10 th

EDITION

CHEMISTRY

Raymond Chang
Williams College
70 Atoms, Molecules, and Ions

The chemical properties of these molecules can be predicted based on the reactivity
of the functional groups. Although the nomenclature of the major classes of organic
compounds and their properties in terms of the functional groups will not be discussed
until Chapter 24, we will frequently use organic compounds as examples to illustrate
chemical bonding, acid-base reactions, and other properties throughout the book.

Key Equation
mass number 5 number of protons 1 number of neutrons
5 atomic number 1 number of neutrons (2.1)

Summary of Facts and Concepts
1. Modern chemistry began with Dalton’s atomic theory,
which states that all matter is composed of tiny, indivis-
ible particles called atoms; that all atoms of the same
element are identical; that compounds contain atoms of
different elements combined in whole-number ratios;
and that atoms are neither created nor destroyed in
chemical reactions (the law of conservation of mass).
2. Atoms of constituent elements in a particular compound
are always combined in the same proportions by mass
(law of definite proportions). When two elements can
combine to form more than one type of compound, the
masses of one element that combine with a fixed mass
of the other element are in a ratio of small whole num-
bers (law of multiple proportions).
3. An atom consists of a very dense central nucleus con-
taining protons and neutrons, with electrons moving
about the nucleus at a relatively large distance from it.
10.
4. Protons are positively charged, neutrons have no charge,
and electrons are negatively charged. Protons and neu-
trons have roughly the same mass, which is about 1840
11.
times greater than the mass of an electron.
5. The atomic number of an element is the number of pro-
tons in the nucleus of an atom of the element; it deter-
mines the identity of an element. The mass number is
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Chapter Summary
the sum of the number of protons and the number of
neutrons in the nucleus.
6. Isotopes are atoms of the same element with the same
number of protons but different numbers of neutrons.
7. Chemical formulas combine the symbols for the con-
stituent elements with whole-number subscripts to show
the type and number of atoms contained in the smallest
unit of a compound.
8. The molecular formula conveys the specific number
and type of atoms combined in each molecule of a com-
pound. The empirical formula shows the simplest ratios
of the atoms combined in a molecule.
9. Chemical compounds are either molecular compounds
(in which the smallest units are discrete, individual mol-
ecules) or ionic compounds, which are made of cations
and anions.
The names of many inorganic compounds can be de-
duced from a set of simple rules. The formulas can be
written from the names of the compounds.
Organic compounds contain carbon and elements like
hydrogen, oxygen, and nitrogen. Hydrocarbon is the
simplest type of organic compound.

Key Words
Acid, p. 65 Atom, p. 43 Chemical formula, p. 55 Halogens, p. 53
Alkali metals, p. 53 Atomic number (Z ), p. 49 Diatomic molecule, p. 53 Hydrate, p. 67
Alkaline earth metals, p. 53 Base, p. 67 Electron, p. 44 Inorganic
Allotrope, p. 55 Beta (b) particles, p. 46 Empirical formula, p. 56 compounds, p. 59
Alpha (a) particles, p. 46 Beta (b) rays, p. 46 Families, p. 51 Ion, p. 54
Alpha (a) rays, p. 46 Binary compound, p. 59 Gamma (g) rays, p. 46 Ionic compound, p. 54
Anion, p. 54 Cation, p. 54 Groups, p. 51 Isotope, p. 49
214 Gases

Key Equations
P 1V 1 5 P 2V 2 (5.2) Boyle’s law. For calculating pressure or
volume changes.
V1 V2
5 (5.4) Charles’s law. For calculating temperature
T1 T2 or volume changes.
P1 P2
5 (5.6) Charles’s law. For calculating temperature
T1 T2 or pressure changes.
V 5 k4n (5.7) Avogadro’s law. Constant P and T.
PV 5 nRT (5.8) Ideal gas equation.
P 1V 1 P 2V 2
5 (5.9) For calculating changes in pressure,
n1T 1 n2T 2 temperature, volume, or amount of gas.
P 1V 1 P 2V 2
5 (5.10) For calculating changes in pressure,
T1 T2 temperature, or volume when n is constant.
Pm
d5 (5.11) For calculating density or molar mass.
RT
ni
Xi 5 (5.13) Definition of mole fraction.
nT
P i 5 X iP T (5.14) Dalton’s law of partial pressures. For
calculating partial pressures.
KE 5 12 mu2 5 CT (5.15) Relating the average kinetic energy of a gas
to its absolute temperature.
3RT
urms 5 (5.16) For calculating the root-mean-square speed
B m
of gas molecules.
r1 m2
5 (5.17) Graham’s law of diffusion and effusion.
r2 B m1
an2
aP 1 b(V 2 nb) 5 nRT (5.18) van der Waals equation. For calculating the
V2 pressure of a nonideal gas.

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Summary of Facts and Concepts Chapter Summary

1. At 25°C and 1 atm, a number of elements and molecular
compounds exist as gases. Ionic compounds are solids
rather than gases under atmospheric conditions.
2. Gases exert pressure because their molecules move
freely and collide with any surface with which they
make contact. Units of gas pressure include millimeters
of mercury (mmHg), torr, pascals, and atmospheres.
One atmosphere equals 760 mmHg, or 760 torr.
3. The pressure-volume relationships of ideal gases are
governed by Boyle’s law: Volume is inversely propor-
tional to pressure (at constant T and n).
4. The temperature-volume relationships of ideal gases
are described by Charles’s and Gay-Lussac’s law: Vol-
ume is directly proportional to temperature (at constant
P and n).
5. Absolute zero (2273.15°C) is the lowest theoretically
attainable temperature. The Kelvin temperature scale
takes 0 K as absolute zero. In all gas law calculations,
temperature must be expressed in kelvins.
6. The amount-volume relationships of ideal gases are de-
scribed by Avogadro’s law: Equal volumes of gases
contain equal numbers of molecules (at the same T
and P).
7. The ideal gas equation, PV 5 nRT, combines the laws
of Boyle, Charles, and Avogadro. This equation de-
scribes the behavior of an ideal gas.
8. Dalton’s law of partial pressures states that each gas in
a mixture of gases exerts the same pressure that it would
if it were alone and occupied the same volume.
 Summary of Facts and Concepts 261

2 percent water by mass. Diluting it with water releases considerable amount of Generations of chemistry students have
been reminded of the safe procedure for
heat to the surroundings. This process is so exothermic that you must never attempt diluting acids by the venerable saying,
to dilute the concentrated acid by adding water to it. The heat generated could “Do as you oughter, add acid to water.”

cause the acid solution to boil and splatter. The recommended procedure is to add
the concentrated acid slowly to the water (while constantly stirring).

Key Equations

¢E 5 q 1 w (6.1) Mathematical statement of the first law of

thermodynamics.
w 5 2P¢V (6.3) Calculating work done in gas expansion or
gas compression.
H 5 E 1 PV (6.6) Definition of enthalpy.
¢H 5 ¢E 1 P¢V (6.8) Calculating enthalpy (or energy) change for a
constant-pressure process.
C 5 ms (6.11) Definition of heat capacity.
q 5 ms¢t (6.12) Calculating heat change in terms of specific heat.
q 5 C¢t (6.13) Calculating heat change in terms of heat capacity.
¢H °rxn 5 o n¢H °f (products) 2 o m¢H °f (reactants)
      (6.18) Calculating standard enthalpy of reaction.
¢H soln 5 U 1 ¢H hydr (6.20) Lattice energy and hydration contributions to heat
of solution.

