VSEPR (Valence-Shell Electron-Pair Repulsions) Model

1. For a particular number of electron-pairs around a central atom, there is a unique distribution that will
keep them as far apart as possible
2. Steric number = # of lone pairs or bonds of any types (objects) about the central atom
Possibility
Electron Arrangement
Molecular Shape
Bond Angle
Steric Number: 2
AX2
Linear
Linear
180
Steric Number: 3
AX3
Trigonal planar
Trigonal planar
120
AX2E
Trigonal planar
Bent
<120
Steric Number: 4
AX4
Tetrahedral
Tetrahedral
109.5
AX3E
Tetrahedral
Trigonal pyramidal
<109.5
AX2E2
Tetrahedral
Bent
<109.5
Steric Number: 5
AX5
Trigonal bipyramidal
Trigonal bipyramidal
120 equatorial, 90 else
AX4E
Trigonal bipyramidal
Seesaw
<120, <90
AX3E2
Trigonal bipyramidal
T-shaped
<90 (lone pairs in eq)
AX2E3
Trigonal bipyramidal
Linear
180
Steric Number: 6
AX6
Octahedral
Octahedral
90
AX5E
Octahedral
Square pyramidal
<90
AX4E2
Octahedral
Square planar
90
Drawing Lewis Structures
1. Write the skeletal structure
2. Determine the total number of valence electrons (accounting for the total charge)
3. Connect each pair of bonded atoms with a pair of electrons and then complete the octets of all atoms
other than the central atom (and hydrogen)
4. Place the remaining electrons (if any) on the central atom
5. If the central atom does not already have an octet, consider whether double or triple bonding will satisfy
it; if so, determine whether double or triple bonding is possible
6. Elements that do not double/triple bond: beryllium, boron, fluorine (and metals, typically); other
halogens can but very rarely do
7. Exceptions to the octet rule:
a. Incomplete octet has a valence less than eight
b. Odd-electron molecules will obtain a valence less than eight
c. Expanded octet many elements in the 3rd period and beyond (because of d orbitals)
1.
2.
3.
4.
5.

Formal Charge
Formal charge = # valence e- - # nonbonding e- - (# bonding e-)
Sum of formal charges in the Lewis structure = net charge on molecule or ion
Circle formal charges
The Lewis structure with the lowest total formal charge (and the lowest individual charges) is the best
Draw all resonance structures

Molecular Polarity
1. Molecules with no polar bonds or lone pairs (thus, no dipoles) on the central atom will not be polar
2. If molecule has polar bonds (dipoles) that point in opposite directions, it will not be polar
3. Lone pairs screw up symmetry (causing dipoles), making the molecule polar

1.
2.

3.
4.

Bond Energies and Heats of Reaction

Generally performed for reactions taking place entirely in the gaseous state (weak intermolecular forces)
Steps:
a. Bonds in reactant molecules break all endothermic (+H, add up for all bonds in the molecule)
b. Bonds in product molecules form all exothermic (-H, add up for all bonds in the molecule)
c. Take the net thats the heat of reaction (H)
This is like Hesss Law, but it isnt the same (this reaction is BE(reactants) BE(products))
This is an estimate not all bonds are the same, so this differs from thermodynamic values
Properties of Gases

1.
2.
3.
4.

No definite shape or volume

Volume is highly temperature and pressure dependent
Low densities
Gases that dont react with each other mix completely and uniformly

1.
2.
3.
4.
5.

Gas Pressure
Pressure a measure of the force exerted by collisions of gas molecules in a given area of the surface
SI unit is the pascal (Pa), but we generally use atmospheres (atm), torrs, or millimeters mercury (mmHg)
Barometer measures pressure by balancing force of gravity and force due to the pressure of the gas
Standard pressure 760 mmHg = 760 torr = 1 atm = 101,325 Pa
Manometer determines the pressure of a gas created by reaction; works like a barometer but contains
the gas being measured

