Chapter 9

I. Electrons
a. Valence: the outer electrons
i. If you finish the d subshell, those count as the core (because 4s3d4p)
ii. Except for helium, the number of valence electrons = the group number
b. Sizes of atoms are determined by their:
i. Electronic structure (electron groups—electron geometry)
ii. Interactions between their nucleus and electrons
1. Interactions follow electrostatic principles
2. Greater charge = greater attraction
3. Electron-electron repulsion
iii. Atomic radius increases down a column, decreases across a period
1. Additional protons outweigh the effects of additional electrons
iv. Cations are smaller than neutral atoms, neutral atoms smaller than anions
c. Zeffective
i. The net positive charge from the nucleus that an electron “feels”
ii. Greater Zeffective = stronger pull on electrons from nucleus = smaller size
1. If same number of core electrons, the one with more protons will
be smaller in size and have a greater Z
Z
iii. eff =Z−S
1. Z: number of protons
2. S: shielding; measure of how much the core electrons and other
valence electrons prevent and electron from feeling the full
strength of the protons in the nucleus
a. DON’T COUNT THE LAST ELECTRON
b. Valence electrons: #(0.35)
c. Core electrons: #(0.85)
d. Example?
II. Energy
a. Ionization energy
i. The energy required to remove an electron from an atom to make it a
cation
ii. First ionization energy: removes the first electron (always one at a time)
iii. IE decreases down a column and increases across a period (generally, but
half-filled p orbitals and completed orbitals have higher IEs
iv. Greater Zeff = greater IE
v. Exceptions
1. IEBe > IEB and IEN > IEO, even though they’re earlier in the period
a. Be: 1s22s2 and B: 1s22s22p1 but harder to remove electron
from Be because now it’s full like a core orbital
 2. When a new subshell begins, the IE of that element is lower
because it’s easier to remove that one electron
3. Half-filled p subshells have a lower energy because it doesn’t want
to lose that last electron, so its IE is high
vi. The second IE is always greater than the first!
1. Takes more energy to remove an electron from a cation than an
anion (making it even more positive)
2. Even if it’s a naturally occurring ion! Need more energy to get
from Mg+ to Mg2+ than from Mg to Mg+
b. Electron affinity
i. The change in energy when an electron is added to an atom to form an
anion
1. Energy needed for an atom to accept an electron
ii. Energy is released to accept an electron, negative EA
iii. If EA is positive, energy must be added for an atom to accept the electron
iv. EA generally become more negative across a period (stops at nobles)
v. Look at photo of electron configurations about adding/taking e-
c. Ionic bonding
i. Cations-anions joining through electrostatic attractions
1. Na (thru ionization energy)  Na+ and e-
2. Ca (thru electron affinity), takes Na+’s electron  Cl-
ii. Ionic lattices: the repetition of a compound in a 3D structure
iii. Lattice energy
1. When an ionic compound forms, energy is released (the energy
needed to separate a compound into its ions) (bond formation is
exothermic)
2. More energy is released when the ions are smaller or highly
charged
3. Compare charges first (higher charge = higher lattice energy) then
compare radii (smaller = higher lattice energy)
k (q 1 q 2)
iv. Eelectron =
d
1. Eelectron = Potential energy
2. k = constant
3. q 1 = the charge of one ion
4. d = the distance between the ions
5. Greater distance = lower energy = weaker bond
6. Greater charge = greater energy
7. Greater radii = lower energy
Chapter 10
I. Covalency
a. Based on the electron sharing between atoms (nonmetal-nonmetal)
b. Octet rule: 8 valence electrons are the most stable
i. Full s and full p
ii. Exceptions
1. Incomplete octets
a. He and H form duplets
b. B forms only 3 bonds (BCl3, no lone pairs)
c. Be usually forms 2 bonds instead (BeH2)
2. Expanded octets
a. Has 5 bonds or extra lone pairs on the central atom
b. n ≤ 3 for the central element
c. Electrons can be shared
i. Electrons act as a wave and a particle
ii. The shared electrons exist as overlapping charge clouds that are accessible
to both atoms
II. Lewis structures
a. Each line = 1 pair of electrons
b. To draw
i. Sum all of the valence electrons of the atoms in the molecule
ii. The central atom is the least electronegative (never is hydrogen, usually
the single atom, often carbon)
iii. Draw a single bond and then fill up the valence electrons on the outer
atoms
iv. Only use double and triple bonds if insufficient total to have 6 extra/atom
c. Resonance
i. Equivalent Lewis structures
ii. The complete structure shows all of the resonance structures
1. Only applicable when a molecule has a double or triple bond that
could’ve been on a different pair of atoms
iii. Delocalized electron: the electron pairs that swap places
iv. Delocalized bond: the bond that swaps places
III. Polarity
a. Electronegativity
i. Electron affinity: adding electrons to a molecule (energy is required);
experimental values
ii. Electronegativity: the ability of an atom to attract electrons to itself;
mathematically calculated values
1. the difference between the two is that electronegativity is a
chemical property that shows how well an atom can
attract electrons towards itself while electron affinity is defined
 as the amount of energy released when an electron is added to a
neutral atom
iii. Pauling scale
1. EN increases across a period, decreases down a column
2. High EN: electrons pulled closer (smaller radii); less likely to share
electrons (won’t be the central atom)
a. Central atom is the least EN
3. Electrons are only shared equally when the ENA = ENB
iv. EN
1. ALWAYS POSITIVE
2. EN = 0, nonpolar covalent
3. EN = low, polar covalent
4. EN = high, more ionic
b. Dipoles
i. Dipole: two points of positive and negative charges; show the unequal
sharing of electrons between two atoms
ii. +: partial positive
iii. -: partial negative; more EN
iv. Dipole moment: indicates the degree of “ionic character” present in a bond
c. Bond enthalpy
i. Decreased multiplicity = weaker bond—single bonds are weaker than
double bonds
ii. Measures bond strength; the change in enthalpy associated when breaking
1 specific bond in 1 mol of gas molecules
iii. ENDOTHERMIC
1. Bond formation is exothermic
iv. H rxn=∑ H bonds broken−∑ H bonds formed
1. Reactants – products
v. Shorter bond = stronger