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Summary of Facts and Concepts Chapter Summary

1. Energy is the capacity to do work. There are many
forms of energy and they are interconvertible. The law
of conservation of energy states that the total amount of
energy in the universe is constant.
2. A process that gives off heat to the surroundings is exo-
thermic; a process that absorbs heat from the surround-
ings is endothermic.
3. The state of a system is defined by properties such as
composition, volume, temperature, and pressure. These
properties are called state functions.
4. The change in a state function for a system depends
only on the initial and final states of the system, and not
on the path by which the change is accomplished. En-
ergy is a state function; work and heat are not.
5. Energy can be converted from one form to another, but it
cannot be created or destroyed (first law of thermodynam-
ics). In chemistry we are concerned mainly with thermal
energy, electrical energy, and mechanical energy, which
is usually associated with pressure-volume work.
6. Enthalpy is a state function. A change in enthalpy DH is
equal to DE 1 PDV for a constant-pressure process.
7. The change in enthalpy (DH, usually given in kilo-
joules) is a measure of the heat of reaction (or any other
process) at constant pressure.
8. Constant-volume and constant-pressure calorimeters
are used to measure heat changes that occur in physical
and chemical processes.
9. Hess’s law states that the overall enthalpy change in a
reaction is equal to the sum of enthalpy changes for in-
dividual steps in the overall reaction.
10. The standard enthalpy of a reaction can be calculated
from the standard enthalpies of formation of reactants
and products.
11. The heat of solution of an ionic compound in water
is the sum of the lattice energy of the compound and
the heat of hydration. The relative magnitudes of
these two quantities determine whether the solution
process is endothermic or exothermic. The heat of di-
lution is the heat absorbed or evolved when a solution
is diluted.
 Summary of Facts and Concepts 311

Key Equations
u 5 ln (7.1) Relating speed of a wave to its wavelength and frequency.
E 5 hn (7.2) Relating energy of a quantum (and of a photon) to the frequency.
c
E5h (7.3) Relating energy of a quantum (and of a photon) to the wavelength.
l
hn 5 KE 1 W (7.4) The photoelectric effect.
1
En 5 2RH a b (7.5) Energy of an electron in the nth state in a hydrogen atom.
n2
1 1
¢E 5 hn 5 RH a 2 b (7.6) Energy of a photon absorbed or emitted as the electron undergoes a transition
n2i n2f from the ni level to the nf level.
h
l5 (7.8) Relating wavelength of a particle to its mass m and velocity u.
mu
h
¢x¢p $ (7.9) Calculating the uncertainty in the position or in the momentum of a particle.
4p

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Summary of Facts and Concepts Chapter Summary

1. The quantum theory developed by Planck successfully
explains the emission of radiation by heated solids. The
quantum theory states that radiant energy is emitted by
atoms and molecules in small discrete amounts (quanta),
rather than over a continuous range. This behavior is
governed by the relationship E 5 hn, where E is the
energy of the radiation, h is Planck’s constant, and n is
the frequency of the radiation. Energy is always emitted
in whole-number multiples of hn (1 hn, 2 hn, 3 hn, . . . ).
2. Using quantum theory, Einstein solved another mys-
tery of physics—the photoelectric effect. Einstein pro-
posed that light can behave like a stream of particles
(photons).
3. The line spectrum of hydrogen, yet another mystery to
nineteenth-century physicists, was also explained by
applying the quantum theory. Bohr developed a
model of the hydrogen atom in which the energy of
its single electron is quantized—limited to certain
energy values determined by an integer, the principal
quantum number.
4. An electron in its most stable energy state is said to be
in the ground state, and an electron at an energy level
higher than its most stable state is said to be in an ex-
cited state. In the Bohr model, an electron emits a pho-
ton when it drops from a higher-energy state (an excited
state) to a lower-energy state (the ground state or an-
other, less excited state). The release of specific amounts
of energy in the form of photons accounts for the lines
in the hydrogen emission spectrum.
5. De Broglie extended Einstein’s wave-particle descrip-
tion of light to all matter in motion. The wavelength of
a moving particle of mass m and velocity u is given by
the de Broglie equation l 5 h/mu.
6. The Schrödinger equation describes the motions and
energies of submicroscopic particles. This equation
launched quantum mechanics and a new era in physics.
7. The Schrödinger equation tells us the possible energy
states of the electron in a hydrogen atom and the prob-
ability of its location in a particular region surrounding
the nucleus. These results can be applied with reason-
able accuracy to many-electron atoms.
8. An atomic orbital is a function (c) that defines the dis-
tribution of electron density (c 2) in space. Orbitals are
represented by electron density diagrams or boundary
surface diagrams.
9. Four quantum numbers characterize each electron in an
atom: the principal quantum number n identifies the
main energy level, or shell, of the orbital; the angular
momentum quantum number / indicates the shape of
the orbital; the magnetic quantum number m/ specifies
the orientation of the orbital in space; and the electron
spin quantum number ms indicates the direction of the
electron’s spin on its own axis.
10. The single s orbital for each energy level is spherical
and centered on the nucleus. The three p orbitals present
at n 5 2 and higher; each has two lobes, and the pairs of
lobes are arranged at right angles to one another. Start-
ing with n 5 3, there are five d orbitals, with more com-
plex shapes and orientations.
11. The energy of the electron in a hydrogen atom is
determined solely by its principal quantum number. In
356 Periodic Relationships Among the Elements
Key Equation
Zeff 5 Z 2 s (8.2) Definition of effective nuclear charge.
Summary of Facts and Concepts
1. Nineteenth-century chemists developed the periodic
table by arranging elements in the increasing order of
their atomic masses. Discrepancies in early versions of
the periodic table were resolved by arranging the ele-
ments in order of their atomic numbers.
2. Electron configuration determines the properties of an
element. The modern periodic table classifies the ele-
ments according to their atomic numbers, and thus also
by their electron configurations. The configuration of
the valence electrons directly affects the properties of
the atoms of the representative elements.
3. Periodic variations in the physical properties of the ele-
ments reflect differences in atomic structure. The metal-
lic character of elements decreases across a period from
metals through the metalloids to nonmetals and in-
creases from top to bottom within a particular group of
representative elements.
4. Atomic radius varies periodically with the arrangement
of the elements in the periodic table. It decreases from
left to right and increases from top to bottom.
Key Words
Amphoteric oxide, p. 353 Diagonal relationship, p. 344
Atomic radius, p. 331 Effective nuclear charge, p. 330 Ionization energy, p. 337
Core electrons, p. 327 Electron affinity, p. 341
Electronic Homework Problems
The following problems are available at www.aris.mhhe.com
if assigned by your instructor as electronic homework.
Quantum Tutor problems are also available at the
same site.
Questions and Problems
Development of the Periodic Table
Review Questions
8.1 Briefly describe the significance of Mendeleev’s peri-
odic table.
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Chapter Summary
5. Ionization energy is a measure of the tendency of an
atom to resist the loss of an electron. The higher the
ionization energy, the stronger the attraction between
the nucleus and an electron. Electron affinity is a mea-
sure of the tendency of an atom to gain an electron. The
more positive the electron affinity, the greater the ten-
dency for the atom to gain an electron. Metals usually
have low ionization energies, and nonmetals usually
have high electron affinities.
6. Noble gases are very stable because their outer ns and
np subshells are completely filled. The metals among
the representative elements (in Groups 1A, 2A, and 3A)
tend to lose electrons until their cations become isoelec-
tronic with the noble gases that precede them in the
periodic table. The nonmetals in Groups 5A, 6A, and 7A
tend to accept electrons until their anions become iso-
electronic with the noble gases that follow them in the
periodic table.
Ionic radius, p. 333 Representative elements, p. 326
Valence electrons, p. 327
Isoelectronic, p. 330
ARIS Problems: 8.5, 8.10, 8.23, 8.25, 8.27, 8.29,
8.31, 8.38, 8.44, 8.46, 8.51, 8.57, 8.58, 8.61, 8.72, 8.77,
8.83, 8.85, 8.91, 8.93, 8.95, 8.98, 8.99, 8.100, 8.102, 8.103,
8.110, 8.114, 8.120, 8.123, 8.125, 8.131.
8.2 What is Moseley’s contribution to the modern peri-
odic table?
8.3 Describe the general layout of a modern periodic
table.
 Electronic Homework Problems 399

