CHM 474: INORGANIC CHEMISTRY I

Chapter outline

The Chemistry of the Elements

-To know the periodic classification of the elements

-Able to construct its electron configuration
-Identify the periodic variation in physical properties:
Effective nuclear charge (Zeff)
Atomic & ionic radii
Ionization Energy
Electron Affinity
- Identify the periodic variation in chemical properties

ns2np5

ns2np4

ns2np3

d10

d5

d1

n = principal quantum number of

the outermost subshell

ns2np2

ns2
Dmitri Mendeleev- Work on periodic
classification of elements according to
their properties..
-Most significant achievement in 19th
century..

ns2np1

PERIODIC CLASSIFICATION OF THE ELEMENTS

ns1

Introduction.

ns2np6

4f
5f
4
3

Ground State Electron Configurations of the Elements

Classification of the Elements

Continued.
Group 1A 7A (known as representative elements/main
group elements) Have incompletely filled s or p subshells
Group 8A (except He) Show completely filled p subshells.
Example:- He 1s2 and ns2np6 for other noble gases (Ne: 1s2
2s2 2p6)
Group 3B 8B Known as d-block transition elements. Have
incompletely filled d subshells.
They will produce cations with these incompletely filled d
subshells.
Group 4F & 5F Known as f block transition elements.
Have incompletely filled f subshells
Lanthanides Actinides
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In the ground state of the atom,

electrons will occupy the lowest
energy orbitals first, and only
fill the higher energy orbitals
when no lower energy orbitals
are left.

Ground state electronic

configurations (it is an electronic
arrangement described for each
atom)

Hunds first rule:- electrons

occupy all the orbitals of a given
subshell singly before pairing
begins. These unpaired electrons
have parallel spins.

The aufbau Principle

Aufbau means building up
Used together with Hunds rules and
Pauli exclusion principle
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Fig. Order for filling

energy sublevels
with electrons.

Pauli exclusion principle:- no two

electrons in the same atom may
have the same set of n, l, ml, ms
quantum numbers

Electron Configurations of Cations and Anions

Of Representative Elements

Condensed ground-state electron configurations in

the first three periods

Na+ [Ne]

Na [Ne]3s1
Ca

[Ar]4s2

Al

[Ne]3s23p1

Ca2+

[Ar]

Al3+

[Ne]

Atoms lose electrons so

that cation has a stable
noble-gas outer electron
configuration.

H- 1s2 or [He]

H 1s1
Atoms gain electrons
so that anion has a
stable noble-gas outer
electron configuration.

Figure 8.4

F 1s22s22p5
O 1s22s22p4

F- 1s22s22p6 or
[Ne]
O2- 1s22s22p6 or [Ne]

N 1s22s22p3 N3- 1s22s22p6 or [Ne]

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Isoelectronic
-1

-2

-3

+3

+2

+1

Cations and Anions of Representative Elements.

Examples:Na+: [Ne]
Al3+: [Ne]

They have the same

number of electrons
and ground state
electron
configuration

F-: 1s22s22p6 or [Ne]

O2-: 1s22s22p6 or [Ne]
N3-: 1s22s22p6 or [Ne]

Na+, Al3+, F-, O2-, and N3- are all isoelectronic with Ne
Quiz 2: What neutral atom is isoelectronic with H- ?
Answer: H-: 1s2 same electron configuration as He
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Electron Configurations of Cations of Transition Metals

ALL Periodic Table Trends

When a cation is formed from an atom of a transition

metal,electrons are always removed first from the ns
orbital and then from the (n 1)d orbitals.

Influenced by three factors:

1. Energy Level
Higher energy levels are further away from the nucleus.

Examples:Fe:

[Ar]4s23d6

Mn:

[Ar]4s23d5

Fe2+: [Ar]4s03d6 or [Ar]3d6

Mn2+: [Ar]4s03d5 or [Ar]3d5

Fe3+: [Ar]4s03d5 or [Ar]3d5

Mn2+:

.. 2

[Ar]4s23d3

2. Charge on nucleus (# protons)

More charge pulls electrons in closer. (+ and attract each
other)

3d orbital is more stable

than the 4s orbital in
transition metal ions..

