I.

Quantitative Chemistry
1. Matter
a. Occupies space and has mass
b. Can be subdivided into mixtures and pure substances
i. Mixtures: different substances not chemically combined
ii. Pure substance: one substance, consistent physical and chemical properties
throughout the substance
2. Element
a. A substance that only contains one type of atom, so it cannot be converted into
anything simpler.
b. Isotopes are atoms with different atom masses, because of more neutrons in the
nucleus.
c. 92 elements
3. Atoms
a. Moles: a quantity measuring the amount of substance (in the unit mol), that is
proportional to the number of particles in a sample of substance.
i. Consistent with the amount of atoms in 12 grams of
12
6
C.
b. 1 mol =
23
6.02 10 particles
4. Stoichiometry
a. The study of quantitative aspects of chemical equations
b. Using a balanced equation, one is able to find the amount of substance used and
amount of substance made.
i. Should be equal
c. If given a mass of substance reacted with excess of another substance, one can
find the amount of product made.
i. Calculate the amount of substance whose mass is given (convert from
grams to mols)
ii. Use the balanced equation to calculate the amount of required substance in
the reaction
iii. Calculate the mass of the required substance from the amount given.
d. Limiting reagents
i. The reactant which limits the amount of product made
ii. Can be found by calculating the amount of reagent present and dividing it
by the number of mols given in the formula, i.e. the number of mols that
are given and the number of mols that are needed
e. Applied to gases
i. At a constant temperature and pressure, a volume of any gas will always
contain the same number of particles.
ii. Called Avogadros hypothesis.
iii. This means that the coefficients of the chemical reaction show the ratio of
the volumes
iv. If temperature and pressure are given, one can calculate the molar mass.
The equation
22.4
stp
V
n = shows this, where V
stp
is the volume of gas and
22.4 is the molar mass.
v. This can be rearranged to do calculations in the same way as other
stoichiometric problems
5. Ideal Gas Equation
a. An ideal gas is one in which the particles have negligible volume, no attractive
forces between particles, and the kinetic energy of the particles is proportional to
the absolute temperature.
b. Equation: PV nRT = , where P is pressure, V is volume, n is number of mols, R is
a gas constant (in most cases, 0.08206), and T is temperature (mostly in Kelvin).
c. This equation can be used to find any one of those values, granted that all other
values are known
6. Gas Equations
a. Used when some values (for example, n and T) are constant
i. Boyle-Mariotte Law: at a constant n and T,
1 1 2 2
PV PV =

This graph shows the relationship between pressure and volume; the y-
axis is volume, and the x-axis is pressure. When volume is high, pressure
is low, and vice versa. (They have a inverse relationship). This is
explained by the fact that more pressure means less space for the particles
of the gas to occupy.

ii. Charles law: when n and P are constant,
1 2
1 2
V V
T T
= (T will be measured in
Kelvin)

This shows that they have a direct relationship; as temperature increases,
so does volume. This is explained by the fact that the higher the
temperature, the more kinetic energy each particle has, which causes the
gas to expand i.e. takes up more space
iii. Gay-Lussacs law: when n and V are constant,
1 2
1 2
P P
T T
=

This law states that as temperature increases, so does pressure. This can be
explained, once again, by kinetic energy. Temperature is a measure of
kinetic energy; it shows us how rapid the particles move. As the
temperature increases, the particles are colliding with the container more
and more, making the pressure increase (volume is held at a constant).





