Chemistry

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FE Exam
Chemistry Review
Prentice Hall © 2005

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Topics
• Introduction
• Basic Concepts, definitions
• Basic calculations
• Gas laws
• Chemical reactions
• Colligative properties of solutions
• Acids, bases, salts
• Chemical equilibrium
• Solubility product constant
• Chemical kinetics
• Thermochemistry & thermodynamics
• Electrochemistry
• Organic chemistry
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Key Terms
• Atoms are the smallest distinctive units in a
sample of matter.
• Molecules are larger units in which two or
more atoms are joined together.
‫ ٭‬Examples: Water consists of molecules, each
having two atoms of hydrogen and one of
oxygen.
‫ ٭‬Oxygen gas consists of molecules, each
having two atoms of oxygen.
Water Oxygen
molecule molecule

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Key Terms: Properties

• In a physical change, there is
no change in composition.
• No new substances are
formed.
‫ ٭‬Examples include:
evaporation; melting; cutting a
piece of wood; dissolving
sugar in water.
• In a chemical change or
chemical reaction, the matter
undergoes a change in
composition.
• New substances are formed. The vapor burns, The liquid fuel
combining with evaporates: a
‫ ٭‬Examples include: burning physical change.
gasoline; dissolving metal in oxygen: a
chemical change.
acid; spoilage of food.
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Atoms Molecules
Classifying make up
Matter ALL MATTER
Figure 1.3
which exists as
Substances Mixtures
which may be which may be
Elements Compounds Homogeneous Heterogeneous

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3.1. Basic Concepts, Definitions,

Notation, Units

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Laws of Chemical Combination
• Law of Conservation of Mass

– The total mass remains constant during a chemical
reaction.
• Law of Definite Proportions
– All samples of a compound have the same composition,
or …
– All samples have the same proportions, by mass, of the
elements present.

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Law of Multiple Proportions
When two or more different compounds of the same

two elements are compared, the masses of one
element that combine with a fixed mass of the
second element are in the ratio of small whole
numbers.

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Law of Multiple Proportions (cont’d)

• Four different oxides of nitrogen can be formed by
combining 28 g of nitrogen with:
• 16 g oxygen, forming Compound I
• 48 g oxygen, forming Compound II
• 64 g oxygen, forming Compound III
• 80 g oxygen, forming Compound IV
What is the ratio 16:48:64:80
expressed as small whole numbers?
• Compounds I–IV are N2O, N2O3, N2O4, N2O5

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Subatomic Particles
• Protons and neutrons are located at the center of

an atom (at the nucleus).
• Electrons are dispersed around the nucleus.

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Isotopes
• Atoms that have the same number of protons but

different numbers of neutrons are called isotopes.
• The atomic number (Z) is the number of protons
in the nucleus of a given atom of a given element.
• The mass number (A) is an integral number that
is the sum of the numbers of protons and neutrons
in an atom.
• The number of neutrons = A – Z.

Electron Configurations
• An electron configuration describes the
distribution of electrons among the various
orbitals in the atom.
• Electron configuration is represented in
two ways.
The spdf notation uses
numbers to designate a
principal shell and letters
(s, p, d, f) to identify a
subshell; a superscript
indicates the number of
electrons in a designated 12
subshell.
Electron Configurations
In an orbital (box) diagram a box
represents each orbital within subshells, and
arrows represent electrons. The arrows’
directions represent electron spins;
opposing spins are paired.
N:
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Order of Subshell Energies
• Follow the arrows

from the top: 1s, 2s,
2p, 3s, 3p, 4s, 3d,
4p, etc.
• Subshells that are
far from the nucleus
may exhibit
exceptions to the
filling order.
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The Modern Periodic Table
Except for H,
elements left of
the zigzag line
are metals.
To the right of
the line we find
nonmetals,
including the
noble gases.
Some elements
adjacent to the
line are called
metalloids.

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Molecules and Formulas

• A molecule is a group of two or more atoms held
together by covalent bonds.
• A molecular formula gives the number of each kind
of atom in a molecule.
• An empirical formula simply gives the (whole
number) ratio of atoms of elements in a compound.
Compound Molecular formula Empirical formula

Hydrogen peroxide H2O2 HO
Octane C8H18 ????

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Structural Formulas and Models

• Structural formulas and models show how atoms
are attached to one another.
The condensed structural formula for acetic acid is
CH3COOH. C2H4O2: two C atoms, four H atoms, two O atoms.
CH3COOH shows how the atoms are arranged.
Ball-and-stick model Space-filling model

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Naming Binary Molecular

Compounds
• The name consists of two words.
• First word: name of the element that appears
first in the formula.
• Second word: stem of the name of the second
element, ending with -ide.
• Names are further modified by adding prefixes
to denote the numbers of atoms of each element
in the molecule.

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Which element is named first?
Begin with boron and follow

the line to determine the
order of naming.
Rule of thumb: the element

that is farthest down and to
the left on the periodic table
is usually written first.
In a compound consisting of
arsenic (As) and sulfur (S),
which element is named first?

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Ions and Ionic Compounds
• An atom that either gains or loses electron(s) is

an ion.
• There is no change in the number of protons or
neutrons in the nucleus of the atom.
• Cation – has a positive charge from loss of
electron(s).
• Anion – has a negative charge from gain of
electron(s).

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Ions and Ionic Compounds (cont’d)
In an ionic compound,
oppositely charged ions
are attracted to each
other such that the
compound has no net
charge.
There are no
distinct molecules
of sodium chloride.
Sodium chloride simply consists

of sodium ions and chloride ions,
regularly arranged.

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Monatomic Ions
• Group IA metals form ions of 1+ charge.

• Group IIA metals form ions of 2+ charge.
• Aluminum, a group IIIA metal, forms ions with a 3+ charge.
• Nonmetal ions of groups V, VI, and VII usually have charges of 3–,
2–, and 1–, respectively.
• Group B metal ions (transition metal ions) often have more than one
possible charge. A Roman numeral is used to indicate the actual
charge.
• A few transition elements have only one common ion (Ag, Zn, Cd),
and a Roman numeral is not often used.

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Polyatomic Ions
• A polyatomic ion is a charged group of covalently bonded
atoms.
• There are many more polyatomic anions than there are
polyatomic cations.
• You should (eventually!) commit to memory much of Table
2.4
• hypo- and per- are sometimes seen as prefixes in oxygen-
containing polyatomic ions (oxoanions).
• -ite and -ate are commonly found as suffixes in oxygen-
containing polyatomic ions.

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Hydrates
• A hydrate is an ionic compound in which the formula unit includes a
fixed number of water molecules associated with cations and anions.
• To name a hydrate, the compound name is followed by “___hydrate”
where the blank is a prefix to indicate the number of water molecules.
• The number of water molecules associated with each formula unit is
written as an appendage to the formula unit name separated by a dot.
• Examples: BaCl2 . 2 H2O; CuSO4 . 5 H2O

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3.2. Basic Calculations

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Molecular Masses and

Formula Masses
• Molecular mass: sum of the masses of the
atoms represented in a molecular formula.
• Simply put: the mass of a molecule.
• Molecular mass is specifically for
molecules.
• Ionic compounds don’t exist as molecules;
for them we use …
• Formula mass: sum of the masses of the
atoms or ions present in a formula unit.
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Determining the Formula Mass

of Ammonium Sulfate

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The Mole & Avogadro’s Number

• Mole (mol): amount of substance that contains as many
elementary entities as there are atoms in exactly 12 g of the
carbon-12 isotope.
• Atoms are small, so this is a BIG number …
• Avogadro’s number (NA) = 6.022 × 1023 mol–1
• 1 mol = 6.022 × 1023 “things” (atoms, molecules, ions,
formula units, oranges, etc.)
– A mole of oranges would weigh about as much as the
earth!
• Mole is NOT abbreviated as either M or m.

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Example 3.3
Determine (a) the mass of a 0.0750-mol sample
of Na, (b) the number of moles of Na in a 62.5-
g sample, (c) the mass of a sample of Na
containing 1.00 × 1025 Na atoms, and (d) the
mass of a single Na atom.

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The Mole and Molar Mass

• Molar mass is the mass of one mole of a substance.
• Molar mass is numerically equal to atomic mass,
molecular mass, or formula mass. However …
• … the units of molar mass are grams (g/mol).
• Examples:
1 atom Na = 22.99 u 1 mol Na = 22.99 g
1 molecule CO2 = 44.01 u 1 mol CO2 = 44.01 g
1 formula unit KCl = 74.56 u 1 mol KCl = 74.56 g

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We can read formulas in terms of

moles of atoms or ions.

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Mass Percent Composition

from Chemical Formulas
The mass percent composition of a compound refers to the
proportion of the constituent elements, expressed as the
number of grams of each element per 100 grams of the
compound. In other words …
X g element
X % element = –––––––––––––– OR …
100 g compound
g element
% element = ––––––––––– × 100
g compound

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Percentage Composition of Butane

Chemical Formulas from Mass
Percent Composition
Phenol has the composition: 76.57% C,
6.43% H, and 17% O by mass. Determine its
empirical formula.
A 5-step solution:
Step 1: a 100-g sample of phenol contains 76.57 g C,
6.43 g H, and 17 g O
Step 2: Convert the masses of C, H, and O to moles
? Mol C = 76.57 g C X 1 mol/12.011 gC = 6.375 mol C
? Mol H = 6.34 gH X 1 mol H/1.0079 gH = 6.38 mol H
? Mol O = 17 g O X 1 mol O / 15.999 g O = 1.064 mol O
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Continue..
Step 3: Use the numbers of moles in step 2
as subscripts in a tentative formula
C6.375H6.38O1.063
Step 4: Divide each subscript by the
smallest (1.063) to get integral subscripts
C6.375/1.063H6.38/1.063O1.063/1.063
Step 5: Empirical formula of phenol is
C6H6O
Note that you may need to multiply subscripts by a
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common factor to convert them all to integers
Relating molecular Formulas
to Empirical Formulas
The empirical formula of hydroquinone, a
chemical used in photography, is C3H3O
and its molecular mass is 110 u. What is its
molecular formula?
Empirical formula mass = 3 X 12 u + 3 X
1.0 u + 1 X 16 u = 55.0 u
Integral factor = molecular mass/empirical
formula mass = 110.0u/55.0u = 2
Molecular formula is C6H6O2
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Elemental Analysis …
… is one method of determining
empirical formulas in the laboratory.
This method is used primarily for
simple organic compounds (that
contain carbon, hydrogen, oxygen).
The organic compound is burned in oxygen.
The products of combustion (usually CO2 and
H2O) are weighed.
The amount of each element is determined from
the mass of products.
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Elemental Analysis (cont’d)
… H2O, which is absorbed

