PREPRE-UNIVERSITY SEMESTER 1 CHAPTER 3 CHEMICAL BONDING

Chemical Bonding can be generally divide to 5 main group

Electrovalent bonding (ionic) Covalent bonding Metallic bonding Hydrogen bonding Van der Waals bonding

To represent the types of bonding, a Lewis diagram (dot-and(dot-andcross) is used. Each dot or cross represent one electron in valence shell and its a more convenient way in showing electrovalent. For both ionic & covalent bonding, octet rule must be fulfill where tendency of atoms to achieve noble gas configuration. Table 6.2 show some cation/anion with difference number of valence electron.

Electrovalent bond (ionic bond) Formed by transfering 1 or more e- from outer orbital to eanother. The atom donate electron is name as cation and the atom who receive electron is name as anion. The bond form when electrostatic attraction occur between 2 opposite charge ions. Formation of ionic compound involving a metal with low IE and a non-metal with high EA. Example for lithium fluoride (LiF). nonThe electronic structure of the lithium and fluorine are : Lithium (Li) = 1s2 2s1 Fluorine (F) = 1s2 2s2 2p5

Practice : Draw the Lewis dot and cross diagram for these ionic compound
Sodium chloride Magnesium fluoride

+ Na + Cl -

_ Mg

2+

_ F 2

Na

Cl 3+

Mg
Aluminium oxide

2+

2O Al 3 3+ 2 O 23

Al 2

Covalent Bonding : Sharing of Electron Covalent bond is bond that formed in between atoms by sharing electron from its atoms in order to achieve a stable electronic configuration of ns2 np6 for atoms involve. (hydrogen achieve 1s2) Some non-metallic elements exist naturally as diatomic nonmolecules like hydrogen, and halogens groups. groups.
Hydrogen molecule Chlorine molecule Oxygen molecule Nitrogen molecule

From example above, we can see that in covalent bond, molecules may form single bond, double bond or triple bond in order to achieve stable valence electrons. Though, there are some molecules with the exceptions of achieving stable valence electrons.

Electron deficient compounds compounds which the molecule (especially the center atom) does not achieve octet electron arrangement. Examples of these molecules are BeCl2 ; BF3 and AlCl3.
Beryllium dichloride Boron trifluoride Aluminium trichloride

Cl

Be

Cl

Electron rich compounds compounds which have more than 8 electrons at center atom of molecules, such as PCl5, SF6 and ICl5.
Phosphorous pentachloride Sulphur hexachloride Iodine pentachloride

However, not all compounds can have more or less than 8 electrons in the center of the atom. There are certain limitation towards the application of the expansion of center atom

For example, nitrogen (N) and phosphorous (P) are both from Group 15 but phosphorous can exist as PCl3 and PCl5 while

nitrogen can only have NCl3 but not NCl5. This is because nitrogen which only have 2 shell, do not have empty d-orbital d..................... available, but phosphorous contain d-orbital to fill in more electron d.................................. Same things occur when it come to hydrolysis of CCl4 and SiCl4. SiCl4 can undergoes hydrolysis with water according to the equation

SiCl4 + 2 H2O

SiO2 + 4 HCl

while CCl4 cannot. Despite the factors that they are from the same group (Group 14 ), CCl4 cannot undergoes hydrolysis as carbon which only have 2 shell, do not have empty d-orbital d... available, so water cannot form coordinative with carbon hence cannot undergoes hydrolysis.

Examples : Draw the Lewis structure for the following molecules.

CO2 HCN CH3COOH

C2H2

NH3

CO32-

SO42-

C3H6

6.2.1 Dative bond Now, try drawing the Lewis structure for these molecules : SO2, SO3, NO3- or CO.
SO2 SO3 NO3CO

Dative bond is formed when an atom that has lone pair electrons which can donate to molecule/ion that has empty unhybridise orbital. Following are a few applications of dative bond in covalent molecules

1. Dative bond in helping molecule to achieve octet.

NH4+

BF3.NH3

Dative bond in forming dimer ~ 2 monomer combine forming a dimer. dimer.

