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AP Chemistry
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
2H
2
+ O
2
2H
2
O
2. Decomposition of water
2H
2
O 2H
2
+ O
2
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
2
C. SI Prefixes
mega M 1,000,000
10
6
nano n 0.000000001
10
-9
kilo k 1,000 10
3
micro 0.000001 10
-6
hecto h 100
10
2
milli m 0.001
10
-3
deka da 10
10
1
centi c 0.01
10
-2
deci n 0.1
10
-1
1.4 Uncertainty in Measurement
A. Recording Measurements (Significant figures)
1. Record all digits that are certain
2. Record the first digit that is uncertain (all measurements have some
degree of uncertainty)
3. Uncertainty in the last number is + 1, unless otherwise noted
B. Accuracy
1. The agreement of a particular value with the accepted value
C. Precision
1. The degree of agreement among several measurements made in the
same way
"You can be precise, but not accurate. If you are accurate, you are
necessarily precise."
D. Errors
1. Random Errors (indeterminate errors)
a. Measurements may be high or low
b. Causes:
1) Interpretation of the uncertain digit
2) Procedural ineptness
2. Systematic Errors
a. Always occur in the same direction
b. Caused by poor measurement calibration
1) gun sight set too high/low
2) balance improperly zeroed
3) thermometer improperly marked
3
1.5 Significant Figures and Calculations
A. Rules for Counting Significant Figures
Number Rule Example
Nonzero integers Always significant 6.34 m (3 sig figs)
Leading zeroes Never significant 0.00634 m ( 3 sig figs)
Captive zeroes Always significant 6.0034 (5 sig figs)
Trailing zeroes Significant if after a decimal 63400 (3 sig figs)
0.63400 (5 sig figs)
Exact numbers Infinite significance e.g. There is 1 star at the
center of our solar system.
There is no doubt about
the number "1"
Scientific notation All digits are significant
6.3400 x 10
6
(5 sig figs)
B. Multiplication and Division
1. Keep as many sig figs in your answer as are in the piece of data with
the least number of sig figs
2.37 cm x 15.67 cm x 7.4 cm = 274.82046
(keep two sig figs) = 2.7 x 10
2
cm
3
C. Addition and Subtraction
1. Keep the same number of decimal places as the least precise
measurement in your calculation
34.039 m + 0.24 m + 1.332 m + 12.7 m = 48.311 m
(keep one decimal place) = 48.3 m
D. Rules for Rounding
1. Round at the end of a series of calculations, NOT after each step
2. Use only the first number to the right of the last sig fig to decide
whether or not to round
a. Less than 5, the last significant digit is unchanged
b. 5 or more, the last significant digit is increased by 1
Note from this section in your book: Detailed solutions and stepwise examples of
problems in this text show correct sig figs at each step. Since you will most often do a
sequence of calculations and then round to correct sig figs at the end, your answer will
often be slightly different (usually only in the last place) than the answer given in the
book.
1. Significant figures rules will be observed in all calculations throughout
the year in this course. You need never ask, "Do we have to watch our
sig figs?" The answer is always "Yes!"
4
1.6 Dimensional Analysis
A. Examine examples
1. pages 18 - 21
B. Unit Conversions Questions
1. What units am I given?
2. What units must be in my answer?
3. What is conversion factor?
Full credit can never be given for working a problem in which you do not do all of the
following:
1. Observe significant figures rules
2. Label all steps of your work with the correct units
3. Correctly label and identify your answer
4. Solve the problem in a manner that can be understood by the reader.
1.7 Temperature
A. Celsius (C) and Kelvin (K)
1. Kelvin = Celsius + 273.15
2. Celsius = Kelvin - 273.15
3. Size of the temperature unit (degree) is the same
B. Fahrenheit
1. T
C
= (T
F
- 32F)(5C/9F)
2. T
F
= T
C
x (9F/5C) + 32F
1.8 Density
A. Density = mass/volume
1.9 Classification of Matter
A. Matter
1. Anything that occupies space and has mass
B. States of Matter
1. Solids - rigid, fixed volume and shape
2. Liquids - definite volume, no specific shape
3. Gases - no fixed volume or shape, highly compressible
C. Mixtures - Matter of variable composition
1. Heterogeneous mixtures
a. Having visibly distinguishable parts
2. Homogeneous mixtures (solutions)
a. Having visibly indistinguishable parts
D. Components of Mixtures can be Separated by Physical Means
1. Distillation
2. Filtration
3. Chromatography
5
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 Electrons
Protons Neutrons
Quarks 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
23
11
Na Element symbol
Atomic Number
2.6 Molecules and Ions
A. Chemical Bonding
1. Covalent bonding - Sharing of electrons
2. Ionic bonding - Attraction of oppositely charged ions due to a reaction
in which electrons are transferred
B. Representing Molecules (Covalently bonded)
1. Chemical formula
a. Symbols for atoms and subscripts
1) H
2
0
2) CH
4
2. Structural formula
a. Bonds represented by lines
Ball and Stick 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
2.8 Naming Simple Compounds
A. Ionic Compounds
1. Positive ion is always named first, negative ion second
You were given a list of ions to memorize on the first day of class
Tips for memorizing the polyatomics:
a. Find the "ate" ion (sulfate, for instance)
sulfate = SO
4
2-
b. The "ite" ion always has one less oxygen than the "ate" ion
sulfite = SO
3
2-
c. The prefix "per" (think hyper, meaning "above") is used with the
"ate" prefix to indicate one more oxygen than the "ate" ion
persulfate = SO
5
2-
d. The prefix "hypo" (meaning "under" or "below") is used with the
"ite" prefix to indicate one less oxygen than the "ite" ion
hyposulfite = SO
2
2-
Examples (Just because you can name it doesn't mean it exists!)
Perchlorate
ClO
4
- Pernitrate
NO
4
-
Chlorate
ClO
3
- Nitrate
NO
3
-
Chlorite
ClO
2
- Nitrite
NO
2
-
hypochlorite
ClO
- hyponitrite
NO
-
2. Metals with more than one oxidation state (transition metals) must have a
roman numeral to indicate the oxidation state
Fe
3+
= 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 (H
2
SO
4
= 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
(H
2
SO
3
= 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 (
12
C) 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 10
23
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 (C
2
H
6
):
Mass of 2 moles of C = 2(12.01 g)
Mass of 6 moles of H = 6(1.008 g)
30.07 g
3.4 Percent Composition of Compounds
A. Calculating any percentage
1. "The part, divided by the whole, multiplied by 100"
B. Percentage Composition
1. Calculate the percent of each element in the total mass of the
compound
(#atoms of the element)(atomic mass of element) x 100
(molar mass of the compound)
3.5 Determining the Formula of a Compound
A. Determining the empirical formula
1. Determine the percentage of each element in your compound
2. Treat % as grams, and convert grams of each element to moles of
each element
3. Find the smallest whole number ratio of atoms
4. If the ratio is not all whole number, multiply each by an integer so that
all elements are in whole number ratio
B. Determining the molecular formula
1. Find the empirical formula mass
2. Divide the known molecular mass by the empirical formula mass,
deriving a whole number, n
3. Multiply the empirical formula by n to derive the molecular formula
3.6 Chemical Equations
A. Chemical reactions
1. Reactants are listed on the left hand side
2. Products are listed on the right hand side
3. Atoms are neither created nor destroyed
a. All atoms present in the reactants must be accounted for among
the products, in the same number
b. No new atoms may appear in the products that were not present
in the reactants
B. The Meaning of a Chemical Reaction
1. Physical States
a. Solid - (s)
b. Liquid - (l)
c. Gas - (g)
d. Dissolved in water (aqueous solution) - (aq)
2. Relative numbers of reactants and products
a. Coefficients give atomic/molecular/mole ratios
3.7 Balancing Chemical Equations
A. Determine what reaction is occurring
1. It is sometimes helpful to write this in word form:
Hydrogen + oxygen water
B. Write the unbalanced equation
1. Focus on writing correctly atomic and compound formulas
H
2
+ O
2
H
2
O
C. Balance the equation by inspection
1. It is often helpful to work systematically from left to right
2H
2
+ O
2
2H
2
O
D. Include phase information
2H
2
(g) + O
2
(g) 2H
2
O (l)
3.8 Stoichiometric Calculations: Amounts of Reactants and Products
A. Balance the chemical equation
B. Convert grams of reactant or product to moles
C. Compare moles of the known to moles of the desired substance
1. A ratio derived from the coefficients in the balanced equation
D. Convert from moles back to grams if required
3.9 Calculations Involving a Limiting Reactant
A. Concept of limiting reactant (limiting reagent):
" I want to make chocolate chip cookies. I look around my kitchen (I have a BIG
kitchen!) and find 40 lbs. of butter, two lbs. of salt, 1 gallon of vanilla extract, 80 lbs. of
chocolate chips, 200 lbs. of flour, 150 lbs. of sugar, 150 lbs. of brown sugar, ten lbs. of
baking soda and TWO eggs. It should be clear that it is the number of eggs that will
determine the number of cookies that I can make."
1. The limiting reactant controls the amount of product that can form
B. Solving limiting reactant problems
1. Convert grams of reactants to moles
2. Use stoichiometric ratios to determine the limiting reactant
3. Solve as before, beginning the stoichiometric calculation with the
grams of the limiting reactant
C. Calculating Percent Yield
1. Actual yield - what you got by actually performing the reaction
2. Theoretical yield - what stoichiometric calculation says the reaction
SHOULD have produced
Actual Yield x 100% = percent yield
Theoretical 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 (HNO
3
(aq), H
2
SO
4
(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
B. Concentration of Ions in Solution
1. Ionic compounds dissociate in solution, multiplying the molarity by the
number of ions present
C. Moles from Concentration
1. Liters of solution x molarity = moles of solute
D. Solutions of Known Concentration
1. Standard solution - a solution whose concentration is accurately known
2. Preparation of Standard solutions
How much x How strong x What does it weigh?
L x mol/L x g/mol = grams required to prepare
the standard
E. Dilution
1. Dilution of a volume of solution with water does not change the number
of moles present
2. Solving dilution problems
M
1
V
1
= M
2
V
2
4.4 Types of Chemical Reactions
A. Precipitation reactions
1. When two solutions are mixed, an insoluble solid forms
B. Acid-Base reactions
1. A soluble hydroxide and a soluble acid react to form water and a salt
C. Oxidation-Reduction reactions (redox rxns)
1. Reactions in which one or more electrons are transferred
4.5 Precipitation Reactions
A. Dissociation
1. Ionic compounds dissolve in water and the ions separate and move
independently
AgNO
3
(aq) + NaCl(aq) products
Ag
+
(aq) + NO
3
-
(aq) + Na
+
(aq) + Cl
-
products
B. Determination of Products
1. Recombination of ions
a. AgNO
3
NaCl AgCl NaNO
3
2. Elimination of reactants as products
a. AgNO
3
and NaCl are reactants and can't be products
3. Identifying the precipitate
a. "Switch Partners" of reactant pairs to determine the names of
the products.
b. AgCl and NaNO
3
are the products
c. AgCl is insoluble, so it is the white precipitate
d. If there is no insoluble product, the reaction does not occur
a. NaCl(aq) + KNO
3
(aq) NaNO
3
(aq) + KCl(aq)
Both products are soluble and all ions remain
independent in solution; no reaction occurs
Na
+
(aq) + Cl
-
(aq) + K
+
(aq) + NO
3
-
(aq)
Table 4.1 Simple Rules for the Solubility of Salts in Water
1. Most nitrate (NO3
-
)salts are soluble.
2. Most salts containing the alkali metal ions (Li
+
, Na
+
, K
+
, Cs
+
, Rb
+
) and
the ammonium (NH
4
+
) ion are soluble.
3. Most chloride, bromide and iodide salts are soluble. Exceptions are salts
containing the ions Ag
+
, Pb
2+
, and Hg
2+
.
4. Most sulfate salts are soluble. Notable exceptions are BaSO
4
, PbSO
4
,
HgSO
4
and CaSO
4
.
5. Most hydroxide salts are only slightly soluble. The important soluble
hydroxides are NaOH and KOH. The hydroxides of barium, strontium and
calcium are marginally soluble.
6. Most sulfide (S
2-
), carbonate (CO
3
2-
), chromate (CrO
4
2-
) and phosphate
(PO
4
3-
) salts are only slightly soluble.
4.6 Describing Reactions in Solution
A. The Molecular Equation
1. Gives the overall reaction stoichiometry, not necessarily the actual
forms of reactants and products in solution
Na
2
CO
3
(aq) + Ca(NO
3
)
2
(aq) 2NaNO
3
(aq) + CaCO
3
(s)
B. The Complete Ionic Equation
1. Represents as ions all reactants and products that are strong
electrolytes
2Na
+
(aq) + CO
3
2-
(aq) + Ca
2+
(aq) + 2NO
3
-
(aq) 2Na
+
(aq) + 2NO
3
-
(aq) + CaCO
3
(s)
C. The Net Ionic Equation
1. Includes only those components that take part in the chemical change
2. Spectators are eliminated
Ca
2+
(aq) + CO
3
2-
(aq) CaCO
3
(s)
4.7 Stoichiometry of Precipitation Reactions
A. Determine what reaction takes place
B. Write the balanced net ionic equation for the reaction
C. Calculate the moles of reactants
D. Determine which reactant is limiting
E. Calculate the moles of product or products
F. Convert to grams or other units, as required
4.8 Acid-Base Reactions (Neutralization Reactions)
A. Definitions
1. Brnsted:Acids are proton donors, bases are proton acceptors
2. Arrhenius: Acids produce H
+
ions in water, bases produce OH
-
ions in
solution
B. Net ionic equation for acid-base reactions
1. H
+
(aq) + OH
-
(aq) H
2
O(l)
2. The hydroxide ion can be assumed to completely react with even a
weak acid in solution
C. Stoichiometry Calculations for Acid-Base Reactions
1. List the species present in the combined solution before any reaction
occurs; decide what reaction will occur
2. Write the balanced net ionic equation for this reaction
3. Calculate the moles or reactants
a. For reactions in solution, use volumes of the original solutions
and their molarities
4. Determine the limiting reactant where appropriate
5. Calculate the moles of the required reactant or product
6. Convert to grams or volume of solution as required
D. Acid-Base Titrations
1. Vocabulary
a. Titrant - Solution of known concentration
b. Analyte - Solution of unknown concentration
c. Equivalence point - Point at which the amount of titrant added to
analyte results in perfect neutralization
d. Indicator - a substance added at the beginning of the titration
that changes color at the equivalence point
e. Endpoint - the point at which the indicator changes color
2. Requirements for a successful titration
a. the exact reaction between titrant and analyte must be known
b. the reaction must proceed rapidly
c. the equivalence point must be marked accurately (select the
appropriate indicator)
d. the volume of titrant required to reach the equivalence point
must be known accurately
e. for acid-base titrations, the titrant should be a strong acid or a
strong base
4.9 Oxidation-Reduction Reactions (redox)
A. Electron transfer (LEO says GER)
1. Gain electrons = reduction
2. Lose electrons = oxidation
B. Examples of redox rxns
1. Photosynthesis
2. Combustion of fuels
3. Oxidation of sugars, fats, proteins for energy
Rules for Assigning Oxidation Numbers Summary
1. the oxidation number of the atom of a free element
is zero
Element = 0
2. the oxidation number of a monatomic ion equals its
charge
3. In compounds, oxygen has an oxidation number of -
2, except in peroxides, where it is -1
Oxygen = -2
4. In compounds containing hydrogen, hydrogen has
an oxidation number of +1
Hydrogen = +1
5. In compounds, fluorine is ALWAYS assigned an
oxidation number of -1
Fluorine = -1
6. The sum of the oxidation states for an electrically
neutral compound must be zero
C. Noninteger Oxidation states
1. Fe
3
O
4
- Magnetite
a. Oxidation number for each iron averages to +8/3
b. Magnetite contains two Fe
3+
ions and one Fe
2+
D. Characteristics of Oxidation-Reduction Reactions
1. the oxidized substance:
a. loses electrons
b. increases oxidation state
c. is the reducing agent
2. the reduced substance
a. gains electrons
b. decreases oxidation state
c. is the oxidizing agent
4.10 Balancing Oxidation-Reduction Equations
There are no notes for this section. The only way to master the balancing of
redox equations is to actually balance them. While there are some minor variations in
the processes used for acidic and basic solutions, the skills involved are identical. We
will practice balancing numerous redox equations as a class.
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/meter
2
= 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
k PV
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. P
1
V
1
= k = P
2
V
2

