Periodic Properties of the Elements

Mendeleev
• order elements by atomic mass
• saw a repeating pattern of properties
• Periodic Law – When the elements are arranged in
order of increasing atomic mass, certain sets of
properties recur periodically
• put elements with similar properties in the same
column
• used pattern to predict properties of undiscovered
elements
• where atomic mass order did not fit other properties,
he re-ordered by other properties
• Te & I
1
 The Periodic Table
• A map of the building block of matter.
1 18
IA VIIIA
1 H
1 2
IIA
Periodic Table 13
IIIA
14
IVA
15
VA
16
VIA
17
VIIA He
2

1.00797 4.0026
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.939 9.0122 10.811 12.0112 14.0067 15.9994 18.9984 20.179
11 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
3 Na Mg IIIB IVB VB VIB VIIB VIIIB IB IIB Al Si P S Cl Ar
22.9898 24.305 26.9815 28.086 30.9738 32.064 35.453 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.102 40.08 44.956 47.90 50.942 51.996 54.9380 55.847 58.9332 58.71 63.54 65.37 65.37 72.59 74.9216 78.96 79.909 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.905 91.22 92.906 95.94 [99] 101.07 102.905 106.4 107.870 112.40 114.82 118.69 121.75 127.60 126.904 131.30
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.905 137.34 138.91 178.49 180.948 183.85 186.2 190.2 192.2 195.09 196.967 200.59 204.37 207.19 208.980 [210] [210] [222]
87 88 89 104 105 106 107 108 109
7 Fr Ra Ac Ku
[223] [226] [227] [260]

2
• Mendeleev’s Periodic Law allows us to predict what the properties of
an element will be based on its position on the table
• it doesn’t explain why the pattern exists
• Quantum Mechanics is a theory that explains why the periodic trends
in the properties exist

3
 Penetrating and Shielding
• the radial distribution function shows that
the 2s orbital penetrates more deeply into
the 1s orbital than does the 2p
• the weaker penetration of the 2p sublevel
means that electrons in the 2p sublevel
experience more repulsive force, they are
more shielded from the attractive force of
the nucleus
• the deeper penetration of the 2s electrons
means electrons in the 2s sublevel
experience a greater attractive force to
the nucleus and are not shielded as
effectively
• the result is that the electrons in the 2s
sublevel are lower in energy than the
electrons in the 2p
4
Penetration & Shielding

5
 7s 6d 5f
6p 5d
6s 4f
5p
4d
5s
4p
Energy

3d
4s
3p Notice the following:
1. because of penetration, sublevels within
3s an energy level are not degenerate
2p 2. penetration of the 4th and higher energy
levels is so strong that their s sublevel is
2s lower in energy than the d sublevel of the
previous energy level
3. the energy difference between levels
1s becomes smaller for higher energy levels6
Valence Electrons
• the electrons in all the subshells with the highest
principal energy shell are called the valence
electrons
• electrons in lower energy shells are called core
electrons
• chemists have observed that one of the most
important factors in the way an atom behaves,
both chemically and physically, is the number of
valence electrons

7
Properties & Electron Configuration

• elements in the same column

have similar chemical and
physical properties because
they have the same number of
valence electrons in the same
kinds of orbitals

8
Electron Configuration & Element Properties
• the number of valence electrons largely determines the behavior
of an element
• chemical and some physical
• since the number of valence electrons follows a Periodic pattern,
the properties of the elements should also be periodic
• quantum mechanical calculations show that 8 valence electrons
should result in a very unreactive atom, an atom that is very
stable – and the noble gases, that have 8 valence electrons are
all very stable and unreactive
• conversely, elements that have either one more or one less
electron should be very reactive – and the halogens are the most
reactive nonmetals and alkali metals the most reactive metals
• as a group

9
 Electron Configuration and Ion Charge
• we have seen that many metals and nonmetals form one ion, and
that the charge on that ion is predictable based on its position on the
Periodic Table
• Group 1A = +1, Group 2A = +2, Group 7A = -1, Group 6A = -2, etc.
• these atoms form ions that will result in an electron configuration
that is the same as the nearest noble gas

10
 Electron Configuration of Anions in
their Ground State
• anions are formed when atoms gain enough electrons
to have 8 valence electrons
• filling the s and p sublevels of the valence shell
• the sulfur atom has 6 valence electrons
S atom = 1s22s22p63s23p4
• in order to have 8 valence electrons, it must gain 2
more
S2- anion = 1s22s22p63s23p6

