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Prepared by Mr. Chau Chi Keung, Richard Page 1
Modern College AL Chemistry Notes (2009 – 10) Section 4B
(a) (b)
Helium atom has the electronic configuration 1s2. The two valence electrons of helium atom
fill its valence orbital (1s orbital).
The completely filled orbital of a helium atom cannot be occupied by the valence electrons
of the other helium atom because each orbital can accommodate a maximum of two
electrons only; otherwise, it will violate Pauli’s Exclusion Principle.
Therefore, helium forms no covalent bonds and is a monoatomic molecule.
Example 1
Write the structural formulae of the following compounds, showing the lone pair electrons of the
central atom (if any).
Hydrogen fluoride (HF) Water (H2O) Ammonia (NH3)
Before
3s 3p 3d
After
3s 3p 3d
Phosphorus can expand its octet by promoting its 3s electrons to the low-lying
vacant d-orbitals in order to form covalent bonds with 5 chlorine atoms.
Hence, phosphorus can form two chlorides – PCl3 and PCl5.
In contrast, since nitrogen does not have those low-lying vacant d-orbitals, it only
has a maximum of three half-filled p orbitals to form three bonds.
Hence, nitrogen is only able to form one chloride – NCl3.
There also exist species which violate the octet rule due to an “electron deficiency”
Example: Boron trifluoride (BF3)
The central boron atom only has 6 electrons (In this case, that B atom is said to be
Surely, the donor must have at least one lone pair of electrons for bond formation while
the acceptor must have an empty orbital to take up that pair of electrons.
Dative covalent bond and covalent bond are identical once they have been formed. There is
no real distinction between them except that in dative covalent bond only one of the bonded
atoms provides the two electrons which are shared.
Dative covalent bond is sometimes designated by drawing an arrow from the donor to the
acceptor atom.
Example 1: NH3BX3 molecule (X = F or Cl)
Aluminium chloride (AlCl3) and nitric acid are another two noteworthy examples of dative
covalent bond.
Similar to its Group III counterpart boron, the atomic size of aluminium is relatively
small.
The I.E. required for Al to form a cation of +3 charge will be very high. Therefore
AlCl3 is a covalent compound rather than being ionic.
Being in Period 3, Al also has low-lying vacant d-orbitals to accept the lone pair
electrons from Cl.
Therefore, dative covalent bonds can be formed and this explains why AlCl3 can form
Al2Cl6 – a dimer (二聚物), particularly in liquid and gas phases.
Based on this structure, it is predictable that dative covalent bond also exists in nitrate
ions (the detailed structure of nitrate ions will be discussed later in this part).
The value obtained is called the average bond enthalpy (平均鍵焓) of the C–H bond
(denoted as E(C–H))
In general, the average bond enthalpy is defined as the average of the bond dissociation
enthalpies required to break a particular chemical bond (denoted as E(X–Y)).
For example, E(C–H) is the average value of bond dissociation energies of C–H bond
in all kinds of hydrocarbons.
E(X–Y) can be deduced from the energetic data of many compounds.
Do not mix up with the bond dissociation enthalpy, which refers specifically to a
particular bond of a particular compound.
By convention, “bond enthalpy” refers to “average bond enthalpy” if not specified.
Some bond enthalpy values are shown in the table below:
Bond Bond Enthalpy / kJmol–1
C–C 348
C=C 612
H–H 436
O–O 146
O=O 496
N–N 163
N=N 409
N≡N 944
F–F 158
Cl–Cl 242
Example 2
Given that:
Standard enthalpy change of formation of methane = –75 kJ mol–1
Standard enthalpy change of atomization of graphite = +718 kJ mol–1
Standard enthalpy change of atomization of hydrogen = +218 kJ mol–1
Construct an enthalpy cycle and determine the average bond enthalpy of the C–H bond.
4E (C–H)
C(g) + 4H(g)
C(graphite) + 2H2(g)
Example 3
Construct an enthalpy cycle and determine the bond enthalpy of the C–C bond. Given that:
Standard enthalpy change of formation of ethane = – 85 kJ mol–1
Standard enthalpy change of atomization of graphite = + 718 kJ mol–1
Standard enthalpy change of atomization of hydrogen = + 218 kJ mol–1
Average bond enthalpy of C–H bond = + 416 kJ mol–1
Example 4
Given that:
Standard enthalpy change of formation of carbon dioxide = – 393 kJ mol–1
Standard enthalpy change of atomization of graphite = +718 kJ mol–1
Standard enthalpy change of atomization of oxygen = +249 kJ mol–1
Construct an enthalpy cycle and determine the bond enthalpy of the C=O bond.