V P V P 2 2 1 1
or
V
V
P
P
1
2
2
1

3. Boyle's law works best at low pressures


4. Gases that obey Boyle's law are called Ideal gases
B. Charles' Law (Jacques Charles, 1746 - 1823)
1. The volume of a gas increase linearly with temperature provided the
pressure remains constant
a. V = bT V/T = b
(1) V
1
/T
1
= b = V
2
/T
2

T
V
T
V
2
2
1
1
or
T
T
V
V
2
1
2
1

b. Temperature must be measured in degrees Kelvin


(1) K = C + 273
(2) 0 K is "absolute zero"
C. Avogadro's Law (Amedeo Avogadro, 1811)
1. For a gas at constant temperature and pressure, the volume is directly
proportional to the number of moles, n
a. V = an V/n = a
(1) V
1
/n
1
= a = V
2
/n
2


n
V
n
V
2
2
1
1

5.3 The Ideal Gas Law


A. Derivation from existing laws
1. V = k/P V = bT V = an
2. Constants k, b, a are combined into universal gas constant, R
P
nRT
V
or
nRT PV

mol K
atm L
R

0826 . 0
B. Limitations of the Ideal Gas Law
1. Works well at low pressures and high temperatures
2. Most gases do not behave ideally above 1 atm pressure
3. Does not work well near the condensation conditions of a gas
C. Solving for new volumes, temp or pressure (n remaining constant)
1. Combined law (from general chem)
2.
T
V P
R n
T
V P
2
2 2
1
1 1
or
T
V P
T
V P
2
2 2
1
1 1

,
_

,
_

T
T
P
P
V V
1
2
2
1
1 2
( )( )( )

,
_

P
Tn
a b k V
5.4 Gas Stiochiometry
A. Standard temperature and pressure (STP)
1. 0 C, 273 K
2. 760 torr, 1 atm
B. Molar volume
1. One mole of an ideal gas occupies 22.42 liters of volume at STP
C. Things to remember

volume
mass
Density

mass molar
ce subs of grams
n
tan

5.5 Dalton's Law of Partial Pressures (John Dalton, 1803)


A. Statement of law
1. "For a mixture of gases in a container, the total pressure exerted is the
sum of the pressures each gas would exert if it were alone"
2. It is the total number of moles of particles that is important, not the
identity or composition of the gas particles
B. Derivation
1. ...
3 2 1
+ + +
P P P PTOTAL
2.
V
T R n
P
1
1

V
T R n
P
2
2

V
T R n
P
3
3
. . .
3.
PTOTAL
V
T R n1
+
V
T R n2
+
V
T R n3
4. ( )

,
_

+ + +
V
T R
n n n PTOTAL
...
3 2 1
5.

,
_

V
T R
n P TOTAL TOTAL
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):
P
P
n
n
x
TOTAL TOTAL
1 1
1

5.6 The Kinetic Molecular Theory of Gases (KMT)
A. Postulates of the KMT Related to Ideal Gases
1. The particles are so small compared with the distances between them
that the volume of the individual particles can be assumed to be zero
2. The particles are in constant motion. Collisions of the particles with the
walls of the container cause pressure
3. Assume that the particles exert no forces on each other.
4. The average kinetic energy of a collection of gas particles is assumed
to be directly proportional to the Kelvin temperature of the gas
B. Explaining Observed Behavior with KMT
1. P and V (T = constant)
a. As V is decreased, P increases:
V decrease causes a decrease in the surface area. Since P
is force/area, the decrease in V causes the area to
decrease, increasing the P
2. P and T (V = constant)
a. As T increase, P increases
The increase in T causes an increase in average kinetic
energy. Molecules moving faster collide with the walls of the
container more frequently, and with greater force
3. V and T (P = constant)
a. As T increases, V also increases
Increased T creates more frequent, more forceful collisions.
V must increase proportionally to increase the surface area,
and maintain P
4. V and n (T and P constant)
a. As n increases, V must increase
Increasing the number of particles increases the number of
collisions. This can be balanced by an increase in V to
maintain constant P
5. Dalton's law of partial pressures
a. P is independent of the type of gas molecule
KMT states that particles are independent, and V is
assumed to be zero. The identity of the molecule is therefore
unimportant
C. Root Mean Square Velocity
1. Velocity of a gas is dependent on mass and temperature.
2. Velocity of gases is determined as an average
a. M = mass of one mole of gas particles in kg
b. R = 8.3145 J/Kmol
(1) joule = kgm
2
/s
2
M
T R
urms
3

D. Mean Free Path


1. Average distance a molecule travels between collisions
a. 1 x 10
-7
m for O
2
at STP
5.7 Effusion and Diffusion
A. Effusion
1. Movement of a gas through a small opening into an evacuated
container (vacuum)
2. Graham's law of effusion
2
1
gas for effusion of
Rate
gas for effusion of
Rate
M
M
1
2

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
V
T R n
P

b n V
T R n
P

'
B. Pressure
1. Molecules of real gases do experience attractive forces
a. a = proportionality constant determined by observation of the
gas

,
_


V
n
a P Pobs
2
'
C. Combining to derive van der Waal's eqn

,
_

V
n
a
b n V
T R n
Pobs
2
and then rearranging
( )
T R n b n V
V
n
a Pobs

1
1
1
1
]
1

,
_

2
5.9 Chemistry in the Atmosphere
A. Composition of the Troposphere
Composition of dry air (sea level
Component Mole Fraction
Nitrogen 0.78084
Oxygen 0.20948
Argon 0.00934
Carbon dioxide 0.000345
Neon 0.00001818
Helium 0.00000524
Methane 0.00000168
B. Photochemical Smog - the problem of nitrogen oxides (NO
x
)
1. Auto exhaust contains small amounts of NO, which is quickly oxidized
2NO(g) + O
2
(g) 2NO
2
(g)
2. Radiant energy causes NO
2
to decompose
NO
2
(g) NO(g) + O(g)
3. Free oxygen atoms combine with oxygen molecules to form ozone
O(g) + O
2
(g) O
3
(g)
4. Ozone may absorb light energy and decompose to excited oxygen
atoms and excited oxygen molecules
O
3
(g) O
2
* + O*
5. Excited oxygen atoms react with water to form the hydroxyl radical
O* + H
2
O 2OH
6. Hydroxyl can react with NO
2
to form nitric acid
OH + NO
2
HNO
3
C. Coal and acid rain
1. Most coal, especially cheap coal, contains sulfer
S (in coal) + O
2
(g) SO
2
(g)
2. Sulfur dioxide is oxidized in air
2SO
2
(g) + O
2
(g) 2SO
3
(g)
3. Acid rain forms at the SO3 combines with water in the air
SO
3
(g) + H
2
O (l) H
2
SO
4
(aq)

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
(2)
v m KE
2
2
1
=
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
c. Products are generally less stable (weaker bonds) than the
reactants
F. Thermodynamics
1. System Energy
w
q
E
+ =

a. q = heat
(1) q is positive in endothermic reactions
(2) q is negative in exothermic reactions
b. w = work
(1) w is negative if the system does work
(2) w is positive if work is done on the system
2. Work done by gases
V P w
=
a. by a gas (through expansion)
(1) V is positive
(2) w is negative
b. to a gas (by compression)
(1) V is negative
(2) w is positive
6.2 Enthalpy and Calorimetry
A. Enthalpy
PV E H
+ =
1. In systems at constant pressure, where the only work is PV, the
change in enthalpy is due only to energy flow as heat (H = heat of
rxn)
H H H ts reac products tan
=

a. H is negative for exothermic rxns


b. H is positive for endothermic rxns
B. Calorimetry - science of measuring heat
1. Heat capacity (C)
a. ratio of heat absorbed to increase in temperature
increase e Temperatur
absorbed heat
C
=
2. Specific Heat Capacity
a. Energy required to raise the temp of 1 gram of a substance by
1 C
3. Molar heat capacity
a. Energy required to raise the temp of 1 mole of a substance by
1 C
C. Constant Pressure Calorimetry (solutions)
1. Calculating Heat of Rxn, H
a. H = specific heat capacity x mass of sol'n x increase in temp
T m s H
x x

=
2. Heat of rxn is an extensive property - dependent on the amount of
substance
a. H moles of reactant
D. Constant Volume Calorimetry
1. Volume of bomb calorimeter cannot change, so no work is done
2. The heat capacity of the calorimeter must be known, generally in kJ/C
2.
w
q
E
+ =

,
0
=
w

q
E
=

6.3 Hess's Law


A. Statement of Hess's Law
1. In going from a particular set of reactants to a particular set of
products, the change in enthalpy (H) is the same whether the reaction
takes place in one step or in a series of steps
One step:
N
2
(g) + 2O
2
(g) 2NO
2
(g) H
1
= 68kJ
Two step
N
2
(g) + O
2
(g) 2NO (g) H
2
= 180kJ
2NO (g) + O
2
(g) 2NO
2
(g) H
3
= -112kJ
N
2
(g) + 2O
2
(g) 2NO
2
(g) H
2
+ H
3
= 68kJ
B. Characteristics of Enthalpy Changes
1. If a reaction is reversed the sign on H is reversed
N
2
(g) + 2O
2
(g) 2NO
2
(g) H = 68kJ
2NO
2
(g) N
2
(g) + 2O
2
(g) H = - 68kJ
2. The magnitude of H is directly proportional to the quantities of
reactants and products in a reaction. If the coefficients in a balanced
reaction are multiplied by an integer, the value of H is multiplied by
the same integer
C. Using Hess's Law
1. Work backward from the final reaction
2. Reverse reactions as needed, being sure to also reverse H
3. Remember that identical substances found on both sides of the
summed equation cancel each other
6.4 Standard Enthalpies of Formation
A. Standard State
1. For a compound
a. Gaseous state
(1) pressure of 1 atm
b. Pure liquid or solid
(1) standard state is the pure liquid or solid
c. Substance in solution
(1) concentration of 1 M
2. For an element
a. the form in which the element exists at 1 atm and 25C
B. Standard Enthalpy of Formation (H
f
)
1. The change in enthalpy that accompanies the formation of one mole of
a compound from its elements with all elements in their standard state
C. Calculating enthalpy change
1. When a rxn is reversed, the magnitude of H remains the same, but its
sign changes
2. When the balanced eqn for a rxn is multiplied by an integer, the value
of H must be multiplied by the same integer
3. The change in enthalpy for a rxn can be calculated from the enthalpies
of formation of the reactants and products
( ) ( ) ts reac products
H n H n H f r f p reaction
tan