Gas Laws
1. Boyles Law volume is inversely proportional to pressure (V1P1 = V2P2)
2. Charless Law temperature is directly proportional to temperature (V1/T1 = V2T2)
a. Temperature measured in Kelvin
b. Absolute zero = -273.15 degrees Celsius; any real gas will liquefy at this temperature; 0K
3. Gay-Lussacs Law pressure is directly proportional to temperature (P1/T1 = P2/T2)
a. We didnt talk about this in class, but I put it in just in case
b. Gas has to be held under constant volume
4. Avogadros Law volume is directly proportional to moles of gas (V1P1/T1 = V2P2/T2 for the same
number of moles)
a. From Halpins Notes: V (proportional to) n
b. For gaseous species involved in reactions taking place at constant P and T, stoichiometric
calculations may be performed in terms of volumes
5. Ideal Gas Law PV = nRT; MM = dRT/P; P1V1/n1T1 = P2V2/n2T2
a. This R is in (atm L / mol K)
b. Most gases will be ideal at low temperature and pressure, with high volume
c. STP = standard temperature and pressure = 0 degrees Celsius, 1 atm
d. 1 mol of a gas occupies 22.414 L at STP
e. For
6. Ideal Gas Properties:
a. Infinitely small particles
b. Particles exert no forces upon one another except during collisions
c. No real gas is ideal, but deviations can generally be neglected
7. Daltons Law of Partial Pressures Pt = Pa + Pb; Pt = ntRT/V
a. Mole fraction (X) Pa/Pt = na/(na + nb) = Xa; Pa = XaPt
b. Xa + Xb = 1
c. Gas collected over water: Pgas = Pt PH2O
Kinetic-Molecular Theory

1. Gases consist of large numbers of particles that are in continuous random motion
2. Total volume of all the particles of the gas is negligible compared to the total volume in which the gas is
contained
3. Attractive and repulsive forces between gas molecules are negligible (except during collisions)
4. Collisions between molecules and between molecules and the walls of their container are perfectly
elastic (energy can be transferred, but average kinetic energy of the collection remains constant)
5. Temperature of the gas is proportional to the average kinetic energy of the molecules; at a given
temperature, the average kinetic energy of the molecules of a gas will be the same no matter the identity
of the gas
6. These explain the observations behind the gas laws
7. Constant average kinetic energy does not mean all the gas particles have the same kinetic energy (or
speed, for that matter)
8. Avg u2 = 3RT/MM
9. Urms = sqrt(3RT/MM)
10. Effusion the escape of a gas from a container through a small hole
a. Heavier molecules (bigger MM) effuse more slowly; lighter (smaller MM) effuse quickly
b. Grahams Law: ratea/rateb = sqrt(MMb/MMa)
11. Diffusion a gas spreads through a space which may or may not already be occupied by another gas
Earths Atmosphere (from the book)
Pressure of the atmosphere decreases smoothly with distance from earths surface
10,000 km is technically space, although no specific boundary distinguishes the atmosphere from space
99% of the atmospheres mass lies within 30km of the surface; 75% within the lowest 11km
Temperature does not decrease smoothly atmosphere usually classified by direction of temperature
range
a. Troposphere surface to 11km, temperatures drop; weather occurs here
b. Stratosphere 11km to 50 km, temperatures rise
c. Mesosphere 50km to 80 km, temperatures drop
d. Thermosphere 80 km to 500km, temperatures rise
e. Exosphere 500km and outward, maintains thermosphere temperatures, merges with space
f. Further out is very cold, even though it has high temperature; this is because most particles have
very low kinetic energies, with a few having incredibly high KEs from solar radiation
5. Homosphere Mostly nitrogen gas, some oxygen gas, very little other gasses (mostly argon)
a. Gases behave ideally
b. Convective mixing (warm air rises, cool air sinks, mixing the composition) makes composition
uniform
i. Thermals rising warm air currents helps birds and glider pilots fly
ii. Convection cleans air
c. Temperature inversion occurs when warm air mass remains stationary over a cool one; blocks
normal convection and causes buildup of harmful pollutants
6. Heterosphere variable composition; convective heating does not reach these hights,s o gas particles
become layered according to molar mass (lower MM on top)
7. Stratospheric ozone absorbs much of the solar UV radiation from the sun
1.
2.
3.
4.