by MgClO4, and …
The sample is
burned in a
stream of oxygen … CO2, which is
gas, producing … absorbed by NaOH.
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Elemental Analysis
2CH3OH + excess O2 Î 2 CO2 + 4 H2O +
unreacted O2
g CO2→ mol CO2 → mol C → g C →%C

in original sample
g H2O→ mol H2O → mol H → g H →%

H in original sample
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Balancing Chemical Equations
A chemical equation is a shorthand
description of a chemical reaction
Chemical reaction
Reactants and products
Physical forms: (g), (l), (s), (aq)
Conditions: heat (delta)
Stoichiometric coefficients: numbers
placed in front of formulas in a chemical
reaction to balance the equation
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Balance the following chemical equations:
H2(g) + O2 Î H2O (l)
Balancing by inspection
Strategies to reduce trial and errors:
If an element is present in just one compound on each side of the
equation Î balance that element first
If polyatomic ions remain unchanged, balance these groupings as a
unit
Balance reactants or products existing as free elements last
You may balance using fractional coefficients then multiply by
common factor
IMPORTANT!! For each element, the same number
of atoms must appear on each side of the arrow
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Guidelines for Balancing
Chemical Equations
If an element is present in just one compound on each
side of the equation, try balancing that element first.
Balance any reactants or products that exist as the free
element last.
In some reactions, certain groupings of atoms (such as
polyatomic ions) remain unchanged. In such cases, treat
these groupings as a unit.
At times, an equation can be balanced by first using a
fractional coefficient(s). The fraction is then cleared by
multiplying each coefficient by a common factor.
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Balance the following reactions:
Fe + O2 Î Fe2O3
SiCl4 + H2O Î SiO2 + HCl
C2H6 + O2 Î CO2 + H2O
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Solutions and
Solution Stoichiometry
• Solute: the substance being dissolved.
• Solvent: the substance doing the dissolving.
• Concentration of a solution: the quantity of
a solute in a given quantity of solution (or
solvent).
– A concentrated solution contains a relatively large
amount of solute vs. the solvent (or solution).
– A dilute solution contains a relatively small
concentration of solute vs. the solvent (or solution).
– “Concentrated” and “dilute” aren’t very quantitative …
Molar Concentration
Molarity (M) is the amount of solute in moles per one liter
of solution
Molarity (M) = moles of solute / liters of solution
Use volumetric flasks to prepare solutions of fixed molarity
Examples: what is the molarity of a solution in which 333 g
of potassium hydrogen carbonate is dissolved in enough
water to make 10.0L of solution?
Solution:
One mole KHCO3 = 101 g

333 g KHCO3 = 333/101 = 3.33 moles
Molarity = 3.33/10 = 0.333 M KHCO3
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Exercise
A) How many moles of NaOH are needed to
prepare 0.500 L of 6.68 M NaOH
B) How many liters of 6.68 M NaOH can we
prepare with 2.35 kg NaOH?
Solution:
a) 6.68 / 2 = 3.34 M NaOH
b) 1 mol NaOH = 23 + 16 + 1 = 40 g NaOH
6.68 M NaOH = 6.68 X 40 = 267.2 g
NaOH
2350 / 267.2 = 8.79 L of 6.68 M NaOH
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Dilution Calculations …
• … couldn’t be easier.
• Moles of solute does not change on dilution.
• Moles of solute = M × V
• Therefore …
Mconc × Vconc = Mdil × Vdil

Dilution of Solutions
Addition of solvent does not change the
amount of solute in a solution but does
change the solution concentration
M1 X V1 = M2 X V2
Examples: How many mL of a 2.00 M
CuSO4 stock solution are needed to prepare
a 0.250 L of 0.400 M CuSO4?
? X 2.00 M = 250 mL X 0.40 M
= 50 mL 50
Exercise
How many grams of CaCO3 are consumed in a reaction
with 225 mL of 3.25 M HCl?
CaCO3 (s) + 2 HCl (aq) Î CaCl2 (aq) + H2O (l) + CO2 (g)
? Moles of HCl in 225 mL of 3.25 M HCl = 3.25 M X 0.225 L
/ 1 L = 0.73 M HCl
? Moles of CaCO3 are consumed in a reaction with 0.73 M
HCl = 1 mol CaCO3X 0.73 M HCl/ 2 M HCl = 0.365 mol
CaCO3
Molar mass of CaCO3 = 40 + 12 + 16 X3 = 100 g
0.365 mol CaCO3 = 100 X 0.365 / 1= 36.5 g
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3.3. Gas Laws

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Boyle’s Law:
Pressure-Volume Relationship
• For a fixed amount of a gas at constant
temperature, the volume of the gas varies
inversely with its pressure.
• For a fixed amount of a gas at constant
temperature, the product of pressure and
volume is a constant.
PV = constant or PinitialVinitial = PfinalVfinal

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Avogadro’s Law:
Mole-Volume Relationship
• At a fixed temperature and pressure, the volume of a gas is
directly proportional to the amount of gas in moles (n) or to the
number of molecules of gas.
Vαn ⇒ V = cn ⇒ V/n = c
• Standard temperature and pressure (STP) is equal to 0 °C and
1 atm.
• The molar volume of a gas is the volume occupied by one mole
of the gas.
• At STP, molar volume of an ideal gas is 22.4 liters.

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Example 5.8
Calculate the volume occupied by 4.11 kg of
methane gas, CH4(g), at STP.

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The Combined Gas Law
a
V = —— V = bT V = cn
P
nT We can cancel any term
Therefore V α —— (P, V, n, T) that is the
P same on both sides.
PV P1V1 P2V2
and —— = a constant OR —— = ——
nT n1T1 n2T2

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The Ideal Gas Law
PV
—— = constant = R
nT R = 0.08206 (L·atm)/(mol·K)
The ideal gas constant
PV = nRT Å The ideal gas law
• P in atm, V in L, n in moles, T in kelvins.

• If any other units are used for these variables, a
different value for R must be used …

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Applications of the Ideal Gas Law:
Molecular Mass Determination
M = molar mass and m = mass in grams
m (grams) m
M = ————— so n= —
n (moles) M
PV
The ideal gas equation rearranges to: n = ——
RT
Setting the equations equal to one another: m PV

— = ——
M RT
Alternative to equation: (A) find
mRT n using the ideal gas equation;
… and solving for M: M = ——— (B) Divide m (grams) by n (moles)
PV to get grams/mol.

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Applications of the Ideal Gas Law:
Gas Densities
• Gases are much less dense than liquids and solids, so gas
densities are usually reported in g/L.
Alternative: find
mRT m MP volume of one mole
M = ——— rearranges to — = —— (n = 1) or other fixed
PV V RT quantity of gas.
Divide mass of that
quantity by volume
m MP to find g/L.
and density = — so d = ——
V RT
Density of a gas is directly proportional to its molar mass

and pressure, and is inversely proportional to Kelvin
temperature.
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Mixtures of Gases:
Dalton’s Law of Partial Pressures
• Dalton’s law of partial pressures is used in
dealing with mixtures of gases.
• The total pressure exerted by a mixture of gases
is equal to the sum of the partial pressures
exerted by the separate gases:
Ptotal = P1 + P2 + P3 + …
Partial pressure: the pressure a gas would exert
if it were alone in the container. n RT
n1RT n2RT 3
P1 = ——— P2 = ——— P3 = ——— …
V V V

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Effusion
• Effusion is the process in • Effusion is (mathematically)
which a gas escapes from its simpler than diffusion since
container through a tiny effusion does not involve
hole, or orifice, into a molecular collisions.
vacuum. • At a fixed T, the rates of effusion
Heavier molecules of gas molecules are inversely
move more slowly proportional to the square roots
and so they effuse of their molar masses:
more slowly.
Fewer light molecules, more

heavy molecules remain.
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Intermolecular Forces
• … are forces between molecules.

• They determine melting points, freezing
points, and other physical properties.
• Types of intermolecular forces include:
• dispersion forces
• Dipole–dipole forces
• hydrogen bonding

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Dispersion Forces
• … exist between any two particles.

• Also called London forces (after Fritz
London, who offered a theoretical
explanation of these forces in 1928).
• Dispersion forces arise because the electron
cloud is not perfectly uniform.
• Tiny, momentary dipole moments can exist
even in nonpolar molecules.

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Dispersion Forces Illustrated (1)

At a given instant, electron
density, even in a nonpolar
molecule like this one, is
not perfectly uniform.

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… the other end
The region of of the molecule is
(momentary) higher slightly (+).
electron density attains
a small (–) charge …
When another
nonpolar molecule
approaches …

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… this molecule
… in this
induces a tiny
molecule.
dipole moment …
Opposite charges ________.

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Dipole–Dipole Forces
• A polar molecule has a positively charged

“end” (δ+) and a negatively charged “end”
(δ–).
• When molecules come close to one another,
repulsions occur between like-charged
regions of dipoles. Opposite charges tend to
attract one another.
• The more polar a molecule, the more
pronounced is the effect of dipole–dipole
forces on physical properties.
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Dipole–Dipole Interactions
Opposites
attract!

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Hydrogen Bonds
• A hydrogen bond is an intermolecular force

in which:
– a hydrogen atom that is covalently bonded to a (small,
electronegative) nonmetal atom in one molecule …
– is simultaneously attracted to a (small, electronegative)
nonmetal atom of a neighboring molecule.
Y ––– H - - - Z ~~~~
When Y and Z are small … this force is called a
and highly electronegative hydrogen bond; a special,
(N, O, F) … strong type of dipole–
dipole force.

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Hydrogen Bonds in Water

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3.4. Chemical Reactions

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Reactions Involving
Oxidation and Reduction
• Oxidation: Loss of electrons

• Reduction: Gain of electrons
• Both oxidation and reduction must occur simultaneously.
‫ ٭‬A species that loses electrons must lose them to something
else (something that gains them).
‫ ٭‬A species that gains electrons must gain them from
something else (something that loses them).
• Historical: “oxidation” used to mean “combines with
oxygen”; the modern definition is much more general.

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Oxidation Numbers
• An oxidation number is the charge on an ion, or a

hypothetical charge assigned to an atom in a molecule or
polyatomic ion.
• Examples: in NaCl, the oxidation number of Na is +1, that
of Cl is –1 (the actual charge).
• In CO2 (a molecular compound, no ions) the oxidation
number of oxygen is –2, because oxygen as an ion would
be expected to have a 2– charge.
• The carbon in CO2 has an oxidation number of +4 (Why?)

