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FOUNDATION CHEMISTRY I

CHM092

CHAPTER 2: ATOMS, MOLECULES


AND IONS AND ELECTRONIC
STRUCTURE OF ATOMS AND
PERIODICITY
Topic

WEEK 4

2.1 Elements and Compounds


2.2 Atomic Structure; Electrons, Protons and
Neutrons
2.3 Atomic Number, Mass Number and
Isotopes
2.4 Quantum Mechanics
Learning Outcomes
Students should able to:

Define the terminologies of elements, compounds and atomic structure

Define the nucleus, proton, neutron and electron.

Define the atomic number, mass number and isotope symbols.

Identify the number of protons and neutrons in an isotope using the


isotope symbol and the mass number.

Define the Bohr’s model of hydrogen atom.

Define orbital and wave function.

State the properties and allowed values of the principal quantum number,
n, the angular momentum quantum number, l, the magnetic quantum
number, ml and the spin quantum number, ms.
Topic
2.1 Elements and Compounds
5
2.1 Elements and Compounds
2.1 Elements and Compounds
Classifying Elements & Compounds
• Atomic elements = elements whose particles
are single atoms
• Molecular elements = elements whose particles
are multi-atom molecules
• Molecular compounds = compounds whose
particles are molecules made of only nonmetals
• Ionic compounds = compounds whose particles
are cations and anions
2.1 Elements and Compounds

Atoms
are submicroscopic particles
are the fundamental building blocks of ordinary
matter
2.1 Elements and Compounds
Molecules
are two or more atoms attached together in a
specific geometrical arrangement
attachments are called bonds
attachments come in different strengths
come in different shapes and patterns
2.1 Elements and Compounds

Elements
•Most elements have single atoms as their
constituent particles
•The atoms may be physically attracted to each
other, but are not chemically bonded together
•A few elements have molecules as their
constituent particles
•The molecules are made of two or more atoms
chemically bonded together by covalent bonds
2.1 Elements and Compounds

Elements
Elements combine together to make an almost
limitless number of compounds
The properties of the compound are totally different
from the constituent elements
2.1 Elements and Compounds

Formation of Water from Its Elements


2.1 Elements and Compounds
Molecular Elements
• Certain elements occur as 2 atom molecules
 rule of 7’s
• Other elements occur as polyatomic molecules
 P4, S8, Se8

7A
H2 N2 O2 F2

Cl2

Br2

I2
2.1 Elements and Compounds
2.1 Elements and Compounds

Compound
a substance composed of two or more
elements which are chemically combined.
2.1 Elements and Compounds
Compounds
•Some compounds are composed of ions
arranged in a 3-dimensional pattern – these are
called ionic compounds
–each cation is surrounded by anions, and vice-
versa
•Other compounds are composed of individual
molecule units
•Each molecule contains atoms of different
elements chemically attached by covalent
bonds
2.1 Elements and Compounds
Ionic vs. Molecular Compounds

Propane – contains Table salt – contains


individual C3H8 an array of Na+ ions
molecules and Cl- ions
2.1 Elements and Compounds
Ionic Compounds
•Compounds of metals with nonmetals are
made of ions
–metal atoms form cations, nonmetal atoms
form anions
•No individual molecule units, instead they
have a 3-dimensional array of cations and
anions made of formula units
2.1 Elements and Compounds
Ionic Compounds
•Many contain polyatomic ions
–several atoms attached together by covalent
bonds into one ion
2.1 Elements and Compounds
Mixture
A group of two or more elements and/or
compounds that are physically intermingled.
2.1 Elements and Compounds

Exercise 1: Classify each of the following as either an


Atomic Element, Molecular Element, Molecular
Compound, or Ionic Compound

Aluminum, Al atomic element


Aluminum chloride, AlCl3 ionic compound
Chlorine, Cl2 molecular element
Acetone, C3H6O molecular compound
Carbon monoxide, CO molecular compound
Cobalt, Co atomic element
2.1 Elements and Compounds
Exercise 2:The following scenes represent an atomic-
scale view of three samples of matter. Describe each
sample as an element, compound, or mixture.
2.1 Elements and Compounds
Sample (a) contains three different types of particles and is
therefore a mixture.

Sample (b) contains only one type of particle and each


particle has only one atom. This is an element.

Sample (c) contains only one type of particle, each of which


contains two different types of atoms. This is a compound.
Topic
2.2 Atomic Structure
2.2 Atomic Structure

Dalton’s Atomic Theory (1808)


1. Elements are composed of extremely small particles called atoms.
2. All atoms of a given element are identical, having the same size,
mass and chemical properties. The atoms of one element are
different from the atoms of all other elements.
3. Compounds are composed of atoms of more than one element. In
any compound, the ratio of the numbers of atoms of any two of the
elements present is either an integer or a simple fraction.
4. A chemical reaction involves only the separation, combination, or
rearrangement of atoms; it does not result in their creation or
destruction.
2.2 Atomic Structure
Thomson’s Plum Pudding Atom
2.2 Atomic Structure

The Electron

• Streams of negatively charged particles were found to


emanate from cathode tubes.
• J. J. Thompson is credited with their discovery (1897).
• Thompson measured the charge/mass ratio of the electron
to be 1.76  108 coulombs/g.
2.2 Atomic Structure
Millikan’s Experiment
Measured mass of e- (1923 Nobel Prize in Physics)

e-charge = -1.60 x 10-19 C


Thomson’s charge/mass of e- = -1.76 x 108 C/g
e- mass = 9.10 x 10-28 g 28
2.2 Atomic Structure
Rutherford’s Experiment
2.2 Atomic Structure
Rutherford’s Experiment
Plum Pudding
Atom

• •
If atom was like
• •
• • a plum pudding,

• • all the a particles
• •
• • should go

• • • straight through
• •
• •

2.2 Atomic Structure
Rutherford’s Results

A few of the
a particles Nuclear Atom
do not go through
. Almost all a particles
go straight through
.
Some a particles
. go through, but are deflected due to
+:+ repulsion from the nucleus
2.2 Atomic Structure
Rutherford’s Model of the Atom
2.2 Atomic Structure

Protons were discovered by Rutherford in 1919.


Neutrons were discovered by James Chadwick
in 1932.
2.2 Atomic Structure
2.2 Atomic Structure
Properties of the Three Key Subatomic
Particles
Charge Mass

Name Relative Absolute (C)* Relative Absolute (g) Location in


(Symbol) (amu)† Atom

Proton 1+ +1.60218x10-19 1.00727 1.67262x10-24 Nucleus


(p+)

Neutron 0 0 1.00866 1.67493x10-24 Nucleus


(n0)

Electron 1- -1.60218x10-19 0.00054858 9.10939x10-28 Outside nucleus


(e-)

mass p ≈ mass n ≈ 1840 x mass e-


2.2 Atomic Structure
Just Imagine!

“If the atom is the Houston Astrodome, then the nucleus is a


marble on the 50-yard line.”
Topic
2.3
Atomic Number,Mass
Number and Isotopes
2.3 Atomic Number, Mass Number and
Isotopes
•Each element has a unique number of protons
in its nucleus
Atomic number (Z) = number of protons in nucleus
•The number of protons in the nucleus
Mass number (A) = number of protons + number of neutrons
of an
atom is called the atomic number
= atomic number (Z) + number of neutrons
–the
Isotopes elements
are atoms areelement
of the same arranged on thenumbers
(X) with different Periodic Table
of neutrons in their
in order of their atomicnuclei numbers
•Each element has a unique name and symbol
–symbol either one or two letters
•one capital letter or one capital letter and one lowercase
letter
2.3 Atomic Number, Mass Number and
Isotopes