Deviations from Ideal Gas Behavior

1. Non-ideal conditions:
a. Low volume gasses collide more often, imfs take over
b. Large particles volume rules violated
c. High temperature and/or pressure same as low volume
2. For ideal gasses: PV/nRT = 1
3. Van der Waals equation: (P + n2a/V2)(V-nb) = nRT
a. Attempt to model real gasses

b. Large value for constant a means large pressure correction (imfs must be strong)
c. Large value for constant b means large volume correction (particles must be large)
Intermolecular Forces
1. Intermolecular forces forces between independent particles (NOT CHEMICAL BONDS)
2. Intramolecular forces chemical bonds
3. In order of decreasing relative strength (absolute strength depends on how many of each force)
a. Ion-ion forces: oppositely charged ions; occurs in a mixture of substances (i.e. a solution); this
force can be attractive (cation/anion) or repulsive (anion/anion or cation/anion)
b. Ion-dipole forces: occur between ions and polar molecules (note: there will probably also be
ion-ion and dipole-dipole forces in such a mixture)
c. Dipole-dipole forces: occur between two polar molecules
d. Ion-induced dipole forces: ion causes a dipole in a nonpolar molecule
e. Dipole-induced dipole forces: polar molecule causes a dipole in a nonpolar molecule
i. Heavy atoms tend to be more polarizable
ii. Tend to be temporary
f. London dispersion forces: always present; temporary dipoles created at random all the time
4. Other factors affecting imfs:
a. Protrusions on molecules weaken dispersion forces
b. High polarizability results in stronger dispersion forces (harder to vaporize)
c. Repulsive force between electron clouds; also occurs between nuclei
1.
2.
3.
4.
5.

Hydrogen Bonding
Hydrogen bonding a special case of dipole-dipole which is unusually strong
Hydrogen must be bonded to N, O, or F
Slightly positive hydrogen is attracted to LONE PAIR on the highly electronegative atom of another
molecule
Hydrogen bonded to N can hydrogen bond to O with lone pairs, etc.
Drastically changes physical properties (responsible for the uniqueness of water)

Properties of Liquids
1. IMFs are weak enough that particles slide past each other, but cannot expand freely
2. Liquids flow and take the shape of their container
3. A suspended drop forms a sphere minimal surface area for a given volume; this occurs because IMFs
act differently on surface molecules than on interior molecules
a. Surface action the amount of energy required to increase the surface area by one area unit
b. The stronger the IMFs, the larger the surface tension
4. Capillary action liquid particles rise up a thin tube
a. Cohesive forces IMFs keep liquid together
b. Adhesive forces IMFs attract liquid particles to container particles
c. Makes a meniscus (concave up) adhesion > cohesion
d. Can also make a negative meniscus (concave down) adhesion < cohesion
5. Viscosity a measure of a fluids resistance; stronger IMFs = more viscosity; chained molecules are
especially viscous
Water
1. Water undergoes hydrogen bonding; every water molecule can have four hydrogen bonds
2. Water has a very high surface tension for such a small molecule
3. Water is significantly viscous, has high heat capacity, melting, and boiling points, a large enthalpy of
vaporization and enthalpy of fusion, and is a very good solvent
4. Most important: ICE IS LESS DENSE THAN WATER IT FLOATS!!!
a. 3D network is formed when water freezes