11
 Electron Configuration of Cations in
their Ground State
• cations are formed when an atom loses all its valence
electrons
• resulting in a new lower energy level valence shell
• however the process is always endothermic
• the magnesium atom has 2 valence electrons
Mg atom = 1s22s22p63s2
• when it forms a cation, it loses its valence electrons
Mg2+ cation = 1s22s22p6

12
 Trend in Atomic Radius – Main Group
• Different methods for measuring the radius of an
atom, and they give slightly different trends
• van der Waals radius = nonbonding
• covalent radius = bonding radius
• atomic radius is an average radius of an atom based on
measuring large numbers of elements and compounds
• Atomic Radius Increases down group
• valence shell farther from nucleus
• effective nuclear charge fairly close
• Atomic Radius Decreases across period (left to right)
• adding electrons to same valence shell
• effective nuclear charge increases
• valence shell held closer

13
 Effective Nuclear Charge
• in a multi-electron system, electrons are simultaneously
attracted to the nucleus and repelled by each other
• outer electrons are shielded from full strength of nucleus
• screening effect
• effective nuclear charge is net positive charge that is
attracting a particular electron
• Z is nuclear charge, S is electrons in lower energy levels
• electrons in same energy level contribute to screening, but
very little
• effective nuclear charge on sublevels trend, s > p > d > f
Zeffective = Z - S

14
Screening & Effective Nuclear Charge

15
Trends in Atomic Radius
Transition Metals
• increase in size down the Group
• atomic radii of transition metals roughly the same size across the d
block
• must less difference than across main group elements
• valence shell ns2, not the d electrons
• effective nuclear charge on the ns2 electrons approximately the same

16
17
18
 Electron Configuration of Cations in
their Ground State
• cations form when the atom loses electrons from the
valence shell
• for transition metals electrons, may be removed from
the sublevel closest to the valence shell
Al atom = 1s22s22p63s23p1
Al+3 ion = 1s22s22p6
Fe atom = 1s22s22p63s23p64s23d6
Fe+2 ion = 1s22s22p63s23p63d6
Fe+3 ion = 1s22s22p63s23p63d5
Cu atom = 1s22s22p63s23p64s13d10
Cu+1 ion = 1s22s22p63s23p63d10

19
Trends in Ionic Radius
• Ions in same group have same charge
• Ion size increases down the group
• higher valence shell, larger
• Cations smaller than neutral atom; Anions bigger
than neutral atom
• Cations smaller than anions
• except Rb+1 & Cs+1 bigger or same size as F-1 and O-2
• Larger positive charge = smaller cation
• for isoelectronic species
• isoelectronic = same electron configuration
• Larger negative charge = larger anion
• for isoelectronic series
20
 1A Periodic Pattern - Ionic Radius (Å)
-1 +1
H 2A 3A 4A 5A 6A 7A
+1 +2 +3 -4 -3 -2 -1
Li 0.68 Be 0.31 B 0.23 C N 1.71 O 1.40 F 1.33
+1 +2 +3 -4 -3 -2 -1
Na 0.97 Mg 0.66 Al 0.51 Si P 2.12 S 1.84 Cl 1.81
+1 +2 0.62 +3 -4 -3 -2 -1
K 1.33 Ca 0.99 Ga +1 Ge As 2.22 Se 1.98 Br 1.96
+1 +2 0.81 +3 0.71 +4 -2 -1
Rb 1.47 Sr 1.13 In +1 Sn +2 Sb Te 2.21 I 2.20
+1 +2 0.95 +3 0.84 +4
Cs 1.69 Ba 1.35 Tl +1 Pb +2 Bi 21
22
Ionization Energy
• minimum energy needed to remove an electron from
an atom
• gas state
• endothermic process
• valence electron easiest to remove
• M(g) + IE1  M1+(g) + 1 e-
• M+1(g) + IE2  M2+(g) + 1 e-
• first ionization energy = energy to remove electron from neutral
atom; 2nd IE = energy to remove from +1 ion; etc.