Forming Al2Cl6
Cl Be Cl Be Cl

Forming polymer of BeCl2

Cl Be Cl Cl

3.

Dative bond in formation of complex ion. Molecule / ion form dative bond (also known as coordinative bond) by donating lone pair electron, which act as a ligand .. in the formation of complex ions. For example
tetraamminenickel (II) ion ; Hexacyanoferrate (III) ion ; [Ni(NH3)42+] [Fe(CN)6]3-

hexaaquacopper (II) ion ; [Cu(H2O)6]2+

6.2.3 Resonance ~ a molecule/polyatomic ion in which two or more plausible Lewis structure can be written but the actual structure cannot be written at all
Sulphur dioxide, SO2

Ethanoate ion, CH3COO

Nitrogen dioxide, NO2

Sulphur trioxide, SO3

Carbonate ion, CO32-

O C O O

2-

O C O O

2-

O C O O

2-

Since the resonance structure cannot be determined as it does not have a permanent structure so it is expressed as a combined of resonance structure known as resonance hybrid

Resonance hybrid

O C O O

2-

Covalent Bonds : Overlapping of Orbitals 2 ways in explaining how covalent bond are attached :
Valence bond theory ValenceValence-shell electron-pair repulsion theory (VSEPR) electron-

Here we can explain and predict what type of molecular bond and shape will form through the bonding formation but it does not explain the stability of covalent bond. For valence bond theory, it used atomic orbital overlapping that result the formation of a new molecular orbital embracing both nuclei. The strength of covalent bond is proportional to the area where the atomic orbital overlap. Larger the area overlap, stronger the covalent bond.

Hybrid Atomic Orbitals 3 basic types of hybrid orbital

sp3 hybrid orbital (tetrahedral arrangement) sp2 hybrid orbital (trigonal planar arrangement) (trigonal sp hybrid orbital (linear arrangement)

6.3.2 sp3 hybridisation The term sp3 gives an impression of the hybridisation involved 1 3 _____ s orbital and _____ p orbitals Examples of molecules which give sp3 hybridisation are
Methane sulphate ion

CH4 SO42-

silicon tetrachloride Perchlorate ion

SiCl4 ClO4-

14 For example, in methane, CH4, since carbon is in Group _____so 2s2 2p2 the valance electron of C is _______

State of molecules

Orbital diagram

Illustration / Explanation

_____ _____ _____ 2p Ground state ____ 2s

Excited state

____ 2s

____ ____ ____ 2p

Hybridisati on state

_____ _____ _____ _____ sp3

109.50 tetrahedral

6.3.3 sp2 hybridisation The term sp2 gives an impression of the hybridisation involved 1 2 _____ s orbital and _____ p orbitals Examples of molecules which give sp2 hybridisation are
Sulphur trioxide Nitrate ion

SO3 NO3-

Boron trifluoride Carbonate ion

BF3 CO32-

13 Since boron is Group ______ element so the electron valance 2s2 2p1 of B is _________

State of molecules

Orbital diagram

Illustration / Explanation

_____ _____ _____ 2p Ground state ____ 2s

Excited state

____ 2s

____ ____ ____ 2p

Hybridisati on state

_____ _____ _____ sp2

____ pz

Formation of sp2 Hybrid Orbitals

Shape of molecule Trigonal planar Angle between bond pair 120o

6.3.4 sp hybridisation The term sp gives an impression of the hybridisation involved _____ s orbital and _____ p orbitals 1 1 Examples of molecules which give sp hybridisation are
Carbon dioxide

CO2 HCN

Beryllium chloride

BeCl2 C2H2

Cyanic acid

Ethyne

Lets use beryllium chloride as example. 2 Since beryllium is Group ______ element so the electron 2s2 valance of Be is ___________