Atomic
Atomic numbernumber
(Z) = number of(Z) = number
protons in nucleus of protons in
Mass number (A) = number ofnucleus
protons + number of neutrons
= atomic number (Z) + number of neutrons
Mass number (A) = number of protons +
Isotopes are atoms of the same element (X) with different numbers of neutrons in their
numbernuclei of neutrons
= atomic number (Z) +
number of neutrons
2.3 Atomic Number, Mass Number and
Isotopes
Structure of the Nucleus
• Soddy discovered that the same element could have atoms
with different masses, which he called isotopes
Atomic number (Z) = number of protons in nucleus
– there are two isotopes of chlorine found in nature, one that has a
Mass number
mass(A)of=about
number35
of amu
protons
and+ number of neutrons
the other about 37 amu
• The observed = atomicmass
numberis(Z)a+ number of neutrons
weighted average of the weights
of allarethe
Isotopes naturally
atoms occurring
of the same element (X) atoms
with different numbers of neutrons in their
– the percentage of an element
nuclei
that is one isotope is called the
isotope’s natural abundance
– the atomic mass of chlorine is 35.45 amu
2.3 Atomic Number, Mass Number and
Isotopes
Isotopes
• All isotopes of an element are chemically identical
– number
Atomic undergo the exact
(Z) = number same
of protons chemical reactions
in nucleus
•Mass
Allnumber
isotopes of an of
(A) = number element have the
protons + number same number of
of neutrons
protons = atomic number (Z) + number of neutrons
• Isotopes
Isotopes of an
are atoms element
of the have
same element (X)different masses
with different numbers of neutrons in their
• Isotopes of an element have nuclei
different numbers of
neutrons
• Isotopes are identified by their mass numbers, which is
the sum of all the protons and neutrons in the nucleus
2.3 Atomic Number, Mass Number and
Isotopes

Isotopes
Percent
Number of Number of A, Mass Natural
Symbol Protons Neutrons Number Abundance

Ne-20 or 20
10 Ne 10 10 20 90.48%

21Ne
Ne-21 or 10 10 11 21 0.27%

22 Ne
Ne-22 or 10 10 12 22 9.25%
2.3 Atomic Number, Mass Number and
Isotopes

Isotopes
2.3 Atomic Number, Mass Number and
Isotopes
• Atomic number
 Number of protons= 92
 Z

• Mass Number
 Protons + neutrons = 235
 whole number
 A

• Abundance = relative
amount found in a sample
2.3 Atomic Number, Mass Number and
Isotopes
Exercise 3 – Complete the table
2.3 Atomic Number, Mass Number and
Isotopes
Practice – Complete the table

13
6C
96
42Mo
27
13 Al
133
55 Cs

47
Tro: Chemistry: A Molecular Approach, 2/e
2.3 Atomic Number, Mass Number and
Isotopes
Exercise 4 : The natural abundance of 3He is 0.000137%

a. How many protons and neutrons are in this isotope?


b. Based on the sum of the masses of their atomic particles,
which is expected to more massive, an atom of 3He or an
atom 3H(tritium)
Given: Proton mass = 1.673 x 10-24g
Neutron mass =1.675 x 10-24g
Electron mass = 9.109 x 10-28g
2.3 Atomic Number, Mass Number and
Isotopes
Answer

a. 3He has 2 protons and 1 neutron and 2 electrons

a. 3H has 1 proton, 2 neutrons and 1 electron

b. Which is expected to more massive, an atom of 3He or an


atom 3H(tritium)
3He=2(1.673 x 10-24g) + (1.675 x 10-24g) + 2(9.109 x 10-28g)
=5.022 x 10-24 g

3H=1.673x 10-24g + 2(1.675 x 10-24g) +9.109 x 10-28g


= 5.023 x 10-24g
2.3 Atomic Number, Mass Number and
Isotopes
Reacting Atoms
• When elements undergo chemical reactions, the reacting
elements do not turn into other elements
– Statement 4 of Dalton’s Atomic Theory
• This requires that all the atoms present when you start the
reaction will still be there after the reaction
• Because the number of protons determines the kind of
element, the number of protons in the atom does not
change in a chemical reaction
• However, many reactions involve transferring electrons
from one atom to another
2.3 Atomic Number, Mass Number and
Isotopes
Charged Atoms
• When atoms gain or lose electrons, they acquire a charge
• Charged atoms or groups of atoms are called ions
• When atoms gain electrons, they become negatively
charged ions, called anions
• When atoms lose electrons, they become positively
charged ions, called cations
2.3 Atomic Number, Mass Number and
Isotopes
Ions and Compounds
•Ions behave much differently than the neutral atoms
•e.g., the metal sodium, made of neutral Na atoms, is
highly reactive and quite unstable; however, the sodium
cations, Na+, found in table salt are very nonreactive and
stable
•Because materials such as table salt are neutral,
there must be equal amounts of charge from cations
and anions in them
2.3 Atomic Number, Mass Number and
Isotopes
Atomic Structures of Anions
• Nonmetals form anions
• For each negative charge, the ion has one more
electron than the neutral atom
– F = 9 p+ and 9 e−, F− = 9 p+ and 10 e−
– P = 15 p+ and 15 e−, P3− = 15 p+ and 18 e−
• Anions are named by changing the ending of the
name to -ide
fluorine F + 1e−  F− fluoride ion
oxygen O + 2e−  O2− oxide ion
2.3 Atomic Number, Mass Number and
Isotopes
Atomic Structures of Cations
• Metals form cations
• For each positive charge, the ion has one less
electron than the neutral atom
– Na atom = 11 p+ and 11 e−, Na+ ion = 11 p+ and 10 e−
– Ca atom = 20 p+ and 20 e−, Ca2+ ion = 20 p+ and 18 e−
• Cations are named the same as the metal
sodium Na  Na+ + 1e− sodium ion
calcium Ca  Ca2+ + 2e− calcium ion
2.3 Atomic Number, Mass Number and
Isotopes
Ion Charge and the Periodic Table
• The charge on an ion can often be determined
from an element’s position on the Periodic Table
• Metals always form positively charged cations
• For many main group metals, the charge = the
group number
• Nonmetals form negatively charged anions
• For nonmetals, the charge = the group number − 8
2.3 Atomic Number, Mass Number and
Isotopes
2.3 Atomic Number, Mass Number and
Isotopes

Exercise 5: What is the charge on each of


the following ions?
• potassium cation K+
• sulfide anion S2−
• calcium cation Ca2+
• bromide anion Br−
• aluminum cation Al3+
2.3 Atomic Number, Mass Number and
Isotopes

Exercise 6: Complete the table


2.3 Atomic Number, Mass Number and
Isotopes

2
S
Mg2
3
Al
Br 
2.3 Atomic Number, Mass Number and
Isotopes

Exercise 7: If copper is 69.17% Cu-63 with a mass of


62.9396 amu and the rest Cu-65 with a mass of 64.9278
amu, find the atomic mass of copper
2.3 Atomic Number, Mass Number and
Isotopes
Cu-63 = 69.17%, 62.9396 amu
Cu-65 = 100-69.17%, 64.9278 amu
atomic mass, amu
isotope masses, avg. atomic mass
isotope fractions
2.3 Atomic Number, Mass Number and
Isotopes
Exercise 8
There are two isotopes of Gallium:
Ga-69 with mass 68.9256 amu and abundance
of 60.11%; and Ga-71 with mass 70.9247 amu
and abundance of 39.89%.
Calculate the atomic mass of gallium.
2.3 Atomic Number, Mass Number and
Isotopes
Ga-69 = 60.11%, 68.9256 amu
Ga-71 = 39.89%, 70.9247 amu
atomic mass, amu
isotope masses, avg. atomic mass
isotope fractions
2.3 Atomic Number, Mass Number and
Isotopes
Comprehensive Question

An α particle is the nucleus of an 4He atom

a. How many protons and neutrons are in an 4He


b. What force holds the protons and neutrons together in the nucleus
c. What is the charge on an α particles in units of electronic charge?
d. The charge-to-mass ratio of an α particles is 4.8224 x 104 C/g. Based
on the charge on the particle, calculate its mass in grams and in
amu?

