Inorganic and analytical Chemistry

Lecture 2

Dr.: Sameh Araby El-Mekawy

Outlines
 Quantum Numbers
 Periodic Trends in Atomic Properties
– atomic radius
– effective nuclear charge
– ionic radius
– ionization energy
– electron affinity
– metallic character
– electronegativity
 Quantum Numbers
• A wave function for an electron in an atom is called an atomic orbital; this atomic
orbital describes a region of space in which there is a high probability of finding the
electron.
• Each electron in an atom is described by four different quantum numbers.
– Principal quantum number, n: energy and size.
– Angular momentum quantum number, l: shape.
– Magnetic quantum number, ml: orientation in space.
– Spin quantum number, ms: orientation of spin axis.
Principal Quantum Number, n
• The Principal Quantum Number, n is an integer that can range
from 1 to infinity: n = 1, 2, 3, …, ∞.
• It specifies the size and energy level of an orbital.
– For one-electron atoms, such as H, the energy depends only on
n; for atoms with more than one electron, the energy depends on
both n and l.
– As n increases, the number of allowed orbitals increases and
the size of those orbitals increases, allowing an electron to be
farther from the nucleus; this requires it to be higher in energy.
• All orbitals that have the same value of n are said to be in the
same shell (level).
• The total number of orbitals for a given n value is n2.
Angular Momentum Quantum Number, l

The Angular-Momentum Quantum Number (secondary or azimunthal),

l, is an integer that ranges from 0 to n-1:
l = 0, ..., n-1.
• It specifies the shape of an orbital with a particular value of n.
• The angular-momentum quantum number divides the shells into
smaller groups of orbitals called subshells (sublevels).
• Usually, a letter code is used to identify l to avoid confusion with n:
l= 0 1 2 3 4 5 . . .
Letter s p d f g h
Examples:
– If n=1, the possible values for l are 0.
– If n=2, the possible values for l are 0 and 1.
– The subshell with n=2 and l=0 is the 2s subshell;
the subshell with n=2 and l=1 is the 2p subshell.
– When n=3, l has three possible values:
• n=3, l=0  3s subshell
• n=3, l=1  3p subshell
• n=3, l=2  3d subshell
• The value of l also has a slight effect on the energy of the subshell; the
energy of the subshell increases with l (s < p < d < f).
 Magnetic Quantum Number, ml

• The Magnetic Quantum Number, ml , is an integer which runs

from -l to +l:
ml = -l, ..., 0, ..., +l.
• It specifies the orientation in space of an orbital of a given energy
(n) and shape (l).
• This number divides the subshell into individual orbitals which
hold the electrons. There are 2l+1 orbitals in each subshell, and n2
orbitals in each shell.
• Thus the s subshell has only one orbital, the p subshell has three
orbitals, and so on.
The First Three Quantum Numbers
The following table summarizes the available orbitals in the shells from n=1 to n=4:
The Spin Quantum Number, ms,
• The Spin Quantum Number, ms, has only two
possible values:
ms = +½ (↑, spin up) or -½ (↓, spin down)
• It specifies the orientation of the spin axis of an
electron.
– Because an electron spins either clockwise or
counter-clockwise, it creates a tiny magnetic field,
which can be oriented either up or down.
– ms tells us how many electrons can occupy a
particular orbital.
Table 2 Summary of Quantum Numbers of Electrons in Atoms

Name Symbol Permitted Values Property

principal n positive integers (1, 2, 3, …) orbital energy (size)

angular l integers from 0 to n-1 orbital shape (The l values

momentum 0, 1, 2, and 3 correspond to
s, p, d, and f orbitals,
respectively.)
magnetic ml integers from -l to 0 to +l orbital orientation

spin ms +½ or -½ direction of e- spin

Question:
Each of the following sets of quantum numbers is supposed to
specify an orbital. However, each set contains one quantum
number that is not allowed. Replace the quantum number that is
not allowed with one that is allowed.

a. n = 3, l = 3, ml = +2
b. n = 2, l = 1, ml = -2
c. n = 1, l = 1, ml = 0
 Periodic Properties
•A number of element and ion properties vary in a periodic,
predictable way across the periodic table. These include:

– effective nuclear charge

– atomic radius
– ionic radius
– ionization energy
– electron affinity
– metallic character
– electronegativity
Types of electrons
The effective nuclear charge (Zeff )
• Valence (outer) electrons are the electrons in the outermost shell (with the
highest value of n). All the elements in the same group on the periodic table have
similar electron configurations for their valence shells, and therefore have similar
chemical properties.

