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FARRAH CAAVERA BUELVAS, PH. D

farrahcanavera@mail.uniatlantico.edu.co

! Inorganic chemistry is the chemistry of all elements

except carbon.
! Inorganic chemistry is not simply the study of elements
and compounds; it is also the study of physical
principles.
! For example, in order to understand why some
compounds are soluble in a given solvent and others are
not, we apply laws of thermodynamics.
! If our aim is to propose details of a reaction mechanism,
then a knowledge of reaction kinetics is needed.
! Overlap between physical and inorganic chemistry is
also significant in the study of molecular structure.
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! In 1869 and 1870 respectively, Dmitri Mendelev and

Lothar Meyer stated that the properties of the elements
can be represented as periodic functions of their atomic
weights, and set out their ideas in the form of a periodic
table.
! It is now recognized that periodicity is a consequence of
the variation in ground state electronic configurations.
! A modern periodic table emphasizes the blocks of 2, 6, 10
and 14 elements which result from the filling of the s, p,
d and f atomic orbitals respectively.
! An exception is He, which, for reasons of its chemistry, is
placed in a group with Ne, Ar, Kr, Xe and Rn.
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! blocks of elements may be designated by use

of the letters s, p, d or f.
! elements (except H) in groups 1, 2 and 1318
are called main group elements.
! with the exception of group 18, the first two
elements of each main group are called
typical elements.
! elements in groups 311 (i.e. those with
partially filled d orbitals) are called transition
elements.
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Note the distinction between a

transition and d-block element.
! Elements in groups 312 inclusive are
collectively called d-block elements.
! But a transition metal is an element, an atom
of which possesses an incomplete d-shell or
which gives rise to a cation with an
incomplete d-shell.
! Ni: [Ar]3d84s2 transition metal
! Zn: [Ar]3d 10 4s 2 d-block elements no
transition metal
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Ground state electronic configurations.

! The organization of the elements in the periodic
table depends on the number, and arrangement, of
electrons that each element possesses.
! Establishing the ground state electronic
configuration of an atom is the key to
understanding its chemistry.
! The aufbau principle: aufbau means building up
in German.
! Is used in conjunction with Hunds rules and the
Pauli exclusion principle to determine electronic
ground state configurations
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! Orbitals are filled in order of energy, the

lowest energy orbitals being filled first.
! Hunds first rule (often referred to simply
as Hunds rule): in a set of degenerate
orbitals, electrons may not be spin-paired
in an orbital until each orbital in the set
contains one electron; electrons singly
occupying orbitals in a degenerate set
have parallel spins, i.e. they have the same
values of ms.
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! Pauli exclusion principle: no two electrons

in the same atom may have the same set of
n, l, ml and ms quantum numbers; it
follows that each orbital can accommodate
a maximum of two electrons with different
ms values (different spins = spin-paired).

Determine (with reasoning) the ground state

electronic configurations of (a) Be (Z = 4) and (b)
P (Z = 15).
The value of Z gives the number of electrons to be
accommodated in atomic orbitals in the ground
state of the atom.
Assume an order of atomic orbitals (lowest energy
first) as follows: 1s < 2s < 2p < 3s < 3p

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(a) Be Z = 4
Two electrons (spin-paired) are accommodated in
the lowest energy 1s atomic orbital.
The next two electrons (spin-paired) are
accommodated in the 2s atomic orbital.
The ground state electronic configuration of Be is
therefore
1s22s2.

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(b) P Z =15
Two electrons (spin-paired) are accommodated in the
lowest energy 1s atomic orbital. The next two electrons
(spin-paired) are accommodated in the 2s atomic orbital.
The next six electrons are accommodated in the three
degenerate 2p atomic orbitals, two spin-paired electrons
per orbital. The next two electrons (spin-paired) are
accommodated in the 3s atomic orbital.
Three electrons remain and applying Hunds rule, these
singly occupy each of the three degenerate 3p atomic
orbitals.
The ground state electronic configuration of P is therefore
1s22s22p63s23p3.
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! The configuration of the outer or valence

electrons determines the chemical properties of
an element.
! Electrons that occupy lower energy quantum
levels are called core electrons.
! The core electrons shield the valence electrons
from the nuclear charge, resulting in the valence
electrons experiencing only the effective nuclear
charge, Zeff.
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Figure 1. Diagrammatic representations of the ground

state electronic configurations of O and Si.
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! Confirm that the configuration shown for oxygen in

Figure 1.14 is consistent with each electron possessing a
unique set of four quantum numbers.

