PPTBK 1 CH 08 EE

8
Covalent Bonding
8.1 Formation of Covalent Bonds 8.2 Dative Covalent Bonds 8.3 Bond Enthalpies 8.4 Estimation of Average Bond Enthalpies using Data from Energetics
New Way Chemistry for Hong Kong A-Level Book 1
8.5
8.6 Radii 8.7 Shapes of Covalent Molecules and Polyatomic Ions 8.8 Multiple Bonds 8.9 Covalent Crystals
Use of Average Bond Enthalpies to Estimate the Enthalpy Changes of Reactions Bond Enthalpies, Bond Lengths and Covalent
8. 1 Formation of Covalent Bonds
8.1 Formation of Covalent Bonds (SB p.213)
A. Electron Sharing in Covalent Bonds

H H
Shared electrons Attraction between oppositely charged nuclei and shared electrons electrostatic ( _____________ in nature)
ee-
The shared electron pair spends most of the time between the two nuclei.
Overlapping of atomic orbitals covalent bond formation Overlapping of atomic orbitals covalent bond formation
4 New Way Chemistry for Hong Kong A-Level Book 1
A hydrogen molecule is achieved by partial overlapping of 1s orbitals
Electron density map for covalent compounds

There is substantial electron density at all points along the internuclear axis. Thus electrons are shared between the two atoms.
Compare electrondensity-map for ionic compounds:
B. Covalent Bonds in Elements

Hydrogen molecule
Dot and cross diagram Dot and cross diagram
Chlorine molecule
Oxygen molecule
Nitrogen molecule
C. Covalent Bonds in Compounds
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8.1 Formation of Covalent Bonds (SB p.216 217)
D. Octet Rule and its Limitations

In forming chemical bonds, atoms tend to In forming chemical bonds, atoms tend to achieve the stable noble gas electronic achieve the stable noble gas electronic configuration with 8 electrons in the valence configuration with 8 electrons in the valence shell (except helium which has 2 electrons in shell (except helium which has 2 electrons in the valence shell) by gaining, losing or the valence shell) by gaining, losing or sharing of electrons. sharing of electrons.
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1. Boron Trifluoride (BF3)

electrons from F
not fullfilling octect (electron deficient)
B: small atomic B: small atomic size high I.E.s size high I.E.s required to required to become a cation. become a cation.
Why doesnt B form ionic compounds with F? Why doesnt B form ionic compounds with F?
2. Phosphorus Pentachloride (PCl5)
electrons from Cl There is low-lying There is low-lying vacant d-orbital in vacant d-orbital in P. P.
Why Phosphorus can expand its octet to form PCl ? Why Phosphorus can expand its octet to form PCl55?
Check Point 8-1
8. 2 Dative Covalent Bonds
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8.2 Dative Covalent Bonds (SB p.218)
Dative Covalent Bonds

A dative covalent bond is formed by the A dative covalent bond is formed by the overlapping of an empty orbital of an atom overlapping of an empty orbital of an atom with an orbital occupied by a lone pair of with an orbital occupied by a lone pair of electrons of another atom. electrons of another atom.
Remarks (1) The atom that supplies the shared pair of electrons is known as the donor while the other atom involved in the dative covalent bond is known as the acceptor. (2) Once formed, a dative covalent bond cannot be distinguished from a normal covalent bond.
8.2 Dative Covalent Bonds (SB p.218 219)
A. NH3BF3 molecule
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B. Ammonium Ion (NH4+)
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D. Aluminium Chloride Dimer (Al2Cl6)

Al: relative small Al: relative small atomic size; high atomic size; high I.E.s required to I.E.s required to become a cation become a cation of +3 charge. of +3 charge. AlCl3
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D. Aluminium Chloride Dimer (Al2Cl6)