Given: Charge for one electron = -1.6022 x 10-19 C


Charge for one proton = +1.6022 x 10-19 C
1 amu = 1.66054 x 10-24 g
Topic
2.4 Quantum Mechanics and
the Atom
2.4 Quantum Mechanics
Electron Behavior
•Quantum mechanics forms the foundation of chemistry –
explaining the periodic table and the behavior of the elements
in chemical bonding
•Electrons are incredibly small
amechanics
Quantum single speck of foundation
forms the dust hasofmore electrons
chemistry than
– explaining thethe
periodic table
andnumber
the behavior of the elements
of people who in chemical
have ever lived –on
bonding as well
earthas providing the
practical basis for lasers, computers, and countless other applications
•Electron behavior determines much of the behavior of atoms
•Directly observing electrons in the atom is impossible, the
electron is so small that observing it changes its behavior
even shining a light on the electron would affect it
2.4 Quantum Mechanics
Electron Behavior
The quantum-mechanical model explains the
manner in which electrons exist and behave in
atoms
It helps us understand and predict the properties of
Quantum mechanics forms the foundation of chemistry – explaining the periodic table
atoms that are
and the behavior directly
of the related
elements in to the– behavior
chemical bonding of the
as well as providing the
practical basis for lasers, computers, and countless other applications
electrons
why some elements are metals and others are nonmetals
why some elements gain one electron when forming an
anion, whereas others gain two
why some elements are very reactive while others are
practically inert
and other periodic patterns we see in the properties of the
elements
2.4 Quantum Mechanics
Problems with Rutherford’s Nuclear
Model of the Atom
• Electrons are moving charged particles
• According to classical physics, moving charged
Quantum mechanics forms the foundation of chemistry – explaining the periodic table
particles give off energy
and the behavior of the elements in chemical bonding – as well as providing the
• Therefore
practical basis for lasers, computers, and countless other applications
electrons should constantly be giving
off energy
– should cause the atom to glow!
• The electrons should lose energy, crash into the
nucleus, and the atom should collapse!!
– but it doesn’t!
2.4 Quantum Mechanics
Bohr’s Atomic Model
• The nuclear model of the atom does not explain what
structural changes occur when the atom gains or
loses energy
• Bohr developed a model of the atom to explain how
the structure of the atom changes when it undergoes
energy transitions
• Bohr’s major idea was that the energy of the atom was
quantized, and that the amount of energy in the atom
was related to the electron’s position in the atom
– quantized means that the atom could only have very specific
amounts of energy
2.4 Quantum Mechanics
The Bohr Model of the Hydrogen Atom
Bohr’s atomic model postulated the following:
• The single electron in H atom moves around the nucleus
in orbits or energy levels.
• The H atom has only certain energy levels, which Bohr
called stationary states.
– Each state is associated with a fixed circular orbit of
the electron around the nucleus.
– The higher the energy level, the farther the orbit is
from the nucleus.
– When the H electron is in the first orbit, the atom is in
its lowest energy state, called the ground state.
2.4 Quantum Mechanics
The Bohr Model of the Hydrogen Atom

• The atom does not radiate energy while in one of its


stationary states.
• The atom changes to another stationary state only by
absorbing or emitting a photon.
– The energy of the photon (h) equals the difference
between the energies of the two energy states.
E = h
– When the E electron is in any orbit higher than n = 1,
the atom is in an excited state.
2.4 Quantum Mechanics
A quantum “staircase” as an analogy for atomic
energy levels.
2.4 Quantum Mechanics
Bohr’s Atomic Model

n (principal quantum number) = 1,2,3,… 1


En = -RH ( n2 )
RH (Rydberg constant) = 2.18 x 10-18J
2.4 Quantum Mechanics
The Bohr Model of the Hydrogen Atom

• The single electron in H atom moves around the


nucleus in orbits or energy levels
• The orbits are pictured as concentric circles
around the nucleus. Energy levels are arranged in
parallel lines.
• The orbits are given letter notations: k, l, m, n
• The energy levels are specified by the quantum
number ‘n’ (n = 1, 2, 3 etc.)
2.4 Quantum Mechanics
Principal Energy Levels in Hydrogen

n
When n increases, the
spacing between energy
m levels becomes smaller

The energy negative


because the electron’s
energy is lowered by its
interaction with the nucleus

k
2.4 Quantum Mechanics
Electron Transitions
• To transition to a higher energy state, the electron
must gain the correct amount of energy
corresponding to the difference in energy between
the final and initial states

• Electrons in high energy states are unstable. They


are in the excited state, and tend to lose energy
and fall back to lower energy states
2.4 Quantum Mechanics
Quantum Leaps
2.4 Quantum Mechanics
Schrodinger Wave Equation
In 1926 Schrodinger wrote an equation that described both
the particle and wave nature of the e-
Wave function () describes:
1. energy of e- with a given 
2. probability of finding e- in a volume of space
Schrodinger’s equation can only be solved exactly for the
hydrogen atom.
Must approximate its solution for multi-electron systems.
2.4 Quantum Mechanics
The Quantum-Mechanical
Model of the Atom
The matter-wave of the electron occupies the space
near the nucleus and is continuously influenced by it.

The Schrödinger wave equation allows us to solve for


the energy states associated with a particular atomic
orbital.

The square of the wave function Y2 gives the probability


density, a measure of the probability of finding an
electron of a particular energy in a particular region of the
atom.
2.4 Quantum Mechanics
Electron probability density in the ground-state
H atom.

In the electron density diagram, the density of dots represents the


probability of the electron within a tiny volume and decreases with
distance, r, from the nucleus
2.4 Quantum Mechanics
Electron probability density in the ground-state
H atom.

Counting dots within each layer gives the total


probability of the electron being in that layer
2.4 Quantum Mechanics
Electron probability density in the ground-state
H atom.

A 90% probability contour for the ground state of the H


atom
2.4 Quantum Mechanics
Describing an Orbital
• An orbital is a region (space) around the
nucleus in which an electron of certain
energy may be found
• Characterizes the energy of the electron in
a particular orbital
– corresponds to Bohr’s energy level
• Each orbital is given a set of 3 quantum
numbers: n, l, and ml
2.4 Quantum Mechanics
Principal Quantum Number, n
• n can be any integer  1
• The larger the value of n, the more energy the
orbital has
• The larger the value of n, the larger the orbital
• Orbitals with the same value of n are in the same
principal energy level (or same shell)
2.4 Quantum Mechanics
Principal Quantum Number, n
n = 1, 2, 3, 4, ….
distance of e- from the nucleus

n=1 n=2 n=3


2.4 Quantum Mechanics

Angular Momentum Quantum Number, l

• The angular momentum quantum number determines the


shape of the orbital
• l can have integer values from 0 to (n – 1)
• Orbitals with the same values of n and l are said to be in the
same sublevel (or same subshell)
• Each value of l is called by a particular letter name: l
= 0 called s orbitals
l = 1 called p orbitals
l = 2 called d orbitals
l = 3 called f orbitals

