Alzbeta Bavorova

Chapter 3

Assesment statements from

Pearson Baccalaureate HL
Chemistry

Periodicity

Ch 3.1 The Periodic Table

3. 1. 1. Describe the arrangement of elements in the Periodic Table in order
of increasing atomic number.
The elements are arranged on the basis of the atomic number. The atomic number grows to
the right and down.

3. 1. 2. Distinguish between the terms group and period.

Groups are the columns of the periodic table. Elements in one group have similar properties.
Periods are the rows of the periodic table.

3. 1. 3. Apply the relationship between the electron arrangement of

elements and their position in the Periodic Table up to Z = 20.
& 3. 1. 4. Apply the relationship between the number of electrons in the
highest occupied energy level for an element and its position in the Periodic
Table.

(http://www.drcruzan.com/Images/Chemistr
y/Chemistry_PeriodicEconfig.png)

S ELEMENTS: ns1-2
P ELEMENTS: ns2 np1-6
D ELEMENTS: ns2 (n-1)p6 (n1)d1-10
F ELEMENTS: ns2 (n-1)p6 (n2)d10 (n-2)f1-14

Ch 3.2 Physical properties

3. 2. 1. Defi ne the terms fi rst ionization energy and electronegativity.

The first ionization energy of an element is the energy required to remove one mole of
electrons from one mole of gaseous atoms.
Electronegativity is the ability of an atom to attract electron in a covalent bond.

3. 2. 2. Describe and explain the trends in atomic radii, ionic radii, fi rst
ionization energies, electronegativities and melting points for the alkali
metals and the halogens.
& 3. 2. 3. Describe and explain the trends in atomic radii, ionic radii, fi rst
ionization energies and electronegativities for elements across Period 3.
Nuclear charge is the force exerted by the nucleus thanks to the protons +1 charge. It is
equal to the sum of all the charges in the nucleus (and thus to the proton number).
The shielding effect occurs thanks to the negatively charged electron shells. The negative
charge zeroes out a portion of the nuclear charge.
The effective nuclear charge is equal to the nuclear charge minus the shielding effect. It is
the force that the valence electrons actually experience.
The effective nuclear charge grows left to right, but decreases top to bottom. This is because
the shielding effect grows with the addition of a new electron shell (down the group) enough
to decrease the effective nuclear charge. But in the same period, electrons are added to the
existing valence shell only and they provide minimal shielding effect and so the effective
nuclear charge grows.

Atomic radius
Is the radius of an atom. The problem is that there are multiple definitions.

Bohr radius
Is the hypothetical distance between the nucleus and the valence shell of a Bohr atom. The
problem with it is that it cannot be measured, since the atom has no fixed 100% boundary. It
can be calculated and is the only one applicable for noble gasses (which is why in many
graphs, noble gasses have significantly larger atomic radii than the neighboring halogens).
Covalent radius
Is the distance between the nuclei two covalently bound atoms.
Ionic radius
Is the distance between the nuclei of two atoms in an ionic bond.
Metallic radius
Is the distance between the nuclei of two
atoms in a metallic bond.
data and further graphs from:
http://www.webelements.com/periodicity/
The atomic radius increases top to bottom:
The added electron shells repel and
make the atom expand.
It is not directly proportional, because
the electron shells grow closer the further
away from the nucleus we are.
The atomic radius decreases left to right:
The growing effective nuclear charge can pull the electron shells closer to the nucleus.

First ionization energy

Grows left to right
Because of the growing effective nuclear charge, more energy needs to be invested to
ionize the atom.
Falls top to bottom
Because of the increase in atomic radius and decrease in effective nuclear charge, less
energy needs to be invested to ionize the atom.
It is not directly proportional, because the electron shells grow closer the further away from
the nucleus we are.

Electronegativity
(Pauling)
Electronegativity is very much
related to effective nuclear
charge, ionization energy and
electron affinity, so the trends are
similar.

Melting point
The melting point is dependent on the bonding
of the element.

It is high for elements in a metallic

bond.
High for elements in a giant covalent
structure.
Low for covalently bound atoms.

It is more difficult to provide atoms that are

bound by strong intermolecular bonds with
enough kinetic energy to melt them.
Group
1
(alkali metals):
Melting point decreases down the group.
As the size of the atom grows down the group, while
the metallic structure is still composed of +1 ions, the
charge density falls significantly and thus the force
holding the metallic lattice together is weaker.
Group 17 (halogens):
Melting point increases down the group.
As the size of an atom grows down the group, the effect
of the Van der Waals interactions becomes stronger.

