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Chapter 2
Chapter 2
SEMESTER 1
CHAPTER 2
ELECTRONIC STRUCTURE OF ATOMS
Past Year Questions Analysis
2013 2014
2007 2008 2009 2010 2011 2012
Sem 1 Sem 1
Topic
B B,
P1 P2 P1 P2 P1 P2 P1 P2 P1 P2 P1 P2 A A
C C
CHAPTER
2: 2 5a 2 1a 2 1 1 5a 1 1a 1 18 1 18
2.1 Electronic Energy Levels of Atomic Hydrogen
Visible light
Balmer Series
• When an electron drops from an outer orbit to an inner one, the
atom emits a photon of specific energy that gives rise to a spectral
line. In a given series, each electron drop, and thus each emission,
has the same inner orbit, that is, the same value of n1 in the
Rydberg equation, where the orbit radius is proportional to 2n
value.
• An energy diagram shows how the ultraviolet series arises. Within
each series the greater the difference in orbit radii, the greater the
difference in energy levels, and the higher the energy of thethe photon
photon
emitted. For example, in the ultraviolet series, in which n = 1, a
drop from n2 = 5 to n1 = 1 emits a photon with more energy
(shorter wavelength, higher frequency) than a drop from 2n= 2 to
n 1= 1. [The axis shows negative values because n = ∞ is defined as
the atom with zero energy.]
• Since Bohr’s model is a one-electron model. It works beautifully for
the H atom and for other one-electron species, such as He+ (Z = 2),
Li2+ (Z = 3) and Be3+ (Z = 4),
• One of the usefulness of Bohr’s theory, applied when calculating
the energy levels of an atom, which he derived from the classical
principles of electrostatic attraction and circular motion, where the
equation is describe as
Z2
E = − 2.18× 10−18 J ×
n2
−18 1
E = − 2.18× 10 J ×
n2
1 1
−18 J×
∆E= 2.18×10 2
− 2
n
1 n2
c. Further derivation from equation (b) also allowed us to find the
wavelength produce in absorption / emission process. Using
Planck’s equation, where
ΔE = hf or ΔE = hc / λ
−18
1 hc1
2.18× 10 J× −
= ;
2
n 1 n2 2
λ
rearrangeand
rearrange andsubstitute
substitute
−18
1 2.18× 10 J × 1 1
= − 34
−
λ (6.63× 10 )(3.00 × 108 ) n12 n 22
1 = 1.10 × 107 × 1 − 1
λ n 21 n 22
• Ionisation energy of one mole of electron in hydrogen atom can
also be calculated using Bohr’s equation.
H (g) H + (g) + e- ΔH = + x kJ mol-1 (Ionisation energy)
• In order to remove an electron from hydrogen atom, electron must
at least reached the convergence limit of the energy level n = ∞.
Consider the ground state energy level of Lyman series, n = 1.
1 1
−18 J×
∆E = 2.18× 10 2
− 2
;
n1 n2
1 1
−18 J× −
∆E = 2.18× 10 ; ∆E = 2.18× 10−18 J
12 ∞2
1 kJ
For 1 mol e − ; ∆H = ∆E × NA × 3 ;
10 J
1 kJ
∆H = 2.18× 10−18 J × (6.02× 1023) × ; ∆H = 1310 kJ −1
mol
103 J
• To remove 1 mol of electron from ground state, n1 = 1 to
convergence limit, n 2= ∞, a total of 1310 kJ is required.
Example 1 : Calculate the wavelength of the Example 2 : Calculate the wavelength of the
first line of Lyman series third line of Balmer series
In Lyman series, n1= 1 In Balmer series, n1= 2
First line in series, so n2 = 1 + 1 = 2 First line in series, so n2= 2 + 3 = 5
1= R 1 − 1 1= R 1 − 1
H
λ
H
λ n21 n 22 n21 n 22
1= R 1 − 1 1 = R 1 − 1
H
λ H
n21 n22 λ n12 n 22
1= R 1 − 1 1 = R 1 − 1
H
λ H
n21 n22 λ n12 n 22
1 1 1 1
−18 J × − ∆E = 2.18× 10 −18 J × −
∆E = 2.18× 10 2
1 2
6 2
2 32
ΔE = 2.12 x 10-18 J / e- ΔE = 3.03 x 10-19 J / e-
c) the third line of Passchen series d) the last line of Passchen series
In Passchen series, n1 = 3 In Balmer series, n1= 3
First line in series, so n2 = 3 + 3 = 6 Last line in series, so n2 = 3 + ∞ = ∞
1 1 1 1
−18 J ×
∆E = 2.18× 10
−18 J ×
− ∆E = 2.18× 10 − 2
n12 n2 2 n12 n2
1 1 1 1
−18 J × − ∆E = 2.18× 10 −18 J × −
∆E = 2.18× 10
3 2
6 2
32
∞2
ΔE = 1.82 x 10-19 J / e- ΔE = 2.42 x 10-19 J / e-
2.2 Atomic Orbital
• The position of electrons cannot be specified as electron behaves like
wave as it extended it space. Werner Karl Heisenberg, then formulated
what is now known as the Heisenberg uncertainty principle: it is
impossible to know simultaneously both the momentum and the position
of a particle with certainty.