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3. Shielding effect

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Atomic Size

Shielding Effect
The electron on the outermost

energy level has to look through

all the other energy levels to see
the nucleus.

Second electron has same

Radius

shielding, if it is in the same

period
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Measure the Atomic Radius

- this is half the distance between the two

nuclei of a diatomic molecule.
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Periodic Variation in Physical Properties

What do they influence?

A. Effective nuclear charge (Zeff)

It is the positive charge felt by an electron
Given by Zeff = Z s, Z= actual nuclear charge,
s = shielding/screening constant
(0 < s < Z)

Energy levels and Shielding have an effect on the

GROUP
Nuclear charge has an effect on a PERIOD

Zeff Z number of inner or core electrons

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Core

Zeff

Radius

Na

11

10

186

Mg

12

10

160

Al

13

10

143

Si

14

10

132

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increasing Zeff

increasing Zeff

Example:
Li Be
3

B C
Core electron = 1s2

N
7

O F Ne
8

10

1. Core electron > closer to nuclues than valence electron, thus core e shield
valence e> than valence e shield each other.
2. Moving
across the period, core e remains constant , but Z increases.
3. The added e will be valence e, and due to valence e does not shield each other,
thus, moving
across the period, > Z eff will be felt by valence e.
4. Moving
the group, Z eff . As n increases, large shells increases, thus valence e
are added to these large shells. Thus, electrostatic attraction between nuclues
& valence e decreases.
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Which elements outer shell or valence

electrons is predicted to have the largest
Effective nuclear charge? Cl, O, N or Ca?
Cl: Zeff 17 - 10 = 7
O: Zeff 8 - 2 = 6
N: Zeff 7 - 2 = 5
Ca: Zeff 20 - 18 = 2
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Atomic Size - Group trends

Increases down a given group.
the number of electrons and filled

electron shells increases

electrons are found further from
the nucleus
Therefore, the atomic radii
increase.

#1. Atomic Size - Period Trends

H
Li

Decreases across a period from left to right

Electrons are in the same energy level. and unshielded towards

Na
K

attraction by protons.
protons are being added to the nucleus thus creates a "higher
effective nuclear charge."
stronger force of attraction pulling the electrons closer to the
nucleus

Rb
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Na

Mg

Al

Si

S Cl Ar

Atomic Radii

Ionic Radii
1) Anions (negative ions) are larger than their respective atoms.

WHY?
Electron-electron repulsion forces them to spread further apart.
the protons cannot pull the extra electrons as tightly toward the nucleus.

2) Cations (positive ions) are smaller than their respective

atoms.
WHY?
There is less electron-electron repulsion.
Protons outnumber electrons; the protons can pull the fewer electrons toward
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the nucleus more tightly.

Ion Period Trends

Ion Group trends

Each step down a group is

adding an energy level.

Ions therefore get bigger as

you go down, because of

the additional energy level

Across the period from left to right, the nuclear charge increases -

Li1+

so they get smaller.

Na1+
K1+

Notice the energy level changes between anions and cations.

Rb1+

N3Li1+

Cs1+

B3+
Be2+

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O2-

F1-

C4+

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QUIZ 4:
Arrange the following atoms in order of
increasing atomic radius P, Si, N

Size of Isoelectronic ions

Iso- means the same
Isoelectronic ions have the same no. of electrons

STRATEGY: From left to right across periodDecreases

Al3+ Mg2+ Na1+ Ne F1- O2- and N3-

Moving up to down the group - Increases

all have 10 electrons

all have the same configuration: 1s22s22p6

ANSWER: N<P<Si

(which is the noble gas: neon)

N & P same group (Group 5)

Si & P same period (Period 3), Si
to the left of P
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QUIZ 5:
Which one of two species is larger?????
(a)N 3- or F(b)Mg2+ or Ca2+

Size of Isoelectronic ions?

