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4.27 – 4.28 The Shapes of
MoleculesR. Doon – Slough Grammar School
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Learning Objectives• Predict the shape and bond angles for molecules
with four charge centres on the central atom.– Use the valence shell electron pair repulsion
(VSEPR) theory to predict the shapes and bond angles of molecules and ions having four pairs of electrons (charge centres) around the central atom. Suitable examples are NH3, H2O and alkanes (eg CH4).
• Identify the shape and bond angles for species with two and three negative charge centres.– Examples should include species with non-bonding
as well as bonding electron pairs, eg CO2, SO2, C2H2, C2H4, CO32- and NO2-.
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Shapes of molecules, VSEPR
The geometrical arrangement of bonds around the atoms determines the shape of molecules
For the elements in the second row of the periodic table, e.g. carbon, nitrogen and oxygen, the bond angles are determined by one factor: repulsion between pairs of electrons.
Valence Shell Electron Pair Repulsion (VSEPR) theory predicts that the pairs of valence shell electrons around an atom will be arranged as far apart as possible so as to minimise electronic repulsions between them.
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ELECTRON PAIR REPULSION THEORYELECTRON PAIR REPULSION THEORY
“THE SHAPE ADOPTED BY A SIMPLE MOLECULE OR ION IS THAT WHICH KEEPS REPULSIVE FORCES TO A
MINIMUM”
Molecules contain covalent bonds. As covalent bonds consist of a pair of electrons, each bond will repel other bonds.
AlBonds are further apart so repulsive forces are less
Bonds are closer together so repulsive forces are greater
Al
All bonds are equally spaced out as far apart as possible
Bonds will therefore push each other as far apart as possible to reduce the repulsive forces.
Because the repulsions are equal, the bonds will also be equally spaced
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ELECTRON PAIR REPULSION ELECTRON PAIR REPULSION THEORYTHEORY
“THE SHAPE ADOPTED BY A SIMPLE MOLECULE OR ION IS THAT WHICH KEEPS REPULSIVE FORCES TO A
MINIMUM”
Because of the equal repulsive forces between bond pairs, most simple molecules, (ones with a central atom and others bonded to it), have standard shapes with equal bond angles.
However, the presence of lone pairs on the central atom affects the angle between the bonds and thus affects the shape.
O
All bonds are equally spaced out as far apart as possible to give minimum repulsive forces
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VSPER
Bonding pairs and lone pairs will both cause repulsions, so the shape will depend on the total number of pairs of electrons.
However, the two pairs of a double bond or the three pairs of a triple bond are all in the same region of space so they count as only one pair.
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C
2 LINEAR 180º BeCl2
3 TRIGONAL PLANAR 120º AlCl3
4 TETRAHEDRAL 109.5º CH4
5 TRIGONAL BIPYRAMIDAL 90º & 120º PCl5
6 OCTAHEDRAL 90º SF6
BOND BONDPAIRS SHAPE ANGLE(S) EXAMPLE
A covalent bond will repel another covalent bond
REGULAR SHAPESREGULAR SHAPES• Molecules, or ions, possessing ONLY BOND
PAIRS of electrons fit into a set of standard shapes.
• All the bond pair-bond pair repulsions are equal.
• All you need to do is to count up the number of bond pairs and chose one of the following examples...
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BERYLLIUM BERYLLIUM CHLORIDECHLORIDE
ClBe Be ClCl
Beryllium - has two electrons to pair up
Chlorine - needs 1 electron for ‘octet’
Two covalent bonds are formed
Beryllium still has an incomplete shell
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BERYLLIUM CHLORIDEBERYLLIUM CHLORIDE
Cl ClBe180°
BOND PAIRS 2
LONE PAIRS 0
BOND ANGLE...
SHAPE...
180°
LINEAR
ClBe Be ClCl
Beryllium - has two electrons to pair up
Chlorine - needs 1 electron for ‘octet’
Two covalent bonds are formed
Beryllium still has an incomplete shell
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Al
ALUMINIUM CHLORIDEALUMINIUM CHLORIDE
Cl
AlCl
Cl
Cl
Aluminium - has three electrons to pair up
Chlorine - needs 1 electron to complete ‘octet’
Three covalent bonds are formed; aluminium still has an incomplete outer shell.