Example 5
Calculate the bond enthalpy of the H–Br bond from the following data:
ΔH / kJmol–1
1 218
2 H2(g) → H(g)
Br2(l) → Br2(g) 30.6
1 112
2 Br2(g) → Br(g)
1 1 –36.3
2 H2(g) + 2 Br2(g) → HBr(g)
Example 6
Given that the standard enthalpy change of atomization of butane and pentane are +5165 kJmol–1
and +6340 kJmol–1 respectively. Calculate E (C–H) and E (C–C).
We can use the bond enthalpies to estimate the enthalpy change of certain chemical reaction.
Small discrepancies will obviously arise since average bond enthalpies are used.
Take the reaction between hydrogen and ethene as an example:
Example 7
Given that at 298 K, the bond enthalpies of the Cl–Cl, H–H and H–Cl bonds are 242, 436 and
431 kJ mol–1 respectively. Calculate the enthalpy change of formation of hydrogen chloride gas.
Example 8
Example 9
Given the following bond enthalpies:
Bond E (X–Y) / kJmol–1
C–C 348
C–H 412
C–Br 284
Calculate the enthalpy change of atomization of 1-bromobutane.
Example 10
Given the following thermochemical data
ΔH / kJmol–1
Enthalpy Change of vaporization of cyclohexane (ΔHvap [C6H12(l)]) +33
Enthalpy Change of atomization of carbon +718
Enthalpy Change of dissociation of H2 molecules +436
Enthalpy Change of combustion of carbon –393
Prepared by Mr. Chau Chi Keung, Richard Page 15
Modern College AL Chemistry Notes (2009 – 10) Section 4B
Enthalpy Change of combustion of hydrogen –286
Average bond enthalpy of C–C bond +348
Average bond enthalpy of C–H bond +416
Calculate the enthalpy change of combustion of cyclohexane, C6H12(l).
Such predictions are particularly accurate for the bonding atoms have no (or small)
difference in electronegativity. (e.g. for N–Cl bond, Difference in electronegativity =
3.0 – 3.0 = 0).
Larger discrepancies arise for the cases which atoms with a great electronegativity
difference are joined by a covalent bond (e.g. for C–O bond, Difference in
electronegativity = 3.5 – 2.5 = 1.0).
This is because the bonding electrons are drawn closer towards the more
electronegative atom, causing a shortening of internuclear distance.
In fact, the bond between atoms of different electronegativities is not purely covalent
but carries some ionic character (will be discussed in the later part of Section 4).
As mentioned previously, when considering the shape of a molecule or polyatomic ion, both
the number of bond pair and lone pair should be considered. In general, we may use the
formula shown below:
The sum of m + n equal the total number of electron pairs around the central atom and this
determines the shape of molecule or ion.
The number of lone pair in a molecule (n) can be predicted by the following formula:
No. valance e − in A − (Sum of e − required to fill the valance shell of each X)
n=
2
Case 2: AX2E
Shape: Angular / bent / V-shaped (V 形)
Bond angle: ≈120°
Examples: Sulphur dioxide (SO2)
Sulphur dioxide (SO2)
Case 2: AX3E
Shape: Trigonal pyramidal (三角錐體形)
Bond angle: ≈107°
Examples: Ammonia (NH3), phosphorus trichloride (PCl3), hydroxonium ion (H3O+)
Due to the presence of a lone pair in the central N or P atom, there will be an increased
electron pair repulsion, resulting in an compression (壓縮) of bond angle.
(Remember: Lone pair – bond pair > Bond pair – bond pair)
Ammonia (NH3) Phosphorus trichloride Hydroxonium ion (H3O+)
(PCl3)
Case 3: AX2E2
Shape: Angular / bent / V-shaped
Bond angle: ≈ 104.5°
Examples: Water (H2O), hydrogen sulphide (H2S), amide ion (NH2–)
The electron pair repulsion will be even greater since there are 2 lone pairs in the
central atoms. Thus the compression of bond angle will be more prominent.
(Remember: Lone pair – lone pair > Lone pair – bond pair > Bond pair – bond pair)
Water (H2O) Hydrogen sulphide (H2S) Amide ion (NH2–)
Case 2: AX4E
Shape: Seesaw shape / irregular tetrahedral (蹺蹺板形/變形四面體形)
Bond angle: ≈120°(equatorial bonds), <90°(axial bonds)
Examples: Sulphur tetrafluoride (SF4)
Sulphur tetrafluoride (SF4)
Case 3: AX3E2
Shape: T-shaped (T 形)
Bond angle: 90°(axial bond)
Examples: Chlorine trifluoride (ClF3)
Chlorine trifluoride (ClF3)
Case 4: AX2E3
Shape: Linear
Hint: Based on the basic shape, the other variation in shape for 5 electron pairs can be drawn
by deleting the bonds on the equatorial plane one by one (i.e. The lone pairs must lie on
the equatorial plane).
