TOPIC 2

WHAT IS A MASS SPECTROMETER?

A mass spectrometer measures the masses of atoms and molecules. It produces

positive ions that are deflected by a magnetic field according to their mass-to-
charge ratio (m/z). It also calculates the relative abundance of each positive ion
and displays this as a percentage.

 The positive ions could be positively charged atoms, positively charged

molecules or positively charged fragments of molecules.
 Ions with a large mass to charge ratio are deflected less than ions with a
small mass to charge ratio. If all the ions have the same charge, usually 1+,
the extent of the deflection is inversely proportional to their mass.
 molecular ion peak the peak with the highest m/z ratio in the mass spectrum,
the M peak
 There is always a small percentage of the carbon-13 isotope present in the
compounds, which can lead to what is referred to as an M+1 peak. This peak
can often be seen in molecules with large masses, where the percentage of
carbon-13 becomes significant.
 relative atomic mass (Ar) the weighted mean (average) mass of an atom of
the element compared to 1/2 of the mass of an atom of carbon-12
 relative isotopic mass the mass of an individual atom of a particular isotope
relative to 1/2 of the mass of an atom of carbon-12

 The relative atomic mass will always be a number somewhere between the
relative isotopic masses.

 Why are two electrons pushed into the higher-energy 4s orbital?

The reason is that 3d orbitals are more compact than the 4s orbitals and, as a
result, any electrons entering the 3d orbital will experience greater mutual
repulsion than they would in the 4s orbital.
IONISATION ENERGY

 First ionisation energy the energy required to remove an electron from each
atom in one mole of atoms in the gaseous state
 Second ionisation energy the energy required to remove an electron from
each singly charged positive ion in one mole of positive ions in the gaseous
state

SUCCESSIVE IONISATION ENERGIES

When successive energies of an element are listed, there are steady increases,
and big jumps occur when electron removed from the next inner quantum shells.

WHY DO SUCCESSIVE IONISATION ENERGIES INCREASE IN

MAGNITUDE?

 The energy of the electron has to be increased to a particular value for it to

be removed.
 If an electron already has a high energy, then it will not need to gain much
energy to be removed. If, however, the electron is in an orbital of a low-
energy quantum shell, for example the 1s orbital, then it will need to gain a
lot more energy to be removed.
 The difference in energy between the electron when it has been removed and
the energy it has when it is in its original orbital in the quantum shell is known
as the ionisation energy (IE).

IE = energy of electron when removed − energy of electron when in the orbital

 The ionisation energy for a particular electron in a given atom depends solely
on the energy it has when it is in its orbital within the atom.

‘SHIELDING’ AND ‘SCREENING’

They have two different meaning;

 The electrons in an inner quantum shell will set up a barrier to the attractive
force of the nucleus to those electrons in an outer quantum shell. (Not
related to the answer for ionisation energy)
 The effect of electron–electron repulsion is to raise the energy of the
electrons involved above the value they would have if there was no repulsion
between them. This then affects the amount of energy required to remove
 the electron from the atom or ion. That is, it affects the magnitude of the
IE. (This part is the answer for the reason why IE will decrease)

The factors that affect the energy of an electron are:

 the orbital in which the electron exists

 the nuclear charge of the atom (i.e. the number of protons in the nucleus)
 the repulsion (shielding) experienced by the electron from all the other
electrons present.

TRENDS IN IONISATION ENERGIES

Across a period

Nuclear charge increases attraction between the nucleus and the electron
increases the energy of the outermost electron decreases
increase in first ionisation energy.

But, no. of electron in the same quantum shell increases this increases the
electron–electron repulsion within the quantum shell an increase in energy
of the outermost electron decrease in first ionisation energy.

The increase in nuclear charge is more significant than the increase in electron–
electron repulsion. So there is a general increase in first ionisation energy
across the periods (2nd and 3rd perid excluding the d-block elements, scandium
(Sc) to zinc (Zn)).

Down a group

The nuclear charge increases attraction between the nucleus and the
electron increases the energy of the outer electron decreases increase in
the first ionisation energy.

As you go down each group, electrons have more quantum shells with increasing
energy the energy of the outermost electron increases and the outer
electron experiences increased repulsion (i.e. increased shielding) from the inner
electrons.

