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WHAT ARE
THESE REGIONS
CALLED AGAIN?
Helium
atom
electron shells
a) Atomic number = number of Electrons
a) What else does it tell us?????
b) Electrons vary in the amount of energy
they possess, and they occur at certain
energy levels or electron shells.
2 8 18
• the electrons of an atom that can participate
in the formation of chemical bonds with
other atoms
• THESE ARE THE OUTERMOST
ELECTRONS IN THE ATOM!!!
Determining # of Valence
Electrons
• The number of valence electrons of an
element is determined by its periodic table
group (vertical column). The number within
the unit's place identifies how many valence
electrons are present in each group.
• REMEMBER: We skip over the transition
metals because they do not follow the rules.
Let’s Practice
• Elements in Group 1 should have how many
valence electrons?
• Elements in Group 18 should have how
many valence electrons?
• What about Group 16???
Periodic Table: The group number of the group of a column for the main group
elements in the periodic table is the number of valence electrons possessed by the
neutral atom = atomic number = number of protons in the nucleus of an atom.
11Na 12Mg 13Al 14Si 15P 16S 17Cl 18Ar = 18 core electrons
The Duplet Rule
Duplet rule states that when an element gets 2
electrons in its valence or last shell it has achieved
a stable electronic configuration . Hydrogen seems
to be the only element obeying it
The Octet Rule
In forming compounds, atoms gain, lose, or
share electrons to give a stable electron
configuration characterized by 8 valence
electrons.
.. ..
: .. F:
F : ..
HyperChem
Ionic and Covalent Bonds
:
Copyright © 2005 by Pearson Education, Inc.
Publishing as Benjamin Cummings
16
Metals Form Positive Ions
17
Formation of a Sodium Ion, Na+
2, 8, 1 2, 8
Copyright © 2005 by Pearson Education, Inc.
Publishing as Benjamin Cummings
18
Charge of Sodium Ion, Na+
2,
8
Copyright © 2005 by Pearson Education, Inc.
Publishing as Benjamin Cummings
19
Formation of Mg2+
2, 8, 2 2, 8
Copyright © 2005 by Pearson Education, Inc.
Publishing as Benjamin Cummings
20
Charge of Magnesium Ion Mg2+
21
Formation of Negative Ions
23
Formation of a Chloride, Cl-
2, 8, 7 2, 8, 8
Copyright © 2005 by Pearson Education, Inc.
Publishing as Benjamin Cummings
24
Charge of a Chloride Ion, Cl-
25
Ionic Charge from Group Numbers
• The charge of a positive ion is equal to its Group number.
Group 1A(1) = 1+
Group 2A(2) = 2+
Group 3A(3) = 3+
26
Some Ionic Charges
I-
27
Size of cation < size of atom
Reasons:
(1) The number of electron shell decreases
(2) No. of protons > no. of electrons (p/e ratio increases).
The nuclear attraction is more effective to cause a
contraction in the electron cloud.
∙∙ ∙∙
Draw the Lewis dot symbols
∙
Ca∙
of the elements.
∙∙ ∙∙
∙ Cl ∙∙ ∙∙ ∙ Cl ∙∙
∙∙ ∙∙
Transfer all the valance electrons Ca
from the metal to the nonmetal,
adding more of each atom as you
go, until all electrons are lost Ca2+
from the metal atoms and all
nonmetal atoms have 8 electrons.
CaCl2
Why are electrons important?
1) Elements have different electron
configurations
different electron configurations mean
different levels of bonding
When two or more atoms come together it
creates a new substance called a
COMPOUND
This just means that the way compounds are
formed depends on how many valence
electrons an atom has
CHEMICAL BOND
The
Mostnature
matterand
in nature
type of isthe
found
chemical
in form
bond
of is
directly
compounds:
responsible
2 or more
for elements
many physical
held together
and
chemical
through aproperties
chemical bond.
of a substance: (e.g. melting
point, conductivity).
Elements combine together (bond) to fill their
outer energy levels and achieve a stable structure
(low energy).
Noble gases are un-reactive since their energy
levels are complete.
40
CHEMICAL BOND
This
When difference
the conductivity
in
conductivity
apparatus is between
placed insalt
and
salt solution,
sugar is duethe to
bulb
the
different
will light.types of bonds
between
But whentheirit is atoms.
placed in
Two
sugarcommon
solution,types
the bulb
of
bonding
does not are
light.
present:
ionic & covalent.
41
Ions
sulfate SO42- -2 S O O O O
nitrate NO3- -1 N O O O
carbonate CO32- -2 C O O O
ammonium NH4+ +1 N H H H H
K F
K F
K F
K F
K F
K F
K F
+
_
K F
Ionic Compound Names
The cation ion goes first, then the anion
Example: NaCl
Sodium Chloride
MgO
Magnesium Oxide
+
_
K F
The compound potassium fluoride
consists of potassium (K+) ions
and fluoride (F-) ions
+
_
K F
The ionic bond is the attraction
between the positive K+ ion
and the negative F- ion
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.