Case 2: AX5E
Shape: Square pyramidal (正方錐體形)
Bond angle: 90° for both equatorial bonds and axial bonds
Examples: Iodine trifluoride (IF5)
Iodine trifluoride (IF5)
Hint: Unlike the case for 5 electron pairs, the other variations in shape for 6 electron pairs
should be drawn by deleting the axial bonds one by one.
Example 11
For each of the following species, draw a three-dimensional structure showing the bond pairs and
lone pairs (if any) on the central atom. State also the molecular geometry in each case.
Example 12
Explain why in phosphine (PH3), the bond angle between the two P–H bonds is about 94° whereas
the bond angle between the two N–H bonds in ammonia (NH3) is about 107° although both
nitrogen and phosphorus are in Group V of the Periodic Table.
This is because the lone pair on the phosphorus is much more diffuse, owing to the larger size
of P atom when compared with N atom. Therefore the two P–H bond pairs in PH3 are repelled
more by that lone pair than in the case of the two N–H bond pairs in NH3. As a result, the two
P–H bond pairs are pushed closer together, causing a reduction of the H–P–H bond angle.
On the other hand, since N is more electronegative than P, the bonding electrons in NH3 are
drawn closer to the central atom. Because of this, the bonding electrons in NH3 experience
greater repulsion than those in PH3. Hence H–N–H bond angle is greater.
Example 3: Water
In water molecule, two of the four sp3 hybridized orbitals is occupied by an electron pair
from oxygen. These are the two lone pairs of water.
In forming the ethene molecule, one of the three sp2 orbitals on C atom will overlap with a
sp2 orbital from another C atom, while the other two will overlap with two 1s orbitals of the
H atoms. The covalent bonds formed in these two processes are called σ bonds. (兩個碳原子
的一個 sp2 雜化軌態重疊,形成 C–C 鍵。而另外兩個 sp2 雜化軌態則各與一個氫原子的
1s 軌態重疊,形成 C–H 鍵。)
The overlapping involved here is called “head-on overlap”( 迎 頭 重 疊 ) or “linear
overlap”
On the other hand, the extra 2p orbital from each C atom which is at right angle to the plane
of C and H atoms will overlap laterally above and below the plane, resulting in another type
of covalent bond called π bond.
The overlapping involved here is called “sideway overlap” ( 側 面 重 疊 ) or “lateral
overlap”.
Hence, the C=C double bond in ethene is a combination of one σ bond and one π bond.
It should be noted that the lateral overlap between the two unused 2p orbitals is less effective
than the linear overlap which results in formation of σ bonds. (軌態以側面重疊的成鍵方式,
作用遠比軌態以迎頭重疊的成鍵方式遜色。)
Therefore, π bond is weaker than σ bonds. (σ 鍵遠比 π 鍵為強)
In other words, the bond energy of π bond is weaker than σ bonds.
Hence, it can be deduced that,
E (C=C) ≠ 2 × E (C–C) (In fact, E (C=C) < 2 × E (C–C))
This explains why the two bonds in C=C double bond are not equivalent.
In addition, since the sp2 orbitals in both C atoms adopt a planar geometry and the π bond is
not free to rotate, ethene has a planar structure.
The three sp2 hybridized orbitals in B atom overlap with 2p orbitals of the three F atoms to
form 3 σ bonds.
The sp2 hybridized orbitals consists of three lobes with trigonal planar geometry.
It should be noted that there is still an empty 2p orbital in B atom and so it does not fulfill
Hence, the C≡C triple bond in ethyne is a combination of one σ bond and two π bonds.
As a result, P and S can fully utilize their valence electrons to form a wide variety of
compounds or polyatomic ions.
P can form 5 covalent bonds at most. Examples include PO43–, P2O5 and PCl5.
S can form 6 covalent bonds at most. Examples include SO3, SO42– and SF6.
This also explain why P and S can have a wide range of possible oxidation numbers
(e.g. For S: –2 to +6)
It should be noted that such hybridization process is impossible for elements in period 2, as
there is no low-lying vacant d orbital available.
The energy required to promote 2s or 2p electrons to any vacant orbitals in the electron
shell n = 3 will be so large that it cannot be compensated by the subsequent bond
formation process.
Another interesting example is the compound of xenon (氙) ([Kr] 4d105s25p6), a noble gas in
period 5 with atomic number 54.
Not all noble gases can form compound. As the principle quantum number increases,
the energy gap between the orbitals gets smaller. For heavy noble gas atom like xenon,
electrons from lower energy level may be promoted to higher energy level to yield
unpaired electrons for bonding formation.