– However, Bohr’s theory had made a significant contribution to our
understanding of atoms, and his suggestion that the energy of an
electron in an atom is quantized. This concept is the perfected by an
Austrian physicist, Erwin Schrödinger, through his well well-known
-known
equation – Schrödinger’s equation, where the energy of atom can be
calculate.
– Even though Schrödinger equation specifies the possible energy states
the electron can occupy in a hydrogen atom, however, it cannot pin-
point the location of electron in an atom. Therefore, to counter this
problem, we replaced with the term orbital, a region with high
probability to find an electron.
• An atomic orbital is specified by three quantum numbers. One is related
to the orbital’s size, another to its shape, and the third to its orientation
in space. The quantum numbers have a hierarchical relationship: the
size-related number limits the shape-related number, which limits the
orientation-related number
– The principal quantum number (n) (better known as shell) is a positive
integer (1, 2, 3, and so forth). It indicates the relative size of the orbital
and therefore the relative distance from the nucleus of an atom.
– The angular momentum quantum number(l) is an integer from 0 to n –
1. It is related to the shape of the orbital and is sometimes called the
orbital shape (or azimuthal) quantum number. Note that the principal
quantum number sets a limit on the values for the angular momentum
quantum number; that is, n limits l.
• For an orbital (shell) with n = 1, l can have a value of only 0.
• For orbitals (shell) with n = 2, l can have a value of 0 or 1
• For orbitals (shell) with n = 3, l can be 0, 1, or 2; and so forth.
Note that the number of possible l values equals the value of n
• The magnetic quantum number (m )l is an integer from [–l] through
0 to [+l]. It prescribes the orientation of the orbital in the space
around the nucleus (or simple, number of orbitals presence in l).
The possible values of an orbital’s magnetic quantum number are
set by its angular momentum quantum number.
• For (l = 0), magnetic quantum number, (ml ) = 0 [therefore 1 orbital]
• For (l = 1), magnetic quantum number, (m l) = –1, 0, +1 [therefore 3
orbitals]
• For (l(l = 2), magnetic quantum
2), magnetic number,(ml))== –2, –1,
quantum number, –1, 0,
0, +1, +2
+1, +2
[therefore 5 orbitals]
• The electron spin quantum number (m s ) ~ represents the
assumption of electrons act like tiny magnets. According to
electromagnetic theory, a spinning charge generates a magnetic
field, and it is this motion that causes an electron to behave like a
magnet. Therefore, in each m l , two oppositely spin quantum is filed
accordingly and has a value of +½ and –½, and are usually denote as
↑ (for +½) and ↓ (for –½)
• The energy states and orbitals of the atom are described with
specific terms and associated with one or more quantum numbers
– Level. The atom’s energy levels, or shells, are given by the n
value: the smaller the n value, the lower the energy level and
the greater the probability of the electron being closer to the
nucleus. [n = 1 is the closest to nucleus, followed by n = 2, 3
and so forth]
– Sublevel. The atom’s levels contain sublevels, or subshells,
which
which designate
designatethe
theorbital shape. Each
orbitalshape. Each sublevel has aa letter
sublevelhas letter
designation:
l 0 1 2 3 4 5
Name of sublevel
s p d f g h
(orbital)
• Orbital. Each allowed combination of n, l, and m
l values specifies
one of the atom’s orbitals. Thus, the three quantum numbers that
describe an orbital express its size (energy), shape, and spatial
orientation. You can easily give the quantum numbers of the
orbitals in any sublevel if you know the sublevel letter designation
and the quantum number hierarchy
0 0 1 1s
1
0 0 1 2s
2 1 –1, 0 +1 3 2p x, 2p y , 2p z,
0 0 1 3s
3 1 –1, 0 +1 3 3p x, 3p y , 3p z,
2 –2, –1, 0 , +1 , +2 5 3d xy , 3d yz , 3d xz , 3d x2-y2 , 3d z2
2. Shape of each orbitals
• The s Orbital– An orbital with l = 0 has a spherical shape with the
nucleus at its center and is called an s orbital
• The p orbitals
orbitals – An orbital with l = 1, called
orbital with called aa pp orbital,
orbital, has
hastwo
two
regions (lobes)of high probability, one on either side of the nucleus.