iv. If all three variables are present, combined gas law can be used.
Combined gas law: when n is constant,
1 1 2 2
1 2
PV PV
T T
= (Temperature must be
expressed in Kelvin; others may be expressed in any units).
7. Solutions
a. Made up of the liquid (solvent) and the thing being dissolved in the liquid
(solute).
b. Solubility: the quantity of that substance that will dissolve to form a certain
volume of solution in that solvent.
i. Solubility varies with temperature; in general, the higher the temperature
of the solvent, the more soluble the solute is.
ii. For gases being dissolved in solvents, it decreases with higher temperature
iii. Can be considered dilute (little amount of solute) or concentrated (a lot of
solute)
iv. Saturated solution: when no more solute will dissolve at a given
temperature (it reached its limit for the temperature given)
v. Supersaturated solution: when the solute concentration exceeds the stated
limit; usually occurs when the temperature of the solution goes from high
to low, or if the solution is produced using chemical reactions. This is the
cause of precipitation
c. Concentration, or [ ]: the amount of substance contained within a given volume of
solution, given by the equation
n
M
V
= , where M is molarity, n is number of
moles, and V is volume in liters.
8. Titrations
a. Titration is a technique which involves measuring the volume of one solution
which just reacts completely with another solution
b. One solution will have a known concentration. This solution is the called the
standard solution. To check the solution, one may titrate it against a primary
standard, or a solution which is prepared by dissolving a precise mass of solute to
make an accurate concentration
c. An indicator is usually added to the standard solution, and the second, unknown
solution is run in from a burette until the indicator changes colors.
d. The amount of solute can be calculated from the volume of the solution of known
concentration. The amount of unknown may be found using the balanced
equation. The concentration of the unknown can be calculated from this and the
volume of the second solution used.
i. Calculate the amount of moles in the solution of known concentration
ii. Use a balanced equation to calculate the amount of the unknown (ratios)
iii. Calculate the concentration of the unknown using
n
M
V
= .
e. Back titration: an insoluble solid reagent is reacted with a known excess of one
reagent. When the reaction with the sample is complete a titration is then carried
out to determine how much of the reagent in excess remains unreacted.
i. Same basic principle of titrations
II. Atomic Structure
1. Atomic Theory
a. John Dalton-1807
i. All matter is made up of a small number of different kinds of
atoms, which are indivisible and indestructible, but which can
combine to make molecules and compounds
ii. This is mostly true; however, atoms are not indivisible, because
they are composed of many different, smaller parts.
2. Subatomic particles
a. Proton, Neutron, Electron
i. Proton and Neutron have an amu (atomic mass unit) of 1 each,
while the electrons amu is negligible.
ii. Protons and neutrons are located in the nucleus, while electrons are
located in the electron cloud.
iii. Most of the size of the atom is empty space, called the electron
cloud
iv. Electrons: -1
Neutrons: 0
Protons:+1
b. The difference between elements, in essence, is the number of protons in
the nucleus
i. Isotopes have different number of neutrons, but are still the same
element, and one can add or take away (to a certain extent)
electrons, creating ions.
ii. Mass number: the sum of the protons and neutrons in the nucleus
iii. Atomic number: number of protons in the nucleus
c. Isotopic notation:
A
Z
X , where A is the mass number, Z is the atomic
number, and X is the element in question
d. Neutrons and protons are usually the same at light elements (such as
Carbon), but because of proton repulsion (think magnets, when trying to
put positive pole to positive pole), a greater number of neutrons are
needed for stability when more protons are present in the nucleus
e. Protons and electrons are equal in atoms
i. Atoms can gain or lose electrons to form ions, which have a net
electrical charge because the number of protons is different from
the number of electrons.
ii. This is judged by number of electrons; electrons are the ones being
changed
f. Isotopes: atoms that have the same number of protons but different
number of neutrons.
i. Same atomic number, different mass number
ii. Mass number is not how heavy an atom weighs; rather, it is the
average weight of all isotopes of a certain atom.
3. Mass Spectrometer
a. An instrument which separates particles according to their masses and
records the relative proportions of these particles
b. Has six steps
i. Vaporization
1. If the sample is either a solid or liquid, the substance will
be heated to produce vapor
ii. Ionization
1. The particles are converted from neutral atoms or
molecules into positive ions, usually from the
bombardment with fast moving electrons (can knock an
electron from the atom/molecule off)
iii. Positive ions are accelerated by electrical field
1. Positive ions are accelerated by the high electrical potential
difference between the two parallel electrodes with holes in
their centers
iv. Ions deflected by a magnetic field
1. The fast moving electrons enter a magnetic field produced
by an electromagnet, which causes them to deflect
v. Detector records ions of a particular mass
1. Those with greater masses will not travel as far, while those
with smaller masses will travel very far
vi. Vacuum prevents molecules from colliding
4. Electron Configuration
a. Energy levels and sub levels
i. Each energy sub level is divided into orbitals, which can contain
up to two electrons that have opposite spin
1. Pauli exclusion principle-no two electrons can occupy the
same space at the same time
b. s sub level
i. Energy level closest to the nucleus
ii. Only contains one sub level and one orbital; spherical in shape





2 electrons, with opposing orbits

c. p sub level
i. figure eight electron distribution
ii. contain three p sub levels
iii. only differ in that one is oriented along the x-axis, a second along
the y axis, and a third along the z axis
iv. each orbital can hold two electrons, making six p-electrons and a
total of eight in the second level (2s and 2p)
v. because of the increased number of electrons, there is an increase
in the amount of electron-electron repulsion








P
z:
2 electrons P
y
: 2 electrons P
x
:2 electrons







Crudely-drawn p sub level; total of 6 electrons




d. d sub levels
i. 5 d orbitals, all of the same energy
ii. Can hold ten electrons, giving the third level 18 electrons (2 from
3s. 6 from 3p, and 10 from 3d)
iii. Comes after 4s, because d orbitals occur at a higher energy level
Note: this only has a total of 10 electrons, 2 in each level; even
though 4 spaces are made, only 2 can be filled

e. Electrons in atoms always adopt the lowest energy level possible by trying
to fill one sublevel before attempting to fill the next. This is called the
Aufbau principle
f. Hunds rule: the principle of maximum multiplicity, or that sub level
orbitals will be formed with as many same-spinning electrons as possible
g. In general, the 4s orbital will be filled before the 3d orbital.
i. This is because the 3d has a higher energy level
ii. Two exceptions to the rule: Chromium and Copper
1. This is because these elements form cations, and not
anions.
2. Electron configuration: Cr: 3d
5
4s
1
; Cu: 3d
10
4s
1

