ATOMIC BONDING IN SOLIDS

BONDING AND PROPERTIES

ISSUES TO ADDRESS... What promotes bonding? What types of bonds are there? What properties are inferred from bonding?

orbital electrons: n = principal quantum number 1 2 n=3

BOHR ATOM

Nucleus: Z = # protons = 1 for hydrogen to 94 for plutonium N = # neutrons Atomic mass A Z + N

ELECTRON ENERGY STATES

Electrons...
have discrete energy states tend to occupy lowest available energy state.

Increasing energy

n=4 n=3 n=2 n=1

4p 4s 3s 2s 1s 3p 2p

3d

STABLE ELECTRON CONFIGURATIONS

Stable electron configurations...
have complete s and p subshells tend to be unreactive.

Z Element Configuration 2 He 1s2 10 Ne 1s22s 22p6 18 Ar 1s2 2s22p63s23p6 36 Kr 1s2 2s22p63s23p63d10 4s24p6

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element Atomic # Hydrogen 1 Helium 2 Lithium 3 Beryllium 4 Boron 5 Carbon 6 ... Neon 10 Sodium 11 Magnesium 12 Aluminum 13 ... Argon 18 ... ... Krypton 36
Electron configuration 1s 1 1s 2 (stable) 1s 22s 1 1s 22s 2 1s 22s 22p 1 1s 22s 22p 2 ... 1s 22s 22p 6 (stable) 1s 22s 22p 63s 1 1s 22s 22p 63s 2 1s 22s 22p 63s 23p 1 ... (stable) 1s 22s 22p 63s 23p 6 ... 1s 22s 22p 63s 23p 63d 10 4s 24 6 (stable)

Why? Valence (outer) shell usually not filled completely.

THE PERIODIC TABLE

give up 1e give up 2e give up 3e accept 2e accept 1e inert gases
He O S F Ne Cl Ar Se Br Kr Te I Xe Po At Rn

Columns: Similar Valence Structure

Metal Nonmetal Intermediate

Li Be

Na Mg

K Ca Sc Rb Sr Cs Ba Fr Ra Y

Electropositive elements: Readily give up electrons to become + ions.

Electronegative elements: Readily acquire electrons to become - ions.

ELECTRONEGATIVITY
Ranges from 0.7 to 4.0 Large values: tendency to acquire electrons.
H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7 Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9 Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 1.8 As 2.0 F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 He Ne Ar Kr Xe Rn -

Smaller electronegativity

Larger electronegativity

Interatomic Forces

Attractive repulsive Magnitude of each a fn. of interatomic distance Net force bet. two atoms FN=FA + FR When FN and FR balance, FN = 0

r0 corresponds to separation distance at min. of P.E curve, E0 and shape of E vs r curve vary from MATERIAL TO MATERIAL and depend on the TYPE OF ATOMIC BONDING

BONDING IN MATERIALS
Primary Bonding (Intra molecular 150 to 800kJ mol-1 ) Ionic
(NaCl,MgO, CaF2 etc.)

Secondary Bonding (Intermolecular forces 1 to 40kJ mol-1)

(Vanderwaals Bonding) (inert gases)

Covalent

Metallic

(CH4,Ge,C,SiC, (all elemental metals) GaAs,Diamond etc.) When a bond is formed the total energy in BONDED STATE is < that in the FREE STATE For both IONIC and COVALENT BONDING Directional (many non metallic molecules) Association can take place when the bonded state achieves the stability ie A STATE OF MINIMUM ENERGY When two atoms combine,energy must be released so that total energy is lowered. This is known as BONDING ENERGY

Nondirectional

ELECTRONIC CONFIGURATION OF ALL IONS OF A SIMPLE IONIC CRYSTAL SHOWS CLOSE ELECTRONIC SHELLS CHARGE DISTRIBUTION IS SPHERICALLY SYMMETIRC INERT GASES
FOR IONIC CRYSTAL TO BE STABLE,ALL POSITIVE IONS MUST HAVE AS NEAREST NEIGHBOURS NEGATIVELY CHARGED IONS IN A 3D SCHEME. NON DIRECTIONAL BONDING: MAGNITUDE OF THE BOND IS EQUAL IN ALL DIRECTIONS AROUND AN ION ( EACH ION HAS A UNIFORMLY DISTRIBUTED ELECTRIC FIELD,ONE CANNOT PREDICT THAT A PARTICULAR ION IS BONDED TO THIS OR THAT ATOM). PREDOMINANT BONDING IN CERAMIC MATERIALS IS IONIC