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Rules for Assigning Oxidation Numbers
1. For the atoms in a neutral species—an isolated atom, a molecule,
or a formula unit—the sum of all the oxidation numbers is 0.
2. For the atoms in an ion, the sum of the oxidation numbers is equal
to the charge on the ion.
3. In compounds, the group 1A metals all have an oxidation number of
+1 and the group 2A metals all have an oxidation number of +2.
4. In compounds, the oxidation number of fluorine is –1.
5. In compounds, hydrogen has an oxidation number of +1.
6. In most compounds, oxygen has an oxidation number of –2.
7. In binary compounds with metals,
group 7A elements have an oxidation number of –1,
group 6A elements have an oxidation number of –2, and
group 5A elements have an oxidation number of –3.

76
Example 4.7
What are the oxidation numbers assigned to the atoms of each element in
2–
(a) KClO4 (b) Cr2O7 (c) CaH2 (d) Na2O2 (e) Fe3O4
Strategy
In applying the rules for determining oxidation numbers, we must adhere to the priority
order in which they are listed above. Note, however, that except in the case of
uncombined elements, we cannot apply Rule 1 first.
Solution
(a) The oxidation number of K is +1 (Rule 3). The oxidation number of O is –2 (Rule 6),
and the total for four O atoms is –8. For these two elements, the total is +1 – 8 = –7.
The oxidation number of the Cl atom in this ternary compound must be +7, to give a
total of zero (+1 – 8 + 7 = 0) for all atoms in the formula unit (Rule 1).
(b) The oxidation number of O is –2 (Rule 6), and the total for seven O atoms is –14.
The total of the oxidation numbers in this ion must be –2 (Rule 2). Therefore the total
of the oxidation numbers of two Cr atoms is +12, and that of one Cr atom is +6.
(c) Keeping in mind that the total for the formula unit must be 0 (Rule 1) and that the
oxidation number of Ca is +2 (Rule 3), the oxidation number of H must be –1 rather
than its usual +1 (Rule 5). Thus, for CaH2 the sum of the oxidation numbers is +2 +
(2 x –1) = 0.

Reaction Stoichiometry
For the following reaction:
CO + 2H2 Î CH3OH
One mole of CO reacts with two moles
of hydrogen to produce one mole of
methanol
These amounts are said to be
stoichiometrically equivalent
77
Exercise
When 0.105 mol propane is burned in
an excess of oxygen, how many moles
of oxygen are consumed?
Strategy:
Write the chemical reaction
Balance the equation
Relate moles of consumed oxygen to moles of
burned propane (use the ratio of moles of each
species present in the balanced equation)
78
Example 3.17
When 0.105 mol propane is burned in an excess of oxygen, how many moles of oxygen
are consumed? The reaction is
C3H8 + 5 O2 ⎯→ 3 CO2 + 4 H2O
Strategy
We will relate the moles of consumed oxygen to moles of propane burned, using as
our conversion factor the ratio of the number of moles of each species present in the
balanced chemical equation.
Solution
The stoichiometric coefficients in the equation allow us to write the equivalence
From this equivalence, we can derive two conversion factors:
Because we are given the number of moles of propane (substance A in Figure 3.8)
and are seeking the number of moles of O2 consumed (substance B in Figure 3.8),
we need the factor that has the unit “mol O2” in the numerator and the unit “mol
C3H8 ” in the denominator. This is the conversion factor shown in red above:
79
Exercise
The final step in the production of nitric
acid involves the reaction of nitrogen
dioxide with water; nitrogen monoxide
is also produced. How many grams of
nitric acid are produced for every 100.0
grams of nitrogen dioxide that reacts?
Strategy:
1. Write the chemical reaction
2. Balance the equation
3. Determine moles produced
4. Convert from moles to grams 80
Example 3.18
The final step in the production of nitric acid involves the reaction of nitrogen dioxide
with water; nitrogen monoxide is also produced. How many grams of nitric acid are
produced for every 100.0 g of nitrogen dioxide that reacts?
Strategy
Working from a balanced chemical equation and using the appropriate
stoichiometric factor, we determine the moles of product produced from the given
moles of reactant. The conversions from grams to moles and moles to grams are
based on conversion factors associated with the respective molar masses.
Solution
Because no equation is given, we
must first write a chemical equation
from the description of the reaction.
Recall that we related the names and
formulas of these reactants and
products in Chapter 2.
To balance the equation, let’s first

balance H atoms because H appears
in one reactant and one product.
Then we can balance N atoms
because they appear on the reactant
side only in NO2. At this point, O
atoms will also be balanced.
81
Example 3.18 continued
Solution continued
Now, we convert the mass of the
given substance, NO2, to an amount
in moles, using the molar mass in
the manner shown in Figure 3.9.
Next, we use coefficients from the
balanced equation to establish
the stoichiometric equivalence of
NO2 and HNO3 .
Because we need to convert from
moles of NO2 to moles of HNO3, we
should use this equivalence to write
the stoichiometric factor needed for
the conversion.
Finally, we can convert from moles
of HNO3 to grams of HNO3 using
its molar mass.
Assessment
As you gain experience with reaction stoichiometry calculations, you will likely
switch to doing all that we have done here in a combined setup that obviates the
need to write intermediate answers.
82
Limiting Reactants
Limiting reactant: a reactant that is completely
consumed in a chemical reaction and limits the
amounts of products formed
Example:
2C8H18(l) + 25 O2 (g) Î 16CO2 (g) + 18 H2O (l)
If we allow octane to burn in a plentiful supply

of oxygen, then octane is the limiting reactant
83
Exercise
Magnesium nitride can be formed by
the reaction of magnesium metal with
nitrogen gas.
How many grams of magnesium nitride
can be made in the reaction of 35.0 g
magnesium and 15 grams of nitrogen?
How many grams of the excess reactant
remain after the reaction?
84
“STEPS FOR SOLVING A STOICHIOMETRY PROBLEM
INVOLVING MASSES OF REACTANTS AND PRODUCTS”
STEP 1
Write and balance the equation for the reaction.
STEP 2
Convert the known masses of substances to moles.
STEP 3
Determine which reactant is limiting.
STEP 4
Using the amount of the limiting reactant and the appropriate
mole ratios, compute the number of moles of the desired
product.
STEP 5
Convert from moles to grams, using the molar mass.”
85
Zumdahl Fifth Eidition
Exercise
Mg (s) + N2 (g) Î Mg3N2 (s)
Balance the equation: 3Mg (s) + N2 (g) Î Mg3N2 (s)

Assuming Mg is the limiting reactant:
1 mol Mg = 23.4 g
35 g Mg = 1.44 mol Mg
From the equation: 0.48 mol Mg3N2 will be formed
Assuming N2 is the limiting reactant:
1 mol N2 = 28 g
15 g nitrogen = 0.53 mol
From the equation; 0.53 mol Mg3N2 will be formed
Magnesium is the limiting reactant (smaller yield of Mg3N2)

Therefore, 0.48 mol Mg3N2 formed = 48.5 g (1 mol Mg3N2 = 101 g)
Amount of N2 consumed = 0.48 mol = 13.44 g N2
15 g N2 (initially) – 13.45 g N2 (consumed) = 1.44 g N2 (excess)
86
YIELD of Chemical
Reactions
The calculated quantity of product in a given
reaction is called the Theoretical yield
The Actual yield
Often less than the theoretical yield
Reasons include: purity of reactants, purification
of products, side reactions
The Percent yield =
Actual yield / Theoretical yield X 100%
87
Exercise
What mass of acetic acid is needed to
prepare 252 g ethyl acetate if the expected
percent yield is 85%? Assume that the
other reactant is present in excess. The
equation for the reaction carried out in
presence of H2SO4 is:
CH3COOH + C2H5OH Î CH3COOC2H5 + H2O
88
Exercise (continue)
252 g ethyl acetate is an actual yield
The Percent yield = Actual yield / Theoretical yield X 100%
Theoretical yield = actual yield/ percent yield X 100%
= 252/85% X 100%= 296 g ethyl acetate
Because: 1 mol ethyl acetate CH3COOC2H5= 88 g
Then: 296 g ethyl acetate = 3.36 mol
CH3COOH + C2H5OH Î CH3COOC2H5 + H2O
From the equation, we deduce that 3.36 mol acetic acid are needed
1 mol acetic acid CH3COOH = 60 g
Mass of acetic acid needed to produce 296 g ethyl acetate =
60 g X 3.36 mol = 201.6 g acetic acid needed 89
90
3.5. Colligative Properties &

Solutions

91
Some Types of Solutions

Solution: Solute dispersed in a solvent.

92
Example 12.8
Predict whether each combination is likely to be a solution or a heterogeneous mixture:
(a) methanol, CH3OH, and water, HOH
(b) pentane, CH3(CH2)3CH3, and octane, CH3(CH2)6CH3
(c) sodium chloride, NaCl, and carbon tetrachloride, CCl4
(d) 1-decanol, CH3(CH2)8CH2OH, and water, HOH
Solution
(a) Both molecules feature an OH group. This group is attached to a H atom in
water and to a CH3 group in methanol. The molecules are similar in that
hydrogen bonding is the major intermolecular force in both pure liquids and in
their mixtures. We expect methanol and water to form a solution.
(b) The hydrocarbons pentane and octane are quite similar; they differ by only
three CH2 groups. Intermolecular forces are dispersion forces and are all of
similar magnitude. We expect pentane and octane to form a solution (like
dissolves like).
(c) Sodium chloride and carbon tetrachloride are both chlorides, but the similarity
ends there. NaCl is an ionic compound, but CCl4 is molecular. Moreover,
because the tetrahedral CCl4 molecule is nonpolar, there are no ion–dipole
forces available to separate the ions in NaCl(s). There is no dissolving, and we
expect the mixture to be heterogeneous.

93
Solution Concentration
Most concentration Amount of solute
units are expressed as: Amount of solvent or solution
• Molarity: moles of solute/liter of solution

• Percent by mass: grams of solute/grams of solution (then multiplied
by 100%)
• Percent by volume: milliliters of solute/milliliters of solution (then
multiplied by 100%)
• Mass/volume percent: grams of solute/milliliters of solution (then
multiplied by 100%)

94
Solution Concentration (cont’d)

Most concentration Amount of solute
units are expressed as: Amount of solvent or solution
Molality (m): moles of solute/kilograms of solvent.
• Molarity varies with temperature (expansion or contraction of

solution).
• Molality is based on mass of solvent (not solution!) and is
independent of temperature.
• We will use molality in describing certain properties of solutions.

95
Solution Concentration (cont’d)

Concentration Amount of solute
expressed as: Amount of solvent or solution
• Mole fraction (xi): moles of component i per moles of all components
(the solution).
• The sum of the mole fractions of all components of a solution is ____.
• Mole percent: mole fraction times 100%.

