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A. Allan
Chapter 1 Notes - Chemical Foundations
1.1 Chemistry: An Overview
A. Reaction of hydrogen and oxygen
1. Two molecules of hydrogen react with one molecule of oxygen to form
two molecules of water
2H2 + O2 2H2O
2. Decomposition of water
2H2O 2H2 + O2
B. Problem Solving in Chemistry (and life)
1. Making observations
2. Making a prediction
3. Do experiments to test the prediction
1.2 The Scientific Method
A. General Framework
1. Making observations
a. Quantitative ( measurement)
b. Qualitative (color, phase, shape, etc)
2. Making a prediction
3. Do experiments to test the prediction
B. Vocabulary
1. Observation
a. Something that is witnessed and can be recorded
2. Theory (Model)
a. Tested hypotheses that explains WHY nature behaves in a
certain way
b. Theories change as more information becomes available
3. Natural Law
a. A summary of observed, measurable behavior
1.3 Units of Measurement
A. Measurements
1. Number and Scale (units) are both essential
"The number without the units is worthless!"
B. SI system
Important SI Units for Chemistry
Mass
kilogram
kg
Length
meter
m
Time
second
s
Temperature
Kelvin
K
Amount of Substance
mole
mol
Volume
liter
L
C. SI Prefixes
mega
M
1,000,000
kilo
k
1,000
hecto
h
100
deka
da
10
106
103
102
101
nano
micro
milli
centi
deci
m
c
n
0.000000001
0.000001
0.001
0.01
0.1
10-9
10-6
10-3
10-2
10-1
Infinite significance
Scientific notation
Example
6.34 m (3 sig figs)
0.00634 m ( 3 sig figs)
6.0034 (5 sig figs)
63400 (3 sig figs)
0.63400 (5 sig figs)
e.g. There is 1 star at the
center of our solar system.
There is no doubt about
the number "1"
6.3400 x 106 (5 sig figs)
E. Pure substances
1. Elements
a. Cannot be decomposed into simpler substances by physical or
chemical means
2. Compounds
a. Constant composition
b. Can be broken into simpler substances by chemical means, not
by physical means
The Organization of Matter
(Slightly different than your book)
Matter
Mixtures:
a) Homogeneous
(Solutions)
b) Heterogeneous
Pure Substances
Compounds
s
Elements
Atoms
Nucleus
Protons
Quarks
Electrons
Neutrons
Quarks
AP Chemistry
A. Allan
Chapter 2 Notes - Atoms, Molecules and Ions
2.1 The Early History
Refer to the Chemistry History Timeline for this chapter
2.2 Fundamental Chemical Laws
A. Law of Conservation of Mass
1. "Mass is neither created nor destroyed"
2. Translation: In ordinary chemical reactions, the total mass of the
reactants is equal to the total mass of the products
B. Law of Definite Proportion
1. "A given compound always contains the same proportions of elements
by mass"
2. Translation: Compounds have an unchanging chemical formula
C. Law of Multiple Proportions
1. "When two elements form a series of compounds, the ratios of the
masses of the second element that combine with one gram of the first
element can always be reduced to small whole numbers
2. Translation: Sometimes two elements can come together in more than
one way, forming compounds with similar, though not identical
formulas
2.3 Dalton's Atomic Theory
A. Atomic Theory
1. Each element is made up of tiny particles called atoms
2. The atoms of a given element are identical
3. Chemical compounds are formed when atoms combine with each
other. A given compound always has the same relative numbers and
types of atoms
4. Chemical reactions involve reorganizations of the atoms. The atoms
themselves are not changed in a chemical reaction
B. Avogadro's Hypothesis
1. At the same conditions of temperature and pressure, equal volumes of
different gases contain the same number of particles.
2.4 Early Experiments to Characterize the Atom
A. J.J. Thomson and the Electron
1. Determined the charge to mass ratio of the electron
2. Reasoned that all atoms must contain electrons
3. Reasoned that all atoms must contain positive charges
B. Robert Millikan and the Oil Drop
1. Oil drop experiments determined the charge on an electron
2. With charge information, and Thomson's charge/mass ratio, he
determined the mass of an electron (9.11 x 10-31 kg)
C. Radioactivity
1. Gamma () rays - high energy light
2. Beta () particles - high speed electrons
3. Alpha () particles - nuclear particle with a 2+ charge
D. The Nuclear Atom - Rutherford's Metal Foil Experiment
1. Most alpha particles pass straight through thin metal foil
2. Some particles were greatly deflected ("like a howitzer shell bouncing
off of a piece of paper")
a. Could not have been deflected by electrons or single protons
b. Must have been deflected by a positively charged object of
substantial mass
1) Supported concept of a small, central, positive nucleus
where most of the atom's mass was concentrated
2) Disproved Thomson's "plum pudding" model
2.5 The Modern View of Atomic Structure: An Introduction
A. Nucleus
1. Protons - positively charged
2. Neutrons - no charge
3. Small size, high density
a. The mass of all of the cars in the United States in an object that
would easily fit in a teaspoon
b. A pea with the mass of 250 million tons
B. Electrons
1. Negatively charged
2. The source of varying reactivity of different elements
3. Provide most of the atomic volume
C. Atomic Number
1. Number of protons
D. Mass Number
1. Number of protons + number of neutrons
E. Isotopes
1. Atoms with the same number of protons (same element) but different
numbers of neutrons (mass numbers)
F. Symbols for the Elements
1.