Why doesnt Al form ionic compounds with Cl? Why doesnt Al form ionic compounds with Cl? (a dimer of AlCl3)
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Check Point New Way Chemistry for Hong Kong A-Level Book 1 8-2
8. 3 Bond Enthalpies
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8.3 Bond Enthalpies (SB p.220)
Bond Enthalpy
Bond enthalpy is the energy associated with a Bond enthalpy is the energy associated with a chemical bond. When a chemical bond is chemical bond. When a chemical bond is broken or formed, a certain amount of energy broken or formed, a certain amount of energy is absorbed from or released to the is absorbed from or released to the surroundings. surroundings.
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Example: Combustion of methane
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Standard enthalpy changes of combustion of the homologous series of alkanes and alkanols
Bond Dissoication Enthalpy

Bond dissociation enthalpy is the enthalpy Bond dissociation enthalpy is the enthalpy change when one mole of a particular bond in change when one mole of a particular bond in a particular environment is broken under a particular environment is broken under standard conditions. standard conditions.
e.g. H-H(g) 2H(g) H = +431 kJ mol-1
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CH4(g) CH3(g) CH2(g) CH(g)
CH3(g) + H(g) CH2(g) + H(g) CH(g) + H(g) C(g) + H(g)
H = +422 kJ mol-1 H = +480 kJ mol-1 H = +425 kJ mol-1 H = +335 kJ mol-1

Why do successive B.D.E. of C-H differ? Why do successive B.D.E. of C-H differ? (Average) bond enthalpy; E(C-H) ( +422) + ( +480) + ( +425) + ( +335) = 4 = +415.5 kJ mol-1
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Average Bond Enthalpies

Average bond enthalpy is the average of the Average bond enthalpy is the average of the bond dissociation enthalpies required to break bond dissociation enthalpies required to break a particular chemical bond. a particular chemical bond.
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8. 4 Estimation of Average Bond Enthalpies using Data from

8.4 Estimation of Average Bond Enthalpies using Data from Enegetics (SB p.223)
A. Derived from the Enthalpy Change of Atomization of a Compound

Atomization of a compound means the Atomization of a compound means the breaking down of one mole of the gaseous breaking down of one mole of the gaseous compound into its constituent atoms in the compound into its constituent atoms in the gaseous state. gaseous state.
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Example: Atomization of methane

C(g) + 4H(g) H = +1 662 kJ mol-1
The atomization of methane involves the breaking of a four C-H bonds. Assume that all four C-H bonds are equal in strength. The average bond enthalpy of C-H bonds = x (+1 662) kJ mol-1 = +415.5 kJ mol-1 E(C-H) = +415.5 kJ mol-1 E(C-H) = +415.5 kJ mol-1
Two ways to determine the enthalpy change of atomization of methane: 1. From successive bond dissociation enthalpies 2. From enthalpy cycle and Hesss law
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8.4 Estimation of Average Bond Enthalpies using Data from Enegetics (SB p.224 225)
B. Derived from the Enthalpy Changes of Atomization of Two Compounds

The enthalpy change of atomization of butane (C4H10 ) and pentane (C5H12 ) are +5165 kJ mol-1 and +6337 kJ mol-1 respectively. Find a values for the bond enthalpies of C-H and C-C based on the above data.
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8.4 Estimation of Average Bond Enthalpies using Data from Enegetics (SB p.224 225)
B. Derived from the Enthalpy Changes of Atomization of Two Compounds

For butane, 3 E(C-C) + 10 E(C-H) = +5 165 kJ mol-1 .(1) For pentane, 4 E(C-C) + 12 E(C-H) = +6 337 kJ mol-1 .(2) Solving simultaneous equations (1) and (2), we obtain the following bond enthalpy values. E (C-H) = +412.25 kJ mol-1 E (C-C) = +347.5 kJ mol-1
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8. 5 Use of Average Bond Enthalpies to Estimate the Enthalpy Changes of Reactions

8.5 Use of Average Bond Enthalpies to Estimate the Enthalpy Changes of Reactions (SB p.225)
Reaction between ethene and hydrogen
Enthalpy change of reaction

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Sum of bond enthalpies of reactants
Sum of bond enthalpies of products
Enthalpy level diagram for the reaction between ethene and hydrogen
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Reaction between methane and oxygen
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Check Point New Way Chemistry for Hong Kong A-Level Book 1 8-5
8. 6 Bond Enthalpies, Bond Lengths and Covalent Radii