96
Types of Electrolytes
• A strong electrolyte dissociates completely.
‫ ٭‬A strong electrolyte is present in solution almost exclusively as
ions.
‫ ٭‬Strong electrolyte solutions are good conductors.
• A nonelectrolyte does not dissociate.
‫ ٭‬A nonelectrolyte is present in solution almost exclusively as
molecules.
‫ ٭‬Nonelectrolyte solutions do not conduct electricity.
• A weak electrolyte dissociates partially.
‫ ٭‬Weak electrolyte solutions are poor conductors.
‫ ٭‬Different weak electrolytes dissociate to different extents.

97
Calculating Ion Concentrations in Solution
• In 0.010 M Na2SO4:
‫ ٭‬two moles of Na+ ions are formed for each mole
of Na2SO4 in solution, so [Na+] = 0.020 M.
‫ ٭‬one mole of SO42– ion is formed for each mole
of Na2SO4 in solution, so [SO42–] = 0.010 M.
• An ion can have only one concentration in a
solution, even if the ion has two or more
sources.

98
Colligative Properties of Solutions
• Colligative properties of a solution depend only on the concentration

of solute particles, and not on the nature of the solute.
• Non-colligative properties include: color, odor, density, viscosity,
toxicity, reactivity, etc.
• We will examine four colligative properties of solutions:
‫٭‬ Vapor pressure (of the solvent)
‫٭‬ Freezing point depression
‫٭‬ Boiling point elevation
‫٭‬ Osmotic pressure

99
Vapor Pressure of a Solution

• The vapor pressure of solvent above a solution is less than the vapor
pressure above the pure solvent.
• Raoult’s law: the vapor pressure of the solvent above a solution (Psolv)
is the product of the vapor pressure of the pure solvent (P°solv) and the
mole fraction of the solvent in the solution (xsolv):
Psolv = xsolv ·P°solv
• The vapor in equilibrium with an ideal solution of two volatile

components has a higher mole fraction of the more volatile component
than is found in the liquid.

100
Colligative Properties
Freezing Point Depression (FPD)
Boiling Point Elevation (BPE)
Consider situations with a volatile solvent and a
solute that is nonvolatile, nonelectrolytic, and soluble
in the liquid solvent, but not the solid solvent
The vapor pressure of the solution is that of the

solvent in the solution, and at all temperatures this
vapor pressure is lower than that of the pure solvent
EOS

101
Freezing Point Depression and
Boiling Point Elevation
ΔTf = –Kf × m ΔTb = Kb × m

102
Example 12.14
What is the freezing point of an aqueous sucrose solution that has 25.0 g C12H22O11 per
100.0 g H2O?
Strategy
The freezing point of the solution is that of pure water (0.00 °C ) plus the freezing
point depression (∆Tf). We can find ∆Tf with Equation (12.7). To do so, we will
need to obtain the value of Kf for water from Table 12.2. We also need to determine
the value of m, the molality of the solution.
Solution
First, let us determine the number of moles of sucrose in 25.0 g.
Now, we can calculate the molality of the sucrose from the number of moles of
sucrose and the quantity of water.
We use the molality and the constant to determine the depression

of the freezing point, ∆Tf .

103
Solution continued
The freezing point of the solution is the sum of ∆Tf and the freezing point of the
pure solvent, fp0.
Assessment
Because the value of Kf is the freezing point depression for a 1 m solution and the
sucrose solution is less than 1 m, we should expect the freezing point to be below 0
°C but not as low as as –1.86 °C, as indeed we found to be the case.
Exercise 12.14A
What is the freezing point of a solution in which 10.0 g of naphthalene [C10H8(s)] is
dissolved in 50.0 g of benzene [C6H6(l)]?
Exercise 12.14B
What mass of sucrose, C12H22O11, should be added to 75.0 g H2O to raise the boiling
point to 100.35 °C?

104
Osmotic Pressure
• A semipermeable membrane has microscopic pores, through which
small solvent molecules can pass but larger solute molecules cannot.
• During osmosis, there is a net flow of solvent molecules through a
semipermeable membrane, from a region of lower concentration to a
region of higher concentration.
• The pressure required to stop osmosis is called the osmotic pressure
(π) of the solution.
π = (nRT/V) = (n/V)RT = M RT
This equation should

look familiar …
105
Solutions of Electrolytes
• Whereas electrolytes dissociate, the number of solute particles
ordinarily is greater than the number of formula units dissolved. One
mole of NaCl dissolved in water produces more than one mole of
solute particles.
• The van’t Hoff factor (i) is used to modify the colligative-property
equations for electrolytes:
ΔTf = i × (–Kf) × m
ΔTb = i × Kb × m
π = i × M RT
• For nonelectrolyte solutes, i = 1.
• For electrolytes, we expect i to be equal to the number of ions into
which a substance dissociates into in solution.

106
Cumulative Example
A 375-mL sample of hexane vapor in equilibrium with liquid hexane, C6H14
(d = 0.6548 g/mL), at 25.0 °C is dissolved in 50.0 mL of liquid cyclohexane,
C6H12 (d = 0.7739 g/mL; vp = 97.58 Torr), at 25.0 °C. Calculate the total
vapor pressure above the solution at 25.0 °C. How reliable is this calculation?
Strategy
We must sum the partial pressures of the two components to obtain the total vapor
pressure of the solution. Assuming ideal solution behavior, we can obtain these
partial pressures with Raoult’s law (Equation 12.6). In that equation, concentrations
must be expressed in mole fractions, which requires that we first determine the
number of moles of each solution component and then use Equation (12.3). We can
use the ideal gas Equation (5.9) to calculate the number of moles of hexane vapor;
this is the amount of hexane dissolved in the hexane–cyclohexane solution. We can
then determine the number of moles of cyclohexane from its volume, density, and
molar mass.
Solution
First, we rearrange the ideal gas equation to solve for number of moles and
substitute the vapor equilibrium data, using the value 151 Torr from Example 11.3
for the vapor pressure of hexane at 25 °C.

107
Cumulative Example continued
Solution continued
Then, we calculate the number of moles of cyclohexane in the solution from the
given volume and density.
We get the mole fraction of hexane and cyclohexane from their molar quantities.
Next, we use Equation (12.6) to determine the partial pressures of hexane and
cyclohexane.
Finally, we calculate the total vapor pressure of the solution from Dalton’s law of
partial pressures.

108
3.6. Acids, Bases & Salts

109
Reactions of Acids and Bases:

Strong and Weak Acids
• Strong acids are strong electrolytes; completely ionized in water.
In water: HCl(g) → H+(aq) + Cl–(aq) No HCl in solution,
only H+ and Cl– ions.
• Weak acids are weak electrolytes. Some of the dissolved

molecules ionize; the rest remain as molecules.
In water: CH3COOH(l) H+(aq) + CH3COO–(aq)
Just a little H+ forms.
Some acids have more than one ionizable hydrogen atom.

They ionize in “steps” (more in Chapter 15).
H2SO4 → H+ + HSO4–
HSO4– H+ + SO42–
110
Strong and Weak Bases

• Strong bases: Most are ionic hydroxides (Group IA and IIA, though some
IIA hydroxides aren’t very soluble).
• Weak bases: Like weak acids, they ionize partially. Ionization process is
different.
• Weak bases form OH– by accepting H+ from water …
NH3 + H2O NH4+ + OH–
CH3NH2 + H2O CH3NH3+ + OH–

methylamine methylammonium ion
Just a little OH– forms.

Most of the weak base remains
in the molecular form.

111
The pH Scale
• Concentration of H3O+ can vary over a wide range in aqueous

solution, from about 10 M to about 10–14 M.
• A more convenient expression for H3O+ is pH.
pH = –log [H3O+] and so [H3O+] = 10–pH
• The “negative logarithm” function of pH is so useful that it has
been applied to other species and constants.
pOH = –log [OH–] and so [OH–] = 10–pOH
pKw = –log Kw
• At 25 °C, pKw = 14.00
• pKw = pH + pOH = 14.00

112
The pH Scale
Since pH is a logarithmic scale,

cola drinks (pH about 2.5) are
about ____ times as acidic as
tomatoes (pH about 4.5)

113
Example 15.5 A Conceptual Example
Is the solution 1.0 x 10–8 M HCl acidic, basic, or neutral?
Analysis and Conclusions

Because the solute is a strong acid, our first thought is that the solution should be
acidic. However, let us check our assumption by calculating the pH:
HCl + H2O ⎯→ H3O+ + Cl–
[H3O+] = 1.0 x 10–8 M and pH = –log[H3O+] = – log(1.0 x 10–8) = 8.00
Because the pH is greater than 7.00, the solution appears to be basic.
A quandary arises here because the HCl(aq) is so dilute that the self-ionization
of water produces more H3O+ than does the strong acid. Still, the total [H3O+] from
the two sources must be somewhat greater than 1.0 x 10–7 M. The pH is therefore
somewhat less than 7.00; the solution is acidic. We conclude that we can generally
ignore the slight self-ionization of water when other ionization processes
predominate. However, we cannot ignore it when the pH is within one unit or so of
pH = 7.
Exercise 15.5A
Is a solution that is 1.0 x 10–8 M NaOH acidic, basic, or neutral? Explain.
Exercise 15.5B
Is a solution formed by mixing 25.0 mL of 1.0 x 10–8 M HCl and 25.0 mL of 1.0 x 10–8 M
NaOH with 25.0 mL of pure water acidic, basic, or neutral? Explain.

114
Example 15.14
Calculate the pH of a solution that is 0.25 M CH3COONa(aq).
Strategy
Acetate ion hydrolyzes as a base, and we just derived a numerical value of Kb for
that hydrolysis. We can use the usual ICE format and Kb = 5.6 x 10–10 to obtain a
quadratic equation that we can solve for [OH–]. The pH of the solution follows
easily from that point.
Solution
We present the data under the equation for the hydrolysis reaction in the usual way.

115
Solution continued
Let us assume that x << 0.25, so that (0.25 – x) = 0.25. Then

116
3.7. Chemical Equilibrium

11
7
Dynamic Nature of Equilibrium
When a system reaches equilibrium, the forward and reverse
reactions continue to occur … but at equal rates.
We are usually concerned

with the situation after
equilibrium is reached.
After equilibrium the concentrations of reactants and

products remain constant.
11
8
The Equilibrium Constant Expression
For the general reaction:
aA + bB → gG + hH
Each concentration is
The equilibrium expression is: simply raised to the
power of its coefficient
[G]g[H]h
Products in
Kc = numerator.
[A]a[B]b
Reactants in
denominator.

