Chemical Bonding
Momtahina Tabassum
Chemistry teacher
Syllabus
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Ionic bonding
How are ions formed?
One way of forming ions is for atoms to gain or lose one or more electrons.
■■ Positive ions are formed when an atom loses one or more electrons. Metal atoms usually lose electrons and form positive
ions.
■■ Negative ions are formed when an atom gains one or more electrons. Non-metal atoms usually gain electrons and form
negative ions
The charge on the ion depends on the number of electrons lost or gained .When metals combine with non-metals, the
electrons in the outer shell of the metal atoms are transferred to the non-metal atoms.
Each non-metal atom usually gains enough electrons to fill its outer shell. As a result of this, the metal and non-metal atoms
usually end up with outer electron shells that are complete – they have an electronic configuration of a noble gas.
■■ the sodium ion has the electronic structure [2,8]+ , the same as that of neon
■■ the chloride ion has the electronic structure [2,8,8]–, the same as that of argon.
• Cations and anions are oppositely charged and therefore attracted to each
other
• Electrostatic attractions are formed between the oppositely charged ions to
form ionic compounds
• The ionic bond is the electrostatic attraction formed between the
oppositely charged ions, which occurs in all directions.
Magnesium oxide
Magnesium is a Group 2 metal
It loses its 2 outer electrons to form a magnesium ion with a +2 charge (Mg2+)
Oxygen is a Group 6 non-metal
It gains 2 electrons to form an oxide ion with a -2 charge (O2-)
The oppositely charged ions are attracted to each other to by electrostatic forces to form MgO (ionic
bonds).
By losing two electrons, each magnesium atom achieves the electronic configuration [2,8].
By gaining two electrons, each oxygen atom achieves the electronic configuration [2,8]. [2,8] is the electronic
configuration of neon; it is a ‘noble-gas configuration’
The final ionic solid is neutral in charge .
Calcium chloride
Each calcium atom has two electrons in its outer shell, and these can be transferred to two chlorine
atoms.
By losing two electrons, each calcium atom achieves the electronic configuration [2,8,8].
The two chlorine atoms each gain one electron to achieve the electronic configuration [2,8,8]. [2,8,8] is
the electronic configuration of argon; it is a ‘noble-gas configuration.
Covalent bonding
• Covalent bonding occurs between two nonmetals
• A covalent bond involves the electrostatic attraction between nuclei of
two atoms and the bonding electrons of their outer shells
• No electrons are transferred but only shared in this type of bonding .
• Non-metals are able to share pairs of electrons to form different types of
covalent bonds
• Sharing electrons in the covalent bond allows each of the 2 atoms to achieve
an electron configuration similar to a noble gas
• This makes each atom more stable
Covalent bonds & shared electrons table
Single covalent bonds
A shared pair of electrons is called a single covalent bond, or a bond pair.
A single covalent bond is represented by a single line between the atoms: for example,
Cl –Cl
Figure : Atoms of chlorine share electrons to form a single covalent bond.
There are some cases in which the electrons around a central atom may not have a noble gas
configuration. For example:
■■ boron trifluoride, BF3, has only six electrons around the boron atom; we say that the boron
atom is ‘electron deficient’
■■ sulfur hexafluoride, SF6, has twelve electrons around the central sulfur atom; we say that the
sulfur atom has an ‘expanded octet.
Multiple covalent bonds
Some atoms can bond together by sharing two pairs of electrons. this i double covalent bond. A
double covalent bond is represented by a double line between the atoms: for example, O= O. The
dot-and-cross diagrams for oxygen, carbon dioxide and ethene, all of which have double covalent
bonds, are shown in Figure .
■■In order to form an oxygen molecule, each oxygen atom needs to gain two electrons to complete its outer
shell. So two pairs of electrons are shared and two covalent bonds are formed.
■■ For carbon dioxide, each oxygen atom needs to gain two electrons as before. But the carbon atom needs to
gain four electrons to complete its outer shell. So two oxygen atoms each form two bonds with carbon, so that
the carbon atom has eight electrons around it.
■■ In ethene, two hydrogen atoms share a pair of electrons with each carbon atom. This leaves each carbon
atom with two outer shell electrons for bonding with each other. A double bond is formed.
