ChemistryandIntermolecularForces

MTE207MaterialsScienceandEngineering
Sept.30,2014
JonathanPuthoff
DepartmentofChemicalandMaterialsEngineering
CalPolyPomona

MaterialsEngineeringMinor@CPP
Engineersareconstantlycalledupontointroducenew
materialsintotheirdesignsandprojects.Inmanyways,
thematerialsavailablearetheprimarylimitingfactorin
engineering.
ForCHEs
MTE207
MTE317L
CHE313
CHE333L
CHE302
+3electives

ForMEs
ME315
ME350L
ME218
ME220L
ME301
+3electives

ForAROs
MTE207
MTE317L
ARO326
ARO357L
CHE302
+3electives

Review MaterialsKnowHow
Properties

Performance

Structure

Processing

MaterialsTetrahedron

Review EngineeringMaterials

Crystals regular arrangements of

atoms/molecules
H

Glasses irregular arrangements of

atoms/molecules

H
H

C
C

Polymers molecular
spaghetti
H
C
H

C
H

Composites combinations of two

(or more) different materials

Plus: carbon-based materials

and biomaterials

Review PropertiesofMaterials
Opticalproperties

Mechanicalproperties

absorptivity
color
photosensitivity
reflectivity
refractiveindex
transmittance

ductility
fracturetoughness
hardness
elasticity
yieldstrength
viscosity

Thermal
properties

Electrical/
magnetic
properties
conductivity
dielectricstrength
permeability
permittivity
piezoelectricity
diamagnetism
paramagnetism
ferromagnetism

Other
acousticproperties
surfaceproperties
processability
reactivity

boilingpoint
emissivity
heatoffusion
meltingpoint
heatofvaporization
transitiontemperature
thermalexpansion
specificheat
thermalconductivity

Review AtomicStructure
The motions of electron are probabilistic,
but their states can be categorized
using quantum numbers
1. The first quantum number n gives the
electrons energy level
2. The second quantum number
describes the shape of its orbit
3. The third quantum number m gives the
orientation of its orbit
4. (The fourth quantum number ms
indicates the orientation of the
electrons axis of rotation and is 1/2)
Energylevels

neutron(n0)
proton(p+)
electron(e)

Shorthand: n,,m

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

1s n =1, = 0 (ground state)

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

2s

1s

n =2, = 0

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

2s

1s

2p

n =2, = 1

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy
2p
levelsplitting

2s

1s

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

3s
2p
2s

1s

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

3s

3p
2p

2s

1s

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

4s
3s

3p
2p

2s

1s

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

3d

4s
3s

3p
2p

2s

1s

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

4s
3s

4p
3p
2p

2s

1s

3d

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

5s
4s
3s

4p
3p
2p

2s

1s

3d

BuildinganAtomwithElectrons
Levelstructurediagram
0
Energy

5s
4s
3s

4p

3d

3p
2p

2s

Start

1s

Electronicconfigurationsare
stablewhentheorbitalsare
filledintheorderoftheir
energy

TrendsinElectronicStructure
Periodictable
E.g.Nhas
only1more
electron
thanC,but
itsprop
erties are
moresimilar
tothoseofP

Whenplacedinorderandspacedaccordingtoelectronicstructure,theelementsfall
naturallyintogroupswhosemembershavesimilarproperties
http://www.kde.org/applications/education/kalzium/

Mutations
Ion =atomwithmoreorfewerelectrons
Isotope =atomwithmoreorfewerneutrons
E.g.

Ion

additionalelectron
meanstheionhas
anoverallnegative
charge

Vs.
missingelectron
meanstheionhas
anoverallpositive
charge

Isotope

12
C6

13
C6

1%ofCatoms
onEarthhave7
neutrons
insteadof6

ElectronicExcitations
Atomsthathaveobtainedadditionalenergymay
experiencechangesintheirelectronicstates
0
Energy

4s
3s

3p
2p

2s

1s

Promotion of
electronfromn =2
ton =3

AtomicInteractions
repulsion between overlapping e clouds (the
number of e in each energy state is limited)

attraction between oppositely-charged ions

repulsion between similarly-charged ions

+
+

attraction between polarized atoms

IonicInteractions
IonsinteractviatheelectrostaticorCoulomb force.
[Fromfaraway:]

Oppositechargesattract..

andlikechargesrepel.

(separationr)

Coulombforce :F =

q1q2

2
2
4 0r
r

IonicSolid
35
Cl17
23
Na11
saltmolecule
saltcrystal

Forcevs.Separation

PolarSpecies
Molecules(oratomsorpartsofmolecules)whichhavenonetchargeoverallbut
whichhavewelldefinedpositiveandnegativeendsarecalledpolar.

