Calculations Used in Analytical Chemistry

Contents
2.1 Some Important Units of Measurements -S.I. Units
2.2 Distinction Between Mass and Weight
2.3 Types of Solutions
2.4 Significant Figure
2.5 Molar Concentrations
2.6 Dilatant Volume Ratio
2.7 Chemical Stoichiometry
2.7.1 Empirical Formula
2.7.2 Molecular Formula
Some Important Units of Measurements
International System of Units (S.I.):
 The international system of units is the modern form of the metric system and is the
most widely used system of measurement.
 It comprises a coherent system of units of measurement built on seven basic units,
which are the second, meter, kilogram, ampere, Kelvin, mole, candela, and a set of
twenty prefixes to the unit names and unit symbols that maybe used when specifying
multiples and fractions of the unit used.
 The system also specifies names for 22 derived units such as lumen and watt for other
common physical quantities.
 The base units are defined in terms of invariant constants of nature such as speed of
light in vacuum and the charge of electron which can be measured with great
accuracy.
 Seven constants are used in various combinations to define the seven base units.
 The reliability of S.I. units depend not only on the precise measurement of standards
for the base units in terms of various physical constants of nature, but also on precise
definitions of those constants.
 The set of underlying constants is modified as more stable constants are found, or
may be more precisely measured.
 For example, in 1983 the meter was defined as the distance that light propagates in
vacuum in a given fraction of a second, thus making the value of the speed of light in
terms of the defined units exact.
Table: The seven S.I. base Units
Quantity Name Symbol
Time Second S
Length meter M
Mass kilogram kg
Electric current ampere A
Temperature Kelvin K
Amount of Substance mole Mol
Luminous intensity candela cd

 The motivation for the development of S.I. units was the diversity of units that had
sprung up within centimeter-gram-second (CGS) systems and the lack of
coordination between the various disciplines that used them.
 The General Conference on Weights and Measures which was established by the
meter convention of 1875, brought together many international organizations to
establish the definitions and standards of new systems and to standardize the rules
for writing and presenting measurements.
 The system was published in 1960 as a result of an initiative that began in 1948, It is
based on meter-kilogram-second system of units (MKS) rather than any variant of the
CGS.
 The derived units in the S.I. are formed by powers, products or quotients of the base
units and are potentially unlimited in number.
 Derived units are associated with derived quantities, for example, velocity is quantity
that is derived from the base quantities of time and length and thus the S.I. derived
unit is meter per second (symbol: Velocity (V) = m/s).
 The dimensions of derived units can be expressed in terms of the dimensions.
 Combination of base and derived units may be used to express other derived units.
For example, the S.I. unit of force is the newton (N), the SI unit of pressure is the pascal
(Pa) and the pascal can be defined as one newton per square meter (N/m 2).
 Force (F) = Newton (N)
Pressure (P) = Pascal (Pa) = N/m2

 In May 2019, the international system of units redefined the basic units.
 In the redefinition, four of the seven S.I. base units - the kilogram, ampere, Kelvin,
and mole were redefined by setting exact numerical values for the Planck constant
(h), the elementary electric charge (e), the Boltzmann constant (k) and the Avogadro's
constant (NA), respectively.
S.I. base units Redefined S.I. base units based on
Kilogram Planck constant (h)
Ampere The elementary electric charge (e)
Kelvin The Boltzmann constant (k)
mole The Avogadro’s constant (NA)

 The second, meter and candela are already defined by physical constants and were
subject to correction to their definitions.
 The new definitions aimed to improve the S.I. without changing the value of any
units ensuring continuity with existing measurements.
 Table : S.I. Prefixes is given below.
Distinction Between Mass and Weight
 The terms 'mass' and ‘weight’ are used interchangeably in ordinary conversation but
the two words don't mean the same thing.
Mass Weight
Mass is the amount of matter in a Weight is a measure of how the force of
material/body. gravity acts upon that mass.
Or
Weight is the measure of the amount of
force acting on a mass due to the
acceleration due to gravity.
Mass is denoted using m or M. Weight is usually denoted by W.
Weight is the mass multiplied by the
acceleration of gravity (g).
W=mxg
 The difference between mass and Weight is given below.
Mass Weight
(1) Mass is the property of matter. (1) Weight depends on the effect of
gravity.
(2) The mass of an object is the same (2) Weight increases or decreases with
everywhere. higher or lower gravity. (W = m x g)
(3) Mass can never be zero. (3) Weight can be zero if no gravity acts
upon an object as in space.
(4) Mass does not according to location. (4) Weight varies according to location.
(5) Mass is a scalar quantity. (5) Weight is a vector quantity.
(6) Mass may be measured using an (6) Weight is measured using
ordinary balance. spring balance.
(7) Mass is usually measured in grams and (7) Weight is often measured in newtons
kilograms. unit of force.
 On earth our weight is slightly lower on a mountain top than at sea level.
 Similarly, our weight will be different on other planets.

