CHEM 15 Chapter 3-1

CHEM 15
Chapter 3 ATOMIC STRUCTURE

Bohr model of a hydrogen atom (Neils Bohr, 1913) - The electron of the atom can exist only
in certain circular orbits around the nucleus in certain specific radii.
s orbital
According to the Bohr’s model:
1. The electron has a definite energy characteristic of the orbit in which it is moving (like the
planetary model of the solar system).
2. When the electron of an atom is as close to the nucleus as possible, it is in a state of lowest
possible energy called the ground state. The ground state is the lowest energy state for
atom when the electron is in most stable orbit.
3. When the atom absorbs energy, an electron can jump from a lower energy level to a higher
energy level. The electron is said to be in the excited state when the electron is in a higher
energy orbit (n = 2, 3, 4, etc.).
p orbitals
4. When an electron falls back to the lower level, it emits a definite amount of energy in the
form of a quantum of light.

Quantum numbers - dimensionless numbers which completely describe the state of an

electron. Four quantum numbers describe distribution and behavior of electrons in atoms. Each
wave function, ψ, corresponds to a set of three quantum numbers and is referred to as an
atomic orbital.

The four quantum numbers:

1. Principal quantum number, n - describes the distance between the nucleus and the
shell. A shell is the level to which the electrons belong - as n increases, on the average, the
electron is found farther out of the nucleus. It also describes the energy level of the shell - as
n increases, the energy of the electron increases and is therefore less tightly bound to the
nucleus.
The principal quantum number, n can have integral values 1, 2, 3, etc.
The number of electrons that can be accommodated in a given shell is equal to 2n2.

2. Azimuthal quantum number, l - defines the shape of the orbital. It describes the
energy level of the subshells. The number of subshells in a shell is equal to n.
It has any integral value starting from 0  (n - 1).
d orbitals

Table 3.2 Azimuthal quantum number values

l values Symbol No. of orbitals Shape
0 s 1 spherical
1 p 3 dumbbell
2 d 5 four-lobe
3 f 7 eight-lobe
 CHEM 15 Chapter 3-2
EXERCISE 3.2
1. a. What is the designation for the subshell with n = 5 and l = 1?
b. How many orbital are in this subshell?
c. Indicate the ml values for each of these orbitals.
2. What is the maximum number of electrons that can occupy the each of the following
subshells:
a. 3d c. 2p
b. 4s d. 5f
3. Give the subshell designation for:
a. n = 3, l = 1 c. n = 2, l = 0
b. n = 6, l = 4 d. n = 4, l = 3
4. Give the complete set of quantum numbers for the following:
f orbitals a. 2p2 d. 4s1
Figure 3.10 Shapes of the s, p, d, and f orbitals, respectively b. 3d 4
e. 5f3
c. 4p 6
f. 5d9
Electronic Configuration of an Atom
Each subshell consists of a set of orbitals. All the orbitals in the same subshell have the same Electronic configuration - the arrangement of electrons in the orbital of an atom.
energy. So within a given shell, the energies of electrons in the orbitals increase in the It is described by:
following order: ns < np < nd < nf. a. a number that designates the number of principal shell
b. a letter that designates the subshell (orbital)
b. Magnetic quantum number, ml - determines the spatial orientation of an orbital (the c. a superscript that designates the number of electrons in that particular subshell (orbital)
axes/planes to which the orbital is oriented). It has an integral value of +l, … 0, … ,-l. e.g. 2p4 indicates 4 electrons in the p subshell of the 2nd shell
3d8 indicates 8 electrons in the d subshell of the 3rd shell
c. Spin quantum number, ms - describes the direction of spin of an electron about its own
axis: counterclockwise, ms = -½; and clockwise, ms = +½. Guidelines:
Electrons with the same spin quantum numbers are said to have parallel spins while 1. Aufbau (building-up) principle
those with different ms values are said to have opposite spins. Electrons are distributed in orbitals of increasing energy levels where the lowest energy
orbitals are filled first. Once an orbital has the maximum number of electrons it can hold, it is
Table 3.3 Relationship among n, l, ml values through n = 4 considered “filled.” Remaining electrons must then be placed into the next highest energy
No. of Total no. of orbital, and so on.
l Subshell The orbitals in order of increasing energy:
n ml values orbitals in orbitals in
values designation 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d
subshell subshell
1 0 1s 0 1 1 < 7p
2 0 2s 0 1
1 2p 1, 0, -1 3 4
3 0 3s 0 1
1 3p 1, 0, -1 3
2 3d 2, 1, 0, -1, -2 5 9
4 0 4s 0 1
1 4p 1, 0, -1 3
2 4d 2, 1, 0, -1, -2 5 Figure 3.11 The Aufbau principle
3 4f 3, 2, 1, 0, -1, -2, -3 7 16 2. Pauli’s exclusion principle - No two electrons in the same atom can have the same set of
four quantum numbers. That is, the maximum number of electron in an orbital is limited to
two and the two electrons in the same orbital must have opposite spins.
 CHEM 15 Chapter 3-3
For 1s orbital: one electron: n = 1, l = 0, ml = 0, ms = +½ He 2  1s2 2
another electron: n = 1, l = 0, ml = 0, ms = -½ Li 3   1s2 2s1 1
Be 4   1s2 2s2 2
For example, with the helium atom, there are three ways to represent two electrons in 1s orbital B 5    1s2 2s2 2p1 3
C 6     1s2 2s2 2p2 4
N 7      1s2 2s2 2p3 5
(where spin is represented with the electron pointing up or down): Ne 10      1s2 2s2 2p6 8
But the Pauli exclusion principle rules out (a) and (b) since these show two electrons in the same Na 11       1s2 2s2 2p6 3s1 1
orbital with the same spin. Valence electrons - outer shell electrons.