h. Electron waves
i. Schrodinger wave equation
1. Describes wave like nature in atoms
2. Involves the quantum numbers
a. Principle quantum number (n)
i. Dictates the energy level (1,2,3,4 etc.)
b. Azimuthal (subsidiary) quantum number (l)
i. Dictates the sublevel (when l=0, the sublevel
is s, when l=1, the sublevel is p, etc.)
c. Magnetic quantum number (m)
i. Dictates the orbital in which the electron
resides (for example, p
x
or d
xy
) The value of
m can be dictated from the value of l. For
example, when l is 0, m is 0. When l is 1, m
can be -1,0, and 1. When l is 2, m can be -2,-
1,0,1, or 2, and so on.
d. Spin quantum number
i. Differentiates between the two electrons in
the orbital by spin direction. In an electron
configuration model, upward pointing
arrows are equal to +1/2, while
downward point arrows are equal to -1/2.
3. Pauli exclusion principle: no two electrons in a given atom
can have the same four quantum numbers
i. Ionization energies
i. The minimum amount of energy required to remove a mole of
electrons from a mole of gaseous atoms to form a mole of gaseous
ions.
ii. The more electrons that have been removed from an atom, the
greater the energy required to remove the next electron.
iii. Going down a group, the ionization energy decreases. This is
because the nuclear charge stays constant (the new protons are
being canceled out by the new electrons), but the valence shell is
farther away from the nucleus
iv. Going across a period, the ionization energy increases. This is
because all of the electrons are in the same energy level going
across a period, but the charge of the nucleus increases because of
increasing protons.


III. Periodicity
a. Physical properties
i. Electronegativity, effective nuclear charge, atomic radii, ionic radii,
melting points, electron affinity, ionization energy
1. Electronegativity: a measure of how strongly the atom attracts the
electrons in a covalent bond
2. Effective nuclear charge: the amount of force which the nucleus
exerts on the electrons on the valence electrons
3. Atomic radius: the average distance from the nucleus to the edge
of the electron cloud (like the radius of a circle)
4. Ionic radius: same thing as atomic radius, but for ions
5. Melting point: the temperature at which a transition from the solid
state to the liquid state occurs
6. Electron affinity: the amount of energy released when a neutral
atom is turned into a negative ion
7. Ionization energy: the amount of energy needed to take an electron
from a gaseous mole of atoms or ions
Note: Electron affinity is the amount of energy released, while
ionization energy is the amount of energy needed.
ii. Trends
1. Effective nuclear charge: relatively the same for each element,
because with each increasing interval on the periodic table, both a
proton and a neutron are added. These charges cancel each other
out.
2. Electronegativity: decreases down a group and increases across a
period. Can be explained by effective nuclear charge. Going down
the group, for successive elements, there are more energy levels
filled with electrons, so the outer valences are farther away from
the nucleus. So, when going down a period, the valence electrons
are farther away from the nucleus, which means the attraction is
much less. This makes it harder for the nucleus to attract electrons
for a covalent bond; ergo, as one goes down a period, the
electronegativity decreases. Going across the period, another
proton is added to the nucleus, thus making it strong. This makes
the effective nuclear charge increase, which pulls the valence
electrons in closer. This also means that, in a covalent bond, the
nucleus would exert more force on the shared electron. Thus, as
one goes across a period, the electronegativity increases.
3. Atomic and ionic radius: increases down a group and decreases
across a period. As one goes down the group, the electrons are
farther away from the nucleus, so they are loosely attracted, so the
atomic and ionic radii increase. As one goes across the period, the
increasing amount of protons cause the electron cloud to become
more compact; thus, as one goes across the period, the atomic and
ionic radii decrease.
4. Ionization energy: decreases down a group and increases across a
period. This is because down a group, the electrons are not very
compacted, and the nuclear charge is decreasing; across a period,
the protons cause the electron cloud to become more compacted,
thus making it harder for an electron to be taken away.
5. Electron affinity: electron affinity decreases down a group and
increases across a per


b. Chemical properties
i. Alkali metals
1. Li, Na, K, Rb, Cs.
a. Soft, malleable metals with low melting points and low
densities
i. Low density is the result of the atoms of alkali
metals being the largest atoms in their period
ii. Softness/low melting point a result of their lone
electron
b. Alkali metals are very chemically reactive
Down:
Electronegativity, ionization
energy, and electron affinity
decrease; Atomic/ionic radii
increase
Across
Electronegativity, ionization
energy, and electron affinity
increase
Atomic/ionic radii decrease

