Further'practice'

Molecular'orbitals'and'covalent'bonding'
Threshold'Questions'
1' Decide whether the following statements are true or false.

a' Pi bonds can be formed using s orbitals.

b' Sigma bonds always involve s orbitals.

c' The sideways overlap of a p orbital with an s orbital results in the formation of a
pi bond.

d' Two sigma bonds form a double bond.

e' A pi bond always forms before a sigma bond.

f' A triple bond is a sigma bond and two pi bonds.

g' The bonding in NH3 is formed when sp2 hybrids on nitrogen overlap with s
orbitals on hydrogen.

h' The triangular planar shape of CH2O involves sp2 hybrid orbitals on carbon.

i' The bonding between chlorine and carbon in CCl4 involves sp3 hybride orbitals
on both carbon overlaping with sp3 hybrid orbitals on chlorine.

j' The sigma bonds in CO2 involve the overlap of sp hybrid orbitals on carbon
overlapping with sp2 hybrid orbitals on oxygen.

k' The pi bonds in CO2 involve the overlap of p orbitals on carbon with p orbitals on
oxygen.

2' Diatomic molecules are always linear. Predict the hybridisation of each atom in the
following diatomic molecules and describe the chemical bond, (single, double, triple,
number of sigma bonds, number of pi bonds) between each atom .

a' H2

b' O2

c' CO

d' Cl2

e' N2

3' Nitrogen trifluoride,NF3, is a colourless gas with a boiling point of ‒129 oC.

a' Using VSEPR theory, predict the shape of NF3.

b' What is the hybridisation of the nitrogen atom in NF3?

c' What is the hybridisation of each fluorine atom in NF3?

d' What is the bond angle in NF3?

4' Silicon tetrafluoride is a colourless gas.

 a' Using VSEPR theory, predict the shape of SiF4.

b' What is the hybridisation of the silicon atom in SiF4?

c' What is the hybridisation of each fluorine atom in SiF4?

d' What is the bond angle in SiF4?

5' Describe the hybrid orbitals used by each carbon atom in the following molecules.

a' N≡C‒C≡N

b' H2C=CHCH2OH

c' CO2

d' CH2Cl2

e' H2CO

f' H2CO3
Intermediate'Questions'
6' Sketch diagrams to show how the following bonds between are formed:

a' A sigma bond between an s orbital and a sp2 hybrid orbital.

b' A sigma bond between an sp3 hybrid and a sp2 hybrid orbital.

c' A pi bond between two p orbitals.

d' A sigma bond between two s orbitals

7' Draw orbital diagrams to show bonding electron pairs, non-bonding electron pairs
and the angle between them for the following molecules:

a' H2O

b' CO2

c' CH4

d' Cl2

e' O2

Advanced'Questions'
8' The nitrite ion has the formula NO2‒.

a' Draw a lewis diagram for the nitrite ion.

b' How many sigma bonds and pi bonds does nitrogen form in nitrigte ion?

c' All three atoms in nitrite ion are sp2 hybridised. Draw an orbital diagram for the
nitrite ion.

d' Explain how the negative charge in nitrite ion can be delocalised over both
oxygen atoms.

9' Benzene has the molecular formula of C6H6 and its structural formula is shown
below.

a' What is the hybridisation of each carbon in benzene?

b' Draw an orbital diagram for benzene showing the formation of the each pi bond.

c' Show how the pi bonds in benzene are delocalised.

d' A C‒C single bond length is 153 pm; a C=C bond length is 134 pm and a C≡C
bond length is 120 pm. Estimate the bond length of the carbon to carbon bonds
in benzene, providing a brief explanation to support your answer.
Bond'energies'
Threshold'Questions'
1' Decide whether the following statements are true or false.

a' Average bond energies can be used to determine the precise enthalpy change for
the following reaction: CH2=CH2(g) + HOH(g) → CH3CH2OH(g) .

b' Average bond energies can be used to estimate the enthalpy changes associated
with a following reaction: CH2=CH2(g) + HOH(l) → CH3CH2OH(aq)

c' The bond dissociation energy for an O‒H bond depends on the compound.

d' The bond energy for a C=C bond is twice the bond energy of a C‒C bond.

e' The stronger the bond, the shorter the bond distance.

f' The average bond energy of O2 is equal to the heat of atomisation of oxygen.

g' The heat of formation of Br(g) is equal to ½ the bond energy of bromine.

