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Why we should study the bonding in solids?

The type of bond allows us to explain a materials properties

Consider carbon (exist as both graphite and diamond)

Graphite is relatively a soft material where as the Diamond is the hardest known material Graphite is opaque and metallic while Diamond is transparent This dramatic disparity in properties is directly attributable to a type of interatomic bonding found in graphite that does not exist in diamond

Graphite (Layered Structure)

The individual Carbon atoms link up to form sheets (layers) of Carbon atoms Within each sheet (layer), every C atom is bonded to 3 adjacent C atoms Three of four valence electron of carbon are used to form strong covalent bonds with the adjacent atoms in the sheet (Fourth electron is free to move over the surface making graphite an electrical conductor) The layers are held together by weak van der Waals forces Distance between the two layers is longer than that of the distance between the C atoms within each layer

Diamond (Rigid 3-D Structure)

Each carbon atom is strongly bonded to four adjacent atoms (All 4 electrons participate in the bond)
These bonds have same strength in all directions Each C atom is the same distance to each of its neighboring C atoms In this rigid network, the atoms can not move and thats why diamonds are so hard and have such a high melting point

Molecules and General Bonding Principles

When two atoms are brought together, the valence electrons interact with each other and with the neighbor's positively charged nucleus

Formation of a bond between the two atoms (A molecule is produced)

The energy of the system of two atoms together must be less than that of the two atoms separated, so that the molecule formation is energetically favorable (Molecule will be more stable)

Molecules and General Bonding Principles

Interatomic forces that bind the atoms together predicts the physical properties of the materials

At large interatomic distances, the interaction between the atoms is negligible

When the two atoms approach each other, the atoms exert two types of forces due to mutual electrostatic interactions Attractive forces Repulsive forces The magnitude of the forces can be expressed as a function of separation between the two atoms or interatomic distance

At small interatomic distances

Attractive force (FA) dominates over the Repulsive force (FR) (Initially it is attractive)
(Lowering of energy corresponds to an attractive interaction between the two atoms)

Net Force FN FA FR
Potential Energy E(r) of the two atoms

dE FN dr

FA varies slowly & FR varies strongly with separation FR is strongest when two atoms are very close When the atoms are so close, individual electron shells overlap (very strong electronto-electron shell repulsion) FR dominates When FA just balances FR, equilibrium will be reached (Net force is Zero)

At equilibrium, the atoms are separated by a certain distance (ro)
Equilibrium separation (ro) is effectively called as bond length

FN 0

dE 0 dr

At the equilibrium, the potential energy of the system will be minimum

Molecule will be formed only if the energy of the two atoms attain a minimum when they approach each other This minimum energy (E0) is the bond energy

An energy of E0 is required to separate the two atoms (Bond Energy)

We can apply this similar arguments to bonding between many atoms Only the actual details of FA and FR will be different for different materials But the general principle of bonding energy (E0) and an equilibrium interatomic separation (ro) will be still valid

Types of Bonding in Solids

Primary Bonding
1. 2. 3. Covalent Bonding Metallic Bonding Ionic Bonding

Secondary Bonding
1. 2. van der Waals Bond Hydrogen Bonding

Covalent Bonding
Two atoms can form a bond with each other by sharing some or all of their valence electrons (Overall potential energy is reduced when a bond is formed)
Covalent Bond between two Hydrogen atoms Covalent Bond Sharing of valence electrons to complete the subshells of each atom When the 1s subshells overlap, the electrons are shared by both atoms and each atom has a complete subshell Electrons 1 & 2 orbit both the atoms and they cross the overlap region more frequently Greater concentration of negative charge in the region between the two nuclei and keep the two nuclei bonded to each other Electrons 1 and 2 can avoid crossing the overlap region at the same time when their motions are synchronized

Covalent Bonding
When the electro-negativity between two atoms is small, the two atoms can form Covalent Bond by sharing a pair of electrons (one from each atom)
The electrons forming the bond tend to be partly localized in the region between the two atoms joined by the bond The spins of the two electrons in the bond are anti-parallel In CH4 molecule, C has 4 valence electrons and 4 H atoms has single valence electron Each H atom can get a He electron configuration (1s2), when the C atom shares one electron with H atom