=
4. Elements in their standard states are not included
a. For elements in their standard state, H
f
= 0
6.5 Present Sources of Energy
A. Fossil Fuels
1. Energy derived from these fuels was initially captured from solar
energy by photosynthesis
2. Combustion of fossil fuels always produces H
2
O and CO
2
B. Petroleum and Natural Gas
1. Petroleum
a. Thick, dark liquid composed of hydrocarbon
2. Natural gas
a. Methane, with smaller amounts of ethane, propane and butane
Some Common Hydrocarbons
CH
4
Methane
C
2
H
6
Ethane
C
3
H
8
Propane
C
4
H
10
Butane
C
5
H
12
Pentane
C
6
H
14
Hexane
C
7
H
16
Heptane
C
8
H
18
Octane
C. Petroleum Refining
1. Original refining isolated kerosene (gasoline was a waste product)
2. Tetraethyl lead added as an "anti-knock" agent
Petroleum Fraction Major Uses
C
5
- C
10
Gasoline
C
10
- C
18
Kerosene, Jet fuel
C
15
- C
25
Diesel fuel, Heating oil, lubricating oil
> C
25
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 S
Lignite 71 4 23 1 1
Subbituminous 77 5 16 1 1
Bituminous 80 6 8 1 5
Anthracite 92 3 3 1 1
E. CO
2
and Earth's Climate
1. CO
2
is a by-product of cellular respiration
2. CO
2
is a by-product of burning fossil fuels
3. CO
2
is a greenhouse gas
4. Atmospheric CO
2
increased 16% from 1880 to 1980
5. Long-term climatic change seems imminent but is difficult to predict
6.6 New Energy Sources
A. Coal Conversion
1. Gasification
a. Reduce length of hydrocarbon molecules to create liquid or
gaseous fuels
b. Produce Syngas (CO and H
2
)
2. Coal Slurry
a. Coal dust suspended in water used as a heavy fuel oil
replacement
3. Coal limitations
a. Mining of coal has a serious environmental impact
B. Hydrogen as a fuel
1. Freeing hydrogen from compounds requires substantial energy
a. CH
4
(g) + H
2
O (g) 3H
2
(g) + CO (g) H = 206 kJ
b. H
2
O (l) + H
2
(g) + 1/2 O
2
(g) H = 286 kJ
2. Hydrogen is difficult to transport
a. Hydrogen in contact with metal produces free hydrogen atoms
b. Hydrogen attempts penetrate the metal and make it brittle
3. Hydrogen is not dense
a. The fuel equivalent of 20 gallons of gasoline occupies a volume
of 238,000 liters.
b. Liquid hydrogen is stored under great pressure and is potentially
explosive
C. Other Energy Alternatives
1. Shale
a. Must be heated to extract fuel molecules, and produces
immense amounts of waste rock
2. Ethanol from fermentation
a. Mixture of ethanol and gasoline - gasohol
b. Ethanol is renewable
3. Methanol
4. Seed oils
a. Renewable
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
10
-8
4 to 7x10
-7
10
-4
10
-2
1 10
2
10
4
Wavelength increases
Frequency decreases
Energy decreases
Speed is constant = 2.9979 x 10
8
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
=

gamma xrays UV visible IR micro Radio waves
FM short AM
7.2 The Nature of Matter
A. Max Planck and Quantum Theory
1. Energy is gained or lost in whole number multiples of the quantity hv
Frequency = v
Planck's constant = h = 6.626 x 10
-34
JS

nhv E
=

2. Energy is transferred to matter in packets of energy, each called a


quantum
B. Einstein and the Particle Nature of Matter
1. EM radiation is a stream of particles - "photons"

hc
hv Ephoton
= =
2. Energy and mass are inter-related

mc E
2
=
C. de Broglie and the Dual Nature of Light
1. Light travels through space as a wave
2. Light transmits energy as a particle
3. Particle's have wavelength, exhibited by diffraction patterns
mv
h
=

a. large particles have very short wavelengths


b. All matter exhibits both particle and wave properties
7.3 The Atomic Spectrum of Hydrogen
A. Continuous spectra
1. Contains all wavelengths of light
B. Bright line spectra
410nm 434nm 486nm 656nm
1. Excited electrons in an atom return to lower energy states
2. Energy is emitted in the form of a photon of definite wavelength
3. Definite change in energy corresponds to:
a. Definite frequency
b. Definite wavelength

hc
hv E
= =

4. Only certain energies are possible within any atom


7.4 Bohr Model (Neils Bohr, 1913)
A. Quantum Model
1. The electron moves around the nucleus only in certain allowed circular
orbits
2. Bright line spectra confirms that only certain energies exist in the atom,
and atom emits photons with definite wavelengths when the electron
returns to a lower energy state
3. Energy levels available to the electron in the hydrogen atom

=

n
Z
J E
x
2
2
18
10 178 . 2
n = an integer Z = nuclear charge J = energy in joules
B. Calculating the energy of the emitted photon
1. Calculate electron energy in outer level
2. Calculate electron energy in inner level
3. Calculate the change in energy (E)
E = energy of final state - energy of initial state
4. Use the equation:
E
hc

to calculate the wavelength of the emitted photon


C. Energy Change in Hydrogen atoms
1. Calculate energy change between any two energy levels

n n
J E
initial final
x
2 2
18
1 1
10 178 . 2
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:

E
V
dx
d
m
h
= +
2
2
2
2
8
2. Solution of the equation has demonstrated that E (energy) must occur
in integer multiples
3. Your book has done you the favor of greatly simplifying this and
presents the general equation:

E
H
=

= a set of mathematical functions called an "operator"

= a wave function. Specific wave functions are called


"orbitals"
4. Orbitals
1. Orbitals are not circular orbits for electron
2. Orbitals are areas of probability for locating electrons
C. Heisenberg Uncertainty Principle (Werner Heisenberg)
1. "There is a fundamental limitation on how precisely we can know both
the position and momentum of a particle at a given time"
4
) (
h
mv
x

=
x
uncertainty in the particle's position
=
) (mv
uncertainty in the particle's momentum
2. The more accurately we know the position of any particle, the less
accurately we can know its momentum, and vice-versa
D. Physical Meaning of a Wave Function
1. Square of the absolute value of the wave function gives a probability
distribution.
2

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 (m
l
)
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
n l Orbital
designation
m
l
# of
orbitals
1 0 1s 0 1
2 0 2s 0 1
1 2p -1, 0, 1 3
3 0 3s 0 1
1 3p -1, 0, 1 3
2 3d -2, -1, 0, 1, 2 5
4 0 4s 0 1
1 4p -1, 0, 1 3
2 4d -2, -1, 0, 1, 2 5
3 4f -3, -2, -1, 0, 1, 2, 3 7
7.7 Orbital Shapes and Energies
A. Size of orbitals
1. Defined as the surface that contains 90% of the total electron
probability
2. Orbitals of the same shape (s, for instance) grow larger as n increases
B. s Orbitals
1. Spherical shape
2. Nodes (s orbitals of n=2 or greater)
a. Internal regions of zero probability
C. p Orbitals
1. Two lobes each
2. Occur in levels n=2 and greater
3. Each orbital lies along an axis (2p
x
, 2p
y
, 2p
z
)
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
d
xz
d
yz
d
xy
d
x
2
- y
2
b. Fifth orbital is uniquely shaped - two lobes along the z axis and
a belt centered in the xy plane
d
z
2
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
2. We approximate the average repulsions of all other electrons
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
E
ns
< E
np
< E
nd
< E
nf
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)
a. Found along the border between metals and nonmetals
b. Exhibit properties of metals and nonmetals
7.12 Periodic Trends in Atomic Properties
A. Ionization Energy - the energy required to remove an electron from an atom
1. Ionization energy increases for successive electrons
2. Ionization energy tends to increase across a period
a. electrons in the same quantum level do not shield as effectively
as electrons in inner levels
b. irregularities at half filled and filled sublevels due to extra
repulsion of electrons paired in orbitals, making them easier to
remove
3. Ionization energy decreases with increasing atomic number within a
group
a. electrons farther from the nucleus are easier to remove
B. Electron Affinity - the energy change associated with the addition of an
electron
1. Affinity tends to increase across a period
2. Affinity tends to decrease as you go down in a period
a. electrons farther from the nucleus experience less nuclear
attraction
b. Some irregularities due to repulsive forces in the relatively small
p orbitals
C. Atomic Radius
1. Determination of radius
a. half of the distance between radii in a covalently bonded
diatomic molecule - "covalent atomic radii"
2r
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
1.

=

r
Q Q
E
nm J x
2 1 19
10 31 . 2
a. E = energy in joules
b. Q
1
and Q
2
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.
8.3 Bond Polarity and Dipole Moments
A. Dipolar Molecules
1. Molecules with a somewhat negative end and a somewhat positive end
(a dipole moment)
2. Molecules with preferential orientation in an electric field
+ + +
- - -
3. All diatomic molecules with a polar covalent bond are dipolar
B. Molecules with Polar Bonds but no Dipole Moment
1. Linear, radial or tetrahedral symmetry of charge distribution
a. CO
2
- linear
b. CCl
4
- tetrahedral
2. See table 8.2 in your text
8.4 Ions: Electron Configurations and Sizes
A. Bonding and Noble Gas Electron Configurations
1. Ionic bonds
a. Electrons are transferred until each species attains a noble gas
electron configuration
2. Covalent bonds
a. Electrons are shared in order to complete the valence
configurations of both atoms
B. Predicting Formulas of Ionic Compounds
1. Placement of elements on the periodic table suggests how many
electrons are lost or gained to achieve a noble-gas configuration
a. Group I loses one electron, Group II loses two, Group VI gains
two, Group VII gains one.
2. Formulas for compounds are balanced so that the total positive ionic
charge is equal to the total negative ionic charge
O Al
2
3
3
2
+
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
8.5 Formation of Binary Ionic Compounds
A. Lattice Energy
1. The change in energy that takes place when separated gaseous ions
are packed together to form an ionic solid
M
+
(g) + X
-
(g) MX (s)
2. Energy change is exothermic (negative sign)
Example: Formation of lithium fluoride
Process Description Energy Change (kJ)
Li(s) Li(g) Sublimation energy 161
Li(g) Li
+
(g) + e
-
Ionization energy 520
1/2F
2
F(g) Bond energy (1/2 mole) 77
F(g) + e
-
F
-
(g) Electron affinity -328
Li
+
(g) + F
-
(g) LiF(s) Lattice energy -1047
Li(s) + 1/2F
2
(g) LiF(s) H -617
3. The formation of ionic compounds is endothermic until the formation of
the lattice
4. The lattice formed by alkali metals and halogens (1:1 ratio) is cubic
except for cesium salts
B. Lattice Energy Calculations
1.

=
r
Q Q
k
Energy Lattice
2 1
a. k = a proportionality constant dependent on the solid structure
and the electron configuration
b. Q
1
and Q
2
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
% 100 x
Y X of moment dipole calculated
Y X of moment dipole measured
character ionic Percent


=
+
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
8.7 The Covalent Chemical Bond: A Model
A. Strengths of the Bond Model
1. Associates quantities of energy with the formation of bonds between
elements
2. Allows the drawing of structures showing the spatial relationship
between atoms in a molecule
3. Provides a visual tool to understanding chemical structure
B. Weaknesses of the Bond Model
1. Bonds are not actual physical structures
2. Bonds can not adequately explain some phenomena
a. resonance
8.8 Covalent Bond Energies and Chemical Reactions
A. Average Bond Energies
Process Energy Required (kJ/mol)
CH
4
(g) CH
3
(g) + H(g) 435
CH
3
(g) CH
2
(g) + H(g) 453
CH
2
(g) CH(g) + H(g) 425
CH(g) C(g) + H(g) 339
Total 1652
Average 413
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
CC 839 N=N 418
O=O 495 NN 941
C=O 745 CN 891
CO 1072 C=N 615
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.