• Core (inner) electrons are those in complete principal energy levels, and do not
participate in bonding.
• Electrons in inner levels or shells tend to shield outer electrons from the full
nuclear charge, which is reduced to effective nuclear charge (Zeff). Electrons
that have a greater penetration shield others more effectively. For example,
electrons in level n = 1 shield those in level n = 2 very effectively, and those in
n = 1 and n = 2 shield electrons in level n = 3. Electrons at the same level, but
in different sublevels, also shield other electrons to some extent. The extent of
penetration and shielding effect is in the order: s > p > d > f.

• The effective nuclear charge (Zeff) greatly influence atomic properties.

• In general, Zeff increases significantly across a period (left-to-right)
Zeff increases slightly down a group.
Atomic radius
 Definition:
- The total distance from an atom’s nucleus to the outermost orbital of electron.
- Atoms do not have specific outer boundary; their atomic size is based on atomic
radius, which is one-half the internuclear distance of two bonded identical atoms.
 Types of Radius
1- Covalent Radius 2- Ionic Radius 3- Metallic Radius
The atomic radius of an atom can be measured by taking one-half of the distance
between atoms in an atomic solid (the metallic radius), or by taking one half of
the distance between two identical bonded nuclei or between atoms in a metallic
crystal (the covalent radius). The ionic radius is derived from the distances
between the centers in ionic crystals.
Periodic Trends of Atomic Radius
Trends in Atomic Size
Atomic size increases as the principal quantum number n
increases.
As n increases, the probability that the outer electrons will be further
from the nucleus increases.

For main group elements:

atomic size increases down a group in the periodic table
and decreases across a period.
Question:
Using only the periodic table, rank each set of main-group
elements in order of decreasing atomic size:

(a) Ca, Mg, Sr

(b) K, Ga, Ca

(c) Br, Rb, Kr

(d) Sr, Ca, Rb

SOLUTION:
(a) Sr > Ca > Mg
Ca, Mg, and Sr are in Group 2. Size increases down the group.

(b) K > Ca > Ga

K, Ga, and Ca are all in Period 4. Size decreases across the period.

(c) Rb > Br > Kr

Rb is the largest because it has one more energy level than the other
elements. Kr is smaller than Br because Kr is further to the right in the
same period.

(d) Rb > Sr > Ca

Ca is the smallest because it has one fewer energy level. Sr is smaller
than Rb because it is smaller to the right in the same period.
Ionic radius
  Cations have smaller ionic radii than their neutral atoms. In
contrast, anions have bigger ionic radii than their
corresponding neutral atoms. Why?
The loss of the outermost valence shell has two effects:
1)The atoms radius shrinks because it loses it’s outermost principle quantum level
2) The Nucleus now has more positive charge than the total negative charge from
electrons. The larger effective nuclear charge will now pull electrons in closer to
the nucleus

 The greater the positive charge, the smaller the ionic radius
(e.g., Fe3+ < Fe2+).
 An isoelectronic series is a series of ions that have the same
electron configuration. Within the series, ion size decreases with
increasing nuclear charge.

3- > 2- > 1- > 1+ > 2+ > 3+

PROBLEM: Rank each set of ions in order of decreasing size, and
explain your ranking:
(a) Ca2+, Sr2+, Mg2+ (b) K+, S2−, Cl− (c) Au+, Au3+

PLAN: Find the position of each element on the periodic table and
apply the trends for ionic size.
SOLUTION:
(a) Sr2+ > Ca2+ > Mg2+
All these ions are from Group 2, so size increases down the group.
(b) S2− > Cl− > K+
These ions are isoelectronic, so size decreases as nuclear charge
increases.