Sometimes called the Azimuthal quantum number


2.4 Quantum Mechanics
Angular Momentum Quantum Number, l

for a given value of n, l = 0, 1, 2, 3, … n-1

n = 1, l = 0
n = 2, l = 0 or 1
n = 3, l = 0, 1, or 2

Shape of the “volume” of space


that the e- occupies
2.4 Quantum Mechanics
Angular Momentum Quantum Number, l

l = 0 (s orbitals)
2.4 Quantum Mechanics
Angular Momentum Quantum Number, l

l = 1 (p orbitals)
2.4 Quantum Mechanics
Angular Momentum Quantum Number, l

l = 2 (d orbitals)
2.4 Quantum Mechanics
Magnetic Quantum Number, ml
• The magnetic quantum number is an integer that
specifies the orientation of the orbital
– the direction in space the orbital is aligned relative to
the other orbitals
• Values of ml are integers from −l to +l including
zero
2.4 Quantum Mechanics
Magnetic Quantum Number, ml
for a given value of l
ml = -l, …., 0, …. +l

if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

orientation of the orbital in space


2.4 Quantum Mechanics
Magnetic Quantum Number, ml

3 orientations is space ml = -1, 0, or 1


5 orientations is space ml = -2, -1, 0, 1, or 2
2.4 Quantum Mechanics
Spin Quantum Number ms
This spin quantum number
describes the properties of
electron

ms = +½ or -½

ms = +½ ms = -½
2.4 Quantum Mechanics
Energy Shells and Subshells

Atomic
orbital
1s 2s, 2px, 2py, 2pz 3s, 3px, 3py, 3pz 3dyz, 3dxy,
designations 3dxz,
3(dx2-y2),
3dz2
Example 1: What are the quantum numbers and names
(for example, 2s, 2p) of the orbitals in the
n = 4 principal level? How many orbitals exist?
Given: n = 4
Find: orbital designations, number of orbitals
Conceptual n l ml
Plan:
0 → (n − 1) −l → +l
Relationships: l: 0 → (n − 1); ml: −l → +l
Solve: n=4
 l : 0, 1, 2, 3

n = 4, l = 0 (s) n = 4, l = 1 (p) n = 4, l = 2 (d) n = 4, l = 3 (f)


ml : 0 ml : −1,0,+1 ml : −2,−1,0,+1,+2 ml : −3,−2,−1,0,+1,+2,+3
1 orbital 3 orbitals 5 orbitals 7 orbitals
4s 4p 4d 4f
total of 16 orbitals: 1 + 3 + 5 + 7 = 42 : n2
Exercise 9 Determining Quantum Numbers for an Energy
Level, n =3
PROBLEM: What values of the angular momentum (l) and magnetic
(ml) quantum numbers are allowed for a principal quantum
number (n) of 3? How many orbitals are allowed for n = 3?

PLAN: Values of l are determined from the value for n, since l can take
values from 0 to (n-1). The values of ml then follow from the
values of l.

SOLUTION: For n = 3, allowed values of l are = 0, 1, and 2

For l = 0 ml = 0 For l = 1 ml = -1, 0, or +1

For l = 2 ml = -2, -1, 0, +1, or +2

There are 9 ml values and therefore 9 orbitals with n = 3.


Exercise 10 Determining Sublevel Names and Orbital
Quantum Numbers
PROBLEM: Give the name, magnetic quantum numbers, and number of
orbitals for each sublevel with the following quantum numbers:

(a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l = 3

PLAN: Combine the n value and l designation to name the sublevel. Knowing
l, we can find ml and the number of orbitals.

SOLUTION:
n l sublevel namepossible ml values # of orbitals

(a) 3 2 3d -2, -1, 0, 1, 2 5

(b) 2 0 2s 0 1

(c) 5 1 5p -1, 0, 1 3

(d) 4 3 4f -3, -2, -1, 0, 1, 2, 3 7


Exercise 11 Identifying Incorrect Quantum Numbers

PROBLEM: What is wrong with each of the following quantum numbers


designations and/or sublevel names?
n l ml Name

(a) 1 1 0 1p
(b) 4 3 +1 4d
(c) 3 1 -2 3p
SOLUTION:
(a) A sublevel with n = 1 can only have l = 0, not l = 1. The only possible
sublevel name is 1s.
(b) A sublevel with l = 3 is an f sublevel, to a d sublevel. The name
should be 4f.
(c) A sublevel with l = 1 can only have ml values of -1, 0, or +1, not -2.
Topic

WEEK 5

2.5 Atomic Orbitals


2.6 Electronic Configurations and Orbital
Diagrams
2.7 Periodic Classification of the Elements (up
to first transition series only)
Learning Outcomes
Students should able to:
Recognize the shape of the s, p, d, and f orbital and their respective
quantum numbers.
Explain the Pauli Exclusion Principle, Auffbau Principle and Hund’s Rule.
Draw the electron configurations of atoms and ions (inclusive the first
series of transition elements only) in terms of sublevel notation and orbital
diagram.
Determine the number of electrons if given certain quantum numbers.
Write the set quantum numbers for the particular electron or atom.
Explain the general principles of electron shielding and orbital penetration.
Define valence and core electrons.
Identify the s, p, d, and f blocks of elements in the periodic table.
Apply the periodic table to predict electron configurations.
Define the periodic law and its characteristic.
Topic
2.5 Atomic Orbitals
2.5 The Shapes of Atomic Orbitals

• The l quantum number primarily determines


the shape of the orbital
• l can have integer values from 0 to (n – 1)
• Each value of l is called by a particular letter
that designates the shape of the orbital
– s orbitals are spherical
– p orbitals are like two balloons tied at the knots
– d orbitals are mainly like four balloons tied at the
knot
– f orbitals are mainly like eight balloons tied at the
knot
2.5 The Shapes of Atomic Orbitals
l = 0, the s orbital

• Each principal energy


level has one s orbital
• Lowest energy orbital in a
principal energy state
• Spherical
• As n increases, the s-
orbitals get larger.
2.5 The Shapes of Atomic Orbitals
l = 0, the s orbital
2.5 The Shapes of Atomic Orbitals
l = 1, p orbitals
• Each principal energy state above n = 1 has three p
orbitals
– ml = −1, 0, +1
• Each of the three orbitals points along a different axis
– px, py, pz
• 2nd lowest energy orbitals in a principal energy state
• Two-lobed
p orbitals
The 2p orbitals.
2.5 The Shapes of Atomic Orbitals

l = 2, d orbitals
• Principal energy level where n = 3 or greater has five d
orbitals
– ml = −2, − 1, 0, +1, +2
• Four of the five orbitals are aligned in a different plane
– dxy, dyz, dxz, dx2 – y2
– the fifth is aligned with the z axis, dz2
• Mainly four-lobed
– one is two-lobed with a donut-shaped ring along the xy plane
3d orbitals
3d orbitals
3d orbitals
2.5 The Shapes of Atomic Orbitals
l = 3, f orbitals

• Each principal energy state with n = 4 or greater


has seven f orbitals
– ml = −3, −2, −1, 0, +1, +2, +3
• 4th lowest energy orbitals in a principal energy
state
• Mainly eight-lobed
– other complex structures
4f orbitals
2.5 The Shapes of Atomic Orbitals
The 4fxyz orbital, one of the seven 4f
orbitals.
Topic
2.6 Electron Configurations and
Orbital Diagrams
2.6 Electron Configurations and Orbital
Diagram

The Property of Electron Spin

• Spin is a fundamental property of all electrons


• The orientation of the electron spin is quantized, it can only
be in one direction (clockwise) or its opposite
(counterclockwise)
– spin up or spin down
• The electron spin adds a fourth quantum number to the
description of electrons in an atom, called the Spin
Quantum Number, ms
2.6 Electron Configurations and Orbital
Diagram
Spin Quantum Number, ms, and Orbital
Diagrams

• ms can have values of +½ or −½


• Orbital Diagrams use a square to represent
each orbital and a half-arrow to represent each
electron in the orbital
• By convention, a half-arrow pointing up is used
to represent an electron in an orbital with spin
up
• Spins must cancel in an orbital with 2 electrons
(paired e-)
2.6 Electron Configurations and Orbital
Diagram

Orbital Diagrams

• We often represent an orbital as a square and


the electrons in that orbital as arrows
– the direction of the arrow represents the spin of the
electron

unoccupied orbital with orbital with


orbital one electron two electrons
2.6 Electron Configurations and Orbital
Diagram
Electron Configuration: How Electrons
Occupy Orbitals
Electron configuration is indicated by a shorthand notation:

The electron configuration is a listing of the sublevels in order of filling with the
number of electrons in that sublevel written as a superscript.