Mass Number
23Na
Element symbol
11
Atomic Number
Space Filling
C. Ions
1. Cations
a. Positive ions formed by the loss of electrons
2. Anions
a. Negative ions formed by gaining electrons
D. Ionic Bonding
1. Bond formed by the attraction between oppositely charged ions
2. Ionic bonding forms ionic solids (salts)
3. Ions can be monatomic (one atom) or polyatomic (more than one
atom)
2.7 An Introduction to the Periodic Table
A. Organization
1. Horizontal row is called a "period" (or series)
2. Vertical column is called a "group" or "family"
a. Group 1A - Alkali metals
b. Group 2A - Alkaline earth metals
c. Group 7A - Halogens (Gr, "salt makers")
d. Group 8A - Noble gases
B. Naming Elements 104 and beyond
Nil = 0
un = 1
bi = 2
tri = 3
quad = 4
Pent = 5
hex = 6
sept = 7
oct = 8
enn = 9
Element 109 = un (1) nil(0) enn(9) ium = unnilennium
ClO3ClO2-
Nitrate
Nitrite
NO3NO2-
hypochlorite
hyponitrite
ClONO2. Metals with more than one oxidation state (transition metals) must have a
roman numeral to indicate the oxidation state
Fe3+ = iron (III)
Mn+2 = manganese (II)
B. Binary Covalent Compounds
1. Must contain two elements, BOTH nonmetals
a. First element
1) full element name
2) prefix only if there is more than one atom
b. Second element
1) named as if it were an anion (-ide suffix)
2) always gets a prefix
mono - 1
penta - 5
octa - 8
di - 2
hexa - 6
nona - 9
tri - 3
hepta - 7
deca - 10
tetra - 4
C. Naming Acids
1. Binary Acids (two elements - hydrogen + one other)
a. prefix "Hydro" + root of second element + "ic" suffix
2. Oxyacids
a. If the acid contains an anion whose name ends in "ate":
Use root of anion name and an "ic" ending (H2SO4 = sulfuric acid)
b. If the acid contains an anion whose name ends in "ite":
Use the root of the anion name and an "ous" ending
(H2SO3 = sulfurous acid)
AP Chemistry
A. Allan
Chapter 3 Notes - Stoichiometry
3.1 Atomic Masses
A. C-12, the Relative Standard
1. C-12 is assigned a mass of exactly 12 atomic mass units (amu)
2. Masses of all elements are determined in comparison to the carbon 12 atom (12C) the most common isotope of carbon
3. Comparisons are made using a mass spectrometer
B. Atomic Mass (Average atomic mass, atomic weight)
1. Atomic masses are the average of the naturally occurring isotopes of
an element
2. Atomic mass does not represent the mass of any actual atom
3. Atomic mass can be used to "weigh out" large numbers of atoms
3.2 The Mole
A. Avogadro's number
1. 6.022 x 1023 units = 1 mole
2. Named in honor of Avogadro (he did NOT discover it)
B. Measuring moles
1. An element's atomic mass expressed in grams contains 1 mole of
atoms of that element
a. 12.01 grams of carbon is 1 mole of carbon
b. 12 grams of carbon-12 is 1 mole of carbon-12
3.3 Molar Mass
A. Molar Mass (Gram molecular weight)
1. The mass in grams of one mole of a compound
2. The sum of the masses of the component atoms in a compound
a. Molar mass of ethane (C2H6):
Mass of 2 moles of C = 2(12.01 g)
Mass of 6 moles of H = 6(1.008 g)
30.07 g
= percent yield
AP Chemistry
A. Allan
Chapter 4 Notes - Types of Chemical Reactions and Solution Chemistry
4.1 Water, the Common Solvent
A. Structure of water
1. Oxygen's electronegativity is high
(3.5) and hydrogen's is low (2.1)
2. Water is a bent molecule
3. Water is a polar molecule
B. Hydration of Ionic Solute Molecules
1. Positive ions attracted to the oxygen
end of water
2. Negative ions attracted to the hydrogen end of water
C. Hydration of Polar Solute Molecules
1. Negative end of polar solute molecules are attracted to water's
hydrogen
2. Positive end of polar solute molecules are attracted to water's oxygen
D. "Like Dissolves Like"
1. Polar and ionic compounds dissolve in polar solvents like water
2. Nonpolar compounds like fats dissolve in nonpolar solvents like
____?_____
4.2 The Nature of Aqueous Solutions: Strong and Weak Electrolytes
A. Definition of Electrolytes
1. A substance that when dissolved in water produces a solution that can
conduct an electric current
B. Strong electrolytes conduct current very efficiently
1. Completely ionized when dissolved in water
a. Ionic compounds
b. Strong acids (HNO3(aq), H2SO4(aq), HCl(aq))
c. Strong bases (KOH NaOH)
C. Weak electrolytes conduct only a small current
1. Slightly ionized in solution
a. Weak acids (organic acids
- acetic, citric, butyric,
malic)
b. Weak bases (ammonia)
D. Nonelectrolytes conduct no current
1. No ions present in solution
a. alcohols, sugars
4.3 The Composition of Solutions
A. Molarity
1. Moles of solute per liter of solution
M = molarity = moles of solute/liters of solution
Summary
Element = 0
Oxygen = -2
Hydrogen = +1
Fluorine = -1
AP Chemistry
A. Allan
Chapter 5 - Gases
5.1 Pressure
A. Properties of gases
1. Gases uniformly fill any container
2. Gases are easily compressed
3. Gases mix completely with any other gas
4. Gases exert pressure on their surroundings
a. Pressure = force/area
B. Measuring barometric pressure
1. The barometer
a. Inventor - Evangelista Torricelli (1643)
2. Units
a. mm Hg (torr)
(1) 760 torr = Standard pressure
b. newtons/meter2 = pascal (Pa)
(1) 101,325 Pa = Standard pressure
c. atmospheres
(1) 1 atmosphere = Standard pressure
5.2 The Gas Laws of Boyle, Charles, and Avogadro
A. Boyle's Law (Robert Boyle, 1627 - 1691)
1. the product of pressure times volume is a constant, provided the
temperature remains the same
PV = k
a. P is inversely related to V
b. The graph of P versus V is hyperbolic
c. Volume increases linearly as the pressure decreases (1/P)
2. At constant temperature, Boyle's law can be used to find a new
volumes or a new pressure
a. P1V1 = k = P2V2
PV
1
= P 2V 2
P =V
P V
or
V
T
1
1
=V2
or
V
V
1
2
T
T
1
2
V =V
n n
1
Tn
V = (k )(b )(a )
P
2. Constants k, b, a are combined into universal gas constant, R
V =
nRT
P
or
R = 0.0826
PV = nRT
L atm
K mol
PV
T
1
=n
PV
T
2
or
PV
T
P1 T 2
=
V 2 V 1
P 2 T 1
PV
T
2
Density =
mass
volume
n=
nRT
V
1
2.
3.
4.
PTOTAL =
5.
TOTAL
nRT
V
1
n RT
n RT
P=
V
V
2
n RT
V
2
(n + n + n + ...) R T
V
1
R T
=
PTOTAL nTOTAL
V
. . .
n RT
V
3
C. Mole Fraction
1. The ratio of the number of moles of a given component in a mixture to
the total number of moles in the mixture
2. For an ideal gas, the mole fraction (x):
TOTAL
P
P
TOTAL
rms
3RT
M
M
M
2
1
B. Diffusion
1. The mixing of gases
2. Diffusion is complicated to describe theoretically and mathematically
5.8 Real Gases and van der Waals Equation (Johannes van der Waals, 1873)
A. Volume
1. Real gas molecules do have volume
2. Volume available is not 100% of the container volume
a. n = number of moles
b. b = is an empirical constant, derived from experimental results
Ideal
Real
n RT
V
P=
'
n RT
V n b
B. Pressure
1. Molecules of real gases do experience attractive forces
a. a = proportionality constant determined by observation of the
gas
n
=
P P a
V
'
obs
n
n
R
T
a
P =
V
V nb
obs
Pobs + a
(V n b ) = n R T
AP Chemistry
A. Allan
Chapter Six Notes - Thermochemistry
6.1 The Nature of Energy
A. Definition
1. Energy is the capacity to do work (or to produce heat*)
a. Work is a force acting over a distance (moving an object)
b. *Heat is actually a form of energy.
(1) chemicals may store potential energy in their bonds that
can be released as heat energy
B. Law of Conservation of Energy
1. Energy can be converted from one form to another, but cannot be
created or destroyed
a. Potential energy
(1) energy due to position or composition
b. Kinetic energy
(1) energy due to the motion of an object
1
2
(2)
KE = 2 m v
C. Heat and Temperature
1. Temperature reflects random motion of particles in a substance
2. Temperature indicates the direction in which heat energy will flow
3. Heat is a measure of energy content
4. Heat is what is transferred during a temperature change
D. State Functions
1. A property of a system that depends only on its present state.
2. State functions do not depend on what has happened in the system, or
what might happen in the system in the future
3. State functions are independent of the pathway taken to get to that
state.
Example: a liter of water behind a dam has the same potential energy for
work regardless of whether it flowed downhill to the dam, or was taken
uphill to the dam in a bucket. The potential energy is a state function
dependent only on the current position of the water, not on how the water
got there.
E. Chemical Energy
1. Exothermic reactions
a. Reactions that give off energy as they progress
b. Some of the potential energy stored in the chemical bonds is
converted to thermal energy (random KE) through heat
c. Products are generally more stable (stronger bonds) than
reactants
2. Endothermic reactions
a. Reactions in which energy is absorbed from the surroundings
b. Energy flows into the system to increase the potential energy of
the system
E + PV
heat absorbed
Temperature increase
2.