2' Xenon trioxide can (in theory) be prepared from xenon and oxygen gases:

Xe(g) + /2 O2(g) →
3
XeO3(g) !H = + 502 kJ/mol

The molecule contains a central Xe atom bonded to three O atoms.

If the bond energy of O = O bonds is 498 kJ/mol, calculate the average bond energy
of a Xe — O bond.

3' The bond dissociation energies (B.E) of H — H bonds in H2 molecules are

436 kJ/mol and of F — F bonds in F2 molecules are 159 kJ/mol.

If the enthalpy of formation (!Hf) of HF(g) is "271 kJ/mol, predict the bond energy
of the H — F bond.

4' Given the following information, predict the average bond energy for
the N — H bonds in ammonia.

!Hf for NH3 (g) = – 46 kJ/mol, #.$. H – H is 436 kJ/mol, #.$. N≡N is 945 kJ/mol,

5' Methane and chlorine react to produce chloromethane and hydrogen chloride gas
according to the equation:

CH4(g) + Cl2(g) → CH3Cl (g) + HCl(g)

Given the following information (in kJ/mol), predict the enthalpy change for the
reaction between methane and chlorine:
B.E.C — H = 414, B.E.C — Cl = 327, B.E.H — Cl = 431, B.E.Cl — Cl = 242.

6' Ethene (C2H4) reacts with hydrogen gas producing ethane (C2H6):

C2H4 (g) + H2 (g)→ C2H6 (g) !H = – 136 kJ/mol

a' Rewrite this equation using structural formulas for the three molecules.

b' Predict the bond energy of C = C bonds in ethene given the following
bond energies: C — C (346 kJ/mol), C — H (414 kJ/mol), H — H (436 kJ/mol).
 c' Predict the enthalpy change for the reaction of buta-1,3-diene (CH2=CH‒
CH=CH2) with two moles of hydrogen gas to butane (CH3‒CH2‒CH2‒CH3).

Intermediate'Questions'
The following table lists several bond energies and the heats of formation that apply
to question 7 to 11 below.

Average Bond Energies Enthalpy of Formation

(kJ/ mol of bonds) (kJ/mol of compound)

C—C 346 O—H 463 C2H2(g) +227

C=C 614 C—O 358 H2O(g) -242

C=O 804 (in

C≡C 839 CO2) CH3CHO(g) -166
C=O 745 (most
C=O)
CO2(g)
C—H 414 O=O 498
-396

7' Ethyne (C2H2) gas reacts with steam to produce ethanal (CH3CHO) according to the
equation:

a' Calculate the enthalpy change for this reaction at 25oC using bond energies. The
bond energy of the C=O bond in CH3CHO is 745 kJ/mol.

b' Calculate the enthalpy change for this reaction at at 25oC standard using
enthalpy of formation values.

c' The two methods above give different answers. Which method is more accurate
for determining the enthalpy change for a reaction? Justify your choice.

8' Consider the reaction of ethyne gas with oxygen to give carbon dixoide gas and
steam.
2 C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(g)

a' Using bond energies given above, predict the enthalpy change for this reaction.

(Use the data presented in question 7, BEC=O bond in CO2 is 804 kJ/mol).

b' Calculate the enthalpy change for this reaction at at 25oC standard using
enthalpy of formation values.
 c' The standard heat of combustion of ethyne has been experimentally measured
and found to be ‒1300 kJ/mol. Compare the experimental value with the values
determined in parts (a) and (b) above and account for any differences between
all three values.

