NB

VA × NA = VB × ×

Wt (B) (gm)=

Or wt(B) (mg) = VA × NA × eq.wt (B)

%(B) = × 100

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 Chemistry lec.5

Example 1:
A solution of Ba(OH)2 was standardized by titration against (0.128 N) HCl.
Exactly 31.76 ml of the base were required to neutralize 46.25 ml of the
acid. What is the normality of the Ba(OH)2 solution?
Sol.
At equivalent point
Ba(OH)2 = HCl
N1 × V1 = N2 × V2
N1 × 31.76 = 0.128 × 46.25
N1 = 0.1864 gm.eq/l

Example2:
a. What the volume of (5N) H2SO4 is required to neutralize a solution
containing 2.5 gm NaOH? M.wt (NaOH) = 40.
b. How many grams of pure H2SO4 are required? M.wt(H2SO4) = 98.
Sol.

a. Wt.(NaOH) =

2.5= M.wt(NaOH) = eq.wt (NaOH)

V = 12.5 ml

b. N= ×

5= ×

Wt = 3.06 gm
Not: H2SO4 include 2 hydrogens , thus: eq.wt = = 98/2= 49.

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Chemistry lec.5

Example 3:
A 0.25 gm sample of a solid acid was dissolved in water and exactly
neutralized by 40 ml of 0.125 N base.
What is the equivalent weight of the acid?
Sol.

Wt(acid) =

:
:
:
:
Examole 4:
A sample of soda ash (impure Na2CO3) is titrated with 0.5 N H2SO4.
If the sample weight 1.1 gm and required 35 ml of the acid for
complete neutralization, what is the percentage of Na2CO3 in the ash?
M.wtNa2Co3= 106

Sol.
Eq.wt(Na2CO3) = = 106/2 = 53

Wt(Na2Co3)=

= = 0.928 gm

%= × 100 =84.36 %

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