The combined effect of adding an extra shell and increasing the shielding is
more significant than the increase in nuclear charge. So the first ionisation
energy decreases down Group.
ANOMALIES

 (B-Be) Although the nuclear charge of the B atom is greater than that of the
Be atom, the outer electron of B has more energy, since it is in a 2p orbital
as opposed to the 2s orbital for Be. For this reason, the energy required to
remove 2p electron in B is less than the energy required to remove a 2s
electron from a Be atom. In addition, the 2p electron in B experiences
greater electron–electron repulsion (i.e. greater shielding) because there are
two inner electron sub-shells as opposed to only one in the Be atom. A similar
argument applies to Mg and Al, except that in this case it involves the 3s and
3p electrons.
 (O-N) The first electron removed from the oxygen atom is one of the two
paired electrons in the 2px orbital. The presence of two electrons in a single
orbital increases the electron–electron repulsion in this orbital. So less
energy is required to remove one of these electrons than is required to
remove a 2p electron from a nitrogen atom, despite the larger nuclear charge
of the oxygen atom.

PERIODIC TREND IN MELTING AND BOILING TEMPERATURES

TOPIC 3

IONIC BONDING - the electrostatic attraction between oppositely charged

ions

Formation of NaCl molecule and NaCl compound (ionic solid)

Half reactions:

In an ionic solid, there are strong electrostatic interactions between the ions.
The ions are arranged in such a way that the electrostatic attractions between
the oppositely charged ions are greater than the electrostatic repulsions
between ions with the same charge. The electrostatic interaction between ions
is not directional: all that matters is the distance between two ions, not their
orientation with respect to one another.

 Avoid saying that there is an ‘ionic bond’ between two ions. This is because in
an ionic solid, each ion interacts with many other ions, of both the same and
opposite charge to itself.

THE STRENGTH OF IONIC BONDING

 The strength of ionic bonding is described by calculating the amount of

energy required in one mole of solid to separate the ions to infinity (into gas
phase).
 In general, the smaller the ions and the larger the charge on the ions, the
stronger the ionic bonding.

EVIDENCE FOR THE EXISTENCE OF IONS

Ionic compounds can conduct electricity and undergo electrolysis when either
molten or in aqueous solution. This is the most convincing evidence for the
existence of ions. We can demonstrate the movement of ions by passing a direct
current through copper(II) chromate(VI) solution. Aqueous copper(II) ions, Cu 2+
(aq), are blue and aqueous chromate(VI) ions, CrO42−(aq), are yellow.

The Cu2+(aq) ions migrate towards the negative electrode and the solution around
this electrode turns blue. The CrO 42−(aq) ions migrate towards the positive
terminal and the solution around this electrode turns yellow.

Cu2+ ions (blue) CrO42− ions (yellow)

TRENDS IN IONIC RADII

 Ionic radii are difficult to measure accurately, and vary according to the
environment of the ion.
 As you go down each group, the ions have more electron shells; therefore,
the ions get larger.
 The ionic radius decreases as the number of protons increases.
 For the same period; you should compare ionic radius between metals and
nonmetals separately. For isoelectronic (species with same no. of electron)
metals ionic radius decreases as move across period, as the positive charge
of the nucleus increases, the electrons are attracted more strongly and are
therefore pulled closer to the nucleus. In the same period, when nonmetal is
reached first its ionic radius decrease. Then, between the isoelectronic
(species with same no. of electron) nonmetals ionic radius decreases as move
across period.

POLARISATION AND POLARISING POWER OF IONS

In an ionic lattice, the positive ion will attract the electrons of the anion. If the
electrons are pulled towards the cation, the anion is polarised since the even
distribution of its electron density has been distorted.

Polarization will be increased by (Fajan’s rules):

 high charge and small size of the cation. The ability of a cation to attract
electrons from the anion towards itself is called its polarising power.

Polarizing power related to charge density of cation

 high charge and large size of the anion. The polarizability of an anion is
related to the deformability of its electron cloud.