An orbital can hold a maximum of two electrons:

 An s orbital can hold up to 2 electrons. Isoelectronic - atoms or ions of different elements that have the same electronic configuration.
 A set of p orbitals can hold up to 6 electrons. For example, O2-, F-, Ne, Na+, and Mg2+ have a total number of electrons which is equal to 10. If
 A set of d orbitals can hold up to 10 electrons. this is so, hence, they have the same electronic configuration 1s2 2s2 2p6 and are therefore
 A set of f orbitals can hold up to 14 electrons. isoelectronic.

3. Hund’s rule - Every orbital in a subshell (degenerate orbitals - same energy) is occupied Magnetic behavior - the effect of magnetic field on an atom.
with one electron first before any one orbital is doubly-filled and all electrons in singly- 1. Diamagnetism - atoms with completely paired electrons which are slightly affected by
occupied orbitals have the same spin. magnetic field.
The most stable arrangement of electrons in subshells has the greatest number of 2. Paramagnetism - atoms with unpaired electrons which are greatly affected by magnetic
parallel spins. field.
To do this, distribute electrons with same spin (up or down) and do not pair electrons until all
subshells have an electron.
EXERCISE 3.3
For example, the electron configuration of carbon is: 1s2 2s2 2p2. 1. Give the electronic configuration of the following elements:
The orbital diagram can be shown in the following ways: a. Ca d. Mo
b. Al e. As
c. Sr
2. Determine whether the following elements are diamagnetic or paramagnetic by drawing the
orbital diagram of the valence shell. Determine also the number of valence electrons.
a. O d. Zn
b. Br e. Mg
c. Ti

Exceptions to the Building-Up Principle

Atoms gain extra stability when their d subshells are half-filled or completely filled.
But from Hund's rule, we know (c) would be the most stable. If we can fill or half-fill a d subshell by promoting an electron from an s orbital to a d orbital, we
do so to gain the extra stability.

