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CHEMISTRY 9701

Chapter 1 : ATOMS, MOLECULES AND STOICHIOMETRY

1.01 Atoms and Molecules

1. Atom is the smallest particle in which an element can be derived without losing its identity.
2. A molecule is a group of atoms (held by covalent bond) that exists under ordinary conditions. E.g. Cl2 ,
H 2 O , CH4

1.02 The Atomic Theory of John Dalton

1. All matter consists of indivisible particles called atoms. (False: Atoms can be subdivided into electrons,
neutrons and protons.)
2. Atoms of the same element are similar in shape and mass, but differ from atoms of other elements.
(Isotopes have different masses.)
3. Atoms cannot be destroyed or created.
4. Atoms combine together to form “compound atoms” or molecules in simple ratio.

1.0 3 Relative Masses of Atoms, Molecules and Ionic Compounds

The mass of an atom is compared with the mass of a standard atom of carbon – 12 isotope because carbon
is a solid at room temperature and hence, easier to store and transport.

12 B mass of one particle

The relative mass of a particle  fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
mass of one atom of C @12

Relative mass has no unit since it is a ratio. Isotopes are atoms of the same element with different masses.

12 B mass of an isotope
The relative isotopic mass of a particle  fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
mass of one atom of C @12

12 B mass of one atom of an element

The relative atomic mass of a particle  ffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
mass of one atom of C @12

Naturally occurring element has a mixture of isotopes.

E.g. Chlorine has 2 isotopes of 35Cl and 37Cl in the ratio of 3:1.

The % of isotopes is known as abundance.

3ffff
The abundance of 35Cl = B 100%  75%
4
1ffff
The abundance of 37Cl = B 100%  25%
4 b c ` a
relative isotopic mass B abundance
Pffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
The relative atomic mass of an element 
` a ` a total abundance
75 B 35  25 B 37
fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
Ar of Chlorine 
100
 35.5
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Question:
39 40
K exists as K and K . Calculate the abundance of each isotope. (Ar of K = 39.1)

K be x
39
Let the abundance of
40
Let the abundance of K be 100 @x
` a ` a
x 39  100 @x 40
39.1  fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
100
x  90
39
K = 90%
40
K = 10%

1.0 4 Relative Molecular Mass (Mr) of a Molecule

12 B mass of one molecule of a substance

The relative molecular mass, Mr  ffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
mass of one atom of C @12

Mr is the sum of the Ar of all the atoms shown in the formula.

2@ ` a` a
Mr of SO 4  32.1  16 4
 96.1

1.0 5 Relative Formula Mass (Fr) of an Ionic Compound

12 B mass of a formula unit of a compound

The relative formula mass of an ionic compound, Fr  ffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
mass of one atom of C @12

1.06 The Mole

The mole is the amount of substance which contains as many particles (atoms, ions or molecules) as in
exactly 12g of Carbon – 12.

Molar mass is the Ar of Mr in grams.

@1
The unit for molar mass is gmol

Avogadro Constant (L) is the no. of atoms that exist in exactly 12g of C – 12. This no. is 6.02 B10 23
` a mass
No Aof mol n  ffffffffffffffffffffffffffff
Ar or Mr
No Aof particles  n B L

Question:
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a) What is the mass of one mole of aspirin C9 H 8 O 4 ? (C = 12, H = 1, O = 16)

b) How many mole of aspirin are there in
i. 146g
ii. 1.00g if this substance
c) What is the mass in grams of 0.4333 moles of aspirin?
d) How many aspirin molecules are there in 1.74g of this substance?
e) What is the mass in grams of 1 B10 23 molecules of aspirin?
f) How many carbon atoms are there in 1 mole of aspirin?
g) How many oxygen molecules are in 1 mole of aspirin?