Chapter 11
I. VSEPR
a. VSEPR theory: predicts shape, minimizes the repulsion between electron
domains; doesn’t account for the differences between lone pair and bond pair
repulsion (just electron geometry)
b. Electron domains
i. Regions of electron density; charge clouds
ii. Regions where electrons can be found around the central atom
iii. Lone pairs or a (collection of) bond
 iv. Lone pair-lone pair repulsion > bond-lone pair repulsion > bond-bond
repulsion
c. Electron geometry: looks only at the number of electron domains
d. Molecular geometry: shows the difference between lone pair and bonds
i. If no lone pairs, electron geometry = molecular geometry
e. CHART
f. Multiple central atoms
i. Larger molecules are a series of smaller shapes linked together
II. Polarity
a. If bond dipoles are unequal in magnitude = polar
i. HF, H2O, SF4, PCl4F
b. If no bond dipoles = nonpolar
i. C-H is always nonpolar (because difference in EN is so small)
ii. F2, CO2, I3-
III. Valence bond theory
a. Comparison
i. Lewis: shows how the atoms connect
ii. VSEPR: only makes the Lewis structure 3-D
iii. VB Theory: shows covalent bonding
1. Based on quantum
2. Involves the overlapping of atomic orbitals
b. When two atoms approach each other, their electrons and nuclei interact
i. Graph of energy vs distance shows that when atoms are really close, their
energy is very high; when they’re really far, little to no energy shared; at a
medium distance, the energy is minimized and this is where the bond
forms
c. Not as good for describing complex molecules
i. Each atom brings one unpaired electron which both share
ii. H2O diagram—oxygen atom with 2 half-filled 2p orbitals overlapping
with half-filled 1s orbital
iii. Good for diatomic
1. HCl diagram of orbitals
d. Bond types
i. Sigma: single bond; every bond is a sigma bond; head-to-head; formed via
constructive interference between nuclei; always formed from the
hybrid orbital of the central atom can happen from s-p or s-s
ii. Pi: double bond; side-to-side; above and below the nuclei; formed from
the extra p orbitals
iii. Hybrid orbitals
iv. Double bond: sigma and pi bond
v. Triple bond: 1 sigma and 2 pi bonds
e. Hybridization
i. Orbitals
1. A linear combination of orbitals, producing an equal number of
hybrid orbitals
2. Molecular geometry matches the orientation of these orbitals
a. VB theory shows the 3D structure of hybridized orbitals
3. Hybridize central atoms, not external
4. D orbitals aren’t involved in hybridization
ii. Promotion: makes more unpaired electrons (not always needed, NOT
hybridization, just the set-up to it) need example where you promote then
hybridize
1. CH4-- C: ^^ ^^_ (2s22p2)
2. Promoted: C: ^_ ^^^ (2s12p3)
3. Hybridized: 1 s orbital + 3 p orbitals = 4 sp3 orbitals
iii. Hybridization: to make orbitals the same size/shape/energy/have
correct bond angles
1. Done to the orbitals, not the electrons
iv. Types
1. Sp3 hybridization
a. 4 electron domains: tetrahedral
b. 4 hybrid orbitals (3+1)