State of molecules

Orbital diagram

Illustration / Explanation

Ground state

_____ _____ _____ 2p ____ 2s

Excited state

____ 2s

____ ____ ____ 2p

Hybridisati _____ _____ sp on state

___ ___ py pz

Formation of sp Hybrid Orbitals

Shape of molecule Linear Angle between bond pair 180o

6.4 Hybridisation in organic molecules In this subtopic, were going to witness how is the formation of the bonding that exist in some organic molecules. The 3 organic molecules which will be discussed in this sub-topic are : submethane, CH4 ethene, ethene, C2H4 ethyne, ethyne, C2H2 All of the molecules above has carbon in it 14 Carbon is a group _____ element. It has the electronic configuration 2s2 2p2 of ______________ The orbital diagram Ground state of carbon : _____ _____ _____ _____ 2s 2p

Methane, CH4 Excited state of carbon :

Type of hybridisation : _____ 2s _____ _____ _____ 2p sp3

Hybridised state

_____ _____ _____ _____

Molecular shape

tetrahedral
Angle between the bonding pair :

109.50

..

Ethene, Ethene, C2H4

Type of hybridisation :

sp2

Excited state of C : _____ 2s Hybridised state

_____ _____ _____ 2p _____

: _____ _____ _____

sp2 Molecular shape

Trigonal planar

pz

Angle between bond pair bond pair

120o

Ethyne, Ethyne, C2H2

Type of hybridisation :

sp

Excited state of C : _____ _____ _____ _____ 2s 2p Hybridised state : _____ _____ _____ _____

sp Molecular shape
Linear

py pz

Angle between bond pair bond pair

180o

As a conclusion, the formation of double one bond (C=C) is due to ______sigma bond ______sigma one () and _____pi bond () _____pi ( While the formation of triple bond (CC) is one two due to ______sigma bond () and _____pi ______sigma ( _____pi bond () (

The Hybridisation of s and p orbitals in Carbon atom Weve discussed methane molecule by using sp3 hybrid orbitals in forming the CH bond in methane C Ethene molecules, C2H4 a planar molecule with a bond angle of 120o, it can be explain below :
Formation of bonds using sp2 hybrid orbitals ~ Since 2 of the bond is use to overlap the bonding between CH, the third sp2 C orbital is use to overlap between CC bond. This type of bond is C what we name as sigma, bonds. Formation of bonds using pz orbital ~ the p orbital which remain unhybridises (adjacent carbon atom) undergo sideways overlapping to form a bond. In a bond, electron cloud is located above and below the CC bond. Thus, the double bond C in ethene consist and bonds.

10.5

10.5

Ethyne Molecules C2H2 (Acetylene) A linear molecule containing triple bond HCCH. The H C bonding in ethyne can be explained as follows.
Formation of bond using sp hybrid orbital ~ as explain earlier, bond is formed when the remain sp orbital is overlapping with each other. Formation of bonds using py and pz orbital ~ each carbon atom still has 2 unhybridised 2p orbitals oriented at right angles to each other and to the axis of the sp hybrid orbitals. These p orbital undergo sideways overlapping to form a pair of bonds. Thus, the triple bond in ethyne consists of a bond and two bonds.

10.5

The Hybridisation of s and p orbitals in the Oxygen atom When we sketch the orbital diagram, we should notice that theres 2 more space for e- to fill into the p orbital. In the ebond form within water, H2O, we found that it has geometrical structure nearly similar to a tetrahedral, but the angle between 2 OH bond is 104.5o instead of 109.5o as in O tetrahedral. Here, we can use bonding pair and lone pair repulsion theory to explain the situation.

Ground State

Hybridised State

Hybridisation of s and p orbital in Nitrogen Atom Same as oxygen case, nitrogen also uses a sp3 hybrid orbital for forming covalent bond between N and 3 H atoms. One of the lone pair electron occupied the orbital and this will cause repulsion of bonding to occur that makes the angle of the bond become 107o instead of 109.5o. The shape of molecule is pyramidal where 3 H form the base of pyramid