Key Equation
DHº 5 ©BE(reactants) 2 ©BE(products) (9.3) Calculating enthalpy change of a
reaction from bond enthalpies.
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Summary of Facts and Concepts Chapter Summary

1. A Lewis dot symbol shows the number of valence elec-
trons possessed by an atom of a given element. Lewis
dot symbols are useful mainly for the representative
elements.
2. The elements most likely to form ionic compounds have
low ionization energies (such as the alkali metals and
the alkaline earth metals, which form cations) or high
electron affinities (such as the halogens and oxygen,
which form anions).
3. An ionic bond is the product of the electrostatic forces
of attraction between positive and negative ions. An
ionic compound consists of a large network of ions in
which positive and negative charges are balanced. The
structure of a solid ionic compound maximizes the net
attractive forces among the ions.
4. Lattice energy is a measure of the stability of an ionic
solid. It can be calculated by means of the Born-Haber
cycle, which is based on Hess’s law.
5. In a covalent bond, two electrons (one pair) are shared
by two atoms. In multiple covalent bonds, two or three
pairs of electrons are shared by two atoms. Some cova-
lently bonded atoms also have lone pairs, that is, pairs
of valence electrons that are not involved in bonding.
The arrangement of bonding electrons and lone pairs in
a molecule is represented by a Lewis structure.
6. Electronegativity is a measure of an atom’s ability to
attract electrons in a chemical bond.
7. The octet rule predicts that atoms form enough covalent
bonds to surround themselves with eight electrons each.
When one atom in a covalently bonded pair donates two
electrons to the bond, the Lewis structure can include
the formal charge on each atom as a means of keeping
track of the valence electrons. There are exceptions to
the octet rule, particularly for covalent beryllium com-
pounds, elements in Group 3A, odd-electron molecules,
and elements in the third period and beyond in the peri-
odic table.
8. For some molecules or polyatomic ions, two or more
Lewis structures based on the same skeletal structure
satisfy the octet rule and appear chemically reasonable.
Taken together, such resonance structures represent the
molecule or ion more accurately than any single Lewis
structure does.
9. The strength of a covalent bond is measured in terms of
its bond enthalpy. Bond enthalpies can be used to esti-
mate the enthalpy of reactions.

Key Words
Bond enthalpy, p. 394
Bond length, p. 376
Born-Haber cycle, p. 369
Coordinate covalent
bond, p. 390
Coulomb’s law, p. 369
Covalent bond, p. 374
Covalent compound, p. 374
Double bond, p. 375
Electronegativity, p. 377
Formal charge, p. 384
Ionic bond, p. 367
Lewis dot symbol, p. 366
Lewis structure, p. 375
Lone pair, p. 374
Multiple bond, p. 375
Octet rule, p. 375
Polar covalent bond, p. 377
Resonance, p. 387
Resonance structure, p. 387
Single bond, p. 375
Triple bond, p. 375

Electronic Homework Problems

The following problems are available at www.aris.mhhe.com Quantum Tutor Problems: 9.16, 9.20, 9.39, 9.40,
if assigned by your instructor as electronic homework. 9.43, 9.44, 9.45, 9.46, 9.48, 9.51, 9.52, 9.53, 9.54,
Quantum Tutor problems are also available at the same site. 9.55, 9.56, 9.61, 9.62, 9.63, 9.64, 9.65, 9.66, 9.73,
9.74, 9.76, 9.78, 9.80, 9.83, 9.85, 9.93, 9.95, 9.98,
ARIS Problems: 9.13, 9.14, 9.15, 9.16, 9.18,
9.99, 9.101, 9.102, 9.103, 9.105, 9.106, 9.109, 9.115,
9.19, 9.26, 9.36, 9.37, 9.39, 9.40, 9.43, 9.44, 9.45, 9.46,
9.117, 9.121, 9.122, 9.125.
9.47, 9.52, 9.54, 9.55, 9.63, 9.65, 9.66, 9.69, 9.71, 9.73,
9.77, 9.79, 9.85, 9.90, 9.105, 9.107, 9.109, 9.111, 9.117,
9.118, 9.120, 9.123, 9.125.

Key Equations
2d sin u 5 nl (11.1) Bragg equation for calculating the distance
between planes of atoms in a crystal lattice.
¢H vap
ln P 5 2 1C (11.2) Clausius-Clapeyron equation for determining
RT DHvap of a liquid.
P1 ¢H vap T1 2 T2
ln 5 a b (11.5) For calculating DHvap, vapor pressure, or
P2 R T 1T 2 boiling point of a liquid.
¢H sub 5 ¢H fus 1 ¢H vap (11.6) Application of Hess’s law.
Summary of Facts and Concepts
1. All substances exist in one of three states: gas, liquid,
or solid. The major difference between the condensed
state and the gaseous state is the distance separating 10.
molecules.
2. Intermolecular forces act between molecules or be-
tween molecules and ions. Generally, these attractive
forces are much weaker than bonding forces. 11.
3. Dipole-dipole forces and ion-dipole forces attract mol-
ecules with dipole moments to other polar molecules
or ions.
4. Dispersion forces are the result of temporary dipole mo- 12.
ments induced in ordinarily nonpolar molecules. The
extent to which a dipole moment can be induced in a
molecule is called its polarizability. The term “van der
Waals forces” refers to dipole-dipole, dipole-induced
dipole, and dispersion forces.
5. Hydrogen bonding is a relatively strong dipole-dipole 13.
interaction between a polar bond containing a hydro-
gen atom and an electronegative O, N, or F atom. Hy-
drogen bonds between water molecules are particularly
strong.
6. Liquids tend to assume a geometry that minimizes sur- 14.
face area. Surface tension is the energy needed to ex-
pand a liquid surface area; strong intermolecular forces
lead to greater surface tension.
7. Viscosity is a measure of the resistance of a liquid to
flow; it decreases with increasing temperature.
8. Water molecules in the solid state form a three-
dimensional network in which each oxygen atom is
covalently bonded to two hydrogen atoms and is 15.
hydrogen-bonded to two hydrogen atoms. This unique
structure accounts for the fact that ice is less dense than
liquid water, a property that enables life to survive under 16.
the ice in ponds and lakes in cold climates.
9. Water is also ideally suited for its ecological role by its
high specific heat, another property imparted by its
strong hydrogen bonding. Large bodies of water are
able to moderate Earth’s climate by giving off and
Summary of Facts and Concepts 503
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Chapter Summary
absorbing substantial amounts of heat with only small
changes in the water temperature.
All solids are either crystalline (with a regular structure
of atoms, ions, or molecules) or amorphous (without a
regular structure). Glass is an example of an amorphous
solid.
The basic structural unit of a crystalline solid is the unit
cell, which is repeated to form a three-dimensional
crystal lattice. X-ray diffraction has provided much of
our knowledge about crystal structure.
The four types of crystals and the forces that hold
their particles together are ionic crystals, held to-
gether by ionic bonding; covalent crystals, covalent
bonding; molecular crystals, van der Waals forces
and/or hydrogen bonding; and metallic crystals, me-
tallic bonding.
A liquid in a closed vessel eventually establishes a dy-
namic equilibrium between evaporation and condensa-
tion. The vapor pressure over the liquid under these
conditions is the equilibrium vapor pressure, which is
often referred to simply as “vapor pressure.”
At the boiling point, the vapor pressure of a liquid
equals the external pressure. The molar heat of vapor-
ization of a liquid is the energy required to vaporize one
mole of the liquid. It can be determined by measuring
the vapor pressure of the liquid as a function of tem-
perature and using the Clausius-Clapeyron equation
[Equation (11.2)]. The molar heat of fusion of a solid is
the energy required to melt one mole of the solid.
For every substance there is a temperature, called the
critical temperature, above which its gas phase cannot
be made to liquefy.
The relationships among the phases of a single sub-
stance are illustrated by a phase diagram, in which each
region represents a pure phase and the boundaries be-
tween the regions show the temperatures and pressures
at which the two phases are in equilibrium. At the triple
point, all three phases are in equilibrium.
 Key Words 545