23
General Trends in 1st Ionization Energy
• larger the effective nuclear charge on the electron, the
more energy it takes to remove it
• the farther the most probable distance the electron is
from the nucleus, the less energy it takes to remove it
• 1st IE decreases down the group
• valence electron farther from nucleus
• 1st IE generally increases across the period
• effective nuclear charge increases

24
25
26
Choose the Atom in Each Pair with the
Higher First Ionization Energy
1) Al or S
S, Al is further left
2) As or Sb
Sb, Sb is further down
3) N or Si
Si, Si is further down & left
4) O or Cl? opposing trends

27
 Irregularities in the Trend
• Ionization Energy generally increases from left to right
across a Period
• except from 2A to 3A, 5A to 6A

    
Be   N
1s 2s 2p 1s 2s 2p

B    O     
1s 2s 2p 1s 2s 2p
Which
Which is
is easier
easier to
to remove
remove an
an electron
electron from
from B
N or
or Be?
O? Why?
Why?

28
Irregularities in the
First Ionization Energy Trends

Be   Be+  
1s 2s 2p 1s 2s 2p
To ionize Be you must break up a full sublevel, cost extra energy

B    B+  
1s 2s 2p 1s 2s 2p
When you ionize B you get a full sublevel, costs less energy

29
Irregularities in the
First Ionization Energy Trends

N      N+    
1s 2s 2p 1s 2s 2p
To ionize N you must break up a half-full sublevel, cost extra energy

O      O+     
1s 2s 2p 1s 2s 2p
When you ionize O you get a half-full sublevel, costs less energy

30
 Trends in Successive
Ionization Energies
• removal of each successive
electron costs more energy
• shrinkage in size due to having more
protons than electrons
• outer electrons closer to the nucleus,
therefore harder to remove
• regular increase in energy for each
successive valence electron
• large increase in energy when start
removing core electrons

31
32
 Trends in Electron Affinity
• energy released when an neutral atom gains an electron
• gas state
• M(g) + 1e-  M-1(g) + EA
• defined as exothermic (-), but may actually be
endothermic (+)
• alkali earth metals & noble gases endothermic, WHY?
• more energy released (more -); the larger the EA
• generally increases across period
• becomes more negative from left to right
• not absolute
• lowest EA in period = alkali earth metal or noble gas
• highest EA in period = halogen

33
34
 Metallic Character
• Metals
• malleable & ductile
• shiny, lusterous, reflect light
• conduct heat and electricity
• most oxides basic and ionic
• form cations in solution
• lose electrons in reactions - oxidized
• Nonmetals
• brittle in solid state
• dull
• electrical and thermal insulators
• most oxides are acidic and molecular
• form anions and polyatomic anions
• gain electrons in reactions - reduced
• metallic character increases left
• metallic character increase down

35
36
Trends in the Alkali Metals
• atomic radius increases down the column
• ionization energy decreases down the column
• very low ionization energies
• good reducing agents, easy to oxidize
• very reactive, not found uncombined in nature
• react with nonmetals to form salts
• compounds generally soluble in water  found in seawater
• electron affinity decreases down the column
• melting point decreases down the column
• all very low MP for metals
• density increases down the column
• except K
• in general, the increase in mass is greater than the increase
in volume

37
2 Na(s) + 2 H2O(l)  2 NaOH(aq) + H2(g)
38
Trends in the Halogens
• atomic radius increases down the column
• ionization energy decreases down the column
• very high electron affinities
• good oxidizing agents, easy to reduce
• very reactive, not found uncombined in nature
• react with metals to form salts
• compounds generally soluble in water  found in seawater
• reactivity increases down the column
• react with hydrogen to form HX, acids
• melting point and boiling point increases down the
column
• density increases down the column
• in general, the increase in mass is greater than the increase
in volume

39
40
Trends in the Noble Gases
• atomic radius increases down the column
• ionization energy decreases down the column
• very high IE
• very unreactive
• only found uncombined in nature
• used as “inert” atmosphere when reactions with other gases
would be undersirable
• melting point and boiling point increases down the
column
• all gases at room temperature
• very low boiling points
• density increases down the column
• in general, the increase in mass is greater than the increase
in volume
41
 Chemical Bonding
A comparison of metals and nonmetals.

42
 Types of Chemical Bonding

Ionic bonding involves the transfer of electrons and is

usually observed when a metal bonds to a nonmetal.

Covalent bonding involves the sharing of electrons and is

usually observed when a nonmetal bonds to a nonmetal.

Metallic bonding involves electron pooling and occurs

when a metal bonds to another metal.