i. This a result of only having one electron in their
valence shell
ii. Electron is very easily lost
iii. They will always form cations
iv. Tend to react with group 7 elements (O, Cl, Br)
c. Going down the period, atomic radius increases, the
ionization energy of the elements decreases, and the
reactivity increases
ii. The Halogens
1. F,Cl,Br,I.
a. Mostly nonreactive
b. All exist as diatomic molecules (
2
X )
i. Joined by covalent bonding
c. F and Cl are gases, Br is liquid, and I is solid
i. This is a result of the increasing strength of the Van
Der Waals forces
d. Because they only require one electron to complete the
octet, they are very electronegative
i. Electronegativity decreases down the group,
because they valence shell is farther away from the
nucleus
ii. Means reactivity decreases down the group
e. Oxidizing power decreases down the group
i. This means that a higher halogen will displace a
lower halogen from its salt (e.g. Cl would displace
I
-
)
iii. Trends in oxides of period 3 elements
1. At the left hand side of the periodic table, Na and Mg have
relatively low ionization energies and so they bond to other
elements to form ionic compounds in which they have lost their
electron. The oxides of these therefore are ionic, and have an oxide
ion. The oxide ion can form a bond to hydrogen ions and as a
result, act as bases dissolving water.
2. Toward the middle, ionization energy increases, which causes
covalent bonding. As such, these elements (C and Si) become
slightly acidic
3. At the far right, the elements continue to form covalent bonds by
sharing electrons, but taking electrons from metals is an option.
The oxides of these are able to make acidic solutions
c. First row d-block elements
i. D-block elements are all dense, hard metallic elements.
ii. 3d electrons effectively shield the outer 4s electrons
1. This means the first ionization energy remains somewhat constant
2. Also indicates that they have similar physical and chemical
properties
iii. Because of the semi-filled 4s orbital, the d block elements have the ability
to form a variety of stable oxidation states, to form complex ions, to form
colored ions, and to be used as a catalyst in some reactions
1. Variable oxidation states: occurs because of how close 3d and 4s
are in energy levels. All d block elements have an oxidation state
of +2 except for Scandium. All d block elements also show an
oxidation state of +3 except for Zinc.
2. Complex ions: ions of d block metals and those in the low p-
section (such as lead) have a low energy unfilled d and p orbitals.
These orbitals are able to accept a lone pair of electrons from
ligands to form a bond between the ligand and the metal ion.
3. Colored ions: complexes including d block elements are usually
colored
a. Exception: d
0
(Sc
3+
and Ti
4+
) d
10
(Zn
2+
) ions
b. These colors can be explained by:
i. Electron transitions of d-electrons within the d sub
shell.
ii. Electron transitions from the metal ion to the ligand
or the ligand to the metal ion, which are known as
charge transfer transitions
iii. Ligands themselves may be colored and this color
colors the comples.
c. The electrons move from one lower energy orbital to a
higher energy orbital, which creates color as light passes
through and absorbs the energy
4. Catalytic activity
a. Occurs because d block elements can form complex ions
with ligands donating one lone pair of electrons, and the
fact that they have multiple oxidation states, so they can
readily gain and lose electrons in reduction-oxidation
reactions.
i. Two important mentions: Haber process, which
uses iron to create ammonia; Contact process,
which uses vanadium(V) oxide to create sulfuric
acid.

IV. Chemical Bonding
a. A chemical bond is an interaction between atoms or ions that results in a
reduction in the potential energy of the system which hence becomes more stable.
i. The bond type depends on the extent to which the atoms involved attract
valence (electronegativities)
1. If the elements have very different electronegativities, then ionic
bonding results
2. If the elements have very similar electronegativities, covalent
bonding results
b. Ionic bonding
i. Occurs between elements that have a large difference in electronegativities
1. In ionic bonding, a metal atom with a low electronegativity loses
electrons to form a positively charged cation, while a nonmetal
atom with a high electronegativity gains electrons from the metal
to form an anion.
2. The resulting electrostatic connection between these ions causes
ionic bonding.
3. This means we can predict ionic bonding.
a. In most cases, ionic compounds are isoelectric with the
noble gases.
b. The three dimensional shape of the anions and cations in
ionic crystals account for the high melting points and
stability of ionic solids.
4. In most s block elements, the elements lose all electrons from their
valence.
a. This means that the alkali metals (group 1), which only
have one electron, create an X
+
cation. The alkaline earth
metals (group 2) for X
2+
cations.
5. Outside of the s block, predictions become harder.
a. In transition metals, the atoms can make multiple stable
cations
6. Nonmetals usually gain electrons, because they have higher
electronegativities
a. Happens for the same reason metals lose electrons
7. The anions and cations have opposite electrical charges and are
attracted to each other into a crystal lattice
a. Each anion is surrounded by cations and vice versa. (shown
below)

+ - +
- + -
+ + -
- + -
+ - +
-
- +

b. In these lattices, the charges add up to a net charge of zero
i. This means that the formulas of the ionic
compounds must equal charges of 0; no positive or
negative compounds
c. This model can be made into three dimensions
d. An ionic substance is held together by strong electrostatic
attractions in all three dimensions. This means that no
molecules are present in the ionic substance
e. Physical properties
i. Hard, brittle crystalline solids
ii. Relatively high melting and boiling points
iii. Do not conduct electricity when solid, but do when
molten or in aqueous solution (electrolytes)
iv. Are more soluble in water than in other solvents
c. Covalent bonding
1. Occurs between atoms that have quite high electronegativities
a. Usually nonmetals
2. In covalent bonding, the two atoms involved share some of their
valence electrons since neither element loses electrons easily.
a. The attraction of the two positively charged nuclei for these
shared pairs of electrons results in the two atoms bonding