= ) ( ) ( formed Bonds D broken Bonds D H
a. D always has a positive sign
8.9 The Localized Electron Bonding Model
A. Lone electron pairs
1. Electrons localized on an atom (unshared)
B. Bonding electron pairs
1. Electrons found in the space between atoms (shared pairs)
C. Localized Electron Model
1. "A molecule is composed of atoms that are bound together by sharing
pairs of electrons using the atomic orbitals of the bound atoms
D. Derivations of the Localized Model
1. Valence electron arrangement using Lewis structures
2. Prediction of molecular geometry using VSEPR (valence shell electron
pair repulsion)
3. Description of the type of atomic orbitals used to share or hold lone
pairs of electrons
8.10 Lewis Structures
A. Electrons and Stability
1. "the most important requirement for the formation of a stable
compound is that the atoms achieve noble gas configurations
2. Duet rule
a. Hydrogen, lithium, beryllium, and boron form stable molecules
when they share two electrons (helium configuration)
3. Octet Rule
a. Elements carbon and beyond form stable molecules when they
are surrounded by eight electrons
B. Writing Lewis Structures
1. Rules
a. Add up the TOTAL number of valence electrons from all atoms
b. Use a pair of electrons to form a bond between each pair of
bound atoms. Lines instead of dots are used to indicate each
pair of bonding electrons
c. Arrange the remaining atoms to satisfy the duet rule for
hydrogen and the octet rule for the second row elements

8.11 Exceptions to the Octet Rule
A. Boron Trifluoride
1. Note that boron only has six electrons around it
2. BF
3
is electron deficient and acts as a Lewis acid
(electron pair acceptor)
3. Boron often forms molecules that obey the octet
rule
B. Sulfur Hexafluoride
1. Note that sulfur has 12 electrons around it,
exeeding the octet rule
2. Sulfur hexafluoride is very stable
3. SF6 fills the 3s and 3p orbitals with 8 of the
valence electrons, and places the other 4 in the
higher energy 3d orbital
C. More About the Octet Rule
1. Second row elements C, N, O and F should always obey the octet rule
2. B and Be (second row) often have fewer then eight electrons around
them, and form electron deficient, highly reactive molecules
3. Second row elements never exceed the octet rule
4. Third row and heavier elements often satisfy (or exceed) the octet rule
5. Satisfy the octet rule first. If extra electrons remain, place them on
elements having available d orbitals
a. When necessary to exceed the octet rule for one of several third
row elements, assume that the extra electrons be placed on the
central atom
8.12 Resonance
A. Nitrate ion
1. Experiments show that all N-O bonds are equal
2. A single Lewis structure cannot represent the
nitrate ion
3. A resonance structure is drawn by writing the three
variant structures, connected by a double-headed
arrow
B. Resonance
1. When more than one valid Lewis structure can be written for a
particular molecule
2. The actual structure is an average of the depicted resonance
structures
C. Odd Electron Molecules
1. Molecules in which there is not an even number of electrons
2. Does not fit localized electron model
D. Formal Charge
1. Number of valence electrons on the free atom
minus
Number of valence electrons assigned to the atom in the molecule
a. Lone pair (unshared) electrons belong completely to the atom in
question
b. Shared electrons are divided equally between the sharing atoms
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
Pairs
Shape Arrangement of Electron Pairs
2 Linear

3 Trigonal Planar

4 Tetrahedral

5 Trigonal bipyramidal

6 Octahedral

B. Effect of Unshared Electron Pairs
1. The ideal tetrahedral angle is 109.5
Comparison of Tetrahedral Bond Angles
Compound Structure Angle between
Hydrogens
Methane

109.5
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
Chapter 9 - Covalent Bonding: Orbitals
9.1 Hybridization and the Localized Electron Model
A. Hybridization
1. The mixing of two or more atomic orbitals of similar energies on the
same atom to produce new orbitals of equal energies
B. Hybrid Orbitals
1. Orbitals of equal energy produced by the combination of two or more
orbitals on the same atom
C. Evidence for hybridization of carbon - Methane and sp
3
1. Four bonds of equal length and strength
Carbon's isolated configuration Carbon's hybridized configuration
2. Four effective pairs of electrons surround the carbon
3. "Whenever a set of equivalent tetrahedral atomic orbitals is required by
an atom, this model assumes that the atom adopts a set of sp
3
orbitals;
the atom becomes hybridized"
D. sp
2
hybridization
1. Trigonal planar structure, 120 angle, in ethene
(ethylene) rules out sp
3
hybridization
2. sp
2
hybridization creates 3 identical orbitals of
intermediate energy and length and leaves one
unhybridized p orbital
3. 3 effective pairs of electrons surround the carbon (double bond treated
as one effective pair)
2
4. Sigma bonds ( bond)
a. Bond in which the electron pair is
shared in an area centered on a line
running between the atoms
b. Lobes of bonding orbital point toward
each other
c. All bonds in methane are sigma bonds
5. Pi bonds ( bonds)
a. Electron pair above and below the
bond
b. Created by overlapping of
nonhybridized 2p orbitals on each
carbon
6. Double bonds
a. Double bonds always consist of one
bond and one bond
C. sp Hybridization
1. Each carbon has two hybrid orbitals and two unhybridized 2p orbitals
3
2. Carbon dioxide
a. Oxygens have 3 effective pairs of electrons (sp
2
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. dsp
3
Hybridization
1. Five effective pairs around a central atom
2. Trigonal bypyramidal shape
3. PCl
5
is an example
E. d
2
sp
3
Hybridization
1. Six effective pairs around a central atom
2. Octahedral structure
3. SF
6
is an example
Question: Why doesn't carbon undergo dsp
3
or d
2
sp
3
hybridization, while phosphorous
and sulfur do undergo this type of hybridization?
Atomic
Orbitals
Type of
hybridization
# of hybrid
orbitals
Geometry # of Effective
pairs
s, p sp 2 Linear 2
s, p, p sp
2
3 Trigonal-planar 3
s, p, p, p sp
3
4 Tetrahedral 4
s, p, p,
p, d
dsp
3
5 Trigonal
bipyramidal
5
s, p, p,
p, d, d
d
2
sp
3
6 Octagonal 6
4
9.2 The Molecular Orbital Model
A. Shortcomings of the Localized Electron Model
1. Electrons are not actually localized
2. Does not deal effectively with molecules containing unpaired electrons
3. Gives no direct information about bond energies
B. Molecular Orbitals
1. Can hold two electrons with opposite spins
2. Square of the orbital's wave function indicates electron probability
C. The Hydrogen Molecule (H
2
)
1. Two possible bonding orbitals, shapes determine by
2
2. Bonding takes place in MO
1
in which electrons achieve lower energy
(greater stability), with electrons
between the two nuclei
3. Both orbitals are in line with the nuclei,
so they are molecular orbitals
4. Higher energy orbital is designated as
antibonding (*).
5. Electron configuration of H2 can be
written as
1s
2
D. Bond Order
1. Bond order is the difference between the number of bonding electrons and
the number of antibonding electrons, divided by two
2. Larger bond order =
a. greater bond strength
b. greater bond energy
c. shorter bond length
9.3 Bonding in Homonuclear Diatomic Molecules
A. In order to participate in molecular orbitals, atomic orbitals must overlap in space
B. Larger bond order is favored
A. When molecular orbitals are formed from p orbitals, orbitals are favored over
orbitals ( interactions are stronger than interactions)
1. Electrons are closer to the nucleus = lower energy
5
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
B
2
C
2
N
2
O
2
F
2

2p
* _______ _______ _______
2p
* _______ _______

2p
* ___ ___ ___ ___ ___ ___
2p
* ___ ___ ___ ___

2p
_______ _______ _______
2p
___ ___ ___ ___

2p
___ ___ ___ ___ ___ ___

2p
_______ _______

2s
*
_______ _______ _______

2s
*
_______ _______













































E
n
e
r
g
y

2s
_______ _______ _______
2s
_______ _______
Magnetism Para Dia Dia Para Dia
Bond Order 1 2 3 2 1
Observed bond
dissocation energy
(kJ/mol)
290 620 942 495 154
Observed bond
length (pm)
159 131 110 121 143
One can measure magnetic properties FIRST, and use the results (dia- or para-) to
determine the energy order of the molecular orbitals
6
9.4 Bonding in Heteronuclear Diatomic Molecules
A. Similar, but not identical atoms
1. Use molecular orbital diagrams for homonuclear molecules
B. Significantly different atoms
1. Each molecule must be examined individually
2. There is no universally accepted molecular orbital energy order
9.5 Combining the Localized Electron and Molecular Orbital Models
A. Resonance
1. Attempt to draw localized electrons in a structure in which electrons are not
localized
2. bonds can be described using localized electron model
3. bonds (delocalized) must be described using the molecular orbital model
B. Benzene
1. bonds (C - H and C - C) are sp2 hybridized
a. Localized model
2. bonds are a result of remaining p orbitals above and below the plane of
the benzene ring
1
Chapter 10 - Liquids and Solids
10.1 Intermolecular Forces
A. Dipole-Dipole Forces
1. Attraction between molecules with dipole moments
a. Maximizes (+) ----- ( - ) interactions
b. Minimizes (+) ----- ( + ) and (-) ----- ( - ) interactions
2. About 1% of strength of ionic bonds
a. Unimportant in gas phase due to distance between molecules
B. Hydrogen Bonding
1. Special dipole-dipole attraction
a. Hydrogen covalently bonded to highly electronegative elements (N,
O, F) has a higher than normal + charge
2. Bond strength is higher than other dipole-dipole attractions
3. Important in the bonding of molecules such as water and DNA
C. London Dispersion Forces
1. Instantaneous dipoles
a. Random movement of electrons can create a momentary
nonsymmetrical distribution of charge even in nonpolar molecules
b. Instantaneous dipoles can induce a short-lived dipole in a
neighboring molecule
2. London dispersion forces exist between all molecules, but are the weakest
forces of attraction
3. "Polarizability" increases with the number of electrons in a molecule
a. CCl
4
experiences greater London forces than CH
4
10.2 The Liquid State
A. Surface Tension
1. The resistance of a liquid to an increase in its surface area
2. High intermolecular forces greater high surface tension
B. Capillary Action
1. Cohesive forces between liquid molecules
2. Adhesive forces between polar liquid molecules and polar bonds in the
material making up the container
a. Water's adhesive forces are greater than its cohesive forces, thus
the increase in surface area (concave meniscus)
b. Oxygen in glass is attracted to hydrogen in water
C. Viscosity
1. Measure of a liquid's resistance to flow
a. Viscosity increases with intermolecular forces
b. Viscosity increase with molecular size
D. Structural Model for Liquids
1. Strong intermolecular forces (like solids)
2. Considerable molecular motion (like gases)
2
10.3 An Introduction to Structures and Types of Solids
A. Types of solids
1. Crystalline solids
a. Highly regular arrangement of components
b. Components organized in a three-dimensional lattice
(1) Smallest repeating unit of the lattice is a unit cell
2. Amorphous solids
a. Components "frozen in place" and lacking orderly arrangement
(1) glass
(2) plastic
B. X-ray Analysis of Solids
1. Structure of crystalline solids can be determined by xray diffraction
a. waves in parallel beams that are "in phase" produce constructive
interference
b. waves in parallel beams that are "out of phase" produce destructive
interference
= angle of incidence and reflection
d = distance between atoms
n = integer
= wavelength
2. Bragg's Law
a. 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
3
C. Types of Crystalline Solids
1. Ionic solids
a. Ions occupy lattice points
b. Sodium chloride is an example
2. Molecular solids
a. Discrete covalent molecules occupy lattice points
b. Ice and sucrose are examples
3. Atomic Solids (pure elements)
a. Metallic solids
b. Network solids
c. Group 8A solids
10.4 Structure and Bonding in Metals
A. Closest Packing
1. Arrangement of metallic atoms in the tightest pattern possible
a. Each atom has twelve nearest neighbors
(1) six in same layer
(2) three above
(3) three below
2. Hexagonal closest packed structure (a, b, a, b, a )
a. Each layer is identical to the layer two below it
3. Cubic closest packed structure (a, b, c, a, b, c, )
a. Each layer is identical to the layer three below it
4. Not all metals crystallize in closest packing
B. Bonding Models for Metals
1. Electron sea model
a. Metal cations
b. Mobile sea of valence electrons that conduct heat and electricity
2. Band Model (Molecular Orbital Model)
a. Electrons travel within molecular orbitals formed by the valence
orbitals of the metallic atoms
b. Molecular orbitals occupied by conducting electrons are called
conduction bands
C. Metal Alloys
1. Alloys are substances that contain a mixture of elements and have metallic
properties
2. Substitutional alloys
a. Host metal atoms are replaced in the lattice by other atoms of similar
size
(1) Brass, sterling silver, pewter
3. Interstitial alloys
a. Holes in the closest packed metallic structure are filled by small
atoms
b. Carbon is often added to iron to produce steels with higher than
normal hardness
***Ignore the references to steel frame bikes in Table 14.4. Everyone knows that REAL
racing bikes are made out of TITANIUM! Don't believe me? See page 950!
4
10.5 Carbon and Silicon: Network Atomic Solids
A. Network Solids
1. Atomic solids with strong directional covalent bonds
B. Diamond
1. Large gap in energy between occupied orbitals and unoccupied orbitals
makes diamond a poor conductor of electricity
2. Bonds formed by overlap of hybridized sp
3
orbitals
C. Graphite
1. Very strong bonds between carbons in fused rings using sp
2
hybridization
2. molecular orbitals provide weaker bonding between layers
a. Delocalized electrons make graphite an electrical conductor
D. Silica
1. Quartz (SiO
2
) is actually based on interconnected SiO
4
tetrahedra
2. Glass is produced by quickly cooling silica, producing an amorphous solid
a. Other compounds added to molten silica prior to cooling produce
glass with varying properties (see table 10.5)
E. Ceramics
1. Made from clays containing silicates (silicon-oxygen anions)
2. Heterogeneous
a. crystals of silicates suspended in a glassy cement
3. Remarkable range of uses
F. Semiconductors
1. Silicon
a. Energy gap between occupied and unoccupied orbitals is smaller
than in diamond, allowing some electrons to be conducted
b. Conductivity increases with temperature
2. n-type semiconductors
a. "Dope" silicon with elements such as arsenic
(1) extra valence electron increases conductivity
3. p-type semiconductors
a. "Dope" silicon with elements such as boron
(1) shortage of valence electrons creates a "hole" that electrons fill
as they move (conduct)
10.6 Molecular Solids
A. Examples
1. Water
2. Dry ice
3. P
4
4. S
8
B. Bonding
1. London dispersion forces
2. Dipole-dipole (including hydrogen bonding)
a. Only in polar molecules
5
10.7 Ionic Solids
A. Closest Packing
1. Large particles (usually anions) arrange in closest packing
2. Smaller particles (usually cations) fit into holes between anions
a. not all holes need be filled
3. Maximize (+) ---- (-) attraction
4. Minimize (+) ---- (+) and (-) ---- (-) repulsion
B. Types of holes
1. Trigonal holes - three spheres in the same layer
2. Tetrahedral holes - a sphere sits in the dimple of three spheres in the same
layer
3. Octahedral holes - two layers of three spheres in adjoining layers
10.8 Vapor Pressure and Changes of State
A. Vaporization (Evaporation)
1. The escape of molecules of a liquid from the surface to form a gas
2. Vaporization is always endothermic
a. Heat of vaporization (Enthalpy of vaporization, H
vap
) is the energy
required to vaporize one mole of a liquid at 1 atm
B. Vapor Pressure
1. Pressure of the vapor present at equilibrium (also called equilibrium vapor
pressure)
***remember vapor pressure corrections made in gas law problems
involving water displacement
2. Variation in Vapor Pressure
a. Liquids with high intermolecular attraction have relatively low vapor
pressures
b. Liquids with low intermolecular attraction have relatively high vapor
pressures (the are "volatile")
c. Vapor pressure increases with temperature
3. Clausius-Clapeyron equation