Ground State

Hybridised State

From the 2 examples above, we can tell how the lone pair electrons affecting the angle between the bonding pair and bonding pair. In ammonia, not only that there is the repulsion between bonding pair and bonding pair but theres also the repulsion between bonding pair and lone pair. Since the angle between the bonding pair and bonding pair decrease, theres a probability that its due to the effect of stronger repulsion between the bonding pair and lone pair electron. This statement is supported as in the repulsion between the HOH in water is smaller than in ammonia, H NH3. as a conclusion, we can conclude that

lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding > > repulsion pair repulsion pair repulsion

Valence Shell Electron Pair Repulsion (VSEPR) Theory ~ state that the electron-pair repulsion stated that electron electronpairs around central atom repel each other 3 main rules
Bonding pairs and lone pairs of electrons arrange themselves to be as far apart as possible. The order of repulsion strength of lone pair and bond pair are lonelone-pair & lone-pair > lone-pair & bond-pair > bond-pair & bond-pair lonelonebondbondbondDouble / triple bond are considered as 1 bonding pair when predicting the shape of molecules or ions

Diagram below shows the type of bonding and the molecular shape predicted.

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB2 AB3 AB4 AB5 AB6

2 3 4 5 6

0 0 0 0 0

linear trigonal planar tetrahedral trigonal bipyramidal octahedral

linear trigonal planar tetrahedral trigonal bipyramidal octahedral

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB3 AB2E

3 2

0 1

trigonal planar trigonal planar

trigonal planar bent

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB4 AB3E

4 3

0 1

tetrahedral tetrahedral

tetrahedral trigonal pyramidal

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB4 AB3E AB2E2

4 3 2

0 1 2

tetrahedral tetrahedral tetrahedral

tetrahedral trigonal pyramidal bent O H H

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB5 AB4E

5 4

0 1

trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal See-saw

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB5 AB4E AB3E2

5 4 3

0 1 2

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped F F Cl F

10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB5 AB4E AB3E2 AB2E3

5 4 3 2

0 1 2 3

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped linear I I I

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB6 AB5E

6 5

0 1

octahedral octahedral

octahedral square pyramidal F F F Br F F

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

Class

AB6 AB5E AB4E2

6 5 4

0 1 2

octahedral octahedral octahedral

octahedral square pyramidal square planar F Xe F F F

5 GENERAL STEPS TAKEN WHEN WRITING LEWIS STRUCTURE FOR MOLECULES AND IONS
Calculate the total number of valence electrons from all atoms Arrange all the atoms surrounding the central atom by using a pair of electron per bond Assign the remaining electrons to the terminal atoms so that each terminal atom has 8 electrons (H = 2 e-) ePlace any left-over electron on the central atom. left@ Form multiple bonds if there are not enough electrons to give the central atom an octet of electrons.

6.6 Electronegativity and Polar Molecules Electronegativity are measurement of ability of an atom in molecules to attract a pair of electron For 2 identical atoms, since they have same electronegativity so they have no difference in electronegativity. These molecules are electronegativity. called polar molecules While if 2 not identical form a covalent bond, the bonding electrons will attracted more strongly by more electronegative element. We can indicate the polarity of hydrogen chloride molecules in 2 ways.

Cl

The separation of charge (between + and ) in a poplar molecule is called dipole When 2 electrical charges of opposite sign are separated by small distance, dipole moment is established

Molecules that are polar have large dipole moments. Molecules that are non polar have zero dipole moment. Still, for some molecules, even there are different in electronegativity but it doesnt mean that these molecules there are polar molecules. When the surrounding atom are symmetrically surrounded by identical (same) atom, they are nonnon-polar Example of molecules which are non polar