11
Example 14.1 9
If the equilibrium concentrations of Cl2 and COCl2 are the same at 395 °C, find the
equilibrium concentration of CO in the reaction
Strategy
When asked to determine the concentration of a substance involved in a reversible
reaction at equilibrium, we must write the equilibrium constant expression, enter
the data given, and solve for the unknown concentration.
Solution
Because [Cl2] equals [COCl2] in the
equilibrium mixture at 395 °C, these two
terms cancel in the equilibrium constant
expression.
We can then solve this expression for [CO].

Assessment
This purely algebraic solution leads to the conclusion that there is only one possible
value of [CO] for the condition of equal concentrations of Cl2 and COCl2,
regardless of what those concentrations are.

12
0
The Condition of Equilibrium
• The kinetics view:

Kc = (forward rate)/(reverse rate) = kf/kr
• The thermodynamics view:

– The equilibrium constant can be related to other
fundamental thermodynamic properties and is called
the thermodynamic equilibrium constant, Keq.
– The thermodynamic equilibrium constant expression
uses dimensionless quantities known as activities in
place of molar concentrations.

12
1
Modifying the Chemical Equation
Consider the reaction: 2 NO(g) + O2(g) 2 NO2(g)

[NO2]2
Kc = ––––––––– = 4.67 x 1013 (at 298 K)
[NO]2 [O2]
Now consider the reaction: 2 NO2(g) 2 NO(g) + O2(g)
What will be the equilibrium constant K'c for the new reaction?
[NO]2 [O2] 1 1 1
K'c = ––––––––– = ––––––––––– = –– = ––––––––– = 2.14 x 10–14
[NO2]2 [NO2]2 Kc 4.67 x 1013
–––––––––
[NO]2 [O2]

12
2
Modifying the Chemical Equation (cont’d)
• For the reverse reaction, K is the reciprocal of K for the

forward reaction.
• When an equation is divided by two, K for the new
reaction is the square root of K for the original reaction.
• General rule:
– When the coefficients of an equation are multiplied by a
common factor n to produce a new equation, we raise
the original Kc value to the power n to obtain the new
equilibrium constant.
• It should be clear that we must write a balanced chemical
equation when citing a value for Kc.

12
3
Equilibria Involving Gases
• In reactions involving gases, it is often convenient to
measure partial pressures rather than molarities.
• In these cases, a partial pressure equilibrium constant, Kp,
is used.
(PG)g(PH)h
Kp =
(PA)a(PB)b
Kc and Kp are related by: Kp = Kc (RT)Δn(gas)

where Δn(gas) is the change in number of moles of gas as the
reaction occurs in the forward direction.
Δn(gas) = mol gaseous products – mol gaseous reactants

12
4
Example 14.3
Consider the equilibrium between dinitrogen tetroxide and
nitrogen dioxide:
N2O4(g) 2 NO2(g) Kp = 0.660 at 319 K
(a) What is the value of Kc for this reaction? (b) What is the
value of Kp for the reaction 2 NO2(g) N2O4(g)? (c) If
the equilibrium partial pressure of NO2(g) is 0.332 atm,
what is the equilibrium partial pressure of N2O4(g)?

12
Example 14.3 continued 5
Solution
(a) To find Kc we will use
Equation (14.3), which relates Kc
and Kp.
For this reaction, ∆ngas is equal

to the difference between the
number of moles of NO2 and
of N2O4 in the balanced
equation.
We can now solve for Kc by

using the known values of Kp,
T, and R.
(b) The constant Kp for the

reaction specified in this part
is the inverse of the Kp value
for the reaction initially
given. We therefore must
invert the known value
(0.660).

12
Solution continued
(c) To find the partial pressure of
N2O4(g), we can use either the
original Kp expression or the one
derived in part (b). Here we use
the original one and substitute in
the equilibrium partial pressure
of NO2 .
Assessment
Note that in parts (a) and (b) we did not substitute units into the equilibrium
constant expressions; we were seeking the values of Kc and Kp, which are
dimensionless quantities. In part (c), we started with a dimensionless quantity (Kp),
but we did show a unit in our final result (0.167 atm) because the value Kp = 0.660
is valid only if the pressure unit used for the gases is atmospheres.
Exercise 14.3A
Given Kc = 1.8 × 10–6 for the reaction
at 457 K, determine the value of Kp at 457 K for the reaction
Exercise 14.3B
For the reaction
What is Kc at 900 K for the reaction

12
7
Equilibria Involving Pure
Solids and Liquids
• The equilibrium constant expression does not include
terms for pure solid and liquid phases because their
concentrations do not change in a reaction.
• Although the amounts of pure solid and liquid phases
change during a reaction, these phases remain pure and
their concentrations do not change.
Example: CaCO3(s) CaO(s) + CO2(g)
[CaO] [CO2]
Kc = –––––––––– Kc = [CO2]
[CaCO3]

12
8
Equilibrium Constants: When Do We
Need Them and When Do We Not?
• A very large numerical value of Kc or Kp signifies that a
reaction goes (essentially) to completion.
• A very small numerical value of Kc or Kp signifies that the
forward reaction, as written, occurs only to a slight extent.
• An equilibrium constant expression applies only to a
reversible reaction at equilibrium.
• Although a reaction may be thermodynamically favored, it
may be kinetically controlled …
• Thermodynamics tells us “it’s possible (or not)”
• Kinetics tells us “it’s practical (or not)”

12
9
The Reaction Quotient, Q
• For nonequilibrium conditions, the expression having the

same form as Kc or Kp is called the reaction quotient, Qc
or Qp.
• The reaction quotient is not constant for a reaction, but is
useful for predicting the direction in which a net change
must occur to establish equilibrium.
• To determine the direction of net change, we compare
the magnitude of Qc to that of Kc.

13
0
The Reaction Quotient, Q
When Q is smaller
than K, the
denominator of Q is
too big; we have “too
much reactants.”
When Q = K,
equilibrium has been
reached.
When Q is larger
than K, the
numerator of Q is
too big; we have “too
much products.”

13
1
Le Châtelier’s Principle
• When any change in concentration,

temperature, pressure, or volume is
imposed on a system at equilibrium, the
system responds by attaining a new
equilibrium condition that minimizes the
impact of the imposed change.

13
2
Changing the Amounts of
Reacting Species
• At equilibrium, Q = Kc.
• If the concentration of one of the reactants is increased,
the denominator of the reaction quotient increases.
• Q is now less than Kc.
• This condition is only temporary, however, because the
concentrations of all species must change in such a way so
as to make Q = Kc again.
• In order to do this, the concentrations of the products
increase; the equilibrium is shifted to the right.

13
3
Example 14.7
Water can be removed from an equilibrium mixture in the
reaction of 1-octanol and acetic acid, for example, by
using a solid drying agent that is insoluble in the reaction
mixture. Describe how the removal of a small quantity of
water affects the equilibrium.
H+
CH3(CH2)6CH2OH(soln) + CH3COOH(soln)
CH3(CH2)6CH2OCOCH3(soln) + H2O(soln)
Solution
As water is removed, the reverse reaction is slowed and the forward, water-forming
reaction is stimulated. Not all of the water that is removed can be replaced, however,
because a new equilibrium could not tolerate a constant concentration of H2O at the same
time that the other three concentrations change. Thus, in the new equilibrium the amount
of water is somewhat less than in the original equilibrium, the amount of octyl acetate is
greater, and the amounts of both 1-octanol and acetic acid are less.

13
4
Temperature Changes and Catalysis
• Raising the temperature of an equilibrium mixture shifts
equilibrium in the direction of the endothermic reaction;
lowering the temperature shifts equilibrium in the direction
of the exothermic reaction.
– Consider heat as though it is a product of an exothermic reaction
or as a reactant of an endothermic reaction, and apply Le
Châtelier’s principle.
• A catalyst lowers the activation energy … of both the
forward and the reverse reaction.
• Adding a catalyst does not affect an equilibrium state.
• A catalyst merely causes equilibrium to be achieved faster.

13
5
Example 14.8
An equilibrium mixture of O2(g), SO2(g), and SO3(g) is
transferred from a 1.00-L flask to a 2.00-L flask. In which
direction does a net reaction proceed to restore
equilibrium? The balanced equation for the reaction is
2 SO3(g) 2 SO2(g) + O2(g)
Solution
Transferring the mixture to a larger flask increases the volume to
be filled with molecules. We expect the equilibrium to shift in
the direction that produces the larger number of moles of gas—in
this case, the forward reaction. Some of the SO3(g) is converted
to SO2(g) and O2(g), and equilibrium shifts to the right.

13
6
Determining Values of Equilibrium
Constants Experimentally
• When initial amounts of one or more species, and
equilibrium amounts of one or more species, are given, the
amounts of the remaining species in the equilibrium state
and, therefore, the equilibrium concentrations often can be
established.
• A useful general approach is to tabulate under the chemical
equation:
– the concentrations of substances present initially
– changes in these concentrations that occur in reaching equilibrium
– the equilibrium concentrations.
• This sort of table is sometimes called an “ICE” table:
Initial/Change/Equilibrium.

13
7
Calculating Equilibrium Quantities
from Kc and Kp Values
• When starting with initial reactants and no products and
with the known value of the equilibrium constant, these
data are used to calculate the amount of substances present
at equilibrium.
• Typically, an ICE table is constructed, and the symbol x is
used to identify one of the changes in concentration that
occurs in establishing equilibrium.
• Then, all the other concentration changes are related to x,
the appropriate terms are substituted into the equilibrium
constant expression, and the equation solved for x.

13
Example 14.14 8
Carbon monoxide and chlorine react to form phosgene, COCl2, which is used in the
manufacture of pesticides, herbicides, and plastics:
How much of each substance, in moles, will there be at equilibrium in a reaction mixture
that initially has 0.0100 mol CO, 0.0100 mol Cl2, and 0.100 mol COCl2 in a 10.0-L flask?
Strategy
Because all reactant and products are present initially, it is not immediately obvious
in which direction a net change will occur to establish equilibrium. We can easily
find out, though, by evaluating the reaction quotient Qc for the initial concentrations
and comparing it with Kc. Knowing the direction of net change will help us to choose
an appropriate quantity to represent as x. Once we have done this, the calculation is
very much as in previous examples.
Solution
Let us first
determine
the initial
concentrations
and evaluate Qc.