1 2
1 1
ln
2
1
T T R
H
P
P
vap
vap
T
vap
T
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
6
D. Changes of State
1. Heating curve
a. Note that temperature remains constant during a phase change
b. Chemical bonds are not being broken during phase changes
2. Heat of fusion (Enthalpy of fusion, H
fus
)
a. Energy required to convert a mole of solid substance to a mole of
liquid substance
3. Normal melting point
a. The temperature at which the solid and liquid states have the same
vapor pressure under conditions where the total pressure is 1 atm
4. Normal boiling point
a. The temperature at which the vapor pressure of the liquid is exactly 1
atmosphere
5. Supercooling
a. Rapid cooling of a liquid may allow it to exist as a liquid at
temperatures below its normal melting point
(1) quick temperature change does not allow time for molecules to
become organized as they must be to become solids
(2) When crystallization does begin, it occurs rapidly
6. Superheating
a. Rapid heating of a liquid may allow it to exist as a liquid at
temperatures above the normal boiling point
(1) not enough high energy molecules accumulate in one place to
form bubbles
(2) when bubbles do form, they tend to be very large
(3) superheating can be avoided by adding boiling chips
7
10.9 Phase Diagrams
A. Diagram for a closed system
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 P
atm
(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
1
B A
A
A
n n
n
x componentA of fraction Mole
+
= =
Chapter 11 Properties of Solutions
11.1 Solution Composition
A. Molarity
1.
solution of liters
solute moles
M Molarity = ) (
B. Mass Percent
1. 100

=
solution of mass
solute of mass
percent Mass
C. Mole Fraction
1.
D. Molality
1.
solvent of ram ki
solute of moles
Molality
log
=
E. Normality
1.
solution of liter
s equivalent
Normality =
2. Equivalents of acids and bases
a. Mass that donates or accepts a mole of protons
3. Equivalents of oxidizing and reducing agents
a. Mass that provides or accepts a mole of electrons
11.2 The Energies of Solution Formation
A. Like Dissolves Like
1. Polar molecules and ionic compounds tend to dissolve in polar solvents
2. Nonpolar molecules dissolve in nonpolar compounds
B. Steps of Solution Formation
1. Breaking up the solute into individual components (expanding the solute)
a. Endothermic
2. Overcoming intermolecular forces in the solvent to make room for the solute
(expanding the solvent)
a. Endothermic
3. Allowing the solute and solvent to interact to form the solution
a. Often exothermic
C. Enthalpy (Heat) of Solution
1.
3 2 1 ' step step step n sol
H H H H + + =
1.
soln
may have a positive sign or a negative sign
3. Enthalpy (Heat) of Hydration,
hyd
a. Include of step 2 and step 3
2
D. Factors Favoring the Solution Process
1. Negative value for
soln
2. Increase in entropy
3. For positive values of
soln
it is the increase in entropy that outweighs the
increase in energy and causes the solution process of occur
11.3 Factors Affecting Solubility
A. Structure Effects
1. Polar (hydrophilic) dissolves in polar
a. Water soluble vitamins
2. Nonpolar (hydrophobic) in nonpolar
a. Fat soluble vitamins
B. Pressure Effects
1. Henrys Law
a. The amount of a gas dissolved in a solution is directly proportional to
the pressure of the gas above the solution
b. P = kC
(1) P = partial pressure of the gaseous solute above the solution
(2) C = concentration of the dissolved gas
(3) k = constant characteristic of a particular solution
c. Henrys Law works best for dilute solutions of gases that do not
dissociate or react with the solvent
C. Temperature Effects
1. Solids
a. Increases in temperature always cause dissolving to occur more
rapidly
b. Increases in temperature usually increases solubility (the amount that
can be dissolved)
2. Gases
a. Solubility of gases always decreases with increasing temperature
11.4 The Vapor Pressure of Solutions
A. Nonvolatile Solutes
1. Nonvolatile electrolytes lower the vapor pressure of a solute
a. Nonvolatile molecules do not enter the vapor phase
b. Fewer molecules are available to enter the vapor phase
B. Raoult's Law
1.
0
ln solvent solvent so
P X P = where X
solvent
is the mole fraction of the solvent in
the solution
a. a linear equation (y = mx)
2. Molar mass of a solute can be calculated from experimental results for vapor
pressure lowering
C. Ionic solutes
1. Dissociation of ionic compounds has nearly two, three or more times the
vapor pressure lowering of nonionic (nonelectrolyte) solutes.
3
D. Non-ideal Solutions
1. Liquid-liquid solutions in which both components are volatile
2. Modified Raoult's Law:

0 0
B B A A B A TOTAL
P X P X P P P + = + =
a. P
0
is the vapor pressure of the pure solvent
b. P
A
and P
B
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. H
sol'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
solute b
m K T =
a. is the boiling point elevation
b. K
b
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
solute f
m K T =
a. is the freezing point depression
b. K
f
is the molal freezing point depression constant of the solvent
c. m
solute
is the molality of the solute in the solution
4
11.6 Osmotic Pressure
A. Osmosis
1. The flow of solvent molecules into a solution through a semipermeable
membrane
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
5
11.7 Colligative Properties of Electrolyte Solutions
A. van't Hoff factor i:
1.
dissolved solute of moles
solution in particles of moles
i =
2. For ionic compounds, the expected value of i is an integer greater than 1
a. NaCl, i = 2
b. BaCl
2
, i = 3
c. Al
2
(SO
4
)
3
, i = 5
B. Actual values of i
1. Values of i are less than expected due to ion pairing (clustering)
2. Refer to table11.6
3. Values of i are closer to the expected the more dilute the solution becomes
C. Incorporation of van't Hoff factor in Problem Solving
1. Boiling-elevation and freezing-point depression
a. T = imK
2. Osmotic pressure
a. = iMRT
11.8 Colloids
A. Colloidal Dispersions (Colloids)
1. Tiny particles suspended in some medium
2. Particles range in size from 1 to 1000 nm.
B. Tyndall Effect
1. Scattering of light by particles
a. Light passes through a solution
b. Light is scattered in a colloid
Table 11.7 Types of Colloids
Examples
Dispersing
Medium
Dispersed
Substance
Colloid Type
Fog, aerosol sprays Gas Liquid Aerosol
Smoke, airborne bacteria Gas Solid Aerosol
Whipped cream, soap suds Liquid Gas Foam
Milk, mayonnaise Liquid Liquid Emulsion
Paint, clays, gelatin Liquid Solid Sol
Marshmallow, polystyrene foam Solid Gas Solid foam
Butter, cheese Solid Liquid Solid emulsion
Ruby glass Solid Solid Solid sol
1
Chapter 12 - Chemical Kinetics
12.1 Reaction Rates
A. Chemical kinetics
1. Study of the speed with which reactants are converted to products
B. Reaction Rate
1. The change in concentration of a reactant or product per unit of time

[ ]
t
A
t t
t time at A of ion concentrat t time at A of ion concentrat
Rate

=
1 2
1 2
a. Rates decrease with time
b. It is customary to express reaction rates as positive values
c. Instantaneous rate can be determined by finding the slope of a line
tangent to a point representing a particular time
C. Decomposition of NO
2
2NO
2
(g) 2NO(g) + O
2
(g)
Rate of consumption of NO
2
= rate of production of NO = 2(rate of production of O
2
)

[ ]
t
NO

2
=
[ ]
t
NO

=
[ ]

t
O
2
2
2
12.2 Rate Laws: An Introduction
A. Reversibility of reactions
1. For the reaction 2NO
2
(g) 2NO(g) + O
2
(g)
The reverse reaction 2NO(g) + O
2
(g) 2NO
2
(g) may also take place
2. The reverse reaction effects the rate of change in concentrations
a. [A] depends on the difference in the rates of the forward and reverse
reactions
B. Rate Law (Ignoring reverse reaction)
1. Rate = k[NO
2
]
n
a. k is a proportionality constant called the rate constant
n is the order of the reactant (an integer, including zero, or a fraction)
(1) k and n must be determined experimentally
2. Concentrations of products do not appear in the rate law
C. Types of Rate Laws
1. Differential Rate Law (Rate Law)
a. Expresses how the rate of a reaction depends upon concentration
Rate = k[NO
2
]
n
2. Integrated Rate Law
a. Expresses how the concentration of a species (reactant or product) in
a reaction depend on time
[ ]
t
NO

2
=
[ ]
t
NO

=
[ ]

t
O
2
2
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/Ls)
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
3. Example:
Table 12-4 Intial Rates from Three Experiments for the Reaction:
NH
4
+
(aq) + NO
2
-
(aq) N
2
(g) + 2H
2
O(l)
Experiment Initial
Concentration
Of NH
4
+
Initial
Concentration
Of NO
2
-
Initial rate
(mol/Ls)
1 0.100 M 0.0050 M 1.35 x 10
-7
2 0.100 M 0.010 M 2.70 x 10
-7
3 0.200 M 0.010 M 5.40 x 10
-7
a. In experiment 1 and 2, the concentration of NH
4
+
is held constant
b. In experiment 2 and 3, the concentration of NO
2
-
is held constant
c. Basic rate law for the reaction:
Rate = k[NH
4
+
]
n
[NO
2
-
]
m
4. Calculations
a. Experiment 1 and 2
(1) Rate doubles when concentration of NO
2
-
doubles
(2) m = 1 (first order)
b. Experiment 2 and 3
(1) Rate doubles when concentration of NH
4
+
doubles
(2) n = 1 (first order)
5. Overall reaction order
a. Overall reaction order is the sum of m and n
(1) m +n = 2 so overall the reaction is second order
Rate = k[NH
4
+
][NO
2
-
]
6. Calculate k, the rate constant
a. Rate is known
b. Both concentrations are known
c. Exponents are known
1.35 x 10
-7
mol/Ls = k(0.100 M)(0.0050 M)
k = 1.35 x 10
-7
mol/Ls
(0.100 M)(0.0050 M)
12.4 The Integrated Rate Law
A. Integrated First-Order Rate Law (single reactant)
1. ln[A] = -kt + ln[A]
0
or
[ ]
[ ]
kt
A
A
=

0
ln
a. [A] is concentration of reactant A at time = t
b. [A]
0
is concentration of reactant A at t = 0
c. Equation is linear (y = mx + b)
2. Half-life of a First-Order Reaction
a. Half life of a reaction is the time required for a reactant to reach half
its original concentration