8.6 Bond Enthalpies, Bond Lengths and Covalent Radii (SB p.227)
A. Bond Enthalpies as an Indication of the Strength of Covalent Bonds

Gives a direct measure of the strength of a covalent bond It is the energy required to break the bond Not in proportion to the bond order (The number of bonding electrons divided by two)
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B. Bond Lengths
The distance between the two bonded nuclei Inversely related to bond strength Not constant Depends on the local environment of that particular bond Determined experimentally by electron diffraction, X-ray diffraction or spectroscopic techniques
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C. Relationship between Bond Lengths and Bond Enthalpies

Bond H-H Cl-Cl Br-Br I-I H-F H-Cl H-Br H-I
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Bond length (nm) 0.074 0.199 0.228 0.266 0.092 0.127 0.141 0.161
Bond enthalpy (kJ mol-1 ) 436 242 193 151 565 431 364 299
Any conclusion for Any conclusion for the relationship the relationship between bond between bond length & bond length & bond enthalpy? enthalpy? Usually a longer Usually a longer bond length bond length corresponds to corresponds to a lower value of a lower value of bond enthalpy bond enthalpy (weaker bond). (weaker bond).
Special Situation for F2

Bond F-F Cl-Cl Br-Br I-I Bond Length /nm 0.142 0.199 0.228 0.266 Bond Enthalpy / kJ mol-1 158 242 193 151
Explain why the bond enthalpy of F-F is smaller than that of Cl-Cl even though the bond length of F-F is the shortest among the halogens.
As the size of fluorine atom is very small, the repulsion between the non-bonding pairs of electrons on the fluorine atoms weaken the F-F bond.
Non-bonding e/ lone pair of eF F
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D. Covalent Radii
Half the internuclear distance between two atoms in a covalently bonded molecule Generally taken as half of the bond length of homoatomic covalent molecules (where identical atoms are bonded together)
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The covalent radius of an atom is taken as half of the bond length of a homoatomic molecule
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The covalent radii (in nm) of some elements

Predicting bond length of A-B if A & B are known Predicting bond length of A-B if rrA& rrBare known Bond length of a covalent bond A-B
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Covalent radius of atom A
Covalent radius of atom B
8.6 Bond Enthalpies, Bond Lengths and Covalent Radii (SB p.229 230)
Calculated and experimentally determined bond length

Similar electronegativity Bond C-O C-F C-Cl C-Br C-C H-Cl C-H N-Cl
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By what technique can the bond lengths By what technique can the bond lengths be determined experimentally? be determined experimentally?
Calculated bond length Experimentally determined (nm) bond length (nm) 0.150 0.149 0.176 0.191 0.154 0.136 0.114 0.173
0.143 0.138 0.177 0.193 0.154 0.128 0.109 0.174
8.6 Bond Enthalpies, Bond Lengths and Covalent Radii (SB p.229 230)
Calculated and experimentally determined bond length

Quite different electronegativity Bond C-O C-F C-Cl C-Br C-C H-Cl C-H N-Cl
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Check Point 8-6

0.150 0.149 0.176 0.191 0.154 0.136 0.114 0.173 0.143 0.138 0.177 0.193 0.154 0.128 0.109 0.174
Calculated bond length Experimentally determined (nm) bond length (nm)
8. 7 Shapes of Covalent Molecules and Polyatomic Ions

8.6 Shapes of Covalent Molecules and Polyatomic Ions (SB p.231)
Shapes of Covalent Molecules and Polyatomic Ions

Geometric arrangement of atoms within the molecules or ions The non-bonding electrons (i.e. the lone pair electrons) are not taken into account
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Valence shell electron pair repulsion theory