Types of Solutions
(i) Solute:
 The substance which dissolves in solution or which is present in less amount is called
solute.
(ii) Solvent:
 The substance in which solute dissolves or which is present in large amount is called
solvent.
 The three states of matter-solid, liquid and gas may play role of either solvent or
solute.
 There are nine types of solutions depending on the physical states of solvents and
solutes.
Molar concentration [or Molarity (M)]:
 Molarity (M) is defined as the number of moles of solute per litre of solution.

Molarity (M) =

Molal solution or Molality (m):

 Molality (m) is defined as the number of moles of solute per kilogram of solvent.

Molality (m) =

 Molarity is the measurement of moles in the total volume of solution, whereas,

molality is the measurement of moles in relationship to the mass of solvent.
 When water is a solvent and the concentration of the solution is low these differences
can be negligible (d = 1.00 g/ml).
 However, when the density of the solvent is significantly different, than one or the
concentration of the solution is high, these changes become much more evident.
Example: Compare the molar and molal volumes of 1 mol of a solute dissolved in CCl 4
(d = 1.59 g/ml).
Solution:
For a 1 molar solution, 1 mole of solute is dissolved in CCl 4 until the final volume of
solution is one litre.
For 1 molal solution, 1 mol of solute is dissolved in 1 kg of CCl 4.
( ) ( )
Density (d) = Volume (ml) =
( )

1kg = 1000 gram Volume (ml) = = 629 ml CCl4

.

∴ 1 kg CCl4 = 629 ml CCl4

Normality:
 Normality (N) is defined as the number of mole equivalents per litre of solution.

Normality (N) =

 Like molarity, normality relates the amount of solute to the total volume of solution,
however, normality is specifically used for acids and bases.
 How to calculate normality from molarity?
 The mole equivalents of an acid or base are calculated by determining the number of
H+ or OH- ions per molecule.
N = n x M (where n is an integer)

Equivalent weight =
.
 For an acid solution, n is the number of H+ ions provided by a formula unit of
acid.
Example: A 3M H2SO4 solution is the same as 6N H2SO4 solution.
Molecular weight of H2SO4 = 98 gm/mole Equivalent weight of H2SO4 = 49
3M H2SO4 = 3 x 98 = 249 gm 6N H2SO4 = 6 x 49 = 249 gm
∴ 3M H2SO4 = 6N H2SO4
or
N=nxM
where n = no. of H+ ions liberated in H2SO4 = 2
6N=2x3M,
∴ 6N H2SO4 = 3M H2SO4
 For a basic solution, n is the number of OH- ions provided by a formula unit of
base.
Example: A 1M Ca(OH)2 solution is the same as 2N Ca(OH)2.
Molecular weight of Ca(OH)2 = 74.09 g/mol Equivalent weight of Ca(OH)2 = 37.05
1M Ca(OH)2 = 1 x 74.09 = 74.09 gm 2N Ca(OH)2 = 2 x 37.05 = 74.09 gm
∴ 1M Ca(OH)2 = 2N Ca(OH)2
 or
N=nxM
where n = no. of OH- ions liberated in Ca(OH)2 = 2
1 N Ca(OH)2 = 2 x 1M Ca(OH)2
∴ 1 N Ca(OH)2 = 2 M Ca(OH)2
 The normality of a solution is never less than its molarity.

Number of moles (n):

( )
Number of moles (n) =
( )

Ex. how many moles are present in 50 g of O 2.

( ) ( )
Number of moles (n) = = = 1.56 mol
( ) ( / )

 One mole of a substance is equal to 6.022 × 1023 units of that substance (such as
atoms, molecules or ions).
1 mole of a substance = 6.022 × 1023 units of that substance
 The number 6.022 × 1023 is known as Avogadro's number or Avogadro's constant
(NA).
 One mole is defined as the amount of substance containing as many elementary
entities (atoms, molecules, ions, electrons, radicals etc.) as there are atom in 12
grams of 12C (6.023 x 1023).
1 mole substance = Atoms in 12 grams of 12C (6.023 x 1023)
 The mass of one mole of substance is equal to its relative molecular mass expressed
in grams. It is also spelled as mol.
 Moles can be scaled just like grams or litres.
1 mole = 1000 millimoles (m mol).
 To convert moles to millimoles multiplied 1000 and to convert millimoles to moles,
divide by 1000.
Example: A solution of NaOH (molar mass 40 g/mol) was prepared by dissolving 4.6 g
of NaOH in 500 cm3 of water. Calculate molarity of NaOH.
Solution:
Mass of NaOH = 4.6 x 10-3 kg 1 kg = 1000 g
Volume of solution 500 cm3 = 0.5 dm3 1000 ml or cm3 = 1 decimeter (dm) = 1 lit.