Dipole Moments and Polar Molecules

electron rich region

electron poor region

=Qxr
Q is the charge r is the distance between charges 1 D = 3.36 x 10-30 C m

Which of the following molecules have a dipole moment? H2O, CO2, SO2, and CH4 O dipole moment polar molecule S dipole moment polar molecule H O C O H C H no dipole moment nonpolar molecule H

no dipole moment nonpolar molecule

Nitrogen dioxide, NO2

Methane, CH4

Ethene, C2H4

Benzene, C6H6

Boron trifluoride, BF3

Cyanide acid, HCN

Sulphur dioxide, SO2

Sulphur trioxide, SO3

Ammonia, NH3

Ammonium ion, NH4+

Ethane, C2H6

Chloroethane, C2H5Cl

N H H H

Cyclohexane, C6H12

Chlorocyclohexane, C6H11Cl

Carbon dioxide, CO2

Carbonate ion, CO32-

O C O
Phosphorous trichloride, PCl3 Phosphorous pentachloride, PCl5 cisbut-2-ene

2O

transbut-2-ene

H3C C H C

H CH3

A simple experiment which can be used to determine either a molecule is polar or non polar is illustrated below By using the liquid form of the compound, it is flow out slowly from burette while a negative charged rod is bring close to the flow of the liquid. If the liquid is deflected to the direction of negative charged, this liquid is polar If it remain undeflected, this undeflected, nonliquid is non-polar .

From the example above, classified which compounds can be deflected and which cannot

Compound which can be deflected by charged rod

Nitrogen dioxide, Cyanide acid, Sulphur dioxide, Ammonia, Chloroethane, Chloroethane, Chlorocyclohexane, Chlorocyclohexane, Phosphorous trichloride Cis-but-2-ene Cis-but-

Compound which cannot be deflected by charged rod

Methane, ethene, benzene, ethene, Sulphur trioxide, Ammonium ion, Ethane, cyclohexane, cyclohexane, Carbon dioxide, Carbonate ion, Phosphorous pentachloride, pentachloride, Trans-butTrans-but-2-ene

Electronegativity and Type of Chemical Bond. Actually, the type of bond that would form can be tell by using the difference of electronegativity ( EN). More larger the difference, the more tendency of electron form low EN move an electron to higher EN atom and ionic compound is formed. The relationship between the ionic character and the difference in the electronegativity of the bonded atom is shown on next slide (or page 220). The presence of dipoles gives ionic character to polar covalent molecules. When the polarity of the covalent molecule increases, the ionic character also increase. An ionic bond is formed if the cation has a small ionic radius anion has a large ionic radius both cation & anion carries a low electrical charge. Polarisation ~ the distortion of the charge cloud of the negative ion by a neighbouring positive ion.

Fig. 9.18

3.6.1

Covalency Properties in Ionic Molecules

From the graph above, the dotted line represent the arbitrary line between ionic and covalent characteristic of a molecule. To be more specific, there more likely an ionic compound may have high covalent characteristic (exemplified by LiI), or conversely covalent compound LiI), having high ionic characteristic (exemplified by HF). The covalent characteristic of a molecule is dependent on the ability of a cation to polarise an anion. Polarisation indicates the ability of a cation to attract the electron density of an anion when put next to the cation involved. When a cation is able to pull the electron density of the anion closer to it, as if the anion wanted to share electron with cation, hence increase the covalency of the cation, molecule

A+

B+

Highly ionic compound Large cationic size Small anionic size

Highly covalent compound small cationic size large anionic size

The covalency properties of a molecule is dependent on the cation and anion where they can be explained qualitatively via Polarisation power of cation Polarisability of anion

3.6.1.1 Polarisation Power of Cation Polarisation Power of Cation measure the ability of a cation to polarise the electron cloud of the anion. 2 factors determining the polarisation power of cation
Charge of cation Size of cation Greater the charge of ion, higher the Smaller the size of cation, closer the effective nuclear charge of cation, neighboring anion to the nucleus of hence it will be able to attract the cation, hence easier for the cation to neighboring electron density of anion. polarise the anion and result an This will caused the polarization power increment in the polarization power of of cation increase, hence increase the cation, and increase the covalent covalent characteristic of cation. characteristic of cation. Both factors can be explained in another term called as charge density where Charge Density = Charge / Ionic Radius From the equation above, Charge Density will have a greater value, provided that cation has a high charge and small cationic radius. Greater the charge density, higher the polarization power, greater the covalent characteristic of the cation.

