Bonding and Structure
Bonding and Structure
The electron transferred from Sodium atom fits in the singly occupied
orbital of the 3P of the Chlorine atom i.e.
Sketch Px Py Pz
Before transfer
After transfer
Px Py Pz
i. Ionization energy:
The lower the ionization energy the most loosely held is an electron
and the more electropositive the element.
ii. Electron affinity:
Is the ease with which the atoms form anions/negatively charged ions.
The greater the value of electron affinity, the easier is negatively
charged ion formed.
The covalent bond character arises because the electrons are partially shared.
i.e.
Polarizing power is the extent to which a positive ion can attract electrons from negative ion
back into the region between the nuclei.
Factors affecting polarizing power.
Interpretation
Polarizing power of the cations increases in the order of Na+ < Mg2+ < Al 3+.
Al 3+ having a high polarizing power exerts the strongest polarization in Aluminium (III)
chloride resulting in a high degree of Covalence in Aluminium chloride giving aluminium
chloride the lowest melting point.
Low polarizing power of Na+, sodium chloride remains essentially an ionic compound with a
very high melting point.
Questions:
1. Briefly explain why NaCl melts at 8000C where as AlCl3 sublimes at 180OC
Solution
Both NaCl and AlCl3 have ionic bonding; but because of small size and large charge of Al3+
ions; which gives it large polarizing power; the electron on the outermost shell of the chloride
ions are greatly displaced (polarised) towards the Al3+; such that aluminium chloride, AlCl3
develops some covalent character; making it have low melting point just like covalent
compounds;
NaCl is purely ionic hence very high melting point.
b) Polarizability of the anions
The extent to which a positive ion can pull electrons back into the space between the two
nuclei depends not only on the polarizing power of the cat ion but also how easily it is to
polarize a negative ion.
The polarisability of a negative ion measures the ease with which its electron density can be
distorted.
Factors affecting polarisability:
i. Charge on the negative ion
Polarisability increases with increase in the charge on the anion.
This is because as the charge on the anion increases, the anion repels its outermost electrons
strongly and effectively.
b) COVALENT BONDING
A Covalent bond is formed by sharing a pair of unpaired electrons between atoms, each of
which donates an electron to the bond.
It‟s formed between atoms with either no electronegativity difference or a small
electronegativity difference e.g. in chlorine molecule and hydrogen chloride.
Occurs in non – metals and results into the formation of molecules.
Illustration:
i. Hydrogen chloride
H +
The lack of an overall dipole moment on the molecules makes the molecule non – polar and it
is an indicator for the symmetry within that molecule.
Unsymmetrical molecules like water, Ammonia and trichloromethane have an overall dipole
moment over the molecule and are said to be polar.
i. Trichloromethane
Cl Cl Cl
ii. Water
O 2δ-
𝛅+ 𝛅+
H H
This explains why trichloromethane is deflected by a charged rod while tetrachlomethane is
not, when liquid trichloromethane and tetra chloromethane are passed separately from the
beaker closer to the charged rods.
Example:
Explain why Boron trichloride, is a non – polar molecule while Nitrogen
trichloride (NCl3) is polar.
Soln:
Boron trichloride has a trigonal planar structure in which the chloride atoms are arranged
symmetrically around the central Boron atom.
Therefore because of this symmetry, the net dipole moments cancel out to zero.
Cl
Cl Cl
However Nitrogen trichloride has a trigonal pyramidal structure in which the
chloride ions are not symmetrically arranged.
•
More soluble in organic solvents but insoluble in water.
• Do not conduct electricity due to absence of free ions in them except a few which form
ions when dissolved in water e.g. hydrogen chloride.
• Consists of discrete molecules and not ions.
• Mainly gases, liquids with very low melting points.
Is a covalent bond whereby an electron rich atom in a molecule gets bonded to another atom/
ion of a species which is electron deficient.