Key Equations
moles of solute
molality (m) 5 (12.2) Calculating the molality of a solution.
mass of solvent (kg)
c 5 kP (12.3) Henry’s law for calculating solubility of gases.
P1 5 X1P°1 (12.4) Raoult’s law relating the vapor pressure of
a liquid to its vapor pressure in a solution.
¢P 5 X2P°1 (12.5) Vapor pressure lowering in terms of the
concentration of solution.
¢T b 5 K b m (12.6) Boiling-point elevation.
¢T f 5 K f m (12.7) Freezing-point depression.
p 5 MRT (12.8) Osmotic pressure of a solution.
actual number of particles in soln after dissociation
i5 (12.9) Calculating the van’t Hoff factor for an
number of formula units initially dissolved in soln electrolyte solution.

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Summary of Facts and Concepts Chapter Summary

1. Solutions are homogeneous mixtures of two or more
substances, which may be solids, liquids, or gases.
2. The ease of dissolving a solute in a solvent is governed by
intermolecular forces. Energy and the disorder that results
when molecules of the solute and solvent mix to form a
solution are the forces driving the solution process.
3. The concentration of a solution can be expressed as per-
cent by mass, mole fraction, molarity, and molality. The
choice of units depends on the circumstances.
4. Increasing temperature usually increases the solubility
of solid and liquid substances and usually decreases the
solubility of gases in water.
5. According to Henry’s law, the solubility of a gas in a
liquid is directly proportional to the partial pressure of
the gas over the solution.
6. Raoult’s law states that the partial pressure of a sub-
stance A over a solution is equal to the mole fraction
(XA) of A times the vapor pressure (P°A) of pure A. An
ideal solution obeys Raoult’s law over the entire range
of concentration. In practice, very few solutions exhibit
ideal behavior.
7. Vapor-pressure lowering, boiling-point elevation, freezing-
point depression, and osmotic pressure are colligative
properties of solutions; that is, they depend only on the
number of solute particles that are present and not on
their nature.
8. In electrolyte solutions, the interaction between ions
leads to the formation of ion pairs. The van’t Hoff fac-
tor provides a measure of the extent of dissociation of
electrolytes in solution.
9. A colloid is a dispersion of particles (about 1 3 103 pm
to 1 3 106 pm) of one substance in another substance.
A colloid is distinguished from a regular solution by the
Tyndall effect, which is the scattering of visible light by
colloidal particles. Colloids in water are classified as
hydrophilic colloids and hydrophobic colloids.

Key Words
Boiling-point elevation Freezing-point depression Molality, p. 518 Semipermeable
(DTb), p. 531 (DTf), p. 532 Nonvolatile, p. 527 membrane, p. 534
Colligative properties, p. 526 Henry’s law, p. 524 Osmosis, p. 534 Solvation, p. 516
Colloid, p. 541 Hydrophilic, p. 541 Osmotic pressure Supersaturated
Crystallization, p. 514 Hydrophobic, p. 541 (p), p. 534 solution, p. 514
Fractional Ideal solution, p. 529 Percent by mass, p. 517 Unsaturated solution, p. 514
crystallization, p. 522 Ion pair, p. 539 Raoult’s law, p. 527 van’t Hoff factor (i), p. 539
Fractional distillation, p. 529 Miscible, p. 516 Saturated solution, p. 514 Volatile, p. 528
 Key Equations 601

The mathematical treatment of enzyme kinetics is quite complex, even when we

All active sites
know the basic steps involved in the reaction. A simplified scheme is given by the

Rate of product formation

are occupied
following elementary steps: at and beyond
this substrate
k1
ESΔ
k
ES concentration
1

k2
ES ¡ E  P

where E, S, and P represent enzyme, substrate, and product, and ES is the enzyme-
substrate intermediate. It is often assumed that the formation of ES and its decom-
position back to enzyme and substrate molecules occur rapidly and that the rate- [S]
determining step is the formation of product. (This is similar to the formation of HI Figure 13.30 Plot of the rate
discussed on p. 591.) of product formation versus
In general, the rate of such a reaction is given by the equation substrate concentration in an
enzyme-catalyzed reaction.
¢[P]
rate 5
¢t
5 k2[ES]

The concentration of the ES intermediate is itself proportional to the amount of the

substrate present, and a plot of the rate versus the concentration of substrate typically
yields a curve like that shown in Figure 13.30. Initially the rate rises rapidly with
increasing substrate concentration. However, above a certain concentration all the
active sites are occupied, and the reaction becomes zero order in the substrate. In
other words, the rate remains the same even though the substrate concentration
increases. At and beyond this point, the rate of formation of product depends only
on how fast the ES intermediate breaks down, not on the number of substrate mol-
ecules present.

Key Equations
rate 5 k[A]x[B]y (13.1) Rate law expressions. The sum (x 1 y) gives
the overall order of the reaction.
[A]t
ln 5 2kt (13.3) Relationship between concentration and time
[A]0 for a first-order reaction.
ln [A]t 5 2kt 1 ln [A]0 (13.4) Equation for the graphical determination of k
for a first-order reaction.
0.693
t12  (13.6) Half-life for a first order reaction.
k
1 1
5 kt 1 (13.7) Relationship between concentration and time
[A]t [A]0 for a second-order reaction.
k 5 Ae 2 Ea/RT (13.11) The Arrhenius equation expressing the
dependence of the rate constant on activation
energy and temperature.
Ea 1
ln k 5 a2 ba b 1 ln A (13.13) Equation for the graphical determination of
R T activation energy.
k1 Ea T1 2 T2
ln 5 a b (13.14) Relationships of rate constants at two
k2 R T 1T 2 different temperatures.
602 Chemical Kinetics