Electron pairs in the valence shell of the Electron pairs in the valence shell of the central atom of a molecule will stay as far central atom of a molecule will stay as far apart as possible to minimize the electrostatic apart as possible to minimize the electrostatic repulsion between electron pairs in the repulsion between electron pairs in the valence shell. The electron pairs are oriented valence shell. The electron pairs are oriented with the maximum separation in space so as with the maximum separation in space so as to minimize the coulombic repulsion of to minimize the coulombic repulsion of electron clouds. electron clouds.
A. Molecules and Polyatomic Ions without Lone Pair Electrons on the Central Atom
Examples: 1. Beryllium Chloride (BeCl2) Molecule 2. Boron Trifluoride (BF3) Molecule 3. Methane (CH4) Molecule 4. Ammonium Ion (NH4+) 5. Phosphorus Pentachloride (PCl5) Molecule
53 New Hexafluoride (SF ) Molecule 6. SulphurWay Chemistry for Hong Kong A-Level Book 1 6
1. Beryllium Chloride Molecule (BeCl2)

Electronic Diagram Shape in Diagram
Cl
Be
Cl
Shape in word
Linear
Bond angle Bond angle = angle between = angle between 2 bonds 2 bonds
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2. Boron Trifluoride Molecule (BF3)

B F F
Shape in word Trigonal planar
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3. Methane (CH4) Molecule

Shape in word Tetrahedral
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4. Ammonium Molecule (NH4+)

Shape in word Tetrahedral
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5. Phosphorus Pentachloride (PCl5) Molecule

Cl Cl P Cl Cl Cl
Shape in word Trigonal bipyramidal

6. Sulphur Hexafluoride (SF6) Molecule

F F S F F F F
Shape in word Octahedral
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B. Molecules and Polyatomic Ions with Lone Pair Electrons on the Central Atom
The valence shell electron pair repulsion theory states Electrostatic repulsion decreases in the following order: Lone pair lone pair > Lone pair bond pair > Bond pair bond pair
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B. Molecules and Polyatomic Ions with Lone Pair Electrons on the Central Atom
Examples: 1. Ammonia (NH3) Molecule 2. Water (H2O) Molecule 3. Amide Ion (NH2)
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1. Ammonia (NH3) Molecule

lp-lp repulsion > lp-bp repulsion lp-lp repulsion > lp-bp repulsion
Shape in word Trigonal pyramidal
> bp-bp repulsion > bp-bp repulsion Chemistry for Hong Kong A-Level Book 1 62 New Way
2. Water (H2O) Molecule

lp-lp repulsion > lp-bp repulsion lp-lp repulsion > lp-bp repulsion > bp-bp repulsion > bp-bp repulsion
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Shape in word V-shaped
3. Amide Ion (NH2)

lp-lp repulsion > lp-bp repulsion lp-lp repulsion > lp-bp repulsion > bp-bp repulsion > bp-bp repulsion
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8.6 Shapes of Covalent Molecules and Polyatomic Ions (SB p.237 238)
Example 8-7A
Example 8-7B
Check Point 8-7
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8. 8 Multiple Bonds Multiple
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8.8 Multiple Bonds (SB p.238)
Single Bonds
A covalent bond with two shared electrons
Multiple Bonds
Some atoms share more than two electrons in a bond e.g. double bond, triple bond
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Comparison of bond lengths and bond enthalpies between single and multiple bonds
Bond CC C=C C C NN N=N N N CO C=O Bond order 1 2 3 1 2 3 1 2 Bond length (nm) 0.154 0.134 0.120 0.146 0.120 0.110 0.143 0.122 Bond enthalpy (kJ mol-1 ) +348 +612 +837 +163 +409 +944 +360 +743
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Effect of Multiple Bonding on Shapes of Molecules

Predict the shapes of molecules or polyatomic ions with multiple bonds Examples: 1. Ethene (CH2 = CH2) Molecule 2. Ethyne (CH CH) Molecule 3. Carbon Dioxide (CO2) Molecule 4. Sulphur Dioxide (SO2) Molecule
1. Ethene (CH2 = CH2) Molecule