Molarity (M) =

( )
Number of moles (n) =
( )

Molarity of NaOH solution (M) =

×

. ×
Molar mass of NaOH =
× × .

= 0.23 mol dm-3

= 0.23 M
Example: Find the milli equivalent of NaOH in 20 g.
Solution:
/
equivalent wt. of NaOH = =
.

Milli equivalent of NaOH = x 1000

Milli equivalent of NaOH = x 1000 = 500

Example: Find milli equivalent of H2SO4 in 2.45 g.

Solution:
/
equivalent wt. of H2SO4 =
.
= = 49

Milli equivalent of H2SO4 = x 1000

.
Milli equivalent of H2SO4 = x 1000 = 50
Example: Find normality of H2SO4 having 50 milli equivalent in 2 litres.
Solution:
1 equivalent = 1000 milli equivalent N x V (in L) = Equiv. wt.

Normality (N) = Nx2L=

N = 0.025 N

Example: Describe the preparation of 2.0 L of 0.10 M BaCl 2 from BaCl2 2H2O (244.3
g/mol).
Solution:
To produce this solution, we need,
0.10 M BaCl2 2H2O means,
1 L = 0.10 mol BaCl2 2H2O
0.10 mol BaCl2 2H2 O
 How many mole in 2 L = 2.0 L X = 0.2 mol BaCl2 2H2O
L
244.3 g/mol BaCl2 2H2O means,
1 mol = 244.3 g BaCl2 2H2O
 How much gram in 0.2 mol BaCl2 2H2O
.
= 0.2 mol BaCl2 2H2O X
= 48.86 g BaCl2 2H2O
Or
1 mol = 244.3 g BaCl2 2H2O = 1 M =1.0 L
 How much gram required to prepare 2.0 L, 0.1 M BaCl 2 2H2O
.
= X 2.0 L X 0.1 M BaCl2 2H2O
= 48.86 g BaCl2 2H2O
Example: Describe the preparation of 500 ml of 0.074 M Cl- solution from solid BaCl2
2H2O (244.3 g/mol).
Solution:
500 ml = 0.5 L
244.3 g/mol BaCl2 2H2O
1 mol = 244.3 g BaCl2 2H2O = 1 M
How many gram for 0.074 M BaCl2 2H2O
.
= X 244.3 g BaCl 2H O = 18.078 g BaCl 2H O
.

18.078 g BaCl 2H O = 1.0 L

How many gram for 0.5 L BaCl2 2H2O
.
= X 0.500 L = 9.0391 g BaCl2 2H2O
.

9.0391 g BaCl2 2H2O = 2 Cl-

How many gram for one Cl-
.
= X 1 Cl = 4.519 g BaCl2 2H2O

 Dissolve 4.5195 g of BaCl2 2H2O in water and dilute to 500 ml.

Or
244.3 g/mol BaCl2 2H2O
1 mol = 244.3 g BaCl2 2H2O = 1 M = 1 L
How many gram for 0.5L, 0.074 M BaCl2 2H2O
. .
= X X 0.5 L= 9.039 g BaCl 2H O
. .

9.0391 g BaCl2 2H2O = 2 Cl-

How many gram for one Cl-
.
= X 1 Cl = 4.519 g BaCl2 2H2O

 Dissolve 4.5195 g of BaCl2 2H2O in water and dilute to 500 ml.

Example: Calculate normality and molarity of the following:
(a) 3.65 g of HCl in 200 ml of solution.
Solution:
.
Normality (N) = Normality (N) =
.
( ) N = 0.5 N
Equivalent of HCI =
( / )
.
= = 0.1
.

Volume of solution = = = 0.2 litre

.
Molarity (M) = Molarity (M) =

Valency of H+ = 1 M = 0.5 M

(b) 1/10 mole of H2SO4 in 500 ml of solution.