The donor atom donates the non-bonding pair of electrons (lone pair) to the acceptor atom
which must be either a;
positively charged species or
must have an empty orbital.
Examples;
H2O + H+ ⟶
+
ii. Formation of Ammonium ion from H and NH3
H
H
H N: + H ⟶ + H N⟶H
H H
iv. Formation of transition metal complexes; ligands (bonding atoms) donate their lone
pairs of electrons to empty d. orbital of transition metal ions. E.g.
H3N NH3
Cu
H3N NH3
H3C CH3
−−−−−−− Cδ+ = 0 δ−
+
C =O
CH3 CH3
Van der waal‟s bond
A + -B
δ− C−P
A + - B
N.B.
High relative molecular mass molecules have high van der waal‟s forces of attraction;
because of increase in the number of electrons which are loosely bound in a molecule.
Energy associated with vanderwaal‟s bond is small compared to the normal covalent bond.
F) HYDROGEN BONDING:
O HO
H3C –C C – CH3
OH------------------ O
H H
d) Water molecules
+
H H O
+ +
H H
c) 4 – nitrophenol − Hδ+
− ∂-
O2 N - -O
O𝛅−
N - OH
O
OH δ− Hδ+ Intramolecular
NO2
forming N O δ− hydrogen bond
O
C H Forming
OH
Hydrogen bonding increases the viscosity of liquids leading to reduced volatility and reduced
vapour pressure of that liquid eg in water
Association of molecules:
Hydrogen bonded molecules like Ammonia, water, hydrogen fluoride have abnormally high
boiling points compared to those of the hydrides of other elements in group (V), (VI), (VII)
respectively, this is because the hydrides of nitrogen, Oxygen and fluorine associate through
hydrogen bonding.
Boiling points of alcohols, amines and carboxylic acids are higher than boiling points of
corresponding alkanes with similar molar mass because of association through hydrogen
bonding and therefore excess energy is needed to break the hydrogen bond.
Solubility in water:
Phenols, alcohols and carboxylic acids, primary and secondary amines are more soluble in water
than other alkanes of similar molecular mass because of the ability to form hydrogen bonds with
water.
2 – Nitro phenol and 2 – hydroxyBenzaldehyde are less soluble in water than their
corresponding isomers because formation of intramolecular hydrogen bond prevents
interaction with neighboring molecules.
NB: This also explains why 2 – nitro phenol boils at a low temperature than 4 – nitro phenol.
Increased volume and decreased density of ice:
Ice is less dense than water and thus floats on it; because the water molecules associate via
extensive intermolecular hydrogen bonding; giving ice an open tetrahedral structure; with a
bigger volume than that of water with the same mass; and since density is inversely proportional
to volume, then ice will have a less density than water for a given mass.
Therefore when ice is heated, hydrogen bonding is progressively broken giving rise to closely
packed liquid structure in the liquid water with decrease in volume and increase in density.
A needle covered on the surface of water may float because of surface tension and
hydrogen bonding in water.
Explain the following observations;
i) Hydrogen fluoride has a higher boiling point than hydrogen chloride.
ii) Melting point of 4 – nitrophenol is much higher than that of 2 – nitrophenol.
SHAPES OF MOLECULES/IONS
• Determining shapes of molecules and ions of non –transition elements is based on the
Valence shell Electron pair repulsion theory (VSEPR Theory) which states “
electron pairs around a central atom repel each other to take up positions as far apart as
possible.”
• The electron pairs take up this arrangement so that potential energy due to their
electrostatic repulsion is at a minimums.
• The electron pairs can be bonding (shared) pairs which contribute to the covalent bond
or unshared (lone pairs) i.e. not used in bonding.
• Lone pairs of electrons give a greater repulsion as they are closer to the nucleus.
Electron pair repulsion is in order L.P ↔ L.P > L.P ↔ B.P > B.P ↔ B.P
• According to this theory, multiple bonds (double/ triple bonds) act as single shared
pairs of electrons.