H C H C
Shape in word Trigonal planar

2. Ethyne (CH CH) Molecule

Shape in word Linear

3. Carbon dioxide (CO2) Molecule

Shape in word Linear

4. Sulphur dioxide (SO2) Molecule

Check Point 8-8

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8. 9 Covalent Crystals
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8.9 Covalent Crystals (SB p.240)
Covalent Crystals
May have simple molecular structures or giant covalent structures
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Substances with Simple Molecular Structures

Consist of discrete molecules held together by weak intermolecular forces Atoms in a molecule are held together by strong covalent bonds Examples: H2 , O2 , H2O, CO2, I2
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Substances with Giant Covalent Structures

Consist of millions of atoms bonded covalently together in a structural network No simple molecules present Examples: diamond, graphite and quartz (silicon(IV) oxide)
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1. Diamond
Each C atom is covalently bonded to 4 other C atoms to form a three-dimensional network The C C bonding pattern accounts for the high m.p., stability and extreme hardness Applications: scratch proof cookware, watch crystals, ball bearings and razor blade
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A diamond crystal
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The structure of diamond
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2. Graphite
Each C atom is covalently bonded to 3 other C atoms in the same layer. A network of coplanar hexagons is formed Weak van der Waals forces hold the layers togetherDelocalized e- free to move within layers Properties: soft and slippery (used as pencil lead), conductor
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Graphite
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The structure of graphite

Comparison of the properties of diamond and graphite

Property Density (g cm-3 ) Hardness Melting point (C) Colour Electrical conductivity Diamond 3.51 10 (hardest) 3 827 Colourless None Graphite 2.27 < 1 (very soft) 3 652 (sublime) Shiny black High
Why graphite has a high m.p. than that of diamond? Why graphite has a high m.p. than that of diamond?
3. Quartz
Each Si atom is bonded tetrahedrally to 4 neighbouring O atoms Each O atom is bonded to 2 Si atoms, one at the centre of each of two adjacent tetrahedral Gives rise to a tetrahedral diamondlike structure in quartz
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Quartz
The structure of quartz