3.6.1.2 Polarisability of Anion Polarisability of an anion ~ ability of the anion to allow the electron density to be polarised by cation. cation. 2 factors determining the polarisability of an anion
Charge of anion Size of anion

Greater the charge of anion, lower the Larger the size of anion, further the effective nuclear charge of anion. This will outermost electron from the nucleus weakened the electrostatic attraction forces of the anion, easier for the cation to between nucleus and the outermost polarise the anion, and cause the electron in anion, and increase the polarisability to increase, hence polarisability of the anion, hence increase increase the covalent characteristic the covalent characteristic of anion of anion.

Unlike cation, anion does not have a term that combined both cation, factors of charge and ionic radius. However, information of polarisability of anion enable the prediction of the covalent characteristic of a molecule, since in order to form a covalent bond, it depend on both polarisation power of cation and polarisability of the anion

3.6.2 Prediction of Chemical Bond :Fajans Rule :Fajans In 1923, Kazimierz Fajans formulated an easy guidance to predict 1923, whether a chemical bond will be covalent or ionic, and depend on the charge on the cation and the relative sizes of the cation and anion. They can be summarized in the following table
Ionic compound Covalent compound Low positive charge High positive charge Large cation Small cation Small anion Large anion

Based on these guidance, the bonding of a few compounds shall be discussed to understand the application of Fajans Fajans Rule in the chemical bonding

Lithium halide (LiX) (LiX) Lithium ion, Li+ (1s2) has a small size due to only 1 shell present in its ion. But since it has a low charge, so its charge density is not too high. That is why, all lithium halide are ionic compound. The covalency of lithium halide varies from a highly ioniccharacteristic to highly covalency, depending on covalency, the polarisability of the anion next to Li+ When a group of halide, F ; Cl; Br; I is put close to Li+, the covalency of lithium halide increase when going down to Group 17 halide. LiF is highly ionic, since the fluoride ion has small ionic size and low charge, hence has low polarisability. polarisability. Ionic size increase with the increasing shell when going down to Group 17 halide, hence increase the polarisability, which polarisability, allowed lithium ion to polarise the anions electron density, hence increase the covalency

Cl Br Li+

Aluminium halide (AlX3) and aluminium oxide (Al2O3) Aluminium ion (Al3+) has high charge density, due to its high charge unit and its small ionic radius. So, depending on the anion, radius. aluminium has a high tendency to form covalent compound. For compound. example, when going down to Group 17 halide, aluminium fluoride (AlF3) forms ionic compound (since F- has a low polarisability), polarisability), while aluminium trichloride (AlCl3), aluminium tribromide (AlBr3) and aluminium iodide (AlI3) form covalent compound (since chloride, bromide and iodide have high polarisability). This polarisability) explained why aluminium fluoride has a high melting point (10400C), while aluminium trichloride and tribromide are 1920C and 780C respectively. respectively. As for aluminium oxide (Al2O3), it is an ionic compound with high covalent characteristic, as aluminium ion has high covalent characteristic due to its high charge density. This explained the density. high melting point of Al2O3 (20500C) yet it is insoluble in water. It water. also explained the amphoteric properties of aluminium oxide where aluminium oxide can act as an acid (covalent characteristic), as well as a base (ionic characteristic). characteristic).

Metallic Bonding The properties of metals cannot be explained in terms of the ionic / covalent bond. In ionic / covalent compound, electron are not free to move under the influence of applied potential (charge) difference. Therefore, ionic solid and covalent compound are insulator. insulator. In metal, electron are delocalised and metal atoms are effectively ionised. ionised. Metallic bond ~ electrostatic attraction between the positively charged metal ion and the electron delocalised. delocalised. Because of this, electron now can freely move from cathode to anode when a metal is subjected to an electrical potential. The mobile electron can also conduct heat by carrying the kinetic energy from a hot part of the metal to a cold part. This electron delocalised can also use to explain the electrical and thermal conductivities of metal

The Band Theory : Overlapping of Orbital The number of molecular orbitals produced is equal to the number of atomic orbitals that overlap. In a metal, the number of atomic orbitals that overlap is very large. Thus the number of molecular orbital produced is also very large. The energy separations between these metal orbitals are extremely small. So, we may regard the orbital as merging together to form a continuous band of allowed energy state. This collection of very closed molecular orbital energy levels is called an energy band. This theory for metal is called band theory

Electrical Conductors Molecular orbital model == 2 group of energy level.