Positive ions that have more protons would be smaller (more

protons would pull the same no. of electrons in closer)

STRATEGY: Think whether they are isoelectronic ions or are they

from the same group or period?????

Al3+
13

Mg2+
12

Na1+
11

Ne

F1-

10

O28

N3-

ANSWER:
(a) N3(both are isoelectronic and have 10 electrons.
However, N3- (7 protons), F-(9 protons)thus less
attraction exerted by nuclues on the electrons in
larger N3-

(b) Ca2+
Both are in Group 2A. Ca in larger shell (n =4)
Mg in n = 3.

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C. Ionization Energy

1) Down a group, first ionization energy decreases.

Electrons are further from the nucleus
more shielding
easier to remove the outermost electron

Ionization energy is the minimum energy (kJ/mol)

required to remove an electron from a gaseous atom in its
ground state.
- Depends on how tightly the is held in the atom

I1 + X (g)

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Higher the ionization energy,

the > difficult to remove the
I1 first ionization energy
X+(g) + e-

I2 + X (g)

X2+(g) + e-

I2 second ionization energy

I3 + X (g)

X3+(g) + e-

I3 third ionization energy

I1 < I2 < I3

2) Across a period, first ionization energy increases.

the atomic radius decreases
The outer electrons are closer to the nucleus and more
strongly attracted to the center
Similar shielding effect
more difficult to remove the outermost electron.
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First Ionization Energy

He

Ne
N F

Exceptions to First Ionization Energy

Trends

First Ionization
Energy (IE) Trends

1) Xs2 > Xp1

Example : 4Be > 5B
The energy of an electron in an Xp orbital is greater than Xs orbital.

C O

Be

less energy to remove the first electron in a p orbital than it is to remove one

from a filled s orbital.

2) Xp3 > Xp4

example : 7N > 8O

Li

After the separate degenerate orbitals have been filled with single electrons,

Na

the fourth electron must be paired. The electron-electron repulsion makes it

easier to remove the outermost, paired electron. (Hund's Rule)

Atomic number

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Second

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Ionization Energy (IE)

and Higher Ionization Energies

Definition: Second Ionization Energy is the energy required to

remove a second outermost electron from a ground state atom.

Subsequent ionization energies increase greatly once an ion has

reached the state like that of a noble gas.

For elements that reach a filled or half-filled orbital by removing 2

electrons, 2nd IE is lower than expected.

(True for s2 )

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Symbol

First

H
He
Li
Be
B
C
N
O
F
Ne

1312
2731
520
900
800
1086
1402
1314
1681
2080

Second

Third

5247
7297
1757
2430
2352
2857
3391
3375
3963

11810
14840
3569
4619
4577
5301
6045
6276

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D. Electron affinity

factors determine IE

What

Electron affinity is the negative of the energy change

that occurs when an electron is accepted by an atom
in the gaseous state to form an anion.

The greater the nuclear charge, the greater IE.

Greater distance from nucleus decreases IE

X (g) + e-

X-(g)

F (g) + e-

F-(g)

DH = -328 kJ/mol

EA = +328 kJ/mol

O (g) + e-

O-(g)

DH = -141 kJ/mol

EA = +141 kJ/mol

Filled and half-filled orbitals have lower energy,

so achieving them is easier, lower IE.

Shielding effect

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Electron

Affinity
Exceptions on electron affinity trends
Nonmetals elements in the first period have lower electron

Definition: The energy given off when a neutral atom in the gas

affinities than the elements below them in their respective groups.

phase gains an extra electron to form a negatively charged ion.

Elements with electron configurations of Xs2, Xp3, and Xp6 have

1) down a group, electron affinity decreases. H

electron affinities less than zero because they are unusually

stable. e.g. Be, N, Ne

Li
Na
K

WHY? - Electron affinities are all much smaller than ionization

energies.

2) across a period, electron affinity increases.

Xs2 < 0: Stable, diamagnetic atom with no unpaired electrons.