The END
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(a) How many lone pair and bond pair electrons are present in NH3 and H2O Answer molecules one lone pair and three bond pairs of electrons. respectively? (a) Ammonia has
Water has two lone pairs and two bond pairs of electrons.
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(b) Nitrogen can only form one chloride, NCl3, while phosphorus can form two chlorides, PCl3 and PCl5. Explain briefly.
Answer
(b) The electronic configuration of nitrogen is 1s22s22px12py12pz1. Its outermost shell electrons are filled in the second quantum shell. There are no lowlying d orbitals available for nitrogen to expand octet. It has a maximum of three half-filled p orbitals to form three bonds, i.e. NCl3.
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(b) The ground state electronic configuration of phosphorus is 1s22s22p63s23px13py13pz1. It has three half-filled p obitals for bond formation. Thus, three chlorine atoms can form bonds with it to give PCl3. After promoting one 3s electron to the low-lying d orbitals, the excited state electronic configuration of phosphorus becomes 1s22s22p63s13px13py13pz13d1. It now has five half-filled orbitals available for bond formation. Therefore, five chloride atoms can form bonds with it to give PCl5.
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(b) Phosphorus has low-lying d orbitals which allow it to expand octet (contain more than eight outermost shell electrons) whereas nitrogen has not.
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(a) Draw a dot and cross diagram for the product formed in the reaction between an ammonia molecule and a hydrogen chloride Answer molecule.
(a)
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(b) There is a dative covalent bond present in a HNO3 molecule. Draw a dot and cross diagram of the molecule.
Answer
(b)
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(c) State the major difference between an ordinary and a dative covalent bond.
(c) A dative covalent bond is covalent bond in which the shared pair of electrons is supplied by only one of the bonded atoms, whereas electrons in an ordinary covalent bond come from both bonded atoms.
Answer
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Why do two atoms bond together? How does covalent bond strength compare with ionic bond strength?
They are of similar strength. For example, the lattice enthalpy of NaCl is 771 kJ mol1 while the HH bond enthaly is 436 kJ mol1 . It is a misconception that ionic bond must be stronger (or weaker) than covalent bond.
Answer
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(a) (i)
(a) Referring to Table 8-2 on page 222, calculate the enthalpy change for the following reactions and state whether the reactions are endothermic or exothermic. (i) Reaction between nitrogen and hydrogen. Answer N2(g) + 3H2(g) 2NH3( g)
Sum of average bond enthalpies of reactants = E(N N) + 3 E(H H) = [+944 + 3 (+436)] kJ mol1 = +2 252 kJ mol1
(a) (i) Sum of average bond enthalpies of products = 6 E(N H) = 6 (+388) kJ mol1 = +2 238 kJ mol1 H = [+2 252 (+2 328)] kJ mol1 = 76 kJ mol1 The reaction is exothermic.
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(a) (ii) Reaction between hydrogen and chlorine. H2(g) + Cl2(g) 2HCl(g) Answer
(a) (ii) H H + Cl Cl 2H Cl Sum of average bond enthalpies of reactants = E(H H) + E(Cl Cl) = (+436 + 242) kJ mol1 = +678 kJ mol1
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(a) (ii) Sum of average bond enthalpies of products = 2 E(N Cl) = 2 (+431) kJ mol1 = +862 kJ mol1 H = [+678 (+862)] kJ mol1 = 184 kJ mol1 The reaction is exothermic.
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(a)
(a) (iii)
(iii) Complete combustion of hydrogen.
Answer
Sum of average bond enthalpies of reactants = 2 E(H H) + E(O = O) = [2 (+436) + 496] kJ mol1 = +1 368 kJ mol1
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(a) (iii) Sum of average bond enthalpies of products = 4 E(O H) = 4 (+463) kJ mol1 = +1 852 kJ mol1 H = [+1 368 (+1 852)] kJ mol1 = 484 kJ mol1 The reaction is exothermic.
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(a)
(a) (iv)
(iv) Complete combustion of ethanol.
Answer
Sum of average bond enthalpies of reactants = E(C C) + E(C O) + E(O H) + 5 E(C H) + 3 E(O = O) = [+348 + 360 + 463 + 5 (+412) + 3 (+496)] kJ mol1 = +4 719 kJ mol1
(a) (iv) Sum of average bond enthalpies of products = 4 E(C = O) + 6 E(O H) = [4 (+743) + 6 (+463)] kJ mol1 = +5 750 kJ mol1 H = [+4 719 (+5 750)] kJ mol1 = 1031 kJ mol1 The reaction is exothermic.
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(a)
(a) (v)
(v)
Complete combustion of octane.
Answer
Sum of average bond enthalpies of reactants = 14 E(C C) + 36 E(C H) + 25 E(O = O) = [14 (+348) + 36 (+412) + 25 (+496)] kJ mol1 = +32 104 kJ mol1
(a) (iv) Sum of average bond enthalpies of products = 32 E(C = O) + 36 E(O H) = [32 (+743) + 36 (+463)] kJ mol1 = +40 444 kJ mol1 H = [+32 104 (+40 444)] kJ mol1 = 8 340 kJ mol1 The reaction is exothermic.
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(b) Calculate the enthalpy change for the reaction CH4(g) + H2O(g) CO(g) + 3H2(g) using the following bond enthalpies. E(C H in CH4) = +435 kJ mol1 E(C O in CO) = +1 078 kJ mol1 E(H H in H2) = +436 kJ mol1 E(H O in H2O) = +464 kJ mol
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1
Answer
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(b) CH4(g) + H2O CO(g) + 3H2(g) Sum of average bond enthalpies of reactants = 4 E(C H) + 2 E(O H) = [4 (+435) + 2 (+464)] kJ mol1 = +2 668 kJ mol1 Sum of average bond enthalpies of products = E(C O) + 3 E(H H) = [+1 078 + 3 (+436)] kJ mol1 = +2 386 kJ mol1 H = [+2 668 (+2 386)] kJ mol1 = +282 kJ mol1
Why does the covalent radius of a given element change from one compound to another compound?
The size of an atom (its covalent radius) is not fixed. It is because the size of an atom is determined by its electron cloud which has a diffuse shape. In different compounds, the electron cloud of a given atom may vary slightly due to the different internal environment (i.e. the atom that is bonded to).
Answer
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(a)
Predict the approximate bond lengths of
Si H, P H, S H and H Cl from the following data: Bond Bond length (nm) HH Si Si P P (P4) S S (S4) Cl Cl 0.074 0.235 0.221 0.207 0.199
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(Hint: Assume that covalent radii are additive.) New Way Chemistry for Hong Kong A-Level Book 1
Answer
0.235 0.074 nm + nm (a) Bond length of Si H = 2 2 = 0.154 5 nm 0.221 0.074 nm + nm Bond length of P H = 2 2 = 0.147 5 nm 0.207 0.074 nm + nm Bond length of S H = 2 2 = 0.140 5 nm 0.074 0.199 nm + nm Bond length of H Cl = 2 2 = 0.136 5 nm
(b) The bond enthalpies of Si H, P H, S H and H Cl are given in the following table: Bond Si H PH SH Cl H Bond enthalpies (kJ mol1 ) +318 +322 +338 +431
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Assume the actual bond lengths are very close to that calculated in (a), describe the relationship between bond length and bond Answer enthalpy. New Way Chemistry for Hong Kong A-Level Book 1
(b) The bond enthalpy of a covalent bond is related to the length. The larger the bond length, the weaker the attractive force between the two bonded atoms and the smaller is the bond enthalpy.
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(a) Explain why a molecule of CCl4 is tetrahedral, but a molecule of NCl3 is trigonal pyramidal in shape. (a) In a CCl molecule, there are four bond pairs of electrons Answer on the central
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carbon atom. The bond pairs have to stay as far away as possible. They take up the shape of a tetrahedron and thus the molecule is tetrahedral in shape. The four electron pairs in a NCl3 molecule take up the shape of a tetrahedron as well. However, one of the electron pairs is a lone pair and the other three are bond pairs. The shape of a NCl3 molecule is thus trigonal pyramidal.
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(b) Deduce the shape of a molecule of BCl3.
(b) A BCl3 molecule has six outermost shell electrons around the central boron atom, forming three bond pairs. The shape of the BCl3 molecule is thus trigonal planar.
Answer
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7.5 Ionic Radii (SB p.208)
(c) Draw the structures of molecules of XeF2, XeF4 and XeF6 where Xe is a noble gas element with eight electrons in its outermost Answer shell.
(c)
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The following data refer to the molecules NH3, H2O and HF. Molecule Bond length (nm) Bond angle NH3 H2O HF 0.101 0.096 0.092 107 104.5
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(a) Briefly explain the variation in bond length.

