Chapter 1

Introduction to Analytical Chemistry

Chemistry: Chemistry is that branch of science which deals with the study of matter.
Anything that having mass and occupy space is called matter. There are four different
types of matter i.e. Gas, liquid, solid and plasma. Gas is that type of matter having no
proper shape and no proper volume i.e. air, nitrogen gas etc. Liquid is that type of matter
having proper volume but no proper shape adopt the shape of the pot in that it is putted
like water, milk etc. Solid is that type of matter having proper shape and proper volume
i.e. stone, book, wood etc.
Plasma is that type of matter which is in between solid and liquid. It is found on sun.
ANALYTICAL CHEMISTRY: The Science of Chemical Measurements.
Or
Analytical chemistry is that branch of chemistry which deals with the analysis or
characterization of analyte species. Analyte is that species which is under consideration
or observation or about that we don’t know. Its chemical composition is unknown to us.
The process that we are using to get know about the chemical composition of analyte
species is called analysis. In analytical chemistry there are two types of analysis, one is
known is qualitative analysis and the other type is called quantitative analysis.
Qualitative analysis is used for identification or knowing the chemical nature of the
analyte species from which the analyte is made up, while the quantitative analysis is used
to know about the unknown amount of analyte species.
2.) Types of Questions asked in Analytical Chemistry
a.) What is in the sample? (Qualitative analysis)
b.) How much is in the sample? (Quantitative analysis)
c.) How pure is it? (Separation analysis)
Analysis can be done with the help of using analytical techniques. Analytical techniques
are valid procedures that are used for analysis. There are two groups of analytical
techniques. One group is called as Qualitative analytical techniques used for
identification of chemical nature of analyte species i.e. salt analysis, FTIR analysis,
NMR analysis. While the other group of analytical techniques called Quantitative
analytical techniques used to know about the unknown amount of analyte. Quantitative
analytical techniques are further sub classified into classical techniques, while the other
group of Quantitative analytical techniques is called Instrumental techniques. In case of
classical techniques simple equipments like burette, pipette, flasks, cylinder, balance etc
are used, while in case of Instrumental techniques the modern instruments are used to do
analysis.
Classical techniques are further sub classified as volumetric techniques, gravimetric
techniques and separative techniques, while the instrumental techniques are sub
classified as spectroscopic techniques, electroanalytical techniques and separative
techniques.
Volumetric techniques consist of a group of classical techniques based on volume
measurement therefore are called as volumetric techniques, it include acid base titration
(neutralization titration), redox titration, precipitation titration and complexomtric
titration.
Gravimetric techniques is another class of classical techniques based on mass
measurement like precipitation, volatilization etc.
While the 3rd group of classical techniques is based on separation for purification
purposes include distillation, filtration, crystallization, sublimation, solvent
extraction, chromatography, electrophoresis etc.
Instrumental Techniques: It is a group of Quantitative analytical techniques used for
analysis of analyte species and can be practiced by using some instruments. Instrumental
techniques are further sub classified as spectroscopic techniques, electroanalytical
techniques and separative techniques.
Spectroscopic techniques are that kind of instrumental analytical technique in
which spectrophotometer is used as an instrument and it is used both for
identification as well quantification (determination the unknown amount) of
analyte. It is based on interaction of electromagnetic radiations with matter. Some
time the matter absorbs or sometimes emits radiations. So in spectroscopy we
measure the magnitude of absorbed or emitted radiations and then relate that
magnitude of radiations with the concentration of analyte species.
Electroanalytical techniques include a group of instrumental techniques like
potentiometry, voltammetry, conductometry, coulometry, electrogravimetry in all
those techniques there is interaction of electricity with matter and in all the above
mentioned techniques we measure the electrochemical properties like potential,
current, charge etc with help of different instruments like potentiometer, pH meter,
conductometer, voltammeter etc,.