43
Three models of chemical bonding.

44
Gradations in bond type among Period 3 (black type) and Group
4A (red type) elements.

45
 Lewis Electron-Dot Symbols
To draw the Lewis symbol for any main-group element:
• Note the A-group number, which gives the number of
valence electrons.
• Place one dot at a time on each of the four sides of the
element symbol.
• Keep adding dots, pairing them, until all are used up.
Example:
Nitrogen, N, is in Group 5A and therefore has 5 valence electrons.

•• • • •
•N• • N• or • N N•

••

••
or or
• •• • •
46
 Lewis Symbols and Bonding

For a metal, the total number of dots in the Lewis symbol

is the number of electrons the atom loses to form a cation.
For a nonmetal, the number of unpaired dots equals
- the number of electrons the atom gains to form an anion
- or the number it shares to form covalent bonds.
The octet rule states that when atoms bond, they lose,
gain, or share electrons to attain a filled outer level of 8
electrons (or 2, for H and Li).

47
Lewis electron-dot symbols for elements in Periods 2 and 3.

48
 Lewis Symbols

Represent the number of valence electrons as dots

n = 1 Valence number is the same as the Periodic Table Group Number
H He
n=2 Li Be B C N O F Ne
Groups 1 2 3 4 5 6 7 8

For example,
Na; Is2, 2s2, 2p6, 3s1 = [Ne] 3s1

Lewis Structure = Na
49
 Elements want to achieve the stable electron configuration
of the nearest noble gas

n=2
n=3

Ne
Atoms tend to gain, lose or share electrons until
they are surrounded by 8 electrons

Octet Rule
50
 Nobel Gas Has a Stable Electron Configuration

Ne; 1s2, 2s2, 2p6

Ar; [Ne] 3s2, 3p6

Ar
Example of Ionic Bonding
+
_
Na + F Na + [ F ]
11 9 10
Electronic configuration of Neon achieved in both cases

51
 Carbon has 4 valence electrons

H H
H C H H C H Ne
H H Neon
methane
H C

Stable Octet required

Covalent Bonding – Atoms Share Electrons

52
 Hydrogen molecule, H2
Concentration of negative charge
between two nuclei occurs in a
covalent bond

7A elements (e.g. F) have one valence electron for covalent bonding,

so to achieve octet

6A elements (e.g. O) use two valence electrons for covalent bonding,

so to achieve octet

5A elements (e.g. N) use three valence electrons for covalent bonding,

so to achieve octet

4A elements (e.g. C) use four valence electrons for covalent bonding,

so to achieve octet 53
Carbon dioxide, CO2 Total Number of valence electrons = 4 + (2 x 6) = 16

O + C + O O C O = O C O
Double bonds
Rules for Drawing Lewis Structures
• First sum the number of valence electrons from each atom
• The central atom is usually written first in the formula
• Complete the octets of atoms bonded to the central atom (remember that H can
only have two electrons)
• Place any left over electrons on the central atom, even if doing so it results in
more than an octet
• If there are not enough electrons to give the central atom an octet , try multiple
bonds
Total Number of valence electrons = 5 + (3 x 7) = 26
E.g. 1. PCl3
Cl P Cl Cl P Cl Cl P Cl
Cl Cl
Cl
54
 E.g. 2; CHBr3
Total Number of valence electrons = 4 + 1 + (3 x 7) = 26

Br
Br C H
Br
Exceptions to the Octet Rule in Covalent Bonding

1. Molecules with an odd number of electrons

2. Other Natural Radicals, which do not obey Lewis Structures

(e.g. O2)

2. Molecules in which an atom has less than an octet

3. Molecules in which an atom has more than an octet

55
 1. Odd Number of Electrons
NO Number of valence electrons = 11
N O Resonace Arrows
N O
Resonance occurs when more than one valid Lewis structure can be
written for a particular molecule (i.e. rearrange electrons)
NO2
Number of valence electrons = 17
O N O O N O O N O
Molecules and atoms which are neutral (contain no formal
charge) and with an unpaired electron are called Radicals
O2 O O O O
Oxygen is a ground state
"diradical"
56
 2. Less than an Octet
Includes Lewis acids such as halides of B, Al and compounds of Be

BCl3 Cl
B Group 3A atom only has six electrons around it
Cl Cl
However, Lewis acids “accept” a pair of electrons readily from
Lewis bases to establish a stable octet