PHYSICAL PROPERTIES OF IONIC COMPOUNDS

 High melting temperatures: A large amount of energy is required to overcome

the forces of attraction sufficiently for the ions to break free from the
lattice.
 Brittleness: If a stress is applied to a crystal of an ionic solid, then the
layers of ions may slide over one another.
 Poor electrical conductivity when solid but good when molten: There are no
delocalised electrons in solid state and the ions are also not free to move
under the influence of an applied potential difference.
 Often soluble in water: The energy required to break apart the lattice
structure and separate the ions can, in some instances, be supplied by the
hydration of the separated ions produced.

COVALENT BONDING- the electrostatic attraction between the two nuclei of

the bonded atoms and the pair of electrons shared between them.

 Covalent bond forms between two atoms when an atomic orbital containing a
single electron from one atom overlaps with an atomic orbital, which also
contains a single electron, of another atom.
 A H atom has an electronic configuration of 1s 1. When two H atoms bond
together to form a H2 molecule, the two s-orbitals overlap to form a new
molecular orbital. The two electrons then exist in this new orbital. The
highest electron density is between the two nuclei.

H2 molecule

 A Cl atom has an electronic configuration of 1s 2 2s2 2p6 3s2 3px23py23pz1.

When two Cl atoms bond together, the two p orbitals (each containing a
single electron) overlap.

Cl2 molecule

 A N atom has an electronic configuration of 1s2 2s2 2px12py12pz1. When two N

atoms bond together, the two px orbitals (each containing a single electron)
end on overlap and form one σ bond. And, the two py and two pz orbitals
(each containing a single electron) sideways overlap and form two π bonds.
The triple bond in the N2 molecule (N ≡ N):

N2 molecule

BOND LENGTH AND BOND STRENGTH

 The bond length is the distance between the nuclei of two atoms that are
covalently bonded together.
 The strength of a covalent bond is measured in terms of the amount of
energy required to break one mole of the bond in the gaseous state.
 The general relationship between bond length and bond strength, for bonds
that are of a similar nature, is the shorter the bond, the greater the bond
 strength. This is a result of an increase in electrostatic attraction between
the two nuclei and the electrons in the overlapping atomic orbitals.
 trend in bond strengths:
C—C > Si—Si > Ge—Ge and C—C > N—N > O—O : The electrostatic
attraction between the nuclei and the bonding electrons decreases as the
distance between them increases so bond strength decrease.

In case of I—I > Br—Br > Cl—Cl > F—F : The non-bonding (lone) pairs of
electrons on the two fluorine atoms are very close to one another. They
therefore repel one another quite strongly and so reduce the bond strength.
Same relation with Cl, Br, I, since lone pair electron distance coming longer,
there will be less repulsion and higher the bond strength.

When making a comparison between bond length and bond strength, it is

important to compare ‘like with like’, in other words, compare things that are the
same or very similar.

WHAT IS ELECTRONEGATIVITY?

Electronegativity is the ability of an atom to attract a bonding pair of electrons.

The electronegativity of elements, in general:

 decreases down a group of the Periodic Table, that is, from top to bottom
 increases from left to right across a period.

DISTRIBUTION OF ELECTRON DENSITY

If two atoms of the same element are bonded together by the overlap of atomic
orbitals, the distribution of electron density between the two nuclei will be
symmetrical. This is because the ability of each atom to attract the bonding pair
of electrons is identical.

Electron density map for chlorine (Cl2):

POLAR COVALENT BONDS

If the two atoms bonded together are from elements that have different
electronegativities, then the distribution of electron density will not be
symmetrical about the two nuclei.

The electron density map for the HCl molecule.

The contour lines are more closely spaced near to the chlorine atom, which is the
atom with the higher electronegativity. Since the electron density is higher
around the chlorine atom, that end of the molecule has acquired a slightly
negative charge. This is represented by the symbol δ–. The other end of the
molecule carries a slightly positive charge, represented by the symbol δ+.

Hδ+ — Clδ−

A bond like this is called a polar covalent bond or sometimes just a ‘polar bond’.

Another way of representing a polar covalent bond is to use an arrow to show

the direction of electron drift.

H Cl

CONTINUUM OF BONDING TYPE

Polar covalent bonds can be thought of as being between two ideals of bonding
types. These ideals are:

• pure (100%) covalent

• pure (100%) ionic.

Consider a polar covalent bond as a covalent bond that has some degree of ionic
character.

If the electronegativity difference is large enough, then the main type of

bonding is ionic.