Separative techniques are that group of instrumental technique in that the

instruments like HPLC, GC, Ion chromatograph etc are used for separation,
purification identification as well as quantification of analyte specie.
 Analytical Chemistry

Analysis

Qualitative analysis Quantitative analysis

Analytical techniques

Qualitative analytical techniques Quantitative analytical techniques

Salt analysis FTIR analysis NMR analysis

Classical techniques Instrumental techniques

Volumetric techniques Gravimetric techniques Separative techniques

Spectroscopic techniques Electroanalytical techniques Separative techniques

Schematic Introduction to Analytical Chemistry

Units of Amount

Amount is that mass of solute which containing know number of particles i.e. atoms, ions
or molecule. In analytical chemistry different units of amount like mole, equivalent and
formals are used.

Mole:

Mole is a unit of amount and can be defined as, one mole is that amount which containing
Avogadro number (6.0221415 × 1023) of particles. It can be also defined as when the
atomic mass of an atom or ion or molecular mass of a molecule is expressed in grams,
then that gram atomic or molecular mass is called one mole amount and it will be
containing Avogadro number of particle.

Examples:

Carbon = 12amu = 12g = 1mole = 6.0221415 × 1023 carbon atoms

Sodium ion = 23amu = 23g = 1mole = 6.0221415 × 1023 Na+

Water = 18amu = 18g = 1mole = 6.0221415 × 1023 H2O molecules

In analytical Chemistry number of moles is calculated as below

Mass in grams of solute

Number of moles of solute =
Atomic mass/ Molecular mass

Examples: Calculate the number of moles for 4g mass of NaOH.

Solution:

Using the above expression as we know

Mass in grams of NaOH

Number of moles of NaOH =
Molecular mass of NaOH

As we know Molecular mass of NaOH = 23+16+1 = 40amu

Put the values in the above expression

4
Number of moles of NaOH =
40

Number of moles of NaOH = 0.1 moles

It will be containing (0.1 x 6.0221415 × 1023) = 6.0221415 × 1022 molecules of NaOH

In case of solutions number of moles is calculated as

VmL
Number of moles = Molarity x Volume in liters = M x VL = M x
1000

Example: Calculate the number of moles for a solution having concentration 0.1M and
its total volume is 250mL.

Solution: As we know

Number of moles = Molarity x Volume in liters = M x VL = M x VmL

1000

So putting the values in this expression as

250
Number of moles = M x VmL = 0.1 x = 0.025 moles
1000 1000

Equivalent:

Equivalent is also a unit of amount and it can be defined as, one equivalent is that amount
which containing Avogadro number (6.0221415 × 1023) of reactive specie. In case of acid
base reaction reactive specie is hydrogen ion (H+) for acid and hydroxyl ion (OH-) for
base, while in case of redox reaction the reactive specie is the number of electron lost or
gained. In analytical chemistry number of equivalent can be calculated as below

Mass in grams of solute

Number of equivalents of solute =
Equivalent mass of solute
Equivalent mass can be defined as molecular mass of the analyte divided by number of
reacting units as

Molecular Mass of solute

Equivalent mass of solute =
Number of reacting units

Number of reacting units in case of acid base reaction is the number of hydrogen or
hydroxyl ions per molecule, while in case of oxidation reduction is the number of
electron lost or gained by an atom or molecule.

Examples: Calculate the number of moles for 8g mass of Na2CO3.

Solution:

Using the above expression as we know

As we know Na2CO3 on hydrolysis produce two hydroxyl ions so it

106
Equivalent mass of Na2CO3 = = 53
2

It means 53g of Na2CO3 containing Avogadro number (6.0221415 × 1023) of hydroxyl

ion (OH-)

Now

8
Number of equivalents of Na2CO3 = = 0.15equivalents
53

In case of solutions number of equivalent is calculated as

VmL
Number of equivalent = Normality x Volume in liters = N x VL = N x
1000
Example: Calculate the number of equivalents for a solution having concentration 0.1N
and its total volume is 250mL.

Solution: As we know

VmL
Number of equivalent = Normality x Volume in liters = N x VL = N x
1000

So putting the values in this expression as

VmL = 0.1 x 250 = 0.025 equivalents

Number of equivalents = N x
1000 1000

Formals

Formal is also a unit of amount similar to mole but in case of crystalline ionic compounds
like NaCl we are writing formula unit mass instead of molecular mass i.e.