E = q + w
w =0
E = q
H1 = 68kJ
Two step
N2 (g) + O2 (g) 2NO (g)
2NO (g) + O2 (g) 2NO2 (g)
N2 (g) + 2O2 (g) 2NO2 (g)
H2 = 180kJ
H3 = -112kJ
H2 + H3 = 68kJ
Major Uses
Gasoline
Kerosene, Jet fuel
Diesel fuel, Heating oil, lubricating oil
Asphalt
D. Coal
1. Four stages of Coal
2. Carbon content increases over time
3. Value of coal is proportional to carbon content
Mass Percent of Each Element
Type of Coal
C
H
O
N
Lignite
71
4
23
1
Subbituminous
77
5
16
1
Bituminous
80
6
8
1
Anthracite
92
3
3
1
S
1
1
5
1
AP Chemistry
A. Allan
Chapter 7 Notes - Atomic Structure and Periodicity
7.1 Electromagnetic Radiation
A. Types of EM Radiation (wavelengths in meters)
10-12
10-10
gamma
xrays
10-8
4 to 7x10
-7
UV
visible
10-4
IR
10-2
micro
102
104
Radio waves
FM
short
AM
Wavelength increases
Frequency decreases
Energy decreases
Speed is constant = 2.9979 x 108 m/sec
B. Properties of EM Waves
1. Wavelength ()
a. Distance between two consecutive peaks or troughs in a wave
b. Measured in meters (SI system)
2. Frequency ()
a. Number of waves that pass a given point per second
b. Measured in hertz (sec-1)
3. Speed ( c )
a. Measured in meters/sec
4. Relationship of properties
a.
=c
photon
= hv =
hc
h
mv
434nm
486nm
656nm
E = hv
hc
hc
E
18
1 1
=
x
E 2.178 10 J 2
2
n final ninitial
D. Shortcomings of the Bohr Model
1. Bohr's model does not work for atoms other than hydrogen
2. Electron's do not move in circular orbits
7.5 The Quantum Mechanical Model of the Atom
A. The Electron as a standing wave
1. Standing waves do not propagate through space
2. Standing waves are fixed at both ends
3. Only certain size orbits can contain whole numbers of half wave
lengths
a. fits the observation of fixed energy quantities - "quanta"
B. The Schrdinger Equation (Erwin Schrdinger)
1. For the motion of one particle, in the along the x axis in space:
h d +V
8 m dx
2
= E
x (mv)
h
4
2. Electron density map indicates the most probable distance from the
nucleus
3. Wave functions and probability maps do not describe:
a. How an electron arrived at its location
b. Where the electron will go next
c. When the electron will be in a particular location
7.6 Quantum Numbers
A. Principal Quantum Number (n)
1. Integral values: 1, 2, 3, .
2. Indicates probable distance from the nucleus
a. Higher numbers = greater distance
b. Greater distance = less tightly bound = higher energy
B. Angular Momentum Quantum (l)
(this was called the "orbital quantum number" in your general chem book)
1. Integral values from 0 to n - 1 for each principal quantum number n
2. Indicates the shape of the atomic orbitals
Table 7.1 Angular momentum quantum numbers
and corresponding atomic orbital numbers
Value of l
0
1
2
3
4
Letter used
s
p
d
f
g
C. Magnetic Quantum Number (ml)
1. Integral values from l to -l, including zero
2. Magnetic quantum number relates to the orientation of the orbital in
space relative to the other orbitals
D. Spin Quantum Number
1. Covered in section 7.8
Table 7.2 Quantum numbers for the first four levels of orbitals in the
hydrogen atom
Orbital
# of
n
l
ml
designation
orbitals
1
0
1s
0
1
2
0
1
2s
2p
0
-1, 0, 1
1
3
0
1
2
3s
3p
3d
0
-1, 0, 1
-2, -1, 0, 1, 2
1
3
5
0
1
2
3
4s
4p
4d
4f
0
-1, 0, 1
-2, -1, 0, 1, 2
-3, -2, -1, 0, 1, 2, 3
1
3
5
7
D. d Orbitals
1. Occur in levels n=3 and greater
2. Two fundamental shapes
a. Four orbitals with four lobes each, centered in the plane
indicated in the orbital label
dxz dyz dxy dx2- y2
b. Fifth orbital is uniquely shaped - two lobes along the z axis and
a belt centered in the xy plane
dz2
E. f Orbitals
1. Occur in levels n=4 and greater
2. Highly complex shapes
3. Not involved in bonding in most compounds
F. Orbital Energies
1. All orbitals with the same value of n have the same energy
a. "degenerate orbitals" (hydrogen only!)
2. The lowest energy state is called the "ground state"
3. When the atom absorbs energy, electrons may move to higher energy
orbitals - "excited state"
7.8 Electron Spin and the Pauli Principle
A. Electronic Spin Quantum Number
1. An orbital can hold only two electrons, and they must have opposite
spins
2. Spin can have two values, +1/2 and -1/2
B. Pauli Exclusion Principle (Wolfgang Pauli)
1. "In a given atom no two electrons can have the same set of four
quantum numbers"
7.9 Polyelectronic Atoms
A. Internal Atomic energies
1. Kinetic energy of moving electrons
2. Potential energy of attraction between nucleus and electrons
3. Potential energy of repulsion between electrons
B. The Electron Correlation Problem
1. Electron pathways are not known, so electron replusive forces cannot
be calculated exactly
C. Screening or Shielding
1. Electrons are attracted to the nucleus
2. Electrons are repulsed by other electrons
3. Electrons would be bound more tightly if other electrons weren't
present
D. Variations in energy within the same quantum level
1. Atoms other than hydrogen have variations in energy for orbitals
having the same principal quantum number
2. Electrons fill orbitals of the same n value in preferential order
Ens < Enp < End < Enf
3. Electron density profiles show that s electrons penetrate to the nucleus
more than other orbital types
a. Closer proximity to the nucleus = lower energy
7.10 The History of the Periodic Table
No notes. Read this section. Notice especially Table 7.3 and 7.4. The periodic
table is as useful for predicting properties of undiscovered elements today as it
was in Mendeleev's time
7.11 The Aufbau Principle and the Periodic Table
A. The Aufbau Principle
1. "As protons are added one by one to the nucleus to build up elements,
electrons are similarly added to these hydrogen-like orbitals
B. Hund's Rule
1. "The lowest energy configuration for an atom is the one having the
maximum number of unpaired electrons allowed by the Pauli principle
in a particular set of degenerate orbitals
***Note: We will review configuration and orbital notation in class. This was
covered extensively in General Chem, and will come back to you quickly
C. Period Table Vocabulary
1. Valence Electrons
a. Electrons in the outermost principal quantum level of an atom
b. Elements in the same group (vertical column) have the same
valence electron configuration
2. Transition metals
a. What we have called the "d" block
3. Lanthanide and Actinide Series
a. The sets of 14 elements following lanthanum and actinium
b. What we have called the "f" block
4. Main-group, or Representative Elements
a. Groups 1A through 8A
b. Configurations are consistent
5. Metalloids (semi-metals)
2. Periodic Trends
a. Radius decreases across a period
(1) increased effective nuclear charge due to decreased
shielding
b. Radius increases down a group
(1) addition of principal quantum levels
7.13 The Properties of a Group: the Alkali Metals
A. Easily lose valence electron (Reducing agents)
1. React with halogens to form salts
2. React violently with water
a. Lithium is not the most reactive because the heat of reaction is
insufficient to melt lithium and expose all of its surface area
B. Large hydration energy
1. Positive ionic charge makes ions attractive to polar water molecules
C. Radius and Ionization energy follow expected trends
See Table 7.8 for other properties of the Alkali metal group
AP Chemistry
A. Allan
Chapter 8 Notes - Bonding: General Concepts
8.1 Types of Chemical Bonds
A. Ionic Bonding
1. Electrons are transferred
2. Metals react with nonmetals
3. Ions paired have lower energy (greater stability) than separated ions
B. Coulomb's Law
Q Q
19
1 2
1.