Cl H Cl H
_ +
Cl Al + N H Cl Al N H
Cl H Cl H
Lewis acid Lewis base salt
57
Octet Rule Always Applies to the Second Period = n2 ; number of
orbitals
2s, 2px, 2py, 2pz orbitals cannot hold more than two electrons
Ne [He]; 2s2, 2px2, 2py2, 2pz2

n=2
n=3

58
 Third Period ; n2 = 32 = 9 orbitals
Ar [Ne]; 3s2, 3px2, 3py2, 3pz2 3d0 3d0 3d0 3d0 3d0

n=3

59
 3. More than an Octet

Elements from the third Period and beyond, have ns, np and unfilled nd orbitals which
can be used in bonding

PCl5 P : (Ne) 3s2 3p3 3d0

Number of valence electrons = 5 + (5 x 7) = 40 Cl
10 electrons around the phosphorus
Cl
Cl P
Cl
SF4 Cl
S : (Ne) 3s2 3p4 3d0
Number of valence electrons = 6 + (4 x 7) = 34
F F
S
The Larger the central atom, the more atoms you can F F
bond to it – usually small atoms such as F, Cl and O allow
central atoms such as P and S to expand their valency.

60
Electronegativity is defined as the ability of an atom in a molecule to attract electrons
to itself

Electronegativity is a function of two properties of isolated

atoms;
The atom’s ionization energy (how strongly an atom holds
onto its own electrons)
The atom’s electron affinity (how strongly the atom attracts
other electrons)
For example, an element which has:
Prof. Linus Pauling
A large (negative) electron affinity
Nobel Prize for Chemistry 1954
A high ionization (always endothermic, or positive
for neutral atoms) Nobel Prize for Peace 1962
Will: Attract electrons from other atoms and Resist having electrons attracted away

Such atoms will be highly electronegative

61
 The Ionic Bonding Model

An ionic bond is formed when a metal transfers electrons

to a nonmetal to form ions, which attract each other to
give a solid compound.

The total number of electrons lost by the metal atom(s)

equals the total number of electrons gained by the
nonmetal atoms.

62
Figure 9.5 Three ways to depict electron transfer in the formation
of Li+ and F-.

Electron configurations Li 1s22s1 + F 1s22p5 → Li+ 1s2 + F- 1s22s22p6

Orbital diagrams

Li ↑↓ ↑ Li+ ↑↓
+ 1s 2s 2p 1s 2s 2p
F ↑↓ ↑↓ ↑↓ ↑↓ ↑ F- ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
1s 2s 2p 1s 2s 2p
Lewis electron-dot symbols
•• •• -
Li • •F Li+
••

+ F

••
••
•• ••
63
 Depicting Ion Formation

PROBLEM: Use partial orbital diagrams and Lewis symbols to depict the
formation of Na+ and O2− ions from the atoms, and
determine the formula of the compound formed.
PLAN: Draw orbital diagrams and Lewis symbols for Na and O
atoms. To attain filled outer levels, Na loses one electron and
O gains two. Two Na atoms are needed for each O atom so
that the number of electrons lost equals the number of
electrons gained.
SOLUTION:
Na• •• •• 2-
•O + O

••
••
•• 2Na+ ••
Na• •

64
Sample Problem 9.1

Na ↑
3s 3p + O ↑↓ ↑↓ ↑ ↑
Na ↑ 2s 2p
3s 3p

2Na+ + O2- ↑↓ ↑↓ ↑↓ ↑↓
2s 2p

The formula is Na2O

65
The Born-Haber cycle for lithium fluoride.

66
 Periodic Trends in Lattice Energy
Lattice energy is the energy required to separate 1 mol of
an ionic solid into gaseous ions.
Lattice energy is a measure of the strength of the ionic bond.
Coloumb’s Law

Electrostatic energy  charge A x charge B

distance
cation charge x anion charge
Electrostatic energy   DHolattice
cation radius + anion radius

67
 Periodic Trends in Lattice Energy

Lattice energy is affected by ionic size and ionic charge.

As ionic size increases, lattice energy decreases.

Lattice energy therefore decreases down a group on the
periodic table.
As ionic charge increases, lattice energy increases.

68
Trends in lattice energy.

69
 Properties of Ionic Compounds

• Ionic compounds tend to be hard, rigid, and brittle, with

high melting points.
• Ionic compounds do not conduct electricity in the solid
state.
• In the solid state, the ions are fixed in place in the lattice and do
not move.
• Ionic compounds conduct electricity when melted or
dissolved.
• In the liquid state or in solution, the ions are free to move and
carry a current.

