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H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr.

School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 1

Atomic Structure
Atomic structure means which particles and how these particles are arranged in an atom.
Q-1 Define relative isotopic mass, relative atomic mass, atomic mass unit, relative
formula mass and relative molecular mass. (You can consult your book or notebook but be
specific while using the terminology)
In these definitions do not use weight instead of mass.
When the word relative or mass of single particle (atom, molecule, ion or formula unit)
is there, do not use a unit. Use gmol
-1
when the words molar or mass of one mole is
there.

Measuring the masses of atoms------------Mass Spectrometer
1. Sample should be vaporized first so that
particles can move easily in the machine.
2. Ionization: These particles are bombarded
with high speed electrons. These in-
coming electrons knock out one or more
electrons from the particles of sample,
making the particles positively charged.
3. The positively charged ions are now
accelerated through electric field.
4. They passed through a velocity selector,
which allows only those ions to go to the
next chamber, which are moving at the
same velocity. Purpose: we will separate
the ions, next in the magnetic field, on the
basis of the differences in their masses
and charges (m/e).

5. Magnetic field deflects the beam of ions on the basis of their m/e. Higher is the m/e lesser
will be the deflection, shown in diagram of mass spectrometer. So the beam of ions is the now
separated into groups of ions of different masses. By setting the magnetic, ions of the same m/e
are made to fall on the detector through an outlet. This falling of ions on the detector takes
place turn by turn in groups.
6. The detector detects that how many types of the ions are coming. An electric current is
produced, directly proportional to the ions falling, in the detector. This strength of electric
current give the relative or percentage abundances of the ions.
H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 2

7. The current is of very low strength, so first current is amplified in each case.
8. This current is fed, after amplification, to the recorder.
Mass spectrum: The results from the mass spectrometer are obtained in the form of a graph called mass
spectrum. On x-axis m/e of the ions or simply the relative mass (because most of the ions have +1
charge) and y-axis relative abundances of the ions are taken.
Q-2 The fig. opposite shows the mass
spectrum of atomic chlorine.
(a) Label the x-axis and y-axis.
(b) Explain how many isotopes chlorine has.
Suggest a reason for your answer.
(c) Write the formulae of the ions responsible
for the peaks at 35 and 37.
(d) Find the relative abundance of each isotope.
(You will use a ruler scale)
(e) From the relative abundance, calculate the
percentage abundance of each isotope.

(f) Calculate relative atomic mass of chlorine up to four significant figures.
In many exam questions you are given the percentage abundances directly.
Uses and Advantages of Mass Spectrometer:
It needs very small amount of the sample for analysis being very sensitive.
It determines the structure formulae of the compounds discovered or synthesized. So isomers
(they look very similar to each other) can be differentiated.
Homework: Note: For question 1 you are to write only the names of all the 8 parts of mass
spectrometer and for question two read carefully HSW on page 53. Write answers in the notebooks of
questions on page 53 of the book.
Mass spectrums of molecular substances:
If a sample of bromine (Br
2
) is analyzed in
the mass spectrometer we will get two sets
of peaks as shown. First set is for atomic
ions
79
Br
+
and
81
Br
+
, other for molecular
ions
79
Br
79
Br
+
,
79
Br
81
Br
+
and
81
Br
81
Br
+
.
The two isotopes of bromine have almost
equal relative abundances.
The last peak in molecular spectrum gives
relative molecular mass of the molecule.


H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 3

Q-3
Chlorine has two isotopes
35
Cl and
37
Cl. The
fig. opposite shows the mass spectrum of
molecular chorine.
(a) Suggest the masses at which the three
peaks appeared.
(b) Write the formulae of the particles
responsible for each peak.
(c) Calculate relative abundances of the
particles. (use ruler scale and statistical
way)


