Answers''

Molecular'orbitals'and'covalent'bonding'
1' a false b false c false d false e
false
f true g false h false i true j
true k true
2' a Unhybridized s orbitals forming sigma bonds (single bond between each H atom)
b A double bond between each oxygen resulting from sp2 hybrid orbitals on each oxygen
forming a sigma bond between O atoms and two p orbitals forming an additional pi
bond.
c A triple bond between oxygen and carbon resulting from sp hybrid orbitals on each
oxygen forming a sigma (between sp hybrids) and a 2 pi bonds (between 2 pairs of
adjacent p orbitals).
d A single bond between each chlorine atom resulting from a sigma bond on each
chlorine atom (between sp3 hybrid orbitals)
e A triple bond between the nitrogen atoms resulting from sp hybrid orbitals on each
nitrogen forming a sigma (between sp hybrids) and a 2 pi bonds (between 2 pairs of
adjacent p orbitals).
3' a Valence shell electron pair repulsion theory (VSEPR theory) predicts that groups of
electrons around the central atom will repel and position groups of electrons as far
apart as possible.
NF3 has three bonded F atoms and a lone pair giving an AB3L system. This gives a
tetrahedral geometry. One position of the tetrahedral structure is occupied by a lone
pair, leaving a triangular pyramidal structure.
b All tetrahedral geometries, including the AB3L system are sp3 hybridised.
c The F atoms have 3 lone pairs and 1 bonded atom, giving an ABL3 system. There are
4 groups of electrons around F resulting in tetrahedral geometry giving sp 3
hybridisation.
d. The ideal bond angle for a tetrahedral system is 109.5o, however the presence of a
lone pair on the central nitrogen atom will result in a bond angle compression giving a
final bond angle that is less than this value. Most times the bond angle compression is
2 – 3 o , and gives a predicted value of about 107o for NF3.
(NOTE: The experimentally measured bond angle in NF3 is actually 102.5o, much less
than the predicted value of 107 – this is because of additional lone pairs on F atoms
interacting with the lone pair on the central N atom)
4' a Valence shell electron pair repulsion theory (VSEPR theory) predicts that groups of
electrons around the central atom will repel and position groups of electrons as far
apart as possible.
SiF4 has four bonded F atoms and no lone pair giving an AB4 system. This gives a
tetrahedral geometry. Since all position of the tetrahedral structure are occupied by F
atoms the shape is also tetrahedral.
b All tetrahedral geometries, including the AB4 system are sp3 hybridised.
c The F atoms have 3 lone pairs and 1 bonded atom, giving an ABL3 system. There are
4 groups of electrons around F resulting in tetrahedral geometry giving sp 3
hybridisation.
d. The ideal bond angle for a tetrahedral system is 109.5o, and this is the actual bond
angle in tetrahedral shapes. As there are no lone pairs on the central Si atom to cause
bond angle compressions.
5' a Both carbons are sp hybridised (both AB2 systems, linear)
b Both carbons involved in the C=C system are sp2 hybridised (both being AB3 systems,
triangular planar), The remaining –CH2– OH carbon is sp3 hybridised (being AB4
system, tetrahedral)
c The carbon in CO2 is sp hybridised (being an AB2 system, linear)
d The carbon in CH2Cl2 is sp3 hybridised (being an AB4 system, tetrahedral)
e The carbon in H2CO is sp2 hybridised (being an AB3 system, triangular planar)
f The carbon in H2CO3 is sp2 hybridised (being an AB3 system, triangular planar,
remember that carbonic acid has hydrogens attached to oxygen acids – carbonic acid
is an “oxy acid”)
6' a One s and two p orbitals hybridise to give three sp2 hybrid orbitals arranged in a
triangular planar geometry. A sigma bond results when 2
electrons are placed into the orbital formed when an s
orbital, for example on a H atom, and a sp2 hybrid orbital,
for example on a C atom, overlap

Three sp2 hybrid orbitals

(120 o bond angles, coplanar)

sp2 hybrid s orbital sigma bond

orbital
b One s and three p orbitals hybridise to give four sp3 hybrid orbitals arranged in a
tetrahedral geometry. A sigma bond results when 2 electrons are placed into the
orbital formed when an s orbital, for example on a H atom,
!
and a sp2 hybrid orbital, for example on a C atom, overlap

Four sp3 hybrid orbitals

(109.5 o bond angles, tetrahedral)

sp3 hybrid s orbital sigma bond

c A pi bondorbital
forms when two parallel p orbitals overlap (sideways overlap).