=
2
.
31
x
10
J
nm
E
r
a. E = energy in joules
b. Q1 and Q2 are numerical ion charges
c. r = distance between ion center in nanometers
d. negative sign indicates an attractive force
C. Bond Length (covalent)
1. Distance at which the system energy is at a minimum
2. Forces at work
a. Attractive forces (proton - electron)
b. Repulsive forces (electron - electron, proton - proton)
3. Energy is given off (bond energy) when two atoms achieve greater
stability together than apart
D. Covalent Bonds
1. Electrons are shared by nuclei
2. Pure covalent (non-polar covalent)
a. Electrons are shared evenly
3. Polar covalent bonds
a. Electrons are shared unequally
b. Atoms end up with fractional charges
(1) + or 8.2 Electronegativity
A. Electronegativity
1. The ability of an atom in a molecule to attract shared electrons to itself
B. Electronegativity Trends
1. Electronegativity generally increases across a period (why?)
2. Electronegativity generally decrease within a family (why?)
C. Characterizing bonds
1. Greater electronegativity difference between two elements means less
covalent character and greater ionic character
2. We will not use the subtraction of electronegativities to determine ionic
character. This text uses a practical definition to identify ionic
compounds:
Any compound that conducts an electric current when melted is an
ionic compound.
Al O
Total positive = +6
Total negative = -6
C. Sizes of Ions
1. Anions are larger than the parent atom
2. Cations are smaller than the parent atom
3. Ion size increases within a family
4. Isoelectronic ions
a. Ions with the same number of electrons
b. Size decreases as the nuclear charge Z increases
Li(g) Li+(g) + e-
Ionization energy
520
1/2F2 F(g)
77
F(g) + e- F-(g)
Electron affinity
-328
Lattice energy
-1047
-617
r
a. k = a proportionality constant dependent on the solid structure
and the electron configuration
b. Q1 and Q2 are charges on the ions
c. r = shortest distance between centers of the cations and the
anions
2. Lattice energy increases as the ionic charge increases and the
distance between anions and cations decreases
8.6 Partial Ionic Character of Covalent Bonds
A. Calculating Percent Ionic Character
measured dipole moment of X Y
x100%
Percent ionic character =
+
calculated dipole moment of X Y
B. Ionic vs. Covalent
1. Ionic compounds generally have greater than 50% ionic character
2. Ionic compounds generally have electronegativity differences greater
than 1.6
3. Percent ionic character is difficult to calculate for compounds
containing polyatomic ions
B. Multiple Bonds
1. Single bonds - 1 pair of shared electrons
2. Double bonds - 2 pairs of shared electrons
3. Triple bonds - 3 pairs of shared electrons
Multiple Bonds, Average Energy (kJ/mole)
C=C
614
N=O
607
839
N=N
418
CC
O=O
495
941
NN
C=O
745
891
CN
1072
C=N
615
CO
4. As the number of shared electrons increases, the bond length shortens
(see table 8.5)
C. Bond Energy and Enthalpy (using bond energy to calculate approximate
energies for rxns)
1. H = sum of the energies required to break old bonds(endothermic)
+
sum of the energies released in forming new bonds (exothermic)
2. H = D ( Bonds broken) D ( Bonds formed )
a. D always has a positive sign
2. The sum of the formal charges of all atoms in a given molecule or ion
must equal the overall charge on that species
a. If the charge on an ion is -2, the sum of the formal charges must
be -2
E. Using Formal Charge to Evaluate Lewis Structures
1. If nonequivalent Lewis structures exist for a species, those with the
formal charges closest to zero, and with negative formal charges on
the most electronegative atoms are considered the best candidates
2. Only experimental evidence can conclusively determine the correct
bonding situation in a molecule
8.13 Molecular Structure: The VSEPR Model
A. Valence Shell Electron Pair Repulsion (VSEPR)
1. The structure around a given atom is determined principally by
minimizing electron-pair repulsions
2. Non-bonding and bonding electron pairs will be as far apart as possible
Arrangement of Electron Pairs Around an Atom Yielding Minimum
Repulsion
# of Electron Shape
Arrangement of Electron Pairs
Pairs
2
Linear
Trigonal Planar
Tetrahedral
Trigonal bipyramidal
Octahedral
Ammonia
107
Water
104.5
2. Lone (unshared) electron pairs require more room than bonding pairs
(they have greater repulsive forces) and tend to compress the angles
between bonding pairs
3. Lone pairs do not cause distortion when bond angles are 120 or
greater
C. VSEPR and Multiple Bonds
1. For the VSEPR model, multiple bonds count as one effective electron
pair
2. When a molecule exhibits resonance, ANY of the resonance structures
can be used to predict the molecular structure using the VSEPR model
D. Molecules Containing No Single Central Atom
1. Apply the principal of distancing shared and unshared electron pairs
2. Look at real 3-dimensional, rotatable models to develop predictive
skills
E. How Well Does VSEPR Work?
1. For non-ionic compounds, VSEPR works in most cases
1. Each carbon has two hybrid orbitals and two unhybridized 2p orbitals
2. Carbon dioxide
a. Oxygens have 3 effective pairs of electrons (sp2 hybrids)
(1) 1 double bond, two lone pairs
b. Carbons have 2 effective pairs (2 double bonds)
Notice that the sp2 orbitals on the two oxygens are at 90 angles, as are the
bond between carbon and oxygen
D. dsp3 Hybridization
1. Five effective pairs around a central
2. Trigonal bypyramidal shape
3. PCl5 is an example
atom
E. d2sp3 Hybridization
1. Six effective pairs around a central atom
2. Octahedral structure
3. SF6 is an example
Question: Why doesn't carbon undergo dsp3 or d 2sp3 hybridization, while phosphorous
and sulfur do undergo this type of hybridization?
Atomic
Orbitals
s, p
s, p, p
s, p, p, p
s, p, p,
p, d
s, p, p,
p, d, d
Type of
hybridization
sp
sp2
sp3
dsp3
# of hybrid
orbitals
2
3
4
5
d2sp3
Geometry
Linear
Trigonal-planar
Tetrahedral
Trigonal
bipyramidal
Octagonal
# of Effective
pairs
2
3
4
5
6
Energy
D. Paramagnetism
1. Magnetism can be induced in some nonmagnetic materials when in the
presence of a magnetic field
a. Paramagnetism causes the substance to be attracted into the
inducing magnetic field
(1) associated with unpaired electrons
b. Diamagnetism causes the substance to be repelled from the inducing
magnetic field
(1) associated with paired electrons
Figure 9.39
B2
C2
N2
2p*
_______
_______
_______
2p*
2p*
___ ___
___ ___
___ ___
2p*
___ ___
___ ___
2p
_______
_______
_______
2p
___ ___
___ ___
2p
___ ___
___ ___
___ ___
2p
_______
_______
2s *
_______
_______
_______
2s *
_______
_______
2s
_______
_______
_______
2s
_______
_______
Para
1
290
Dia
2
620
Dia
3
942
Para
2
495
Dia
1
154
159
131
110
121
143
Magnetism
Bond Order
Observed bond
dissocation energy
(kJ/mol)
Observed bond
length (pm)
O2
_______
F2
_______
One can measure magnetic properties FIRST, and use the results (dia- or para-) to
determine the energy order of the molecular orbitals
xy + yz = n
and
xy + yz = 2d sin
n = 2d sin
3. Diffractometer
a. computerized device to rotate crystal samples in an x-ray field, gather
incidence and reflection data, and construct models of crystal
structure
H vap
=
1 1
T2 T1
C. Sublimation
1. A process in which a substance goes directly from the solid to the gaseous
state
2. Reasons for sublimation
a. Solids have vapor pressure, but it is normally very low
b. Solids with little intermolecular attraction may have substantial vapor
pressures and be able to sublime at room conditions
D. Changes of State
1. Heating curve
2.