Formula mass of NaCl = 23 + 35.5 = 58.5amu

Units of Concentration

Concentration is the ratio between the amount of solute and solvent. Solution is a mixture
of solute and solvent. In analytical chemistry for analysis solutions of different
concentrations are used. To prepare solutions of different concentrations there are
different types of concentration units like molarity, normality, formality, molality, %age
solutions, ppm (parts per million), ppb (parts per billion) etc are used in analytical
chemistry.

Molarity

It is a unit of concentration and is denoted by “M”. It can be defined as the number of

moles of solute dissolved per unit volume of solution

Number of moles of solute

M =
Volume in Liter of solution

Mole is unit of amount and can be defined as

 Mass in grams of solute
Number of moles of solute =
Atomic mass/ Molecular mass

Substituting the values of no of moles of solute in above equation so

Mass in grams of solute

M =
Atomic mass or Molecular mass x Volume in Liter of solution

Rearranging the above expression as

Mass in grams of solute = M x Atomic mass or Molecular mass x Volume in Liter of solution
As we know

1L = 1000ml, so replace volume in letter by volume in mL in above expression

like this

M x Atomic mass or Molecular mass x Volume in mL of solution

Mass in grams of solute =
1000
Applications: The above expression is generally applied to calculate the weight
in grams of solute for preparation of solutions of different concentrations in
molarity and volumes of analyte like this.

Example: 1.1. Prepare 0.1M NaOH solution of 250ml volume.

To prepare 0.1M NaOH solution of 250ml volume, the job is to calculate weight
of NaOH. It can be calculated by using the above express as

M x Atomic mass or Molecular mass x Volume in mL of solution

Mass in grams of solute =
1000
As we know Molecular Mass of NaOH = 23+16+1 = 40amu
So feed the values in the above expression as

0.1 x 40 x 250
Mass in grams of solute =
1000

Weight in grams of NaOH = 1g

 It means to prepare 0.1M solution of NaOH of 250ml volume capacity we need to
dissolve 1gram weight of NaOH that we calculated with the help of above
expression

Normality

It is also a unit of concentration and denoted by N. It can be defined as the number of

equivalents of solute dissolved per unit volume of solution

Number of equivalent of solute

N =
Volume in Liter of solution

Equivalent is also a unit of amount and can be defined as

Mass in grams of solute
Number of equivalents of solute =
Equivalent mass of solute

Equivalent mass can be defined as molecular mass of the analyte divided by

number of reacting units as

Molecular Mass of solute

Equivalent mass of solute =
Number of reacting units

Number of reacting units in case of acid base reaction called to number of

hydrogen or hydroxyl ions per molecule, while in case of oxidation reduction the
no of electron lost or gained by an atom or molecule.

Substituting the values of number of equivalents of solute in above expression so

Mass in grams of solute

N =
Equivalent mass of solute x Volume in Liter of solution

Rearranging the above expression as

Weight in grams of solute = Equivalent mass of solute x N x Volume in L
As we know
1L = 1000ml, so replace volume in letter by volume in mL in above expression
like this

N x Equivalent mass of solute x Volume in mL of solution

Mass in grams of solute =
1000

Applications:

The above expression is used to calculate weight in grams of solute for different
concentrations and volumes of analyte like this.

Example: 1.2. Prepare 0.1N H2SO4 solution of 250ml volume.

Solution:

This example can be solved by using expression as we know

N x Equivalent mass of solute x Volume in mL of solution

Mass in grams of solute =
1000
+
As H2SO4 molecule containing 2 H so it equivalent mass will be as
molecular mass
Equivalent mas =
Number of H+

Molecular mass of H2SO4 = 98amu, so put this value in above expression

98
Equivalent mas =
2

Equivalent mass=49
So put the values in above expression as

0.1 x 49 x 250
Mass in grams of solute =
1000

Weight in grams of H2SO4= 1.22g

As H2SO4 is a liquid in case of liquids instead of mass we are taking volume, so to

calculate the volume we should use expression of density as
 Mass in grams
Density =
Voulme in mL

Rearranging the above expression as below

Mass in grams
Voulme in mL =
Density

Substituting the values

1.22g
Volume in mL =
1.84

Volume in mL = 2.24mL
But we know the percent purity of available H2SO4 is 98%. It means if we need
98mL of pure H2SO4 that will be present in 100mL of available bottle H2SO4.
Now 2.24mL of pure H2SO4 will be present in how much volume of bottle
H2SO4?