The arrows represent the nuclear force on the shared
electrons, which causes the covalent bonding
b. In most cases, each atom donates one electron
i. In some cases, known as dative covalent bonding, one
atom can donate both electrons.
c. When forming covalent bonds, the atoms involved usually fill
their valence shell.
i. The number of bonds formed are equal to the number
of electrons needed to form the valence shell (since, in
general, each atom donates one electron).
1. Good example: carbon needs 4 electrons, and is
able to make 4 bonds
+ +
Shared e
-

ii. Octet rule: atoms in compounds usually have eight
electrons in their valence shell
d. If two pairs of electrons are shared, a double bond is formed
i. Joins the two atoms more tightly and closer together.
ii. Carbon forms four bonds and oxygen forms two bonds;
when oxygen and carbon atoms bond, two double
bonds are used
e. Two atoms can also share three pairs of electrons, giving a triple
bond
f. Covalent bonding can lead to two different types of structures
i. They can form molecules, which are two atoms bonded
together.
1. Physical properties of being soft in the solid
state, not conducting electricity, and being
more soluble in nonpolar solvents
ii. A lattice can be held together using covalent bonds
occasionally
1. Physical properties: very hard, very high melting
and boiling points
d. VSEPR theory
1. Valence Shell Electron Pair Repulsion
a. Determines the shape of a molecule
b. Most molecules have filled valence levels that contain four pairs
of electrons
i. To be as widely separated as possible, these electrons
distribute themselves so that they are pointing toward
the corners of the tetrahedron.
ii. Some molecules have nonbonding pairs of electrons,
which increase electron-electron repulsion and affect
the shape of the electron
Number of regions of
high electron density
Number of non-
bonding electron pairs
Example Shape and bond angle
Two None Carbon dioxide Linear; 180 degrees

Three None Boron trifluoride Trigonal Planar; 120
degrees

Three One Sulfur dioxide V-shaped; 117 degrees

Four None Methane Tetrahedral; 109.5
degrees

Four One Ammonia Trigonal pyramidal; 107
degrees

Four Two Water Bent; 104 degrees

Five None Phosphorus
pentafluoride
Trigonal bipyramidal; 90
and 120

Five One Sulfur tetrafluoride See-saw; 90 and 117

Five Two Iodine trichloride T-shaped; 90

Five Three Xenon difluoride Linear; 180






















Six

None

Sulfur hexafluoride

Octahedral; 90

Six One Bromine pentafluoride Square pyramid; 88

Six Two Xenon tetrafluoride Square planar; 90

2. Molecules with more than four electron pairs
a. Happen in the third and lower p-block because the p block
can promote one or more electron from a doubly filled s or
p orbital into an unfilled low d orbital.
i. In essence, taking an electron from one level and
bringing it up to a higher level
ii. This causes them to have an expanded valence shell
1. A valence shell with more than 8 electrons
in it
iii. This usually only happens when the atom is able to
form very strong covalent bonds
1. This means they are very, very
electronegative elements; so mostly groups
7 and 8 (esp Fl O Cl)
iv. These atoms attach to small central atoms, so that
they can fit around without much electron-electron
repulsion
v. Molecules with expanded valence shells can only
have octahedral, trigonal bipyramidal, or square
pyramidal
1. Trigonal bipyramidal: has 5 electron areas;
two axial (along the y axis) and three
equatorial (sticking out from the origin, to
create that pyramid shape)
2. Square planar=Octahedral shape two filled
electron areas
3. Polarity
a. Based off of electronegativities
i. In a polar bond, one is very, very electronegative,
the other is weakly electronegative
ii. This causes the electrons of the less electronegative
atom to basically attach to the more electronegative
one, creating a positive (the less electronegative)
and negative (greater electronegative)
iii. The greater the difference in the electronegativity,
the greater the polarity of the bond
iv. Dipole: a separation between the positive and
negative ends.
1. This is based off of symmetry as well. Some
dipoles can cancel themselves out if they
have a linear symmetry; others have a dipole
because the shape is not symmetrical
v. Dipole moment: a measure of the polarity of a
molecule; the greater the polarity, the higher the
dipole moment is.
e. Hybridization
1. When an atom bonds the atomic orbitals involved in forming the
o bonds, or accommodating the lone pair of electrons, interact
with each other to form an equal number of directional hybrid
orbitals of equal energy
a. When atoms join together to form molecules, their outer
atomic orbitals interact with each other to produce hybrid
orbitals.
b. The shapes of the hybrid orbitals correspond with the
shapes of the molecules according to VSEPR.
i. The best way to determine the hybridization of a
molecule is to look at the shape of the molecule
Geometry Hybrid Orbitals Number of Orbitals
Atomic Orbitals used
to form Hybrid
Orbitals
linear sp 2 s, pz
trigonal planar sp2 3 s, py, pz
tetrahedral sp3 4 s, px, py, pz
trigonal bipyramidal dsp3 5 s, px, py, pz, dz2
octahedral d2sp3 6
s, px, py, pz, dz2,
dx2-y2
square planar dsp2 4 s, px, py, dx2-y2
f. Multiple bonds
1. Double bonds formed between two atoms are not identical
a. The first is formed by either the interaction with the s
orbital or a hybrid orbital.
i. When they interact, they produce a bond in which
the electron density is at its greatest on the inter-
nuclear axis, and symmetrical about it
ii. This is a o bond
b. The second bond in a double bond is formed by the side-on
interaction of electrons in p orbitals at right angles to the
inter-nuclear axis.
i. This bond has a low electron density on the inter-
nuclear axis, but regions of high electron density on
opposite sides of this.
ii. This is called a t bond.