3.
4.
5.
6.
1. Triple Point
a. Solid and liquid have identical vapor pressure
b. All three phases exist together in equilibrium
***Note that the "great outdoors" does not constitute a closed system. Seeing snow, water,
and water vapor on a day at the slopes does not constitute the triple point, since the system
is not closed and is not at equilibrium
2. Critical temperature
a. The temperature above which the substance cannot exist as a liquid,
regardless of how great the pressure
3. Critical pressure
a. The pressure required to produce liquefaction at the critical
temperature
4. Critical point
a. Point defined by the critical temperature and critical pressure
b. For water: 374C and 218 atm
***I sincerely apologize about the references to ice skating on page 486 and 487. Ignore the
references and think HOCKEY instead!
Table 10.10
Boiling Point of Water at Various Locations
Location
Feet above sea level Patm (torr)
Boiling Poing (C)
Top of Mt. Everest, Tibet
29,028
240
70
Top of Mt. Denali, Alaska
20,320
340
79
Top of Mt. Whitney, California
14,494
430
85
Leadville, Colorado
10,150
510
89
Top of Mt. Washington, N.H.
6,293
590
93
Boulder, Colorado
5,430
610
94
Madison, Wisconsin
900
730
99
New York City, New York
10
760
100
Death Valley, California
-282
770
100.3
Molarity( M ) =
moles solute
liters of solution
B. Mass Percent
mass of solute
1.
Mass percent =
100
mass of solution
C. Mole Fraction
Mole fraction of componentA = x A =
1.
nA
nA + nB
D. Molality
1.
moles of solute
Molality =
Normality =
equivalent s
liter of solution
Equivalents of acids and bases
a. Mass that donates or accepts a mole of protons
Equivalents of oxidizing and reducing agents
a. Mass that provides or accepts a mole of electrons
D. Non-ideal Solutions
1. Liquid-liquid solutions in which both components are volatile
2. Modified Raoult's Law:
PTOTAL = PA + PB = X A PA0 + X B PB0
a. P0 is the vapor pressure of the pure solvent
b. PA and PB are the partial pressures
E. Ideal Solutions
1. Liquid-liquid solution that obeys Raoult's law
a. No solution is perfectly ideal, though some are close
2. Negative deviations from Raoult's law (lower than predicted vapor pressure
for the solution)
a. Solute and solvent are similar, with strong forces of attraction
b. Hsol'n is large and negative
3. Positive deviations from Raoult's law (higher than predicted vapor pressure
for the solution)
a. Solute and solvent are dissimiliar, with only weak forces of attraction
b. Particles easily escape attractions in solution to enter the vapor
phase
11.5 Boiling Point Elevation and Freezing-Point Depression
A. Colligative Properties
1. Properties dependent on the number of solute particles but not on their
identity
a. Boiling-Point elevation
b. Freezing-Point depression
c. Osmotic Pressure
B. Boiling-Point Elevation
1. Nonvolatile solutes elevate the boiling point of the solvent
T = K b msolute
a. is the boiling point elevation
b. Kb is the molal boiling point elevation constant of the solvent
c. m solute is the molality of the solute in the solution
C. Freezing-Point Depression
1. Solutes depress the freezing point of the solvent
T = K f msolute
a. is the freezing point depression
b. Kf is the molal freezing point depression constant of the solvent
c. m solute is the molality of the solute in the solution
B. Osmotic Pressure
1. The pressure necessary to keep water from flowing across a semipermeable
membrane
2. Osmotic pressure can be used to characterize solutions and determine
molar masses
= MRT
a. is osmotic pressure in atmospheres
b. M is the molarity of the solution
c. R is the gas law constant
d. T is the Kelvin temperature
C. Dialysis
1. Transfer of solvent molecules as well as small solute molecules and ions
D. Isotonic Solutions
1. Solutions that have the same osmotic pressure
E. Osmotic Pressure and Living Cells
1. Crenation
a. Cells placed in a hypertonic solution lose water to the solution, and
shrink
2. Hemolysis
a. Cells placed in a hypotonic solution gain water from the solution and
swell, possibly bursting
F. Reverse Osmosis
1. External pressure applied to a solution can cause water to leave the solution
a. Concentrates impurities (such as salt) in the remaining solution
b. Pure solvent (such as water) is recovered on the other side of the
semipermeable membrane
i=
moles of
particles in solution
Types of Colloids
Examples
Fog, aerosol sprays
Smoke, airborne bacteria
Whipped cream, soap suds
Milk, mayonnaise
Paint, clays, gelatin
Marshmallow, polystyrene foam
Butter, cheese
Ruby glass
Dispersing
Medium
Gas
Gas
Liquid
Liquid
Liquid
Solid
Solid
Solid
Dispersed
Substance
Liquid
Solid
Gas
Liquid
Solid
Gas
Liquid
Solid
Colloid Type
Aerosol
Aerosol
Foam
Emulsion
Sol
Solid foam
Solid emulsion
Solid sol
concentration of
[NO2 ]
t
[ NO]
t
1
[O2 ]
2
t
t
t
3. Choice of rate law depends on what data is easiest to collect
***Why study rate law? Re-read the paragraph at the bottom of page 556.
12.3 Determining the Form of the Rate Law
A. Determining the value of n (Order of the reactant)
1. Example
[A]
Rate (mol/L s)
1.00 M
8.4 x 10-3
0.50 M
2.1 x 10-3
a. Doubling the concentration of species A quadruples the rate of the
reaction. Therefore, the reaction is of second order with respect to A
Rate = k[A]2
B. Method of Initial Rates
1. Initial rate
a. Instantaneous rate just after t = 0
2. Experimental method
a. Vary initial concentration of reactant(s)
b. Determine initial rate for each concentration
c. Examine relationship between rate and initial concentration
3. Example:
Table 12-4
Experiment
1
2
3
2
k
[A]
[A]0 / 2
3
D. Molecularity
1. The number of species that must collide to produce the reaction indicated by
that step
a. Unimolecular step - a reaction involving one molecule
b. Bimolecular step - reaction involving the collisions of two species
c. Termolecular step - reaction involving the collisions of three species
Table 12.7 Examples of Elementary Steps
Elementary Step
Molecularity
A products
Unimolecular
A + A products
Bimolecular
(2A products)
A + B products
Bimolecular
A + A + B products
Termolecular
(2A + B products)
A + B + C products
Termolecular
Rate Law
Rate = k[A]
Rate = k[A]2
Rate = k[A][B]
Rate = k[A]2[B]
Rate = k[A][B][C]
E. Rate-Determining Step
1. The slowest step in a reaction determines the rate of the reaction
F. Example
1. Overall rxn:
NO2(g) + CO(g) NO(g) + CO2 (g)
2. Rate law determined experimentally:
Rate = k[NO2]2
3. Elementary Steps
k1
NO2(g) + NO2(g)
NO3(g) + NO(g)
k2
NO3(g) + CO(g)
NO2 (g) + CO2(g)