The nucleus lies at the nodal plane of this dumbbell-shaped orbital
as described in diagram below
• The d Orbital – An orbital with l = 2 is called a d orbital. There are
five possible m l values for the l = 2 value: –2, –1, 0 , +1 , +2. Thus, a
d orbital can have any one of five different orientations, as describe
in diagram below
Correct Incorrect
Filling in 3 electrons in p-orbitals Filling in 7 electrons in d-orbitals (After positive spin is first
(more stable) filled, negative spin is then filled to each orbital)
No Electronic
Element Orbital diagram
of e- configuration
Hydrogen
H 1 ____ 1s 1
1s
Helium
He 2 ____ 1s 2
1s
Lithium
Li 3 ____ ____ 1s 2 2s1
1s 2s
Beryllium
Be 4 ____ ____ 1s 2 2s2
1s 2s
Boron
B 5 ____ ____ ____ ____ ____ 1s 2 2s2 2p1
1s 2s 2p
Carbon
C 6 ____ ____ ____ ____ ____ 1s 2 2s2 2p2
1s 2s 2p
Nitrogen
N 7 ____ ____ ____ ____ ____ 1s 2 2s2 2p3
1s 2s 2p
No Electronic
Element Orbital diagram
of e- configuration
Oxygen
O 8 ____ ____ ____ ____ ____ 1s 22s2 2p 4
1s 2s 2p
Fluorine
F 9 ____ ____ ____ ____ ____ 1s 2 2s2 2p5
1s 2s 2p
Neon
Ne 10 ____ ____ ____ ____ ____ 1s 2 2s2 2p6
1s 2s 2p
Sodium
Sodium
Na 11 ____
____ ____
____ ____
________ ____
____ ________
____ 1s 222s22 2p 663s11
1s 2s 2p 3s
Magnesium
12 ____ ____ ____ ____ ____ ____ 1s 22s2 2p 63s2
Mg
1s 2s 2p 3s
Aluminium
Al 13 ____ ____ ____ ____ ____ ____ ___ ___ ___ 1s 2 2s2 2p 63s2 3p 1
1s 2s 2p 3s 3p
Silicon
Si 14 ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2 2s2 2p 63s2 3p 2
1s 2s 2p 3s 3p
No of
Element Orbital diagram Electronic configuration
e-
Phospho- ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2 2s2 2p 6 3s 2 3p 3
rous, P 15 1s 2s 2p 3s 3p
Sulphur
S 16 ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2 2s2 2p 63s2 3p 4
1s 2s 2p 3s 3p
Chlorine
Cl 17 ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2 2s2 2p 63s2 3p 5
Cl 1s
1s 2s
2s 2 p2 p 3s 3s 3p 3p
Argon
Ar 18 ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2 2s2 2p 6 3s 2 3p 6
1s 2s 2p 3s 3p
Potassium
K 19 ____ ____ ____ ____ ____ ____ ____ ____ ____ ___ 1s 22s2 2p 63s2 3p 64s1
1s 2s 2p 3s 3p 4s
Calcium
Ca 20 ____
1s
____
2s
____ ____ ____
2p
____ ____ ____ ____
3s 3p
___
4s
1s 22s2 2p 63s2 3p 64s2
1s 22s2 2p 63s2 3p 63d 14s2
Formation of Na → Na
+ + e- F + e- → F-
+1 and -1 1s22s2 2p6 3s1 1s22s2 2p6 1s22s2 2p5 1s22s2 2p6
Formation of Mg → Mg
2+ + 2e- O + 2e- → O2-
+2 and -2 1s22s2 2p6 3s2 1s22s2 2p6 1s22s2 2p4 1s22s2 2p6
2. From the example above, it is shown that, when electron(s) are
donated, electron(s) are first removed from higher energy level,
and conversely when electron(s) are received, electron(s) are filled
from the lower possible energy level. Most of the main group
elements donate and received electron(s) to achieve a stable
valence electronic configuration of ns2 np6 (also known as octet
configuration)
Al 3+ : 1s22s2 2p6 P3- 1s22s2 2p6 3s2 3p6
[Since electronic configuration of [Since electronic configuration of
aluminium is 1s 22s 22p 63s 23p 1, when 3 aluminium is 1s 22s 22p 63s 23p 3, when 3
electrons are removed, it shall be removed electrons are added, it shall be added to 3p
from 3p, then 3s] orbital as its not yet complete]