PLAN: Draw orbital diagrams for the atoms and then move electrons to
make filled outer levels. It can be seen that two sodiums are
needed for each oxygen.
SOLUTION:
Na O2-
2s 2p
3s 3p O
2s 2p 2 Na+
Na
Na
.
.
:
3s 3p + : O: 2Na+ + :O: 2-
:
.
Na.
9-66
Figure 9.4
Three ways to represent the formation of Li+ and F-
through electron transfer
1. Electron configurations
2. Orbital diagrams
Li+
Li
1s 2s 2p
1s 2s 2p
+ F + F-
1s 2s 2p 1s 2s 2p
:
Li . + :F: Li+ + : F: -
:
:
9-67
Oppositely charged particles (ions)
attract and form neutral compounds.
Electron affinity
Cl + e– Cl– – 349
Lattice energy
Cl– + Na+ Cl– Na+ – 766
• Problem: the sum is +147. A spontaneous
change must involve a net lowering of energy
• Solution: the lattice energy provides the
energy needed
• Note that although we represent this as a
three step process it actual occurs all at once
Must Consider Lattice Energy
1. Lattice Energy
– PE lowering due to the attraction of anions to
cations
– Highly Exothermic
2. Ionic bonding will only result when......
– Lattice Energy is more exothermic than
E. A. + I.E. is endothermic
E.g Li (s) + ½ F2 (g) LiF (s)
• Lattice energy = the energy required to
completely separate one mole of a solid ionic
compound into gaseous ions
- + - + -
+
- + - + - +
- + + -
• Electron Affinity
– Enthalpy change when one mole of gaseous
atoms or anions gains electrons to form a mole
of negatively charged gaseous ions.
• Cl(g) + e- Cl-(g) ΔHo = -364 kJmol-1
– For most atoms = exothermic, but gaining a 2nd
electron is endothermic due to the repulsion
between the anion and the electron
Becoming cations
• Ionisation energy
– Enthalpy change for one mole of a gaseous
element or cation to lose electrons to form a
mole of positively charged gaseous ions
• Na(g) Na+(g) + e- IE1= +494 kJmol-1
Lattice Enthalpy
• Energy required to convert one mole of the
solid compound into gaseous ions.
• NaCl (s) Na+(g) + Cl-(g) ΔHolat
= +771kJmol-1
• It is highly endothermic
• We cannot directly calculate ΔHolat , but
values are obtained indirectly through
Hess’s law for the formation of the ionic
compound
Calculations
• Calculate the lattice energy of NaCl(s)
using the following: (kJmol-1)
– Enthalpy of formation of NaCl = - 411
– Enthalpy of atomisation of Na = +109
– Enthalpy of atomisation of Cl = +121
– Electron affinity of Cl = - 364
– Ionisation energy of Na = + 494
KI 632 631
Hθ1st IE Na HθEA Cl
IONISATION LATTICE
H θ
NaCl LE
Na (g) + Cl (g) ENTHALPY
Hθat Na Hθat Cl
ATOMISATION H NaCl θ
f
FORMATION
Na (s) + ½ Cl (g) 2 NaCl (s)
Trends in Lattice Energy: Ion Size
• Lewis theory implies that if the ions are displaced from their
position in the crystal lattice, repulsive forces should occur.
• This predicts the crystal will become unstable and break apart.
Lewis theory predicts ionic solids will be brittle.
• Lewis theory implies that, in the ionic solid, the ions are locked
in position and cannot move around.
Ions in solid
lattice Ions in solution
Lattice enthalpy, HLE
• The enthalpy change when 1 mole of solid
is formed from the separate ions
-HLE is a positive
• This is always an exothermic
valueprocess
• Small ionic charge
• Large ionic charge
• Small ionic radius
• Large ionic radius
Where does the energy come from to
break up the lattice?
• Hydration
3+ 3-
Enthalpy of hydration,Hhyd
• Hhyd is the enthalpy change when a
solution of ions is made from 1 mole of
gaseous ions
Exothermic –
because bonds
Is hydration are made
exothermic or
endothermic?
Example of hydration
• Na+ (g) + aq Na+ (aq)
• Small ionic charge
• Large ionic charge
• Small ionic radius
• Large ionic radius
Water is not the only solvent
l
ΔH
solution
p Solution
y
ΔHsolution = -ΔHLE + ΔHhyd(cat) + ΔHhyd(an)
e Gaseous ions
n ΔHhyd(cat)
t -ΔHLE ΔHhyd(an)
h Solution
a ΔHsolution Is ΔHsolution
l Solute + solvent
exothermic or
endothermic?
p
y
ΔHsolution = -ΔHLE + ΔHhyd(cat) + ΔHhyd(an)
Solubility
• The more negative the value for ΔHsolution
the more likely the solute is to dissolve.
--General form:
• Stable structures:
--maximize the # of nearest oppositely charged neighbors.
15
COORDINATION # AND IONIC
•
RADII
Coordination # increases with
Issue: How many anions can you
arrange around a cation?
--General form:
• Stable structures:
--maximize the # of nearest oppositely charged neighbors.