The living organisms contain carbon, which they take from the air in the form of CO
2
, as one
of the main elements in them. Carbon has three isotopes
12
C,
13
C and
14
C. Carbon-14 is
radioactive and slowly decays and a living organism maintains (from their foods) its
12
C :
14
C
in its life. This ratio in a living organism is just equal to this ratio in the air which is constant.
When an organism dies, its
12
C :
14
C starts increasing.
14
C has a very long half-life (the time
required for a substance to become half of its original amount in a reaction, for carbon-14 it
is 5730 years). So by comparing its
12
C :
14
C when it was alive (it is a known fixed value)
and at the time when we are calculating this ratio to calculate the age of the organism, the age
of the organism can be calculated. Mass spectrometer is used to find
12
C :
14
C. See fig 1.3.8
also see the table 1.3.4
Similarly uranium-235 has half-life 704 million years and uranium-238 billion years, these
can help us to calculate the ages or the rocks and even the age of the earth.
After first, second and third half-life the substance remains 50%, 25% and 12.5%
respectively and so on.
Revise the concept of isotopes and relative properties of the subatomic particles from
chapter#1.1.
mass abundance = relative mass x relative abundance or percentage abundance
Homework: Write answers in the notebooks of questions on page 55 of the book and question 2 page 59.
The chemical properties of the elements depend upon the electronic configurations of the elements.
Emission line spectrum:
If a gas is heated or electric current is given to it, a light is given by this gas. When this light is
passed through a prism, it splits to form a spectrum. This spectrum is a characteristic of an
element.
H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 4

This is the evidence of the fact that an atom has different energy levels in it. The energy gaps
between the energy levels decrease as we move away from nucleus. The electrons when de-excite
in these shells give light and hence spectrum.
The energy and the color (if visible) depend upon the frequency of this light. Only a few
frequencies out of million suggest that a few energy levels are there in an atom.
The electron going away from the nucleus absorbs energy and releases when it comes back.
Energy levels and electron shells:
The electrons around the nucleus are arranged in a series of shells, which resemble the layers
of an onion. The number, n, for a shell is also called principle quantum number.
n = 1,2,3,..
Subshells
Shells are split further into subshells which are s,p,d,f.
Shell Subshells
1 1s
2 2s, 2p
3 3s, 3p, 3d
4 4s, 4p, 4d, 4f
The energy order of the subshells of a shell is
s < p < d < f
The number 1, 2,3,.. with the subshells is
the shell number or principal quantum
number.



Arranging the subshells in the increasing order of their energies:

Q-4 Rank the following subshells in the increasing order of energies. 3p, 1s, 2s, 3d, 4s.
Orbitals: The subshells contain orbitals in them further. orbital is a 3D region around the nucleus
where the electrons are most likely to be found.
H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 5

Subshell Orbitals
s s
p p
x
, p
y
, p
z

d d
xy
, d
yz
, d
xz
, d
x
2
-y
2
, d
z
2

f f has seven orbitals. (names are complicated, not in your syllabus)
Q-5 Write names and number of subshells and orbitals in the fourth shell.
Electron density maps/Orbitals:
According to the modern theories electrons and other microscopic particles moving at very
high speeds behave like waves so electron around the nucleus looks like a cloud. Calculations
from quantum mechanics (mathematical models for solving the electrons behavior around
the nucleus) help us to draw electron density maps or probabilities of finding the electron
around the nucleus.
The figure opposite shows the electron
density map for 1s, 2s and 3s (1,2 and 3
are the principal Quantum numbers)
around the nucleus. We can notice that the
s orbital of each quantum number has
same shape (spherically symmetrical), it
is only the size which is different.
It may be called as a subshell or an orbital.




Node is a plane where the probability of finding the electron is almost zero.
The shapes and orientation of p and d orbitals:


H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 6

Electronic configuration in subshells and orbitals:
Before knowing how to write the electronic configurations when the electrons are in their normal state
(ground state), we should learn the following few points.
An orbital like s, p
x
, d
xy
etc can accommodate two electrons maximum.
So s, p, d, and f subshells can accommodate maximum 2, 6, 10 and 14 electrons respectively.

All orbitals of a subshell have equal energies but the
subshells of a shell have slightly different energies as their
energy arrangement has been shown on page 4.
Electrons first fill the low energy subshells. The order of
their increasing energy is shown on page 4 or, for shortcut,
write each row, given below, twice.
s
p s
d p s
f d p s
After writing this sequence, assign principal quantum number values for each subshell as:
s from 1, p from 2, d from 3, f from 4
Q-6 Arrange the subshells, 4s3s3p3d, in the increasing order of their energies.
An electron in an orbital orbits and spins around its axis. The two electrons in an orbital have
opposite spins (two electrons of the same orbital are spin paired---Paulis Exclusion Principle).
This spin of electrons creates a magnetic field. The two electrons in an orbital have opposite
spin and opposite magnetic fields. Clockwise ( ) and anticlockwise ( )
Hunds Rule: As orbitals like p
x
, p
y
and p
z
of a subshell like p have equal energies, so one
electron should be given to each orbital with same spin first then the other electron to each
orbital with the opposite spin.