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Al
ALUMINIUM CHLORIDEALUMINIUM CHLORIDE
Cl
Cl
Al120°
Cl
ClAl
Cl
Cl
Cl
BOND PAIRS 3
LONE PAIRS 0
BOND ANGLE...
SHAPE...
120°
TRIGONAL PLANAR
Aluminium - has three electrons to pair up
Chlorine - needs 1 electron to complete ‘octet’
Three covalent bonds are formed; aluminium still has an incomplete outer shell.
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METHANEMETHANE
C H CH
H
H
H
Carbon - has four electrons to pair up
Hydrogen - 1 electron to complete shell
Four covalent bonds are formed
C and H now have complete shells
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METHANEMETHANE
BOND PAIRS 4
LONE PAIRS 0
BOND ANGLE...
SHAPE...
109.5°
TETRAHEDRAL
C H CH
H
H
H
109.5°
H H
C
H
H
Carbon - has four electrons to pair up
Hydrogen - 1 electron to complete shell
Four covalent bonds are formed
C and H now have complete shells
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METHANEMETHANE
BOND PAIRS 4
LONE PAIRS 0
BOND ANGLE...
SHAPE...
109.5°
TETRAHEDRAL
C H CH
H
H
H
Carbon - has four electrons to pair up
Hydrogen - 1 electron to complete shell
Four covalent bonds are formed
C and H now have complete shells
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PHOSPHORUS(V) FLUORIDEPHOSPHORUS(V) FLUORIDE
FP
P
F
F
F
F
FPhosphorus - has five electrons to pair up
Fluorine - needs one electron to complete ‘octet’
Five covalent bonds are formed; phosphorus can make use of d orbitals to expand its ‘octet’
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Antibiotics, part 2, slide 18
Learning Objectives - Higher
• 14.1.1• State and predict the shape and bond
angles using the VSEPR theory for 5- and 6- negative charge centres.– The shape of the molecules/ions and bond
angles if all pairs of electrons are shared, and the shape of the molecules/ions if one or more lone pairs surround the central atom, should be considered. Examples such as PCl5, SF6 and XeF4 can be used.
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PHOSPHORUS(V) FLUORIDEPHOSPHORUS(V) FLUORIDE
FP
P
F
F
F
F
F
BOND PAIRS 5
LONE PAIRS 0
BOND ANGLE...
SHAPE...
120° & 90°
TRIGONAL BIPYRAMIDAL
120°F
F
P
F
FF
90°
Phosphorus - has five electrons to pair up
Fluorine - needs one electron to complete ‘octet’
Five covalent bonds are formed; phosphorus can make use of d orbitals to expand its ‘octet’
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SULPHUR(VI) FLUORIDESULPHUR(VI) FLUORIDE
FS
S
F
F
F
F
F
FSulphur - has six electrons to pair up
Fluorine - needs one electron to complete ‘octet’
Six covalent bonds are formed; sulphur can make use of d orbitals to expand its ‘octet’
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SULPHUR(VI) FLUORIDESULPHUR(VI) FLUORIDE
FS
BOND PAIRS 6
LONE PAIRS 0
BOND ANGLE...
SHAPE...
90°
OCTAHEDRAL
S
F
F
F
F
F
F
Sulphur - has six electrons to pair up
Fluorine - needs one electron to complete ‘octet’
Six covalent bonds are formed; sulphur can make use of d orbitals to expand its ‘octet’
F
F F
FS
F
F
90°
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SULPHUR(VI) FLUORIDESULPHUR(VI) FLUORIDE
FS
BOND PAIRS 6
LONE PAIRS 0
BOND ANGLE...
SHAPE...
90°
OCTAHEDRAL
S
F
F
F
F
F
F
Sulphur - has six electrons to pair up
Fluorine - needs one electron to complete ‘octet’
Six covalent bonds are formed; sulphur can make use of d orbitals to expand its ‘octet’
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IRREGULAR SHAPESIRREGULAR SHAPES
• If a molecule, or ion, has lone pairs on the central atom, the shapes are slightly distorted away from the regular shapes.
• This is because of the extra repulsion caused by the lone pairs.
BOND PAIR - BOND PAIR < LONE PAIR - BOND PAIR < LONE PAIR - LONE PAIR
OO O
As a result of the extra repulsion, bond angles tend to be slightly less as the bonds are squeezed
together.