# # of electrons in the sublevel


n l
as s, p, d, f

Orbital diagrams make use of a box, circle, or line for each orbital in the energy
level. An arrow is used to represent an electron and its spin.

↑↓ ↑↓ ↑↓
2.6 Electron Configurations and Orbital
Diagram

Electron Configuration of H atom

number of electrons in
the orbital
1s1
principal energy level of
orbital occupied by the sublevel of orbital
electron occupied by the
electron
Order of Sublevel Filling in Ground
State Electron Configurations
Start by drawing a diagram
putting each energy shell on a
row and listing the sublevels, (s,
p, d, f), for that shell in order of
energy (left-to-right)

Next, draw arrows through


the diagonals, looping back
to the next diagonal each
time
Order for filling energy
sublevels with electrons.

In general, energies of sublevels


increase as n increases (1 < 2 < 3,
etc.)
and as l increases (s < p < d < f).

As n increases, some sublevels


overlap.
Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

1
En = -RH ( n2 )

n=1

125
Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
126
“Fill up” electrons in lowest energy orbitals
(Aufbau principle)
The most stable arrangement of electrons in subshells is the
one with the greatest number of parallel spins (Hund’s rule).
• No two electrons in an atom may have the same set of four
quantum numbers (n, l, ml, ms)
• Therefore the exclusion principle states that each orbital
may contain a maximum of 2 electrons, which must have
opposite spins.
A horizontal orbital
↑↓ ↑
Li (Z = 3) 1s2, 2s1 diagram for the Li
ground state.
1s 2s

A vertical orbital
diagram for the Li
ground state.
Quantum Numbers of Electrons for helium
• Helium has two electrons
• Both electrons are in the first energy level
• Both electrons are in the s orbital of the first energy level
• Because they are in the same orbital, they must have
opposite spins
Example 2: What is the maximum number of electrons
that can be present in the principal level for which n =
3?
Strategy We are given the principal quantum number (n) so
we can determine all the possible values of the angular
momentum quantum number (ℓ). The preceding rule shows
that the number of orbitals for each value of ℓ is (2 ℓ + 1). Thus,
we can determine the total number of orbitals. How many
electrons can each orbital accommodate?

Solution When n = 3, ℓ = 0, 1, and 2. The number of orbitals


for each value of ℓ is given by
The total number of orbitals is nine. Because each orbital can
accommodate two electrons, the maximum number of electrons
that can reside in the orbitals is 2 × 9, or 18.

Check If we use the formula (n2) in Example 7.8, we find that


the total number of orbitals is 32 and the total number of
electrons is 2(32) or 18. In general, the number of
electrons in a given principal energy level n is 2n2.
Exercise 12: An oxygen atom has a total of eight
electrons. Write the four quantum numbers for each
of the eight electrons in the ground state.
Strategy
We start with n = 1 and proceed to fill orbitals in the order
shown in Figure 7.24.

For each value of n we determine the possible values of ℓ.

For each value of ℓ, we assign the possible values of mℓ.

We can place electrons in the orbitals according to the Pauli


exclusion principle and Hund’s rule.
Solution
We start with n = 1, so ℓ = 0, a subshell corresponding to the 1s
orbital. This orbital can accommodate a total of two electrons.
Next, n = 2, and / may be either 0 or 1. The ℓ = 0 subshell
contains one 2s orbital, which can accommodate two electrons.
The remaining four electrons are placed in the ℓ = 1 subshell,
which contains three 2p orbitals. The orbital diagram is
The results are summarized in the following table:

Of course, the placement of the eighth electron in the orbital


labeled mℓ = 1 is completely arbitrary. It would be equally
correct to assign it to mℓ = 0 or mℓ = −1.
Exercise 13 Determining Quantum Numbers from Orbital
Diagrams
PROBLEM: Write a set of quantum numbers for the third electron and
a set for the eighth electron of the F atom.

PLAN: Identify the electron of interest and note its level (n), sublevel,
(l), orbital (ml) and spin (ms). Count the electrons in the order in
which they are placed in the diagram.

SOLUTION:

F (Z = 9) 1s22s22p3 ↑↓ ↑↓ ↑↓ ↑ ↑

1s 2s 2p
For the 3rd electron: n = 2, l = 0, ml = 0, ms = +½

For the 8th electron: n = 2, l = 1, ml = -1, ms = -½


2.6 Electron Configurations and Orbital
Diagram
Splitting of Levels into Sublevels
Each energy level is split into sublevels of
differing energy.
Splitting is caused by penetration and its effect on
shielding.
For a given n value, a lower l value indicates a
lower energy sublevel.
Order of sublevel energies: s < p < d < f
2.6 Electron Configurations and Orbital
Diagram
Penetration and sublevel energy.

Orbital shape causes electrons


in some orbitals to “penetrate”
close to the nucleus.

Penetration increases nuclear


attraction and decreases
shielding.
2.6 Electron Configurations and Orbital
Diagram
Penetration and Shielding
• The radial distribution function shows that the 2s orbital
penetrates more deeply into the 1s orbital than does the 2p
• The weaker penetration of the 2p sublevel means that
electrons in the 2p sublevel experience more repulsive force,
they are more shielded from the attractive force of the
nucleus
• The deeper penetration of the 2s electrons means electrons
in the 2s sublevel experience a greater attractive force to the
nucleus and are not shielded as effectively
Effect of Penetration and Shielding
• Penetration causes the energies of sublevels in the same
principal level to not be degenerate
• In the fourth and fifth principal levels, the effects of
penetration become so important that the s orbital lies lower
in energy than the d orbitals of the previous principal level
• The energy separations between one set of orbitals and the
next become smaller beyond the 4s
– the ordering can therefore vary among elements
– causing variations in the electron configurations of the
transition metals and their ions
6d
7s
5f
6p
5d
6s 4f
5p
4d
5s
4p

3d
4s
Energy

3p
Notice the following:
3s 1. because of penetration, sublevels within an
energy level are not degenerate
2p 2. penetration of the 4th and higher energy levels is
so strong that their s sublevel is lower in energy
2s than the d sublevel of the previous energy level
3. the energy difference between levels becomes
smaller for higher energy levels (and can cause
anomalous electron configurations for certain
elements)
1s
Example 3 — Write the full ground state
electron configuration of carbon

1s sublevel : 2e
2s sublevel : 2e
2p sublevel : 2e

Therefore the electron


configuration is
1s2 2s2 2p2
2.6 Electron Configurations and Orbital
Diagram
Electron Configurations
2.6 Electron Configurations and Orbital
Diagram
Depicting orbital occupancy for the first 10
elements.
Partial Orbital Diagrams and
Condensed Configurations
A partial orbital diagram shows only the highest energy sublevels
being filled.

Al (Z = 13) 1s22s22p63s23p1
↑↓ ↑

3s 3p

A condensed electron configuration has the element symbol of the


previous noble gas in square brackets.

Al has the condensed configuration [Ne]3s23p1


2.6 Electron Configurations and Orbital
Diagram
Partial Orbital Diagrams and Electron Configurations* for the
Elements in Period 3.