If an atomic orbital contains two electrons, they must have opposite

spins so that the sets of quantum numbers for the two electrons are
different: e.g. in the 1s atomic orbital

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! It often define atomic size in terms of how closely

one atom lies next to another.
! In practice, we measure the distance between
identical, adjacent atomic nuclei in a sample of
an element and divide that distance in half.
! Because atoms do not have hard surfaces, the
size of an atom in a compound depends
somewhat on the atoms near it.
! In other words, atomic size varies slightly from
substance to substance.
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The metallic radius is one-half the distance

between nuclei of adjacent atoms in a
crystal of the element; we typically use this
definition for metals.

The covalent radius is one-half the

distance between bonded nuclei in a
molecule of the element. In effect, it is
one-half the bond length.
In a covalent compound, the bond length and
known covalent radii are used to determine
other radii. Ex.: CCl bond length (177 pm)
and the covalent radius of Cl (100 pm) are
used to find a value for the covalent radius of
C (177 100 = 77)
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! Atomic size greatly influences other atomic properties

and is critical to understanding element behavior.
! Among the main-group elements, the atomic size varies
within both a group and a period.
! These variations in atomic size are the result of two
opposing influences:
1.! Changes in n. As the principal quantum number (n)
increases, the probability that the outer electrons will
spend more time farther from the nucleus increases as
well; thus, the atoms are larger.
2.! Changes in Zeff. As the effective nuclear charge (Zeff)
increases, outer electrons are pulled closer to the
nucleus; thus, the atoms are smaller.
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! The net effect of these influences depends on shielding of

the increasing nuclear charge by inner electrons:
! Down a group, n dominates. As we move down a main
group, each member has one more level of inner
electrons that shield the outer electrons very effectively
and Zeff on the outer electrons rising moderately for each
element in the group, the atoms get larger as a result of
the increasing n value. Atomic radius generally increases in
a group from top to bottom.
! Across a period, Zeff dominates. As we move across a
period of main-group elements, electrons are added to
the same outer level, so the shielding by inner electrons
does not change. Because outer electrons shield each
other poorly, Zeff on the outer electrons rises significantly,
and so they are pulled closer to the nucleus. Atomic
radius generally decreases in a period from left to right.
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Moving from left to right, size shrinks through the first two or three
transition elements because of the increasing nuclear charge.
But, from then on, the size remains relatively constant because shielding by
the inner d electrons counteracts the usual increase in Zeff.

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Periodicity of atomic radius.

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(1)

! The first ionization energy, IE1, of an atom is the

internal energy change at 0K, !U(0K), associated
with the removal of the first valence electron
(equation 1).
! The energy change is defined for a gas phase
process.
! Because energy flows into the system, the ionization
energy is always positive (like H of an endothermic
reaction)
! The units are kJ mol1 or electron volts (eV).
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! It is often necessary to incorporate ionization

energies into thermochemical calculations (e.g.
BornHaber or Hess cycles).
! It is convenient to define an associated enthalpy
change, !H(298K).
! Since the difference between !H(298K) and !U
(0K) is very small , values of IE can be used in
thermochemical cycles so long as extremely
accurate answers are not required.

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! The first ionization energy is a key factor

in an elements chemical reactivity.
! Atoms with a low IE1 tend to form cations
during reactions, whereas those with a high
IE1 (except the noble gases) often form anions.

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The second ionization energy, IE2

The third ionization energy, IE3
The high values of IE1 associated with the noble gases
The very low values of IE1 associated with the group 1 elements
The general increase in values of IE1 as a given period is
crossed

Fig. 2. The values of the first ionization energies of the

elements up to Rn.

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1.! Size of the atom: decreases as the size of

atom increases.
2.! Nuclear charge: increases as Z increases.
3.! Type of electron: shield effect.
Zef= Nuclear charge effective!
n = quantum number!
!

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Increase of Ionic Energy

Increase of Ionic Energy
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Be: 1s2 2s2

B: 1s2 2s2 2p1

N: [He]2s2 2px1 2py1 2pz1

O: [He]2s2 2px2 2py1 2pz1

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The first electron affinity (EA1) is minus the internal energy

change (equation 2) for the gain of an electron by a gaseous
atom (equation 3).
The second electron affinity of atom Y is defined for process
4. Each reaction occurs in the gas phase
Equation 2
Equation 3
Process 4
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The first electron affinity, EA1, of an atom is minus the

internal energy change at 0 K associated with the gain of
one electron by a gaseous atom:

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The attachment of an electron to an

atom is usually exothermic.
Two electrostatic forces oppose one
another: the repulsion between the
valence shell electrons and the
a d d i t i o n a l e l e c t ro n , a n d t h e
attraction between the nucleus and
the incoming electron

In contrast, repulsive interactions are dominant

when an electron is added to an anion and the
process is endothermic

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