c.
d. Ex: carbon has each sp3 hybrid orbital overlapping with a
1s orbital of H in CH4
2
2. Sp hybridization
a. 3 electron domains: trigonal planar, 3 hybrid orbitals, 3
atomic orbitals

b.
3. Sp hybridization
 a. 2 electron domains: linear, 2 hybrid orbitals, 2 atomic
orbitals

b.
f. VB Theory can’t explain:
i. The electronic energy levels for a molecule—their principle quantum
numbers
ii. Magnetic properties of a molecule
iii. Molecular orbital theory can explain the above!

Chapter 12
I. Intermolecular Forces
a. Intramolecular forces: the chemical bonds that holds a single molecule together;
much stronger than IMFs; stay intact during phase changes
b. IMFs: the forces of attraction between distinct molecules
i. Are overcome during phase changes
ii. Stronger IMFs = higher boiling point, higher melting point, lower vapor
pressure
c. Interaction types
i. Cation – anion
ii. Permanent positive – permanent negative
iii. Temporary positive – permanent negative
iv. Cation -- permanent negative
v. Anion – permanent positive
d. Types
i. Ion-dipole
1. Full charge of anion/cation and a partial opposite charge
(permanent pos/neg)
2. NaCl where its ions are surrounded by H2O molecules
3. Very strong because a full charge with a partial
ii. Dipole-dipole
1. 2 polar molecules interacting with each other
2. Usually nonmetal-nonmetal
3. Weaker than ion-dipole, but still affects boiling point
iii. H-bonding (subset of dipole-dipole)
1. H atom (partial pos) covalently bonded (DIRECT) to N/O/F
 2. N/O/F on other molecule must have a lone pair of electrons—not
necessarily the central atom though
3. Stronger than dipole-dipole because the EN differences between H
and N/O/F are so great—greater partial charges
4. Responsible for the low density of ice (vs the density of water) and
the helical structure of DNA
iv. London dispersion forces
1. Between the instantaneous dipole in one molecule and that in
another molecule
2. Temporary
3. Occurs when there’s a distortion of the electron cloud—both
electrons in an orbital are on the same side of the atom and leave
one side exposed…domino effect on surrounding atoms as
electrons move towards other atom’s positive, exposed nucleus
4. Weakest, but strength is also dependent on polarizability
a. Polarizability: ease with which an electron cloud can be
distorted
b. Larger molecules have more electrons and moving all of
them has a big effect
c. Larger dipoles/larger molecules (look at total electron
count): stronger IMFs, more polarizable
d. Larger radius/heavier: more polarizable, higher boiling
point
v. Ion-dipole > H-bonding > dipole-dipole > LDFs
II. Phase Changes
a. Energy needed to overcome a phase; NO TEMPERATURE CHANGE
b. Enthalpy
i. In kJ/mol: q=n∗∆ H
ii. In g/mol: q=m∗∆ H
c. Heating curves
i. Show the variation in temperature of a sample when it’s heated at a
constant rate and pressure
ii. CHART
1. Warming: q=mc ∆T
2. Melting point: q=n∗∆ H fusion
3. Boiling point: q=n∗∆ H vaporization
4. ∆ H vaporization > ∆ H fusion because of IMFs
iii. Condensing: now exothermic so negate the energy
d. Phase diagram
i. CHART
 ii. On the line: range of temperature/pressure combination in which both
phases are occurring in equilibrium
iii. Triple point: all three phases are occurring
iv. Critical point: past this, neither in gas nor liquid phase (superfluid)
III. Vapor Pressure
a. The pressure exerted by a gas on the surface of the liquid from which it
evaporated
b. Volatile: substance is easily vaporized
i. IMFs are easily overcome in the liquid phase
c. Stronger IMF = lower VP
d. Chart: more molecules can escape at 300K than at 320K
i. Increased temperature = more evaporation = higher VP
ii. Closed system: gas molecules trapped = higher VP until condensation and
eventually the rate of evaporation = rate of condensation (equilibrium)
e. Boiling Point
i. The temperature at which the VP of a substance = the atmospheric
pressure
ii. If you know the pressure at a certain temperature, subtract the pressure of
the atmosphere to find the pressure of a gas
1. P at 300K= 1.2 atm and atmospheric pressure = .9 atm then the
pressure of the gas = .3atm
iii. Normal boiling point: the temperature at which the VP of the substance =
1 atm
IV. Unit Cells
a. The simplest repeating unit of a crystal structure
b. Simple cubic
i. 1 atom
ii. Diagram
iii. Edges are 1/8 of an atom
c. Body-centered cubic
i. 2 atoms
ii. Diagram
d. Face-centered cubic unit
i. 4 atoms
ii. Diagram