Solution:
.
Normality (N) = Normality (N) =
.
Valency = 2 N = 0.4 N
Equivalent of H2SO4 = Mole x Valency

= x 2 = 0.2

Volume of solution = = = 0.5 litre

.
Molarity (M) = Molarity (M) =

Valency = 2 M = 0.2 M
Example: Calculate normality of mixture obtained by mixing
(a) 100 ml of 0.1 N HCl + 50 ml of 0.25 N NaOH
Solution:
Milli equivalent of HCI = 100 x 0.1 = 10
Milli equivalent of NaOH = 50 x 0.25 = 12.5
HCl and NaOH are neutralized each other with equal equivalents.
Milli equivalent of NaOH left = 12.5 - 10 = 2.5
Total volume of solution 100 + 50= 150 ml
.
Normality of NaOH left (Nleft) = = 0.0167 N

(b) 100 ml of 0.2 M H2SO4 + 100 ml of 0.2 M NaOH

Solution:
Milli equivalent of H2SO4 = 100 x 0.2 x 2 = 40
Milli equivalent of NaOH = 100 x 0.2 x 1 = 20
Milli equivalent of H2SO4 left = 40 - 20 = 20
Total volume of solution = 200 ml

Normality of H2SO4 left = = 0.1 N

Percentage by mass (W/W):

 The mass of solute in grams dissolved in solvent to form 100 grams of solution is
called percentage by mass.

Percentage by mass of solute (W/W) = × 100

Percentage by mass of solute = × 100

Example: 12 g of urea was dissolved in 750 g of water. Calculate percentage by mass of
urea in solution.
Solution:

Percentage by mass of urea (W/W) = × 100

= × 100

= 1.5748

Percentage by volume (V/V):

 It is defined as the ratio of number of parts by volume of the solute to one hundred
parts by volume of solution.

Percentage by volume of solute (V/V) = × 100

 When both the components of the solution are in liquid phase then determination
of their precise volume is possible using burettes, pipettes, measuring cylinders,
volumetric flasks, etc.
 It must be noted that the total volume of solutions may not be equal to the sum of
volumes of solute and solvents as some of the particles may occupy empty spaces.
 Ex. voids present in the structure of liquids.
 Volume is temperature dependent quantity, hence percentage by volume changes
with change of temperature.
Example: 68 cm3 of ethyl alcohol was dissolved in 500 cm3 water to form 564 cm3 of
solution of ethyl alcohol. Calculate percentage volume of ethyl alcohol in water. (Note:
Volume are not additive)
Solution:

Percentage by volume of ethyl alcohol (V/V) = × 100

= × 100
= 12.05 %

Example: HNO3 has specific gravity of 1.42 g/ml and contains 70% by strength HNO 3
Calculate normality of acid [Eq. wt. = 63].
Solution:
Valency of HNO3 = 1
Normality (N) =
Strength of HNO3 =70% (v/v)
.
Means 70 ml HNO3 + 30 ml solvent = 100 ml Normality (N) =
.
total solution
N = 15.8 N
1000 ml = 1 litre
Volume of solution = 100 ml = 0.1 liter
Volume of HNO3 = 70 ml

Density (d) =

Density (d) x Volume = Mass

Weight of HNO3 in solution
= 1.42 (g/ml) x 70 ml

Equivalent of HNO3 =

.
= = 1.58
/
Mole fraction:
 Mole fraction is a more scientific way of expressing concentration components of
solutions.
 The mole fraction of any component of solution is defined as the ratio of number
of moles of that component present in the solution to the total number of moles of
all the components of the solution.

 For binary solution, if n1 and n2 are number of moles of solvent and solute,

respectively present in the solution, then

Mole fraction of solvent (N1 or X) =

Mole fraction of solute (N2 or X) =

 Note that the sum of mole fractions of all components of solution is always unity.
N1 +N2 = 1
 Mole fraction is also unitless quantity.
Example: 25 g of sodium chloride (molar mass 58.5 g/mol) dissolved in 400 g of
water (molar mass 18 g/mol). Calculate the mole fraction of sodium chloride and
water in the solution.
 Solution:
Moles of sodium chloride (n1) Moles of water (n2)

= =

= = 0.4274 mol = = 22.22 mol

. / /

Mole fraction of sodium chloride (X1) Mole fraction of water (X2)

= =

. .
= = 0.01887 = = 0.9811
. .
Parts per million (ppm):
 The concentration of solute present in trace quantity is expressed in parts per
million (ppm).
 It is the mass or volume of solute in gram or cm3 per 106 g or 106 cm3 of the solution.

Parts per million (ppm) = × 106

Example: If 0.5 g of solute is present in 107 g of a solution then find out concentration
in the ppm.