Lower energy level valence band form from overlap of outer most orbital containing valence electron of each atom. Higher energy level conduction band energy level filled with mobile electron

But there are some case where valence band can also serve as conduction band (caused by the movement of delocalised molecular orbital) Electrical conductivities decrease when temperature increase vibration of the lattice of ion impedes the free movement of electron in conduction band. conduction band valence band

Insulator Difference between conductors, semi-conductors, and semiinsulator depend on the energy gap between the 2 bands. Conductor 2 bands overlaps so conduction band always partly filled. Insulator gap between the band is large and no electron exist in the conduction band. E.g. insulator diamond When 2s and 2p orbital of C is combine to form 2 energy bands, valence band is filled with electron. In insulator, the energy gap between the band is large. Under normal condition, few electrons in valence band can jump across to conduction band. If electron cannot reach conduction band across the gaps, the electrical conduction cannot take place.

Semiconductor Theres still energy gaps between 2 bands in semiconductor, but it is smaller than insulator. In semiconductor, some electrons have sufficient energy to jump across the energy gaps and electron can move freely in conduction band thus enable electrical conduction. Still, the electrical activity is not as good as metal (conductor) Increasing temperature can help to improve the conductivity because electron gain thermal energy and are able to reach conduction band. It can also improve its effectiveness by adding small amount of substance. This adding is what we called doping. It can help to increase electrons to fill in valence band. Example of doping is Si dope P (n-type). Si dope Ge (p-type) (n(pDepend on the needs, this process can help to create the various type of semiconductor in electronic characteristic.

7.1 Van der Waals forces Van Der Waals forces are the intermolecular forces formed between covalently bond molecules which exist as simple molecules. There are 2 types of Van Der Waals forces namely Permanent Dipole Permanent dipole forces Temporary dipole induced dipole forces

7.1.1 Dipole-dipole attraction forces Dipole1. Polar molecule possessed dipole moment. Each of the polar molecules have an overall magnitude. For example in hydrogen chloride H Cl + 2. The dipole inside polar molecules is permanent and the forces between the molecule form as the positive end of dipole will attract to the negative end of another molecules dipole.

3. This kind of forced are called permanent dipole-dipole forces. dipole4. The strength of the attraction depends on two factors : dipole moment and relative molecular mass

5. Higher the dipole moment the more polar the molecule stronger the Van Der Waals forces 6. Comparisons were made between 4 molecules that have nearly equaled of molecular mass, but with different dipole moment
Compounds Propane , CH3CH2CH3 Methyl methoxide, CH3OCH3 Chloromethane Methyl cyanide, CH3CN RMM 44 44 50.5 41 DM 0.1 1.3 1.9 3.9 Boiling point (C) - 18.0 4.0 6.0 56.0

7. Methyl cyanide exhibit the highest boiling point among the 3 molecules as it has the highest dipole moment among these molecules, which makes the attraction between the dipoledipoledipole attraction become stronger, and required a higher temperature to break the attraction forces among CH3CN----CN----CH3CN. CN.

8. Another factor which influence the strength of permanent dipoledipole-dipole forces, are the factor of relative molecular mass. 9. Higher the mass, stronger the forces of attraction ( Van Der Waals forces ), higher the boiling point or melting point of the substance Melting point (C) - 114 - 87 - 51 Boiling point (C) - 85 - 66 - 35

RMM Hydrogen chloride, H Cl Hydrogen bromide, H Br Hydrogen iodide, H I 36.5 81.0 128

7.1.2 Temporary dipole induce dipole forces NonNon-polar molecules have a dipole moment = 0. Basically, they wont have any attraction between the molecules as there are no significant poles with charge in the molecule, so how they interact ??!!! For non-polar molecules, they may have a chance to nonform asymmetrical structure, as the distribution of electron within the molecule are not even, giving the atom a temporary dipole moment. During the formation of temporary dipole moment, moment, induction process takes place where the distribution of electron are uneven and give the atom which are temporary rich of electron to form dipole. These dipoles also known as induce dipole. When induced dipole is formed , a temporary interaction between the molecules formed and produces weak forces among them.