9' When heated, ethanal decomposes according to:

CH3CHO(g) → CH4(g) + CO(g) !H = – 20 kJ/mol

a' Calculate the energy of the bond in the CO molecule and explain why this bond is
stronger than a C=O bond.

b' Estimate the heat of combustion of carbon monoxide.

(Use the data presented in question 7).

c Briefly account for the difference between the average bond energies of the
bond between carbon and oxygen in carbon dioxide and carbon monoxide.

10' Under special conditions ethanal, CH3CHO(g), reacts with oxygen gas to form acetic
acid:
!

a' Using the bond energies given in question 7, predict the enthalpy change for this
reaction.

b' Estimate the heat of formation of acetic acid vapour.

Advanced'Questions'
11' Oxygen exists as O2 and O3 (ozone):

a' Using the bond energies (O=O is 498 kJ/mol and O " O is 144 kJ/mol) explain
why ozone molecules, O3, tend to easily convert into oxygen O2, molecules.

b' Ozone could have the bonding arrangements:

Which of these arrangements is the most favourable energetically i.e. which

would release the greatest amount of energy when the molecule formed from
three separate oxygen atoms?

c' In the upper atmosphere lone oxygen atoms can combine with ozone to form
oxygen molecules according to: O3(g) + O (g) → 2O2(g)
Using the bond energy data, estimate the enthalpy change for this reaction.
12' Atoms bond together so as to minimise their total energy i.e. a molecule has less
energy than the total energy of its separated atoms. The common forms of the
Group15 elements nitrogen and phosphorus are N2 and P4 respectively.

Using&the&data&below,&explain&why&the&most&stable&(i.e.&lowest&energy)&arrangement&
of:&
a' four nitrogen atoms is as two N2 molecules and not as one N4 molecule.

b' four phosphorus atoms is as one P4 molecule and not as two P2 molecules.
(Bond energies in kJ/mol: N≡N is 945, N"N is 158, P≡P is 481 and P"P is 198).

13' Atoms in the compound whose formula is HOCN are able to bond together as either
H"O"C≡N or as H"N=C=O and still obey the bonding rules. Which of these two
possible arrangements of the four atoms is the more energetically favourable?
Bond energies in kJ/mol: H"O is 463, O"C is 358, C≡N is 890 in H–O–C≡N,
H"N is 391, N=C is 615, C=O is ~745 in H–N=C=O

14' Atoms form covalent bonds by overlapping their outermost (valence electron shell)
orbitals. The table shows bond lengths (in pm) and bond energies (in kJ/mol) for
covalent single bonds attaching hydrogen to several other elements.

Bond H'" N" H'" O" H'" F" H'" P" H'" S" H'" Cl"

Bond length 101 97 92 142 134 128

Bond energy 391 463 567 322 364 431

a' Explain why these bond lengths tend to decrease on going across a period but
increase on going down a group.

b' Explain why short bonds are stronger (i.e. require more energy to break them)
than are longer bonds.

15' The table shows bond lengths (in pm) and bond energies (in kJ/mol) for covalent
bonds between carbon and several other elements.

Bond C"C" C=C" C≡C" C"N" C=N" C≡N" C"O" C=O"

Bond length 154 134 120 147 130 116 143 122

Bond energy 346 614 839 286 615 890 358 745

a' Explain why a double bond is shorter than a single bond but longer than a triple
bond for any pair of atoms.

b' Explain why a double bond is stronger than a single bond but weaker than a
triple bond for any pair of atoms.
 c' Explain why a bond between a carbon atom and a nitrogen atom is shorter than a
similar bond between two carbon atoms but is longer than a similar bond
between a carbon atom and an oxygen atom.

d' Using these data, estimate the bond length and bond energy of the triple bond in
the C≡O (carbon monoxide) molecule.

"