c. Single bonds are always o bonds, and double bonds are
always made up of one o and one t bond.
i. Triple bonds are made up of 1 sigma and two pi
bonds.
ii. Double and triple bonds are much stronger than
single bonds, so the nuclei involved are closer
together.
1. This means bond energies increase, while
bond lengths decrease
g.Intermolecular forces
i. van der Waals forces, dipole dipole forces, and hydrogen bonding
1. van der Waals forces: London forces are relatively weak forces of
attraction that exist between nonpolar molecules and noble gas
atoms.
a. They are caused by instantaneous dipole formation; in this
process, electron distribution in the individual molecules
suddenly become asymmetrical, and the newly formed
dipoles are now attracted to one another.
i. The larger the molecules electron cloud, the strong
van der Waals forces which exist.
2. Dipole-dipole: take place when two or more neutral polar
molecules are oriented such that their positive and negative ends
are close to each other,
a. Because this is an attraction between unlike charges, they
tend to be a strong form of bonding
3. Hydrogen bonding: not true bonds
a. In essence, just held together by the strong attraction
between hydrogen (lowest electronegativity) to a highly
electronegative atom on a nearby molecule
i. This means that it is found constantly in bonds with
oxygen, nitrogen, and fluorine: the three most
electronegative atoms on the periodic table
ii. Explains the unique characteristics of water, such as
high specific heat and boiling point.
iii. Hydrogen bonds have a high partial positive charge,
while the more the other atom has a negative
charge. This results in bonding
iv. Hydrogen bonding is one of the stronger bonds that
can occur.
h. Metallic bonding
i. Occurs between atoms which all have low electronegativities
1. Close packed lattice: when metal atoms are all packed together in a
fashion so that all molecules are as closely packed together as
possible.
2. In this fashion, no valence electrons belong to a specific atom-
they are delocalized among all atoms in the lattice.
3. Because the electrons are not with any of the atoms, each of the
atoms becomes a cation
4. The attraction between the cations and the free floating electrons
causing the force which holds the structure together.
a. A lattice of cations within a sea of electrons
ii. Because the atoms are attracted to the free floating electrons and not the
ions themselves, this allows the layers of ions to slide past each other
without any bonds breaking.
1. If another ion is introduced, the ability to slide without any bonds
breaking is lessened, those making alloys harder than pure metals.
2. The delocalized electrons are free to move from one side of the
lattice to the other when some sort of potential difference occurs.
a. This makes them good electrical and thermal conductors

i. Covalent bonding: part II
i. Diamond
1. Diamond is the most common example of a substance that has a
giant three dimensional covalent structure. Each carbon atom in
diamond is sp
3
hybridized, and is joined to four others, arranged in
a tetrahedron.
a. This means that there is strong bonding in all three
dimensions.
2. Silicon has an almost identical structure to diamond.
a. The sideways overlap between the p orbitals of the larger
atoms is less, so other allotropes that involve pi bonding do
not occur.
b. Silicon dioxide has a similar structure, but each C is
replaced with Si, and the C-C bonds are replaced with
oxygen bridges.
3. Fullerences: recently discovered allotrope of pure carbon.
a. They contain approximately spherical molecules made up
of five and six membered carbon rings.
b. C
60