*Colored type indicates the sublevel to which the last electron is added.
2.6 Electron Configurations and Orbital
Diagram
Electron Configuration and
Group
Elements in the same group of the periodic table have the
same outer electron configuration.

Elements in the same group of the periodic table exhibit


similar chemical behavior.

Similar outer electron configurations correlate with


similar chemical behavior.
2.6 Electron Configurations and Orbital
Diagram
Condensed electron configurations in
the first three periods.
Topic
2.7
Electron Configurations,
Valence Electrons and
Periodic Table
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Valence Electrons
• The electrons in all the sublevels with the highest
principal energy shell are called the valence
electrons
• Electrons in lower energy shells are called core
electrons
• Chemists have observed that one of the most
important factors in the way an atom behaves, both
chemically and physically, is the number of valence
electrons
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Electron Configuration of Atoms in
their Ground State
• Kr = 36 electrons
1s22s22p63s23p64s23d104p6
– there are 28 core electrons and 8 valence electrons
• Rb = 37 electrons
1s22s22p63s23p64s23d104p65s1
[Kr]5s1
• For the 5s1 electron in Rb the set of quantum numbers is n
= 5, l = 0, ml = 0, ms = +½
• For an electron in the 2p sublevel, the set of quantum
numbers is n = 2, l = 1, ml = −1 or (0,+1), and ms = −½ or
(+½)
2.7 Electron Configurations, Valence
Electrons and Periodic Table

Electron Configuration & the


Periodic Table
• The Group number corresponds to the number of valence
electrons
• The length of each “block” is the maximum number of
electrons the sublevel can hold
• The Period number corresponds to the principal energy
level of the valence electrons
Exercise 14 – Use the Periodic Table to write the short
electron configuration and short orbital diagram for each
of the following

• Na (at. no. 11) [Ne]3s1


3s

• Te (at. no. 52) [Kr]5s24d105p4

5s 4d 5p

• Tc (at. no. 43) [Kr]5s24d5

5s 4d
2.7 Electron Configurations, Valence
Electrons and Periodic Table

Orbital filling and the periodic table.

The order in which the orbitals are filled can be obtained directly
from the periodic table.
Electron Configuration from
the Periodic Table
1A 8A
1 2A 3A 4A 5A 6A 7A
2
Ne
3
4 3s2 P
5 3p3
6
7

P = [Ne]3s23p3
P has five valence electrons
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Transition Elements

• For the d block metals, the principal energy level is one


less than valence shell
– one less than the Period number
– sometimes an s electron is “promoted” to d sublevel

Zn
Z = 30, Period 4, Group 2B
4s 3d
[Ar]4s23d10
Electron Configuration from
the Periodic Table
1A 8A
1 2A 3A 4A 5A 6A 7A
2
3
4 3d10 Ar
5 4s2 As
6
4p3
7

As = [Ar]4s23d104p3
As has five valence electrons
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Irregular Electron Configurations
• We know that because of sublevel splitting, the 4s
sublevel is lower in energy than the 3d; and therefore
the 4s fills before the 3d
• But the difference in energy is not large
• Some of the transition metals have irregular electron
configurations in which the ns only partially fills before
the (n−1)d or doesn’t fill at all
• Their electron configuration has stability associated
with half-filled or completely filled subshell.
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Anomalous Electron Configurations
Half-filled or full
Expected subshells
• Cr = [Ar]4s23d4 • Cr = [Ar]4s13d5
• Cu = [Ar]4s23d9 • Cu = [Ar]4s13d10
• Mo = [Kr]5s24d4 • Mo = [Kr]5s14d5
• Pd = [Kr]5s24d8 • Pd = [Kr]5s04d10
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Partial Orbital Diagrams and Electron Configurations* for the
Elements in Period 4.

*Colored type indicates the sublevel to which the last electron is added.
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Partial Orbital Diagrams and Electron Configurations* for the
Elements in Period 4.

*Colored type indicates the sublevel to which the last electron is added.
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Properties & Electron
Configuration

• The properties of the


elements follow a periodic
pattern
– elements in the same column
have similar properties
– the elements in a period show
a pattern that repeats
2.7 Electron Configurations, Valence
Electrons and Periodic Table
The Noble Gas
Electron Configuration
• The noble gases have eight valence
electrons.
– except for He, which has only two
electrons
• We know the noble gases are
especially non-reactive
– He and Ne are practically inert
• The reason the noble gases are so
non-reactive is that the electron
configuration of the noble gases is
especially stable
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Everyone Wants to Be Like
a Noble Gas!
The Alkali Metals

• The alkali metals have one more electron


than the previous noble gas
• In their reactions, the alkali metals tend to
lose one electron, resulting in the same
electron configuration as a noble gas
– forming a cation with a 1+ charge
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Everyone Wants to Be Like
a Noble Gas!The Halogens
• The electron configurations of the halogens
all have one fewer electron than the next
noble gas
• In their reactions with metals, the halogens
tend to gain an electron and attain the
electron configuration of the next noble gas
– Forming an anion with charge 1−
• In their reactions with nonmetals, they tend
to share electrons with the other nonmetal
so that each attains the electron
configuration of a noble gas
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Eight Valence Electrons
• Quantum mechanical calculations show that eight
valence electrons should result in a very unreactive
atom
– an atom that is very stable
– the noble gases have eight valence electrons and are
all very stable and unreactive
• He has two valence electrons, but that fills its valence shell

• Conversely, elements that have either one more or


one less electron should be very reactive
– the halogen atoms have seven valence electrons and
are the most reactive nonmetals
– the alkali metals have one more electron than a noble
gas atom and are the most reactive metals
• as a group
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Electron Configuration &
Ion Charge
• We have seen that many metals and nonmetals
form one ion, and that the charge on that ion is
predictable based on its position on the Periodic
Table
– Group 1A = 1+, Group 2A = 2+, Group 7A = 1−, Group
6A = 2−, etc.
• These atoms form ions that will result in an
electron configuration that is the same as the
nearest noble gas
2.7 Electron Configurations, Valence
Electrons and Periodic Table
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Electron Configuration of Anions in
Their Ground State
• Anions are formed when nonmetal atoms gain
enough electrons to have eight valence electrons
– filling the s and p sublevels of the valence shell
• The sulfur atom has six valence electrons
S atom = 1s22s22p63s23p4
• To have eight valence electrons, sulfur must gain
two more
S2− anion = 1s22s22p63s23p6
2.7 Electron Configurations, Valence
Electrons and Periodic Table
Electron Configuration of Cations in
Their Ground State
• Cations are formed when a metal atom loses all its
valence electrons
– resulting in a new lower energy level valence shell
– however the process is always endothermic
• The magnesium atom has two valence electrons
Mg atom = 1s22s22p63s2
• When magnesium forms a cation, it loses its
valence electrons
Mg2+ cation = 1s22s22p6
2.7 Electron Configurations, Valence
Electrons and Periodic Table

Electron Configurations of Main Group


Cations in Their Ground State
• Cations form when the atom loses electrons from
the valence shell
Al atom = 1s22s22p63s23p1
Al3+ ion = 1s22s22p6
Electron Configurations of Transition
Metal Cations in Their Ground State
• When transition metals form cations, the first
electrons removed are the valence electrons, even
though other electrons were added after
• Electrons may also be removed from the sublevel
closest to the valence shell after the valence
electrons
• The iron atom has two valence electrons
Fe atom = 1s22s22p63s23p64s23d6
• When iron forms a cation, it first loses its valence
electrons
Fe2+ cation = 1s22s22p63s23p63d6
• It can then lose 3d electrons
Fe3+ cation = 1s22s22p63s23p63d5
Topic

