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

Chapter 2 Outline www.people.virginia.edu/~rej/class209/mse209.html Review of Atomic Structure Electrons, Protons, Neutrons, Quantum mechanics, Electron states, The Periodic Table

Interatomic bonding
First step in understanding material properties Atomic Bonding in Solids Energies vs. Forces Periodic Table Primary Interatomic Bonds Ionic Covalent Metallic Secondary Bonding (Van der Waals) Molecules and Molecular Solids
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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 (-): protons(+) 1.6 10-19 Coulombs.

Neutrons are electrically neutral.

Masses: Protons and Neutrons ~1.67 10-27 kg.

Electron 9.11 10-31 kg

Atomic mass = # protons + # neutrons

Atomic number (Z) = # protons chemical identification of element

Isotope number # neutrons
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic mass units. Atomic weight.

Atomic mass unit (amu) 1 amu = 1/12 of mass of most common isotope of C 6 protons (Z=6) and six neutrons (N=6). The atomic mass of
12C

atom is 12 amu.

Atomic weight: A Weighted average of atomic masses of naturally occurring isotopes. Atomic weight of carbon is 12.011 amu.
Atomic weight is often in mass per mole.

A mole
Amount of matter with mass in grams equal to the atomic mass in amu (A mole of carbon has a mass of 12 grams).

One Mole contains Avogadros number of atoms, 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

Number density, n: (number of atoms per cm3) Mass density, (g/cm3) Atomic mass, A (g/mol):
n = Nav / A Graphite (carbon): = 2.3 g/cm3, A = 12 g/mol n = 61023 atoms/mol 2.3 g/cm3 / 12 g/mol = 1.15 1023 atoms/cm3 Diamond (carbon): = 3.5 g/cm3, A = 12 g/mol n = 61023 atoms/mol 3.5 g/cm3 / 12 g/mol = 1.75 1023 atoms/cm3 Water (H2O) = 1 g/cm3, A = 18 g/mol n = 61023 molecules/mol 1 g/cm3 / 18 g/mol = 3.3 1022 molecules/cm3

SIZE of a Atom or Molecule If n = 6 1022 atoms/cm3 Mean separation between atoms L = (1/n)1/3 = 0.25 nm. scale of atomic structure in solids a fraction of 1 nm or a few Angstroms
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (I)

Electrons form a cloud around the nucleus Radius ~ 0.05 1nm.

Picture looks like a mini planetary system. But Quantum Mechanics says this analogy is not correct

Electrons orbits are 'fuzzy Can only discuss probability of finding it at some distance from the nucleus. Only certain orbits or shells are allowed. Shells identified by principal quantum number n, n related to size of radius (and energy) n = 1, smallest; n = 2, 3 .. are larger.
Second quantum number l, defines subshells. Two more quantum numbers characterize states within subshells.
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (II) Quantum Numbers came from solution of Schrodingers equation Pauli Exclusion Principle: only one electron can have a given set of the four quantum numbers.
Maximum Number of Electrons in Shells and Subshells
Principal Q. N., n 1 (l=0) 2 (l=0) 2 (l=1) 3 (l=0) 3 (l=1) 3 (l=2) 4 (l=0) 4 (l=1) 4 (l=2) 4 (l=3) Subshells s s p s p d s p d f Number of States 1 1 3 1 3 5 1 3 5 7 Number of Electrons Per Subshell Per Shell 2 2 2 8 6 2 18 6 10 2 32 6 10 14

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

Electrons in Atoms (III)

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

Electrons fill levels in order of increasing energy (only n, make a significant difference). Example: Iron, Z = 26: 1s22s22p63s23p63d64s2 Outermost shell the valence electrons responsible for bonding.
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Periodic Table

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

Periodic Table - Electronegativity

Figure 2.7 from text Electronegativity - 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 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

attraction

equilibrium
Typical potential between two atoms Repulsion when they are brought close together Related to Pauli principle (As electron clouds overlap energy increases) Attractive part: at large distances (Depends on type of bonding)

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

Bonding Energies and Forces

a0

Potential Energy

Ut=Ur+Ua

E0

a0

E0 bond energy F= dE/da a0 equilibrium distance at a0, dE/da = 0, Fa = Fr

Tensile (+)

Compressive (-)

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

The electron volt (eV) Energy unit convenient for atomic bonding Electron volt energy lost / gained when an electron 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: Example - Na+Cl Strong Coulomb interaction between a positive atom (lost an electron, Na+) and a negative atom (an extra electron, Cl-) Covalent: electrons shared between the atoms. Example - H2 Metallic: Atoms lose some electrons from valence band Those electrons are shared by all the material 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 dipoles (polar molecules - H2O, HCl...)
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (I)

Mutual ionization by electron transfer (remember electronegativity table) Anion = negatively charged atom Cation = positively charged atom
Ions are attracted by strong coulombic interaction Oppositely charged atoms attract An ionic bond is non-directional

Example: NaCl Na has 11 electrons, 1 more than needed for a full outer shell (Neon) 11 Protons Na 1S2 2S2 2P6 3S1 11 Protons Na+ 1S2 2S2 2P6 donates e10 e- left

Cl has 17 electron, 1 less than needed for a full outer shell (Argon) 17 Protons Cl 1S2 2S2 2P6 3S2 3P5 17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 receives e18 e14

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

Ionic Bonding (II) eNa Cl Na+ Cl-

Electron transfer reduces energy of the system

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

Covalent Bonding (I)

Electrons shared between the atoms. Valence electrons spend more time between nuclei than outside bonding. Covalent bonds- HIGHLY directional in direction of greatest orbital overlap

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)

Example: Carbon 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 (III)

2-D schematic of the spaghetti-like structure of solid polyethylene

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

Covalent Bonding (IV)

Potential energy of system of covalent bonds

P.E.=

Depend on distances between atoms AND angles between bonds

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

Metallic Bonding
Valence electrons are detached from atoms Spread in an 'electron sea' that "glues" the ions together Metallic bond is non-directional atoms pack closely

Electron cloud from valence electrons

ion core

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

Secondary Bonding (I)

Secondary = physical bond (as opposite to chemical bond that involves e- transfer) Interaction of dipoles Is weak, ~0.1 eV/atom or ~10 kJ/mol.

-two dipoles attract

Permanent dipoles exist in some molecules polar molecules: e.g. HCl, H2O Due to asymmetry of positive and negative regions Strongest among secondary bonds. Polar molecule induces a dipole in adjacent non-polar molecule. Attraction between the permanent and induced dipoles. Fluctuations of electron density distribution in one atom A is felt by the electrons of an adjacent atom: Mutual dipoles induced (van der Waals) This bond is the weakest (He-Ne, H2 - H2).
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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

Summary (I)

Examples of bonding in Materials:

Metals: Metallic
Ceramics: Ionic / Covalent Polymers: Covalent and Secondary Semiconductors: Covalent or Covalent / Ionic

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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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