13
Solution continued
Because Qc > Kc
(that is, 1.00 × 104
> 1.2 × 103), a net
reaction must
occur in the
reverse direction,
which means that
at equilibrium
the concentrations
of CO and Cl2 will
be greater than
initially and the
concentration of
COCl2 will be less.
Now we are ready
to calculate the
equilibrium
concentrations.
At this point, we
substitute the
equilibrium
concentrations into
the equilibrium
constant expression
and simplify.
14
Solution continued
Now let us put the
equation into the
quadratic form:
ax2 + bx + c = 0.
From this form, we use
the quadratic formula to
solve for x.
Only one of the two

possible roots to this
quadratic equation is
acceptable—the
positive root.
We can now calculate

the equilibrium
concentrations.
To determine the
equilibrium amounts,
we multiply the
equilibrium
concentration of each
species by the volume
of the equilibrium
mixture.
141
3.8. Solubility Product Constants

142
The Solubility Product Constant, Ksp
• Many important ionic compounds are only slightly soluble

in water (we used to call them “insoluble” – Chapter 4).
• An equation can represent the equilibrium between the
compound and the ions present in a saturated aqueous
solution:
BaSO4(s) Ba2+(aq) + SO42–(aq)
• Solubility product constant, Ksp: the equilibrium constant

expression for the dissolving of a slightly soluble solid.
Ksp = [ Ba2+ ][ SO42–]

143

144
Example 16.1
Write a solubility product constant expression for
equilibrium in a saturated aqueous solution of the
slightly soluble salts (a) iron(III) phosphate, FePO4,
and (b) chromium(III) hydroxide, Cr(OH)3.
Solution

145
Ksp and Molar Solubility

• Ksp is an equilibrium constant
• Molar solubility is the number of moles of compound that
will dissolve per liter of solution.
• Molar solubility is related to the value of Ksp, but molar
solubility and Ksp are not the same thing.
• In fact, “smaller Ksp” doesn’t always mean “lower molar
solubility.”
• Solubility depends on both Ksp and the form of the
equilibrium constant expression.

146
Example 16.2
At 20 °C, a saturated aqueous solution of silver carbonate
contains 32 mg of Ag2CO3 per liter of solution. Calculate
Ksp for Ag2CO3 at 20 °C. The balanced equation is
Ag2CO3(s) 2 Ag+(aq) + CO32–(aq) Ksp = ?
Solution
+ 2–
From the equation for the solubility equilibrium, we see that 2 mol Ag and 1 mol CO3
appear in solution for every 1 mol Ag2CO3 that dissolves. We can represent this fact by
conversion factors (shown in blue).
+ 2 2– –4 2 –4 –12
Ksp = [Ag ] [CO3 ] = (2.3 x 10 ) (1.2 x 10 ) = 6.3 x 10

147
The Common Ion Effect

in Solubility Equilibria
• The common ion effect affects solubility

equilibria as it does other aqueous
equilibria.
• The solubility of a slightly soluble ionic
compound is lowered when a second solute
that furnishes a common ion is added to the
solution.

148
Example 16.5
Calculate the molar solubility of Ag2SO4 in 1.00 M
Na2SO4(aq).
Solution
2–
We can tabulate the relevant data, including the already present 1.00 mol SO4 /L, in the
ICE format introduced in Chapter 14.
+ 2 2–
The equilibrium concentrations from the Ksp = [Ag ] [SO4 ]
ICE table must satisfy the Ksp expression. –5 2
1.4 x 10 = (2s) (1.00 + s)
2 –5
To simplify the equation, let us assume (2s) (1.00) = 1.4 x 10
that s is much smaller than 1.00 M, so that 2
4s = 1.4 x 10
–5
(1.00 + s) ≈ 1.00.
2 –6
We obtain our final result by solving for s. s = 3.5 x 10
–6 1/2
s = molar solubility = (3.5 x 10 )
–3
= 1.9 x 10 mol Ag2SO4/L
149
Solubility and Activities

• Ions that are not common to the precipitate can also affect
solubility.
– CaF2 is more soluble in 0.010 M Na2SO4 than it is in
water.
• Increased solubility occurs because of interionic
attractions.
• Each Ca2+ and F– is surrounded by ions of opposite charge,
which impede the reaction of Ca2+ with F–.
• The effective concentrations, or activities, of Ca2+ and F–
are lower than their actual concentrations.

150
Will Precipitation Occur? Is It

Complete?
• Qip is the ion product reaction quotient and is based on

initial conditions of the reaction.
Qip and Qc: new look,
same great taste!
• Qip can then be compared to Ksp (molar solubility).
• Precipitation should occur if Qip > Ksp.
• Precipitation cannot occur if Qip < Ksp.
• A solution is just saturated if Qip = Ksp.
• In applying the precipitation criteria, the effect of dilution
when solutions are mixed must be considered.

151
Example 16.6
If 1.00 mg of Na2CrO4 is added to 225 mL of 0.00015 M
AgNO3, will a precipitate form?
Ag2CrO4(s) 2 Ag+(aq) + CrO42–(aq) Ksp = 1.1 x 10–12
Solution
+ –4
Step 1: Initial concentrations of ions: The initial concentration of Ag is simply 1.5 x 10
2– 2–
M. To establish CrO4 , we first need to determine the number of moles of CrO4
placed in solution.
2–
We then determine [CrO4 ] in the 225 mL (0.225 L) of solution that contains 6.17
–6 2–
x 10 mol CrO4 .
Step 2: Evaluation of Qip:

+ 2 2– –4 2 –5 –13
Qip = [Ag ]initial [CrO4 ]initial = (1.5 x 10 ) (2.74 x 10 ) = 6.2 x 10

152
Step 3: Comparison of Qip and Ksp:

Qip = 6.2 x 10–13 is less than Ksp = 1.1 x 10–12
Because Qip < Ksp, we conclude that no
precipitation occurs.

153
3.9. Chemical Kinetics

154
Chemical Kinetics: A Preview
• Chemical kinetics is the study of:

– the rates of chemical reactions
– factors that affect these rates
– the mechanisms by which reactions occur
• Reaction rates vary greatly – some are very
fast (burning, precipitation) and some are
very slow (rusting, disintegration of a
plastic bottle in sunlight).

155
Variables in Reaction Rates
• Concentrations of reactants: Reaction rates generally

increase as the concentrations of the reactants are
increased.
• Temperature: Reaction rates generally increase rapidly as
the temperature is increased.
• Surface area: For reactions that occur on a surface rather
than in solution, the rate increases as the surface area is
increased.
• Catalysts: Catalysts speed up reactions and inhibitors slow
them down.

156
The Meaning of Rate

• The rate of a reaction is the change in concentration of a
product per unit of time (rate of formation of product).
• Rate is also viewed as the negative of the change in
concentration of a reactant per unit of time (rate of
disappearance of reactant).
• The rate of reaction often has the units of moles per liter
per unit time (mol L–1 s–1 or M s–1)
rate of disappearance of reactant

or of formation of product
General rate of reaction =
stoichiometric coefficient of that reactant
or product in the balanced equation

157
Example 13.1
Consider the hypothetical reaction
A+2BÆ3C+2D
Suppose that at one point in the reaction, [A] = 0.4658 M
and 125 s later [A] = 0.4282 M. During this time period,
what is the average (a) rate of reaction expressed in M s–1
and (b) rate of formation of C, expressed in M min–1.
Solution
(a) The rate of reaction is equal
to the negative of the rate
of disappearance of A. The
rate of disappearance of A
is equal to the difference in
concentrations at times
1 and 2, divided by
∆t = t2 – t1. We substitute
the relevant data into
Equation (13.1).

158
Example 13.1
Consider the hypothetical reaction
A+2BÆ3C+2D
Suppose that at one point in the reaction, [A] = 0.4658 M
and 125 s later [A] = 0.4282 M. During this time period,
what is the average (a) rate of reaction expressed in M s–1
and (b) rate of formation of C, expressed in M min–1.
Solution continued
(b) Three moles of C are
formed for every mole of
A that disappears. To
express the rate in M min–1
we use the conversion
factor 60 s/1 min.

159
The Rate Law
Rate = k[A]1 = k[A] Reaction is first order in A
Rate = k[A]2 Reaction is second order in A
Rate = k[A]3 Reaction is third order in A

If we triple the
concentration of A in a
second-order reaction,
the rate increases by a
factor of ________.
160
First-Order Reactions
• In a first-order reaction, the exponent in the rate law is 1.
• Rate = k[A]1 = k[A]
• The integrated rate law describes the concentration of a
reactant as a function of time. For a first-order process:
[A]t
ln = –kt
[A]0 Look! It’s an
ln [A]t – ln [A]0 = –kt equation for a
straight line!
ln [A]t = –kt + ln [A]0
• At times, it is convenient to replace molarities in an
integrated rate law by quantities that are proportional to
concentration.
161
Half-life of a Reaction
• The half-life (t½) of a reaction is the time required for one-
half of the reactant originally present to be consumed.
• At t½, [A]t = ½[A]0, and for a first order reaction:
½[A]0
ln = –kt½
[A]0
ln (½) = –kt½
–0.693 = –kt½
t½ = 0.693/k
• Thus, for a first-order reaction, the half-life is a constant; it
depends only on the rate constant, k, and not on the
concentration of reactant.

162
Example 13.5
Use data from Figure 13.7 to evaluate the (a) half-life and (b) rate
constant for the first-order decomposition of N2O5 at 67 °C.
Analysis and Conclusions

(a) When the molarity of N2O5 drops to one-half its initial value, also
drops to one-half its initial value because partial pressure and molarity are
proportional. As the pressure drops from 800 mmHg to 400 mmHg,
one-half the N2O5 originally present is consumed. This occurs in about
120 s, thus t 1/2 ≈ 120 s. The pressure drops to 200 mmHg at about 240 s:
2 x t1/2 ≈ 240 s. Again, t1/2 ≈ 120s, confirming that the decomposition of N2O5
is first order.
(b) We determine the rate constant k using t = 120 s in Equation (13.9).

163
A Zero-Order Reaction
rate = k[A]0
=k
Rate is independent of
initial concentration

164
Second-Order Reactions
• A reaction that is second order in a reactant has a rate law in
which the exponent for that reactant is 2.
Rate = k[A]2
What do we plot
• The integrated rate law has the form: vs. time to get a
1 1 straight line?
–––– = kt + ––––
[A]t [A]0
• The half-life of a second-order reaction depends on the initial

concentration as well as on the rate constant k:
1
t½ = –––––
k[A]0

165
Effect of Temperature on
the Rates of Reactions
• In 1889, Svante Arrhenius proposed the
following expression for the effect of
temperature on the rate constant, k:
• k = A e–Ea/RT
• The constant A, called the frequency factor, is an expression of
collision frequency and orientation; it represents the number of
collisions per unit time that are capable of leading to reaction.
• The term e–Ea/RT represents the fraction of molecular collisions
sufficiently energetic to produce a reaction.