(a) The bond lengths of the three molecules decrease as follows: HN 0.101 nm HO 0.096 nm HF 0.092 nm
Answer
The atomic radius of H is the same in the three molecules, so the bond lengths of the molecules depend on the size of the N, O and F atoms. N, O and F are in the same period in the Periodic Table. Since atomic sizes decrease across a period owing to the increase in effective nuclear charge, the bond lengths of the three molecules decrease accordingly.
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(b) Explain why the bond angle of H2O is less than that of NH3.
theory.
Answer (b) This can be explained by the valence shell electron pair repulsion
The central oxygen atom in H2O has two lone pairs and two bond pairs of electrons while the central nitrogen atom in NH3 has one lone pair and three bond pairs of electrons. The electrostatic repulsion between electron pairs decreases in this order: lone pair and lone pair > lone pair and bond pair > bond pair and bond pair Thus, the bond angle of H2O is less than that of NH3.
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(c) Match the following bond enthalpies to the bonds in the above three molecules: +562 kJ moll , +388 kJ moll , +463 kJ moll
(c) The bond enthalpies are: HN +388 kJ moll HO +463 kJ moll HF +562 kJ moll
Answer
The bond enthalpies increase as shown owing to the decrease in bond length and increase in polarity of bonds.
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What are the shapes of a H2S molecule and a H3O+ ion? Explain their shapes in terms of the valence shell Answer electron pair repulsion theory.
H2S molecule is V-shaped. In H2S molecule, there are two bond pairs and two lone pairs of electrons in the outermost shell of the central sulphur atom. All three types of electrostatic repulsion (lone pair lone pair, lone pair bond pair, bond pair bond pair) are present. The two lone pairs will stay the furthest apart and the separation between the lone pair and a bond will be greater that that between the two bond pairs. Therefore, the H S H bond angle in the H2S molecule is about 104.5 instead of 109.5 in tetrahedron.
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H3O+ ion has a trigonal pyramidal shape. In H3O+ ion, the central oxygen atom forms two covalent bonds with two hydrogen atoms respectively. Also, one dative covalent bond is formed between the oxygen atom and the remaining hydrogen ion. We can regard the central oxygen atom has three bond pairs and one lone pair of electrons. According to the valence shell electron pair repulsion theory, the lone pair will stay further away from the three bond pairs. The three bond pairs are in turn compressed closer together. Thus, the H O H bond angles in the H3O+ ion are about 107 instead of 109.5 in tetrahedron.
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(a) Does sulphur obey the octet rule in forming a SO2 molecule? Explain your answer.
Answer
(a) In the formation of SO2 molecule, sulphur does not obey the octet rule because sulphur has 10 electrons in its outermost shell.
123
Back (b) Draw a dot and cross diagram of the hydrogen cyanide molecule (HCN). Describe and explain the shape of the molecule.
Answer
(b)
HCN molecules has a linear shape as the central carbon atom does not have any lone pair electrons. In order to minimize electrostatic repulsion, the two electron clouds of the central carbon atom are separated at a maximum with bond angles of 180.
124