b. H2O molecules are, on average, further apart as a crystal than in a liquid

c. Max density under 1 atm of pressure occurs at about 4 degrees Celsius
Properties of Solids
1. IMFs are too strong for particles to slide past each other or expand freely
2. Amorphous solid particle positions are fixed, but without a regular, repeating pattern
3. Crystalline solid pattern of fixed particles is regular and repeated throughout the solid
a. Unit cell a single instance of the repeating pattern
b. Lattice points locations occupied by particles
4. Seven crystal systems exist, but we use one: cubic crystals; 3 possible unit cells:
a. Simple cubic (sc) cell: has only corner cells just one particle
b. Body-centered cubic (bcc) cell: has corner cells and a center cell two particles
c. Face-centered cubic (fcc) cell: has corner cells and 6 face cells four particles
5. Type of unit cell formed by a particular substance depends upon types of constituent particles, relative
sizes, and conditions under which the crystal was formed
6. Coordination number the number of neighbors in contact with a given particle; the higher the
coordination number, the less empty space in the crystal
7. Packing efficiency the percent of the lattice which is actually occupied by particles
a. Fcc is the most efficient at about 74%; also called cubic closest packing (ccp)
b. Hexagonal closest packing (hcp) is just as efficient
c. Bcc is about 68%
d. Sc is about 52%
8. Relating atomic radius to face length:
a. Fcc: a = sqrt(8)r
b. Bcc: a = 4r/sqrt(3)
c. Sc: a = 2r
Tools of the Laboratory (from the book)
1. X-ray diffraction analysis used to determine the distance between layers of atoms (in crystal structure)
a. Two waves are diffracted at the same angle by adjacent layers
b. Spots are created on a photographic plate when waves are in phase (peaks and troughs aligned)
c. Crystal is rotated to create a diffraction pattern
d. Diffraction pattern is analyzed mathematically to find the dimensions of the crystal and the
distances and angles within the lattice
e. Used to prove that DNA is a double helix
2. Scanning tunneling microscopy also used to observe surfaces on the atomic scale
a. Electrons far from the nucleus can tunnel to end up closer to another atom
b. Tunneling electrons create a current that can be used to image the atoms of an adjacent surface
c. Probe is used to monitor electron movement
Crystalline Solids
1. Atomic and molecular solids
a. Constituent particles: atoms or molecules
b. Held in place by IMFs, not chemical bonds
c. IMFs vary, but are generally weaker than covalent or ionic bonds soft and have low melting
points; poor conductors of heat and electricity
2. Network covalent solids
a. Constituent particles held in place by strong covalent bonds crystals are hard
b. Bonding extends in 3 dimensions entire crystal is strong (diamond)
c. Boding extends in 2 dimensions strong layers held together weakly by dispersion forces
(graphite)
d. Most are poor conductors of heat and electricity (except carbon crystals)

3. Ionic solids
a. Constituent particles are cations and anions, held together by strong ionic bonds hard, high
melting points
b. Poor conductors in crystalline form, but good when melted
c. Relative sizes and numbers of cations and anions determine the unit cell
4. Metallic solids
a. Constituent particles are metal atoms suspended in a sea of electrons
b. Strength and rigidity vary greatly
c. Delocalized electrons make good conductors of heat and electricity
Phase Changes
1. Phase change the complete conversion of a sample from one physical state to another
2. Not all particles possess the same kinetic energy some particles may be capable of entering a less
ordered phase at any given temperature
a. Open container evaporation occurs regardless of temperature
b. Closed container evaporation and condensation occur; net amount of vapor and vapor pressure
remain constant (dynamic equilibrium)
c. Change in temperature establishes a new equilibrium and vapor pressure
3. Molar enthalpy of vaporization the amount of thermal energy that must be added to a 1 mol sample of
a liquid at its boiling point in order to convert it to 1 mol of gas at that same temperature
4. Molar enthalpy of fusion the amount of thermal energy required to melt 1 mol of a solid at its melting
point
5. H for a phase change and temperature for a phase change are not the same thing
Phase Diagrams
1. Vapor-pressure curve extends from the triple point to the critical point
2. Melting point curve extends upward from the triple point (usually with positive slope, although water
shows a negative slope)
3. Sublimation curve extends downward from the triple point toward the origin

4. Clasius-Clapeyron equation helps estimate molar enthalpy of vaporization from two points on a vaporpressure curve
Advanced Materials (from the book)
1. Crystal defects malformations in crystals that form rapidly; introduced intentionally to create materials
with improved properties (such as strength, hardness, or conductivity)
a. Alloying introduces several kinds of crystal defects
b. Alloyed metals are stronger and harder