We can calculate it with the help of dimensional analysis i.e.

100mL volume of bottle H2SO4

x 2.24mL of pure H2SO4 = 2.29mL of Bottle H2SO4
98mL of pure H2SO4

It means to prepare 0.1N H2SO4 solution of 250ml volume capacity we need to

dissolve 2.29ml of available bottle H2SO4.

Formality

It is a unit of concentration and denoted by “F”. It can be defined as the number of

formals of solute dissolved per unit volume of solution

Number of formals of solute

F =
Volume in Liter of solution

Formal is unit of amount and can be defined as

 Mass in grams of solute
Number formals of solute =
Formula mass

Substituting the values of number formals of solute in above expression as

Mass in grams of solute
F =
Formula mass x Volume in Liter of solution

Rearranging the above expression as

Mass in grams of solute = F x Formula mass x Volume in Liter of solution

As we know
1L = 1000ml, so replace volume in letter by volume in mL in above expression
like this

F x Formula mass x Volume in mL of solution

Mass in grams of solute =
1000

Applications: The above expression is generally applied to calculate the weight

in grams of solute for preparation of solutions of different concentrations in
formality and volume of analyte like this.

Example: 1.3. Prepare 0.1F NaCl solution of 250ml volume.

Solution:

This example can be solved by using expression as we know

Formula mass of NaCl x Volume in mL of solution

Mass in grams of NaCl = F x
1000

So put the values in the above expression as

0.1 x 58.5 x 250

Mass in grams of NaCl =
1000

Weight in grams of NaCl = 1.46g

 It means to prepare 0.1F solution of NaCl of 250ml volume capacity we need to
dissolve 1.46gram weight of NaCl.

Molality

It is also a unit of concentration and denoted by “m”. It can be defined as number of

moles of solute dissolved per Kg of solvent.

Number of moles of solute

m =
Kg of solvent

Mole is unit of amount and can be defined as

Mass in grams of solute

Number of moles of solute =
Atomic mass/ Molecular mass

Substituting the values of no of moles of solute in above equation so

Mass in grams of solute
m =
Atomic mass or Molecular mass x Kg of solvent

Rearranging the above expression as

Mass in grams of solute = m x Atomic mass or Molecular mass x Kg of solvent

As we As we know

1kg = 1000g, so replace mass in kg by mass in g in above expression like this

m x Atomic mass or Molecular mass x grams of solvent

Mass in grams of solute =
1000
Applications: The above expression is generally applied to calculate the weight
in grams of solute for preparation of solutions of different concentrations in
molality and volumes of analyte like this.

Example: 1.4. Prepare 0.1m NaOH solution in 250g of solvent.

Solution:

It can be calculated by using the above expression as

 m x Molecular mass of NaOH x grams of solvent
Mass in grams of NaOH =
1000

As we know Molecular Mass of NaOH = 23+16+1 = 40amu

So feed the values in the above expression as

0.1 x 40 x 250
Mass in grams of solute =
1000

Weight in grams of NaOH = 1g

It means to prepare 0.1m solution of NaOH in 250grams of distilled water we

need to dissolve 1gram weight of NaOH in 250grams of distilled water.

Molality is independent of temperature.

Percentage Solution (%)

In order to prepare solutions of higher concentrations we use the units of
percentage. There are three types of percentage Solution i.e. weight/volume,
weight/ weight and volume/volume.

a) Percentage Solution Weight/Volume

Percentage Solution weight/volume meant how much weight of solute is

dissolved in 100mL volume of solution.

Example: Calculate the mass in grams for preparation 5% solution of NaOH of

250mL volume.

Solution:
As we know 5% solution of NaOH meant 5grams of NaOH have dissolved in
100mL volume of solution. Now to calculate the mass in grams for 250mL
volume we can do it with the help of dimensional analysis i.e. similar units cancel
each others

5grams of NaOH x 250mL volume of solution

100mL volume of solution

So weight of NaOH = 12.5g

It means to prepare 250mL volume of 5% NaOH solution we need to dissolve
12.5g of NaOH and then dilute it with distilled water upto 250mL volume.

b) Percentage Solution Weight/ Weight

Percentage Solution weight/ weight meant how much weight of solute is mixed
with 100g weight of mixture.