Now, C has four additional shared electrons (one from each H) and a total of 8 valence electrons and has the
electron structure of Ne (1s2 2s2 2p6)

Covalently Bonded Solids (Methane CH4)

Covalent Bonding in Methane Electronic Structure of C: 1s2 2s22p2 [He]2s22p2 2s and 2p subshells correspond to L shell C atoms with 4 vacancies in the L shell (capacity of 8 electrons) can readily share electrons with four H atoms
CH4 in 3-D view
Schematic sketch of CH4 on paper The repulsion between the electrons in one bond and the electrons in a neighboring bond causes the bond to spread as far out from each other as possible In 3-D, the H atoms occupy the corners of an imaginary tetrahedron CH bonds are at an angle of 109.5 to each other

Covalently Bonded Solids (Diamond)

Coordination Number (CN) The number of nearest neighbor atoms for a given atom in the solid

Coordination Number (CN) = 4 (Diamond)

Examples of Covalently Bonded Molecules

Hydrogen Chloride (HCl)

Ar (18) electron structure

He (2) electron structure

Chlorine Molecule (Cl2)

Ar (18) electron structure (Ar (18) electron structure)

Examples of Covalently Bonded Molecules

Ne (10) electron structure

Examples of Covalently Bonded Molecules

Boron Trifluoride (BF3)

Boron (5) atom has only 3 electrons in its outer shell No possibility of reaching a Noble element structure

But Boron has formed the maximum number of bonds that can form
This is a perfectly valid structure

Metallic Bonding

High Electrical Conductivity

Large number of electrons in a metal are free to move (Conduction Electrons)

Normally the valence electrons become conduction electrons in solids Energy of the valence electrons in a crystal are lower than that of the free atoms

(The characteristic feature of the Metallic Bonding is the lowering of the energy of the valence electrons in the metal as compared with the free atom)

According to Heisenberg Uncertainty Principle x p h/2

In a free atom Valence electrons are restricted to a small volume (x is small) If x is small, p is large KE of the valence electrons is high

In a crystal, electrons are free to move in a large volume (x is large) If x is large, p is small KE of the valence electrons is reduced

Metallic Bonding
A chemical bond between atoms in a metallic element, formed by the valence electrons moving freely through the metal lattice Found in metals and their alloys Metals have one or two or three valence electrons These valence electrons are not bound to the any atom and free to move throughout the entire metal These electrons are electron cloud or sea of electrons Remaining non-valence electrons and atomic nuclei form Ion cores Ion Cores (net positive charge) = total valence electron charge
Free electrons shield the positively charged ion cores from the repulsive electrostatic forces Free electrons act as a glue to hold the ion cores together

Metallic Bonding
(The valence electrons from the metal atoms form a cloud of electrons which fills the space between the metal ions and glues the ions together through the coulombic attraction between the electrons gas and positive metal ions)

Only a few valence electrons in metals (not difficult to remove) When many metal atoms are brought together to form a solid, valence electrons are lost from individual atoms and become collectively shared by all the electrons Valence electrons become delocalized and form an electron gas (electron cloud) moving in the space between the ions Bonding is essentially due to the attraction between the stationary metal ions and the freely moving electrons between the ions

Metallic Bonding (Properties)

Bonding in Cu Metal Bonding is collective sharing of electrons and so it is nondirectional Metal ions try to get as close as possible leading to a close-packed crystal structures High coordination numbers compared to a covalently bonded solid
Due to nondirectional nature, under an applied force, the metal ions are able to move with respect to each other especially in the presence of certain crystal defects (Ductile nature) Free valence electrons in the electron gas can respond readily to an applied electric field and drift along the force of the field (Metals have high electrical conductivity) If there is a temperature gradient along a metal bar, the free electrons can also contribute to the energy transfer from the hot to the cold regions since they frequently collide with the metal ions and thereby transfer energy (Metals have good thermal conductivities)

Why does a metal object feel cold to touch?

