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Goals Define basic concepts (refortify your chemistry): Filling of Atomic Energy Levels: Pauli Exclusion Principle Atomic Orbitals (s-, p-, d-, and f- type electrons) Types of Bonding between Atoms The Periodic Table (and solid state structures) Bond Energy Curves Describe how types of bonding affect Bond-Energy Curves. Describe how the Bond-Energy Curve describes macroscale properties. Learning Objective Use the Bond-Energy Curve to describe qualitatively the different types of materials and their macroscale properties. Know the origins of stress and strain, melting temperature, and thermal expansion.
letter s p d f
1 2 3
Magnetic, m: Allowed values of m are -l to +l (2l + 1 distinct values) Spin, ms: Allowed values of ms are -1/2 (spin-up) and +1/2 (spin-down).
Pauli Exclusion Principle: No two electrons in the same system can share the same four (n, l, m, ms) quantum numbers!
4s is slightly lower in energy and fills first, but is removed first as it is less tightly bound (remove electron in higher lowest quantum levels first). Electrons in higher states, which resides farther from nuclei, come off first. Consider Mn (1s22s22p63s23p63d54s2), what is Mn2+ state?
Avogadros Number: 1 mole has 6.023 x 1023 atoms (or molecules). (e.g. at. wt. of Fe is 55.85 amu/atom or g/mol) 1 amu/atom (or molecule) = 1 g/mol
Occurs for electronegative (positive) elements that can form close-shell configurations. Requires work to remove (add) efrom Na (to Cl-). Electronegativity plays a role here, e.g., H-F.
Structure is determined by electrostatic attraction EA = A/r (Coulombs Law) and collapse is prevented by electronic and nuclear repulsion ER = +B/rn.
Ionic Solids
Lets find the energy required to transfer an electron from Na to Cl and then to form a NaCl molecule
To remove an electron from Na (ionize the atom) one needs to spend 5.14eV (compare with the ionization energy of a hydrogen atom?)
Cl + e- Cl- + 3.62eV
Ionic Solids
In solid, Na+ and Cl- are brought together at the distance r0 2.51 [ = 10-10m = 0.1nm]
The total energy is lowered due to the Coulomb attraction 1 e2 The results is -5.73 eV
4 0 r
Thus when a NaCl molecular unit of NaCl solid is formed the following occurs Na + 5.14eV Na+ + eCl + e- Cl- + 3.62 eV Cl- + Na+ NaCl + 5.73 eV Na + Cl NaCl + 4.21 eV
Ionic Solids
The energy gain for NaCl solid is ~ 4.21 eV per NaCl pair
This is the energy required to break an NaCl molecule and restore neutral Na and Cl atoms
This energy is huge (in 1 cm3): 4.211.610-19 (Joules per pair) 3 1022 (pairs) = 20200 Joules
To more accurately calculate the total electrostatic energy, need to calculate interaction of each ion with all other ions in the crystal
Ionic Solids
In ionic crystals all electrons are bound to the ions: There are no free electrons!!!
There are ionic conductors, where ions, and not electrons conduct: Example: AgI
Bonding energies (E0): range from 68 kJ/mol (0.7 eV/atom) for Hg to 850 kJ/mol (8.8 eV/atom) for W. Melting temperatures (Tmelt~E0): -39 C for Hg and 3410 C for W. Stronger bonds lead to higher melting temperature: atomic scale property macroscale property.
Sum together, they look like this! Again, bonding determines structure, which also affects properties.
Chapter 3 Materials Principles and Practice, Materials in Action Series, edited by Charles Newey and Graham Weaver.
(really 3D)
How are macroscopic properties (mechanical, structural, thermal, electrical, optical, ...) most simply related to bonding? Are there directionality dependencies in materials response? Can point defects (i.e., vacancies or impurities) change such bonding related properties?
Energy : Etotal = E A + ER
Particular forms if EA and ER depends upon atoms and quantum mechanics, but often described by simple forms. A B EA = and E R = n r r
(e.g., Coulombic, A = ( Z1e)(Z 2 e) ) 4 0
Repulsive force
Force : F =
dE dr
=
r0
dE A dr
r0
dE R dr
r0
F
Hooke's Law
Stress-Strain Curve
F
simple tension test
r0
dU =0 dr r 0 min . ener gy E 0 : U (r 0 ) equil . bond r 0 : F =
Stored energy goes as U0 goes
U F r0 E0
Smaller Tm
Larger Tm
U F r0 E0
Smaller E Less stiff
Larger E More stiffer
E
r0
as E0 (less negative)
Volume Thermal Strain
Larger E Smaller
Parabolic E vs. r shape
V/V0 = V (T - T0)
Symmetric well r(T)=r0: No expansion possible Atoms just vibrate back and forth!
E~(r - r0)2