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AMMONIAAMMONIA
HN NH H
HBOND PAIRS 3
LONE PAIRS 1
TOTAL PAIRS 4
• Nitrogen has five electrons in its outer shell
• It cannot pair up all five - it is restricted to eight electrons in its outer shell
• It pairs up only three of its five electrons
• 3 covalent bonds are formed and a pair of non-bonded electrons is left
• As the total number of electron pairs is 4, the shape is BASED on a tetrahedron
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AMMONIAAMMONIA
ANGLE... 107°
SHAPE... PYRAMIDAL
HN NH H
HBOND PAIRS 3
LONE PAIRS 1
TOTAL PAIRS 4
H
H
N
H
H
H
N
H
107°H
H
N
H
• The shape is based on a tetrahedron but not all the repulsions are the same
• LP-BP REPULSIONS > BP-BP REPULSIONS
• The N-H bonds are pushed closer together
• Lone pairs are not included in the shape
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AMMONIAAMMONIA
HN NH H
HBOND PAIRS 3
LONE PAIRS 1
TOTAL PAIRS 4
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WATERWATER
H OH
HBOND PAIRS 2
LONE PAIRS 2
TOTAL PAIRS 4
O
• Oxygen has six electrons in its outer shell
• It cannot pair up all six - it is restricted to eight electrons in its outer shell
• It pairs up only two of its six electrons
• 2 covalent bonds are formed and 2 pairs of non-bonded electrons are left
• As the total number of electron pairs is 4, the shape is BASED on a tetrahedron
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ANGLE... 104.5°
SHAPE... ANGULAR
H
O
H
H OH
HBOND PAIRS 2
LONE PAIRS 2
TOTAL PAIRS 4
O
H
O
H
104.5°H
O
H
• The shape is based on a tetrahedron but not all the repulsions are the same
• LP-LP REPULSIONS > LP-BP REPULSIONS > BP-BP REPULSIONS
• The O-H bonds are pushed even closer together
• Lone pairs are not included in the shape
WATERWATER
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XENON TETRAFLUORIDEXENON TETRAFLUORIDE
FXe Xe
F
F
F
F
• Xenon has eight electrons in its outer shell
• It pairs up four of its eight electrons
• 4 covalent bonds are formed and 2 pairs of non-bonded electrons are left
• As the total number of electron pairs is 6, the shape is BASED on an octahedron
BOND PAIRS 4
LONE PAIRS 2
TOTAL PAIRS 6
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XENON TETRAFLUORIDEXENON TETRAFLUORIDE
FXe Xe
F
F
F
F
F
F F
FXe
F
F F
FXe
ANGLE... 90°
SHAPE... SQUARE PLANAR
• As the total number of electron pairs is 6, the shape is BASED on an octahedron
• There are two possible spatial arrangements for the lone pairs
• The preferred shape has the two lone pairs opposite each other
BOND PAIRS 4
LONE PAIRS 2
TOTAL PAIRS 6
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CALCULATING THE SHAPE OF IONSCALCULATING THE SHAPE OF IONS
• The shape of a complex ion is calculated in the same way a molecule by...– calculating the number of electrons in the
outer shell of the central species – pairing up electrons, making sure the outer
shell maximum is not exceeded– calculating the number of bond pairs and lone
pairs– using ELECTRON PAIR REPULSION THEORY to
calculate shape and bond angle(s)
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Antibiotics, part 2, slide 32
CALCULATING THE SHAPE OF IONSCALCULATING THE SHAPE OF IONS
• the number of electrons in the outer shell depends on the charge on the ion
• if the ion is positive you remove as many electrons as there are positive charges
• if the ion is negative you add as many electrons as there are negative charges
e..g. for PF6- add one electron to the
outer shell of P
for PCl4+ remove one electron from the outer shell of P
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SHAPES OF IONSSHAPES OF IONS
Draw outer shell electrons of central atom
N
EXAMPLEEXAMPLEEXAMPLEEXAMPLE
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SHAPES OF IONSSHAPES OF IONS
N+ N
NH4+ NH2
-
Draw outer shell electrons of central atom
N
EXAMPLEEXAMPLEEXAMPLEEXAMPLE
For every positive charge on the ion, remove an electron from the outer shell...