Answer:
a) ` a b) (i) b) (ii)
mass g 146g 1.00g
1 mole  ffffffffffffffffffffffffffffffffffffffffffffffffffffffff
` a ` a No Amole  fffffffffffffff No Amole  fffffffffffffffff
9 12  8  4 16 180 180
mass
` a
g  0.81mol  0.006mol
ffffffffffffffffffffffffff
1 mole 
180
mass  180g
c) ` a d) e)
mass g 1.74g Mass  No Amole B Molar mass
0.4333 mol  ffffffffffffffffffffffffff No Amole  fffffffffffffffffB 6.02 B10
23
23
180 180 1 B10
ffffffffffffffffffffffffffffffffff
mass  77.99g  0.01mol  23
B 180
6.02 B10
 29.9mol
f) g)
23 23
No Aparticles  6.02 B10 B 9 No Aparticles  6.02 B10 B 4
24 24
 5.42 B10  1.204 B10

1.07 Molecules and Moles

Concentration of an aqueous solution may be expressed as:
i. Mole of solute per dm³ of solution ( moldm @3 )
@3
ii. Mass of solute per dm³ of solution ( gdm )
b c
MB Vol cm3
fffffffffffffffffffffffffffffffffffffffffffff @3
No Aofmole  M  moldm
1000

Question:
How many moles of water in 1 dm³?

Answer: ` a
3 ` a mass g
1dm  1000cm3  1000g Mr of H2 O  1 2  16 No Amole  ffffffffffffffffffffffffff
1g Mr
Density of water  ffffffffffffff
@1
 18gmol 1000g
1cm3  fffffffffffffffffffffffffffff
@1
18gmol
 1gcm@3  55.56mol
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When a given solution is diluted, the no. of moles of solute remains unchanged after dilution.
M1 V1  M1 V2
Where M1  Initialmolarity
M 2  Finalmolarity after addition of water
V1  Initialvolume of water
V2  Finalvolume of water

1.08 Moles of Gases

1 mole of gas at s.t.p. occupies 22.4dm³
1 mole of gas at r.t.p. occupies 24dm³
S.T.P. = Standard temperature and pressure
f g
0  C and 1atmpressure
273K and 1atmpressure
R.T.P. = Room temperature and pressure
f g
25  C and 1atmpressure
295K and 1atmpressure

1.09 Determination of Ar or Mr
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In a mass spectrometer, bombarding the vaporized with high energy electrons from the hot wire produces
positive ions:
 Positive ions are needed so that it can be deflected by the magnetic field
 The ions are accelerated by an electric field into the magnetic field, which causes the ions to be
deflected from their straight line
 The ions are accelerated to avoid doubly charged ions ( X 2  ) being formed
 The extent of deflection depends on the mass to charge ratio (m/e) of an ion
 A lighter ion is deflected more than heavier one with the same charge
 A doubly charged ion is deflected more than singly charged ion of the same mass

In a mass spectrometer, the field strength is steadily changed so that particles of increasing mass arrive one
after the other at the detector.

A vacuum is maintained inside the mass spectrometer since any air molecules present may hinder the
movement of ions.

A chart record will print a mass spectrum.

35 
Cl

37 
Cl

How many lines in a spectrum represent how many isotopes. Most ions will have charge +1. Hence m/e
ratio = mass of ion

The mass spectrum of an element provides the following information:

1. No. of isotopes present – from the no. of peaks or lines
2. Relative isotopic mass and hence the identity of the isotope from the m/e
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3. Relative abundance of each isotope – from the height of each peak and hence,
4. The relative atomic mass of an element

Question:
The mass spectrum of Mg as shown
24 
Mg

25  26 
Mg Mg

a) What are the isotopes of Mg?

b) What are the species responsible for the peaks?
c) Calculate the Ar of Mg

Answer:
24 25 26
a) Mg , Mg , Mg
24  25  26 
b) Mg , Mg , Mg
` a ` a ` a
24 8  25 1  26 1
c)
Relative abundance  fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
10
 24.3

Question:
85 87
The Ar of Rb is 85.6. Rb exists as Rb and Rb . Draw a predicted mass spectrum of Rb.