2!p!orbitals!form!a!pi!bond!by!sideways!overlap!

d A sigma bond forms when two co-axial p orbitals overlap (head to head overlap).
7' a H2O is an AB2L2 system and is a tetrahedral geometry with ! Lone pairs
a bond angle based on the tetrahedral bond angle of
109.5o. The presence of two lone pairs will result in a bond
angle compression of about 4-5 degrees giving a final bond
angle of about 105o. The oxygen atom will form sp3 hybrid
O"
orbitals, which forms a sigma bond by overlapping with the H" H"
s orbital on the hydrogen atoms.
b CO2 is an AB2 system around the carbon atom and as a sigma bonds
result is a linear molecule and the carbon atom is sp
hybridised. The oxygen has a single bond and two lone pairs resulting in a triangular
planar arrangement of sp2 hybridised orbitals. The lone pairs on oxygen occupy two of
the sp2 hybrid orbitals with the remaining oxygen sp2 hybrid orbital on oxygen
overlapping with an sp hybrid orbital on carbon to form the sigma bond. The pi bond
of each C=O bond is formed by the sideways overlap of p orbitals on carbon and
oxygen.
! Sigma!bonds!
(end!to!end!overlap!of!hybrid!orbitals)!

Lone!e‒pairs!!
on!oxygen!
O" C" O"

pi!bond!
(side!ways!overlap!of!p!orbitals)!
3!sp2!hybrid! 2!sp!hybrid!
orbitals!on! orbitals!on!
oxygen! carbon!

Note: The two pi bonds of carbon dioxide are at right angles to each other.
c CH4 is an AB4 system with a tetrahedral geometry. The bond angles are 109.5o and
the carbon atom uses sp3 hybridised orbitals to form sigma bonds with the s orbitals
on each of the hydrogen atoms.

!
H"
C" H"
H" H"
d Each chlorine in Cl2 forms a single sigma bond and contains 3 lone pairs of electrons
formed from 4 equivalent sp3 hybrid orbitals.
!

Cl# Cl#
! !
 e Each oxygen atom is sp2 hybridised and the double bond is the result of the overlap of
an sp2 hybrid orbital from each oxygen to form the sigma bond and the sideways
overlapping of a p orbital on each oxygen atom to form a pi bond. The remaining
valence electrons are lone pairs that are found in the remaining sp2 hybrid orbitals on
oxygen.
! Sigma!bonds!
(end!to!end!overlap!of!hybrid!orbitals)!

Lone!e‒pairs!!
on!oxygen! O" O"

pi!bond!
(side!ways!overlap!of!p!orbitals)!
3!sp2!hybrid!
orbitals!on!
oxygen!

8' a The Lewis diagram (and the structural formula) for the nitrite ion are shown belos:
b A single bond is a sigma bond, and a double bond is a sigma and a pi bond. There are
2 sigma bonds and a pi bond in a nitrite ion.

! – ! –
O N O O ‒ N= O
Nitrite ion Nitrite ion
(NO2–) (NO2–)
c The orbital diagram for the nitrite ion includes 3 sp2 hybrid orbitals on each atom.
Each atom has an unhybridized p orbital that forms the pi bond and negative charge
as shown below:
! Sigma!bonds!
(end!to!end!overlap!of!hybrid!orbitals)!

Negative!charge!on!oxygen:!!!
lone!pair!in!this!p!orbital!!

