Chemical bond – interaction between atoms/ions that results in a reduction in the potential

energy of the system, making it more stable

Bond type (ionic, covalent, metallic) depends on electronegativities
Very different EN – ionic (EN difference > 1.8)
Metal loses electrons to become cation; non-metal becomes anion; they do not
share electrons
Presence of electrostatic attraction between ions which holds them together
Isoelectronic with noble gases (same electronic structure)
3D arrangement (crystal lattice) of anions/cations results in very strong
electrostatic attractions, resulting in high melting point and stability of ionic solids
Transition metals: +2 charge most common
-Hard brittle crystalline solids
-Relatively high melting and boiling points
-Non volatile
-If one layer is shifted, then that causes the following atoms to repel each other,
causing the substance to break
-firmly held in place so they cannot conduct electricity
 Can conduct electricity when they are not fixed (ie. Molten or in solution)
-Do NOT conduct electricity when SOLID, but do when molten/aqueous
-More soluble in water (highly polar) than other solvents (ion-dipole interactions)
(the ions react with the dipoles in the water molecule), but insoluble in most
solvents
If ion-ion forces too strong, it will not dissolve in water

When naming, don’t forget to include transition state if necessary (III)

High EN – covalent
Acids covalently bond
Usually between non-metals, though metals in high oxidation states can form
covalent bonds
Electrons shared because neither element loses electrons easily
When one atom donates both electrons to form a pair of shared electrons, this is
called a dative covalent bond
Indicate dative covalent bond by drawing an arrow pointing in the direction
that the electron pair is donated (eg from N to H in ammonia)
Dative bonds occur in triple bond in carbon monoxide, in all acid-base
interactions, and in all ligand metal ion interactions
Covalent bonds in molecular are very strong, but IMFs are much weaker
- Soft in solid state
- Don’t conduct electricity
 - More soluble in non-polar solvents than in water
- Low melting/boiling points
Low EN – metallic
Lewis structures must have all electrons listed whereas structural formulas just have bonds
1. Add up number of valence electrons.
2. Decide which one is the central atom
3. Octet rule
4. Calculate lone pairs
5. If molecule is ion, then draw square brackets around it and put charge in upper right
hand corner
Molecular Shapes
Repulsion between a lone pair and a bonding pair is however greater than that between
two bonding pairs
Lone pair distorts geometry, causing angle reductions
0 lone pairs, 4 bonds – tetrahedral, 109.5 degrees (eg. CH4)
1 lone pair, 3 bonds – trigonal pyramidal, 107 degrees (eg. NH3 ammonia)
2 lone pairs, 2 bonds – bent, 104 degrees (eg. Water)
Expanded octet:
Elements with d orbitals can promote one or more electrons from a doubly filled s/p
orbital into an unfilled low energy d-orbital, which increases # of unpaired electrons
available
Usually occurs when the element forms strong polar covalent bonds to small atoms
Non-bonding pairs always occupy the equatorial positions (minimizes electron repulsion)
Page 109, textbook
Polarity
Covalent bonding sharing of electrons is not identical unless the two molecules are
identical because of different EN
Stronger EN atom = dipole negative, weaker EN atom = dipole positive
A covalent bond in which the atoms have dipole/fractional charges = polar bond
Illustrating a dipole bond
Can also be illustrated by drawing arrows pointing to the more EN element parallel
to the bond line
The EN increases across a period, increases when one goes up a group (with N,O,F being
most EN)
The greater the difference in EN, the greater the polarity of the bond
In the extreme case of very large EN differences, like Na and Cl, it is ionic since the
electron can be considered to have been transferred
Polar bonds may result in the molecule having a resultant dipole (positive and negative
end to the molecule)
However this may be negated by the symmetry of the molecule; for example the
centres of positive and negative charge in CO2 neutralize each other since they are
in the same place, so there is no overall dipole
 Water is not symmetrical, so dipoles do not cancel
THEREFORE, for a molecule to be polar:
Must have polar bonds
Shape must be such that the centres of +/- charges are not in the same place
(tetrahedral = nonpolar??)
This can be tested by bringing an electrostatically charged rod close to the jet of
liquid in question; polar liquids will be attracted to the stream of liquid, but non-
polar will be unaffected
Molecules orientate themselves so that the end closest to the rod has the opposite
charge to the rod, so that the electrostatic force of attraction > force of repulsion
Dipole moment – measure of the polarity of a molecule (non-polar = 0 dipole moment,
for polar = greater polarity greater dipole moment)
Hybridization
Sigma bond - “end on” interaction of electrons in a s-orbital; electron density greatest on
the inter-nuclear axis (an imaginary line joining the two nuclei)
Pi bond – “side on” interaction of orbitals in p-orbitals at right-angles to the
aforementioned axis; low electron density on the axis; regions of high electron density on
opposite sides, each p-orbital controls one electron or more?