Answer: Relative Abundance

Ar  85.6 85
Rb

` a ` a 7
85 x  87 100 @x
fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
85.6 
100
8560  85x  8700 @87x
x  70
87 
85 3 Rb
Rb  70%
87
Rb  30%

85 87
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1.10 Mass Spectrum of Molecules

HCl

A mass spectrum of a compound provides the following information:

1) The identity of fragment ions – from the m/e ratio of the ion
2) The identity of the molecular ion and hence the Mr of the compound – from the highest m/e value
3) Relative abundance of fragment ions or molecular ions of each peak

Relative abundance
35 
Cl
35 
H
 H Cl
37 
Cl 37 
H Cl
m/e
1 35 36 37 38

E.g.: A molecule of chlorine gas is subjected to a mass spectrometer

The mass spectrum obtained is

Relative abundance

35 
Cl
35 
Cl2
37 
Cl
35 37 
Cl @ Cl
37 
Cl2

m/e
35 37 70 72 74

Molecule 35
Cl @ Cl
35 35
Cl @ Cl
37 37
Cl @ Cl
37

Molecular species 35 
Cl2
35  37
Cl @ Cl
 37 
Cl2
m/e 70 72 74
Relative height 3ffff 3ffff f g 1ffff 1ffff
B 3ffff 1ffff B
4 4 B B2 4 4
4 4
9 6 1
 fffffff  fffffff  fffffff
16 16 16

Ratio 9 6 1
Question:
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Draw a mass spectrum when a Br 2 molecule is subjected to a mass spectrometer. Calculate the relative
abundance of the molecular species.

Answer:
Molecule 79
Br 2
79
Br Br
81 81
Br 2

Molecular Species 79
Br 2
 79
Br Br
81  81
Br 2


m/e 158 160 162

Relative Abundance 1fff 1fff 1ffff f g 1fff 1fff 1ffff

1fff 1fff 1
B 
2 2 4 B B 2  fff B 
2 2 4
2 2 2

Ratio 1 2 1

Relative Abundance
79 81 
Br Br
2
79  81 
Br 2 Br 2
1

m/e

158 160 162

Draw a mass spectrum when a BrCl molecule is subjected to a mass spectrometer. Calculate the relative
abundance of the molecular species.

Answer:
Molecule 79
Br Cl
35 79
Br Cl
37 81 35
Br Cl
81
Br Cl
37

Molecular 79 35
Br Cl
 79 37
Br Cl
 81
Br Cl
35  81 37
Br Cl


Species
m/e 114 116 116 118
f g f g f g f g
Relative 3ffff 1fff 6 1fff 1ffff 2 1fff 3ffff 6 1fff 1ffff 2
Abundance B B 2  fff B B 2  fff B B 2  fff B B 2  fff
4 2 8 2 4 8 2 4 8 2 4 8

Ratio 3 1 3 1
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Relative Abundance

79 37  81 35 
4 Br Cl , Br Cl
79 35 
3 Br Cl

81 37 
1 Br Cl

m/e
114 116 118

1.11 Empirical and Molecular Formula

 Empirical shows the simplest whole number ratio of the atoms of the different element in the compound
 Molecular formula shows the actual number of atoms of each element present in one molecule of
compound b c
n empiricalformula  molecular formula
b c
n empiricalformula  Mr

1.12 Calculations of Mr from Ideal Gas Equation

mass
Ideal gas equation given by: PV  fffffffffffffffRT
PV  nRT Mr
mass RT
` a Mr  ffffffffffffffffffffffffff
P  Pressure Pa PV
b c RT
V  Volume m3  density ffffffffff
P
mass
n  no Aof mole  fffffffffffffff density  gm@3
Mr b c
@3
R  gas constant  8.31 Jk mol
@1 @1 volume cm3 Q m3 B10
` a b c
T  Temperature K 3
dm Q m3 B10
@3

` a
 C Q K  273

Question:
0.4g of a gas has a volume of 227cm³ at 27  C and a pressure of 100kPa. Calculate the Mr of the gas.

Answer:
mass RT
Mass  0.4g Mr  ffffffffffffffffffffffffff
PV
@6
Volume  227 B10 m3 0.4 B 8.31 B 300
Temperature  27  273  fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
3 @6
100 B10 B 227 B10
 300K 997.2
3  fffffffffffffffff
Pressure  100 B10 Pa 22.7
 43.9
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Question:
A gas has a density of g/dm³ at 373  C and at a pressure of 200kPa. Calculate the Mr of the gas.

Mass  1.7g RT
Mr  density ffffffffff
Volume  1dm
3 P
@3 Mass B RB T
fffffffffffffffffffffffffffffffffffffffffffffffffffffffff
 1 B10 m3 Mr 
Volume B Pressure
Temperature  27  373
1.7 B 8.31 B 400
 400K Mr  fffffffffffffffffffffffffffffffffffffffffffffffffffffffffffffff
@3 3
3 1 B10 B 200 B10
Pressure  200 B10 Pa

Question:
Calculate the volume occupied when 1g of ice is heated to 323K at 1 atm pressure.