Media Player
Summary of Facts and Concepts Chapter Summary

1. The rate of a chemical reaction is the change in the con-
centration of reactants or products over time. The rate is
not constant, but varies continuously as concentrations
change.
2. The rate law expresses the relationship of the rate of a
reaction to the rate constant and the concentrations of the
reactants raised to appropriate powers. The rate constant
k for a given reaction changes only with temperature.
3. Reaction order is the power to which the concentration
of a given reactant is raised in the rate law. Overall reac-
tion order is the sum of the powers to which reactant
concentrations are raised in the rate law. The rate law
and the reaction order cannot be determined from the
stoichiometry of the overall equation for a reaction; they
must be determined by experiment. For a zero-order re-
action, the reaction rate is equal to the rate constant.
4. The half-life of a reaction (the time it takes for the
concentration of a reactant to decrease by one-half) can
be used to determine the rate constant of a first-order
reaction.
5. In terms of collision theory, a reaction occurs when
molecules collide with sufficient energy, called the ac-
tivation energy, to break the bonds and initiate the reac-
tion. The rate constant and the activation energy are
related by the Arrhenius equation.
6. The overall balanced equation for a reaction may be the
sum of a series of simple reactions, called elementary
steps. The complete series of elementary steps for a re-
action is the reaction mechanism.
7. If one step in a reaction mechanism is much slower than
all other steps, it is the rate-determining step.
8. A catalyst speeds up a reaction usually by lowering the
value of Ea. A catalyst can be recovered unchanged at
the end of a reaction.
9. In heterogeneous catalysis, which is of great industrial
importance, the catalyst is a solid and the reactants are
gases or liquids. In homogeneous catalysis, the catalyst
and the reactants are in the same phase. Enzymes are
catalysts in living systems.

Key Words
Activated complex, p. 583
Activation energy (Ea), p. 583
Bimolecular reaction, p. 588
Catalyst, p. 594
Chemical kinetics, p. 558
Elementary step, p. 588
Enzyme, p. 599
First-order reaction, p. 570
Half-life (t12 ), p. 575
Intermediate, p. 588
Molecularity of a
reaction, p. 588
Rate constant (k), p. 561 Second-order
Rate-determining step, p. 589 reaction, p. 577
Rate law, p. 565 Termolecular reaction, p. 588
Reaction mechanism, p. 588 Transition state, p. 583
Reaction order, p. 566 Unimolecular
Reaction rate, p. 558 reaction, p. 588

Electronic Homework Problems

The following problems are available at www.aris.mhhe.com ARIS Problems: 13.6, 13.7, 13.8, 13.15, 13.16,
if assigned by your instructor as electronic homework. 13.18, 13.19, 13.25, 13.26, 13.27, 13.37, 13.40, 13.42, 13.47,
Quantum Tutor problems are also available at the 13.51, 13.53, 13.62, 13.65, 13.68, 13.70, 13.74, 13.76, 13.80,
same site. 13.88, 13.90, 13.94, 13.97, 13.105, 13.111, 13.115, 13.122.

Questions and Problems

The Rate of a Reaction 13.2 Distinguish between average rate and instantaneous
Review Questions rate. Which of the two rates gives us an unambigu-
ous measurement of reaction rate? Why?
13.1 What is meant by the rate of a chemical reaction?
What are the units of the rate of a reaction?
 CHEMISTRY
in Action
The Haber Process

K nowing the factors that affect chemical equilibrium has great

practical value for industrial applications, such as the synthe-
sis of ammonia. The Haber process for synthesizing ammonia
100

80

Mole percent of NH3

from molecular hydrogen and nitrogen uses a heterogeneous cat-
alyst to speed up the reaction (see p. 596). Let us look at the
equilibrium reaction for ammonia synthesis to determine whether 60
there are factors that could be manipulated to enhance the yield.
Suppose, as a prominent industrial chemist at the turn of the 40
twentieth century, you are asked to design an efficient procedure
for synthesizing ammonia from hydrogen and nitrogen. Your 20
main objective is to obtain a high yield of the product while keep-
ing the production costs down. Your first step is to take a careful 0
look at the balanced equation for the production of ammonia: 1000 2000 3000 4000
Pressure (atm)
N2 (g) 1 3H2 (g) Δ 2NH3 (g) ¢H° 5 292.6 kJ/mol
Mole percent of NH3 as a function of the total pressures of the gases at 425°C.
Two ideas strike you: First, because 1 mole of N2 reacts with
3 moles of H2 to produce 2 moles of NH3, a higher yield of NH3 The graph on p. 647 shows that the yield of ammonia increases
can be obtained at equilibrium if the reaction is carried out un- with decreasing temperature. A low-temperature operation (say,
der high pressures. This is indeed the case, as shown by the plot 220 K or 253°C) is desirable in other respects too. The boiling
of mole percent of NH3 versus the total pressure of the reacting point of NH3 is 233.5°C, so as it formed it would quickly con-
system. Second, the exothermic nature of the forward reaction dense to a liquid, which could be conveniently removed from the
tells you that the equilibrium constant for the reaction will de- reacting system. (Both H2 and N2 are still gases at this tempera-
crease with increasing temperature. Thus, for maximum yield of ture.) Consequently, the net reaction would shift from left to right,
NH3, the reaction should be run at the lowest possible temperature. just as desired.

Key Equations
[C]c[D]d
K5 (14.2) Law of mass action. General expression of
[A]a[B]b equilibrium constant.
K P 5 K c (0.0821T) ¢n (14.5) Relationship between KP and Kc.
K c 5 K¿cK–c (14.9) The equilibrium constant for the overall reaction is
given by the product of the equilibrium constants
for the individual reactions.

Media Player
Summary of Facts and Concepts Chapter Summary

1. Dynamic equilibria between phases are called physical
equilibria. Chemical equilibrium is a reversible process
in which the rates of the forward and reverse reactions
are equal and the concentrations of reactants and prod-
ucts do not change with time.
2. For the general chemical reaction
aA 1 bB Δ cC 1 dD
646
the concentrations of reactants and products at equilib-
rium (in moles per liter) are related by the equilibrium
constant expression [Equation (14.2)].
3. The equilibrium constant for gases, KP, expresses the
relationship of the equilibrium partial pressures (in atm)
of reactants and products.
4. A chemical equilibrium process in which all reactants
and products are in the same phase is homogeneous. If
 100 H2 + N2 Reaction
Compressor chamber
NH3 N2 + H2 (catalysts)
80
Mole percent

NH3 + H2 + N2
60

Unreacted Ammonia
40 condenser
H2 + N2

20 Liquid NH3

0
200 300 400 500
Temperature (°C)
The composition (mole percent) of H2 1 N2 and NH3 at equilibrium (for a
certain starting mixture) as a function of temperature.
On paper, then, these are your conclusions. Let us com-
pare your recommendations with the actual conditions in an
industrial plant. Typically, the operating pressures are between
500 atm and 1000 atm, so you are right to advocate high pres-
sure. Furthermore, in the industrial process the NH3 never
reaches its equilibrium value but is constantly removed from
the reaction mixture in a continuous process operation. This
design makes sense, too, as you had anticipated. The only dis-
crepancy is that the operation is usually carried out at about
Storage
tanks
Schematic diagram of the Haber process for ammonia synthesis. The heat
generated from the reaction is used to heat the incoming gases.
500°C. This high-temperature operation is costly and the yield
of NH3 is low. The justification for this choice is that the rate
of NH3 production increases with increasing temperature.
Commercially, faster production of NH3 is preferable even if it
means a lower yield and higher operating cost. For this reason,
the combination of high-pressure, high-temperature conditions
and the proper catalyst is the most efficient way to produce am-
monia on a large scale.