Chapter 13
I. Dissolution
a. Solution: a homogeneous mixture of a solute (less) and a solvent (more)
b. Many types of solutions (all combos of solid, liquid, gas)
 c. If the solute-solvent can form the same IMF attraction (polar-polar, nonpolar-
nonpolar), will dissolve
i. Particles with charges/partial charges are more attractive than substances
without charges (dipole-dipole is stronger than LDF)
ii. Ex: which is a better solvent? H2O or CCl4?
1. C6H4: CCl4 because both are nonpolar
2. CH3O: H2O because both are polar
d. 3 factors
i. Solute-solute attraction
ii. Solvent-solvent attraction
iii. Solute-solvent attraction
iv. CHART
II. Enthalpy of solution (∆ H solution)
a. The overall energy change during solution formation
b. Endothermic (energy input needed)
i. Breaking solute-solute attractions (like dipole-dipole between HCl and
HCl)
ii. Breaking solvent-solvent attractions (like H-bonding between HCl and
H2O)
iii. The amount of energy for the above steps is dependent on IMF
strength
1. If they’re ionic compounds, look at lattice energy
c. Exothermic
i. Solutions are more likely to form when the enthalpy is
negative/exothermic
ii. Forming solvent-solute attractions is exothermic (energy is released)
iii. Entropy: degree of randomness

Chapter 14
I. Rates
a. Reaction rate: the change in concentration of a reactant or product per unit of time
b. Units: M/t or M*t-1, where t is usually in seconds
c. Influencers
i. Reactant concentration
ii. Particle size (for solids)
iii. Temperature
iv. The nature of the reactants
v. The presence of a catalyst
d. Expressed as the rate in which [A] decreases or [B] increases; ALWAYS POS.
 ∆[ A]
i. rate= | | ∆t
−∆ [ A ] ∆[ B]
ii. A  B: =
∆t ∆t
1. Reactant has the negative
−∆ [ A ] ∆[B]
iii. aA  bB: =
a∗∆ t b∗∆ t
1. only include a and b when doing the relationship between the rates
2. 2O3  3O2. Rate of O3 consumption = 2.5 x 10-5 M/s. Rate of O2
production?
−∆ [ O3 ]
a. =2.5 x 10−5 M / s
∆t
b. The 2 isn’t included because not comparing it against O2
yet
−∆ [ A ] ∆ [ B ] 1 ∆ [ C ]
iv. A  B+2C: = =
∆t ∆t 2 ∆t
II. Rate Laws
∆[ M ]
a. Average rate for a reaction: , where [M] is the molar concentration of the
∆t
reactant
b. Instantaneous rate: the rate of the reaction at a single moment – the slope of the
tangent line
c. Initial rate: the instantaneous rate as close as possible to the start of the reaction
i. So you can ignore the concentration of the products! t = 0
d. Differential rate laws
i. rate=k∗¿
1. k = rate constant; dependent on temp (constant T = constant k)
2. n, m = orders of reactants; usually integers; determined
experimentally
ii. first order reactions
1. rate=k ¿
2. Rate is in (M/t); k is in (t-1); [A] is in (M)
3. Rate and concentration are linearly related—directly proportional
iii. Second order reactions
1. rate=k ¿
2. Rate is in (M/t); k is in (M-1*t-1); [A] is in (M2)
3. A change in concentration is squared to determine the rate
a. Double the concentration  4x rate
iv. Zero order reactions
1. rate=k ¿
 2. Change in concentration doesn’t change the rate
v. Overall reaction order = sum of reaction orders
vi. Look at the units of k to know the order of the reaction
e. To determine the order of the reaction:
i. Where did [A] stay constant and [B] changed? Write reaction rates, divide
by each other, and solve for n.
ii. Where did [A] change and [B] also change? Do as above, using known n,
and solve for m.
iii. Write together is differential rate law form. Using the values from one
experiment, solve for k.