Attractive bonding forces are COULOMBIC (between positive and negative ions) For two isolated ions , the attractive energy Ea is a function of the INTERATOMIC DISTANCE according to Ea = -A / r , A=(z1e )(z2e)/40, (MADELUNG Energy) , Similarly for the repulsive energy, E b = B / r n A,B and n are constants and their values depend on the particular ionic system

REAL IONIC CRYSTAL: approximately spherical symmetry ,some distortion near the region of contact with neighbouring atoms

IONIC BONDING

Occurs between + and - ions. Requires electron transfer. Large difference in electronegativity required. Example: NaCl
Na (metal) unstable electron Na (cation) stable Cl (nonmetal) unstable

Coulombic Attraction

Cl (anion) stable

EXAMPLES: IONIC BONDING

Predominant bonding in Ceramics
NaCl MgO CaF2 CsCl
Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 1.8 As 2.0

H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7 Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9

He O F 3.5 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 Ne Ar Kr Xe Rn -

Give up electrons

Acquire electrons

Good conductors of heat and electricity in molten state or aqueous medium

LATTICE is a regular geometrical array formed by a large no. of +ve and ve ions held togetherby elecrostatic attraction. Energy released during the formation of a lattice is known as LATTICE ENERGY Lattice is a highly stable arrangement. For high lattice energy, size of cation < size of anion, more effective is the nucleus of the cation to pull the neighbouring anion towards it

COVALENT BONDING
Requires shared electrons Example: CH4

C: has 4 valence e, CH4 needs 4 more H: has 1 valence e, H needs 1 more Electronegativities are comparable.

shared electrons from carbon atom

H shared electrons from hydrogen atoms

Covalent Bond
ELECTRONS IN COVALENT BOND ARE LOCALIZED IN THE REGIONS BETWEEN THE TWO ATOMS JOINED BY THE BOND POSSIBLE NUMBER OF COVALENT BONDS
NO. OF VALENCE ELECTRONS = N NO. OF COVALENT BONDS = 88-N (by octet rule for stability of atoms) INTER ATOMIC BONDING : PARTIALLY IONIC and PARTIALLY COVALENT GREATER THE DIFF. IN ELECTRONEGATIVITY MORE IONIC NATURE OF THE BOND (larger the separation both
column wise or row wise in the Periodic Table, more ionic nature of the bond)

Percentage ionic character of a bond between elements A and B, (A being more electronegative) = {1{1- exp[exp[-(0.25)(XAXB)2]} X 100

Covalent bonds are less dense than the Ionic/Metallic bonds, because Covalent bonds are directional and they cannot pack together in as dense a manner, yielding a lower mass density

EXAMPLES: COVALENT BONDING

H2
H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7 Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9

column IVA

H2O C(diamond) SiC

Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 1.8 Ga 1.6

F2
He O 2.0 F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 Ne Ar Kr Xe Rn -

C 2.5 Si 1.8 Ge 1.8 Sn 1.8 Pb 1.8

Cl2

As 2.0

GaAs

Molecules with nonmetals Molecules with metals and nonmetals Elemental solids (RHS of Periodic Table) Compound solids (about column IVA)

F0RMATION OF COVALENT BOND:

1.SHARING ELECTRONS BETWEEN ATOMS OF SAME TYPE, eg: H2,Cl2,O2 etc 2.SHARING ELECTRONS BETWEEN ATOMS OF DIFFERENT KINDS, eg:H20,CH4,HCL etc

METALLIC BONDING
Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).