the reactants and products are not all in the same phase,
the equilibrium is heterogeneous. The concentrations of
pure solids, pure liquids, and solvents are constant and
do not appear in the equilibrium constant expression of
a reaction.
5. If a reaction can be expressed as the sum of two or more
reactions, the equilibrium constant for the overall reaction
is given by the product of the equilibrium constants of the
individual reactions.
6. The value of K depends on how the chemical equation
is balanced, and the equilibrium constant for the reverse
of a particular reaction is the reciprocal of the equilib-
rium constant of that reaction.
7. The equilibrium constant is the ratio of the rate constant
for the forward reaction to that for the reverse reaction.
8. The reaction quotient Q has the same form as the equilib-
rium constant, but it applies to a reaction that may not be
at equilibrium. If Q . K, the reaction will proceed from
right to left to achieve equilibrium. If Q , K, the reaction
will proceed from left to right to achieve equilibrium.
9. Le Châtelier’s principle states that if an external stress
is applied to a system at chemical equilibrium, the sys-
tem will adjust to partially offset the stress.
10. Only a change in temperature changes the value of the
equilibrium constant for a particular reaction. Changes
in concentration, pressure, or volume may change the
equilibrium concentrations of reactants and products.
The addition of a catalyst hastens the attainment of
equilibrium but does not affect the equilibrium concen-
trations of reactants and products.

Key Words
Chemical equilibrium, p. 616 Heterogeneous Law of mass action, p. 618 Physical equilibrium, p. 616
Equilibrium constant equilibrium, p. 624 Le Châtelier’s Reaction quotient
(K ), p. 618 Homogeneous principle, p. 638 (Q), p. 632
equilibrium, p. 619
647
 Summary of Facts and Concepts 701

to gain two electrons to complete its octet. This property makes AlCl3 a Lewis acid.
On the other hand, the lone pairs on the oxygen atom in C2H5OC2H5 make the
compound a Lewis base:

What are the formal charges on Al and O in

the product?

(b) Here the Hg21 ion accepts four pairs of electrons from the CN2 ions. Therefore,
Hg21 is the Lewis acid and CN2 is the Lewis base. Similar Problem: 15.92.

Practice Exercise Identify the Lewis acid and Lewis base in the reaction

Co31 (aq) 1 6NH3 (aq) Δ Co(NH3 ) 31

6 (aq)

Key Equations
K w 5 [H 1 ][OH 2] (15.3) Ion-product constant of water.
1
pH 5 2log [H ] (15.4) Definition of pH of a solution.
[H 1 ] 5 102pH (15.5) Calculating H1 ion concentration from pH.
pOH 5 2log [OH 2] (15.7) Definition of pOH of a solution.
2 2pOH
[OH ] 5 10 (15.8) Calculating OH2 ion concentration from pOH.
pH 1 pOH 5 14.00 (15.9) Another form of Equation (15.3).
ionized acid concentration at equilibrium
percent ionization 5 3 100% (15.11)
initial concentration of acid
K aK b 5 K w (15.12) Relationship between the acid and base ionization
constants of a conjugate acid-base pair.

Media Player
Summary of Facts and Concepts Chapter Summary

1. Brønsted acids donate protons, and Brønsted bases ac-
cept protons. These are the definitions that normally
underlie the use of the terms “acid” and “base.”
2. The acidity of an aqueous solution is expressed as its
pH, which is defined as the negative logarithm of the
hydrogen ion concentration (in mol/L).
3. At 25°C, an acidic solution has pH , 7, a basic solu-
tion has pH . 7, and a neutral solution has pH 5 7.
4. In aqueous solution, the following are classified as
strong acids: HClO4, HI, HBr, HCl, H2SO4 (first stage
of ionization), and HNO3. Strong bases in aqueous solu-
tion include hydroxides of alkali metals and of alkaline
earth metals (except beryllium).
5. The acid ionization constant Ka increases with acid
strength. Kb similarly expresses the strengths of bases.
6. Percent ionization is another measure of the strength of
acids. The more dilute a solution of a weak acid, the
greater the percent ionization of the acid.
7. The product of the ionization constant of an acid and
the ionization constant of its conjugate base is equal to
the ion-product constant of water.
8. The relative strengths of acids can be explained qualita-
tively in terms of their molecular structures.
9. Most salts are strong electrolytes that dissociate com-
pletely into ions in solution. The reaction of these
ions with water, called salt hydrolysis, can produce
acidic or basic solutions. In salt hydrolysis, the
conjugate bases of weak acids yield basic solutions,
and the conjugate acids of weak bases yield acidic
solutions.
702 Acids and Bases

10. Small, highly charged metal ions, such as Al31 and Fe31, 12. Lewis acids accept pairs of electrons and Lewis bases
hydrolyze to yield acidic solutions. donate pairs of electrons. The term “Lewis acid” is gen-
11. Most oxides can be classified as acidic, basic, or ampho- erally reserved for substances that can accept electron
teric. Metal hydroxides are either basic or amphoteric. pairs but do not contain ionizable hydrogen atoms.

Key Words
Acid ionization constant Conjugate acid-base Lewis base, p. 697 Strong acid, p. 666
(Ka), p. 671 pair, p. 660 Percent ionization, p. 677 Strong base, p. 667
Base ionization constant Ion-product constant, p. 662 pH, p. 663 Weak acid, p. 667
(Kb), p. 678 Lewis acid, p. 697 Salt hydrolysis, p. 689 Weak base, p. 668

Electronic Homework Problems

The following problems are available at www.aris.mhhe.com ARIS Problems: 15.4, 15.5, 15.6, 15.15, 15.17,
if assigned by your instructor as electronic homework. 15.18, 15.19, 15.23, 15.24, 15.33, 15.35, 15.43, 15.45, 15.47,
Quantum Tutor problems are also available at the 15.53, 15.55, 15.63, 15.74, 15.75, 15.76, 15.79, 15.91, 15.116,
same site. 15.118, 15.123, 15.125, 15.132.

Questions and Problems†

Brønsted Acids and Bases (d) H2PO2 22 32 2 22
4 , (e) HPO4 , (f) PO4 , (g) HSO4 , (h) SO4 ,
Review Questions 22
(i) SO3 .
15.1 Define Brønsted acids and bases. Give an example of 15.7 Oxalic acid (H2C2O4) has the following structure:
a conjugate pair in an acid-base reaction.
OPCOOH
15.2 In order for a species to act as a Brønsted base, an A
atom in the species must possess a lone pair of elec- OPCOOH
trons. Explain why this is so.
An oxalic acid solution contains the following spe-
cies in varying concentrations: H2C2O4, HC2O42,
Problems
C2O422, and H1. (a) Draw Lewis structures of HC2O2 4,
15.3 Classify each of the following species as a Brønsted and C2O422. (b) Which of the above four species can
acid or base, or both: (a) H2O, (b) OH2, (c) H3O1, act only as acids, which can act only as bases, and
(d) NH3, (e) NH1 2 2
4 , (f ) NH2 , (g) NO3 , (h) CO3 ,
22
which can act as both acids and bases?
(i) HBr, ( j) HCN. 15.8 Write the formula for the conjugate base of each
15.4 Write the formulas of the conjugate bases of the of the following acids: (a) CH2ClCOOH, (b) HIO4,
following acids: (a) HNO2, (b) H2SO4, (c) H2S, (c) H3PO4, (d) H 2PO 2 22
4 , (e) HPO 4 , (f) H 2 SO 4 ,
(d) HCN, (e) HCOOH (formic acid).
2
(g) HSO4 , (h) HIO3, (i) HSO 3 , ( j) NH 1
2
4 , (k) H2S,
15.5 Identify the acid-base conjugate pairs in each of the (l) HS2, (m) HClO.
following reactions:
(a) CH 3COO2 1 HCN Δ CH 3COOH 1 CN2
The Acid-Base Properties of Water
(b) HCO 2 2 Review Questions
3 1 HCO 3 Δ H 2 CO 3 1 CO 3
22