Besides, since the size of Xe atom is large, the attraction between the nucleus and the
outermost electrons in a Xe atom will be so weak that they can be easily attracted by
Although it does not completely match with the reality, you may imagine that the
single and double bonds are shifting back and forth.
In benzene molecule, all six carbon atoms are sp2 hybridized. They are joined together
in a ring by overlap of carbon sp2 hybrid orbitals, forming 6 C–C σ bonds.
6 C–H σ bonds are formed by further overlap with hydrogen 1s orbitals.
The unhybridized 2p orbital of each carbon atom will overlap laterally with each other
to form π bonds.
This results in an extensive π electron cloud (also called a “π system”) lying above
and below the plane of C and H atoms.
In this “π system”, the π electrons are not localized at fixed positions. Instead, they will
move freely around the whole ring (苯的 π 電子離域至整個分子).
Such phenomenon is called “delocalization of electrons” or “resonance of electrons”
making all the 6 C–C bonds equivalent.
Enthalpy / kJ mol–1
+221 kJmol–1 –169 kJmol–1
+52 kJmol–1
6C(graphite) + 3H2(g)
In other words, the actual delocalized structure is more stable by 169 kJmol–1 when
compared with the hypothetical cyclic triene structure.
This energy is known as delocalization energy, and it is the amount by which the
delocalized structure is energetically more stable than a cyclic triene.
Another possible energetic approach is the comparison between the enthalpy change of
hydrogenation of benzene and that of the hypothetical cyclic triene structure:
Enthalpy change of hydrogenation (加氫焓變): The enthalpy change when one mole
an unsaturated compound reacts with an excess of hydrogen to become fully saturated.
Consider the hydrogenation of benzene
Delocalization energy
= –166 kJmol–1
–1
Enthalpy / kJ mol
–375 kJmol–1
–209 kJmol–1
It was found that less heat is released than the calculated value. The difference between
these values indicates that the actual structure of benzene is more stable than Kekulé
structure by (–209) – (–375) = 166 kJmol–1.
This extra stability can be attributed to the delocalization of the bonding electrons over
all 6 carbon atoms.
As the π electrons delocalize around the ring, the 6 C–C bonds become equivalent.
Such distribution minimizes the repulsion among the electrons and gives a more stable
structure.
Since one π bond is shared among three N–O bonds, the bond order of the N–O bond
in nitrate ion is 1⅓.
Orbital representation would be a better way to represent the actual structure.
Points to note:
Resonance structures exist only on paper.
In writing resonance structures, only electrons are allowed to move.
The actual molecule or ion will be better represented by a hybrid / combination of all
the resonance structures involved.
The energy of the actual molecule is lower than the energy that might be estimated for
any contributing structure.
This gives a three-dimensional covalent network structure. Such C–C bonding pattern
explains the stability, extreme hardness and very high melting point of diamond (In fact,
diamond is the hardest natural substance in the world).
For a diamond to melt or undergo a chemical change, many strong C–C bonds within the
crystalline structure must be broken.
Because of the incredible hardness and high melting point (3550°C), applications of diamond
are endless: scratch proof cookware, watch crystal, lifetime drill bits and razor blade.
Furthermore, the localization of the electrons within C–C bonds prevents them from moving
freely in an applied electric field and thus diamond does not conduct electricity.
4.12.2. Graphite
Graphite is made up of hexagonal arrays of carbon atoms arranged in layer.
Within each layer, each carbon atom in graphite is sp2 hybridized and forms bonds with three
other carbon atoms (C–C σ bonds).
As a result, network of coplanar hexagons is formed, with a C–C bond length of 0.142 nm.
Weak van der Waals’ forces hold the layers together and distance between adjacent layers is
It should be noted that the C–C bond in graphite has the partial double bond character due to
the delocalization of electrons. Thus the C–C bond length in graphite (0.142 nm) is smaller
than that in diamond (0.154 nm).
For this reason, the C–C bonds in graphite are stronger than that in diamond.
4.12.3. Quartz
Quartz is a three-dimensional lattice of silicon(IV) oxide, SiO2.
In the quartz lattice, each silicon atom is bonded tetrahedrally to four neighboring oxygen
atoms by identical and directional strong Si–O covalent bonds. Thus the coordination
number of Si is 4.
Each oxygen atom is bonded to 2 silicon atoms and so the coordination number of O is 2.
It is very difficult to break a covalent crystal of quartz, because this would involve breaking
many Si – O covalent bonds. As a result, quartz is hard with high melting points (1700℃).
Furthermore, the localization of the electrons within Si–O bonds prevents their moving freely
in an applied electric field and hence quartz does not conduct electricity.
Quartz is one of the major components of the glass and ceramics.