Dot-and-cross diagrams for a. oxygen, O2, [Link] dioxide, CO2, and [Link], C2H4
Triple covalent bond-
• Atoms can also bond together by sharing three pairs of electrons. this a triple covalent bond.
• Figure shows a dot-and-cross diagram for the triple-bonded nitrogen molecule.
• In order to form a nitrogen molecule, each nitrogen atom needs to gain three electrons to
complete its outer shell.
• So three pairs of electrons are shared and three covalent bonds are formed
Practice work –
[Link] dot-and-cross diagrams for the ions in the following ionic compounds. Show only the outer electron shells.
• a Potassium chloride, KCl
• b Sodium oxide, Na2O
• c Calcium oxide, CaO
• d Magnesium chloride, MgCl2
2 Draw dot-and-cross diagrams for the following covalently bonded molecules. Show only the outer electron shells.
Note that in part d the beryllium atom is electron deficient and in part e the phosphorus atom has an expanded
octet.
• a Tetrachloromethane, CCl4
• b Phosphorus(III) chloride
• c Bromine, Br2
• d Beryllium chloride, BeCl2
• e Phosphorus(V) chloride, PCl5
3 Draw dot-and-cross diagrams for the following covalently bonded molecules; show only the outer electron shells:
a ethene, CH2= CH2
b carbon disulfide, CS2
Co-ordinate bonding (dative covalent bonding)
• A co-ordinate bond (or dative covalent bond) is formed when one atom provides both
the electrons needed for a covalent bond.
• Conditions for covalent bond-
■■ one atom having a lone pair of electrons
■■ a second atom having an unfilled orbital to accept the lone pair; in other words, an
electron-deficient compound .
● Donor: the atom that supplies the pair of electrons
● Acceptor: the atom that accepts the pair of electrons
● Coordinate bond is represented by an “ →” drawn from the atom donating to towards the
atom accepting
Co-ordinate bonding
❖ An example of this is the ammonium ion, NH4 +, formed when ammonia combines with a hydrogen ion,
H+.
❖ The hydrogen ion is electron deficient; it has space for two electrons in its shell. The nitrogen atom in the
ammonia molecule has a lone pair of electrons. The lone pair on the nitrogen atom provides both
electrons for the bond.
❖ An example of a dative bond is in an ammonium ion
The hydrogen ion, H+ is electron-deficient and has space for two electrons in its shell
➢ The nitrogen atom in ammonia has a lone pair of electrons which it can donate to the
hydrogen ion to form a dative covalent bond
In a displayed formula (which shows all atoms and bonds), a co-ordinate bond is represented by an arrow.
The head of the arrow points away from the lone pair that forms the bond.
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● Formation of AlCl3 dimer (Al2Cl6):
Another molecule that has co-ordinate bonds is aluminium chloride
• At high temperatures aluminium chloride exists as molecules with the formula AlCl3.
• This molecule is electron deficient; it still needs two electrons to complete the outer shell of the aluminium
atom.
• At lower temperatures two molecules of AlCl3 combine to form a molecule with the formula Al2Cl6.
• The AlCl3 molecules are able to combine because lone pairs of electrons on two of the chlorine atoms form
co-ordinate bonds with the aluminium atoms, as shown in figure.
A dot-and-cross diagram for an aluminium chloride molecule, Al2Cl6.
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Bond energy
● The bond energy is the energy required to break one mole of a particular covalent bond in the gaseous
states
• Bond energy has units of kJ mol-1
• The larger the bond energy, the stronger the covalent bond is
Bond length
• The bond length is internuclear distance of two covalently bonded atoms
• It is the distance from the nucleus of one atom to another atom which forms the covalent
bond
• The greater the forces of attraction between electrons and nuclei, the more the atoms are pulled
closer to each other.