Example: Calculate the mass in grams for preparation 5% mixture in NaCl and
sand of 500grams weight.

Solution:

As we know 5% mixture in NaCl and sand meant 5grams of NaCl have mixed
with 95grams of sand and the total weight of mixture is 100g. Now to calculate
the mass in grams for 500g mixture we can do it with the help of dimensional
analysis i.e.

5grams of NaCl x 500g weight of mixture

100g weight of mixture

So weight of NaCl = 25g
It means to prepare 500g mixture of 5% NaCl we need to mix 25g weight of NaCl
and 475g weight of sand.

c) Percentage Solution Volume /Volume

Percentage Solution volume /volume meant how much volume of solute is

dissolved in 100mL volume of solution.

Example: Calculate the volume in mL for preparation 5% solution of HCl of

250mL volume.

Solution:

As we know 5% solution of HCl meant 5mL of HCl have dissolved in 100mL

volume of solution. Now to calculate the volume in mL for 250mL volume we
can do it with the help of dimensional analysis i.e.

5mL of HCl x 250mL volume of solution

100mL volume of solution

So volume of HCl = 12.5mL

It means to prepare 250mL volume of 5% HCl solution we need to dissolve
12.5mL of HCl and then dilute it with distilled water upto 250mL volume.

Parts per million (PPm)

Parts per million (PPm) is also a unit of concentration used for preparation of
solutions containing trace amount of solute. Parts per million meant how many
parts of solute are present in one million parts of solution.
For example NaOH solution having concentration 1000ppm. It means that there
are 1000 molecules of NaOH are present or dissolved in one million molecules of
solution.

It can be prepared as below

1ppm= 1µg/ml or 1ug/g
1000ppm= 1000µg/ml
Applications: For example some body asked to prepare 1000ppm KMnO4
solution of 100ml volume.
To prepare this solution we need to calculate weight in grams of KMnO4
As we know
1ppm= 1µg/ml
So substitute the values in above expression as

1000µg x 100mL
1000ppm= = 100000 µg
mL

As we know
µ= 10-6
So put it in the above expression

100000 µg = 100000 x 10-6 x g = 10-1 g

Dissolve 0.1g of KMnO4 and dilute it upto 100mL volume with distilled water, so
its concentration will be 1000ppm.

Parts per billion (PPb)

Parts per billion (PPb) is also a unit of concentration used for preparation of
solutions containing trace amount of solute. Parts per billion meant how many
parts of solute are present in one billion parts of solution.

For example NaOH solution having concentration 1000ppb, it means that there
are 1000 molecules of NaOH are present or dissolved in one billion molecules of
solution.
 It can be prepared as below
1ppb= 1ng/ml or 1ng/g
1000ppb= 1000ng/ml
Applications: For example some body asked to prepare 1000ppb KMnO4
solution of 100ml volume.
To prepare this solution we need to calculate weight in grams of KMnO4
As we know
1ppb= 1ng/ml
So substitute the values in above expression as

1000ng x 100mL
1000ppb= = 100000 ng
mL

As we know
n= 10-9
So put it in the above expression

100000 ng = 100000 x 10-9 x g = 10-4 g

Dissolve 1 x 10-4g of KMnO4 and dilute it upto 100mL volume with distilled
water, so its concentration will be 1000ppb.

Dilution Formula

In some cases concentrated solutions are prepared and then with the help of
dilution formula from those concentrated solutions dilute solutions of our required
concentrations are prepared i.e.

Concentrated solution = Dilute solution

C1V1 = C2V2

Example: How much volume of 1000ppm KMnO4 solution is required to prepare

100ppm dilute KMnO4 solution of 100mL volume?

Solution:
As we know the dilution formula is

Concentrated solution = Dilute solution

C1V1 = C2V2

Now substituting the values in the above expression as below

Concentrated solution = Dilute solution

C1V1 = C2V2

1000ppm x V1 = 100ppm x 100mL

100ppm x 100mL
V1 =
1000ppm

V1 = 10mL

It means take 10mL volume from 1000ppm stock or concentrated solution and then
transfer it into 100mL volumetric flask and dilute it with distilled water its final
concentration will be 100ppm.