Parts per million (ppm) = × 106

.
Parts per million (ppm) = × 106 = 0.05

Parts per thousand (ppt):

 It is the mass or volume of solute in gram or cm3 per 103 g or 103 cm3 of the solution.

Parts per thousand (ppt) = × 103

Parts per billion (ppb):
 It is the mass or volume of solution in gram or cm3 per 109 cm3 of solution.

Parts per billion (ppb) = × 109

 These three can also be expressed as mass to mass or volume to volume or mass to
volume.

Specific gravity of solution:

Specific gravity is the weight of 1 ml of solution.

Specific gravity = =
Strength of solution:
 Ihe amount of solute present in one litre of solution is called strength (S).

Strength (S) =

Strength (S) = Normality × Equivalent weight

Example: What is the strength in gram per litre of a solution of H 2SO4, 12 ml of which
neutralized 15 ml of N/10 NaOH solution?
Solution:
Strength of H2SO4 = Normality x Equivalent weight

Equivalent of H2SO4 = Molecular weight / Valency Strength = N1 x Eq. wt.

= 0.125 x 49
= = 49
= 6.125 g/litre
Milli equivalent of H2SO4 = Milli equivalent of NaOH
Milli equivalent = (N x V in ml)
(N1 x V1) = (N2 x V2)

 N1 x 12 = x 15

 N1 = x = 0.125 N

Example: The densities of 3 M solution of Na 2S2O3 is 1.35 g/ml. Calculate:

(i) Percentage by weight of Na2S2O3.
(ii) Mole fraction of Na2S2O3.
(iii) The molalities of Na+ and S2O3-2 ions.
[Given: Mol. wt. of Na2S2O3 = 158 g/mol]
Solution:
Na2S2O3 has molarity = 3 mole/litre Volume of solution 1 litre = 1000 ml
Mole of Na2S2O3 = 3
Density (d) =
Molecular weight of Na2S2O3 = 158 g/mole
Density (d) x Volume = Mass
means,
1 mole of Na2S2O3 = 158 g Na2S2O3 Weight of solution = 1000 x 1.35 = 1350 g
Weight of 3 mol of Na2S2O3 = 3 x 158 = 474 g Weight of water =
[Weight of solution – Weight of Na2S2O3]
= 1350 - 474 = 876 g water
(i) % by weight of Na2S2O3
Weight of Na2 S2 O3
= Weight of solution
X 100

= X 100 = 35.11

(ii) Mole fraction of Na2S2O3 (iii) Molality of Na+

Mole of Na2 S2 O3
= Mole of Na2 S2 O3+Mole of H2O
Na2S2O3 2Na+ + S2O3-2
3M 2X3 1X3
No. of mol. of H2O = Weight of Na
+
= Weight of H2 O in gram
X 1000

= = 48.67 6
= 876
X 1000

= = = 0.058 = 6.85
. .
Molality of S2O3-2
Mole fraction of H2O
−2
Mole of S2 O3
= Mole of H2 O = Weight of H2 O in gram
X 1000
Mole of Na2 S2 O3+Mole of H2O
3
=
.
=
.
= 0.9418 = 876
X 1000
. .
= 3.42

Ionic strength (𝝁):

 Ionic strength (𝜇 ) of a solution is given by

𝝁= ∑C Z
 where, Ci is the concentration (in mol/lit) of ion and Z is its valency
Example: A solution is 0.5 M in MgSO4 0.1 M in AlCl3. What is the total ionic strength
of solution?
Solution:
The ionic strength (𝜇) of the solution is given by

𝝁= ∑C Z
where, C is the concentration and Z is the valency of it.
C1 = 0.5 M for MgSO4, C2 = 0.1 M for AlCl3
MgSO4 → Mg+2 + SO4-2
AlCl3 → Al+3 + 3Cl-

𝝁 = [(0.5 x 22) + (0.5 x 22) + (0.1 x 32) + 3 (0.1 x 12)]

= [(0.5 x 4) + (0.5 x 4) + (0.1 x 9) + (0.3 x1)]

= [2 + 2 + 0.9 + 1.2]