O" N"

pi!bond! O"
(side!ways!overlap!of!p!orbitals)!

d The two structural formulae shown below are both equivalent and show that the
negative charm is equally shared by both oxygen atoms, and that the double bond can
be formed by either oxygen atom. The conclusion is that the bonds and charge in the
nitrite ion are delocalised over the molecule.

‒
O–N=O ↔ O = N – O‒

!
9' a The carbons in the benzene structure are all bonded to two other carbon atoms and a
hydrogen atom making each carbon in benzene an AB3 system which is trigonal planar
in shape and sp2 hybridised.
b&c The first two diagrams shown below illustrate how how p orbitals might overlap to
form pi bonds between adjacent carbons in either one of two ways. Neither is correct,
but rather the p orbitals overlap to form a circular cloud of pi orbitals above and below
the plane containing the carbon and hydrogen atoms, as is shown in the final diagram
on the right.

!
!! H" H"
!
H" H" H" H"
C" C" C" C" C" C"

H" C" C" H" H" C" C" H" H" C" C" H"

C" C" C" C" C" C"

H" H" H" H" H" H"

d. The delocalised nature of the bonding within benzene shows that rather than a system
of alternating single and double bonds, the bonding in benzene is better represented
as half way between a single bond and a double bond. The average of a single bond
length (153 pm) and a double bond length (134 pm) is 143.5 pm (so expect a bond
length of 143 or 144 pm).
Bond'Energies'
1' a true b false c true d false e
true
f false g false
2' B.E. Xe-O = 82 kJ/mol
3' ½ H2(g) + ½ F2(g) → HF(g)
!H = (BE reactants) - (BE products)
‒271 = ( ½ x 436 + ½ x 159) ‒ (B.EH–F)
B.E.H-F = 569 kJ/mol
4' ½ N2(g) + 3/2 H2(g) → NH3(g)
!H = (BE reactants) - (BE products)
‒46 = ( ½ x 945 + 3/2 x 436) ‒ (3 x B.EN–H)
B.E.H-N = 391 kJ/mol
5' CH4(g) + Cl2(g) → CH3Cl (g) + HCl(g)
!H = (BE reactants) - (BE products)
!H = ( 4 x 414 + 242) ‒ (3 x 414 + 327 + 431)
B.E. = ‒ 102 kJ/mol

6' a

b !H = (BE reactants) - (BE products)

‒136 = (4 x 414 + BEC=C + 436) ‒ (6 x 414 + 346)
B.E.C=C = 602 kJ/mol
c CH2=CH – CH=CH2(g) + 2 H2(g) → CH3 – CH2 – CH2 – CH3 (g)
!H = (BE reactants) ‒ (BE products)
!H = (6 x 414 + 346 + 2 x 602 + 2 x 436) ‒ (10 x 414 + 3 x 346) = ‒272 kJ/mol
7' a !H = (BE reactants) - (BE products)
!H = (2 x 414 + 839 + 2 x 463) ‒ (4 x 414 + 346 + 745) = ‒154 kJ/mol
b !H = (!Hformation reactants) ‒ (!Hformation products)
!H = (‒166) - (227 + (‒242)) = ‒151 kJ/mol
c The more accurate calculation uses heat of formation (which are exact values)
(Enthalpy changes calculated from bond energies are estimates because
bond energies are average values)
8' a 2 C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(g)
!H = (BE reactants) ‒ (BE products)
!H = (4 x 414 + 2 x 839 + 5 x 498) ‒ (8 x 804 + 4 x 463) = ‒2460 kJ/mol
b !H = (!Hformation reactants) - (!Hformation products)
!H = (4 x (‒396) + 2 x (‒242)) ‒ (2 x 227 + 5 x zero) = ‒2522 kJ/mol
c The experimentally measured value is 1300 kJ/mol, which is (to 2 significant figures)
half the values calculated in parts a and b. This is because the heat of combustion is
the heat change, at constant pressure, when ONE mole of ethyne is reacted with
sufficient oxygen to produce carbon dioxide gas and liquid water.
C2H2(g) + 5
/2 5 O 2 (g) → 2CO2(g) + H2O(g) !H = ‒1300 kJ/mol
The more accurate calculation uses heat of formation (which are exact values)
(Enthalpy changes calculated from bond energies are estimates because
bond energies are average values).
9' a CH3CHO(g) → CH4(g) + CO(g) !H = – 20 kJ/mol
!H = (BE reactants) ‒ (BE products)
‒20 = (4 x 414 + 346 + 745) ‒ (4 x 414 + BEC≡O)
BEC≡O = 1111 kJ/mol
b CO(g) + ½O2(g) → CO2(g)
!H = (BE reactants) ‒ (BE products) = (1111 + ½ x 498) ‒ (2 x 804)
!H = ‒248 kJ/mol
c Carbon monoxide has a triple bond (one sigma and 2 pi bonds). The double bonds in
carbon dioxide contain a sigma bond and only 1 pi bond.
10' a !H = (BE reactants) ‒ (BE products)