Stoichiometry

The shortest representation of a chemical reaction in terms of formula of compounds is

called chemical equation, while the shortest representation of a balanced chemical
equation in terms of units of amount is called as stiochiometry.e.g.

Chemical Equation…..Na2CO3 + 2 AgNO3 Ag2CO3 + 2 NaNO3

Stiochiometry……… 1mole + 2mole 1mole + 2mole

Example:
 (a) What mass of AgNO3 (169.9 g/mol) is needed to convert 2.33g of Na2CO3 (106.0
g/mol) to Ag2CO3 (275.7 g/mol)?
(b) What mass of Ag2CO3 will be formed?

Chemical Equation…..Na2CO3 + 2 AgNO3 Ag2CO3 + 2 NaNO3

Stiochiometry……… 1mole + 2mole 1mole + 2mole

Solution:

(a). First of all convert the given mass into moles using expression as

Mass in grams of solute

Number of moles of solute =
Atomic mass/ Molecular mass

So for 2.33g of Na2CO3 number of moles=?

2.33g
Number of moles =
106g/mole

Molecular mass of Na2CO3=106g/mole

Number of moles of Na2CO3 = 0.02198 moles

As we know from stiochiometric relationship, 1 mole of Na2CO3 react with 2moles of

AgNO3

So 0.012198 moles will react with how many moles of AgNO3

2moles of AgNO3 x 0.012198 moles of Na2CO3

1 mole of Na2CO3

So number of moles of AgNO3 = 0.0439 moles

Mass is grams of AgNO3 = number of moles x molecular mass of AgNO3

Mass in grams of AgNO3 = 0.0439 x 169.9 = 7.47grams of AgNO3

b). Mass of Ag2CO3 formed?

As from stiochiometric relationship we know 1mole of Na2CO3 form one mole of

Ag2CO3

So 0.01219 moles will also produce 0.01219 mole of Ag2CO3

Now Mass is grams of Ag2CO3 = number of moles x molecular mass of Ag2CO3

= 0.01219 x 275.7 = 6.06g of Ag2CO3

Standard Solution

The solution that is having exact and known concentration is called standard solution.
Standard solutions can be prepared with the help of primary standards.

Primary Standards

Primary standards are those chemical reagents having high percent purity, stability
toward air, having high molecular mass, readily solubility in the solvent, having medium
cost and readily availability. A few primary standards are as follow,

• Potassium hydrogen phthalate (KHP) is used as a primary standard for

standardization of NaOH

• Na2CO3 is used as a primary standard for standardization of HCl

• Na2C2O4 is used as a primary standard for standardization of KMnO4

• Zn pellets or Mg ribbons are used as a primary standard for standardization of

EDTA

Standardization

Standardization is a process used for preparation of solutions of known concentrations. In

this process the solutions of primary standard as well as analyte are prepared. Then
known volume from standard solution with the help of pipette is taken in the titration
flask. In order to locate the end point of this titration one drop of indicator solution is also
added to this solution in the titration flask and it is titrated against analyte solution that is
taken in the burette. The end point will be that point at which indicator shows color
change and at that point titration should be stopped and the volume used from burette
should be measured and then using the relationship of millimoles or milliequivalent the
unknown concentration can be calculated as bellow,

Millimoles of analyte = Millimoles of primary standard solution

M1V1 = M2V2
Secondary Standard Solution

Secondary standard solution is that solution used for further standardization of solution
having not exact known concentration. The preparation of secondary standard solution is
done with the help of primary standard solution. After standardization with primary
standard then we call it secondary standard solution and can be used for further
standardization. For example the NaOH solution after standardization against KHP is
now a secondary standard solution and this solution can be used for standardization of
HCl solution.

Calculation of pH

Acids are those chemical reagents on dissolution in water produce hydrogen ion (H+).
Acids may be strong acids like HCL, H2SO4, and HNO3 or may be weak acids like acetic
acid etc. The strong acid is that which completely dissociate into hydrogen ion while the
weak acid is that which partially dissociate into hydrogen ion. For acidic solution its
strength of acidity can be calculated in term of pH. Experimentally pH can be measured
by using an instrument called pH-meter.