3. 2. 4. Compare the relative

electronegativity values of two or more
elements base on their positions in the
Periodic Table.
see previous graphs

Ch 3.3 Chemical properties

3. 3. 1. Discuss the similarities and diff erences in the chemical properties of
elements in the same group.
Elements within the same group have very similar chemical properties, because chemical
properties depend on their electron configuration and the valence shell of electron within
the same group is the same.
However, their properties are not the same. For example, the reactivity of alkali metals
increases down the group. This is because of the falling ionization energy (because more
reactions will be able to provide enough energy for ionization).

3. 3. 2. Discuss the changes in nature, from ionic to covalent and from basic
to acidic, of the oxides across Period 3.
Ionic compounds are generally formed between metal and non-metal the oxides of
elements Na to Al have a giant ionic structure.
Covalent compounds are formed between non-metals the oxides of P, S and Cl are
molecular covalent.
The oxide of silicon, which is a metalloid, is a giant covalent structure.
The ionic character of a compound depends on the difference in electronegativity between
its elements (the higher, the more ionic).
The oxides become more ionic down the group, as the electronegativity decreases.
The conductivity of the molten oxide can be used as a measure of the ionic character.
Covalent compounds do not conduct electricity, while ionic (in the molten state) do.
Formula

Na2O (s)

MgO (s)

Al2O3 (s)

SiO2 (s)

Ox.
number
E.
conductiv
ity in
molten
state
Structure

+1

+2

+3

+4

Acid-base
character

high

giant ionic
basic

P4O10 (s)
P4O6 (l)
+5
+3

very low

giant
covalent
amphotheric

SO3 (l)
SO2 (g)
+6
+4
none

Cl2O7 (l)
Cl2O (g)
+7
+1

molecular covalent
acidic

The acid-base properties of the oxides depend on their bonding.

Metallic elements and thus ionic oxides are basic. Non-metal oxides, which are covalent, are
acidic. Those on the verge between ionic and covalent are amphoteric. Amphoteric
substances show both acidic and basic properties (such as water).
Note that: Alkalis are bases which are soluble in water. They form hydroxide ions in aqueous
solutions.

Ch 13.1 Trends across Period 3

13. 1. 1. Explain the physical state (under standard conditions) and
electrical conductivity (in the molten state) of the chlorides and oxides of
the elements in Period 3 in terms of their bonding and structure.
Formula
AlCl3 (s)
PCl5 (s)
of
NaCl (s) MgCl2 (s)
SiCl4 (l)
S2Cl2 (l)
Cl2 (g)
Al2Cl6 (g)
PCl3 (l)
chloride
Ox.
+5
+1
+2
+3
+4
+1
0
number
+3
E.
conductiv
ity in
high
poor
none
molten
state
Structure
giant ionic
molecular covalent
Acid-base
weakly
neutral
acidic
character
acidic
Because Cl is less electronegative than oxygen, the transition from ionic to covalent occurs
earlier on in the period than for oxides.
Al2Cl6 is a dimer of AlCl3, where the two bridging Cl atoms form dative covalent bonds formed
between Al atoms. When added to water, these bonds dissociate.

13. 1. 2. Describe the reactions of chlorine and the chlorides referred to in

13. 1. 1. with water.

Chlorine and water

slow, reversible
disproportionation reaction Cl is both reduced and oxidized.

Cl2 ( aq )+ H 2 O (l ) HCl ( aq )+ HOCl ( aq )

2 HOCl ( aq ) 2 HCl ( aq ) +O2 ( g)

Chlorides and water

Hydration of ionic chlorides
( aq)

+ ( aq )+Cl
NaCl ( s ) Na
Ions separated from the lattice can become hydrated.

Hydrolysis of covalent chlorides

Aluminium chloride

(aq )
3+ ( aq ) +3 Cl
Al Cl3 ( s ) Al
This will result in the
complex ion [Al(H2O)6]3+:

formation of the

A complex is when a central ion is surrounded by molecules or ions which posses a lone pair
of electrons. The ligand has an independent existence, as the surrounding species (ligands)
are bound via a dative covalent bond.
Complexes are shown through the use of square brackets.
The [Al(H2O)6]3+ ion is acidic, because the high charge density of Al 3+ attracts the electrons
from the O H bond of the surrounding water molecules, which results in the release of an H +
ion.