Ionic Bonding
Ionic bonding in mostly found in materials having a metal and a nonmetal

Sodium (Na 11 ) Alkali Metal

One valence electron in the 3s subshell Easily removed to form Na+ ion with complete subshells Na+ ion looks like the inert element Ne, but with a positive charge

Chlorine (Cl 17) Halogen atom 3p subshell has five valence electrons Readily accept one electron to close the 3p subshell and becomes Cl ion

Cl ion looks like the inert element Ar with a net negative charge

Ionic Bonding
Transferring the valence electron of Na to Cl results in two oppositely charged ions Na+ (cation) and Cl (anion)
Due to Coulombic force, the two ions pull each other until the attractive force is just balanced by the repulsive force between the close electron shells Initially, energy is needed (ionization energy) to remove the electron from Na atom

This is more than compensated for by the energy of Coulombic attraction between the Na+ and Cl ions
The net effect is lowering of potential energy of the ions pairs (Na+ and Cl ions)

When many Na and Cl atoms are ionized and brought together, the resulting collection of ions is held together by the Coulombic attraction between the Na+ and Cl ions

Ionic Bonding
When many Na and Cl atoms are ionized, then the solid will consist of Na+ cations and Cl anions holding each other through the Coulombic force Coulombic force around a charge is nondirectional

There are also repulsive forces between the Na+ ions and also between the Cl ions For the solid to be stable, each Na+ ion must have Cl ions as nearest neighbors and vice versa so that like-ions are not close to each other

Ionic Bonding in MgO

Ionic bond metal +

donates electrons Dissimilar electro-negativities
ex: MgO Mg 1s2 2s2 2p6 3s2 [Ne] 3s2
Mg2+ 1s2 2s2 2p6 [Ne]

accepts electrons

O 1s2 2s2 2p4

O2- 1s2 2s2 2p6 [Ne]

Ionic Bonding
The ions are in equilibrium and the solid is stable when the net potential energy is minimum Variation of net PE for a pair of ions with the interatomic distance r

dE / dr 0

Zero Energy Neutal Na and Cl atoms are separated About 1.5 eV is required to transfer the electron from Na to Cl and form Na+ and Cl ions As the ions come together, the energy is lowered, until it reaches a minimum at about 6.3 eV below the energy of the separated Na and Cl atoms When r = 0.28 nm, the energy is minimum and the ions are in equilibrium

The bonding energy per ion in solid NaCl = 6.3/2 = 3.15 eV Atomic Cohesive Energy The energy required to take solid NaCl apart into individual Na and Cl atoms (3.15 eV per atom)

Examples: Ionic Bonding

NaCl MgO CaF CsCl 2

Give up electrons

Acquire electrons

Properties of Ionic Solids

They are strong, brittle materials with high melting temperatures

Mostly soluble in polar liquids like water

Typical electrical insulators (all the electrons are positioned within ions no free electrons to move around the crystal)

Low thermal conductivity (ions can not transfer vibrational KE to their neighbors)

Ionic Bond in Fe2O3

Valency of Iron
Fe (2, 3)

Fe2+ Iron [II] or Ferrous

Fe3+ Iron [III] or Ferric 26 Iron: [Ar], 4s2, 4d6 8 Oxygen: [He], 2s2, 2p4

Ionic Bond in MgCl2

12 - Magnesium: [Ne], 3s2

17 Chlorine: [Ne], 3s2, 3p5

Ionic Bond in MgO

12 - Magnesium: [Ne], 3s2 8 Oxygen: [He], 2s2, 2p4

Non-Directional Bonding
Ionic Bonding is non-directional
Magnitude of the Bond is equal in all directions around an ion For ionic crystals to be stable, all positive ions must have as nearest neighbors negatively charged ions in a three-dimensional scheme and vice-versa Electrons have equal forces acting upon them for each of the atoms of the compound No atom has more influence over electrons than the other.

Metallic Bonding is also non-directional

Directional Bonding
Covalent bond is directional Bonding is between specific atoms and may exist only in the direction between one atom and another that participates in the electron sharing The atom that has a higher affinity pulls the shared electron(s) more strongly than the other This gives it a partial negative charge, and a partial positive charge to the other. This results in a directional bond.