[ ]
[ ]
kt
A
A
=

0
ln [ ]
[ ]
2
0
A
A =
[ ]
[ ]
2 / 1
0
0
2 /
ln kt
A
A
=

( )
2 / 1
2 ln kt =
k
t
) 2 ln(
2 / 1
=
4
B. Integrated Second-Order Rate Law (single reactant)
1.
[ ] [ ]
0
1 1
A
kt
A
+ =
a. Graph of 1/[A] versus t is a straight line with slope k
2. Half-life of a Second-Order Reaction (derivation on page 567)
a.
[ ]
0
2 / 1
1
A k
t =
b. For a second-order reaction each successive half-life is double the
preceding one
C. Zero Order reactions
1. Rate is constant; it does not change with changing concentration
2. Zero order sometimes happens with catalysis
3. Integrated rate law for zero-order reactions
a. [ ] [ ]
0
A kt A + =
4. Half-life of a zero-order reaction
a.
[ ]
k
A
t
2
0
2 / 1
=
D. Integrated Rate Laws for Reactions with More than One Reactant
1. Examine rate with one reactant in very low concentration and the others
much higher
Rate = k[A]
n
[B]
m
[C]
p
a. If [B]> >[A] and [C] > >[A] then [B] and [C] do not change as greatly
relative to [A] so
Rate = k'[A]
n
2. Pseudo-first-order rate law (or zero-order , or second-order)
a. Simplification yields a rate law of a particular order
12.5 Rate Laws: A Summary
No Notes - This is review. Rate law problems are a virtual certainty on the AP test.
Bookmark this section and review it thoroughly prior to the exam!
12.6 Reaction Mechanisms
A. Reaction Mechanism
1. A series of elementary steps that must satisfy two requirements
a. The sum of the elementary steps must give the overall balanced
equation for the reaction
b. The mechanism must agree with the experimentally determined rate
law
B. Intermediates
1. A species that is neither a reactant nor a product, but that is formed and
consumed during a chemical reaction
C. Elementary steps
1. Reactions whose rate law can be written from their molecularity (balanced
eqn for the step)
5
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 Rate Law
A products Unimolecular Rate = k[A]
A + A products
(2A products)
Bimolecular Rate = k[A]
2
A + B products Bimolecular Rate = k[A][B]
A + A + B products
(2A + B products)
Termolecular Rate = k[A]
2
[B]
A + B + C products Termolecular 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:
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
2. Rate law determined experimentally:
Rate = k[NO
2
]
2
3. Elementary Steps
NO
2
(g) + NO
2
(g)
1
k
NO
3
(g) + NO(g)
NO
3
(g) + CO(g)
2
k
NO
2
(g) + CO
2
(g)
4. Which step is rate determining?
a. IF step 1, Rate = k[NO
2
]
2
(1) this agrees with experimental results
b. IF step 2, Rate = k[NO
3
][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 (E
a
)
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:
RT E
a
zpe k
/
=
a. z is collision frequency
b. p is the stearic factor representing the fraction of collisions with
correct orientation
6
2. Form #2:
RT E
a
Ae k
/
=
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( ) ln(
/ RT E
a
Ae k

=
) ln( ) ln( ) ln(
/ RT E
a
e A k

+ =
) ln(
1
) ln( A
T R
E
k
a
+

=
a. Linear equation
y = ln(k) slope = -E
a
/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 CO
2
and N
2
D. Homogeneous Catalysis
1. Reactants and catalysts are in the same phase
2. Example - The decomposition of ozone
a. Freon, CCl
2
F
2
(g)
light
CClF
2
(g) + Cl(g)
b. Chlorine catalyzes the decomposition of ozone
Cl(g) + O
3
(g) ClO(g) + O
2
(g)
O(g) + ClO(g) Cl(g) + O
2
(g)
O(g) + O
3
(g) 2O
2
(g)
c. Notice that the Cl(g) is not used up, a qualification for it to be
catalytic. This is also why small amounts of chlorofluorocarbons such
as freon can do immense damage to the ozone layer
1
Chapter 13 - Chemical Equilibrium
Intro
A. Chemical Equilibrium
1. The state where the concentrations of all reactants and products remain
constant with time
2. All reactions carried out in a closed vessel will reach equilibrium
a. If little product is formed, equilibrium lies far to the left
b. If little reactant remains, equilibrium lies far to the right
13.1 The Equilibrium Condition
A. Static Equilibrium does not occur in chemical systems
1. No reaction is taking place
2. All product molecules will remain product
3. All unused reactant molecules will remain unreacted
B. Dynamic Equilibrium
1. Reactions continue to take place
2. Reactant molecules continue to be converted to product
3. Product continues to be converted to reactant (reverse reaction)
4. Forward and reverse reactions take place at the same rate at equilibrium
C. Causes of Equilibrium
1. Beginning of reaction
a. Only reactant molecules exist, so only reactant molecules may collide
2. Middle
a. As product concentration increases, collisions may take place that
lead to the reverse reaction
3. At equilibrium
a. Rates of forward and reverse reactions are identical
D. Example - The Haber Process
1. N
2
(g) + 3H
2
(g) 2NH
3
(g)
a. hydrogen is consumed at 3x the rate of nitrogen
b. ammonia is formed at 2x the rate at which nitrogen is consumed
2
13.2 The Equilibrium Constant
A. The Law of Mass Action
1. For the balanced equation:
jA + kB lC + mD (j, k, l, m) are coefficients
The law of mass action is represented by the equilibrium expression:

k j
m l
B A
D C
K
] [ ] [
] [ ] [
=
a. K is a constant called the equilibrium constant
(1) K varies depending on temperature and upon the coefficients
of the balanced equation
b. [X] represents concentration of chemical species at equilibrium
2. For the reverse reaction
lC + mD jA + kB
The law of mass action is represented by the equilibrium expression:
K D C
B A
K
m l
k j
1
] [ ] [
] [ ] [
'
= =
B. Equilibrium Position
1. A set of equilibrium concentrations
2. There is only one value of K for a reaction at a given temperature, but an
infinite number of possibilities for equilibrium positions
C. Summary of the Equilibrium Expression
1. The equilibrium expression for a reaction is the reciprocal of that for the
reaction written in reverse
2. When the balanced equation for a reaction is multiplied by a factor n, the
equilibrium expression for the new reaction is the original expression raised
to the nth power
K
new
= (K
original
)
n
3. For a particular reaction at a given temperature, the value of K is constant
regardless of the amounts of gases that are mixed together (homogeneous
rxn system)
13.3 Equilibrium Expressions Involving Pressure
A. Derivation of Equilibrium Gas Laws
1. nRT PV = therefore RT
V
n
P

=
n/V is the molar concentration of the gas, represented by C
CRT P =
2. For the reaction N
2
(g) + 3H
2
(g) 2NH
3
(g)
In terms of concentrations
) )( (
3
2
2 2
3
H N
NH
c
C C
C
K =
In terms of partial pressures
) )( (
3
2
2 2
3
H N
NH
p
P P
P
K =
3
B. Relationship between K and K
p
1.
n
p
RT K K

= ) (
a. n = (l + m) - (j + k) the difference in the sums of the coefficients for
the gaseous products and reactants
13.4 Heterogeneous Equilibria
A. The position of a heterogeneous equilibrium does not depend on the amounts of
pure solids or liquids present
B. If pure solids or liquids are involved in a chemical reaction, their concentrations are
not included in the equilibrium expression for the reaction
C. Pure liquids are not the same as solutions, whose concentration can change
13.5 Applications of the Equilibrium Constant
A. Extent of a Reaction
1. Reactions with large equilibrium constants (K>>1) go essentially to
completion
a. Equilibrium position is far
to the right
a. Generally large, negative
E
2. Reactions with small equilibrium
constants (K<<1) consist of
mostly reactants
a. Equilibrium position is far
to the left
3. Time required to achieve
equilibrium
a. Related to reaction rate
and activation energy
b. Not related to the
magnitude of K
B. Reaction Quotient (Q)
1. Apply the law of mass action to initial concentrations in order to determine
what direction the rxn must move in order to achieve equilibrium
3
0 2 0 2
3
0 3
] [ ] [
] [
H N
NH
Q = the subscript zero indicates initial concentrations
2. IF Q is equal to K
a. The system is at equilibrium, no shift will occur
3. IF Q is greater than K
a. The system shifts to the left, consuming products and forming
reactants to reach equilibrium
4. IF Q is less than K
a. The system shifts to the right, consuming reactants and forming
products until equilibrium is reached
4
13.6 Solving Equilibrium Problems
A. Procedure for Solving Equilibrium Problems
1. Write the balanced equation for the reaction
2. Write the equilibrium expression using the law of mass action
3. List the initial concentrations
4. Calculate Q, and determine the direction of the shift to equilibrium
5. Define the change needed to reach equilibrium, and define the equilibrium
concentrations by applying the change to the initial concentration
6. Substitute the equilibrium concentrations into the equilibrium expression,
and solve for the unknown
7. Check you calculated equilibrium concentrations by making sure they give
the correct value of K
B. Treating Systems That Have Small Equilibrium Constants
1. The small value of K and the resulting small shift to the right to reach
equilibrium allows for simplification of the math
13.7 Le Chatelier's Principle
A. Statement of Le Chatelier's Principle (very important!)
1. If a change is imposed on a system at equilibrium, the position of the
equilibrium will shift in a direction that tends to reduce that change
B. The Effect of Change in Concentration
1. If a reactant or product is added to a system at equilibrium, the system will
shift away from the added component (it will attempt to "use up" the added
component)
2. If a reactant or product is removed from a system at equilibrium, the system
will shift toward the removed component (it will attempt to "replace" the
removed component)
C. The Effect of a Change in Pressure
1. Ways to change pressure
a. Add or remove a gaseous reactant or product
(1) covered above
b. Add an inert gas (one not involved in the reaction)
(1) An inert gas increases the total pressure but has no effect on
the concentrations or partial pressures of the reactants or
products
c. Change the volume of the container
(1) When the volume of the container holding a gaseous system is
reduced, the system responds by reducing its own volume.
This is done by decreasing the total number of gaseous
molecules in the system
N
2
(g) + 3H
2
(g) 2NH
3
(g) shifts to the right to decrease
the total molecules of gas present
(2) When the container volume is increased, the system will shift
so as to increase its volume
N
2
(g) + 3H
2
(g) 2NH
3
(g) shifts to the left to increase
the total number of molecules of gas present
5
D. The Effect of a Change in Temperature
1. An increase in temperature increases the energy of the system. Le
Chatelier's principle predicts that the system will shift in the direction that
consumes the energy
a. For an exothermic rxn, energy is a product. The rxn will shift to the
left to use up the excess energy
b. For an endothermic rxn, energy is a reactant. The rxn will shift to the
right to use up the energy
2. A decrease in temperature will cause a system shift in the direction that
"replaces" the lost energy
1
Chapter 14 - Acids and Bases
14.1 The Nature of Acids and Bases
A. Arrhenius Model
1. Acids produce hydrogen ions in aqueous solutions
2. Bases produce hydroxide ions in aqueous solutions
B. Bronsted-Lowry Model
1. Acids are proton donors
2. Bases are proton acceptors
3. H
3
O
+
is called the hydronium ion
C. Conjugate Acid-Base Pairs
1. A conjugate base is what remains after an acid has donated a proton
a. Cl
-
is the conjugate base of HCl
2. A conjugate acid is what is formed when a base accepts a proton
base acid acid base
3. HCl is a stronger base than H
3
O
+
(H
+
) so the equilibrium lies far to the right
D. Acid Dissociation Constant
1.
] [
] ][ [
HCl
Cl H
K
a
+
=
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. K
a
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 K
a
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
2
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)
2. Ion-product constant, K
w
(dissociation constant)
a. At 25C, [H
+
] = [OH
-
] = 1.0 x 10
-7
b. K
w
= [H
+
][OH
-
] = (1.0 x 10
-7
mol/L)( 1.0 x 10
-7
mol/L)
(1) K
w
= 1.0 x 10
-14
mol
2
/L
2
(units often dropped)
3. Solution characteristics
a. Neutral solution, [H
+
] = [OH
-
] = 1.0 x 10
-7
b. Acid solution, [H
+
] > [OH
-
]
c. Basic solution, [H
+
] < [OH
-
]
14.4 The pH Scale
A. pH and pOH
1. pH = -log[H
+
]
a. The number of decimal places in the log is equal to the number of
significant figures in the original number
2. pOH = -log[OH
-
]
3. pH + pOH = 14
B. Solving Acid and Base Problems
1. Please take time to read the advice at the end of this section (Page 658). It
applies to far more than acid-base problems!
3
14.4 Calculating the pH of Strong Acid Solutions
A. What are the components of the solution?
1. HA H
+
(aq) + A
-
(aq)
or
HA + H
2
O H
3
O
+
(aq) + A
-
(aq)
2. H
2
O + H
2
O H
3
O
+
(aq) + OH
-
(aq)
or
H
2
O H
+
(aq) + OH
-
(aq)
B. Focus on the major species
1. At high concentrations of strong acids, the autoionization of water is
insignificant
2. For strong acids, the assumption is that HA is completely ionized
14.5 Calculating the pH of Weak Acid Solutions
A. Steps (from page 662)
1. List the major species in the solution
2. Choose the species that can produce H
+
, and write the balanced equations
for the reactions producing H
+
3. Using the values of the equilibrium constants for the reactions you have
written decide which equilibrium will dominate in producing H
+
4. Write the equilibrium expression for the dominant equilibrium
5. List the initial concentrations of the species participating in the dominant
equilibrium
6. Define the change needed to achieve equilibrium; that is, define x
7. Write the equilibrium concentrations in terms of x
8. Substitute the equilibrium concentrations into the equilibrium expression
9. Solve for x the "easy" way; that is, by assuming that [HA]
0
- x [HA]
0
10. Use the 5% rule to verify whether the approximation is valid
11. Calculate [H
+
] and pH
B. The pH of a Mixture of Weak Acids
1. If one acid has a relatively higher K
a
value, it will be the focus of the solution
C. Percent Dissociation
1. % 100
) / (
) / (
=
L mol ion concentrat initial
L mol n dissocatio amount
on dissociati Percent
2. For a given weak acid, the percent dissocation increases as the acid
becomes more dilute
4
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 K
b
C. Calculating the pH of Strong Bases
1. K
w
= [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. pK
w
= 14.00 = pH + pOH
2. pOH = 14.00 - pH
14.7 Polyprotic Acids
A. Stepwise dissociation
1. H
2
CO
3
(aq) H
+
(aq) + HCO
3
-
(aq)
7
3 2
3
1
10 3 . 4
] ][ [