+(aq)

2+ + H

Al ( H 2 O )5 OH
3+ ( aq )

Al ( H 2 O ) 6

etc.
Silicon and phosphorus chlorides

Si Cl 4 ( l ) +2 H 2 O ( l ) Si O2 ( s ) + 4 HCl
PCl 3 (l ) +3 H 2 O ( l ) H 3 PO 3 ( aq ) +3 HCl ( aq )

PCl 5 ( s )+ 4 H 2 O ( l ) H 3 PO 4 ( aq ) +5 HCl ( aq )

Ch 13.2 First-row d-block elements

13. 2. 1. List the characteristic properties of transition elements.
IUPAC definition of a transition element: "an element whose atom has a partially filled d
sub-shell, or which can give rise to cations with an incomplete d sub-shell"
Transition elements belong in the d-block (but not all d-block elements are transition
elements!).
General properties:

metallic
small increase in effective nuclear charge, because the added electrons go to the 3d
sub-shell, which is not on the valence shell and is pulled inside of the atom they
contribute to the shielding effect strongly
small decrease in atomic radii
in ionization, the 4s electrons are removed first

Physical properties (result of the metallic bonding):

high electrical and thermal conductivity

high melting point
malleable (can be easily beaten into a shape)
high tensile strength (can hold large loads without breaking)
ductile (can be easily pulled into wires)
higher density than their s-block neighbors (due to smaller atomic radii)

Chemical properties:

form compounds with more than one oxidation number

form a variety of complex ions
form coloured compounds
act as catalysts when either elements or compounds

13. 2. 2. Explain why Sc and Zn are not considered to be transition

elements.
Sc has one 3d electron, but is incapable of forming ions with an incomplete d sub-shell.
Zn has 10 3d electrons, and thus not a partially filled d sub-shell.
They also do not form multiple oxidation numbers nor coloured compounds.

13. 2. 3. Explain the existence of variable oxidation number in ions of

transition elements.
Since 3d and 4s orbitals are very close in energy, there is a small jump in ionization energy,
which is why there can be multiple oxidation numbers.

13. 2. 4. Defi ne the term ligand.

A ligand is a species that uses a lone pair of electrons to form a dative covalent bond with a
metal ion.
The number of ligands is expressed by the coordination number.

13. 2. 5. Describe and explain the formation of complexes of d-block

elements.
The relatively high charge density of the transition metal ions allows them to attract the
ligands lone pair of electrons. A dative covalent bond then forms (it is shows as an arrow from
the ligand to the ion).

13. 2. 6. Explain why some complexes of d-block elements are coloured.

White light is composed of all the colours of the spectrum and the ions of transition metals are
capable of absorbing a portion of the visible spectrum. The ion
absorbs one colour and appears to be the complementary colour
(eg. absorbs yellow and appears blue).
In an isolated transition metal atom, the d orbitals are
degenerate. However, a ligands lone pair of electrons produces
an electric field strong enough to split the d orbital into two sublevels. When hit by photons of the appropriate wavelength,
electrons of the lower sub-level are then excited to the higher
sub-level and the light is absorbed (the complementary colour is
transmitted).

http://willkempartschool.com/w
pcontent/uploads/2011/08/colou
rwheel01.gif

The energy separation of the two orbitals and thus the colour of the complex depends on:

the
the
the
the

nuclear change
charge density of the ligand
number of d electrons present (the oxidation number of the central ion)
shape of the complex ion

13. 2. 7. State examples of the catalytic action of transition elements and

their compounds.
& 13. 2. 8. Outline the economic signifi cance of catalysts in the Contact and
Haber process.
There are two different types of catalysts:
HETEROGENOUS
The catalyst is in a different state than the reactant. This also means that the catalyst
can very easily be removed from the reaction mixture by filtration etc. Because of this,
heterogeneous catalysts are preferred in industry.
Transition metals have the ability to form weak bonds to small reactant molecules using
their (n-1)d and ns electrons. They can thus provide a surface for the reactant molecules
to come together with the correct orientation.
HABER PROCESS

uses iron (Fe) as catalyst

N 2 ( g )+3 H 2 ( g ) 2 N H 3 (g)

CONTACT PROCESS

uses V2O5 (divanadium pentoxide) as catalyst

2 S O 2 (g)+O 2 (g) 2 S O 3 (g)

HOMOGENOUS
Homogenous catalysts are in the same state as the reactants. They are fundamental in
many enzyme catalysed reactions in biological organisms.
Transition metals have the ability to form variable oxidation states, which means they
can be very effective as catalysts in redox reactions.
HAEMOGLOBIN

Fe2+ is a part of haem in haemoglobin

haem contains a central Fe2+surrounded by 4 nitrogens
oxygen in bloodstream forms weak bond with haem
the O2- Fe2+ is easily broken when oxygen needs to be released.

VITAMIN B12

Co3+ is a part of the octahedral complex within the vitamin. Five of the sites are
occupied by nitrogen atoms and the sixth is available for biological activity.

This vitamin is necessary in the production of erythrocytes and responsible for a

healthy nervous system.