70
Electrical conductance and ion mobility.

Solid ionic Molten ionic Ionic compound

compound compound dissolved in water 71
Table 9.1 Melting and Boiling Points of Some Ionic Compounds

Compound mp bp
(°C) (°C)
CsBr 636 1300
NaI 661 1304
MgCl2 714 1412
KBr 734 1435
CaCl2 782 >1600
NaCl 801 1413
LiF 845 1676
KF 858 1505
MgO 2852 3600

72
Covalent bond formation in H2.

73
 Distribution of electron density in H2.

At some distance (bond length), Electron density is high around

attractions balance repulsions. and between the nuclei.

74
 Bonding Pairs and Lone Pairs
Atoms share electrons to achieve a full outer level of
electrons. The shared electrons are called a shared pair
or bonding pair.
The shared pair is represented as a pair of dots or a line:

••
H H or H–H
An outer-level electron pair that is not involved in
bonding is called a lone pair, or unshared pair.
•• •• •• ••
••
••
••

F F or F–F
••

••
•• •• •• ••
75
 Properties of a Covalent Bond
The bond order is the number of electron pairs being
shared by a given pair of atoms.
A single bond consists of one bonding pair and has a bond order of 1.
The bond energy (BE) is the energy needed to
overcome the attraction between the nuclei and the
shared electrons. The stronger the bond the higher the
bond energy.
The bond length is the distance between the nuclei of
the bonded atoms.

76
 Trends in bond order, energy, and length
For a given pair of atoms, a higher bond order results in a
shorter bond length and higher bond energy.
For a given pair of atoms, a shorter bond is a stronger bond.

Bond length increases down a group in the periodic table

and decreases across the period.
Bond energy shows the opposite trend.

77
Table . Average Bond Energies (kJ/mol) and Bond Lengths (pm)

78
Table . The Relation of Bond Order, Bond Length, and Bond
Energy

79
 Bond length and covalent radius.

Internuclear distance Covalent Internuclear distance Covalent

(bond length) radius (bond length) radius
72 pm 114 pm

Internuclear distance Covalent Internuclear distance Covalent

(bond length) radius (bond length) radius
100 pm 133 pm

80
 Comparing Bond Length and Bond Strength

PROBLEM: Using the periodic table, but not Tables 9.2 or 9.3, rank
the bonds in each set in order of decreasing bond length
and decreasing bond strength:
(a) S–F, S–Br, S–Cl (b) C=O, C–O, CΞO

PLAN: (a) S is singly bonded to three different halogen atoms, so the

bond order is the same. Bond length increases and bond
strength decreases as the atomic radius of the halogen
increases.
(b) The same two atoms are bonded in each case, but the bond
orders differ. Bond strength increases and bond length
decreases as bond order increases.

81
SOLUTION:

(a) Atomic size increases going down a group, so F < Cl < Br.
Bond length: S–Br > S–Cl > S–F
Bond strength: S–F > S–Cl > S–Br

(b) By ranking the bond orders, we get

Bond length: C–O > C=O > CΞO
Bond strength: CΞO > C=O > C–O

82
 Bond Energies and DHorxn

The heat released or absorbed during a chemical change

is due to differences between the bond energies of
reactants and products.

DH°rxn = SDH°reactant bonds broken+ SDH°product bonds formed

83
 Using Bond Energies to Calculate DH°rxn

PROBLEM: Calculate DH°rxn for the chlorination of methane to form

chloroform.

bonds broken bonds formed

SDH° positive SDH° negative

PLAN: All the reactant bonds break, and all the product bonds form.
Find the bond energies in Table 9.2 and substitute the two
sums, with correct signs, into Equation 9.2.

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 SOLUTION:
For bonds broken:
4 x C-H = (4 mol)(413 kJ/mol) = 1652 kJ
3 x Cl-Cl = (3 mol)(243 kJ/mol) = 729 kJ
SDH°bonds broken = 2381 kJ

For bonds formed:

3 x C-Cl = (3 mol)(-339 kJ/mol) = -1017 kJ
1 x C-H = (1 mol)(-413 kJ/mol) = -413 kJ
3 x H-Cl = (3 mol)(-427 kJ/mol) = -1281 kJ
SDH°bonds formed = -2711 kJ
DH°reaction = SDH°bonds broken + SDH bonds
formed

= 2381 kJ + (-2711 kJ) = - 330 kJ

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Table 9.4 Enthalpies of Reaction for Combustion of Some Foods

Substance DHrxn (kJ/g)

Fats
vegetable oil -37.0
margarine -30.1
butter -30.0

Carbohydrates
table sugar (sucrose) -16.2
brown rice -14.9
maple syrup -10.4

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 Electronegativity and Bond Polarity

A covalent bond in which the shared electron pair is not

shared equally, but remains closer to one atom than the
other, is a polar covalent bond.
The ability of an atom in a covalent bond to attract the
shared electron pair is called its electronegativity.