+
= = x
CO H
HCO H
K
a
2. HCO
3
-
(aq) H
+
(aq) + CO
3
2-
(aq)
11
3
2
3
2
10 6 . 5
] [
] ][ [

+
= = x
HCO
CO H
K
a
B. Weak Polyprotic acids
1. K
a1
> K
a2
> K
a3

C. Sulfuric Acid, the Strong Polyprotic Acid


1. H
2
SO
4
(aq) H
+
(aq) + HSO
4
-
(aq) K
a1
is very large
2. HSO
4
-
(aq) H
+
(aq) + SO
4
2-
(aq) K
a2
= 1.2 x 10
-2
2. Sulfuric acid dissociates to a greater extent in even its second step than
weak acids do in their first step, and the second step cannot be ignored in
calculation of pH for dilute solutions of H
2
SO
4
!
14.8 Acid-Base Properties of Salts
A. Salts That Produce Neutral Solutions
1. Salts that consist of the cations of strong bases and the anions of strong
acids have no effect on pH, ([H
+
]), when dissolved in water
2. Cations of strong bases
a. Na
+
K
+
(Group 1A)
3. Anions of strong acids
a. Cl
-
, NO
3
-
B. Salts that Produce Basic Solutions
1. For any salt whose cation has neutral properties and whose anion is the
conjugate base of a weak acid, the aqueous solution will be basic
C
2
H
3
O
2
-
(aq) + H
2
O(l) HC
2
H
3
O
2
(aq) + OH
-
(aq)
base acid acid base
5
C. Salts that Produce Acidic Solutions
1. Salts in which the anion is not a base and the cation is the conjugate acid
acid of a weak base produce acid solutions
NH
4
+
(aq) NH
3
(aq) + H
+
(aq)
2. Salts that possess a highly charged metallic ion, such as Al
3+
a. Aluminum ion in water is hydrated, Al(H
2
O)
6
3+
b. High metallic charge polarizes O - H bond in water
c. Hydrogens in water become acidic
D. Salts with Acidic and Basic ions
1. IF K
a
for the acidic ion is greater than K
b
for the basic ion, the solution is
acidic
2. IF K
b
for the basic ion is greater than K
a
for the acidic ion, the solution is
basic
3. IF K
b
for the basic ion is equal to K
a
for the acidic ion, the solution is neutral
14.9 The Effect of Structure on Acid-Base Properties
A. Factors Determining Acid Characteristics of Molecules with X - H Bonds
1. Strength of bonds
a. Strong bonds are reluctant to break, even in solution
2. Polarity of the bonds
a. High bond polarity tends to increase the acidity of the hydrogen
B. Molecules of form H - O - X
1. IF X has high electronegativity, the hydrogen tends to be acidic
2. IF X has low electronegativity, the compound tends to be basic (-OH comes
off)
3. The more oxygens around X, the more acidic the compound
14.10 Acid-Base Properties of Oxides
A. Acidic Oxides (also called acid anhydrides)
1. Nonmetal oxides that react with water to form acidic solutions
a. SO
3
(g) + H
2
O(l) H
2
SO
4
(aq)
b. 2NO
2
(g) + H
2
O(l) HNO
3
(aq) + HNO
2
(aq)
B. Basic Oxides (also called basic anhydrides)
1. Metallic oxides of Group 1A and 2A metals react with water to form basic
solutions
a. K
2
O(s) + H
2
O(l) 2KOH(aq)
b. CaO(s) + H
2
O(l) Ca(OH)
2
(aq)
6
14.11 The Lewis Acid-Base Model
A. Lewis Acids
1. Electron pair acceptors
B. Lewis Bases
1. Electron pair donors
14.12 Strategy for Solving Acid-Base Problems
Step 1: List the major species in solution
Step 2: Look for reactions that can be assumed to go to completion, for example, a
strong acid dissociating or H
+
reacting with OH
-
Step 3: For a reaction that can be assumed to go to completion:
a. Determine the concentration of the products
b. Write down the major species in solution after the reaction
Step 4: Look at each major component of the solution and decide if it is an acid or a
base
Step 5: Pick the equilibrium that will control the pH. Use known values of the
dissociation constants for the various species to help decide on the dominant
equilibrium.
a. Write the equation for the reaction and the equilibrium expression
b. Compute the initial concentrations (assuming the dominant equilibrium has
not yet occurred, that is, no acid dissociation, etc)
c. Define x
d. Compute the equilibrium concentrations in terms of x
e. Substitute the concentrations into the equilibrium expression, and solve for x
f. Check the validity of the approximation
g. Calculate the pH and other concentrations as required
1
Chapter 15 - Applications of Aqueous Equilibria
Acid-Base Equilibria
15.1 Solutions of Acids or Bases Containing a Common Ion
A. Common Ion
1. Ion provided in solution by an aqueous acid (or base) as well as a salt
a. HF(aq) and NaF (F
-
in common)
HF(aq) H
+
(aq) + F
-
(aq) Excess F
-
added by NaF
Equilibrium shifts away from added
component. Fewer H
+
ions present.
pH is higher than expected.
b. NH
4
OH and NH
4
Cl (NH
4
+
in common)
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)
Equilibrium shifts to the left. pH of the solution
decreases due to a decrease in OH
-
concentration
B. Equilibrium Calculations
1. Consider initial concentration of ion from salt when calculating values for H
+
and OH
-
15.2 Buffered Solutions
A. Buffered Solution
1. A solution that resists a change in pH when either hydroxide ions or protons
are added.
2. Buffered solutions contain either:
a. A weak acid and its salt
b. A weak base and its salt
B. Calculations Involving Buffered Solutions Containing Weak Acids
1. "Buffered solutions are simply solutions of weak acids or bases containing a
common ion. The pH calculations on buffered solutions require exactly the
same procedures introduced in Chapter 14. This is not a new type of
problem."
2. "When a strong acid or base is added to a buffered solution, it is best to deal
with the stoichiometry of the resulting reaction first. After the stoichiometric
calculations are completed, then consider the equilibrium calculations. This
procedure can be presented as follows:
2
C. Buffering: How Does it Work?
1. OH
-
+ HA A
-
+ H
2
O
weak conjugate
acid base
OH
-
ions are not allowed to accumulate but are replaced by A
-
ions
2.
] [
] ][ [
HA
A H
K
a
+
=
] [
] [
] [

+
=
A
HA
K H
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
3. Buffering also works for addition of protons instead of hydroxide ions
H
+
+ A
-
HA
Conjugate Weak
Base acid
3
D. The Henderson-Hasselbalch Equation
1.

+ =

+ =

] [
] [
log
] [
] [
log
acid
base
pK
HA
A
pK pH
a a
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 OH
-
BH
+
+ OH
-
B + H
2
O
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 pK
a
of the weak acid to be used should be as close as possible to the
desired pH
Table 15.1 Change in [C
2
H
3
O
2
-
]/[HC
2
H
3
O
2
] for two solutions when 0.01 mol H+ is added to
1.0 L of each
Solution orig
O H HC
O H C


] [
] [
2 3 2
2 3 2
new
O H HC
O H C


] [
] [
2 3 2
2 3 2
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%
4
15.4 Titration and pH Curves
A. Titration
1. The controlled addition of a solution of known concentration (the titrant) in
order to determine the concentration of a solution of unknown concentration
2. Equivalence Point (Stoichiometric Point)
a. The point in a titration at which the reaction between titrant and
unknown has just been completed.
3. Indicator
a. A substance which undergoes a color change in the pH interval of the
equivalence point
4. Titration Curve (pH Curve)
a. Plotting of the pH of the solution as a function of the volume of titrant
added
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 K
w
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
5
C. Titrations of Weak Bases with Strong Acids
1. Identify the major species in solution before, at and after equivalence point
2. Study each reaction to determine if the reaction can run to completion
a. Do the stoichiometry problem
b. Do the equilibrium problem
3. At the equivalence point, the pH is always less than 7
a. The conjugate acid of the weak base lowers the pH
15.5 Acid-Base Indicators
A. Determination of Equivalence Point
1. Use a pH meter, find midpoint of vertical line in the titration curve
2. Use of indicators
B. How Indicators Work
1. Most are weak acids and shift from acid to conjugate base forms
HIn (aq) H
+
(aq) + In
-
(aq)
a. Color change occurs as the proton is lost or acquired
C. Using Indicators
1. Indicator color changes will be sharp, occurring with the addition of a single
drop of titrant
2. Suitable indicators must be selected based on the equivalence point
a. Strong acid-strong base titrations may use indicators with end points
as far apart as pH 5 and pH 9
b. Titration of weak acids or weak bases requires more careful selection
of an indicator with appropriate transition interval
6
Solubility Equilibria
15.6 Solubility Equilibria and the Solubility Product
A. Dynamic Equilibrium
CaF
2
(s) Ca
2+
(aq) + 2F
-
(aq)
Ca
2+
(aq) + 2F
-
(aq) CaF
2
CaF
2
(s) Ca
2+
(aq) + 2F
-
(aq)
1. Equilibrium occurs when the solution is saturated
B. K
sp
(Solubility Product Constant, Solubility Product)
K
sp
= [Ca
2+
][F
-
]
2
1. Experimentally determined solubility of an ionic solid can by used to
calculate its K
sp
value
2. The solubility of an ionic solid can be calculated if its K
sp
value is known
C. Relative Solubilities
1. IF the salts being compared produce the same number of ions in solution,
K
sp
can be used to directly compare solubility
a. NaCl(s), KF(s)
K
sp
= [cation][anion] = x
2
2. IF the salts being compared produce different numbers of ions, K
sp
cannot
be directly compared
a. Ag
2
S(s)
K
sp
= [2x]
2
[x]
b. Bi
2
S
3
(s) = [2x]
2
[3x]
3
D. Common Ion Effect
1. The solubility of a solid is lowered if the solution already contains ions
common to the solid
a. Dissolving silver chloride in a solution containing silver ions
b. Dissolving silver chloride in a solution containing chloride ions
7
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-
, CO
3
2-
, C
2
O
4
2-
, CrO
4
2-
15.7 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
1
Chapter 16 - Spontaneity, Entropy, and Free Energy
16.1 Spontaneous Processes and Entropy
A. First Law
1. "Energy can neither be created nor destroyed"
2. The energy of the universe is constant
B. Spontaneous Processes
1. Processes that occur without outside intervention
2. Spontaneous processes may be fast or slow
a. Many forms of combustion are fast
b. Conversion of diamond to graphite is slow
C. Entropy (S)
1. A measure of the randomness or disorder
2. The driving force for a spontaneous process is an increase in the entropy of
the universe
3. Entropy is a thermodynamic function describing the number of
arrangements that are available to a system
a. Nature proceeds toward the states that have the highest probabilities
of existing
D. Positional Entropy
1. The probability of occurrence of a particular state depends on the number of
ways (microstates) in which that arrangement can be achieved
S
solid
< S
liquid
<< S
gas
16.2 Entropy and the Second Law of Thermodynamics
A. Second Law of Thermodynamics
1. "In any spontaneous process there is always an increase in the entropy of
the universe"
2. "The entropy of the universe is increasing"
3. For a given change to be spontaneous, S
univ
must be positive
S
univ
= S
sys
+ S
surr
16.3 The Effect of Temperature on Spontaneity
A. Direction of Heat Flow
1. Entropy changes in the surroundings are primarily determined by heat flow
a. Exothermic reactions in a system at constant temperature increase
the entropy of surroundings
b. Endothermic reactions in a system at constant temperature decrease
the entropy of surroundings
c. The impact of the transfer of a given quantity of energy as heat to or
from the surroundings will be greater at lower temperatures
16.4 Free Energy (G), also called "Gibbs Free Energy"
A. Calculating Free Energy Change (constant temperature and pressure)
1. G = H - TS
a. H is enthalpy
b. T is Kelvin temperature
2
B. Free Energy and Spontaneity
1. Reactions proceed in the direction that lowers their free energy (-G)
Value of H Value of T S Value of G Spontaneity
Negative Positive Negative Spontaneous
Positive Negative Positive Nonspontaneous
Negative Negative ??? Spontaneous if the absolute value of
H is greater than the absolute value
of TS (low temperature)
Positive Positive ??? Spontaneous if the absolute value of
TS is greater than the absolute value
of H (high temperature)
16.5 Entropy Changes in Chemical Reactions
A. Constant Temperature and Pressure
1. Reactions involving gaseous molecules
a. The change in positional entropy is dominated by the relative
numbers of molecules of gaseous reactants and products
2C
2
H
6
(g) + 7O
2
(g) 4CO
2
(g) + 6H
2
O(g)
9 molecules 10 molecules
S increases
B. Third Law of Thermodynamics
1. "The entropy of a perfect crystal at O K is zero" (NO disorder, since
everything is in perfect position)
C. Calculating Entropy Change in a Reaction
o
ts reac r products p reaction
S n S n S
tan
0 0