• This decreases the bond length of a molecule and increases the strength of the covalent bond
• Triple bonds are the shortest and strongest covalent bonds due to the large electron density
between the nuclei of the two atoms
• This increase the forces of attraction between the electrons and nuclei of the atoms
• As a result of this, the atoms are pulled closer together causing a shorter bond length
• The increased forces of attraction also means that the covalent bond is stronger
Examples of values for bond energies and bond lengths
Reactivity of covalent molecules
● The reactivity of a covalent bond is greatly influenced by:
○ The bond polarity
○ The bond strength
○ The bond type (σ/π)
Questions-
a What is the relationship between the bond length and the bond energy for
these hydrogen halides?
b Suggest why the bond energy values decrease in the order HCl > HBr > HI.
c Suggest a value for the bond length in hydrogen fluoride, HF
Answer 1: Going down the halogen group, the atoms are bigger; the attractive force between the
bonding electrons and the nucleus get smaller so less energy is needed to break the atom
Answer 2: Going down the group the increase in bond length is approximately 0.14-0.20 nm
Fluorine is smaller than HCl, so a value between 0.09 and 0.11 nm is acceptable for the bond
length
Answer 3: The hydrogen halide with the longest bond length and therefore smallest bond energy
is the most reactive as it takes the least energy to break apart the hydrogen and halide atoms
[Link], HI is the most reactive hydrogen halide.
Shapes of molecules
Electron-pair repulsion theory
• The valence shell electron pair repulsion theory (VSEPR) predicts the shape and bond angles of
molecules
• Electrons are negatively charged and will repel other electrons when close to each other
• In a molecule, the bonding pair of electrons will repel other electrons around the central
atom forcing the molecule to adopt a shape in which these repulsive forces are minimised
• When determining the shape and bond angles of a molecule, the following VSEPR rules should
be considered:
• Valence shell electrons are those electrons that are found in the outer shell
• Electron pairs repel each other as they have similar charges
• Lone pair electrons repel each other more than bonded pairs
• Repulsion between multiple and single bonds is treated the same as for repulsion between
single bonds
• Repulsion between pairs of double bonds are greater
• The most stable shape is adopted to minimize the repulsion forces
Shapes of molecules
Electron-pair repulsion theory
● Different types of electron pairs have different repulsive forces
○ Lone pairs of electrons have a more concentrated electron charge cloud than
bonding pairs of electrons
○ The cloud charges are wider and closer to the central atom’s nucleus
○ The order of repulsion is therefore:
lone pair – lone pair > lone pair – bond pair > bond pair – bond pair
Shapes of molecules
Shapes of molecules
• The differences in electron-pair repulsion determine the shape and bond angles in a molecule.
Figure : The bond angles in a methane, b ammonia and c water depend on the type of electron-pair
repulsion
Methane has four bonding pairs of electrons surrounding the central carbon atom.
The equal repulsive forces of each bonding pair of electrons results in a tetrahedral
structure with all H- C- H bond angles being 109.5°.
Ammonia has three bonding pairs of electrons and one lone pair. As lone pair–bond pair
repulsion is greater than bond pair–bond pair repulsion, the bonding pairs of electrons
are pushed closer together.
This gives the ammonia molecule a triangular pyramidal shape. The H N H bond angle is
about 107°.
Water has two bonding pairs of electrons and two lone pairs. The greatest electron
pair repulsion is between the two lone pairs. This results in the bonds being pushed
even closer together.
The shape of the water molecule is a nonlinear V shape. The H O H bond angle is
104.5°.
Shapes of molecules
• Boron trifluoride Boron trifluoride is an electron-deficient molecule. It has only
six electrons in its outer shell. The three bonding pairs of electrons repel each
other equally, so the F - B - F bond angles are 120° . We describe the shape of the
molecule as trigonal planar. ‘Trigonal’ means ‘having three angles’.
Shapes of molecules
Carbon dioxide
Carbon dioxide has two carbon–oxygen double bonds and no lone pairs.
The four electrons in each double bond repel other electrons in a similar way to the two
electrons in a single bond.
So, the O =C= O bond angle is 180°,the shape of the carbon dioxide molecule as linear.
Shapes of molecules
Phosphorus pentafluoride
• Phosphorus pentafluoride has five bonding pairs of electrons and no lone pairs.
• The repulsion between the electron pairs results in the most stable structure being a
trigonal bipyramid .
• Three of the fluorine atoms lie in the same plane as the phosphorus atom. The bond angles
F P F within this plane are 120°. Two of the fluorine atoms lie above and below this plane at
90° to it.
Shapes of molecules
Sulfur hexafluoride
Sulfur hexafluoride has six bonding pairs of electrons and no lone pairs.