2 1
(c) H 2PO 4 1 NH 3 Δ HPO 4 1 NH 4 22
15.9 What is the ion-product constant for water?
(d) HClO 1 CH 3NH 2 Δ CH 3NH 1 3 1 ClO
2
15.10 Write an equation relating [H1] and [OH2] in solu-
(e) CO 23 2 1 H 2O Δ HCO 2 3 1 OH
2 tion at 25°C.
15.6 Write the formula for the conjugate acid of each of 15.11 The ion-product constant for water is 1.0 3 10214 at
the following bases: (a) HS2, (b) HCO2 22
3 , (c) CO3 ,
25°C and 3.8 3 10214 at 40°C. Is the forward process
H2O(l) Δ H1 (aq) 1 OH2 (aq)
†
Unless otherwise stated, the temperature is assumed to be 258C. endothermic or exothermic?
756 Acid-Base Equilibria and Solubility Equilibria

Figure 16.13 Left to right: Flame colors of lithium, sodium, potassium, and copper.

Figure 16.14 A flow chart for

the separation of cations in Solution containing ions
qualitative analysis. of all cation groups

+HCl Group 1 precipitates

Filtration AgCl, Hg2Cl2, PbCl2

Solution containing ions

of remaining groups

+H2S Group 2 precipitates

Filtration CuS, CdS, HgS, SnS, Bi2S3

Solution containing ions

of remaining groups

+NaOH Group 3 precipitates

CoS, FeS, MnS, NiS
Filtration ZnS, Al(OH)3, Cr(OH)3

Solution containing ions

of remaining groups

+Na2CO3 Group 4 precipitates

Filtration BaCO3, CaCO3, SrCO3

Solution contains
Na+, K+, NH +4 ions

Key Equations
pKa 5 2log Ka (16.3) Definition of pKa.
[conjugate base]
pH 5 pK a 1 log (16.4) Henderson-Hasselbalch equation.
[acid]

Summary of Facts and Concepts
1. The common ion effect tends to suppress the ionization
of a weak acid or a weak base. This action can be ex-
plained by Le Châtelier’s principle.
2. A buffer solution is a combination of either a weak acid
and its weak conjugate base (supplied by a salt) or a
weak base and its weak conjugate acid (supplied by a
salt); the solution reacts with small amounts of added
acid or base in such a way that the pH of the solution
remains nearly constant. Buffer systems play a vital
role in maintaining the pH of body fluids.
3. The pH at the equivalence point of an acid-base titration
depends on hydrolysis of the salt formed in the neutral-
ization reaction. For strong acid–strong base titrations,
the pH at the equivalence point is 7; for weak acid–
strong base titrations, the pH at the equivalence point is
greater than 7; for strong acid–weak base titrations, the
pH at the equivalence point is less than 7.
4. Acid-base indicators are weak organic acids or bases
that change color near the equivalence point in an acid-
base neutralization reaction.
Key Words
Buffer solution, p. 717 End point, p. 732
Common ion effect, p. 714 Formation constant (Kf),
Complex ion, p. 749 p. 749
Electronic Homework Problems
The following problems are available at www.aris.mhhe.com
if assigned by your instructor as electronic homework.
Quantum Tutor problems are also available at the same site.
Questions and Problems†
The Common Ion Effect
Review Questions
16.1 Use Le Châtelier’s principle to explain how the com-
mon ion effect affects the pH of a solution.
16.2 Describe the effect on pH (increase, decrease, or no
change) that results from each of the following addi-
tions: (a) potassium acetate to an acetic acid solu-
tion; (b) ammonium nitrate to an ammonia solution;
†
The temperature is assumed to be 258C for all the problems.
Questions and Problems 757
Media Player
Chapter Summary
5. The solubility product Ksp expresses the equilibrium be-
tween a solid and its ions in solution. Solubility can be
found from Ksp and vice versa.
6. The presence of a common ion decreases the solubility
of a slightly soluble salt.
7. The solubility of slightly soluble salts containing basic
anions increases as the hydrogen ion concentration in-
creases. The solubility of salts with anions derived from
strong acids is unaffected by pH.
8. Complex ions are formed in solution by the combina-
tion of a metal cation with a Lewis base. The formation
constant Kf measures the tendency toward the forma-
tion of a specific complex ion. Complex ion formation
can increase the solubility of an insoluble substance.
9. Qualitative analysis is the identification of cations and
anions in solution.
Molar solubility, p. 737 Solubility product
Qualitative analysis, p. 754 (Ksp), p. 735
Solubility, p. 737
ARIS Problems: 16.2, 16.5, 16.6, 16.10, 16.17,
16.18, 16.25, 16.28, 16.29, 16.31, 16.42, 16.45, 16.46, 16.50,
16.55, 16.57, 16.59, 16.62, 16.66, 16.67, 16.70, 16.78, 16.83.
(c) sodium formate (HCOONa) to a formic acid
(HCOOH) solution; (d) potassium chloride to a hy-
drochloric acid solution; (e) barium iodide to a hy-
droiodic acid solution.
16.3 Define pKa for a weak acid. What is the relationship
between the value of the pKa and the strength of the
acid? Do the same for a weak base.
16.4 The pKas of two monoprotic acids HA and HB are
5.9 and 8.1, respectively. Which of the two is the
stronger acid?
828 Entropy, Free Energy, and Equilibrium

Key Equations
S 5 k ln W (18.1) Relating entropy to number of microstates.
¢Suniv 5 ¢Ssys 1 ¢Ssurr . 0 (18.4) The second law of thermodynamics
(spontaneous process).
¢Suniv 5 ¢Ssys 1 ¢Ssurr 5 0 (18.5) The second law of thermodynamics
(equilibrium process).
¢S°rxn 5 ©nS°(products)
2 ©mS°(reactants) (18.7) Standard entropy change of a reaction.
G 5 H 2 TS (18.9) Definition of Gibbs free energy.
¢G 5 ¢H 2 T¢S (18.10) Free-energy change at constant temperature.
¢G°rxn 5 ©n¢G°f (products) (18.12) Standard free-energy change of
2 ©m¢G°f (reactants) a reaction.
¢G 5 ¢G° 1 RT ln Q (18.13) Relationship between free-energy
change and standard free-energy change
and reaction quotient.
¢G° 5 2RT ln K (18.14) Relationship between standard free-energy
change and the equilibrium constant.

Media Player
Summary of Facts and Concepts Chapter Summary

1. Entropy is described as a measure of the different ways a
system can disperse its energy. Any spontaneous process
must lead to a net increase in entropy in the universe
(second law of thermodynamics).
2. The standard entropy of a chemical reaction can be calcu-
lated from the absolute entropies of reactants and products.
3. The third law of thermodynamics states that the entropy of
a perfect crystalline substance is zero at 0 K. This law en-
ables us to measure the absolute entropies of substances.
4. Under conditions of constant temperature and pressure,
the free-energy change DG is less than zero for a spon-
taneous process and greater than zero for a nonsponta-
neous process. For an equilibrium process, DG 5 0.
5. For a chemical or physical process at constant
temperature and pressure, DG 5 DH 2 TDS. This
equation can be used to predict the spontaneity of a
process.
6. The standard free-energy change for a reaction, DG°,
can be calculated from the standard free energies of for-
mation of reactants and products.
7. The equilibrium constant of a reaction and the standard
free-energy change of the reaction are related by the
equation DG° 5 2RT ln K.
8. Many biological reactions are nonspontaneous. They
are driven by the hydrolysis of ATP, for which DG° is
negative.