So keeping into mind the above points we can write electronic configurations of the elements as



Q-7 Which subshell will come after each given subshell: 2s, 3p,6s,4f,..
Q-8 Write electronic configurations in the above mode (in the boxes) for Carbon, oxygen, fluorine,
Neon, phosphorus, calcium, manganese and zinc. See atomic number from periodic table.
H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 7

Q-9

Writing electronic configurations of mono-atomic ions:
Atoms or mono-atomic ions having the equal number of electrons have same electronic
configurations. Ga
3+
, Ca
2+
, Ar, Cl
-
, P
3-
each has 18 electrons. So their electronic configuration is same
i.e 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s


Exceptions or anomalies in writing the electronic configurations:
(1) The expected electronic configuration of
24
Cr is 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s

, 3d

3d

3d

3d

3d but
actually 3d contains 5 electrons instead of 4. One electron is promoted/excited (high energy state) from
4s to 3d so it becomes 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s

, 3d

3d

3d

3d

3d

. The same behavior is


shown by Cr and other elements of its group.
(2) Similarly the expected electronic configuration of
29
Cu should be
1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s

, 3d

3d

3d

3d

3d

but again in this case one electron is promoted


from 4s to 3d. So its actual electronic configuration is 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s

, 3d

3d

3d

3d

3d


Same do the other elements of group of copper.
Reason for both above cases lies in the different stabilities of a subshell when it contains different number
of electrons in it. The stability order for a subshell when it contains different number of electrons is:
Full filled subshell > half filled subshell > scarcely filled (any other number of electrons except full
and half). So 3d
5
and 3d
10
are more stable than 3d
4
and 3d
9
respectively. The answer of why for this order is
beyond the scope of AS syllabus.
(3) To make atoms ions we add or remove electrons normally from the highest energy subshell means the last
one. So keeping this thing into minds the expected electronic configuration of
Fe
2+
is 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s

, 3d

3d

3d

3d

3d (two electrons from d are lost) but actually the


electrons are lost from 4s rather 3d. 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s, 3d

3d

3d

3d

3d


But d-block (later we will discuss) elements of all the periods lose electrons first from s than from d.
This is due to some stability measures; this is again beyond the scope of your syllabus.
Q-10 Write electronic configurations of the following atoms or ions (Show the orbitals of last two
subshells and the spins of electrons). Au, Cu
+
, Mo, Ti
3+
.
Q-11

H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 8

Q-12 In which group of the periodic table an element X with the following electronic configuration is likely to
be found? Explain your answer.
Ionization Energy:
The amount of energy required to remove 1 mole of electrons from 1 mole of gaseous atoms
to make 1 mole gaseous ions under standard conditions is called first ionization energy. OR
H=positive
States, which is always gas, must be given.
Equations for the first ionization energies of some elements
H(g) H
+
(g) + e
-
O(g) O
+
(g) + e
-
Na(g) Na
+
(g) + e
-

Ne(g) Ne
+
(g) + e
-
Fe(g) Fe
+
(g) + e
-
U(g) U
+
(g) + e
-

Equations for the second ionization energies of some elements
Al
+
(g) Al
2+
(g) + e
-
Cl
+
(g) Cl
2+
(g) + e
-
Sn
+
(g) Sn
2+
(g) + e
-

Q-13 Write equations which show the third ionization energies of the following elements.
Chromium, fluorine, nitrogen, potassium
Trend of ionization energies down a group: It decreases down a group
The atomic radius increases down a group, nuclear attraction decreases so ionization
energy decreases down a group.
No doubt number of protons in the nucleus increase down a group but effectiveness of the
nuclear charge decreases due to increase in size of atom, so ionization energy decreases.
The number of shells between the nucleus and the outer shell increases (which shield outer
electrons from the attraction of the nucleus, this is called shielding effect), less attraction
between the shell and the nucleus, so ionization energy decreases.
Trend of ionization energies along a period:
It increases along a period due to increase in the effective nuclear charge which is due to
the number of electronic shells remains same.
Shielding effect remains same.
Due to increase in effective charge, size of the atom decreases.
Exceptions/Anomalies in ionization energies along the periods:
According to the above discussions ionization energy should increase regularly along the period.
But if we have look on the graphs of ionization energies on the next page, there are two
anomalies: while moving from group II and V to group III and IV ionization energy decreases.
Reasons: The two anomalies can be explained on the basis of the relative energies of the
subshells and their stability with different number of electrons.
1. Electronic configuration of group II ns