WEEK 6

2.8 Periodic Variations in Physical Properties;


Atomic and Ionic Radii, Ionization Energy,
Electronegativity and Electron Affinity
Learning Outcomes
Students should able to:
Define atomic and ionic radii, first ionization energy and electron affinity.
Predict the trends in atomic radii and ionic radii of elements across the
period and down the group and the factors affecting it.
Predict the trends in ionization energy and electron affinity of elements
across the period and down the group and the factors affecting it.
Explain the abnormality in ionization energy of elements in group 2A and
group 5A.
Predict the group of an element from the values of successive ionization
energy given.
Identify and distinguish between paramagnetic and diamagnetic
atoms/ions.
Recognize the differences in chemical and physical properties of metal
and nonmetal including the basicity of metal oxides and the acidity of
nonmetal oxides.
Topic
2.8 Periodic Trends in the Size of
Atoms and Effective Nuclear
Charge
Trend in Atomic Radius – Main Group
• There are several methods for measuring the
radius of an atom, and they give slightly different
numbers
 van der Waals radius = nonbonding
 covalent radius = bonding radius
 atomic radius is an average radius of an atom
based on measuring large numbers of
elements and compounds
• Atomic Radius Increases down group
 valence shell farther from nucleus
 effective nuclear charge fairly close
• Atomic Radius Decreases across period (left to
right)
 adding electrons to same valence shell
 effective nuclear charge increases
 valence shell held closer
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Group Trend in Atomic Radius
• The size of an atom is related to the distance the valence
electrons are from the nucleus
• The larger the orbital an electron is in, the farther its most
probable distance will be from the nucleus and the less
attraction it will have for the nucleus
• Going down a group , more principal energy levels are
added. Greater shielding of the valence electrons by the
core electrons. Therefore, increasing atomic radius.
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Period Trend in Atomic Radius
• The larger the effective nuclear charge an electron
experiences, the stronger the attraction by the nucleus, the
closer their average distance will be to the nucleus
• Traversing across a period, the effective nuclear charge on
the valence electrons increases. Core electrons number
remains the same. Therefore, decreasing atomic radius
• Shielding by electrons in the same quantum shell is
ineffective.
Defining Atomic Size.

A. The metallic radius of aluminum. B. The covalent radius of chlorine.

C. Known covalent radii and distances


between nuclei can be used to find
unknown radii.
Atomic radii of
the main-group
and transition
elements.
Periodicity of Atomic Radius.
Example 4 : Choose the
Larger Atom in Each Pair
1. N or F,
F N is farther left
2. C or Ge
Ge, Ge is farther down
3. N or Al,
Al Al is farther down & left
4. Al or Ge? opposing trends
Exercise 15 – Choose the
Larger Atom in Each Pair

• C or O C is farther left in the period


• Li or K K is farther down the column
• C or Al Al is farther left and down
• Se or I ? opposing trends
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Factors affecting atomic radius

• Each electron in a multielectron atom


experiences both the attraction to the nucleus
and repulsion by other electrons in the atom

• 1. Shielding
• 2. Effective nuclear charge
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Factors affecting atomic radius
• The energies of atomic orbitals are affected by
– nuclear charge (Z) and
– shielding by other electrons.
• A higher nuclear charge increases nucleus-electron
interactions and lowers sublevel energy.
• Shielding by other electrons reduces the full nuclear
charge to an effective nuclear charge (Zeff).
– Zeff is the nuclear charge an electron actually experiences.
• Orbital shape also affects sublevel energy.
The effect of nuclear charge on sublevel energy.

Greater nuclear charge lowers


sublevel energy.

It takes more energy to remove the


1s electron from He+ than from H.
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Effective Nuclear Charge
• The effective nuclear charge is net
positive charge that is attracting the valence
electrons
• Z is the nuclear charge, S is the number of
core electrons
Zeffective = Z − S
2.8 Periodic Classification of the Elements

Screening & Effective Nuclear Charge


2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Shielding
• Outer electrons repelled by core electrons. They
are shielded from nucleus by the core electrons
 screening or shielding effect
 Shielding among outer electrons is not effective
• The shielding causes the outer electrons to move
further away from the nucleus, tends to increase
the atomic radius
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Shielding and Orbital Energy

• Electrons in the same energy level shield each


other to some extent.
• Electrons in inner energy levels shield the outer
electrons very effectively.
– The further from the nucleus an electron is, the lower
the Zeff for that particular electron.
Shielding and Energy Levels.
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Effective nuclear charge (Zeff) is the “positive charge” felt by an
electron.
Zeff = Z - s 0 < s < Z (s = shielding constant)

Zeff  Z – number of inner or core electrons


Z Core Zeff Radius (pm)

Na 11 10 1 186

Mg 12 10 2 160

Al 13 10 3 143

Si 14 10 4 132
2.8 Periodic Trends in the Size of Atoms
and Effective Nuclear Charge
Effective Nuclear Charge (Zeff)
increasing Zeff
increasing Zeff
Topic
2.8 Ions: Magnetic Properties,
Ionic Radii and Ionization
Energy
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Trends in Ionic Radius
• Ions in same group have same charge

• Ion size increases down the column


 more valence shells, larger size

• Cations smaller than parent atoms; anions larger


than parent atoms

• Most cations are smaller than anions


 except Rb+ & Cs+ bigger or same size as F− and O2−
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy

Trends in Cation Radius


• When atoms form cations, the valence electrons are
removed. The rest of the electrons will be attracted more
strongly and closer to the nucleus
• Result: cations are smaller than their parent atoms
• Traversing down a group, the cations to getting larger, due
to increase no. of inner shells.
• Traversing to the right across a period increases the
effective nuclear charge for isoelectronic cations,
decreases size of the cations.
Example: Na+ > Mg2+ > Al3+
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy

Trends in Anion Radius


• When atoms form anions, electrons are added to the
valence shell, but Zeff remains unchanged. Thus,
increasing the size
• Results: Anions are larger than their parent atoms
• Traversing down a group increases the energy levels,
causing the anions to get larger
• Traversing to the right across a period decreases size for
isoelectronic anions, the more negative charge the anion
the larger the size
Example: N3– > O2– > F –
Periodic Pattern – Ionic Radius (Å)
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Example 5 : Choose the larger of each pair

• S or S2−
– S2− is larger because there are more electrons (18 e−) for the 16
protons to hold
– the anion is larger than the neutral atom
• Ca or Ca2+
– Ca is larger because its valence shell has been lost from Ca2+
– the cation is always smaller than the neutral atom
• Br− or Kr
– the Br− is larger because it has fewer protons (35 p+) to hold the 36
electrons than does Kr (36 p+)
– for isoelectronic species, the more negative the charge the larger
the atom or ion
Exercise 16 – Order the following sets by size
(smallest to largest)

Zr4+, Ti4+, Hf4+ same column & charge,


therefore Ti4+ < Zr4+ < Hf4+

Na+, Mg2+, F−, Ne isoelectronic,


therefore Mg2+ < Na+ < Ne < F−

I−, Br−, Ga3+, In+ Ga3+ < In+ < Br− < I−
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy

Ionization Energy
• Minimum energy needed to remove an electron from an
atom or ion
 gas state
 endothermic process
 valence electron easiest to remove, lowest IE
 M(g) + IE1  M1+(g) + 1 e-
 M+1(g) + IE2  M2+(g) + 1 e-
first ionization energy = energy to remove electron
from neutral atom; 2nd IE = energy to remove from
1+ ion; etc.
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
General Trends in 1st Ionization Energy
• The larger the effective nuclear charge on the
electron, the more energy it takes to remove it
• The farther the most probable distance the electron
is from the nucleus, the less energy it takes to
remove it
• 1st IE decreases down the group
– valence electron farther from nucleus
• 1st IE generally increases across the period
– effective nuclear charge increases
209
Periodicity of first ionization energy (IE1).
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy

Trends in First Ionization Energy


• Moving down a group, the valence electrons are
placed increasingly higher energy level (value of n
increases). Getting further away from the nucleus, and
experiencing less and less attraction. Hence, IE1
getting smaller.
• Traversing across a period, gradual increase in
effective nuclear charge on the valence electrons, the
stronger the attraction on the electrons. Therefore, the
IE1 get larger across a period
Example 6 : Choose the atom in each pair with the
larger first ionization energy
1. Al or S,
S S is farther right
2. As or Sb
Sb, As is farther up
3. N or Si
Si, N is farther up & right
4. O or Cl? opposing trends
Exercise 17 – Choose the atom with the largest
first ionization energy in each pair

• Mg or P

• Ag or Cu

• Ca or Rb

• P or Se ?
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Exceptions in the 1st IE Trends
• First Ionization Energy generally increases from
left to right across a Period
• Except from 2A to 3A, 5A to 6A
      
Be N
1s 2s 2p 1s 2s 2p

       
B O
1s 2s 2p 1s 2s 2p

Which is easier to remove an electron from, N or O? Why?

