Ch08 - Covalent Bonding

Chapter 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
1 New Way Chemistry for Hong Kong A-Level Book 1
8.5 Use of Average Bond Enthalpies to

Estimate Enthalpy Changes of Reactions 8.6 Relationship between Bond Enthalpies and Bond Lengths 8.7 Shapes of Covalent Molecules and Polyatomic Ions 8.8 Multiple Bonds 8.9 Covalent Crystals
8.1 Formation of Covalent Bonds (SB p.213)
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
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 inter-nuclear axis. Electrons are shared between the two atoms.
Compare electrondensity-map for ionic compounds:
Electron density map for ionic compounds
Covalent Bonds in Elements

Some Examples
Dot and cross diagram
Covalent Bonds in Compounds

Some Examples All the above examples obey ____________. Octet rule
Carbon
1s
8
2s
2p
Covalent Bonds in Compounds

Some Examples Octet rule All the above examples obey ____________.
octet Carbon Excited state

9
1s
2s
2p
electrons from H
8.1 Formation of Covalent Bonds (SB p.217-8)
Octet Rule and its limitations

electrons from F
BF3
not fulfilling octet (electron deficient)
B: small atomic size
high I.E.s required to become a cation.
Why doesnt B form ionic compounds with F?

8.1 Formation of Covalent Bonds (SB p.217-8)
Octet Rule and its limitations
PCl5
electrons from Cl There is low-lying vacant d-orbital in P.
Why Phosphorus can expand its octet to form PCl5?

8.2 Dative Covalent Bonds (SB p.218)
A dative covalent bond is formed by the overlapping of an empty orbital of an atom with an orbital occupied by a lone pair of electrons of another atom.
NH3BF3 Molecule
12
Dative Covalent Bonds

The dative covalent bond (also known as the coordinate bond) is a type of covalent bond in which the shared pair of electrons is supplied by only one of the bonded atoms.
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.
Ammonium Ion (NH4+)
14
Aluminium Chloride Dimer (Al2Cl6)

Al: relative small atomic size; high I.E.s required to become a cation of +3 charge.
AlCl3
Why doesnt Al form ionic compounds with Cl? (a dimer of AlCl3)
15
8.3 Bond Enthalpies (SB p.221)
Bond Enthalpies
Bond Dissociation Enthalpies B.D.E of a certain bond is the amount of energy required to break one mole of that bond under standard conditions. e.g. H-H(g) 2H(g) H (H-H) = +431 kJ mol-1 CH4(g) CH3(g) + H(g) H = +422 kJ mol-1 CH3(g) CH2(g) + H(g) H = +480 kJ mol-1
CH2(g)
CH(g)
CH(g) + H(g)
C(g) + H(g)
H = +425 kJ mol-1
H = +335 kJ mol-1
( 422) ( 480) ( 425) ( 335) 4 = +415.5 kJ mol-1
Why do successive B.D.E. of C-H differ?

(Average) bond enthalpy; E(C-H)
17
8.3 Bond Enthalpies (SB p.222)
Bond Enthalpies
Bond Average bond enthalpy (kJ mol-1)
HH CC C C C C CH OH
+436 +348 +612 +837 +412 +463
Why is this value of E(C-H) still different from the previously calculated one (+415.5 kJ mol-1)?
8.4 Estimation of Average Bond Enthalpies using Data from Energetics (SB p.223)
From the Enthalpy Change of Atomization of a Compound

The enthalpy change of atomization of methane (CH4) is +1662 kJ mol-1. Find a value for the bond enthalpy of C-H based on the above data.
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
8.4 Estimation of Average Bond Enthalpies using Data from Energetics (SB p.223)
The standard enthalpy change of atomization of a compound is the enthalpy change when one mole of gaseous compound is broken down into its constituent atoms in the gaseous state under standard conditions, e.g.
CH4(g) C(g) + 4H(g) 1 mole The standard enthalpy change of atomization of a element is the enthalpy change when one mole of gaseous atoms is formed into its constituent atoms in the gaseous state under standard conditions, e.g. Cl2(g) Cl(g) 1 mole
20
8.4 Estimation of Average Bond Enthalpies using Data from Energetics (SB p.224-225)
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. 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
8.5 Use of Average Bond Enthalpies to Estimate Enthalpy Changes of Reactions (SB p.225)
Reaction of ethene and hydrogen
Enthalpy change
of reaction
22
Sum of bond enthalpies of reactants
Sum of bond enthalpies of products
Enthalpy profile for the reaction of ethene and hydrogen
23
Reaction of ethene and hydrogen