Electronic configuration of group III ns

np


The electron to be removed from group II is spin-paired which is stable, difficult to remove.
The electron to be removed from group III is in 2p which is at higher energy level and unstable
than 2s, so at the cost of less energy electron can be removed.
H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 9

2.
Electronic configuration of group V ns

np

np

np


Electronic configuration of group VI ns

np

np

np


The p subshell of group V is half-filled which is more stable than the p subshell of the group VI
which is scarcely-filled and unstable. So electron from group VI elements can be removed easily.
(OR) the electrons in p-subshell of group VI are paired and repulsion between the two makes
removal of one electrons easier.



Q-14 Explain why
11
Na has smaller value of first ionization energy than
10
Ne?
Higher ionization energies:
12
Mg has total twelve values of ionization energies. The every successive ionization energy has more
value than the previous. Second ionization energy value is higher than the first because once first
electron is removed the nuclear charge becomes more effective, size of the atom decreases, it gives
stronger pull to the electrons left and hence ionization energy increases.
There is a very large gap of the values between 2
nd
and 3
rd
and 10
th
and 11
th
values of ionization
energies. After the removal of second electron, third electron is to be removed from the new shell i.e
2
nd
shell. So a lot of energy is required.
Q-15

Q-16

H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 10






Q-17

Q-18
H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 11


Note: A copy of periodic table is given on page 12.
Electronic configuration and the periodic table
The chemical properties of the elements depend upon their electronic configurations.
The elements in the modern periodic table are arranged in the increasing order of atomic
numbers.
All the elements of a group have same number of electrons in their outer shells and
hence the same outer shell electronic configurations.
Elements of a period have equal number of electronic shells e.g all elements of 3
rd
period
have three electronic shells each.
Noble gases have complete outer shells (octets or duplets) and exceptionally high ionization
energies, so nonreactive.
Classification of the periodic table on the basis of the subshell in which highest energy
electron of the element is put
1) s-Block 2) p-Block 3) d-Block 4) f-Block
s-Block: The elements of group 1, 2 hydrogen and helium are called s-block elements because
their highest energy electron is filled in the s-subshell. e.g
11
Na, group 1, [Ne]3s
1
. Elements of
group 1 and 2 have properties of typical metals but they are very much reactive and have low
melting points. On the other hand hydrogen and helium are nonmetals.
d-Block: The elements between group 2 and 3 because their highest energy electron goes in d
subshell. These elements except zinc group and scandium group are called transition
elements. These have very high melting points (except mercury which is a liquid), relatively less
reactive than s-block metals, can be converted into wires and sheets and give coloured
compounds.
H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 12

f-Block: There are two rows each containing 14 elements at the bottom of the periodic table are
f-block elements. First row is lanthanide series in which 4f subshell is filled at the end and the
second row is called actinide series in which 5f subshell is filled at the end.
p-Block: The elements of the groups 3-8 (except He) are p block because their highest energy
electron goes in p-subshell. This block contains non-metals (oxygen, halogens etc),
metalloids (silicon and germanium etc) and metals (tin and lead etc) as well.
Q-19 How the atomic sizes vary along the (a) periods and (b) groups? Give two reasons for
these trends in each case.





H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 13



Elements of the same group have similar chemical properties: It is due to their similar
outer shell electronic structures.
How atoms held in covalent bonds? Electrons are shared between two nuclei. Negative
electrons are tightly attracted by the positive nuclei from both sides.






H. M. Sulman Munir (salus82@hotmail.com) Bright Future Pakistani Intr. School
O / A Level Chemistry Teacher Doha, Qatar
Notes Chapter 1.3 (Atomic Structure) AS Level 14




Arrange the ions in the increasing order of their angle of deflection from the straight path in a
magnetic or electric field.(mass spectrometer)
Transition of electrons involve energy changes
The concept of spectrum should be after the energy levels in the next edition.