i. Acts as an electron deficient molecule readily
accepting electrons from reducing agents.
V. Energetics
a. Thermochemistry
i. The study of energy changes associated with chemical reactions.
1. Most chemical reactions absorb or evolve energy, usually in the
form of heat
ii. Enthalpy
1. The total energy of a system, some of which is stored as chemical
potential energy in the chemical bonds of the system.
2. In chemical reactions, bonds are broken and bonds are made.
a. The energy involved in making new bonds is rarely equal
to the energy absorbed in breaking the old ones.
b. This means that every chemical reaction has an enthalpy
change
i. Given the symbol H A .
ii. It is equal to the difference in enthalpy between the
reactants and the products
c. Two types of reactions: endothermic and exothermic
i. Endothermic: positive H
ii. Exothermic: negative H
1. This is because endothermic needs energy,
which means that the amount of energy in
the system increases; conversely, an
exothermic reaction releases energy, which
causes the energy of the system to be
negative
iii. Enthalpy changes
1. Temperature: the average kinetic energy of the particles measured
a. Is an intensive property
b. The absolute (K) temperature is proportional to the mean
kinetic energy and is independent of the amount of the
substance present.
2. Heat: the measure of the total energy in a substance and does
depend on the amount of substance present
a. Does have an effect on the temperature of a system
3. When temperature increases, heat energy is absorbed from the
surroundings
a. This is dependent on the mass, m, of the substance, the
specific heat capacity, c of the substance, and the amount of
increase of temperature T.
b. Gives the equation: Heat energy=m.c.T
4. Calorimetry: a technique used to measure the enthalpy associated
with a particular change
a. This technique is dependent on the assumption that no heat
is gained or lost from the surroundings.
i. This is why calorimeters tend to be well insulated
5. Hesss law
a. First Law of Thermodynamics (conservation of energy):
states that energy cannot be created or destroyed
i. This means that the total change in chemical
potential energy must be equal to the energy lost or
gained by the system
ii. Also means that the total enthalpy change on
converting a given set of reactants to a particular set
of products is constant, irrespective of the way in
which the change is carried out
iii. This is Hesss law.
1. Basically states that the total enthalpy
change of a reaction is equal to the enthalpy
changes of each step.
2.
1 2 3
H = H H A A A
iv. Bond Enthalpies
a. All chemical reactions involve the breaking and making of
bonds.
b. Bond enthalpies=the measure of the strength of a covalent
bond
i. The stronger the bond, the more tightly the atoms
are joined together.
c. The breaking of bonds is an exothermic reaction; as such, it
releases energy
d. The formation of chemical bonds is an endothermic
reaction i.e. it requires energy from the surroundings to
work.
e. The bond enthalpies are dependent on how the rest of the
molecule is bonded. This means that the average bond
enthalpies may be defined as the enthalpy required to break
a particular covalent bond in a range of molecules.
i.
( ) ( )
o o o
reaction formation formation
H = BH (products) - B H (reactants)


ii. B=the coefficient in the formula
Note: if the bonds being made are weaker than
those being made, the reaction will be exothermic
and vice versa.
1. Also: bond enthalpies are for the conversion
of a mole of gaseous molecules into gaseous
atoms.
2. This means that bond enthalpies are less
precise than other methods.
1. The values, in most cases, are within
10% of the actual value.
f. Bond strength increases from single bonds, through double
bonds to triple bonds.
i. As bonds become stronger, the bonds also become
shorter
1. Recall: electron density in the bond
increases the attraction of the nuclei for this
electrons, pulling the nuclei together.
g. It is not possible to determine bond enthalpies directly, so
they must be determined indirectly.
i. This is done by applying Hesss law.
2. Standard Enthalpy changes of a reaction
a. The amount of energy evolved or absorbed in the formation
of one mole of the compounds, in its standard state, from
its constituent elements in their standard state.
i. Standard state is the state the element is normally
found in at room temperature (298 K).
ii. If there are allotropes, the more stable one is
considered the standard state.
1. O
2
(g) is the standard state of oxygen, not
O
3
(g)
b. The sum of the enthalpies of formation of the reactants will
give the total enthalpy change to form the reactants from
the component elements in their standard states.
i. Similarly, the sum of the enthalpies of formation of
the products will give the total enthalpy to form the
products.
c.
( ) ( )
o
reaction formation formation
H = BH (products) - B H (reactants)
u u

d. Standard enthalpy change of combustion
i. The enthalpy change when one mole of the
compound undergoes complete combustion in
excess oxygen under standard conditions
ii. Many covalent compounds will undergo
combustion and hence it is often easy to determine
the standard enthalpy change of combustion for
molecules.
e. Standard enthalpy change of neutralization
i. The enthalpy change when one mole of the acid
undergoes complete neutralization with a strong
base (can also start with a base and end with an
acid).
ii. Always exothermic
v. Born-Haber cycle
a. The formation of an ionic compound can be considered as
the sum of a number of individual processes converting the
elements from their standard states into gaseous atoms,
losing and gaining electrons to form the cations and the
anions respectively and finally, these gaseous ions coming
together to form the solid compound
b. Standard enthalpy change of atomization: the enthalpy
change required to produce one mole of gaseous atoms of
an element from the element in the standard state.
c. Electron affinity: the enthalpy change when one mole of
gaseous atoms or anions gains electrons to form a mole of
negatively charged gaseous ions.
i. This change is mostly exothermic for the first level;
second level is endothermic because of the electron
repulsions
d. Lattice enthalpy: the energy required to convert one mole
of the solid compound into gaseous ions.
i. Very very highly endothermic
1. Think how much energy it takes to change
solid water into water vapor
ii. Lattice enthalpies depend upon the nature of the
ions involved
1. The greater the charge on the ions, the
greater the electrostatic attraction and hence,
the greater the lattice enthalpy (and vice
versa)
2. The larger the ions, the the greater the
separation of the charges and the lower the
lattice enthalpy (and vice versa)
e. The Born-Haber Cycle
i. Born-Haber cycle, if the magnitude of every term
except one is known, then the remaining value may
be calculated
1. The equation for this is: Enthalpies of
atomization + Electron affinities +Ionization
energy = Enthalpy of formation + Lattice
Enthalpy
