For example, chromium has a total number of electrons equal to 24. Its electron configuration is
Orbital diagrams of some elements 1s2 2s2 2p6 3s2 3p6 4s2 3d4 and an orbital diagram as follows:
Total Orbital diagram Electronic Valence
Element
electrons 1s 2s 2p 3s configuration electrons
H 1  1s1 1
 CHEM 15 Chapter 3-4
Since noble gases are at the end of each row in the periodic table, all of
their electrons are in filled orbitals. Such electrons are called core electrons since they are more
stable (less reactive) when they belong to completely filled orbitals.

However, chromium assumes a more stable configuration by promoting one 4s electron to the 3d Noble gas core notation - noble gas electron configurations can be used to abbreviate the core
subshell to attain half-filled stability. Its actual configuration becomes 1s2 2s2 2p6 3s2 3p6 4s1 electrons of all elements.
3d5 with an orbital diagram as shown.
[He] = 1s2
[Ne] = 1s2 2s2 2p6
[Ar] = 1s2 2s2 2p6 3s2 3p6
[Kr] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
[Xe] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6
Similarly, silver assumes a more stable configuration by promoting one 4s electron to the 3d
orbital via completely filled stability. From 1s2 2s2 2p6 3s2 3p6 4s2 3d9, its actual configuration EXERCISE 3.4
becomes 1s2 2s2 2p6 3s2 3p6 4s1 3d10. 1. Give the noble gas core notation of the following elements:
a. Fe d. Au
b. Cd e. Y
Writing Electron Configurations Using the Periodic Table c. Ni
The periodic table's shape actually corresponds to the filling of energy sublevels. The numbers on 2. Write the electronic configuration for each of the following atoms or ions. Determine the
atop the columns in the following figure gives the ml values of the corresponding subshell. In the quantum number describing the last electron. Identify the number of unpaired electrons and
first half of the set of ml values, the electrons have +½ spin quantum number while the on other indicate whether paramagnetic or diamagnetic. State the number of valence electrons.
half, they will assume -½ spins. a. O d. Fe3+
b. Cd e. Cu+
c. Ge 2-
f. Sr
3. Give the set of quantum numbers that describe the 4th electron in the 3p subshell.
4. How many electrons can be placed in
a. shell where n = 3
b. shell with n = 4 before the first electron enters the shell with n = 5

Development of the Periodic Table

Periodic table - the most significant tool chemists use for organizing and remembering chemical
facts. The periodic table arises from the periodic patterns in the electronic configurations of the
elements. Elements in the same column contain the same number of valence electrons. The
trends within a row or column form patterns that help us make predictions about chemical
properties and reactivity.

Dmitri Mendeleev and Lothar Meyer - arranged the elements in order of increasing atomic
weight.

Periodic law - When the elements are arranged in order of increasing atomic masses, certain
sets of properties recur periodically.
Figure 3.12 The periodic table showing the different sublevels
Abbreviated Electron Configurations Henry Moseley - developed the concept of atomic numbers. He identified the atomic number
with the number of protons in the nucleus of the atom and the number of electrons in the neutral
atom.
 CHEM 15 Chapter 3-5
2. Transition elements - elements that have filled or partially-filled
Modern periodic table - an arrangement of the atoms in increasing order of their atomic inner d subshell. They are found in Groups 1B - 8B.
numbers that collects atoms with similar properties in vertical columns.
3. Inner transition elements - elements that have filled or partially-filled inner f subshell.
Period/series - elements in a row. They are otherwise known as the lanthanoids and actinoids.
Family/group - elements in a column.
4. Noble/inert gases - have filled valence subshell and are thus very stable since they have
Note that it is the loss, gain, or sharing of valence electrons that determines the reactivity of closed shells (ns2 np6). They are the elements in Group 8A.
elements. Hence, the valence electrons of an atom determine its chemical property.