= [6.1] = 2.6

Significant Figure:
 The accuracy of a measurement is suggested by number of digits used to express that
measurement.
 The term digits denote any one of the ten numericals including zero.
 For example, the number 0.30 is less accurate than the number 0.300.
 In weighing operation, 0.300 gram suggested that the weighing operation is carried
out only to the nearest milligram while the number 0.3000 gram suggested that the
weighing is done nearest to ten milligrams.
 In any measurement, the last digit is uncertain.
 The number 0.500 g implies an accuracy of 5 parts per thousand while the number
0.5000 implies an accuracy of 0.5 parts per thousand.
 Significant figure is defined as a digit which denotes the amount of quantity in the
place in which it stands.
 Alternately, it is defined as the number of digits necessary to express the results of a
measured precision.
 For example, the measurement 0.353 is said to have three significant figures.
 The weight 3.750 g is said to have four significant figures.
 While determining the correct numbers of significant figures the presence of zeros
creates confusion.
 To avoid the confusion, it can be stated as a rule that the digit zero is significant figure
except when it is the first figure the number.
Quantities Significant Quantities Significant
figures figures
1.4290 5 0.0027 2
2.0030 5 0.005 1
3.1024 5 0.04120 4
 In the quantities 1.4290, 2.0030, 3.1024 gram the zeros are significant and each contain
five significant figures.
 In the quantity 0.0027 kg zero are not significant figures because they serve to locate
the decimal point can be omitted by proper choice of unit e.g. 2.7 gram. Therefore, this
number contains only two significant figures.
 The number 0.005 has one significant figure, while the number 0.04120 has four
significant figures.
 The computation of results and their presentations with the help of significant figures
can be done using following rules:
 (1) The observations and results expressed by as many significant figures as possible
retaining only one digit uncertain.
 A weight taken on ordinary balance should be written as 15.439 gram which indicates
that it is 15.438 and 15.440 gram i.e. last digit 9 is uncertain. It should not be expressed
as centigram.
 The ordinary balance gives a weight up to accuracy of 1 mg only (1 g = 1000 mg).
Reading Reading in range Uncertain digit Accuracy
15.439 g 15.438 g - 15.440 g 9 1 mg
 Similarly, volume read on burette should be written as 12.8 ml which indicates that it
is between 12.7 ml and 12.9 ml. Therefore, last digit 8 is uncertain.
Reading Reading in range Uncertain digit Accuracy
12.8 ml 12.7 ml -12.9 ml 8 0.1 ml
 It should not be expressed as 12.80 ml because it implies that the volume is in between
12.79 ml and 12.81 ml which indicate an accuracy of 0.01 ml which is not the case.
 The burette can read up to the accuracy of 0.1 ml only.
 (2) In rounding off quantities to the correct number of significant figures if last
rejectable digit is 5 or greater, the earlier digit increases by one unit.
 But if the last digit is less than five, it is dropped.
 For example, the observation 28.376 or 27.585 is rounded off to 28.38 and 27.59, while
the observation 22.374 is rounded off to 22.37.
Reading Rounded off
28.376 28.38
27.585 27.59
22.374 22.37
 (3) In addition, and subtraction, the number of significant figures in the sum or
difference can change from the number of significant figures of the components.
 Only the last digit of the sum or difference may contain uncertainty.
 A sum or difference cannot have decimal places more than that of component number
which has the least number of decimal places.
 For example, consider following additions:
 In first sum, all the three numbers have three significant figures, but 25.1 have least
decimal places one and hence it limits the number of significant figures in the answer.
Therefore, only one decimal place can be used in the answer.
  In second Sum, all three numbers have same four decimal places. The first number
have lowest number of significant figures two. The result can be expressed up to four
decimal places.
 Note that in this case, the answer has one more significant figure than any component
which is allowed.
 In third sum all the three number have different significant figures.
 The number 8.03 has least decimal places namely two hence the answer has only two
decimal places.
1 Dec. pt. Sig. fig. 2 Dec. pt. Sig. fig. 3 Dec. pt. Sig. fig.

25.1 1 3 0.0035 4 2 12.412 3 5

3.23 2 3 5.1263 4 5 0.0027 4 2
0.425 3 3 6.8042 4 5 8.03 2 3
Sum 28.8 3 11.9340 6 20.44 4
Dec. pt. = Decimal point, Sig. fig. = significant figures
 (4) In multiplication and division, in each component one more significant figure is
allowed to be retained than is present in the component which has the largest
uncertainty.
 However, the product or quotient should contain the same number of significant
figures which are present in the component which has the largest uncertainty or
which is least accurate.
 For example, consider the multiplication of 15.3 x 0.2198.
 Out of these components, 15.3 is the number which has larger uncertainty or which is
less accurate.
 It has three significant figures, so the other component can have 3 + 1 = 4 significant
figures. So, we retain the second component as 0.2198.
 The answer will be 3.36294 which is an incorrect increase in the number of significant
figures.
 The component which is less accurate has three significant figures, so the product
should also be expressed in three significant figures.
 Therefore, the product is then written as 3.36 only.
 Consider a division 42.41/0.015.
 Out of two components, 0.015 is the number which has two significant figures.
 So, the other component can have 2 + 1 = 3 significant figures. Hence, it is written as
42.4.
 The answer will be 2.82666 x 103 which is an incorrect answer with increase in number
of significant figures.
 It should be written in two significant figures only.
 Therefore, the answer will be 2.8 x 103.
Multiplication Sig. fig. Next figure
with sig. fig.
15.3 3 3+1=4
0.2198 4 0.2198
15.3 x 0.2198 3
= 3.36 Ans. with lowest sig. fig.

