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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
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)
FN FA FR 0
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
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
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
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)
Coordination Number (CN) The number of nearest neighbor atoms for a given atom in the solid
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
(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)
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
Ionic Bonding
Ionic bonding in mostly found in materials having a metal and a nonmetal
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
nonmetal
accepts electrons
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)
Give up electrons
Acquire electrons
27
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)
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.
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
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
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
Covalent Bond
Covalent Bond
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
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
Examples
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
31 Gallium: [Ar], 4s2, 4d10, 4p1 33 Arsenic: [Ar], 4s2, 4d10, 4p3
Examples
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
Since the hydrogen bond is more stronger than van der Waals, HF will have a higher melting temperature