(c) Au+ > Au3+

Cation size decreases as charge increases.
Problems
1.Which atom is larger: K or Br?
2.Which atom is larger: Na or Cl?
3.Which atom is smaller: Be or Ba?
4.Which atom is larger: K+ or K?
5.Put in order of largest to smallest: F, Ar, Sr, Cs.
6.Which has a bigger atomic radius: Sr2+ or Se2-?
7.If Br has an ionic radius of 100 pm and the total distance between K
and Br in KBr is 150 pm, then what is the ionic radius of K?
8.Which has a smaller atomic radius: Cs+ or Xe?
9.If the distance between the nuclei of two atoms in a metallic bond is
180 pm, what is the atomic radius of one atom?
10.If Z effective is increasing, is the atomic radius also increasing?
Ionization energy (IE)
 Ionization energy (IE) is the amount of energy needed to remove
an electron from a mole of neutral atoms in the gas phase

 IE is a positive energy value; energy must be provided in order to

remove an electron from an atom.
 The energy required to remove the first electron is
the first ionization energy (IE1).
Atoms with a low IE tend to form cations.
Atoms with a high IE tend to form anions (except the
noble gases).
Ionization energy tends to decrease down a group and
increase across a period.
Ranking Elements by First Ionization Energy

PROBLEM: Using the periodic table only, rank the elements in each of
the following sets in order of decreasing IE1:

(a) Kr, He, Ar (b) Sb, Te, Sn

(c) K, Ca, Rb (d) I, Xe, Cs

PLAN: Find each element on the periodic table. IE1 generally

decreases down a group and increases across a period.

SOLUTION:
(a) He > Ar > Kr
Kr, He, and Ar are in Group 18. IE1 decreases down the group.
SOLUTION:

(b) Te > Sb > Sn

Sb, Te, and Sn are in Period 5. IE1 increases across a period.

(c) Ca > K > Rb

K has a higher IE1 than Rb because K is higher up in Group 1. Ca
has a higher IE1 than K because Ca is further to the right in Period 4.

(d) Xe > I > Cs

Xe has a higher IE1 than I because Xe is further to the right in the
same period. Cs has a lower IE1 than I because it is further to the left
in a higher period.
 Higher Ionization Energies

 More energy is required for each successive ionization step (IE3 > IE2 > IE1)
because it is harder to remove an electron from a positively charged ion.
 Large jumps in ionization energy occur when we are trying to remove electrons
from filled shells.
 Ex: The first three ionization energies of beryllium.
Beryllium has 2 valence electrons, so IE3 is much larger than IE2.
 Why is the third ionization energy of Be so much higher than the second
and first?
Table Successive Ionization Energies of the Elements
Lithium Through Sodium
Identifying an Element from Its Ionization Energies

PROBLEM: Name the Period 3 element with the following ionization

energies (in kJ/mol) and write its electron configuration:
IE1 IE2 IE3 IE4 IE5 IE6
1012 1903 2910 4956 6278 22,230

PLAN: Look for a large increase in IE, which occurs after all valence
electrons have been removed.
SOLUTION:

The largest increase occurs after IE5, that is, after the 5th
valence electron has been removed. The Period 3 element
with 5 valence electrons is phosphorus (P; Z = 15).
The complete electron configuration is 1s22s22p63s23p3.
Electron Affinity (Eea)
Electron Affinity (Eea) is the energy change accompanying the
addition of electrons to 1 mole of atoms in the gas phase:

Electron affinity is usually a negative energy value; energy is

usually released when an electron is added to a neutral atom.
 The more negative the electron affinity, the greater the tendency
of the atom to accept an electron and the more stable the resulting
anion will be.
 In general, electron affinity decreases as we move down a group,
and increases from left to right, but the trend is not as smooth as
for ionization energy and size.
Metallic Behavior
 Metals are typically shiny solids with moderate to high
melting points.
 Metals are good conductors of heat and electricity, and
can easily be shaped.
 Metals tend to lose electrons and form cations, i.e., they
are easily oxidized.
 Metals are generally strong reducing agents.
Metallic behavior in Group 15 and Period 3.

Metallic behavior decreases across the period

Metallic behavior increases down the group

Trends in metallic behavior.
Magnetic Properties

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.
Writing Electron Configurations and Predicting Magnetic Behavior

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.
 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.
Electronegativity (EN)
 Electronegativity is a measure of the tendency of an atom to attract
a bonding pair of electrons.

.
EN follows a trend that is opposite to that in atomic size and the
same as that in IE.
EN generally increases across a period: higher shorter distance
from the nucleus strengthen the attraction for the shared electron
pair(s);
EN generally decreases down a group: greater distance from the
nucleus weakens the attraction for the shared electron pair(s).
The difference in electronegativity (ΔEN) between bonded
atoms influences the physical and chemical behavior of the
compound
Summary Trends in atomic properties.