Division
42.41 4 2+1=3
0.015 2 42.4
42.4/0.015
= 2.8 x 103 Ans. with lowest sig. fig

 (5) When large number of multiplications or divisions are to be carried out,

logarithmic tables are used.
Molar Concentrations:
 Molar concentrations can be expressed in two ways
(1) Molar analytical concentration:
 It is the total number of moles of solute, regardless of its chemical state in one litre of
solution.
(2) Molar equilibrium concentration:
 Equilibrium is a state of dynamic balance where the ratio of the product and reactant
concentrations is constant.
 The molar equilibrium concentration or just equilibrium concentration refers to the
molar concentration of a particular species in a solution at equilibrium.
 To specify the molar equilibrium concentration of a species, it is necessary to know
how the solute behaves when it is dissolved in a solvent.
 They are usually symbolized by placing square brackets around the chemical formula
for the species.
 For example, [H2SO4] = 0.01 M, [H+] = 0.01 M etc.
 The molar analytical concentration of [H2SO4] is given by
[H2SO4] = [SO4-2] + [HSO4-2]
 Because [SO4-2] and [HSO4-2] are only two sulphate containing species in the
solution.
 Molar equilibrium concentrations are [SO4-2] and [HSO4-2].
Example 2.1 Calculate the analytical and equilibrium molar concentration of the solute
in an aqueous solution that contains 285 mg of acetic acid (60.0 g/mol) in 10 ml (the acid
is 73% ionized in water).
Solution:
First, we calculate number of moles of acetic acid, which we designate as HA and
divide it by volume of solution, 10.0 ml or 0.0100 L (∵ 1.0 L = 1000 ml)
285 mg of HA = 0.285 g of HA
Now, 60.0 g/mol HA means in 60 g HA = 1 mol

 How many mol in 0.285 g HA = n = 0.285 g HA X

n = 4.75 x 10-3 mol HA

The molar analytical concentration, CHA is then given by
.
C =
.
= 0.475 mol HA/L = 0.475 M
In this solution, 73% of HA dissociated giving H + and A- as
HA ↔ H++A-
The equilibrium concentration of HA is then 27% of C HA. Thus,
( – )
[HA] = CHA X

( . X )
= CHA X

= 0.475 x 0.27
= 0.12825 mol/L
[HA] = 0.128 M
The equilibrium concentration of A- is equal to 73% of analytic concentration of HA. i.
( )
[A-] = X 0.475 mol HA/L = 0.34675 M

Since, 1 mole of H+ is formed for each mole of A-, we can write

[H+] = [A-] = 0.34675 M
Dilatant Volume Ratio
 A dilatant material is one in which viscosity increases with the rate shear strain (shear
strain means an opposite forces in parallel direction to the surface of an object).
 It is a non-Newtonian fluid where the shear viscosity increases with applied shear
stress.
 In Newtonian fluids, viscosity remain constant, no matter the amount of shear applied
for a constant temperature.
 These fluids have a linear relationship between viscosity and shear stress.
 For example, water, mineral oil, gasoline, alcohol, etc.
 Dilatant is only one type of deviation from Newton's law and it is controlled by factors
like particle size, shape and distribution of particle-particle, particle volume fraction,
particle-particle interaction.
 The properties of these suspensions depend on Hamaker theory and Van der Waal's
forces and can be stabilized electrostatically.
 The properties of these systems are due to the surface chemistry of particles in
dispersion, known as colloids.
 This can be readily seen with a mixture of corn starch and water.
 Sand completely soaked with water also serves as dilatant material.

Non-Newtonian Fluids:
 They are opposite to Newtonian fluids. When shear is applied on them the viscosity
of fluid changes.
 They are of four types:
(1) Dilatant:
 Viscosity of fluid increases when shear is applied.
 For example, Quicksand, cornflour and water, silly putty, etc.
(2) Pseudoplastic:
 They are opposite of dilatant, the more shear applied, the viscosity it becomes less.
 For example, ketchup.
(3) Rheopectic:
 They are similar to dilatant but difference is that viscosity increase is time
dependent.
 For example, gypsum paste, cream.
(4) Thixotropic:
 When shear is applied, viscosity decreases. This is time dependent property.
 For example, paint, cosmetics, glue, asphalt.