!H = (4 x 414 + 346 + 745 + ½ x 498) - (3 x 414 + 346 + 745 + 358 + 463)

!H = ‒158 kJ/mol
b !H = (!Hformation Products) – (!Hformation Reactants)
!H = ((!Hf CH3CO2H(g)) – ((!Hf CH3COH(g) – ½ x (!HfCO2(g))
‒158 = (!Hf CH3CO2H(g) – (‒166 + ½ x zero)
!Hf CH3CO2H(g) = ‒324 kJ/mol
11' a 2 O=O–O(g) → 3 O=O(g) O=O–O(g)
!H = (BE reactants) ‒ (BE products) ‒201 kJ/mol

!H = (2 x 498 + 2 x 144) - ( 3 x 498) O=O(g)

!H = ‒201 kJ/mol
O2 is at a lower energy than O3 and is therefore (thermodynamically) stable.

b
‒210 kJ/mol
!H = (BE reactants) ‒ (BE products) O=O–O(g)
!H = = (3 x 144) – (498 + 144) ‒201 kJ/mol
O=O(g)
!H = ‒210 kJ/mol
c O=O – O(g) + O(g) → 2 O=O(g)
!H = (BE reactants) ‒ (BE products) = (498 + 144 + zero) ‒ (2 x 498)
!H = = ‒354 kJ/mol
2 P≡P(g)
12' a For Phosphorous:
!
P!
+ 226 kJ/mol
P4(g)
2P ≡P
P!

P! P!

!H = (BE reactants) ‒ (BE products) = (6 x 198) ‒ (2 x 481) = +226 kJ/mol

b For Nitrogen:
!H = (BE reactants) ‒ (BE products) = (6 x 158) ‒ (2 x 945) = ‒ 942 kJ/mol
 H‒O–C≡N(g)
13' H – O – C ≡ N(g) ⇆ H – N = C = O (g)
‒40 kJ/mol
H = (BE reactants) ‒ (BE products)
H‒N=C=O(g)
H = (463 + 358 + 890) ‒ (391 + 615 + 745) = ‒ 40 kJ/mol
Therefore HNCO is the more stable (lower energy) isomer.
14' a On going across a period the atoms become smaller so the distance between their
nuclei when they are attached (i.e. the bond length) also becomes smaller. On going
down a group the atoms become larger so their bond lengths also become larger.
b The smaller the atoms are, the closer their nuclei are to the shared electrons and the
greater the attraction between them; so the shorter the bond is, the stronger the
attraction.
15' a The more electrons that are shared between two atoms the greater will be the
attraction between these electrons and the nuclei of the atoms so 2 shared pairs will
pull the atoms closer together than 1 shared pair, but not as close as will 3 shared
pairs.
b Two shared pairs exert more attraction on the nuclei, and produce a stronger
attachment, than does one shared pair, and three shared pairs make the bond even
stronger.
c A nitrogen atom is smaller than a carbon atom but is larger than an oxygen atom.
(discuss answer with tutor)
d Estimated bond length ≈110 pm, Estimated bond energy ≈ 1100 kJ/mol.