+
fromfaraway

UPCLOSE
H
Examples:

H
O
H

PolarInteractions
Diploesinteractwith(i)ionsand(ii)otherdipoles

1
Dipole - ion force : F 5
r

Dipole - dipole force : F

1
r7

Polar/Nonpolar Interactions
Supposeyouhaveachemicalspecies(atomormoleculeorsomethingorother)
thatisBOTHneutralANDnonpolar?Whatthen?

Polar/Nonpolar Interactions
Supposeyouhaveachemicalspecies(atomormoleculeorsomethingorother)
thatisBOTHneutralANDnonpolar?Whatthen?
Supposeyouhaveadipoleandaneutralspeciesthatareclosetooneanother:

Polar/Nonpolar Interactions
Supposeyouhaveachemicalspecies(atomormoleculeorsomethingorother)
thatisBOTHneutralANDnonpolar?Whatthen?
Supposeyouhaveadipoleandaneutralspeciesthatareclosetooneanother:

Polar/Nonpolar Interactions
Supposeyouhaveachemicalspecies(atomormoleculeorsomethingorother)
thatisBOTHneutralANDnonpolar?Whatthen?
Supposeyouhaveadipoleandaneutralspeciesthatareclosetooneanother:

Polar/Nonpolar Interactions
Supposeyouhaveachemicalspecies(atomormoleculeorsomethingorother)
thatisBOTHneutralANDnonpolar?Whatthen?
Supposeyouhaveadipoleandaneutralspeciesthatareclosetooneanother:

Polar/Nonpolar Interactions
Supposeyouhaveachemicalspecies(atomormoleculeorsomethingorother)
thatisBOTHneutralANDnonpolar?Whatthen?

induceddipole

dipole - induced dipole : F

1
r7

SpontaneousPolarization
Thiseffectcanevenoccurbetweentwoneutral,nonpolar speciessincethe
electrondistributionsintherespectivespeciescanfluctuate.(Electronstatesare
nottrajectories,theyareprobabilities.)
Thoughatomormoleculemaybenonpolar onaverage,thequantumbehaviorof
theboundelectronsenablesthemtotemporarilyadoptconfigurationsthat
producepolarity.

t =

0
Dipoledecay

Nonpolar/Nonpolar Interactions
Thesetemporarydipolescaninduceotherdipoles.
(Sincethedipolesareelectromagneticfluctuations,theyinteractatthespeedof
light.)

Nonpolar/Nonpolar Interactions
These temporary dipoles can induce other dipoles.
(Since the dipoles are electromagnetic fluctuations, they interact at the
speed of light.)

induceddipole- induceddipole: F

1
r7

Pauli Repulsion

NOT ALLOWED!

SummaryofInteractions
+

ion ion :F 2
r

STRONG

1
ion dipole :F 5
r

MEH
1

dipole dipole :F 7
r

WEAK
1

dipole induceddipole :F 7
r

induceddipole induceddipole:F 7
r

SummaryofInteractions
18371922

vander Waals forces

1

dipole dipole :F 7
r
1

dipole induceddipole :F 7
r
1

induceddipole induceddipole:F 7
r

InteractionForcevs.Energy
In order to move an object from point A to point B in the presence of a
force, you need to do some work (w). That work (or, alternately, the
potential energy you impart to the system) is given by the solution to

dw
F (r) =
dr

InteractionForcevs.Energy
In order to move an object from point A to point B in the presence of a
force, you need to do some work (w). That work (or, alternately, the
potential energy you impart to the system) is given by the solution to

dw
F (r) =
dr
This gives

w(r ) = F (r ) dr

CombinedInteractions
Manytotalattractive/repulsiveinteractionscanbedescribedby

C1

C2

w(r ) = n+6 n
r
r

wheren istheexponentthatdeterminesthestrengthofthe
interaction

E.g.LennardJonesPotential

Calledthe612 potential
Strongrepulsion atsmallseparation
vdW attraction atlargerseparations
Usefulforatomisticsimulations

C1 C2
w(r) = 12 6
r
r
Israelachvili IntermolecularandSurfaceForces (1996)

Chemistry CovalentBonding
Whensomeatomsapproacheachother,theymayforma
complexandsharetheirelectrons
(Thisarrangementlowers thetotalsystemenergyrelativeto
theenergiesoftheindividualatoms)
E.g.water
chemicalbond

H
O

H2O

BasicTypesofBonds
Ionic

Covalent

e transfer

H2O
HybridizedbondinginC

Metallic

Vander Waals

Electronegativities

Electronegativities areusedforguesstimatingwhat
kindofbondyouwillfind largedifferencesin
electronegativity correspondtomoreioniccharacter