In mathematics p is meant negative log

P = -log

So pH can be defined as negative log of hydrogen ion concentration i.e.

pH = -log [ H+]

For strong acidic solution the pH can be calculated as

pH = -log [ H+]

Example: Calculate the pH for 0.1M HCl solution

Solution:

As we know HCl is strong acid and it completely dissociate into hydrogen ion and
produce 0.1M of H+

In this example the hydrogen ion concentration is 0.1M so putting the value in above
expression As we know for strong acid pH
pH = -log [ H+]

So putting values

pH = -log 0.1 = 1

Example: Calculate the pH of 0.1N H2SO4 solution.

Solution:

As we know in case of strong acid,

pH = -log [ H+]

As H2SO4 is strong acid completely dissociate and producing 0.1N hydrogen ion
concentration so putting the magnitude of hydrogen ion concentration in the above pH
expression as

pH = -log 0.1 = 1

pH calculations for weak acids

Weak acids are those acids that dissociate partially into hydrogen ion when dissolve in
water. For example acetic acid

In case of weak acid we cannot write pH as

pH = -log [ H+]

For example acetic acid it does dissociate as below

CH3COOH CH3COO- + H+

The above reaction shows that acetic acid dissociates partially and equilibrium is
established between acetic acid and hydrogen ions and acetate ion. This equilibrium
condition can be expressed by equilibrium constant as
 [CH3COO-] [H+]
Ka =
[CH3COOH]

Re arranging the above expression as

Ka x [CH3COOH] = [CH3COO-] x [H+]

As at equilibrium state the hydrogen ion concentration is equal to acetate ion

concentration i.e.

[H+] = [CH3COO-]

So putting this acetate ion concentration in the above expression as below

Ka x [CH3COOH] = [H+] X [H+]

Or rearranging the above expression as

2 Ca
[H+] = Ka x

[H+] = Ka x Ca

As we know

pH = -log [ H+]

Or

Ka x Ca
pH = -log

Example: Calculate the pH for 0.001N CH3COOH solution of 250ml volume. Ka value
for acetic acid is 1.75 x 105- at 25 Co

Solution:

As we know CH3COOH is a weak acid and in case of weak acid pH can be calculated by
using the expression as given below
 Ka x Ca
pH = -log

So substituting the values in this expression

pH = -log 1.75 x 105- x 0.001

pH = 3.87

Calculation of pOH

So pOH can be defined as negative log hydroxyl ion concentration i.e.

pOH = -log [ -OH]

For basic solution its strength of basicity can be measured in term of pOH. Bases are
those chemicals that can produce hydroxyl ion (-OH) in water. As we know bases may be
strong bases like NaOH, KOH, etc or may be weak bases like Ammonium hydroxide etc.
The strong base is that which completely dissociate into hydroxyl ion while the weak
base is that which partially dissociate into hydroxyl ion. For strong basic solution the
pOH can be calculated as

pOH = -log [ -OH]

Example: Calculate the pOH and pH for 0.01N NaOH of 250ml volume.

Solution:

As we know

pOH = -log [ -OH]

So
pOH = -log [ 0.01]

pOH =2

As we know for water dissociate as below

-
H2O H+ + OH

-
[H+] [ OH]
K=
[H2O]

But the amount of [ H2O] is too much remain nearly constant so we can write it as

K x [H2O] = Kw

So

-
Kw = [H+] [ OH]

Now taking negative log on both sides of the above expression

-log Kw = -log [H+] + -log [-OH]

As we know

p = -log

So the above expression can be written as

pKw = pH + pOH

As we know Kw value for water is 1 x 10-14 at 25 Co

So

pKw = -log 1 x 10-14 = 14

So for this calculation

pH = 12

Calculate the pH of 0.01N NH4OH solution its Kb is 1.75 x 10-5 at 25C0.