The equal repulsion between the electron pairs results in the structure shown in Figure .
All F –S- F bond angles are 90°, the shape is octahedral.
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Practice Questions-
a Predict the shapes of the following molecules,
i tetrachloromethane, CCl4
ii beryllium chloride, BeCl2
iii phosphorus(III) chloride.
b Draw dot-and-cross diagrams for the following molecules and then predict
their shapes:
i hydrogen sulfide, H2S
ii phosphine, PH3.
Electronegativity
● Electronegativity is the ability of an atom to attract a pair of electrons towards
itself in a covalent bond
● This phenomenon arises from the positive nucleus’s ability to attract the negatively
charged electrons, in the outer shells, towards itself.
● Electronegativity depends on: Electronegativity: Affecting Factors
○ Radius of atom (atomic size) inversely ∝ electronegativity
○ Nuclear attraction directly ∝ electronegativity
Nuclear charge
● Attraction exists between the positively charged protons in the nucleus and negatively charged
electrons found in the energy levels of an atom
● An increase in the number of protons leads to an increase in nuclear attraction for the electrons in
the outer shells
● Therefore, an increased nuclear charge results in an increased electronegativity.
Atomic radius
● The atomic radius is the distance between the nucleus and electrons in the outermost shell
● Electrons closer to the nucleus are more strongly attracted towards its positive nucleus
● Those electrons further away from the nucleus are less strongly attracted towards the nucleus
● Therefore, an increased atomic radius results in a decreased electronegativity
● Electronegativity increases across a period because atomic radius ↓ and nuclear attraction ↑, so
polarity ↑
● Electronegativity decreases down a group because atomic radius ↑ and nuclear attraction ↓, so
polarity ↓
Shielding
● Filled energy levels can shield (mask) the effect of the nuclear charge causing the outer electrons to be less
attracted to the nucleus
● Therefore, the addition of extra shells and subshells in an atom will cause the outer electrons to experience
less of the attractive force of the nucleus
○ Sodium (Period 3, Group 1) has higher electronegativity than caesium (Period 6, Group 1) as it has fewer
shells and therefore the outer electrons experience less shielding than in caesium
● Thus, an increased number of inner shells and subshells will result in a decreased electronegativity
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Electronegativity: Trends
● Electronegativity varies across Periods and down the Groups of the Periodic Table
Down a group
● There is a decrease in electronegativity going down the Group
● The nuclear charge increases as more protons are being added to the nucleus
● However, each element has an extra filled electron shell, which increases shielding
● The addition of the extra shells increases the distance between the nucleus and the outer electrons
resulting in larger atomic radii
● Overall, there is decrease in attraction between the nucleus and outer bonding electrons
Across a period
● Electronegativity increases across a Period
● The nuclear charge increases with the addition of protons to the nucleus
● Shielding remains reasonably the same across the Period as no new shells are being added to
the atoms
● The nucleus has an increasingly strong attraction for the bonding pair of electrons of atoms
across the Period of the Periodic Table
● This results in smaller atomic radi
Trends down a group & across a period table
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Ionic or covalent?
Differences in electronegativity values can be used to predict whether a simple compound
has ionic or covalent bonds.
If the electronegativity difference is high, e.g. 2.0 or more, the compound is likely to be ionic.
E.g. sodium chloride: Na = 0.9, Cl = 3.0. Difference = 2.1.
If the electronegativity difference is lower, e.g. below 1.0, the compound is likely to be
covalent.
E.g. methane: C = 2.5, H = 2.1. Difference = 0.4.
A zero value shows that there is no ionic character in the bond, e.g. Cl─Cl.
Some compounds are not entirely covalent and have some ionic character in them. These
have intermediate electronegativity differences, e.g. 1.0.
• Effect of electronegativity on bond angle
• 1) Water and hydrogen sulfide have the same general shape with the same number
of bond pairs and lone pairs. However, their bond angles are different.
• 2) This is because oxygen has a higher electronegativity than sulphur. The bond
pairs of electrons are closer to the oxygen atom compared to the sulfur atom.
• 3) This results in greater repulsion in the O-H bonds than in the S-H bonds.