Xp3 < 0: Stable atom with 3 unpaired p-orbital electrons each occupying its

Li

Be

own subshell.

Xp6 < 0: Stable atom with filled valence (outermost) shell.

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10

Group 7-the highest affinity.

Group 8-the lowest (zero or
ve) valueY????
affinity of Group

2A< 1A and 5A<4A.

Group 2Ans2..added will
fill np orbital
which is
effectively
shielded by ns2
..weaker
interaction to
nucleus..thus, has
lower affinity
than Group 1A.

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Group 2A Elements (ns2, n 2)

Periodic Variation in Chemical Properties

Group 1A Elements (ns1, n 2)
M

M+1 + 1e-

Have low ionization energymost of them unipositive

2M(s) + 2H2O(l)
4M(s) + O2(g)

Be(s) + 2H2O(l)

Example: 4Li(s) + O2(g)

2Li2O(s)

M(s) + 2H2O(l)

M(OH)2(aq) + H2(g)

Reacts slowly
M = Ca, Sr, or Ba

Increasing reactivity

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Mg+2 (aq) + H2(g)

1st,2nd ionization energy
decreases

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Mg(OH)2(aq) + H2(g)

Be, Mg Form BeO, MgO at high T; CaO, SrO,BaO Form at RT

Mg(s) + 2H+
Form different kind
of oxides,peroxide,
superoxides

No Reaction

Mg(s) + 2H2O(g)

2MOH(aq) + H2(g)
2M2O(s)

M+2 + 2e-

Increasing reactivity

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11

Group 4A Elements (ns2np2, n 2)

Group 3A Elements (ns2np1, n 2)

(EXAMPLE: HCl)

4Al(s) + 3O2(g)
2Al(s) + 6H+(aq)

2Al2O3(s)
2Al3+(aq) + 3H2(g)

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unipositive > stable than tripositive

(HCl)

Sn(s) + 2H+(aq)

Sn2+(aq) + H2 (g)

Pb(s) + 2H+(aq)

Pb2+(aq) + H2 (g)

Form +2 and +4 oxidation state

Metalloid
Thus, no reaction with H2O and O2

Non-metal

Metals

Metalloid
No reaction
with H2O

Metal

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Group 5A Elements (ns2np3, n 2)

Group 6A Elements (ns2np4, n 2)

N2 forms oxides NO, N2O, NO2, N2O4, N2O5;

only N2O5 is solid.
N2O5(s) + H2O(l)
P4O10(s) + 6H2O(l)

Important compounds of S SO2, SO3, H2S

SO3(g) + H2O(l)

2HNO3(aq)

H2SO4(aq)

4H3PO4(aq)

Non-metal

Non-metal
Metalloid

Metalloid
Less reactive metal

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Metal

48

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Group 7A Elements (ns2np5, n 2)

Group 8A Elements (ns2np6, n 2)

Nonmetal Formula X2
Show high ionization energy and affinity
Anions Halides
X + 1eX-1
2HX(g)

-No tendency to accept extra electrons

(Hydrogen halide)

Increasing reactivity

X2(g) + H2(g)

-Completely filled outer ns and np subshells

(high stability). Highest ionization energy
of all elements

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Properties of Oxides Across a Period

basic

Amphoteric
(both acidic & basic)

acidic

Na2O(s) + H2O(l)

2NaOH(aq)

MgO(s) + HCl(aq)

Mg2Cl2(aq) + H2O(l)

Al2O3(s) + 6HCl(aq)
2AlCl3(aq) + 3H2O(l)basic properties
Al2O3(s) + 2NaOH(aq)+ 3H2O(l)
2NaAl(OH)4(aq)..acidic
properties
SiO2(s) + 2NaOH(aq)

Na2SiO3(aq) + H2O(l)..acidic

Other three oxides are acidic. React with H2O

Example:
P4O10(s) + 6H2O
4H3PO4(aq)
Conclusion:
Moving left to right the period--- - Metallic element decreases
- Basic-Amphoteric- Acidic
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