Periodic Classification of Elements Properties of some groups of elements

A. Based on Properties 1. Group 1A - Alkali Metals
1. Metals - elements in the left side and in the center of the periodic table. They have lustrous,  with typical valence of 1 corresponding to their ns1 electronic structure
silvery, appearance, good conductors of heat and electricity, malleable and ductile, high  light metals, soft and lustrous but so reactive that they have to be kept from air or
melting point, lose electrons moisture (the most reactive metals)
In terms of reactivity, metals form basic oxides:  their hydroxides have an intensive basic or alkaline action, hence members of this family
Metal oxide + water  metal hydroxide Na 2 O  H 2 O  2 NaOH are referred to as alkali metals

CaO  H 2 O  Ca (OH ) 2 2. Group 2A - Alkaline Earth Metals

Metal oxide + acid  salt + water CaO  2 HCl  CaCl 2  H 2 O
MgO  2 HBr  MgBr2  H 2 O
3.
2. Nonmetals - elements on the right side of the periodic table. They are nonconductors,
nonmalleable, nonductile and have no metallic luster.
On the other hand, nonmetals form acidic oxides:
Nonmetal oxide + water  acid CO2  H 2 O  H 2 CO3
4.
P4 O10  6 H 2 O  4 H 3 PO4
5.
Nonmetal oxide + base  salt + water CO2  2 NaOH  Na2 CO3  H 2 O
SO3  2 KOH  K 2 SO4  H 2 O
Nonmetal + metal  salt 2 Al  3Br2  2 AlBr3
 also active metals but generally less reactive than the alkali metals
 has 2 valence electrons (ns2)
 all form chlorides that are water-soluble and carbonates that are water-insoluble
Hydrogen
 a colorless, diatomic gas and the first element in the periodic table
 it does not belong to any family
 has a 1s1 electronic configuration
Group 6A - Chalcogens - chalk formers
Group 7A - Halogens
 listed in the order of increasing atomic weight, melting and boiling points
 fluorine and chlorine are pale yellow and greenish yellow gases, respectively, bromine is a
volatile reddish brown liquid and iodine is a volatile deep violet solid
 order of increasing activity: iodine < bromine < chlorine < fluorine
 their H compounds are all acids

2 Na  Cl 2  2 NaCl Periodic variation of properties

B. Based on their Electronic Configuration
1. Representative/main group elements - elements in which the last electron added enters
an s or p orbital in the outermost shell but in which this shell is incomplete. They are found in
Groups 1A - 7A.
Periodicity - trends in the behavior of the elements which arise from the periodic patterns in the
electronic configuration of the elements.
Effective nuclear charge (Zeff) - the net positive charge experienced by an electron on a many-
electron atom. It is not the same as the charge on the nucleus because of the effect of the inner
electrons.
 CHEM 15 Chapter 3-6
The electron is attracted to the nucleus but is repelled by the inner-shell electrons that shield or
screen it from the full nuclear charge. This shielding is called the screening effect. The nuclear
charge experienced by an electron depends on its distance from the nucleus (n) and the number
of electrons in the spherical volume out to the electron in question.

For example, for lithium (1s2 2s1) the nuclear charge felt by the lone electron in the 2nd shell is
screened by the two electrons residing in the 1st shell. Figure 3.14 Comparison between ionic size and atomic radius of parent atom

Relationships:
1
S As the average number of screening electrons (S) increases, the
Z eff Isoelectronic series of ions - manifests the effect of varying nuclear charge on ionic radii.

effective nuclear charge decreases.

nS As the distance from the nucleus increases, S increases.