Therefore, the bond angle increases from 92.5° to 104.5°
Bond Polarity
• When two covalently-bonded atoms have the same electronegativity, the electron
cloud is evenly distributed between the two atoms.
• The bond is described as a 'pure' covalent bond or non-polar bond.
• Some examples are H2, Cl2 and Br2
• However, when an atom is more electronegative than the other, the more
electronegative atom will attract the bond pair of electrons more towards itself. The
electron cloud is not evenly distributed or distorted.
• The more electronegative end acquires a partial negative charge while the less
electronegative end acquires a partial positive charge.
• The bond is said to be polarised, or, a polar bond.
• As the difference in electronegativity values of the atoms in a covalent bond
increases, the bond becomes more polar. The degree of polarity of a molecule is
measured as a dipole moment.
• The dipole moment, μ is the product of charges and the distance between the
centre of the charges. The direction of the dipole is shown by the sign
• The arrow points to the partially negatively charged end of the dipole.
• In molecules containing more than two atoms, we have to take into account:
• the polarity of each bond
• the arrangement of the bonds in the molecule.
Trichloromethane, CHCl3, Polar or Nonpolar?
Trichloromethane, CHCl3,is a polar molecule. The three C─Cl dipoles point in a
similar direction.
Their combined effect is not cancelled out by the polarity of the C─H bond. This
is because the C─H bond is virtually non-polar.
The electron distribution is asymmetric. The molecule is polar, with the negative
end towards the chlorine atoms.
Tetrachloromethane,CCl4 Polar or Nonpolar?
Tetrachloromethane has four polar C─Cl bonds pointing towards
the four corners of a tetrahedron. The dipoles in each bond cancel each other,
so tetrachloromethane is non-polar.
Question -
Polarity and chemical reactivity
• Bond polarity influences chemical reactivity.
• For example, both nitrogen, N≡N, and carbon monoxide, C≡O, have triple bonds
requiring a similar amount of energy to break them.
• Nitrogen is a non-polar molecule and is fairly unreactive. But carbon monoxide is
a polar molecule, and this explains its reactivity with oxygen and its use as a
reducing agent.
• Many chemical reactions are started by a reagent attacking one of the electrically
charged ends of a polar molecule. For example, chloroethane, C 2H5Cl, is far more
reactive than ethane, C2H6
• . This is because reagents such as OH− ions can attack the delta-positive carbon
atom of the polarised C─Cl bond
σ bonds and π bonds
• A single covalent bond is formed when two nonmetals combine
• Each atom that combines has an atomic orbital containing a single unpaired electron
• When a covalent bond is formed, the atomic orbitals overlap to form a combined orbital containing two
electrons
• This new orbital is called the molecular orbital
• The greater the atomic orbital overlap, the stronger the bond
• Sigma (σ) bonds are formed by direct overlap of orbitals between the bonding atoms. In a sigma bond,
the electron density is concentrated between the two nuclei
• Pi (π) bonds are formed by the sideways overlap of adjacent above and below the σ bond.
• A pi bond is formed by the p orbitals from two atoms overlapping sideways.
• In a pi bond, there are two regions of high electron density alongside the nuclei.
• A pi bond is weaker than a sigma bond because the overlapping of charge clouds is less than in a
sigma bond.
• In covalent molecules, single bonds are sigma bonds(σ), a double bond consists of one sigma
bond and one pi bond(1σ, 1π), and a triple bond consists of one sigma bond and two pi
bonds(1σ, 2π).
Hybridization
Hybridization is the mixing of atomic orbitals to produce a new set of hybrid
orbitals of equivalent energies.
General steps in hybridization:
i. promotion of electron.
ii. mixing of orbitals to produce a new set of hybrid orbitals of equivalent
energies(sp, sp² or sp³ hybrid orbitals)
iii. forming of a new molecular orbital.
• sp³ hybridisation
1) An example of compound which undergoes sp³ hybridisation is
methane, CH4.
2) The carbon atom uses some energy to promote one of its electron
from 2s to empty 2p orbital so that there are four unpaired
electrons for covalent bonding.
3) The carbon now is said to be in an excited state(C*).
4. The orbitals then 'mix' or hybridise to produce four hybrid orbitals of equivalent energies.
The new orbitals are called sp³ hybrid orbitals because they are made from one s orbital and
three p orbitals.
