Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chapter Outline Review of Atomic Structure Electrons, Protons, Neutrons, Quantum mechanics of atoms, Electron states, The Periodic Table Atomic Bonding in Solids Bonding Energies and Forces Periodic Table Primary Interatomic Bonds Ionic Covalent Metallic Secondary Bonding (Van der Waals)
Three types of Dipole Bonds

Molecules and Molecular Solids Understanding of interatomic bonding is the first step towards understanding/explaining materials properties
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Review of Atomic Structure

Atoms = nucleus (protons and neutrons) + electrons Charges: Electrons (-) and protons (+) have negative and positive charges of the same magnitude, 1.6 10-19 Coulombs. Neutrons are electrically neutral. Masses: Protons and Neutrons have the same mass, 1.67 10-27 kg. Mass of an electron is much smaller, 9.11 10-31 kg and can be neglected in calculation of atomic mass.

The atomic mass (A) = mass of protons + mass of neutrons # protons gives chemical identification of the element # protons = atomic number (Z) # neutrons defines isotope number

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic mass units. Atomic weight.

The atomic mass unit (amu) is often used to express atomic weight. 1 amu is defined as 1/12 of the atomic mass of the most common isotope of carbon atom that has 6 protons (Z=6) and six neutrons (N=6). Mproton Mneutron = 1.66 x 10-24 g = 1 amu. The atomic mass of the 12C atom is 12 amu. The atomic weight of an element = weighted average of the atomic masses of the atoms naturally occurring isotopes. Atomic weight of carbon is 12.011 amu. The atomic weight is often specified in mass per mole. A mole is the amount of matter that has a mass in grams equal to the atomic mass in amu of the atoms (A mole of carbon has a mass of 12 grams). The number of atoms in a mole is called the Avogadro number, Nav = 6.023 1023. Nav = 1 gram/1 amu. Example: Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Some simple calculations

The number of atoms per cm3, n, for material of density d (g/cm3) and atomic mass M (g/mol):
n = Nav d / M Graphite (carbon): d = 2.3 g/cm3, M = 12 g/mol n = 61023 atoms/mol 2.3 g/cm3 / 12 g/mol = 11.5 1022 atoms/cm3 Diamond (carbon): d = 3.5 g/cm3, M = 12 g/mol n = 61023 atoms/mol 3.5 g/cm3 / 12 g/mol = 17.5 1022 atoms/cm3 Water (H2O) d = 1 g/cm3, M = 18 g/mol n = 61023 molecules/mol 1 g/cm3 / 18 g/mol = 3.3 1022 molecules/cm3 For material with n = 6 1022 atoms/cm3 we can calculate mean distance between atoms L = (1/n)1/3 = 0.25 nm. the scale of atomic structures in solids a fraction of 1 nm or a few A.

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (I)

The electrons form a cloud around the nucleus, of radius of 0.05 2 nm. This Bohr picture looks like a mini planetary system. But quantum mechanics tells us that this analogy is not correct:
Electrons move not in circular orbits, but in odd shaped orbitals depending on their quantum numbers.

Only certain orbits or shells of electron probability densities are allowed. The shells are identified by a principal quantum number n, which can be related to the size of the shell, n = 1 is the smallest; n = 2, 3 .. are larger. The second quantum number l, defines subshells within each shell. Two more quantum numbers characterize states within the subshells.
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Quantum Rules n can take any positive integer value l can take any integer value between 0 and n-1. Therefore there are n possible values of l for a given n ml can take any integer value between - l and + l. Thus there are (2 l +1) values of ml for a given l ms can take two values: 1/2 Thus for any given value of l (an electron subshell) there are 2(2 l +1) electrons; for any given value of n (an electron shell) there are 2(2 l +1) electrons (add up all the subshells)

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure Recall Isotopes

C12 where 12 = 6 Protons + 6 Neutrons C13 where 13 = 6 Protons + 7 Neutrons (Isotope) Isotopic abundance of C13 1.1 % Carbon: 12.01 g/mol Atoms having the same atomic number but varying numbers of neutrons are isotopes

Mass of basic particles: Particle Charge Mass (amu*) (1.66x10-24 or 1/Nav) Proton +1 1.00814 (1.6734x10-24g) Neutron 0 1.00898 (1.675x10 -24g) Electron -1 0.00055 (0.000911x10 -24g) The atomic mass unit (amu) is the basic unit of measurement of an atoms mass, one amu = (1/12)*12C6 (1 amu = 1.660420 x 10 -24g)
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (II) The quantum numbers arise from solution of Schrodingers equation Pauli Exclusion Principle: only one electron can have a given set of the four quantum numbers.
The Number of Available Electron States in Some of the Electron Shells and Subshells

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (III)