For every negative charge add an electron to the outer shell...
for NH4+ remove 1 electron
for NH2- add 1 electron
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SHAPES OF IONSSHAPES OF IONS
N+
H
H
H
H N+
N
H
H N
NH4+ NH2
-
Draw outer shell electrons of central atom
For every positive charge on the ion, remove an electron from the outer shell
For every negative charge add an electron to the outer shell..
for NH4+ remove 1 electron
for NH2- add 1 electron
Pair up electrons in the usual way
EXAMPLEEXAMPLEEXAMPLEEXAMPLE
N
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SHAPES OF IONSSHAPES OF IONS
N+
H
H
H
H N+
N
H
H N
NH4+ NH2
-
BOND PAIRS 4
LONE PAIRS 0
TETRADHEDRAL
H-N-H 109.5°
BOND PAIRS 2
LONE PAIRS 2
ANGULAR
H-N-H 104.5°
Draw outer shell electrons of central atom
For every positive charge on the ion, remove an electron from the outer shell
For every negative charge add an electron to the outer shell..
for NH4+ remove 1 electron
for NH2-add 1 electron
Pair up electrons in the usual way
Work out shape and bond angle(s) from number of bond pairs and lone pairs.
EXAMPLEEXAMPLEEXAMPLEEXAMPLE
N
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SHAPES OF IONSSHAPES OF IONS
NBOND PAIRS 3 PYRAMIDAL
LONE PAIRS 1 H-N-H 107°
BOND PAIRS 4 TETRAHEDRAL
LONE PAIRS 0 H-N-H 109.5°
N
H
H
H
N+H
H
H
H N+
BOND PAIRS 2 ANGULAR
LONE PAIRS 2 H-N-H 104.5°N
H
H N
NH4+
NH2-
NH3
REVIEWREVIEWREVIEWREVIEW
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MOLECULES WITH DOUBLE BONDSMOLECULES WITH DOUBLE BONDS
C O
C OO
Carbon - needs four electrons to complete its shell
Oxygen - needs two electron to complete its shell
The atoms share two electrons each to form two double bonds
The shape of a compound with a double bond is
calculated in the same way. A double bond repels other
bonds as if it was single e.g. carbon dioxide
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MOLECULES WITH DOUBLE BONDSMOLECULES WITH DOUBLE BONDS
C O C OO
Carbon - needs four electrons to complete its shell
Oxygen - needs two electron to complete its shell
The atoms share two electrons
each to form two double bonds
DOUBLE BOND PAIRS 2
LONE PAIRS 0
BOND ANGLE...
SHAPE...
180°
LINEAR
O OC180°
Double bonds behave exactly as single bonds for repulsion purposes so the shape will be the same as a molecule with two single bonds and no lone pairs.
The shape of a compound with a double bond is calculated in the same way. A double bond repels other bonds as if it was single e.g.
carbon dioxide
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OTHER EXAMPLESOTHER EXAMPLES
BrF5 BOND PAIRS 5
LONE PAIRS 1
‘UMBRELLA’
ANGLES 90° <90°
F
F F
FBr
F
FF F
F Br
F
BrF3 BOND PAIRS 3
LONE PAIRS 2
’T’ SHAPED
ANGLE <90°
F
F
Br
F
F
F
Br
F
SO42-
O
S
O-
O-
O
O S
O-
O-
OBOND PAIRS 4
LONE PAIRS 0
TETRAHEDRAL
ANGLE 109.5°
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VSEPR in actionPairs Shape Geometry Examples
2 Linear Cl—Be—Cl, H—CN
3Trigonal
Planar;120° angles
4
Tetrahedral
(pyramidal)
(angular) 109°
angles
Methane Ammonia Water tetrahedral pyramidal angular 4 bonds 3 bonds 2 bonds
1 lone pr 2 lone pr
Pyramidal and angular structures are tetrahedral with one or two corners
missing
X A X
180°
XA
X
X120° H
B
H
H HC
H
O
XA
X
XX
109°
XA
X
XX
front of plane
behind plane
HC
H
HH H
N
HH
..
HO
H
..
·.
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VSEPR in actionPairs Shape Geometry Examples
5
Trigonal bipyramidal
90° and 120° angles
PCl5
6Octahedral 90° angles
SF6
120°AX
X
X
X
X
90°
X A XX
XX
X
90°