Secondary Bonding
Primary Bonds: Covalent, Metallic and Ionic Bonds Inert elements Have stable electron configuration
Have completely filled shells (they can not accept or give any electrons)
Can not have primary bonds between the atoms because of having full shells

A solid phase of argon (Ar) exists at low temperatures (< 189C)

There must be some bonding mechanism between the Ar atoms (Secondary Bonding)

The magnitude of this bond cannot be strong because above 189C, solid Ar melts Water molecules attract each other to form the liquid state below 100C and the solid state below 0C There exists a weak type of attraction (van der WaalsLondon force) between all atoms and molecules due to a net electrostatic attraction between the electron distribution of one atom and the positive nucleus of the other

Secondary Bonding
In many molecules, concentrations of negative and positive charges do not coincide

Polar molecules: Molecules with dipole moment

HCl molecule: The electrons spend most of their time around Cl nucleus

Positive nucleus of the H atom is exposed (H has donated its electron to Cl) and the Cl-region acquires more negative charge
When a negative and positive charge of equal magnitude are separated by a distance as in the H+Cl molecule, an electric dipole moment is created

Secondary Bonding
Dipoles can attract or repel each other depending on their relative orientations (arrangements) The magnitude of the net force between the dipoles A and B does not depend on their separation r as 1/r2 because there are both attractions and repulsions between the charges on A and charges on B The net force is only weakly attractive Suitably arranged dipoles can attract each other and form van der Walls bonds The energies of arranged dipoles are less than that of totally isolated dipoles and therefore encourage bonding (Secondary bonding) Secondary bonds are weaker than primary bonds

Hydrogen Bonding

Water molecule (H2O) is a polar molecule It has a net dipole moment as shown here

Attractions between the positive charges on one molecule and the negative charges on a nearby molecule lead to van der Waals bonding between the H2O molecules

When the positive charge of a dipole as in H2O arises from an exposed H nucleus, van der Waals bonding is called as Hydrogen Bonding

Hydrogen Bonds
A Hydrogen Bond is a type of attractive (dipole-dipole) interaction between an electronegative atom and a hydrogen atom bonded to another electronegative atom. (Usually the electronegative atom is Oxygen, Nitrogen or Fluorine)
Hydrogen must be covalently bonded to another electronegative atom to create the bond

This bond always involves a hydrogen atom of one molecule

Hydrogen on one molecule attached to O or N or F is attracted to an O or N or F of a different molecule The hydrogen atom loses its electron to another atom in the molecule The bare proton forms the hydrogen bond The atoms adjacent to the proton are so close and so the hydrogen bonds connects only two atoms

Covalent Bond

Covalent Bond

Hydrogen Bonding in Ice

In ice, the H2O molecules, again attracted by van der Waals forces, bond to form a regular pattern and hence a crystal structure is obtained for ice

Crystal structure of ice

Dashed lines represent hydrogen bonds

Examples of Hydrogen Bonds

Water (H2O) molecules Ammonia (NH3) molecules

Hydrogen Fluoride (HF) molecules

Hydrogen peroxide (H2O2) molecules Methanol (CH3OH) molecules

Acetic acid (CH3COOH) molecules

Methyl amine (CH3NH2) molecules Hydrogen bond is also found in the structures of DNA and Protein

Secondary Bonding in Inert gases

Consider the bonding between the Ne atoms at low temperatures
Each has closed (full) electron shells The center of mass of the electrons in the closed shells coincides (when averaged over time) with the location of the positive nucleus

Some times, the center of mass is displaced from the nucleus due to various motions of the individual electrons around the nucleus

The center of mass of all the electrons fluctuates with time about the nucleus
Electron charge distribution is not static around the nucleus but fluctuates asymmetrically and an instantaneous dipole moment is created

Secondary Bonding in Inert gases

When two Ne atoms, A and B, approach each other, the rapidly fluctuating charge distribution on one affects the motion of the negative charge distribution on the other

A low energy configuration (attraction) is produced when the fluctuations are synchronized Negative charge distribution on A get closer to the nucleus of the other (B), while the negative distribution on B at that instant stays away from that on A The strongest electrostatic interaction arises from the closest charges which are the displaced electrons in A and the nucleus in B This means that there will be a net attraction between the two atoms and hence a lowering of the net energy which in turn leads to bonding This type attraction is due to induced synchronization of the electronic motions around the nuclei (induced dipole-induced dipole interaction)