4. Which step is rate determining?
a. IF step 1 ,
Rate = k[NO2]2
(1) this agrees with experimental results
b. IF step 2 ,
Rate = k[NO3][CO]
(1) this does not agree with experimental results
12.7 A Model for Chemical Kinetics
A. Collision Model
1. Molecules must collide in order to react
a. They must collide with sufficient energy
b. They must collide with correct orientation
B. Activation Energy (Ea)
1. The energy required to convert atoms or molecules into the activated
complex (transition state)
2. The minimum energy required for an effective collision
C. The Arrhenius Equation
1. Form #1:
k = zpe E a / RT
a. z is collision frequency
b. p is the stearic factor representing the fraction of collisions with
correct orientation
5
2. Form #2:
k = Ae E a / RT
a. z and p are combined to make A, the frequency factor (frequency of
effective collisions)
3. Taking the natural log of both sides:
ln( k ) = ln( Ae E a / RT )
ln( k ) = ln( A) + ln( e E a / RT )
ln( k ) =
Ea
R
1 + ln( A)
T
a. Linear equation
y = ln(k)
slope = -Ea/R
x = 1/T
intercept = ln(A)
12.8 Catalysis
A. Catalysts
1. A substance that speeds up a reaction without being consumed itself
B. Effects of Catalysis
1. Catalysts lower activation energy but do not change E for the reaction
2. Catalysts provide alternate reaction pathways
3. Catalysis results in a higher percentage of effective collisions
C. Heterogeneous Catalysis (usually gaseous reactants on a solid surface)
1. Four steps
a. Adsorption and activation of the reactants
(1) Adsorption refers to the collection of one substance on the
surface of another substance
b. Migration of the adsorbed reactants on the surface
c. Reaction of the adsorbed substances
d. Escape, or desorption, of the products
2. Uses
a. Conversion of alkenes to alkanes
b. Conversion of CO and NO in auto exhaust to CO2 and N2
D. Homogeneous Catalysis
1. Reactants and catalysts are in the same phase
2. Example - The decomposition of ozone
a. Freon, CCl2F2(g) light
C NH 3 2
(C N 2 )(C H 2 3 )
PNH 3 2
( PN 2 )( PH 2 3 )
base
acid
acid
base
3. HCl is a stronger base than H3O + (H+) so the equilibrium lies far to the right
D. Acid Dissociation Constant
[ H + ][ Cl ]
1. K a =
[ HCl ]
a. water is not included because, in dilute solution, the concentration of
water is high, and changes so little it is assumed to be constant
b. The dissociation constant is the same as for the dissociation equation
here:
HCl(aq) H+ (aq) + Cl-(aq)
c. Ka is used only for this type of expression
d. For strong acids such as HCl, the equilibrium lies so far to the right
that [HCl] cannot be measured accurately, and an accurate
calculation of Ka is not possible
14.2 Acid Strength
A. Strong Acids
1. Acids for which the equilibrium lies far to the right
a. Strong acids yield weak conjugate bases
2. Common strong acids
a. sulfuric, hydrochloric, nitric, perchloric
B. Weak Acids
1. Acids for which the equilibrium lies far to the left
a. Weak acids yield relatively strong conjugate bases
C. Acid Terminology
1. Monoprotic - one acidic proton
2. Diprotic - two acidic protons
3. Triprotic - three acidic protons
4. Oxyacids - acids in which the acidic proton is attached to an oxygen atom
5. Organic acids - acids containing the mildly
acidic carboxyl group
a. Generally weak acids
b. Equilibrium lies far to the left
D. Water as an Acid and a Base
1. Water can act as an acid or as a base
a. Autoionization of water (Self-ionization)
100%
14.6 Bases
A. Strong Bases
1. Group 1A metal hydroxides
2. Group 2A metal hydroxides
a. Less soluble than Group 1A hydroxides; allows use as antacids
B. Weak Bases
1. Ammonia and other covalent bases
2. Compounds with low values of Kb
C. Calculating the pH of Strong Bases
1. Kw = [H +][OH-] = 1.0 x 10-14
a. If you know [OH-], you can calculate [H+ ] from which you can
calculate the pH
D. Calculation of pOH
1. pKw = 14.00 = pH + pOH
2. pOH = 14.00 - pH
14.7 Polyprotic Acids
A. Stepwise dissociation
Ka 1 =
[ H + ][ HCO3 ]
= 4.3x10 7
H 2 CO3
2
2.
HCO3-(aq)
H (aq) +
+
CO32-(aq)
Ka2 =
[ H + ][CO3 ]
[ HCO3 ]
= 5.6 x10 11
A+
H2 O
weak
conjugate
acid
base
OH- ions are not allowed to accumulate but are replaced by A - ions
2.
[ H + ][ A ]
[ HA]
Ka =
[H + ] = K a
[ HA]
[A ]
a. If the amounts of HA and A - originally present are very large
compared with the amount of OH- added, the change in [HA]/[A -] will
be small. Therefore the pH change will be small
1. pH = pK a + log
[ acid ]
[ HA]
a. For a particular buffering system (acid-conjugate base pair), all
solutions that have the same ratio [A -]/[HA] will have the same pH
E. Buffering with a Weak Base and Its Conjugate Acid
1. Weak base B reacts with any H + added
B + H+ BH+
Base
Conjugate
acid
2. Conjugate acid BH+ reacts with any added OHBH+ + OH- B + H2O
Conjugate
Base
Acid
F. Summary
1. Buffered solutions contain relatively large concentrations of a weak acid and
the corresponding weak base. They can involve a weak acid HA and the
conjugate base A - or a weak base and the conjugate acid BH+
2. When H+ is added to a buffered solution, it reacts essentially to completion
with the weak base present
3. When OH- is added to a buffered solution, it reacts essentially to completion
with the weak acid present
4. The pH in the buffered solution is determined by the ratio of the
concentrations of the weak acid and the weak base. The pH remains
relatively unchanged as long as the concentrations of buffering materials are
large compared with the amounts of H + or OH- added
15.3 Buffer Capacity
A. Buffering Capacity
1. The amount of protons or hydroxide ions the buffer can absorb without a
significant change in pH.
a. The pH of a buffered solution is determined by the ratio [A -]/[HA]
b. The capacity of a buffered solution is determined by the magnitudes
of [HA] and [A -]
B. Preparing a Buffer
1. Optimal buffering occurs when [HA] is equal to [A -] ( [A -]/[HA] = 1 )
2. The pKa of the weak acid to be used should be as close as possible to the
desired pH
Table 15.1 Change in [C 2H3O2-]/[HC 2 H3O2] for two solutions when 0.01 mol H+ is added to
1.0 L of each
[C 2 H 3 O2 ]
[C 2 H 3 O2 ]
[ HC 2 H 3 O2 ]
[ HC 2 H 3 O2 ]
new
orig
Solution
Change
% Change
A
1.00 M/1.00 M = 1.00 0.99 M/1.01 M = 0.98
1.00 0.98
2.00%
B
1.00 M/0.01 M = 100 0.99 M/0.02 M = 49.5
100 49.5
50.5%
Strong Acid/
Weak Acid/
Strong Base
Strong Base
(Note the initial buffering effect created by the relatively high concentration of H+ in solution)
B. Strong Acid-Strong Base Titration
1. Before the equivalence point
a. [H +] (thus the pH) can be calculated
2. At the equivalence point, pH = 7.00
3. After the equivalence point
a. [OH-] can be calculated from the excess OH- and the volume of the
solution
b. [H+] and pH can be calculated from [OH-] and Kw
B. Titrations of Weak Acids and Strong Bases
1. Step 1 - A stoichiometry problem
a. The reaction of OH- with the weak acid is assumed to run to
completion
b. The concentrations of the acid remaining and the conjugate base
formed are determined
2. Step 2 - An equilibrium problem
a. The position of the weak acid equilibrium is determined, and the pH
calculated
3. The pH at the equivalence point of a weak acid/strong base is always
greater than 7
a. The anion of the weak acid is a base. The stronger the basic anion,
the higher the pH of the equivalence point
4
Solubility Equilibria
15.6 Solubility Equilibria and the Solubility Product
A. Dynamic Equilibrium
CaF2(s) Ca2+(aq) + 2F-(aq)
Ca2+(aq) + 2F-(aq) CaF2
CaF2(s) Ca2+(aq) + 2F-(aq)
1. Equilibrium occurs when the solution is saturated
E. pH and Solubility
1. If anion X - is an effective base (HX is a weak acid), the salt MX will show
increased solubility in acidic solution
a. Effective bases include:
OH- , S 2- , CO32- , C 2O42- , CrO4215.7 Precipitation and Qualitative Analysis
Instructor's Note: We will skim over much of sections 7 and 8, hitting only the high points and
performing a lab on selective precipitation
A. Selective Precipitation
1. Mixtures of metal ions in aqueous solution are often separated by using a
reagent whose anion forms a precipitate with only one or a few of the metal
ions in the mixture
Value of T
S
Positive
Negative
Negative
Value of G
Negative
Positive
???