=
1. Entropy is an extensive property (a function of the number of moles)
2. Generally, the more complex the molecule, the higher the standard entropy
value
16.6 Free Energy and Chemical Reactions
A. Standard Free Energy Change
1. G
0
is the change in free energy that will occur if the reactants in their
standard states are converted to the products in their standard states
2. G
0
cannot be measured directly
3. The more negative the value for G
0
, the farther to the right the reaction will
proceed in order to achieve equilibrium
a. Equilibrium is the lowest possible free energy position for a reaction
B. Calculating Free Energy Change
1. Method #1, for reactions at constant temperature:
G
0
= H
0
- TS
0
2. Method #2, an adaptation of Hess's Law:
C
diamond
(s) + O
2
(g) CO
2
(g) G
0
= -397 kJ
C
graphite
(s) + O
2
(g) CO
2
(g) G
0
= -394 kJ
C
diamond
(s) C
graphite
(s) G
0
= -397 kJ - (-394 kJ) = -3kJ
(Complete example is on page 798)
3
3. Method #3, using standard free energy of formation (G
f
0
)
a. Standard Free Energy of Formation is the change in free energy that
accompanies the formation of 1 mole of that substance from its
constituent elements with all reactants and products in their standard
states
b. G
f
0
of an element in its standard state is zero
) tan (
0
) (
0 0
ts reac
f r
products
f p
G n G n G =

16.7 The Dependence of Free Energy on Pressure
A. Enthalpy, H
1. enthalpy is not pressure dependent
B. Entropy, S
1. entropy depends on volume, so it also depends on pressure
S
large volume
> S
small volume
S
low pressure
> S
high pressure
2. G = G
0
+ RTln(P)
a. G
0
is the free energy of the gas at a pressure of 1 atm
b. G is the free energy of the gas at a pressure of P atm
c. R is the universal gas constant, T is Kelvin temperature
3. G = G
0
+ RTln(Q)
a. Q is the reaction quotient (from the law of mass action, section 13.5)
b. R is the gas constant (8.3145 J/Kmol)
c. G
0
is the free energy change for the reaction with all reactants and
products at a pressure of 1 atm
d. G is the free energy change for the reaction for the specified
pressures of reactants and products
16.8 Free Energy and Equilibrium
A. Thermodynamic View of Equilibrium
1. Equilibrium point occurs at the lowest value of free energy available to the
reaction system
2. At equilibrium, G = 0 and Q = K
G
0
= -RTln(K)
G
0
K
G
0
= 0 K = 1
G
0
< 0 K > 1
G
0
> 0 K < 1
B. Temperature Dependence of K
1.
0 0 0
) ln( S T H K RT G = =
2.
R
S
T R
H
R
S
RT
H
K
0 0 0 0
1
) ln(

+

= so ln(K) 1/T
4
16.9 Free Energy and Work
A. Relationship to Work
1. The maximum possible useful work obtainable from a process at constant
temperature and pressure is equal to the change in free energy
("Free energy" is energy "free" to do work)
w
max
= G
2. The amount of work obtained is always less than the maximum
B. Henry Bent's First Two Laws of Thermodynamics
1. First law: You can't win, you can only break even
2. Second law: You can't break even
The amount of available free energy of our system (Earth) is decreasing.
1
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
17.2 Standard Reduction Potentials
A. Measuring Potential
1. Electrode potential is measured in reference to a hydrogen electrode which
is arbitrarily assigned a potential of zero volts
2
B. Calculating Electrode Potential
1. One of the reduction half reactions must be reversed, changing the sign on
the potential for the reversed reaction
2. Potentials are not multiplied by the coefficients in the balanced equation
3. Galvanic cell potentials must be a positive number
C. Line Notation
1. Anode components listed on the left
2. Cathode components listed on the right
3. Double line represents salt bridge or porous disk
Mg(s)Mg
2+
(aq) Al
3+
(aq) Al(s)
D. Complete Description of a Galvanic Cell
1. The cell potential (always positive for a galvanic cell)
2. The direction of electron flow (the direction that yields a positive potential)
3. Designation of the anode and cathode
4. The nature of each electrode and the ions present in each compartment. A
chemically inert conductor (such as Pt) is required if none of the substances
participating in the reaction is a conducting solid
17.3 Cell Potential, Electrical Work, and Free Energy
A. Driving Force
1. emf = potential difference = work (joules)
charge (coulombs)
a. Work leaving the system has a negative charge
= - w/q -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 w
max
is useful for
calculating the efficiency of conversion
w
max
= -q
max
B. Relation to Free Energy
1. w
max
= G
2. G = -q
max
= -nF
max
3. G = -q
max
4. G
0
= -nF
0
a. When
cell
is positive (spontaneous), G will be negative
(spontaneous), so there is agreement
3
17.4 Dependence of Cell Potential on Concentration
A. Standard Potentials
1. All concentrations are 1M
B. Variation in concentrations
1. Write balanced equation for the cell
2. Use Le Chateliers principle to determine the effect on potential
a. Shift to the left reduces potential
b. Shift to the right increases potential
C. Concentration Cells
1. Cells in which both compartments contain the same components, but in
different concentrations
2. Reaction proceeds in the direction that will equalize the ion concentration in
the compartments
3. Voltages are typically small
D. The Nernst Equation
1. Derivation
G = G
0
+ RTln(Q) (from Chapter 16)
-nF = -nF
0
+ RTln(Q)
=
0
- ) ln( Q
nF
RT

2. At 25C
=
0
- ) log(
0592 . 0
Q
n

3. As cells discharge, concentration changes,


cell
changes.
4. Cells spontaneously discharge until they achieve equilibrium
a. At equilibrium, the cell is dead
E. Ion-Selective Electrodes
1. Electrodes that are sensitive to the concentration of a particular ion
2. Electrodes can be manufactured to be selective to a cation/anion pair
F. Calculation of Equilibrium Constants for Redox Reactions
1. At equilibrium,
cell
= 0 and Q = K
2. Substituting into the Nernst equation
0 =
0
- ) log(
0592 . 0
K
n

log(K) = n
0
(at 25C)
0.0592
4
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: Pb + HSO
4
-
PbSO
4
+ H
+
+ 2e
-
Cathode rxn: PbO
2
+ HSO
4
-
+ 3H
+
+ 2e
-
PbSO
4
+ 2H
2
O
Cell rxn: Pb(s) + PbO
2
(s) + 2H
+
(aq) + 2HSO
4
-
(aq) 2PbSO
4
(s) + 2H
2
O(l)
2. Discharge lowers the concentration of sulfuric acid, and the density of the
solution
3. Note this If you learn nothing else in chemistry
When jump starting a car, you MUST connect the ground cable on the DEAD car to a metallic
contact AWAY from the battery. Otherwise, BOOM! (maybe)
C. Common Dry Cell Battery
1. Acid version
a. zinc inner case acts as
the anode
b. carbon rod in contact with
a moist paste of solid
MnO
2
, solid NH
4
Cl and
carbon is the cathode
2. Alkaline dry cell
a. NH4Cl is replaced with
KOH or NaOH
b. Alkaline cells last longer than acid cells because zinc corrodes more
slowly in a basic environment
D. Fuel Cells
1. Galvanic cells for which the reactants are continuously supplied
2. Energy normally lost as heat is captured and used to produce an electric
current
3. The reaction taking place must be a redox reaction
17.6 Corrosion
A. Corrosion = Oxidation of a metal
1. The oxidation of most metals by oxygen is spontaneous
2. Many metals develop a thin coating of metal oxide on the outside that
prevents further oxidation
B. Corrosion of Iron
1. Anode regions
a. Regions of a piece of steel alloy where the iron is more easily
oxidized
Fe Fe
2+
+ 2e
-
5
2. Cathodic regions
a. Areas that are resistant to oxidation
b. Electrons flow from anodic regions and react with oxygen
O
2
+ 2H
2
O + 4e
-
4OH
-
3. 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
a. oxidation at the anode
b. reduction at the cathode
6
B. Electroplating
1. Depositing neutral metal atoms on the electrode by reducing the metal ions
in solution.
a. Anode is a piece of the plating metal
b. Cathode is the object to be plated
C. Electrolysis of Water
1. Requires the presence of a soluble salt or dilute acid to serve as an
electrolyte
a. 2H
2
O 2H
2
+ O
2
D. Electrolysis of Mixtures of Ions
1. Most easily reduced metals (highest values of
0
) will be plated first
7
E. Stoichiometry of Electrolytic Processes
1. Step 1 convert current and time to quantity of charge in coulombs
a. Amps x time = total charge transferred in coulombs
(Coulomb/sec) x sec = coulombs
2. Step 2 convert quantity of charge in coulombs to moles of electrons
coulombs (96,485 coulomb/mol e
-
) = mol e
-
3. Step 3 Convert moles of electrons to moles of substance
Mol e
-
x (mole substance/mol e
-
) = mol substance
4. Step 4 Convert moles of substance to grams of substance
Mol substance x formula mass of substance = mass of substance
17.8 Commercial Electrolytic Processes
A. Production of Aluminum
1. Purification of aluminum from bauxite ore
2. See table 17.3 for prices of aluminum over the last century
B. Electrorefining of Metals
C. Metal Plating
D. Electrolysis of Sodium Chloride
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 CO
2
b. Silicon does not form bonds with oxygen in discrete SiO
2
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 (N
2
)
b. Phosphorus forms aggregates based on the tetrahedral P
4
molecule
(1) Single bonds
(2) Large atoms = weak bonds
6. Oxygen and Sulfur (Group VI)
a. Oxygen forms a diatomic molecule with bonds (O
2
)
b. Sulfur forms aggregates such as the cyclic S
8
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
C. Abundance and Preparation
1. Earth's Crust, Ocean, Atmosphere
Oxygen 49.2% Titanium 0.58%
Silicon 25.7% Chlorine 0.19%
Aluminum 7.50% Phosphorus 0.11%
Iron 4.71% Manganese 0.09%
Calcium 3.39% Carbon 0.08%
Sodium 2.63% Sulfur 0.06%
Potassium 2.40% Barium 0.04%
Magnesium 1.93% Nitrogen 0.03%
Hydrogen 0.87% Fluorine 0.03%
2. Major Elements in the Human Body
Oxygen 65.0% Potassium 0.34%
Carbon 18.0% Sulfur 0.26%
Hydrogen 10.0% Sodium 0.14%
Nitrogen 3.0% Chlorine 0.14%
Calcium 1.4% Iron 0.004%
Phosphorus 1.0% Zinc 0.003%
Magnesium 0.50%
3. Metallurgy - Obtaining a Metal from its Ore
a. Reduction of metal ions to atoms, usually using carbon as the
reducing agent
2SnO(s) + C(s) + heat 2Sn(s) + CO
2
(g)
2PbO(s) + C(s) + heat 2Pb(s) + CO
2
(g)
Hydrogen as reducing agent
SnO(s) + H
2
(g) + heat Sn(s) + H
2
O(g)
b. Electrolysis
(1) purification of highly active metals
4. Purification of Nonmetals
a. Liquefaction
(1) sequential expansion (cooling) followed by compression
of a gas
b. Electrolysis
(1) Hydrogen from water
c. Decomposition
(1) Hydrogen from methane (more common)
18.2 The Group 1A Elements - The Alkali Metals
A. Reactivities
1. With water
a. 2M(s) + 2H
2
O(l) 2M
+
(aq) + 2OH
-
(aq) + H
2
(g)
2. Sodium forms oxides or peroxides
a. 4Na(s) + O
2
(g) 2Na
2
O(s) (limited oxygen)
b. 2Na(s) + O
2
(g) Na
2
O
2
(s) (excess oxygen)
3. K, Rb, Ce react with oxygen to form superoxides, containing the O
2
-
a. K(s) + O
2
(g) KO
2
(s)
b. Superoxides react with water or carbon dioxide to release
oxygen
4. Lithium reacts with nitrogen to form a nitride salt
a. 6Li(s) + N
2
(g) 2Li
3
N(s)
B. Biological Importance of Alkali Metals
1. Na
+
and K
+
are important in nerve conduction and muscle contraction
2. Li
+
affects levels of neurotransmitters and is used to treat bipolar
disorder
18.3 Hydrogen
A. Properties
1. Colorless
2. Odorless
3. Low boiling (-253C) and melting (-260C)points
4. Highly flammable
B. Purification of Hydrogen
1. Decomposition of methane in water, using heat, pressure and a
catalyst
CH
4
(g) + H
2
O(g) CO(g) + 3H
2
(g)
2. Cracking of hydrocarbons in gasoline production
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 H
-
c. Hydrides are powerful reducing agents, explosive in water
d. Examples include LiH and CaH
2
2. Nonmetals + hydrogen (covalent hydrides)
a. Examples include H
2
O, NH
3
, CH
4
, 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) + H
2
O(l) M
2+
(aq) + 2OH
-
(aq)
2. BeO has amphoteric properties
B. Reaction with Water
1. M(s) + H
2
O(l) M
2+
(aq) + 2OH
-
(aq) + H
2
(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. B
2
H
6
(diborane) and others (B
5
H
9
) 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 Diamond Buckminster Fullerene
2. Carbon oxides

carbon monoxide carbon dioxide 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 20% Sn, 80% Cu
Solder 33% Sn, 67% Pb
Pewter 85% Sn, 7% Cu, 6% Bi, 2% Sn
F. Lead
1. Obtained from the galena ore (PbS)
2. Widely used in the anti-knock agent tetraethyl lead, (C
2
H
5
)
4
Pb

3. Produced in greatest quantity for lead storage batteries