Which is easier to remove an electron from B, or Be? Why?


2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Exceptions in the
First Ionization Energy Trends,
Be and B
   
Be Be+
1s 2s 2p 1s 2s 2p

To ionize Be you must break up a full sublevel, costs extra energy

    
B B+
1s 2s 2p 1s 2s 2p
When you ionize B you get a full sublevel, costs less energy
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Exceptions in the
First Ionization Energy Trends,
N and O
        
N N+
1s 2s 2p 1s 2s 2p

To ionize N you must break up a half-full sublevel,


costs extra energy

         
O O+
1s 2s 2p 1s 2s 2p

When you ionize O you get a half-full sublevel,


costs less energy
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy

The first three ionization


energies of beryllium.

Beryllium has 2 valence electrons,


so IE3 is much larger than IE2.
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Successive Ionization Energies of the
Elements Lithium Through Sodium
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Magnetic Properties of Transition Metal
ions
A species with one or more unpaired electrons exhibits
paramagnetism – it is attracted by a magnetic field.

Ag (Z = 47) ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

5s 4d 5p

A species with all its electrons paired exhibits


diamagnetism – it is not attracted (and is slightly repelled)
by a magnetic field.
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Measuring the magnetic behavior of a sample.

The apparent mass of a The apparent mass of a


diamagnetic substance is paramagnetic substance
unaffected by the magnetic increases as it is attracted by the
field. magnetic field.
2.8 Ions: Magnetic Properties, Ionic Radii
and Ionization Energy
Magnetic Properties of Transition Metal
ions
Magnetic behavior can provide evidence for the
electron configuration of a given ion.
Ti (Z = 22) ↑↓ ↑ ↑

4s 3d 4p
Ti2+ ↑ ↑

4s 3d 4p
Ti2+ has 2 unpaired electrons and is paramagnetic,
providing evidence that the 4s electrons are lost
before the 3d electrons.
Exercise 18 Writing Electron Configurations and
Predicting Magnetic Behavior of Transition
Metal Ions

PROBLEM: Use condensed electron configurations to write


the reaction for the formation of each transition
metal ion, and predict whether the ion is
paramagnetic or diamagnetic.

(a) Mn2+(Z = 25) (b) Cr3+(Z = 24) (c) Hg2+(Z = 80)

PLAN: Write the condensed electron configuration for each atom,


recalling the irregularity for Cr. Remove electrons, beginning
with the ns electrons, and determine if there are any unpaired
electrons.
Sample Problem

SOLUTION:

(a) Mn2+(Z = 25) Mn ([Ar] 4s23d5) → Mn2+ ([Ar] 3d5) + 2e−


Since there are 5 d electrons they are all unpaired. Mn2+ is paramagnetic.

(b) Cr3+(Z = 24) Cr ([Ar] 4s13d5) → Cr3+ ([Ar] 3d3) + 3e−


Since there are 3 d electrons they are all unpaired. Cr3+ is paramagnetic.

(c) Hg2+(Z = 80) Hg ([Xe] 6s24f145d10) → Hg2+ ([Xe] 4f145d10) + 2e−


The 4f and the 5s sublevels are filled, so there are no unpaired
electrons. Hg2+ is diamagnetic.
Topic
Electron Affinities,
2.8
Electronegativity and
Metallic Character
2.8 Electron Affinities, Electronegativity
and Metallic Character

Electron Affinity
• Electron Affinity (EA) is the energy change
that occurs when 1 mol of electrons is added
to 1 mol of gaseous atoms or ions.
gas state
M(g) + 1e−  M1−(g) + EA
• The more energy that is released, the larger the
electron affinity, the more stable is the ion.
the more negative the number, the larger the EA
2.8 Electron Affinities, Electronegativity
and Metallic Character

Trends in Electron Affinity


• EA generally increases across period, and
decreases down a group
 becomes more negative from left to right
 but the trends in electron affinity are not as regular as
those for atomic size or IE.

• Highest EA in any period = halogen

• Atoms with a low EA tend to form cations.

• Atoms with a high EA tend to form anions.


2.8 Electron Affinities, Electronegativity
and Metallic Character

Electronegativity
• Electronegativity of an element is a value used to
indicate the ability of an atom to attract electrons to
itself when the atom is sharing electrons with
(covalently bonded to) atom of another element
• Trends in electronegativity are similar to those for
electron affinity.
 EN value decreases from top to bottom within a group
 EN value increases from left to right across a period
Electronegativity (EN) Values for Representative Elements

Group 1A 2A 3A 4A 5A 6A 7A

Period
1 H
2.1
2 Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
3 Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
4 K Ca Ga Ge As Se Br
0.8 1.0 1.6 1.8 2.0 2.4 2.8
5 Rb Sr I
0.8 1.0 2.5
6 Cs Ba
0.7 0.9
Electronegativity Scale
2.8 Electron Affinities, Electronegativity
and Metallic Character

Metallic Character
• Metallic character is how closely an element’s properties
match the ideal properties of a metal
– more malleable and ductile, better conductors, and easier to ionize
• Metallic character decreases left-to-right across a period
– metals are found at the left of the period and nonmetals are to the
right
• Metallic character increases down the column
– nonmetals are found at the top of the middle Main Group elements
and metals are found at the bottom
Example 7 : Choose the
more metallic element in each pair
1. Sn or Te,
Te Sn is farther left
2. P or Sb
Sb, Sb is farther down
3. Ge or In
In, In is farther down & left
4. S or Br? opposing trends
2.8 Electron Affinities, Electronegativity
and Metallic Character

Exercise 19 – Choose the


more metallic element in each pair
• Mg or Al

• Si or Sn

• Br or Te

• Se or I ?
Trends in the Alkali Metals
• Atomic radius increases down the column
• Ionization energy decreases down the column
• Very low ionization energies
– good reducing agents, easy to oxidize
– very reactive, not found uncombined in nature
– react with nonmetals to form salts
– compounds generally soluble in water  found in seawater
• Electron affinity decreases down the column
• Melting point decreases down the column
– all very low MP for metals
• Density increases down the column
– except K
– in general, the increase in mass is greater than the increase in
volume
Alkali Metals
2.8 Electron Affinities, Electronegativity
and Metallic Character

Trends in the Halogens


• Atomic radius increases down the column
• Ionization energy decreases down the column
• Very high electron affinities
– good oxidizing agents, easy to reduce
– very reactive, not found uncombined in nature
– react with metals to form salts
– compounds generally soluble in water  found in seawater
• Reactivity increases down the column
• React with hydrogen to form HX, acids
• Melting point and boiling point increase down the column
• Density increases down the column
– in general, the increase in mass is greater than the increase in
volume
Conclusion Trends in three atomic properties.
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