Positive
Positive
???
Spontaneity
Spontaneous
Nonspontaneous
Spontaneous if the absolute value of
H is greater than the absolute value
of TS (low temperature)
Spontaneous if the absolute value of
TS is greater than the absolute value
of H (high temperature)
K
K=1
K>1
K<1
B. Temperature Dependence of K
1. G 0 = RT ln( K ) = H 0 TS 0
2. ln( K ) =
H 0 S 0
H 0
+
=
RT
R
R
1 S 0
+
R
T
so ln(K) 1/T
Chapter 17 Electrochemistry
17.1 Galvanic Cells
A. Oxidation-Reduction Reactions (Redox Rxns)
1. Oxidation = loss of electrons
a. the substance oxidized is the reducing agent
2. Reduction = gain of electrons
a. the subtance reduced is the oxidizing agent
B. Redox energy
1. Heat is produced
2. Electricity can be produced if the reactants are separated
a. Reactants can be separated by a salt bridge
b. Reactants can be separated by a porous partition
c. Electrons travel through a wire
C. Galvanic Cell
1. A device in which chemical
energy is changed to electrical
energy
a. Oxidation occurs at the
anode
b. Reduction occurs at the
cathode
D. Cell Potential (cell)
1. The driving force (electromotive
force, emf) on the electrons
2. Potential is measured in volts
-w = q
q = nF
(1) n is the number of moles of electrons
(2) F (a faraday) is the charge on a mole of electrons
F = (96 485 C/mol e -)
2. emf is not converted to work with 100% efficiency
a. Energy is always lost in the form of heat, but wmax is useful for
calculating the efficiency of conversion
wmax = -qmax
B. Relation to Free Energy
1. wmax = G
2. G = -qmax = -nFmax
3. G = -qmax
4. G0 = -nF0
a. When cell is positive (spontaneous), G will be negative
(spontaneous), so there is agreement
n0
0.0592
(at 25C)
17.5 Batteries
A. Batteries
1. A galvanic cell, or group of galvanic cells, connected in series
2. Source of direct current
B. Lead Storage Battery
1. Six two-volt cells in series
Anode rxn:
Cathode rxn:
PbO2 +
HSO4-
2. Cathodic regions
a. Areas that are resistant to oxidation
b. Electrons flow from anodic regions and react with oxygen
O2 + 2H2O + 4e- 4OH3. Presence of water is essential to corrosion of iron
4. Presence of salt accelerates the corrosion process by increasing the ease
with which electrons are conducted from anodic to cathodic regions
C. Prevention of Corrosion
1. Coating with a metal that will form an oxide coat to protect a metal that
would not develop a protective coat
2. Galvanizing
a. Placing a sacrificial of a more easily oxidized metal on top of the
metal you desire to protect
(1) zinc over iron
3. Alloying
a. Addition of metals that change steels reduction potential
(1) nickel and chromium alloyed to iron
4. Cathodic Protection
a. Connection of easily oxidized metals (an anode) to less easily
oxidized metals keeps the less from experiencing corrosion
b. The anode corrodes and must be replaced periodically
(1) Magnesium as anode to iron pipe
(2) Titanium as anode to a steel ships hull
17.7 Electrolysis
A. Electrolysis
1. Forcing a current through a cell to produce change for which the cell
potential is negative
B. Electroplating
1. Depositing neutral metal atoms on the electrode by reducing the metal ions
in solution.
AP Chemistry
A. Allan
Chapter 18 - The Representative Elements: Groups 1A through 4A
18.1 A Survey of the Representative Elements
A. Basic Trends
1. Metals tend to lose electrons and form cations
2. Nonmetals tend to gain electrons and form anions
3. Metalloids (semi-metals) have properties of both metals and nonmetals
a. B, Si, Ge, As, Sb, Te, Po, At
4. Metallic character tends to increase as atomic number increases within
a group
B. Atomic Size and Group Anomalies (Anomaly = oddity)
1. Hydrogen vs. Other Group I Elements
a. Very small, relatively high electronegativity (2.1)
b. Forms covalent bonds with nonmetals - other Group I elements
form ionic bonds with nonmetals
2. Beryllium vs. Other Group II Elements
a. Small, electronegativity of 1.5 produces covalent bonds with
many nonmetals (other group II's form ionic bonds)
b. BeO is amphoteric, other group II oxides are basic (form
hydroxides) in solution
3. Boron vs. Other Group III Elements
a. Boron is a nonmetal/semimetal, all others are active metals
4. Carbon vs. Silicon (Group IV Elements)
a. Carbon readily achieves the octet by forming bonds with
oxygen in CO2
b. Silicon does not form bonds with oxygen in discrete SiO2
molecules
(1) Si 3p orbitals do not easily overlap with oxygen 2p
orbitals
(2) Si forms interlocking SiO4 tetrahedra which make up the
crystalline structure of quartz
5. Nitrogen and Phosphorus (Group V)
a. Nitrogen forms a diatomic molecule with bonds (N2)
b. Phosphorus forms aggregates based on the tetrahedral P4
molecule
(1) Single bonds
(2) Large atoms = weak bonds
6. Oxygen and Sulfur (Group VI)
a. Oxygen forms a diatomic molecule with bonds (O2)
b. Sulfur forms aggregates such as the cyclic S8 molecule, with all
single bonds
7. Halogens (Group VII)
a. Chlorine has an unexpectedly higher electron affinity than
fluorine
(1) Small size of fluorine atoms bring unshared (lone) pairs
close together, where they repel each other
49.2%
25.7%
7.50%
4.71%
3.39%
2.63%
2.40%
1.93%
0.87%
Titanium
Chlorine
Phosphorus
Manganese
Carbon
Sulfur
Barium
Nitrogen
Fluorine
0.58%
0.19%
0.11%
0.09%
0.08%
0.06%
0.04%
0.03%
0.03%
65.0%
18.0%
10.0%
3.0%
1.4%
1.0%
0.50%
Potassium
Sulfur
Sodium
Chlorine
Iron
Zinc
0.34%
0.26%
0.14%
0.14%
0.004%
0.003%
C. Industrial Uses
1. Production of Ammonia by the Haber Process
2. Hydrogenating unsaturated vegetable oils
D. Hydrogen Halides
1. Ionic hydrides
a. Hydrogen and a Group I or II metal
b. Hydride ion is Hc. Hydrides are powerful reducing agents, explosive in water
d. Examples include LiH and CaH2
2. Nonmetals + hydrogen (covalent hydrides)
a. Examples include H2O, NH3, CH4, HCl
3. Metallic (Interstitial) Hydrides
a. Hydrogen and a transition metal
b. Hydrogen is absorbed by transition metals
(1) Amount of hydrogen depends on length of exposure
(2) Potential method of storing Hydrogen fuel
18.4 The Group 2A Elements - The Alkaline Earth Metals
A. Basicity of Oxides
1.