Chemical Stoichiometry
Empirical Formula:
 An empirical formula is defined as the formula which represents the simplest ratio
in which the atoms of different elements are present in a molecule of a given
compound.
 For example, (1) Glucose has formula C6H12O6.
 Therefore, in one molecule of glucose there are six atoms of carbon, twelve atoms
of hydrogen and six atoms of oxygen.
 The ratio of C: H: O is 6:12:6 and simply written as 1: 2: 1.
Empirical formula of glucose is CH2O.
 (2) Acetic acid has the formula CH3COOH.
 Therefore, in one molecule of acetic acid, there are two carbon atoms, four
hydrogen atoms and two oxygen atoms.
 The ratio of C:H:O is 2:4:2 which is simply 1:2:1.
Empirical formula of acetic acid is CH2O.
 Thus, compounds may have same empirical formula, but different molecular
formula.
Determine of Empirical Formula:
 (1) The percentage of each element present in the compound is found out.
 If sum of all these percentages is not 100 then remaining percentage will be that of
oxygen.
 If sum is 100, it means in that compound, oxygen is absent.
 (2) These percentage values of atoms are then converted into gram-atom by
dividing respective percentage by atomic weight of the respective atoms.

 Gram atom =

 (3) Then every gram atom value is divided by the smallest common factor to get
simple atomic ratio.

 Atomic ratio =

 (4) To get integral values of each element, the minor fractions are neglected.
 This integral ratio of atoms represents the empirical formula.
Example: An organic compound contains 26.6% C, 2.22% H and 71.18% oxygen. Find
its empirical formula.
Solution: Total percentage = 100
Element % Gram atom = Atomic ratio =
𝐏𝐞𝐫𝐜𝐞𝐧𝐭𝐚𝐠𝐞 𝐨𝐟 𝐚𝐭𝐨𝐦 𝐆𝐫𝐚𝐦 𝐚𝐭𝐨𝐦
𝐀𝐭𝐨𝐦𝐢𝐜 𝐰𝐞𝐢𝐠𝐡𝐭 𝐒𝐦𝐚𝐥𝐥𝐞𝐬𝐭 𝐜𝐨𝐦𝐦𝐨𝐧 𝐟𝐚𝐜𝐭𝐨𝐫

C 26.6 [26.6 / 12] = 2.21 [2.21 / 2.21] = 1

H 2.22 [2.22 / 1] = 2.22 [2.22 / 2.21] = 1.004
O 71.18 [71.18 / 16] = 4.44 [4.44 / 2.21] = 2.009
 The empirical formula of compound is CHO 2.
Example: An organic compound contains 38.74% C, 6.7% H. Find its empirical formula.
Solution:
Total percentage = 38.74 + 6.7= 45.44
 Remaining percentage 100 - 45.44 = 54.56% should be that of oxygen.
Element % 𝐏𝐞𝐫𝐜𝐞𝐧𝐭𝐚𝐠𝐞 Atomic ratio =
Gram atom =
𝐀𝐭𝐨𝐦𝐢𝐜 𝐰𝐞𝐢𝐠𝐡𝐭 𝐆𝐫𝐚𝐦 𝐚𝐭𝐨𝐦
𝐒𝐦𝐚𝐥𝐥𝐞𝐬𝐭 𝐜𝐨𝐦𝐦𝐨𝐧 𝐟𝐚𝐜𝐭𝐨𝐫
C 38.74 [38.74 / 12] = 3.22 [3.22 / 3.22] = 1
H 6.7 [6.7 / 1] = 6.7 [6.7 / 3.22] = 2.08
O 54.56 [54.56 / 16] = 3.41 [3.41 / 3.22] = 1.05
Empirical formula of compound is CH2O.
Molecular Formula
 The empirical formula of a compound gives the simplest ratio of the number of
different atoms present, whereas the molecular formula gives the actual number
of each different atom present in a molecule.
 The molecular formula is commonly used and is a multiple of the empirical
formula.
Molecular formula = n x Empirical formula
 where, n is a whole number
Example: The empirical formula of a compound is CH 2O and its molecular weight is
90.0. Find molecular formula of that compound.
Solution:
Empirical formula weight 12 + 2 + 16 = 30

n= = =3

Molecular formula = n x Empirical formula

= 3 x CH2O
= C3H6O3
 Molecular formula of the compound is C3H6O3.