166
Example 13.9
Estimate a value of k at 375 K for the decomposition of
dinitrogen pentoxide illustrated in Figure 13.15, given that
k = 2.5 x 10–3 s–1 at 332 K.
Solution
We know k1, T1, and T2 from k1 = 2.5 x 10–3 s–1 T1 = 332 K T2 = 375 K
the problem statement, and
Ea = 1.0 x 105 J mol–1 and R = 8.3145 J mol–1 K–1
the legend to Figure 13.15
gives us our Ea value. The k2 = ?
rate constant at T2 is
unknown.
We substitute our known

information into the Arrhenius
equation and solve for the
unknown rate constant.

167
Catalysis
• A catalyst increases the reaction rate without itself
being used up in a chemical reaction.
• In general, a catalyst works by changing the
mechanism of a chemical reaction.
• Often the catalyst is consumed in one step of the
mechanism, but is regenerated in another step.
• The pathway of a catalyzed reaction has a lower
activation energy than that of an uncatalyzed
reaction, so more molecules at a fixed temperature
have the necessary activation energy.

168
3.10. Chemical Thermodynamics &

Thermochemistry

16
9
Thermochemistry: Basic Terms
• Thermochemistry is the study of

energy changes that occur during
chemical reactions.
• System: the part of the universe being
studied.
• Surroundings: the rest of the
universe.
Prentice Hall © 2005 Chapter Six

17
0
Types of Systems
• Open: energy and
matter can be
exchanged with the
surroundings.
• Closed: energy can
be exchanged with
the surroundings,
matter cannot.
• Isolated: neither
energy nor matter
After the lid of the jar
can be exchanged A closed system; is unscrewed, which
with the energy (not matter) kind of system is it?
surroundings. can be exchanged.

17
Internal Energy (U) 1
• Internal energy (U) is the total energy

contained within a system
• Part of U is kinetic energy (from
molecular motion)
– Translational motion, rotational motion,
vibrational motion.
– Collectively, these are sometimes called thermal
energy
• Part of U is potential energy
– Intermolecular and intramolecular forces of
attraction, locations of atoms and of bonds.
– Collectively these are sometimes called
chemical energy
17
2
Heat (q)
• Technically speaking,
heat is not “energy.”
• Heat is energy transfer
between a system and its
surroundings, caused by
a temperature difference.
More energetic … transfer energy to
• Thermal equilibrium molecules … less energetic molecules.
occurs when the system
and surroundings reach
the same temperature How do the root-mean-square
and heat transfer stops. speeds of the Ar atoms and the N2
molecules compare at the point of
thermal equilibrium?

17
3
First Law of Thermodynamics
• “Energy cannot be created or destroyed.”

• Inference: the internal energy change of a
system is simply the difference between its
final and initial states:
ΔU = Ufinal – Uinitial
• Additional inference: if energy change

occurs only as heat (q) and/or work (w),
then:
Prentice Hall © 2005 ΔU = q + w Chapter Six
17
4
Example 6.1
A gas does 135 J of work while expanding, and at the
same time it absorbs 156 J of heat. What is the change
in internal energy?
Strategy
The key to getting the correct value of ∆U in Equation (6.7) is to use the correct signs for
the given quantities, w and q. Note that heat is absorbed by the system; this means q is a
positive quantity: q = +156 J. Work is done by the system; this means w is a negative
quantity: w = –135 J.
Solution
We add the values for q and w, each with its correct sign. Note that
because more heat is absorbed than work done, the internal energy
increases.
∆U = q + w = +156 J + (–135 J) = +21 J

17
5
Heats of Reaction (qrxn)
• qrxn is the quantity of heat exchanged between

a reaction system and its surroundings.
• An exothermic reaction gives off heat
– In an isolated system, the temperature increases.
– The system goes from higher to lower energy;
qrxn is negative.
• An endothermic reaction absorbs heat
– In an isolated system, the temperature decreases.
– The system goes from lower to higher energy;
q is positive.
Prentice Hall © 2005rxn Chapter Six
17
Calculations Based on 6
Standard Enthalpies of Formation

ΔH°rxn = Σνp x ΔHf°(products) – Σνr x ΔHf°(reactants)
• The symbol Σ signifies the summation of several terms.
• The symbol ν signifies the stoichiometric coefficient used
in front of a chemical symbol or formula.
• In other words …
1. Add all of the values for ΔHf° of the products.
2. Add all of the values for ΔHf° of the reactants.
3. Subtract #2 from #1
(This is usually much easier than using Hess’s Law!)

17
Example 6.15
7
Synthesis gas is a mixture of carbon monoxide and hydrogen that is
used to synthesize a variety of organic compounds. One reaction for
producing synthesis gas is
3 CH4(g) + 2 H2O(l) + CO2(g) Æ 4 CO(g) + 8 H2(g) ΔH° = ?
Use standard enthalpies of formation from Table 6.2 to calculate the
standard enthalpy change for this reaction.
Solution

The Concept of Entropy
Consider mixing two gases: this occurs
spontaneously, and the gases form a homogeneous
mixture.
There is essentially
no enthalpy change
involved, so why is
the process
spontaneous?
The driving force is a thermodynamic quantity called
entropy, a mathematical concept that is difficult to
portray visually EOS
178
Entropy
The total energy of a system remains unchanged in
the mixing of the gases but the number of
possibilities for the distribution of that energy
increases
This spreading of the

energy and increase of
entropy correspond to a
greater physical disorder
at the microscopic level
EOS
179
The Second Law
of Thermodynamics
The Second Law of Thermodynamics establishes
that all spontaneous or natural processes increase
the entropy of the universe
ΔStotal = ΔSuniverse = ΔSsystem + ΔSsurroundings
In a process, if entropy increases in both the

system and the surroundings, the process is surely
spontaneous
EOS
180
Free Energy Change
The free energy change (ΔG) for a process at
constant temperature and pressure is given by the
Gibbs equation
ΔGsys = ΔHsys – TΔSsys
If ΔG < 0 (negative), a process
is spontaneous.
If ΔG > 0 (positive), a process
is nonspontaneous.
If ΔG = 0, the process is at
equilibrium.
EOS
181
Standard Free Energy Change
The standard free energy change, ΔGo, of a
reaction is the free energy change when reactants
and products are in their standard states
e.g., O2 is a gas, Br2 is liquid, etc. ...
ΔGo = ΔHo – TΔSo
Be mindful of units; H is usually in kJ

and S is in J K–1
EOS
182
Trouton’s Rule
This rule works best with nonpolar substances and
generally fails for liquids with a more ordered
structure, such as those with extensive hydrogen
bonding
EOS
183
Raoult’s Law Revisited
Psolv = xsolv · Posolv
Because the mole fraction of

solvent in a solution (xsolv) is
less than 1, the vapor
pressure of the solvent (Psolv)
in an ideal solution is lower
than that of the pure solvent
(Posolv)
EOS
184
Relationship of ΔGo and Keq
ΔG = 0 is a criterion for equilibrium at a single
temperature, the one temperature at which the
equilibrium state has all reactants and products in
their standard states
ΔG and ΔGo are related through the reaction
quotient, Q
ΔG = ΔGo + RT ln Q
Under the conditions of ΔG = 0 and ΔGo = −RT ln K

eq
Q = Keq, the equation above becomes
EOS
185
Example 17.9
Determine the value of Keq at 25 °C for the reaction
Strategy
Our first task is to obtain a value of ∆G°, which we can do from tabulated standard
free energies of formation in Appendix C. Then we can calculate Keq using Equation
(17.12).
Solution
The standard free energies of formation of N2O4(g) and NO2(g) from Appendix C are
substituted into Equation (17.9).
Next we list the data required for Equation (17.12), first changing the unit of ∆G°
from kJ to J/mol. Then we can rearrange Equation (17.12) to solve for Keq.
186
The Dependence of
ΔG and Keq on Temperature
o
To obtain equilibrium constants at different

temperatures, it will be assumed that ΔH and ΔS
do not change much with temperature
the 25 oC values of ΔHo

ΔGo = ΔHo – TΔSo
and ΔSo along with the
desired temperature are
substituted
EOS
187
The Dependence of
ΔG and Keq on Temperature
o
To obtain Keq at the desired temperature, the

following equation is used …
⎛K ⎞ ⎡ ⎤
ln Keq = ln ⎜ 2 ⎟ =
⎜ ⎟ ΔH o
⎢1 − 1 ⎥
⎢T ⎥
⎜ K1 ⎟ R T
⎝ ⎠ ⎣⎢ 1 2 ⎦⎥
This is the van’t Hoff equation
EOS
188
Equilibrium with Vapor
ΔHo for either sublimation or vaporization is used
depending on the other component
Partial pressures are exchanged for K’s
⎛ P2 ⎞ ΔH vap
o
⎡1 1 ⎤
ln⎜⎜ ⎟⎟ = ⎢T − T ⎥
⎝ P1 ⎠ R ⎣ 1 2⎦
This is the Clausius–Clapeyron equation
EOS
189
Summary of Concepts
• A spontaneous change is one that occurs by
itself without outside intervention
• The third law of thermodynamics states that
the entropy of a pure, perfect crystal at 0 K
can be taken to be zero
• The direction of spontaneous change is that
in which total entropy increases
• The free energy change, ΔG, is equal to –TΔS, and
it applies just to the system itself
EOS
190
Summary (cont’d)
• The standard free energy change, ΔGo, can

be calculated by substituting standard
enthalpies and entropies of reaction and a
Kelvin temperature into the Gibbs equation,
or, by combining standard free energies of
formation
• The condition of equilibrium is one for which ΔG
=0
EOS
191
Summary (cont’d)
• The value of ΔGo is in itself often sufficient
to determine how a reaction will proceed
• Values of ΔGof, ΔHof, and ΔS are generally
tabulated for 25 oC. To obtain values of Keq at
other temperatures, the van’t Hoff equation must
be used
• The Clausius–Clapeyron equation connects
solid/vapor or liquid/vapor equilibria to varying
temperature
EOS
192
193
3.11. Electrochemistry

194
Oxidation–Reduction:
The Transfer of Electrons

195
Half-Reactions
• Review Chapter Four for details of oxidation–reduction

reactions.
• In any oxidation–reduction reaction, there are two half-
reactions:
– Oxidation: a species loses electrons to another species.
– Reduction: a species gains electrons from another
species.

196
Important Electrochemical Terms

• An electrochemical cell consists of two half-cells with the
appropriate connections between electrodes and solutions.
• Two half-cells may be joined by a salt bridge that permits
migration of ions, without completely mixing the solutions.
• The anode is the electrode at which oxidation occurs.
• The cathode is the electrode at which reduction occurs.
• In a voltaic cell, a spontaneous redox reaction occurs and
current is generated.
• Cell potential (Ecell) is the potential difference in volts
between anode and cathode.
• Ecell is the driving force that moves electrons and ions.