MO(s) + H2O(l) M2+(aq) + 2OH-(aq)
2.
BeO has amphoteric properties
B. Reaction with Water
1.
M(s) + H2O(l) M2+(aq) + 2OH-(aq) + H2(g)
2.
Ca, Sr, Ba react at room temperature, Mg in boiling water
C. Uses
1. Calcium phosphate in bone structure
2. Mg in metabolism and muscle function
3. Mg metal in flash bulbs and metal alloys
D. Removal from "hard" water
1. Cation exchange resin replaces each Mg+2 and Ca+2 in water with 2
sodium ions
Note: Detergents are less soluble in hard water. There is noticeable
difficulty, for instance, washing detergent out of one's hair when the
concentration of Group II ions is high
18.5 The Group 3A Elements
A. Boranes
1. B2H6 (diborane) and others (B5H9) are electron deficient and highly
reactive
B. Aluminum
1. Most abundant metal on earth
2. Oxide (Al2O3) is amphoteric
3. Metallic properties, but covalent bonds to nonmetals
C. Gallium
1. Largest liquid range of any metal
a. melts at 29.8C
b. boils at 2400C
D. Indium and Thallium
1. The Inert Pair Effect
a. Lose one electron to form +1 ion (full s orbital)
b. Lose three electrons to form +3 ion (octet)
18.6 The Group 4A Elements
A. Variation within the Group
1. C is a nonmetal
2. Si and Ge are semimetals
3. Sn and Pb are metals
4. All tend to form 4 covalent bonds to nonmetals (tetravalence)
B. Carbon
1. Three allotropic forms (allotropic = two or more distinct forms)
Graphite
2. Carbon oxides
Diamond
Buckminster Fullerene
carbon suboxide
C. Silicon
1. Found in earth's crust in silica and silicates
2. Semimetal used in semiconductors
D. Germanium
1. Rare semimetal used as a semiconductor in electric devices
E. Tin
1. Widely used in alloys
Bronze
Solder
Pewter
F. Lead
1. Obtained from the galena ore (PbS)
2. Widely used in the anti-knock agent tetraethyl lead, (C2H5)4Pb
Be +
4
2
He 126 C +
1
0
B. Zone of Stability
1. Of 2000 known nuclides, only 279 are
stable with respect to radioactive
decay
2. All nuclides with more than 83
protons (bismuth) are unstable
3. Light nuclides are most stable when
the neutron/proton ratio is 1
4. Heavier nuclides are most stable
when the neutron/proton ratio is
greater than 1
5. Magic numbers
a. Special stability exists when the number of protons or neutrons is:
2, 8, 20, 28, 50, 82, 126
C. Types of Radioactive Decay
1. Alpha Emission
a. Alpha particle () is a helium nucleus ( 24 He ), so it has a 2+ charge
b. Alpha emission is restricted almost entirely to very heavy nuclei
210
84
Po + 206
82 Pb +
4
2
He
2. Beta Emission
a. Beta particle () is an electron emitted from the nucleus during
nuclear decay
n 11 p + 10
b. Beta particles are emitted when a neutron is converted into a proton
and an electron
1
0
14
6
14
7
N +
0
1
3. Positron Emission
a. Positrons are particles that have the same mass as an electron, but a
positive charge
b. Positron emission arises from the conversion of a proton into a
neutron and a positron
1
1
1
0
n +
0
+1
38
19
38
18
Ar +
0
+1
4. Electron Capture
a. Inner orbital electron is captured by the nucleus of its own atom
b. Electron combines with a proton and a neutron is formed
0
1
e +
1
1
p 01 n
106
47
Ag +
0
1
106
46
Pd
5. Gamma Emission
a. Gamma rays () are high-energy electromagnetic waves emitted from
a nucleus as it changes from an excited state to a ground energy
state
b. Gamma rays are produced when nuclear particles undergo
transitions in energy levels
c. Gamma emission usually follows other types of decay that leave the
nucleus in an excited state
D. Decay Series
1. In some cases, multiple decays are needed to produce a stable nuclide
a. Original nuclide is called the "Parent" nuclide
b. Ensuing decay nuclides are called "daughter" nuclides
21.2 The Kinetics of Radioactive Decay
A. Rate of Decay
1. The negative of the change in the number of particles per unit of time
N
N
N
Rate =
= kN
t
t
a. This is a first order rate law, so
N
= kt
ln
N0
N0 = original number of nuclides (at t = 0)
N = the number of nuclides remaining at time t
B. Half-Life (t1/2)
1. The time required for the number of nuclides to reach half the original value
ln( 2) 0.693
t1 / 2 =
=
k
k
Rate =
Nuclide
3
1H
14
6
32
15
218
84
Po
3.0 minutes
14.28 days
218
85
At
1.6 seconds
40
19
1.3 x 10 years
238
92
60
27
Co
10.47 minutes
239
94
Pu
E = mc2
C. Critical Mass
1. The minimum amount of nuclide that provides the number of neutrons
needed to sustain a chain reaction
D. Nuclear Fusion
1. Combining two light nuclei to form a heavier, more stable nucleus
A. Fusion Reactions
1. More energetic than fission rxns
2. Source of energy of the hydrogen bomb
3. Could produce energy for human use if a way can be found to contain a
fusion rxn (magnetic field?)
# of Carbons
1
2
3
4
5
6
7
8
9
10
B. Structural Isomers
1. Same formula, but the atoms are bonded together in a different order
2. Different bonding order results in different properties
C4H10
Butane
C4H10
2-methylpropane
D. Reactions of Alkanes
1. Combustion reactions
a. 2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(g)
2. Substitution reactions
hv
a. CH 4 + Cl2
CH 3 Cl + HCl
methane
chloromethane
3. Dehydrogenation reactions
3 at 500 C
a. CH 3 CH 3 Cr
2O
CH 2 = CH 2 + H 2
ethane
ethylene
Cis 1,2-dichloroethane
Trans 1,2-dichloroethane
2
3. In some isomer pairs, one isomer is biologically active, while the other is not
(specificity of enzymes is the cause)
C. Alkynes
1. Hydrocarbons with triple covalent bonds
a. The simplest alkyne is ethyne, or acetylene (C 2H2)
Propane
b. Halogenation
CH 2 = CHCH 2 CH 2 CH 3 + Br2 CH 2 BrCHBrCH 2 CH 2 CH3
1-Pentene
1-2-dibromopentene
c. Polymerization
(1) small molecules are joined together to form a large molecule
22.3
Aromatic Hydrocarbons
A. Structure of Aromatics
1. Hydrocarbons with six-membered carbon rings and delocalized electrons
a. The simplest aromatic hydrocarbon is benzene (C 6H6)
o-dichlorobenzene
m-dichlorobenzene
3
p-dichlorobenzene
22.4
22.5
Hydrocarbon Derivatives
Classes of Organic Compounds
Class
Functional Group
General Formula
Alcohol
hydroxyl group (-OH)
Alkyl halide
Ether
Aldehyde
carbonyl group
Ketone
carbonyl group
Carboxylic acid
carboxyl group
Ester
Amine
amine group
Examples:
Class: Ether
Name: dimethylether
Class: Ether
Name: diethylether
Class : Alcohol
Class: Aldehyde
Name: methanaldehyde
Class: Ether
Name: ethylmethylether