1s 2s sp 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s 7p

Subshells by energy: 1s,2s,2p,3s,3p,4s,3d,4s,4p,5s,4d,5p,6s,4f,

Electrons that occupy the outermost filled shell the valence electrons they are responsible for bonding. Electrons fill quantum levels in order of increasing energy (due to electron penetration) Example: Iron, Z = 26: 1s22s22p63s23p63d64s2
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Draft of the periodic table, Mendeleev, 1869

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

General Periodic Table: Metals and Non- Metals

Elements in the same column (Elemental Group) share similar properties. Group number indicates the number of electrons available for bonding.
0: Inert gases (He, Ne, Ar...) have filled subshells: chem. inactive IA: Alkali metals (Li, Na, K) have one electron in outermost occupied s subshell - eager to give up electron chem. active VIIA: Halogens (F, Br, Cl...) missing one electron in outermost occupied p shell - want to gain electron - chem. active
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Periodic Table - Electronegativity

The electronegativity values.

Electronegativity - a measure of how willing atoms are to accept electrons Subshells with one electron - low electronegativity Subshells with one missing electron -high electronegativity Electronegativity increases from left to right Metals are electropositive they can give up their few valence electrons to become positively charged ions

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Bonding Energies and Forces

repulsion Potential Energy, E

0 attraction equilibrium

This is typical potential well for two interacting atoms The repulsion between atoms, when they are brought close to each other, is related to the Pauli principle: when the electronic clouds surrounding the atoms starts to overlap, the energy of the system increases abruptly. The origin of the attractive part, dominating at large distances, depends on the particular type of bonding.
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Bonding Behavior But what does it mean??

(a) High melting temperature, high elastic modulus, low thermal expansion coefficient

(b) Low melting temperature, low elastic modulus, high thermal expansion coefficient

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Relevant Equations Coulombic Attraction Force Oppositely Charged Ions Fc = K/r2, r = atomic separation distance between ion centers K = - k0 (Z1q)(Z2q), q = 1.6 x 10-19 coulomb/unit charge Z = valence of the ion (+1,+2,+3,-1,-2,-3) Fc = - [k0 (Z1q)(Z2q)] / r2 Repulsive Force FR = e-a/p ,p are constants At equilibrium: FN = 0 = FA + FR = 0, FA = FR

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

The electron volt (eV) energy unit convenient for description of atomic bonding Electron volt - the energy lost / gained by an electron when it is taken through a potential difference of one volt.

E=qV

For q = 1.6 x 10-19 Coulombs V = 1 volt 1 eV = 1.6 x 10-19 J

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Types of Bonding
Primary bonding: e- are transferred or shared Strong (100-1000 KJ/mol or 1-10 eV/atom) Ionic: Strong Coulomb interaction among negative atoms (have an extra electron each) and positive atoms (lost an electron). Example - Na+Cl Covalent: electrons are shared between the molecules, to saturate the valency. Example - H2 Metallic: the atoms are ionized, loosing some electrons from the valence band. Those electrons form a electron sea, which binds the charged nuclei in place Secondary Bonding: no e- transferred or shared Interaction of atomic/molecular dipoles Weak (< 100 KJ/mol or < 1 eV/atom) Fluctuating Induced Dipole (inert gases, H2, Cl2) Permanent dipole bonds (polar molecules - H2O, HCl...) Polar molecule-induced dipole bonds (a polar molecule like induce a dipole in a nearby nonpolar atom/molecule)
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (I)

Formation of ionic bond: 1. Mutual ionization occurs by electron transfer (remember electronegativity table) Ion = charged atom Anion = negatively charged atom Cation = positively charged atom 2. Ions are attracted by strong coulombic interaction Oppositely charged atoms attract An ionic bond is non-directional (ions may be attracted to one another in any direction Example: NaCl
11 Protons Na Electron Configuration?
17 Protons Cl

Electron Configuration?

Na (metal) unstable electron Na (cation) stable

Cl (nonmetal) unstable

Coulombic Attraction

Cl (anion) stable
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (II) Na eCl Na+ Cl-

Electron transfer reduces the energy of the system of atoms, that is, electron transfer is energetically favorable Note relative sizes of ions: Na shrinks and Cl expands

Ionic bonds: very strong, nondirectional bonds

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Predominant bonding in Ceramics

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

NaCl MgO CaF2 CsCl

Ni 1.8 Zn 1.8 As 2.0

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

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (III)

Crystal Structures in Ceramics with predominantly ionic bonding

Crystal structure is defined by Magnitude of the electrical charge on each ion. Charge balance dictates chemical formula (Ca2+ and F- form CaF2). Relative sizes of the cations and anions. Cations wants maximum possible number of anion nearest neighbors and vice-versa. Stable ceramic crystal structures: anions surrounding a cation are all in contact with that cation. For a specific coordination number there is a critical or minimum cationanion radius ratio rC/rA for which this contact can be maintained.