This theory is introduced by Frite London in 1930. It is known as London dispersion forces.

In (a) the non-polar molecule which does not have a dipole nonwithin the molecule begin to fluctuate and thus forming a temporary dipole as in (b). Thus the forces of attraction will formed between the temporary dipole and this forces is named as London Forces

7.2 Effect of the intermolecular forces ( Van der waals ) on the physical properties of the molecules H vapourisation give a quantitative measurement of strength of attractive forces present in liquid. So, H vapourisation , the boiling point , the intermolecular forces among its molecules. When a molecule increase in size, the number of electron also increase, so the attraction between the electron valence and nucleus become less. This distortion of electron cloud can easily less. occur and increase the polarisability of the negative ion. This can be relating with the dispersion forces among molecules therefore H vapourisation , e.g. : Value of boiling point of halogen gas increase. ( from F2 I2 ) In hydrocarbon, boiling point increase with relative molecular mass (RMM). Molecule with higher RMM will have a higher boiling point. The effect of branched chain in hydrocarbon will also affect the boiling point of hydrocarbon involved

Structure

RMM

Boiling point (C)

2,2dimethyl propane

72

2-methylbutane

72

18

npentane

CH3 CH2 CH2 CH2 CH3

72

36

This is due to a larger surface area in a straight chain of hydrocarbon, and allows greater forces between the molecules giving larger Van der Waals forces compare to branch chain hydrocarbon

7.3 Hydrogen Bonding Hydrogen bond is a special dipoledipole interaction between dipole H atom with other atom with high electronegativity. ( N, O, F ) electronegativity.

It is extra stable than normal Van der waals forces and required a high energy to break the bond. This explained why the boiling point of NH3, H2O and HF are higher than other hydrogen compound from each of their particular group.

Decreasing molar mass Decreasing boiling point

Hydrogen bond can also be used to explain the different of boiling point of some organic compound. In the diagram above, the trend of the compound in the same group deviates for N, O and F, as it form hydrogen bond among themselves. Hydrogen bond can be compared among NH3 , H2O and HF. HF has a higher boiling point than NH3 due to higher electronegativity of fluorine compare to nitrogen. So the dipole moment of HF is greater than NH, which results greater H N hydrogen bond. Though, O has a lower electronegativity than F, but H2O has a greater boiling point compare to HF because in between H2O ---- H2O molecules, they can form 2 hydrogen bond between the molecule but between HF --- HF can only form one hydrogen bond. So, the more the hydrogen formed, greater the forces, higher the boiling point. The factors of hydrogen bonding can also use to explain the solubility of some organic compound in water, like example, ethane cannot dissolve in water but ethanol can dissolve in water, due to the hydrogen bonding.

Some of the molecules gain more stability by forming dimer with its molecules. E.g. : When ethanoic acid is brought to molecules. mass spectrometer for detection and it gives a peak at m/e at 120. This indicates the shows that ethanoic acid (CH3COOH) has a RMM of 120, as CH3COOH , RMM = 60.

This indicate ethanoic acid exist as dimer where interaction of hydrogen bonding between end of each functioning group COOH occur.

There is another application of hydrogen bond, which is the intermolecular forces and intramolecular forces. In 22nitrophenol and 4-nitrophenol, the boiling point of the 2 4compounds can be explain below :

Since 2-nitrophenol form strong hydrogen bond as 2intramolecular forces, the interaction between 2-nitrophenol 2molecules are weaker among each other, compare to 44nitrophenol, which used hydrogen bond as their intermolecular forces. With stronger hydrogen bond which act as the intermolecular forces, the boiling point of 4-nitrophenol 4is expected to be higher than 2-nitrophenol 2-