Eg) methane – one of the pair of electrons in the s-orbital is promoted to a vacant p-
orbital to produce carbon with 4 Ve; these then form hybrid orbitals
Hybridization – when an atom bonds, the atomic orbitals involved in forming the sigma
bonds (or accommodating the lone pairs) interact with each other to form an equal # of
highly directional hybrid orbitals of EQUAL energy
Total energy is unchanged, it has just been redistributed equally amongst the
orbitals
Ie) outer atomic orbitals interact with each other to produce hybrid orbitals
Involves same amount of orbitals, just rearranged
2 electron pairs (bonds/lone pairs) – sp hybridization (linear, one s and one p)
3 electron pairs – sp2 hybridization (trigonal planar, one s and two p)
4 electron pairs – sp3 hybridization (tetrahedral, one s and three p) (even NH3 and
water but 1 or 2 hybrid orbital has lone pair)
Hybrid orbitals can form sigma bonds, pi bonds are only produced by the sideways
interaction of unhybridized p-orbitals
Single, double or triple bonds all count as one bond in hybridization as each only
involves one sigma bond
 Important for organic
Single bonds – 1 sigma bond
Double bonds – one sigma bond and one pi bond
Triple bonds – one sigma bond and two pi bonds (bond lengths very short, bond
energies very high)
Resonance – use double headed arrows
Delocalized bonds
Sigma bonds affect shape along with lone pairs
Pi bonds do not affect molecular shape
Species with unpaired valence electrons are called free radicals
p-orbitals in pi bonds may have differing numbers of electrons and this may cause
delocalized pi bonds to form
Delocalization allows pi electrons to spread over more than two nuclei (are mobile and
shared by many atoms)
Gives the species a lower potential and makes it more stable than it would if it had
only double/single bonds
Eg) benzene – theory predicted alternating double and single bonds, which would
not lead to hexagonal shape
Each carbon is sp2 hybridized; one of these orbitals forms a sigma to the hydrogen it
is attached to, the other two form sigma bonds to the carbons on either side;
remaining 4th electron is in a p-orbital perpendicular to plane of sigma bonds
These p-orbitals interact to produce delocalized pi bond, giving rings of high
electron density above and below the ring of carbon atoms
 In Lewis structure terms, this is known as resonance structures; the actual species is
the resonance hybrid of these extreme structures; same sigma bonds, differ in the
arrangement of the pi bonds
Bond order – average number of bonds in different resonance structures (eg benzene due
to resonance has bond order of 1.5 because of alternating single and double)
Difference in stability known as delocalization energy/stabilization energy
Hydrogenation of benzene yields less heat energy released then expected because
of resonance energy
Graphite (sp2) is similar to benzene in terms of this madness. Can also have delocalized pi
bond. Gives C-C bond order of 1.33333.
READ PAGE 120 AND 121.
Intermolecular forces
Covalent bonding can cause giant structure like diamond/silicon dioxide or simple
molecular structure like methane
Giant covalent substances are very hard and have very high melting and boiling
points because of the strong forces holding the substance together; it follows that
the substance is solid at room temp, and insoluble in all solvents
Does not conduct electricity since electrons are held together (with the
exception of graphite)
Molecular covalent structures have strong covalent bonds but weak IMFs
Therefore liquids/gases at room temp and pressure
Usually quite soft, will dissolve in non-polar solvents like hexane
Insoluble in very polar solvents like water
Does not conduct electricity either since electrons are firmly held in covalent
bonds
Van der Waals’ forces
Exist in all species because temporary dipoles on one molecule from random
movement of electrons (especially valence) can have effect on neighbouring
molecules
Net result is that the attractive forces between molecules are on average stronger
than the repulsive forces, causing temporary attraction
Random accumulation of electrons on one side can cause that side to have a
temporary partial negative, repelling the electrons in a neighbouring atom; hence
causing temporary dipoles on both sides
Does not last long
Strength of this IMF is proportional to molar mass (increase in electrons and size of
instantaneous dipoles)
Therefore, as one goes down group 7 (halogens), molar mass increases, so
IMFs increase. Therefore the state of the element changes from gas
(fluorine/chlorine) to liquid (bromine) to solid (iodine)
Effective over short range, dependent on surface area of molecules
 Eg) elongated molecules have strong van der Waals’ forces, like pentane
(straight chain) which is higher than dimethylpropane (almost spherical)
Can become quite strong in plastics/polymer chains
Dipole-dipole forces
Electrostatic attraction between molecules with permanent dipoles
Significantly stronger than van der Waals’ forces
Molecules with this still have van der Waals’ forces
Hydrogen bonding
Hydrogen bonded to N, O or F
Interaction between non bonding electron pair on one of these atoms with
hydrogen atom that is carrying a high partial positive charge
Part way between dative covalent and dipole-dipole bond
For maximum strength, the two atoms and hydrogen should be in straight line
Considerably stronger than other IMFs
Basis of base pairing in DNA, alpha/beta sheets in proteins
- Higher boiling point, lower volatility, greater solubility in water, higher viscosity,
crystals are harder, more brittle than solids with other IMFs (eg. Sugar)
Hydrides are tetrahedral, non-polar, therefore van der Waals’
Structure of ice:
Tetrahedral because each water molecule can form 4 H-bonds
Similar to diamond structure, H-bonds instead of covalent bonds
Very open structure with large empty spaces, hence low density; thus ponds and
lakes freeze from surface down
As water cools, becomes less dense, stays on top until it freezes
Density of liquid water increases when heated from 0 to 4 because structure
preserved
Solubility:
If can’t H-bond, then insoluble in water
Propanone can’t bond to propanone, but it can bond to water because of the O-H
Metallic Bonding
Occurs in atoms of low EN
Atoms packed as closely together in 3D (close-packed lattice)
Metals have low ionization energies, many low energy unfilled orbitals, so valence
electrons are delocalized (share) amongst the atoms, and the Ve are free to move
throughout the metal
Metal atoms become cations in the process
Metallic structure: lattice of cations filled by mobile sea of valence electrons
Attractions between ions and electrons, not ion-ion, so layers of ions can slide past each
other because of no need to break bonds in the metal; hence metals are malleable and
ductile
If impurities are introduced, the cations slide less easily, so alloys are stronger than
pure metals
Metals conduct electricity because delocalized electrons are free to move from one side
of the lattice to the other when a potential difference is applied; good conductors of
electricity
Mobile electrons also make good conductors of heat and interaction with light
causes lustre of metals
Strength of the bond between metal atoms depends on how many electrons each atom
shares with the others
Eg) K (one Ve) is 337K, calcium (2 Ve) is 1123K for melting points
Also depends on how far the electrons are from the positive nuclei (ie. Ionic radius)
Eg) sodium compared to lithium has lower melting and boiling points, metallic
bonding is weak, substance is soft
 Mercury is an exception.
Physical Properties
Depends on IMF. Melting point is also very dependent on existence of regular lattice
structure. Impurities disrupt the lattice and lower the melting point.
Hence melting point can be used to check for impurities.
It follows that alloys have lower melting points than metals.
Volatility – how easily the substance is converted to a gas – is also dependent on IMFs
Electrical conductivity depends on whether the substance contains electrically charged
particles that are free to move through it when a potential difference is applied.
Dissolving: in order for one substance to dissolve in another the forces between the 2
types of particles must be strong, or stronger than between the particles in the two pure
substances
“like dissolves like”
In metals, the hardness, volatility, melting point, boiling point depend on the delocalized
electrons
Metals can conduct electricity in all states
Metal atoms cannot form bonds of comparable strength to substances that are ionic
or covalent. Metals don’t dissolve in other substances unless they react with them
chemically.
Metals can dissolve in other metals to form alloys or even non-metals in some
circumstances
Alloys generally less malleable and ductile than pure metal though
Mercury can form a wide range of alloys (amalgams)
Solubility Rules
All nitrates are soluble
All sodium, potassium, ammonium compounds are soluble
All sulfates are soluble except barium sulfate, lead sulfate; calcium sulfate is barely soluble
All chlorides, bromides and iodides are soluble except that of silver
Lead halides soluble in boiling water
All other compounds are insoluble though barium hydroxide and calcium hydroxide are
barely soluble
Hydration enthalpy -enthalpy change when one mole of gaseous ions is converted to one
mole of hydrated ions is measure of strength of interaction of water molecule with the ion;
depends on charge to size ratio
Greatest for small highly charged cations like aluminum
Additional covalent bonding
Diamond is sp3, giant 3D covalent structure; tetrahedral
Exceptionally hard, very high melting and boiling point
Graphite – another allotrope
Allotropes – different forms of an element that exist in same physical state
(ozone/oxygen molecules)
 Only in 2D, weak van der Waals’ forces between sheets of carbon atoms
Delocalized pi-bond between all of the sp2 hybridized carbon atoms in a given sheet,
so bond-order of C-C bonds is 1.33
Carbon-carbon bond length is slightly less than that found in diamond
Distance between sheets is quite large, very few forces between them, hence they
can easily slide over each other
Therefore lower density than diamond, can be used as lubricant, “lead” pencils
Delocalized electrons can move between layers so graphite can conduct electricity in
2D
Fullerenes – allotrope of carbon also
Approximately spherical molecules of 5-6 membered carbon rings
C60 – like soccer ball
Sp2 hybridized carbons are bonded by sigma bonds to three other carbons, surface
of sphere is not planar so there is little delocalization of unpaired bonding electrons,
so electrons cannot easily flow from one C60 molecule to the next
Although higher electrical conductivity than diamond, still much less than
graphite/fullerene derivs.
Chemically behaves as electron deficient (accepts electrons from reducing agnets) to
form anions
Addition reactions can also occur
Molecular unlike diamond and graphite, so they will dissolve in non-polar solvents
and have low melting points
Spherical, have compressibility properties
Related to nanotubes
Silicon has an almost identical crystal structure; can also form 4 covalent bonds
Sideways overlap between p-orbitals of larger atoms is less so other allotropes
that involve pi bonding do not occur
Silicon dioxide (quartz) is extremely like diamond, but each carbon is replaced by a
silicon and C-C bonds are replaced by an oxygen bridging the silicon atoms