5. Each hybrid orbital has one big lobe and one small lobe. They rearrange themselves so that
they are as far as possible to form a tetrahedral geometry. The hybrid orbitals are 109.5°
apart.
6. The s orbitals from the hydrogen atoms then overlap with the four hybrid orbitals to form
four sigma bonds because the overlapping is end-to-end. All the bonds are identical
• Another example is ethane, C2H6.
• The two carbon atoms undergo sp³ hybridisation to form four hybrid
orbitals.
• The two carbon atoms are bonded by overlapping one of their hybrid
orbitals. The remaining ones then overlap with the s orbitals of the
hydrogen atoms.
• sp² hybridisation
1) An example of compound which undergoes sp² hybridisation is ethene, C 2H4.
2) The same thing happens as in sp³ hybridisation, except that this time the carbon atoms 'mix'
or hybridise three of the four orbitals only because the carbon atom is bonding with three
other atoms only.
3) This produces three sp² hybrid orbitals because they are made from one s orbital and two p
orbitals. Another p orbital remains unchanged and it is perpendicular to the plane containing
the hybrid orbitals.
4) The hybrid orbitals rearrange themselves so that they are as far as possible, that is, a trigonal
planar arrangement, the hybrid orbitals are 120° apart.
5) The hybrid orbitals then overlap with s orbitals from the hydrogen atoms and another hybrid
orbital from the other carbon atom to form five sigma bonds. The remaining p orbitals overlap
sideways to form a pi bond. A double bond is formed between the two carbon atoms .
• sp hybridisation
• 1) An example of compound which undergoes sp hybridization is ethyne, C2H2.
• 2) The same thing happens as in sp³ and sp² hybridization, except that this time the carbon
atoms 'mix' or hybridise two of the four orbitals only because the carbon atom is bonding with
two other atoms only.
• 3) This produces two sp hybrid orbitals because they are made from one s orbital and one p
orbital. The other two p orbitals remain unchanged and they are perpendicular to each other
and to the two hybrid orbitals.
• 4) The hybrid orbitals rearrange themselves so that they are as far as possible, that is, a linear
arrangement, the hybrid orbitals are 180° apart.
• 5) The hybrid orbitals overlap with the s orbitals from the hydrogen atoms and to the hybrid
orbital from the other carbon atom to form three sigma bonds. The remaining p orbitals overlap
sideways to form two pi bonds. A triple bond is formed between the two carbon atoms
.
Intermolecular Forces
Intermolecular and intramolecular forces -
. Intramolecular force is the force of attraction that hold individual atoms
together in a molecule.
• Intermolecular force is the force of attraction between one molecule and the
neighbouring molecule.
• There are several types of intermolecular forces:
Instantaneous dipole–induced dipole (id–id) forces
● Instantaneous dipole - induced dipole forces or London dispersion forces exist between all
atoms or molecules
● The electron charge cloud in non-polar molecules or atoms are constantly moving
● During this movement, the electron charge cloud can be more on one side of the atom or
molecule than the other .This causes a temporary dipole to arise
● This temporary dipole can induce a dipole on neighbouring molecules.
● When this happens, the δ+ end of the dipole in one molecule and the δ- end of the dipole in a
neighbouring molecule are attracted towards each other
● Because the electron clouds are moving constantly, the dipoles are only temporary
How instantaneous dipole–induced dipole forces arise
Instantaneous dipole–induced dipole forces increase with:
[Link] of electrons in the molecule(Size of molecule) -
• As the number of electrons increases, the size of the molecule also increase.
• This causes the attraction between the nucleus and the electrons to get weaker, the electrons
become progressively easier to be distorted.
• This causes more temporary dipoles to be set up and the dispersion forces get stron ger.
2. Number of contact points between the molecules(Surface area) -
• For two molecules of the same number of electrons, the one which has a larger surface
area has more contact points between the molecules.
• The more contact points between molecules, more temporary dipoles can be set up and
the dispersion forces become stronger.
The effect of increasing the number of contact points can be seen by comparing
the boiling points of pentane (boiling point 36 °C) and 2,2-dimethylpropane
(boiling point 10 °C).