197
Cell Diagrams
• A cell diagram is “shorthand” for an electrochemical cell.
• The anode is placed on the left side of the diagram.
• The cathode is placed on the right side.
• A single vertical line ( | ) represents a boundary between
phases, such as between an electrode and a solution.
• A double vertical line ( || ) represents a salt bridge or
porous barrier separating two half-cells.

198
Example 18.3
Describe the half-reactions and the overall reaction that
occur in the voltaic cell represented by the cell diagram:
Pt(s) | Fe2+(aq), Fe3+(aq) || Cl–(aq) | Cl2(g) | Pt(s)
Solution
The half-reactions occur on the surface of the platinum, but because platinum is
inert, other species are involved in the reactions. According to the cell diagram
conventions, the electrode on the left is the anode, where oxidation occurs. In this
case, Fe2+ is oxidized to Fe3+:
Oxidation: Fe2+(aq) ⎯→ Fe3+(aq) + e–
The electrode on the right is the cathode, where reduction occurs, which in this case
means chlorine gas is reduced to chloride ion:
Reduction: Cl2(g) + 2 e– ⎯→ 2 Cl–(aq)
To combine these half-equations into a redox equation, we must multiply the
oxidation half-equation by the factor 2. Then we can add it to the reduction half-
equation, and the electrons will cancel.

F2 is the strongest F– is the weakest 199
oxidizing agent reducing agent
Li is the
strongest
reducing
agent

200
Important Points about
Electrode and Cell Potentials
• Standard electrode potentials and cell voltages are
intensive properties; they do not depend on the total
amounts of the species present.
• A “flashlight battery” (D-cell) and a “penlight battery”
(AA cell) produce the same potential—1.5 volts.
• E° does depend on the particular species in the reaction (or
half-reaction).
• As we shall learn later, cell and electrode potentials can
depend on concentration of the species present.

201
Electrode Potentials, Spontaneous

Change, and Equilibrium
• An electrochemical cell does work.
welec = nFEcell
n = number of electrons in the balanced equation
F = 96,485 coulombs per mole.
• The amount of electrical work is also equal to –ΔG:
ΔG = –nFEcell
• Under standard conditions:

ΔG° = –nFE°cell

202
The Activity Series Revisited
• In the activity series of metals

(Section 4.4), any metal in the
series will displace a metal
below it from a solution of that
metal’s ions.
• Theoretical basis: The activity
series lists metals in order of
their standard potentials.
• Displacement of a metal from a
solution of its ions by a metal
higher in the series corresponds
to a positive value of Ecell and a
spontaneous reaction.

203
Example 18.6
Will copper metal displace silver ion from aqueous solution? That is, does the reaction
Cu(s) + 2 Ag+(1 M) ⎯→ Cu2+(1 M) + 2 Ag(s)
occur spontaneously from left to right?
Strategy
We must separate the overall equation into its two half-equations, assign the
appropriate E° values, and then recombine the half-equations to obtain
If the resulting is positive, then the reaction is spontaneous in the forward
direction.
Solution
Because E°cell is positive, the forward direction should be the direction of

spontaneous change. Copper metal should displace silver ions from solution.

204
Thermodynamics, Equilibrium, and
Electrochemistry: A Summary
From any one of the three
quantities Keq, ΔG°, E°cell, we
can determine the others.

205
Example 18.9
Calculate the expected voltmeter reading for the voltaic
cell pictured in Figure 18.13.

206
Solution
The direction of electron flow shown in Figure 18.13 enables us to identify the
anode and cathode for the standard half-reactions:
Thus, we seek for a voltaic cell in which = +0.431 V, n = 2, and the cell
reaction is
Cu(s) + 2 Fe3+(0.20 M) ⎯→ Cu2+(0.50 M) + 2 Fe2+(0.10 M)
We begin with the Nernst equation (18.8):

207
3.12. Organic Chemistry

208
Alkanes
• Hydrocarbons are molecules that contain only hydrogen and carbon
atoms.
• Alkanes are saturated (have the maximum number of hydrogen atoms
possible for the number of carbon atoms).

209
Alkanes
Isomers are compounds with the

same molecular formula but
different structural formulas.
Alkane molecules with ring

structures are named with the
prefix cyclo- and are called
cycloalkanes.
210
Propane, used in gas grills,

is an alkane with three
carbon atoms
Butyric acid, which gives

rancid butter its “fragrance,”
contains four carbon atoms.
Octane, a component of
gasoline, is a(n) ______ which
contains _____ carbon atoms.

211
Hydrocarbons
• Alkanes, or saturated hydrocarbons, have the general
formula CnH2n+2. All the bonds between carbon atoms are
single bonds.
• Alkenes have one or more double bonds between carbon
atoms. Those with one double bond have the general
formula CnH2n.
• Alkynes have one or more triple bonds between carbon
atoms. Those with one triple bond have the general
formula CnH2n–2.
• Alkenes and alkynes collectively are called unsaturated
hydrocarbons because they do not hold the maximum
possible number of hydrogen atoms for their carbon atoms.
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212
Alkanes
• Alkanes are essentially nonpolar.
• They are largely unreactive toward ionic
compounds as well as aqueous acids, bases,
and oxidizing agents.
• Alkanes do react with oxygen and halogens,
by free-radical mechanisms.
• The reactions with halogens are substitution
reactions: halogen atoms substitute for one
or more hydrogen atoms.
CH4 + Cl2 Æ CH3Cl + HCl
213
Alkenes and Alkynes

• Like alkanes, alkenes and alkynes are essentially nonpolar.
• Although the physical properties of alkenes and alkynes are
similar to those of alkanes, the unsaturated compounds are
more reactive than alkanes.
• The pi-electrons in alkenes and alkynes are readily
available to electrophilic reagents that are electron-
deficient.
• Alkenes and alkynes tend to undergo addition reactions in
which atoms add to the double/triple bond.
CH2=CH2 + Cl—Cl Æ ClCH2—CH2Cl
• Halogens, hydrogen halides, water, and other small

molecules can add to the double or triple bond.
214
Exercise
• 1) Name the following compound using the
IUPAC nomenclature system.
• A) 2-bromo-3-ethylbutane
• B) 2-ethyl-3-bromobutane
• C) 3-methyl-4-bromopentane
•Answer: E
• D) 4-bromo-3-methylpentane
• E) 2-bromo-3-methylpentane
215
Exercise
• 2) Name the following compound using the
IUPAC nomenclature system.
• A) 3-methylbutane
• B) pentane
• C) 2-pentane
•Answer: D
• D) 2-methylbutane
• E) isopropylethane
216
Conjugated and Aromatic
Compounds
A structure that has
a series of alternate
double and single
bonds is said to
have a conjugated
bonding system.
Aromatic molecules are cyclic (consist of rings of atoms) and

are planar. They contain a set number of delocalized pi-
electrons.
BENZENE:
217
Example 23.1
Which of the following compounds are aromatic and
which are aliphatic? Explain.
Solution
(a) This compound has six π electrons and a conjugated bonding system, but it is
not cyclic. Like all other open-chain compounds, this one is aliphatic.
(b) This compound has six π electrons and a cyclic, conjugated bonding system;
it is aromatic.
(c) This compound has 10 π electrons (n = 2; [4 x 2] + 2 = 10) and a cyclic,
conjugated bonding system; it is aromatic.
(d) This compound has a cyclic, conjugated bonding system, but the bonding
system does not extend all the way around the ring and has only four π
electrons. The compound is aliphatic.
218
Functional Groups
• An organic compound contains a hydrocarbon backbone
(largely unreactive).
• The functional group is where most of the reactivity lies.
• The functional group usually has both electron-rich and
electron-poor sites.
219
Alcohols and Ethers
• Alcohols have the general formula R–OH, where R is an

alkyl group and OH is a hydroxyl group.
• Ethers have two hydrocarbon groups joined through an
oxygen atom and have the general formula R–O–R’.
• Alcohols can undergo substitution reactions to replace the
hydroxyl group with such groups as halides.
• Alcohols can also undergo dehydration reactions
(removal of water) to form alkenes.
• Under milder conditions, the same dehydration reactions
produce ethers instead of alkenes.
220
Aldehydes and Ketones

• Aldehydes and ketones can be formed by the oxidation of
alcohols.
• If the OH group of an alcohol is on a terminal carbon
atom, an aldehyde is formed; if the OH group is bonded to
an interior carbon atom, a ketone is produced.
• The C=O group is called a carbonyl group.
• Aldehydes and ketones undergo reactions at the carbonyl
group.
221
Carboxylic Acids, Esters, and
Amides
• The general structure of a carboxylic acid is RCOOH and
the –COOH is called a carboxyl group.
• The most common reactions of carboxylic acids are as
acids.
• The reaction product of a carboxylic acid and an alcohol is
called an ester and has the general formula RCOOR’.
• The reaction product of a carboxylic acid and an amine is
called an amide and has the general formula RCONHR’.
• An important reaction of esters and of amides is
hydrolysis. This reaction converts an ester back to the
alcohol and carboxylic acid, and converts an amide back to
the amine and carboxylic acid.

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1

Prentice Hall © 2005

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Key Terms: Properties

which may be which may be

Elements Compounds Homogeneous Heterogeneous

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3.1. Basic Concepts, Definitions,

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Laws of Chemical Combination

• Law of Conservation of Mass

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Law of Multiple Proportions

When two or more different compounds of the same

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Law of Multiple Proportions (cont’d)

• Compounds I–IV are N2O, N2O3, N2O4, N2O5

• Protons and neutrons are located at the center of

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• Atoms that have the same number of protons but

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• Follow the arrows

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Molecules and Formulas

Compound Molecular formula Empirical formula

Octane C8H18 ????

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Structural Formulas and Models

Ball-and-stick model Space-filling model

Naming Binary Molecular

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Which element is named first?

Begin with boron and follow

Rule of thumb: the element

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Ions and Ionic Compounds

• An atom that either gains or loses electron(s) is

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Ions and Ionic Compounds (cont’d)

Sodium chloride simply consists

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• Group IA metals form ions of 1+ charge.

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3.2. Basic Calculations

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Molecular Masses and

Determining the Formula Mass

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The Mole & Avogadro’s Number

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The Mole and Molar Mass

1 atom Na = 22.99 u 1 mol Na = 22.99 g

1 molecule CO2 = 44.01 u 1 mol CO2 = 44.01 g

1 formula unit KCl = 74.56 u 1 mol KCl = 74.56 g

We can read formulas in terms of

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Mass Percent Composition

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Percentage Composition of Butane

g CO2→ mol CO2 → mol C → g C →%C

g H2O→ mol H2O → mol H → g H →%

Balance the equation: 3Mg (s) + N2 (g) Î Mg3N2 (s)

Magnesium is the limiting reactant (smaller yield of Mg3N2)