• Therefore the shape of a molecule is based on the electron pairs that it has.
Activity.
the ion has an overall charge of -1, then on top of the number of electrons the central
atom has, we add an extra electron.
the overall charge on the ion is −2, then add 2 electrons on top of the number of
electrons the central atom has.
the overall charge on the ion is + 1, number of electrons contributed a central atom is
reduced by 1 and if its +2, it is reduced by 2.
(ii) carbonate and nitrate ions are able to form many resonance
structures (are
stable) i.e.
−
For NO3
For CO 𝟐−
𝟑
• E.g; CH4, CHCl3, NH+ , SO 2−, CCl4, PO3−, SnCl4 , CrO2−, Etc
4 4 4 4
CH4 NH4
S𝒐𝟐𝟒− HSO−𝟒
PCl5
Activity
Draw the structures and name the shape of the following species.
Species Structure Shape
BF3
CHCl3
−
ClO4
−
NO 3
SO3
SO2
N𝑂2
−
N
O 𝑂
ii. 4 electron pairs (one lone pair and three bonding pairs)
3 bonding pairs and 1 lone pair distribute themselves around the
central atom such that the shape is trigonal pyramidal.
Repulsion is caused by the lone pair and it will lead to a bond angle
smaller than tetrahedral angle of 109.5O in methane
NB. Bond angle of the hydrides, decreases as you move down the group
because,
• Decrease in electro negativity ; decreases the attraction for the bonding electrons
for the elements as you move down the group.
• Phosphorous has higher electro negativity than Nitrogen so the bonding pairs of
electrons are closer to Nitrogen in ammonia than they are to P in PH3.
• Closeness of bonding pairs of electrons to the central atom makes them
experience greater repulsion giving rise to a bigger bonding angle.
• In SbH3, Antimony (Sb) has a much lower electronengativity ; therefore
a lower nuclear attraction for bonding electrons and hence bonding pairs
of electrons are further away from the central atom making them repel
one another to a small extent reducing bond angle further.
iii. Four electron pairs (2 bonding pairs and 2 lone pairs)
• The repulsive effect of two lone pairs on the two bonding pairs
reduces the bond angle to 104.5O giving rise to a bent/ v- shaped
molecule.
−
• E.g H2O, ClO2
Activity
giant structures
simple molecular structures.
Structure of NaCl:
Solid in Giant covalent structure include Diamond, graphite, silicon oxide, silicon carbide
and Boron nitride.
Structure of diamond:
• Each Carbon atom forms 4 bonds to 4 other carbon atoms.
• The 4 atomic orbitals tetrahedrally arrange themselves around the carbon
atom which results in a tetrahedral arrangement of carbon atoms in diamond.
• Carbon atoms are attached to each other in a 3 Dimensional arrangement.
• In diamond, the 4 Valence electrons are all involved in bonding therefore
no free electrons left to conduct electricity.
• It‟s the hardest substance known due to the strength of the carbon –
carbon bonds and the geometrical rigidity of the structure (very closed parked
nature of carbon atoms)
• Structure of graphite:
Consists of two dimensional layers of joined hexagonal rings, the layers are held by weak Van
der waals forces of attraction.
Within each layer, each carbon atom is covalently bonded to 3 other carbon atoms.
remaining valence electrons are delocalized which enable graphite to conduct electricity and
responsible for its shinny appearance.
Weak Van der waals forces between layers result in much wider separation hence graphite has
a low density (2.3 gcm-3) than diamond.
Weak Van der waals forces of attraction cause these layers to slide past each other thus
slippery nature of graphite.
1st layer
2nd layer
Occurs in molecules like Iodine, Solid CO2 (Dry ice), Bromine and Cl2 at low temperatures.
Vander Waals forces of attraction holding molecules are much weaker than forces holding
atoms in the molecules.
Solid CO2 sublimes above −78OC on absorbing heat from the surrounding, thus used