ii. The Born-Haber cycle provides a way in which
lattice enthalpies can be indirectly measured
through experimental techniques.
iii. It is also possible to calculate theoretical lattice
enthalpies for ionic compounds.
1. This is done by assuming the ionic model,
then summing the electrostatic attractive and
repulsive forces between the ions in the
crystal lattice.
f. Enthalpy change of solution
i. The enthalpy change when one mole of the
substance is dissolved in water to form a dilute
aqueous solution
1. Uses lattice enthalpy
2. H
sol
= Lattice enthalpy+ (hydration
enthalpies of the component ions)
g. Enthalpy change of hydration
Elements in
standard states
Solid compound
Enthalpy of formation
Elements in
gaseous ions
Gaseous
anions and
metal atoms
Gaseous anions and
cations
Enthalpies of
atomization
Electron
affinities
Ionization
energies
Lattice enthalpies
i. The enthalpy change (always exothermic) when one
mole of the gaseous ion is added to excess water to
form a dilute solution













vi. Entropy
a. A measure of the degree of disorder or randomness in a
system
i. Some states are inherently more probable than
others
ii. In general, the less order there is in a state, the
greater the probability of the state and the greater its
entropy
iii. There is an increase in entropy going from solid to
liquid, and from going to liquid to gas.
b. A solid, with a regular arrangement of particles, has a low
entropy
i. When it melts, the particles can move more easily
ii. The system has become more disordered, and its
entropy increases
c. Gas molecules move fast and independently of one another
since inter-particle forces are negligible
i. Gases have high entropies.
d. Entropy decreases as gas pressure increases
i. Higher pressure reduces the volume for gas
particles to move in, resulting in less disorder
Solid
compound
Aqueous
solution
Gaseous ions
Lattice
enthalpy
Sum of hydration
enthalpies
Enthalpy of
solution
e. When a solid or liquid dissolves in a solvent, the entropy of
the substance generally increases
i. When a gas does the same, the entropy decreases
ii. Hard solids (diamond) have less entropy than softer
solids (lead)
1. This is because there is less movement in
diamond (thus making it hard) than there is
in lead
f. The entropy of a perfectly ordered crystal at absolute zero
is zero
i. There is no randomness in the crystal form aka no
movement from the particles
ii. Unlike enthalpy, absolute values of the entropy of a
substance in a particle state can be measured
relative to this
iii. Real substances always have a higher randomness
than the crystal; therefore, all entropy is positive
1. And measured in J K
-1
mol
-1

g. Changes in entropy
i. Entropy change will likely be positive if: there is a
decrease in order through a decrease in the number
of moles of solid, or an increase in the number of
moles of gas (meaning a reactant, which is solid, is
converted into a gas, or a gas reacts and creates
more gases); an increase in temperature and an
increase in the number of particles also increases
entropy.
ii. Entropy change will likely be negative if: the
number of moles of solid increases, or a gas turns
into a liquid or a solid.
h. Entropy change:
( ) ( ) S= B S(products) - B S(reactants)


vii. Spontaneity
1. Any change may occur spontaneously if the final state is more
probable than the initial state
a. If, as a result, the system is more stable in the final state,
the final entropy of the universe is greater than the initial
entropy of the universe.
2. S measures the change in the entropy of the system.
a. The major effect of chemical changes on the entropy of the
surroundings results from the gain and loss of heat energy.
b. If chemical potential energy is converted to heat energy,
which is then transferred to the universe, then this results in
an increase in the entropy of the surroundings
i. The opposite is true for an endothermic change (the
above lost energy)
c.

universe surroundings system

H
S =S +S =
T+S

i.

H
T+S
is the magnitude of the entropy change
d. Processes will be spontaneous if: the final state has a lower
enthalpy than the initial state and the final state is more
disordered than the initial state
3. Gibbs Free energy
a. G H T S A = A A
i. This equation tells us if a reaction is spontaneous or
not.
ii. To be spontaneous, G must be negative
b. The Gibbs free energy for a change is equal to the amount
of energy from that system that is available to do useful
work
i. Ergo, for any system in equilibrium, Gibbs free
energy must be exactly zero.
ii. If G is zero, this means that the stoichiometric
amounts of both the reactants and the products are
all mixed together, meaning that no further change
will occur.
iii. If G is negative, it was produce a reaction which
will increase the amount of products and decrease
the amount of reactants until equilibrium is reached
iv. If G is slightly positive, a reaction favoring the
reactants will occur; if G is very positive, the
reaction will be very much non-spontaneous and
will not occur.
v. The values of G can be calculated at any
temperature, as long as one has data about the
reactants and the products, specifically data about
enthalpy and entropy.
c. Gibbs free energy of formation
i. G

under standard conditions (298 K and 101.3

kPa) can be calculated using the standard Gibbs free
energy of formation data in the same way standard
enthalpy of formation data is used.
ii.
( ) ( )

f f f
G = G (products) - G (reactants)