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (I)

In covalent bonding, electrons are shared between the molecules, to saturate the valency. The simplest example is the H2 molecule, where the electrons spend more time in between the nuclei than outside, thus producing bonding. Formation of covalent bonds: Cooperative sharing of valence electrons Can be described by orbital overlap Covalent bonds are HIGHLY directional Bonds - in the direction of the greatest orbital overlap Covalent bond model: an atom can covalently bond with at most 8-N, N = number of valence electrons Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5) N = 7, 8 - N = 1 can form only one covalent bond

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (II)

Whereas the metallic and ionic CN is based on size and hard sphere Packing, covalent bonding is based on a different set of rules. Hard sphere model r/R CN (ionic, metallic) 0.732r/R<1 8 r/R = 1 12 Covalent bond model: 8-N, N = number of valence electrons
El.
C Si GaAs

Config.
(1S)2 2S2 2P2 ..3S2 3P2 Ga ..4S2 4P1 As.. 4S2 4P3

Xtal structure
diamond cubic diamond cubic zinc blend

# valence e4 4 4 average

8-N
4 4 4

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (III)

Example: Carbon materials. Zc = 6 (1S2 2S2 2P2) N = 4, 8 - N = 4 can form up to four covalent bonds ethylene molecule:

polyethylene molecule:

ethylene mer

diamond: (each C atom has four covalent bonds with four other carbon atoms)

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (IV)

Example: Hybridization Diamond if covalently-bonded carbon Expected CN=12 (if ionic, equal sizes, r/R = 1) Observed CN=4 (tetrahedral coordination) Explanation: directional bonding Outer shell electrons 2s and 2p hybridize to form 4equally-spaced orbitals Reason: greater orbital overlap possible

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

EXAMPLES: COVALENT
BONDING
column IVA

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

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

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Metallic Bonding (I)

Valence electrons are detached from atoms, and spread in an 'electron sea' that "glues" the ions together. A metallic bond is non-directional (bonds form in any direction) atoms pack closely

Electron cloud from valence electrons

ion core

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Metallic Bonding (II)

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (I)

Secondary = van der Waals = physical (as opposed to chemical bonding that involves e- transfer) bonding results from interaction of atomic or molecular dipoles and is weak, ~0.1 eV/atom or ~10 kJ/mol.

Arises from interaction between dipoles

Fluctuating dipoles
asymmetric electron clouds

ex: liquid H 2 H2 H2

- secondary +
bonding

H H

secondary bonding

H H

Permanent dipoles-molecule induced

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

secondary bonding

H Cl
secon dary bond

secondary bonding

H Cl

ing

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (II)

Example: hydrogen bond in water. The H end of the molecule is positively charged and can bond to the negative side of another H2O molecule (the O side of the H2O dipole)

+ Dipole
Hydrogen bond secondary bond formed between two permanent dipoles in adjacent water molecules.
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (III)

Hydrogen bonding in liquid water from a molecular-level simulation

Molecules: Primary bonds inside, secondary bonds

among each other
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (IV)

The Crystal Structures of Ice

Hexagonal Symmetry of Ice Snowflakes

Figures by Paul R. Howell

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

PROPERTIES FROM BONDING: TM

Bond length, r Melting Temperature, Tm

Energy (r) ro r smaller Tm larger Tm

r
Bond energy, Eo

Energy (r) ro
unstretched length

r Eo= bond energy

Tm is larger if Eo is larger.

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

PROPERTIES FROM BONDING: E

Elastic modulus, E

Elastic modulus
F L =E Ao Lo
length, Lo

cross sectional area Ao L

undeformed deformed

E ~ curvature at ro Energy
ro
unstretched length

r smaller Elastic Modulus larger Elastic Modulus

E is larger if Eo is larger.
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Coefficient of thermal expansion,

PROPERTIES FROM BONDING:

length, Lo

coeff. thermal expansion L Lo

= (T2-T1)

unheated, T1

heated, T2

~ symmetry at ro

Energy ro larger smaller

is larger if Eo is smaller.
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

SUMMARY: PRIMARY BONDS

Ceramics
(Ionic & covalent bonding):

Large bond energy

large Tm large E small

Metals
(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate

Secondary bonding dominates small T (Covalent & Secondary): small E large

secon d ary b

Polymers

Directional Properties

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (II)

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (III)
Make sure you understand language and concepts: Atomic mass unit (amu) Atomic number Atomic weight Bonding energy Coulombic force Covalent bond Dipole (electric) Electron state Electronegative Electropositive Hydrogen bond Ionic bond Metallic bond Mole Molecule Periodic table Polar molecule Primary bonding Secondary bonding Van der Waals bond Valence electron
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