Ans:
As we know

pOH = -log [ OH-]

But

In case of Weak base

[OH-] = Kb x Cb

Substituting the values in above expression

[ OH-] = 4.18 x 10-4 M

pOH = -log [ OH-]

So

pOH = -log [4.18 x 10-4]

pOH = 3.31

But for pH calculation

pKw = pOH + pH

Rearranging the above expression

pH = pKw - pOH
pH = 14 - 3.31

pH = 10.06
Buffer solutions

Buffer solutions are those solutions when they are added to some other solution they
resist to change in pH if small amount of strong acid or strong base is added to that
solution. Or

We can say the buffer solution has the property to control the pH of that solutions to
which it has been added.

Chemical Composition of a buffer solution

Buffer solution are chemically made of either weak acid or weak base and the salt
derived from that weak acid, or weak base e.g. buffer solution of CH3COOH/CH3COONa
and the other one NH3OH/NH4Cl

Buffer action

The mechanism how the buffer solution control the pH is that as we know buffer solution
containing two components one is weak acid or weak base and the other is its salt.

For example if an acidic buffer solution has been added a few ml of strong acid, so it will
react with the salt component of the buffer solution and will change it back to weak acid
so its effect on the pH change will be less and negligible i.e.

CH3COO- + HCl CH3COOH + Cl-

If few ml of strong base like NaOH has been added to this buffer solution so that will
react with the acidic component of the buffer solution and will produce salt that is again
neutral solution i.e.

CH3COOH + NaOH CH3COONa + H2O

So we can see that the effect of strong acid or strong base that has been added to buffer
solution has been neutralized either by reacting with salt component or with acidic or
basic component of that buffer solution.
Criteria for Selection a buffer solution of a required pH

In order to prepare buffer solution for a required pH range, it is required that we should
select either a buffer mixture of weak acid or weak base and their pKa or pKb values
should be having values very close to the required pH range in that we want to have
control the pH of a solution. For example we need to control pH of a solution near to 5
pH. As we know this pH range is on acidic side so first we should select weak acid and
its salt for preparation of this buffer mixture. As acetic acid is having pKa value i.e. pKa
= 4.76, so we will select acetic acid and sodium salt mixture for preparation of this buffer
solution of pH 5.

Calculation the pH of a buffer solution

The pH of a buffer solution can be calculated by using Handerson Hasselbalch equation

i.e.

In case of acidic buffer solution the Handerson Hasselbalch equation is written as

[salt]
pH = pKa + log
[weak acid]

And for basic buffer solution the Handerson Hasselbalch equation is written as

[salt]
pOH = pKb + log
[weak base]

Example: Calculate the pH of a solution that is 0.01N in CH3COOH and 0.02N in

CH3COONa. Ka value for acetic acid is 1.75 x 105- at 25 Co

Solution:
This can be solved by using Handerson Hasselbalch equation. As for weak acid the
Handerson Hasselbalch equation is

[salt]
pH = pKa + log
[weak acid]

For acetic acid

[CH3COO-]
pH = pKa + log
[CH3COOH]

Putting the values in the above expression

0.02
pH = 4.75 + log
0.01

As

0.02
log = 0.30
0.01

So

pH = 4.75 + 0.30 = 5.05

or
pH = 5.05

Example: Calculate the pH of a solution that is 0.200M in NH3 and 0.300M in NH4Cl.
The dissociation constant vale kb for NH3 is kb= 1.75 x 10-5 at 25 Co

Solution:

This can be solved by using Handerson Hasselbalch equation. As NH3 is weak base and
for basic buffer solution the Handerson Hasselbalch equation is written as
 [salt]
pOH = pKb + log
[weak base]

So for NH3

[NH4Cl ]
pOH = pKb + log
[NH3 ]

Putting the values in the above expression

0.300
pOH = 4.75 + log
0.200

As

0.300
log = 0.176
0.200

So

pOH = 4.75 + 0.176 = 4.92

But for calculation of pH

pKw = pOH + pH

Rearranging the above expression

pH = pKw - pOH

pH = 14 - 4.92

pH = 9.08

Buffer Capacity

Buffer capacity is defined as the number of moles of a strong acid or a strong base that
causes the changes of pH of liter buffer solution by 1 pH unit.

Number of moles of strong acids or base

Buffer capacity =
Change in pH
So a buffer solution that is composed of concentrated mixture solution of both the
components so It means its buffering capacity will be also high and will be neutralize
high amount of strong acid or strong base to bring change in pH.