15
COORDINATION # AND
• Coordination # increases with
IONIC RADII
Issue: How many anions can you
arrange around a cation?
covalent
a Cl2
bond
with
itself
How
will
Cl Cl two
chlorine
atoms
react?
Cl Cl
Each chlorine atom wants to
gain one electron to achieve an octet
Cl Cl
Neither atom will give up an electron –
chlorine is highly electronegative.
What’s the solution – what can they
do to achieve an octet?
Cl Cl
Cl Cl
Cl Cl
Cl Cl
Cl Cl
octet
Cl Cl
octet
O=O 6 12 2
N≡N 5 10 3
Properties of covalent compounds
• Gases, liquids and solids at room
temperature
• May be hard or soft (diamond is a covalent
solid)
• Dissolve in polar and non-polar solvents,
depending on molecule’s polarity
• Solutions and melts do not conduct
electricity
• Most covalent compounds are molecular
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
Cl P Cl Cl P Cl Cl P Cl
Cl Cl
Cl
E.g. 2; CHBr3
Total Number of valence electrons = 4 + 1 + (3 x 7) = 26
Br
Br C H
Br
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"
2. Less than an Octet
BCl3 Cl
Group 3A atom only has six electrons around it
B
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
AlX3
Cl Cl Cl
Al Al
Cl Cl Cl
B2H6
A Lewis structure cannot be written for diborane.
This is explained by a three-centre bond – single electron is
delocalized over a B-H-B
H H H
B B
H H H
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
9-
Factors which Influence the Formation
of Covalent Bonds
(ii) Diamond, Carborandum (SiC), Silica (SiO2), AlN etc. have giant three
dimensional network structures; therefore have exceptionally high melting
points otherwise these compounds have relatively low melting and boiling
points.
(iv) These compounds are generally insoluble in polar solvent like water but
soluble in non-polar solvents like benzene etc. some covalent compounds
like alcohol, dissolve in water due to hydrogen bonding.
9-
(v) The covalent bond is rigid and directional. These compounds, thus
show isomerism (structural and space).
2.0
EN
0.
0
Ionic-To-Covalent Bonding Continuum Across a Period
Non-polar
0 – 0.3
(covalent)
1.7 + Ionic
● Non-metal/non-metal – covalent
● element bonded to itself – non-polar
Ideal ionic
compound completely separate, spherical ions
electron densities are apart from each other
However, if the positive ion has a high charge density it can distort the negative ion by
attracting the outer shell electrons to give an area of electron density between the two
species ... a bit like a covalent bond
INTRODUCTION
The feasibility of having some covalent character can be predicted using Fajan’s Rules.
CATION SMALL SIZE it is “highly polarising” and attracts electrons in the anion
HIGH CHARGE
IONIC BONDING
• 3-DIMENSIONAL GIANT IONIC LATTICE
• ALTERNATE POSITIVE AND NEGATIVE IONS
• HIGH MELTING POINT
• SOLUBLE IN WATER
• MOLTEN STATE CONDUCTS ELECTRICITY
CONTENTS
EXTREMES OF CHEMICAL BONDING
COVALENT BONDING
• MOLECULAR (SIMPLE OR MACRO)
• SIMPLE MOLECULES HAVE LOW MELTING PTS - WEAK INTERMOLECULAR FORCES
• USUALLY INSOLUBLE IN WATER BUT SOME ARE HYDROLYSED
• MOLECULES DON’T CONDUCT ELECTRICITY IN THE MOLTEN STATE
H H H:H
d+ d-
H : Cl H Cl
In some covalent compounds, the electron density
isn’t exactly in the centre between the species
MORE COVALENT
MORE COVALENT
CHARACTER
CHARACTER
FAJAN’S RULES
PROOF
Chlorides can be used to demonstrate changes in bond type as the positive charge
density increases due to higher charge (across Period 3) or larger size (down Group 1)
GREATER POSITIVE
CHARGE DENSITY
Period 3 NaCl 1+ 0.095nm 808 soluble ionic
MgCl2 2+ 0.065nm 714 soluble ionic
AlCl3 3+ 0.050nm 180 hydrolysed covalent
SiCl4 4+ 0.041nm -70 hydrolysed covalent
GREATER POSITIVE
CHARGE DENSITY
• • • •
• •
• O C O •
•
+ • •
•
• O C O •
• • C atom
charge is 0.
6 - (1/ 2)(6) - 2 = +1
•
• • +•
AND the corresponding
resonance form
• O
• •
C O •
H
H—N—H
H
F.C. on H = 1 – (2 × ½) – 0 = 0
F.C. on N = 5 – (8 × ½) – 0 = +1
(CO)
CO
F.C. of C = 4 – (6 × ½) – 2 = –1
F.C. of O = 6 – (6 × ½) – 2 = +1
9-
(NO3)–
–
O=N—O
O
F.C. of O–1 6 – (4 x ½) – 4 = 0
F.C. of O–2 6 – (2 x ½) – 6 = –1
F.C. of O–3 6 – (2 x ½) – 6 = –1
F.C. of N 5 – (8 x ½) – 0 = +1
9-