?
Sum of bond enthalpies of reactants = E(C=C) + 4E(C-H) + E(H-H) = (612) + 4(412) + (436) = +2696 kJmol-1
Sum of bond enthalpies of products = E(C-C) + 6E(C-H) = (348) + 6(412) = +2820 kJmol-1
Hr = 2696 - (+2820) = -124 kJ mol-1
Only an estimated value for Hr .Why?
24
8.6 Relationship between Bond Enthalpies and Bond Lengths (SB p.227)
Bond Enthalpies as an Indication of the Strength of Covalent Bonds Bond Average bond enthalpy (kJ mol-1)
HH CC C C C C CH OH
+436 +348 +612 +837 +412 +463
Consider C-C, C=C and CC

bond order =1 bond order =2 bond order =3
As the bond order increases, the bond strength also increases.

Bond Lengths
Bond length (for covalent bond)
26
Bond lengths of some covalent bonds

Bond O-H Molecule H2O H2 O2 CH3OH HCOOH Diamond C2H6 C3H8 C2H5OH CH4 C2H4 Bond lengths (nm) 0.096 0.097 0.096 0.096 0.154 0.154 0.154 0.155 0.110 0.109
C-C
C-H
By what technique can these bond lengths be measured? X-ray diffraction

Bond enthalpies and bond lengths

Bond Bond length (nm) Bond enthalpy (kJ mol-1) Any conclusion for the relationship between bond length & bond enthalpy?
H-H Cl-Cl Br-Br I-I H-F H-Cl H-Br H-I

28
0.074 0.199 0.228 0.266 0.092 0.127 0.141 0.161
436 242 193 151 565 431 364 299
Usually a longer bond length corresponds to a lower value of bond enthalpy (weaker bond).
8.6 Relationship between Bond Enthalpies and Bond Lengths
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 Non-bonding ethe halogens.
/ lone pair of e-
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.
29
Covalent Radius
(often referred as Atomic radius) The space occupied by an atom in a covalently bonded molecule in the direction of the covalent bond (generally taken as half of the bond length of homoatomic molecules) Where b is the bond length r is the covalent radius
30
The covalent radii (in nm) of some elements
31
Bond length of Covalent molecule A-B
Predicting bond length of A-B if rA & rB are known Bond length of a covalent bond A-B
Covalent radius of atom A
Covalent radius of atom B
32
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
33
By what technique can the bond lengths be determined experimentally?
Calculated bond length (nm) Experimentally determined 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
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
34
Calculated bond length (nm) 0.150 0.149 0.176 0.191 0.154 0.136 0.114 0.173
Experimentally determined bond length (nm) 0.143 0.138 0.177 0.193 0.154 0.128 0.109 0.174
8.7 Shapes of Covalent Molecules and Polyatomic Ions (SB p.231)
Shapes of Molecules and Polyatomic Ions

Shape of a molecule = geometric arrangement of atoms within the molecules Valence Shell Electron Pair Repulsion Theory (VSEPR) The electron pairs in the outermost shell of the central atom in a molecule will stay as far apart as possible to minimize electronic repulsion. The electron pairs are oriented at a maximum separation in space so as to minimize the coulombic repulsion of electron clouds. TWO bond pairs in linear geometry, THREE bond pairs in trigonal planar geometry FOUR bond pairs in tetrahedral geometry FIVE bond pairs in trigonal bipyramidal geometry SIX bond pairs in octahedral geometry
Beryllium chloride molecule (BeCl2)

Electronic Diagram Shape in Diagram
Cl
Be
Cl
Shape in word
36
linear
Bond angle = angle between 2 bonds
Boron trifluoride molecule(BF3)

B F F
Shape in word
trigonal planar
37
Methane (CH4) Molecule

Shape in word tetrahedral
38
Methane (CH4) Molecule

H
H
C H
H C H
H H
bond in the plane of paper bond in front of paper bond behind paper
Shape in word tetrahedral

39
Phosphorus Pentachloride (PCl5) Molecule

Shape in word trigonal bipyramidal

Phosphorus Pentachloride (PCl5) Molecule

Cl Cl Cl P Cl Cl
Shape in word
trigonal bipyramidal
Sulphur Hexafluoride (SF6)

Electronic Diagram F F S F F F Shape in word octahedral
Shape in Diagram
Ammonia (NH3) Molecule