• These compounds have equal numbers of electrons in their molecules.
• The molecules in pentane can line up beside each other so there is a large
number of contact points. The id–id forces are higher, so the boiling point is
higher.
• The molecules of 2,2-dimethylpropane are more compact. The surface area
available for coming into contact with neighbouring molecules is smaller. The
id–id forces are relatively lower, so the boiling point is lower.
Permanent dipole - permanent dipole (pd - pd)
● Polar molecules have permanent dipoles
● The molecule will always have a negatively and positively charged end
● Forces between two molecules that have permanent dipoles are called permanent dipole -
permanent dipole forces
● The δ+ end of the dipole in one molecule and the δ- end of the dipole in a neighbouring molecul
are attracted towards each other
• Propanone (CH3COCH3, Mr =58) has a higher boiling point than butane
(CH3CH2CH2CH3, Mr = 58). This means that more energy is needed to break
the intermolecular forces between propanone molecules than between butane
molecules)
• The permanent dipole–permanent dipole forces between propanone
molecules are strong enough to make this substance a liquid at room
temperature.
• There are only instantaneous dipole–induced dipole forces between butane
molecules.
• These forces are comparatively weak, so butane is a gas at room temperature.
● In general, the intramolecular forces are stronger than intermolecular forces
● The strengths of the types of bond or force are as follows:
Hydrogen bonding
• Hydrogen bonding is the strongest form of intermolecular bonding.
• It is a type of permanent dipole–permanent dipole bonding.
• Hydrogen bond is the force of attraction between a hydrogen atom (which is
covalently bonded to a small and highly electronegative atom) and the lone
pair of electrons of another small and highly electronegative atom.
• The conditions necessary for forming hydrogen bonds:
i. a hydrogen atom bonded directly to a small and electronegative atom, causing
it to acquire a significant amount of partial positive charge.
ii. a lone pair of electrons from the small and electronegative atom
When a hydrogen atom is covalently bonded to a very electronegative atom, the
bond is very highly polarised. The δ+ charge on the hydrogen atom is high enough
for a bond to be formed with a lone pair of electrons on the F, O or N atom of a
neighbouring [Link] force of attraction is about one-tenth of the strength
of a normal covalent bond. For maximum bond strength, the angle between the
covalent bond to the hydrogen atom and the hydrogen bond is usually
180°.
Water can form, on average, two hydrogen
bonds per molecule.
Water has two hydrogen atoms and two lone pairs per molecule (Figure
4.42). So water is extensively
hydrogen bonded with other water molecules. It has an average of two
hydrogen bonds per molecule.
How does hydrogen bonding affect boiling
point?
● Water has high melting and boiling points which is caused by the strong intermolecular forces of
hydrogen bonding between the molecules
● In ice (solid H2O) and water (liquid H2O) the molecules are tightly held together by hydrogen bonds
● A lot of energy is therefore required to break the water molecules apart and melt or boil them
● The graph below compares the enthalpy of vaporisation (energy required to boil a substance) of different hydrides
● The enthalpy changes increase going from H 2S to H2Te due to the increased number of electrons in the Group 16
elements
● This causes an increased instantaneous dipole - induced dipole forces as the molecules become larger
● Based on this, H2O would have a much lower enthalpy change (around 17 kJ mol -1)
● However, the enthalpy change of vaporisation is almost 3 times larger which is caused by the hydrogen bonds
present in water but not in the other hydrides
High surface tension
● Water has a high surface tension
● Surface tension is the ability of a liquid surface to resist any external forces (i.e. to stay unaffected
by forces acting on the surface)
● The water molecules at the surface of liquid are bonded to other water molecules through hydrogen
bonds
● These molecules pull downwards on the surface molecules causing the surface them to become
compressed and more tightly together at the surface
● This increases water’s surface tension
Density
● Solids are denser than their liquids as the particles in solids are more closely packed together than in
their liquid state
● In ice however, the water molecules are packed in a 3D hydrogen-bonded network in a rigid lattice
● Each oxygen atom is surrounded by hydrogen atoms
● This way of packing the molecules in a solid and the relatively long bond lengths of the hydrogen
bonds means that the water molecules are slightly further apart than in the liquid form
● Therefore, ice has a lower density than liquid water