Unequal sharing of electrons causes the more

electronegative atom of the bond to be partially negative
and the less electronegative atom to be partially positive.

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Bonding between the models.

Polar covalent bonds are much

more common than either pure
ionic or pure covalent bonds.

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The Pauling electronegativity (EN) scale.

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 Trends in Electronegativity
The most electronegative element is fluorine.

In general electronegativity decreases down a group as

atomic size increases.

In general electronegativity increases across a period

as atomic size decreases.

Nonmetals are more electronegative than metals.

90
Electronegativity and atomic size.

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 Electronegativity and Oxidation Number
Electronegativities can be used to assign oxidation numbers:
• The more electronegative atom is assigned all the shared
electrons.
• The less electronegative atom is assigned none of the
shared electrons.
• Each atom in a bond is assigned all of its unshared
electrons.
• O.N. = # of valence e- (# of shared e- + # of unshared e-)

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Example:

Cl is more electronegative than H, so for Cl:

valence e- = 7
shared e- =2
unshared e- = 6
O.N. = 7 – (2 + 6) = -1
H is less electronegative than Cl, so for H:
valence e- = 1
shared e- = 0 (all shared e- assigned to Cl)
unshared e- = 0
O.N. = 1 – (0 + 0) = +1
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 Depicting Polar Bonds
The unequal sharing of electrons can be depicted by a
polar arrow. The head of the arrow points to the more
electronegative element.

A polar bond can also be marked using δ+ and δ- symbols.

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ΔEN ranges for classifying the partial ionic character of
bonds.

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Percent ionic character as a function of DEN.

Electron density distributions in H2, F2, and HF.

In HF, the electron density
shifts from H to F.
The H–F bond has partial
ionic character. 96
Determining Bond Polarity from EN Values
PROBLEM: (a) Use a polar arrow to indicate the polarity of each
bond: N–H, F–N, I–Cl.
(b) Rank the following bonds in order of increasing
polarity: H–N, H–O, H–C.
PLAN: (a) We use Figure 9.21 to find the EN values for each
element. The polar arrow points toward the more
electronegative element.
(b) The greater the DEN between the atoms, the more polar
the bond.
SOLUTION: (a) The EN values are:
N = 3.0, H = 2.1; F = 4.0; I = 2.5, Cl = 3.0

N–H F–N I–Cl

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(b) The EN values are:
N = 3.0, H = 2.1; O = 3.5; C = 2.5
DEN for H–N = 3.0 – 2.1 = 0.9
DEN for H–O = 3.5 – 2.1 = 1.4
DEN for H–C = 2.5 – 2.1 = 0.4
H-C < H-N < H-O

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 Properties of the Period 3 chlorides.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

As DEN decreases, melting point and electrical conductivity decrease because

the bond type changes from ionic to polar covalent to nonpolar covalent.

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 Shapes of Molecules

We use Lewis structures to account for formula of covalent compounds.

Lewis structures also account for the number of covalent bonds.
Lewis structures however do not account for the shapes of molecules.
Molecules of ABn have shapes dependent on the value of n
AB2 must be either linear or bent:
Examples of Linear molecules

Linear - No non-bonding electrons 100

Linear Molecules have a bond angle = 180° bent
Bent molecules have a bond angle ≠ 180° A
AB most common shapes place the B atoms
3
B B
at the corners of an equilateral triangle:
Trigonal Planar

The A atom lies in

the same plane as
the B atoms (Flat)

Bond angle = 120°

No non-bonding electrons
101
 The ideal tetrahedron has a bond angle = 109.5°

VSEPR model explains

distortions of molecules

The lone electron pair exerts a little extra repulsion on the three bonding
hydrogen atoms to create a slight compression to a 107° bond angle.
Less repulsion is exerted by a bonding pair of electrons because they feel
attraction from two nuclei, while a non-bonding pair feels attraction from
only one nucleus.
Non-bonding pairs spread out more!
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