+ + +

+ + +

+ + +

Primary bond for metals and their alloys

Metal is a network of ions in a sea of electrons, with the electron sea providing the binding force which holds the metal ions together

Electrons are shared by all atoms,that is they are delocalized throughout the crystal

Arises from interaction between dipoles Fluctuating dipoles ex: liquid H2 asymmetric electron H2 H2 clouds

SECONDARY BONDING

- secondary +
bonding

H H

secondary bonding

H H

Permanent dipoles-molecule induced

-general case: -ex: liquid HCl -ex: polymer

secondary bonding secondary bonding

H Cl
s e c on

H Cl

dary bond in

Coulombic interaction between +ve end of one dipole and ve region of the adjacent dipole Strength of these types of forces decreases with increase in intermolecular separation

Polar HCl Molecule Polar moleculemolecule-Induced dipole bonds

Molecule develops a TEMPORARY DIPOLE (INSTANTANEOUS DIPOLE)

ATTRACTIVE FORCES between TEMPORARY DIPOLE and INDUCED DIPOLE are known as Van der waals forces FLUCTUATING DIPOLE BONDS ARE BETWEEN NON POLAR ATOMS/MOLECULES

HYDROGEN BONDING
EXISTS IN THE MOLECULES THAT HAVE HYDROGEN BONDED TO NITROGEN, OXYGEN or FLUORINE ELECTROSTATIC FORCE OF ATTRACTION EXISTS BETWEEN THE COVALENTLY BONDED HYDROGEN ATOM OF ONE MOLECULE AND THE ELECTRONEGATIVE ATOM OF THE OHER MOLECULE + --------H + F ------------H F-----------

Hydrogen Bond Covalent Bond * H atom must be bonded to a highly electronegative atom * Size of electronegative atom should be small(HCl does not contain a Hydrogen bond,because size of Cl is large) It coexists with the covalent bond ,weaker than primary bonds but stronger than secondary bonds M.P and B.P is high compared to other intermolecular bondings

SUMMARY: BONDING
Type
Ionic

Bond Energy
Large!

Comments
Nondirectional (ceramics)

Covalent

Directional Variable large-Diamond semiconductors, ceramics small-Bismuth polymer chains) Variable large-Tungsten small-Mercury smallest

Metallic

Nondirectional (metals) Directional inter-chain (polymer) inter-molecular

Secondary

 Bond length, r
F

PROPERTIES FROM BONDING: TM

F

Melting Temperature, Tm

Energy (r)

r Bond energy, Eo

ro
r smaller Tm r larger Tm
Tm is larger if Eo is larger.

Energy (r)
unstretched length ro

Eo= bond energy

PROPERTIES FROM BONDING: E

Elastic modulus, E
length, Lo cross sectional area Ao

Elastic modulus
F L =E Ao Lo

undeformed deformed

E ~ curvature at ro Energy
unstretched length ro

E is larger if Eo is larger.

smaller Elastic Modulus larger Elastic Modulus

PROPERTIES FROM BONDING:

Coefficient of thermal expansion,
length, Lo

coeff. thermal expansion

unheated, T1

heated, T2

L Lo

= (T2-T1)

~ symmetry at ro Energy

Small dimensional alterations for changes in temperature

ro larger smaller

is larger if Eo is smaller.

SUMMARY: PRIMARY BONDS Ceramics Large bond energy

(Ionic & covalent bonding): large Tm large E small

Metals
(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate

Polymers
(Covalent & Secondary):
s e c on dary bond in g

Directional Properties
Secondary bonding dominates small T small E large

 Problems: 2.13 to 2.18 2.13 The net Potential Energy bet. two adjacent ions, E N = EA + ER= - A/r + B/rn ------(1) By differentiating EN w.r.t r, dEN /dr = - A/r2 + nB/rn+1 = 0 (r is minimum at E0 = r0 r0= equilibrium inter-ionic spacing), or, A/ r2 = nB/rn+1, A/nB = r2/rn+1, A/nB = r1-n, Therefore, r0 = (A/nB)1/1-n-----(2) , (A=1.436,B=7.32 x 10-6,n=8) Putting these values n the above expression, r0= 0.236nm. Substituting the expression for r0 from (2) in (1) and solving for E (= E0 )and solving it, we get, E0 = -5.32ev

2.15

r0 = (A/nB)1/1-n , E 0 = - A/(A/nB)1/1-n + B/(A/nB)n/1-n Thus we have two simultaneous equations with two unknowns (A and B),substituting the values of r0 and E0 in terms of n, we get, 0.35nm = (A/10B)1/1-10 -6.13ev = - A/(A/10B)1/1-10 + B/(A/nB)10/1-10 simultaneous solutions to these two equations give, A=2.38 and B=1.88X10-5, EA =- A/r = -2.38/r ER = B/rn = 1.88X10-5 / r10