Shape in word lp-lp repulsion > lp-bp repulsion > bp-bp repulsion
43
Trigonal pyramidal
Ammonia (NH3) Molecule

Shape in Diagram Electronic Diagram
lone pair of e-
N
H N H
H H
bond in the plane of paper
bond in front of paper bond behind paper
Shape in word Trigonal pyramidal

Water (H2O) Molecule

lp-lp repulsion > lp-bp repulsion > bp-bp repulsion Shape in word V-shaped / bent
Water (H2O) Molecule

lone pair of e-
O H
Shape in word V-shaped / bent
46
8.8 Multiple Bonds (SB p.239)
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
47
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
Effect of Multiple Bonding on Shapes of Molecules

Ethene (CH2=CH2)
Shape in Diagram
Electronic Diagram
H C H C H H
Shape in word
(planar)
48
Ethyne (CHCH)
Shape in Diagram Shape in word linear
49
Carbon dioxide (CO2)

Shape in Diagram Shape in word
linear
50
Sulphur dioxide (SO2)

Shape in Diagram Shape in word
Angular / (bent)
51
8.9 Covalent Crystals (SB p.241)
Giant Covalent Structures

Structures consist of millions of atoms covalently bonded together in a structural network and there is no simple molecule present.
Examples diamond, graphite and quartz/silicon(IV) oxide
52
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
Graphite
Each C atom is covalently bonded to 3 other C atoms in the same layer. A network of coplanar hexagons is formed (C-C bond length: 0.142 nm) Weak van der Waals forces hold the layers together (distance between adjacent layers: 0.335 nm) Delocalized e- free to move within layers Properties: soft and slippery (used as pencil lead), conductor
Comparison of the properties of diamond and graphite

Property Diamond Graphite
Density (g cm-3) Hardness Melting point (oC) Colour Electrical conductivity
3.51 10 (hardest) 3 827 Colourless transparent None
2.27 < 1 (very soft) 3 652 (sublime) Shiny black High (along sheet)
Why graphite has a high m.p. than that of diamond?
55
Quartz /Silicon(IV) oxide
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

Ch08 - Covalent Bonding

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Ch08 - Covalent Bonding

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Chapter 8

8.5 Use of Average Bond Enthalpies to

8.1 Formation of Covalent Bonds (SB p.213)

Electron Sharing in Covalent Bonds

Overlapping of atomic orbitals covalent bond formation

New Way Chemistry for Hong Kong A-Level Book 1

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.205)

Electron density map for ionic compounds

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.215)

Covalent Bonds in Elements

Dot and cross diagram

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.216)

Covalent Bonds in Compounds

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.216)

Covalent Bonds in Compounds

octet Carbon Excited state

New Way Chemistry for Hong Kong A-Level Book 1

8.1 Formation of Covalent Bonds (SB p.217-8)

Octet Rule and its limitations

not fulfilling octet (electron deficient)

B: small atomic size

high I.E.s required to become a cation.

Why doesnt B form ionic compounds with F?

8.1 Formation of Covalent Bonds (SB p.217-8)

Octet Rule and its limitations

electrons from Cl There is low-lying vacant d-orbital in P.

Why Phosphorus can expand its octet to form PCl5?

8.2 Dative Covalent Bonds (SB p.218)

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.219)

Ammonium Ion (NH4+)

New Way Chemistry for Hong Kong A-Level Book 1

8.2 Dative Covalent Bonds (SB p.220)

Aluminium Chloride Dimer (Al2Cl6)

Why doesnt Al form ionic compounds with Cl? (a dimer of AlCl3)

New Way Chemistry for Hong Kong A-Level Book 1

8.3 Bond Enthalpies (SB p.221)

Why do successive B.D.E. of C-H differ?

New Way Chemistry for Hong Kong A-Level Book 1

8.3 Bond Enthalpies (SB p.222)

+436 +348 +612 +837 +412 +463

From the Enthalpy Change of Atomization of a Compound

New Way Chemistry for Hong Kong A-Level Book 1

From the Enthalpy Changes of Atomization of Two Compounds

Reaction of ethene and hydrogen

Sum of bond enthalpies of reactants

Sum of bond enthalpies of products

New Way Chemistry for Hong Kong A-Level Book 1

Enthalpy profile for the reaction of ethene and hydrogen

New Way Chemistry for Hong Kong A-Level Book 1

Reaction of ethene and hydrogen