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8

New Way Chemistry for Hong Kong A-Level Book 1

New Way Chemistry for Hong Kong A-Level Book 1

8. 1 Formation of Covalent Bonds

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.213)

A. Electron Sharing in Covalent Bonds

8.1 Formation of Covalent Bonds (SB p.213)

A hydrogen molecule is achieved by partial overlapping of 1s orbitals

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.214)

Electron density map for covalent compounds

Compare electrondensity-map for ionic compounds:

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.214)

B. Covalent Bonds in Elements

Dot and cross diagram Dot and cross diagram

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.215)

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.215)

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.216)

C. Covalent Bonds in Compounds

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.216)

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.216 217)

D. Octet Rule and its Limitations

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.217)

1. Boron Trifluoride (BF3)

not fullfilling octect (electron deficient)

2. Phosphorus Pentachloride (PCl5)

8.1 Formation of Covalent Bonds (SB p.207)

Check Point 8-1

8. 2 Dative Covalent Bonds

New Way Chemistry for Hong Kong A-Level Book 1

8.2 Dative Covalent Bonds (SB p.218)

Dative Covalent Bonds

8.2 Dative Covalent Bonds (SB p.218 219)

New Way Chemistry for Hong Kong A-Level Book 1

8.2 Dative Covalent Bonds (SB p.219)

B. Ammonium Ion (NH4+)

New Way Chemistry for Hong Kong A-Level Book 1

8.2 Dative Covalent Bonds (SB p.219 220)

D. Aluminium Chloride Dimer (Al2Cl6)

New Way Chemistry for Hong Kong A-Level Book 1

8.2 Dative Covalent Bonds (SB p.219 220)

D. Aluminium Chloride Dimer (Al2Cl6)

New Way Chemistry for Hong Kong A-Level Book 1

8.3 Bond Enthalpies (SB p.220)

New Way Chemistry for Hong Kong A-Level Book 1

8.3 Bond Enthalpies (SB p.220)

Example: Combustion of methane

New Way Chemistry for Hong Kong A-Level Book 1

8.3 Bond Enthalpies (SB p.221)

8.3 Bond Enthalpies (SB p.221)

Bond Dissoication Enthalpy

New Way Chemistry for Hong Kong A-Level Book 1

8.3 Bond Enthalpies (SB p.221)

CH4(g) CH3(g) CH2(g) CH(g)