1
n As the distance from the nucleus increases, Zeff decreases.
Z eff

Periodic Trends All ions herein are isoelectronic - they have 10 electrons arranged in 1s2 2s2 2p6 electronic
1. Atomic size/atomic radius - derived from the distance between atoms when bonded configuration like Ne but have increasing number of protons. Because the number of
together. electrons remains constant, the radius of the ion decreases with increasing nuclear charge, as
 Within each group - atomic radius increases from top to bottom due to increasing n or the electrons are more strongly attached to the nucleus.
number of shells
 Within each period - atomic radius decreases from left to right - with increasing atomic 2. Ionization energy (IE) - minimum energy required to remove an electron from the ground
number, the number of protons increases but the screening electrons remain constant, state of the isolated gaseous atom.
hence, the effective nuclear charge, Zeff increases and the size decreases.
First ionization energy (I1) - energy needed to remove the first (outermost) electron.
Ionic size - depends on its nuclear charge, the number of electrons it possesses, and the orbitals For the successive removal of 1 electron from magnesium, the following ionization energies
in which the outer-shell electrons reside. are required:
 Cations - generally smaller than the metals from which they were formed. The removal of one Mg ( g ) 
I1
Mg  ( g )  1e  I1 = 738 kJ/mol
or more electrons from the outermost region of the atom not only vacates the outermost  2 
orbitals but also decreases the total electron-electron repulsions. The atom losses electron(s) Mg ( g )  Mg ( g )  1e
I2
I2 = 1450 kJ/mol
but the number of protons remains the same. The effective nuclear charge is distributed to a 2 3 
Mg ( g )  Mg ( g )  1e
I3
I3 = 7730 kJ/mol
lesser number of electrons and each would experience greater attraction to the nucleus. This
would correspondingly decrease the size.
An electron residing in the inner shell is harder to remove than those found in the valence
 Anions - generally larger than the nonmetal from which they were formed. The gained
shell. Generally, I1 < I2 < I3.
electron(s) would reside in the valence shell causing an increase in electron-electron
repulsion. As a result, the electrons spread out more in space.
Table 3.5 Successive values of ionization energies
 CHEM 15 Chapter 3-7
3. Electron affinity (EA) - energy change associated to the addition of
an electron to a gaseous atom/ion. An exothermic process hence, most values are negative.
E
F ( g )  1e   F  (g) E = -328 kJ/mol

Large atoms are expected to have low EA because their valence electrons are farther from the
nucleus.
Small atoms have high EA because added electron will be closest to the nucleus.

 Within a group - EA decreases from top to bottom.

 Within a period - EA increases from left to right.

Small atoms are expected to have high IE because their valence electrons are nearer and
more strongly attracted to the nucleus.
 Within each group - IE decreases with increasing atomic number due to the increase in
size.
 Within each period - IE increases with increasing atomic number due to increase in Zeff.

Figure 3.15 Electron affinity values for representative element

4. Electronegativity (EN) - the ability of a bonded atom to attract electrons to itself.

 Within a group - EN decreases from top to bottom.
 Within a period - EN increases across a period.

Figure 3.14 Periodic trends in ionization energy

 CHEM 15 Chapter 3-8

Figure 3.17 Periodic trends in metallicity

In general, metals have low ionization energy and low electron affinity while nonmetals have
high ionization energy and high electron affinity.

Figure 3.16 Periodic trends in electronegativity

5. Metallicity/metallic character EXERCISE 3.5
 Within a group - metallicity increases from top to bottom. Arrange the following in increasing order of the indicated property:
 Within a period - metallicity decreases from left to right. 1. Co+, Co2+, Co3+ Atomic radius 8. F, Cl, Br Electron affinity
2. S2-, Ar, K+ Atomic radius 9. O, As, P Electronegativity
Nonmetallicity/nonmetallic character 3. Zn, Br, Ge Metallic property 10. K+, Ar, Cl- Ionization energy
 Within a group - nometallic character decreases from top to bottom. 4. Fe, Fe , Fe
2+ 3+
Ionization energy 11. Be, B, Mg Nonmetallic property
 Within a period - nonmetallic character increases from left to right. 5. Fe3+, Na, Zn2+ Paramagnetism 12. Cr3+, V, Mn4+ d electrons
6. Br, Se, Cl Electron affinity 13. Mg2+, Na+, O2- Ionic radius
7. Al, Cl, P Ionization energy