2. Doped semiconductors conductivity greatly enhanced by adding small amounts of other elements to
increase or decrease valence electrons in conductivity bands on semiconductors
a. Adding electrons creates n-type semiconductors (negative charges present)
b. Adding elements with fewer valence electrons creates p-type semiconductors (slightly empty
orbitals create positive sites)
c. P-n junction: created by putting a positive and negative semiconductor together
d. Rectifier a device that converts alternating current into direct current
e. Transistors commonly created by making an n-p-n semiconductor
3. Liquid crystals flow like liquids but pack at the molecular level with a high degree of order
a. Gases and liquids are isotropic physical properties are the same in every direction
b. Crystalline solids are anisotropic physical properties depend on direction
c. Liquid crystals are anisotropic
d. Liquid crystal phases consist of individual molecules; usually a long, cylindrical shape and a
structure that allows intermolecular attractions through dispersion and dipole-dipole or Hbonding forces, but that inhibits perfect crystalline packing
e. Viscosity of liquid crystal phase lowest in direction parallel to long axis
f. Thermotropic phase develops as a result of a change in temperature; acts more like a liquid;
mixed with different molecules in display devices and cells to prevent this
g. Lysotropic phase occurs in solution as the result of changes in concentration; conditions vary
for different substances
h. Exhibit various types of order:
i. Nematic phase molecules lie in same direction but ends are not aligned
ii. Cholesteric / twisted nematic phase molecules lie in layers that exhibit nematic type
ordering, but layers are rotated; helical arrangement
iii. Smectic phase molecules lie parallel to each other with ends aligned; stacked layers
i. Liquid crystal displays depend on changes in molecular orientation in a field (usually use
twested nematic display); current running through display changes orientation of molecules
4. Ceramics nonmetallic, non-polymeric solids hardened by heating to high temperatures
a. Clay ceramics consist of silicate microcrystals suspended in a glassy cementing medium
b. Bricks, porcelain, glazes useful because of their hardness and resistance to heat and chemicals
c. Modern high-heat ceramics use silicon carbide, silicon nitride, boron nitride, and the
superconducting oxides; prepared by driving off a volatile component during reaction
d. Brittleness comes from microfine crystal defects that widen until a crack occurs; modern
ceramics is making this less of an issue
5. Polymeric materials consist of extremely large molecules
a. Polymer mass depends on molar mass of the repeat unit and the degree of polymerization (how
many repeats there are)
b. Polymer size and shape
i. Long axis of a polymer chain is the backbone
ii. Random coil chain turns back on itself and continuously changes direction
iii. IMFs between chain components determine shape
iv. Radius of gyration the average distance from the center of mass of the polymer to the
outer edge of the coil
c. Polymer crystallinity if the molecular structure allows neighboring chains to pack together and
if the chemical groups lead to favorable dipole-dipole, H-bonding, or dispersion forces, portions
of the chains can align regularly and exhibit crystallinity; at best, they are semicrystalline
d. Some polymers can make a solution much more viscous
i. Polymer glass chains dont crystallize
ii. Plastic a material that, when deformed, retains its new shape (not elastic)
e. Architecture of polymers:
i. Branches smaller chains appended to a polymer backbone

ii. Dendrimers ultimate branched polymers; prepared from monomers with three or more
attachment points; no backbone, just branches
iii. Crosslinks branches that link one chain to another
1. Small degree yields thermoplastic polymer (still flows at high temperatures)
2. More crosslinks yields thermoset polymer (no longer flows because it is a single
network)
iv. Elastomers polymers that can be stretched and immediately spring back to their shape
when released (occurs to thermoset above their glass transition temperatures)
v. Homopolymer consists of one type of monomer
vi. Copolymer consists of two or more types
1. Simplest is AB block copolymer (AAAAABBBBB)
2. ABA Block polymer (AAAABBAAAA)
3. Some block polymers act as thermoplastic elastomers materials shaped at high
temperature that become elastomers at room temperature
6. Nanotechnology the science and engineering of nanoscale systems
a. Quantum dots nanoparticles of semiconducting materials; used in imaging of specific cells
b. Nanostructuring construction of bulk materials from nanoscale building blocks; increases
strength, ductility, plasticity, and other properties
i. Nanocomposites behave as liquid magnets, ductile cements, conducting elastomers, etc
ii. Ferrofluid consists of magnetic nanoparticles dispersed in a viscous fluid
c. High-surface-area materials uses carbon nanotubes; may be important in hydrogen powered
cars
d. Nanomachines in nature, the virus; in science, just tiny machines
1.
2.
3.
4.
5.
6.

Born-Haber Cycle
Atomize the metal: solid to gaseous state
Atomize the nonmetal: gaseous to gaseous state
Ionize the metal atoms: gaseous atoms to gaseous ion
Add electrons to the nonmetal atoms: gaseous atom to gaseous ion
Allow ions to combine to form lattice: one ion + other ion product (usually looking for this H)
Hf = H1 + H2 + H3 + H4 + H5 (rearrange to solve for the H you need)