Molecular Solids
Molecular Solids
Solids in which constituent molecules (or atoms) have been bonded by van der Waals forces

Ice Solidified CO2 (dry ice) Solidified O2 Solidified H2 Solidified CH4 Solid inert gases (Ne below 25 K & Ar below 84 K)

Definition of Bonds
Covalent bond is a type of chemical bond formed between the atoms of two or more nonmetal elements by sharing of electrons between the atoms Two non-metal atoms can form a covalent bond with each other by sharing some or all of their valence electrons

Ionic bonds are formed between a cation, which is usually a metal and an anion, which is usually a non-metal (The ions are formed by transferring electrons from one atom to another)
Ionic bond is a type of chemical bond formed through an electrostatic attraction between two oppositely charged ions Metallic bond is a chemical bond between atoms in a metallic element, formed by the valence electrons moving freely through the metal lattice Bonding is essentially due to the attraction between the stationary metal ions and the freely moving electrons between the ions Hydrogen bond is usually formed between the hydrogen atom of one molecule bonded to an electronegative atom and the electronegative atom of another molecule

Mixed Bonding
In many solids, the bonding between atoms is generally a mixture of bonds types

Silicon crystal
Bonding is totally covalent since the bonding is between the same atoms Shared electrons in the bonds are equally attracted by the neighboring positive ion cores The electrons are equally shared between the atoms Covalent Bonding between two different atoms Two neighboring ions are different (Electrons become unequally shared) Atoms have different electron-attracting abilities Bonding is not purely covalent (it has some ionic character) because the shared electrons spend more time close to one of the ion cores

Mixed Bonding
GaAs Crystal

Bonding is not totally covalent since the bonding is between the different two atoms
In GaAs, the electrons in a covalent bond spend slightly more time around the As5+ ion core than the Ga3+ ion core GaAs have polar covalent bonds

POLAR COVALENT BONDS Covalent bonds that have an ionic character, due to an unequal sharing of electrons

Covalent Bond in Si

Each Si atom contributes one of its 4 outer shell electrons with neighboring Si atom This will contribute a pair of shared electrons between two Si atoms to form a covalent bond Two atoms are identical (same) Electrons are equal shared between the atoms Electrons have the highest probability of being located at equal distances between the two atoms

14 Silicon: [Ne], 3s2, 3p2

18 - Argon: [Ne], 3s2, 3p6

Polar Covalent Bond in GaAs

Covalent bond is formed by the sharing of an electron from a Ga atom and one from a neighboring As atom Ga atom has only 3 electrons in its outer shell As atom has 5 electrons in its outer shell

3 covalent bonds due to electrons from Ga and As

1 covalent bond is formed by As atom contributing two electrons Since the atoms involved are different, the electrons in the bonds are more attracted toward the atom with largest nucleus Electrons spend more time on the As5+ ion core than the Ga3+ ion core

31 Gallium: [Ar], 4s2, 4d10, 4p1 33 Arsenic: [Ar], 4s2, 4d10, 4p3

36 Krypton: [Ar], 4s2, 4d10, 4p6

Mixed Bonding in Ceramic Materials

Ceramic Materials
Compounds that generally contain metallic and non-metallic elements They are well known for their brittle mechanical properties, hardness, high melting temperatures and electrical insulating properties Type of bonding may be covalent or ionic or mixture of covalent and ionic

Silicon Nitride (Si3N4) Covalent Bonding

Magnesia (MgO)
Alumina (Al2O3)

Ionic Bonding
Mixture of ionic & covalent bonding

What type of bonding would be expected for each of the following materials: Solid Xenon, Bronze and Rubber Solid Xenon Bonding is van der Waals bond since xenon is an inert gas Bronze Bonding is metallic since it is a metal alloy of copper and tin Rubber Bonding is covalent with some van der Waals bond (Rubber is composed of mainly carbon and hydrogen atoms)

Explain why hydrogen fluoride (HF) has a higher melting temperature than hydrogen chloride (HCl) (19.4C vs 85C), even though HF has a lower molecular weight

The intermolecular bonding in HF The intermolecular bonding is HCl

Hydrogen bonding van der Waals bonding

Since the hydrogen bond is more stronger than van der Waals, HF will have a higher melting temperature