PV  nRT
mass ` a` a
PV  fffffffffffffff R T
Mr
f g
` a ` a 1
fffffffffff
101000Pa B V  8.31 B 323K
189
@3 @3
V  1.48 B10 dm

1.13 Calculations using Combustion Data

The molecular formula of hydrocarbon can be determined by combustion in excess oxygen to form CO2
and H 2 O .
d e
` a yffff ` a yffff ` a
Cx Hy g  x  O 2 Q xCO 2 g  H 2 O l
4 2

Under room temperature or s.t.p. the water produced is a liquid. Hence water is negligible compared with
the volumes of C x H y , O2 and CO2 gases.

Equal volumes gases, under the same conditions of temperature and pressure, contain equal numbers of
molecules or moles. (Avogadro’s Law)

Question:
10cm³ of a gaseous hydrocarbon required 20cm³ of oxygen gas for complete combustion. 10cm³ of CO2
was produced in the combustion. All gases were measured under the same condition. Calculate the relative
molecular formula and hence the relative molecular mass.

Answer: d e
` a y ` a y ` a
C x H y g  x  ffff O2 Q xCO2 g  ffffH2 O l X1
Y
X  fffff 2
4 2 4 Molecular formula  CH 4
10cm³ 20cm³ 10cm³ Y ` a
fffff
 2 @1 Mr  12  4 16
4
Ratio: Y4
1 2 1
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O2 gas can be absorbed completely by soda lime or KOH when the gaseous products of combustion are
passed by over soda lime or KOH, there is a decrease in volume of gas = volume of CO2

Question:
20cm³ of a gaseous hydrocarbon was mixed with 150cm³ of oxygen. The mixture was sparked so that the
hydrocarbon was completely burnt.

The gaseous products had a total volume of 130cm³, when this product was passed over soda lime, the
volume of the product decreased to 90cm³.

Deduce the molecular formula of the hydrocarbon.

d e
` a y ` a y ` a
C x H y g  x  ffff O2 Q xCO2 g  ffffH2 O l
4 2
20cm³ 150cm³

Y
130cm³ - 40cm³ = 90cm³ X2 X  fffff 3
4
20cm³ 60cm³ 40cm³ Y
fffff
 3 @2
4
Ratio 1 3 2 Y4

Question:
25cm³ of C2 H6 was mixed with 35cm³ of oxygen gas. The mixture was electrically sparked so that ethane
gas burnt in oxygen. Calculate:-
a) The volume of gases left after combustion at r.t.p.
b) What is the total change in volume after the reaction.
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1.14 Percentage Composition

E.g. Calculate the percentage composition by mass of benzene C6 H6 .
` a
` a ` a 12 6
fffffffffffffffffffffffffffff
Percentage Composition % of Carbon C  ` a B 100%
12 6  6
 92.3%
` a
` a ` a 1 6
fffffffffffffffffffffffffffff
Percentage Composition % of Hydrogen H  ` a B 100%
12 6  6
 7.7%

1.15 Yield
The mass of product formed in a chemical reaction is called the yield.

Theoretical yield:
Yield of a product calculated from the chemical equation.

Actual yield:
The yield actually obtained in an experiment or in an industrial process. It will be much less due to
incomplete reaction or product loss during the reaction.

Percentage yield:
Is a measure of the efficiency of the reaction.

fffffffActual
ffffffffffffffffffffffyield
ffffffffffffffffffffffff
Percentage yield  B 100%
Theoretical yield

Question:
In an experiment, 23.0g of bromobenzene was obtained from 20g sample of benzene. Calculate the
percentage yield.
C6 H 6  Br Q C6 H5 Br  HBr
Benzene Bromobenzene

20g Actual yield = 23g

20
No Aof mole C6 H6  ffffffff
78
20
Thereoticalyield ofC6 H5 Br  ffffffff
78
20 ` a
Mass ofC6 H5 Br  ffffffffB 72  5  79.9
78
 40g

23g
Percentage yield  ffffffffffffB 100%
40g
 58%