Key Words
Entropy (S), p. 803 Second law of Standard free-energy of Third law of
Free energy (G), p. 815 thermodynamics, p. 808 formation (DG°f ), p. 816 thermodynamics, p. 812
Gibbs free energy Standard entropy of reaction Standard free-energy of
(G), p. 815 (DS°rxn ), p. 809 reaction (DG°rxn ), p. 816

Electronic Homework Problems

The following problems are available at www.aris.mhhe.com ARIS Problems: 18.9, 18.11, 18.12, 18.16, 18.18,
if assigned by your instructor as electronic homework. 18.19, 18.23, 18.24, 18.28, 18.30, 18.38, 18.45, 18.48, 18.52,
Quantum Tutor problems are also available at the same site. 18.54, 18.56, 18.59, 18.60, 18.62, 18.64, 18.73, 18.80.
872 Electrochemistry

From the oxidation half-reaction we see that 1 mol O2 ∞ 4 mol e2. Therefore, the
number of moles of O2 generated is

1 mol O2
0.349 mol e2 3 5 0.0873 mol O2
4 mol e2

The volume of 0.0873 mol O2 at STP is given by

nRT
V5
P
(0.0873 mol) (0.0821 L ? atmyK ? mol) (273 K)
5 5 1.96 L
1 atm

The procedure for hydrogen is similar. To simplify, we combine the first two steps
to calculate the number of moles of H2 generated:

1 mol e2 1 mol H2
3.37 3 104 C 3 3 5 0.175 mol H2
96,500 C 2 mol e2

The volume of 0.175 mol H2 at STP is given by

nRT
V5
P
(0.175 mol) (0.0821 L? atmyK ? mol) (273 K)
5
1 atm
5 3.92 L

Similar problem: 19.49.
Check Note that the volume of H2 is twice that of O2 (see Figure 19.18), which is
what we would expect based on Avogadro’s law (at the same temperature and pressure,
volume is directly proportional to the number of moles of gases).
Practice Exercise A constant current is passed through an electrolytic cell containing
molten MgCl2 for 18 h. If 4.8 3 105 g of Cl2 are obtained, what is the current in amperes?

Key Equations
E°cell 5 E°cathode 2 E°anode (19.1) Calculating the standard emf of a galvanic cell.
¢G 5 2nFEcell (19.2) Relating free-energy change to the emf of the cell.
¢G° 5 2nFE°cell (19.3) Relating the standard free-energy change to the
standard emf of the cell.
0.0257 V
E°cell 5 ln K (19.5) Relating the standard emf of the cell to the
n equilibrium constant.
0.0592 V
E°cell 5 log K (19.6) Relating the standard emf of the cell to the
n equilibrium constant.
0.0257 V
E 5 E° 2 ln Q (19.8) Relating the emf of the cell to the concentrations
n under nonstandard state conditions.
0.0592 V
E 5 E° 2 log Q (19.9) Relating the emf of the cell to the concentrations
n under nonstandard state conditions.

Summary of Facts and Concepts
1. Redox reactions involve the transfer of electrons. Equa-
tions representing redox processes can be balanced
using the ion-electron method.
2. All electrochemical reactions involve the transfer of
electrons and therefore are redox reactions.
3. In a galvanic cell, electricity is produced by a spontane-
ous chemical reaction. Oxidation and reduction take
place separately at the anode and cathode, respectively,
and the electrons flow through an external circuit.
4. The two parts of a galvanic cell are the half-cells, and the
reactions at the electrodes are the half-cell reactions. A
salt bridge allows ions to flow between the half-cells.
5. The electromotive force (emf) of a cell is the voltage
difference between the two electrodes. In the external
circuit, electrons flow from the anode to the cathode in
a galvanic cell. In solution, the anions move toward the
anode and the cations move toward the cathode.
6. The quantity of electricity carried by 1 mole of elec-
trons is equal to 96,500 C.
7. Standard reduction potentials show the relative likeli-
hood of half-cell reduction reactions and can be used to
predict the products, direction, and spontaneity of redox
reactions between various substances.
Key Words
Anode, p. 842 Electrochemistry, p. 838
Battery, p. 857 Electrolysis, p. 866
Cathode, p. 842 Electrolytic cell, p. 866
Cell voltage, p. 843 Electromotive force (emf)
Corrosion, p. 862 (E), p. 843
Electronic Homework Problems
The following problems are available at www.aris.mhhe.com
if assigned by your instructor as electronic homework.
Quantum Tutor problems are also available at the
same site.
Questions and Problems
Balancing Redox Equations
Problems
19.1 Balance the following redox equations by the ion-
electron method:
Questions and Problems 873
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Chapter Summary
8. The decrease in free energy of the system in a spontane-
ous redox reaction is equal to the electrical work done
by the system on the surroundings, or DG 5 2nFE.
9. The equilibrium constant for a redox reaction can be
found from the standard electromotive force of a cell.
10. The Nernst equation gives the relationship between the
cell emf and the concentrations of the reactants and
products under non-standard-state conditions.
11. Batteries, which consist of one or more galvanic cells,
are used widely as self-contained power sources.
Some of the better-known batteries are the dry cell,
such as the Leclanché cell, the mercury battery, and
the lead storage battery used in automobiles. Fuel
cells produce electrical energy from a continuous
supply of reactants.
12. The corrosion of metals, such as the rusting of iron, is
an electrochemical phenomenon.
13. Electric current from an external source is used to drive
a nonspontaneous chemical reaction in an electrolytic
cell. The amount of product formed or reactant con-
sumed depends on the quantity of electricity transferred
at the electrodes.
Faraday constant (F), p. 849 Overvoltage, p. 868
Fuel cell, p. 860 Standard emf (E°cell), p. 844
Galvanic cell, p. 841 Standard reduction
Half-cell reaction, p. 842 potential, p. 843
Nernst equation, p. 853
ARIS Problems: 19.11, 19.15, 19.17, 19.21,
19.23, 19.24, 19.29, 19.32, 19.37, 19.45, 19.49, 19.55,
19.60, 19.61, 19.73, 19.74, 19.81, 19.86, 19.96.
(a) H 2O 2 1 Fe21 ¡ Fe31 1 H 2O (in acidic
solution)
(b) Cu 1 HNO 3 ¡ Cu21 1 NO 1 H 2O (in
acidic solution)
946 Nonmetallic Elements and Their Compounds
Figure 21.20 Cloud seeding
using AgI particles.
Summary of Facts and Concepts
1. Hydrogen atoms contain one proton and one electron.
They are the simplest atoms. Hydrogen combines with
many metals and nonmetals to form hydrides; some hy-
drides are ionic and some are covalent.
2. There are three isotopes of hydrogen: 11H, 21H (deuterium),
and 31H (tritium). Heavy water contains deuterium.
3. The important inorganic compounds of carbon are the
carbides; the cyanides, most of which are extremely
toxic; carbon monoxide, also toxic and a major air
pollutant; the carbonates and bicarbonates; and carbon
dioxide, an end product of metabolism and a compo-
nent of the global carbon cycle.
4. Elemental nitrogen, N2, contains a triple bond and is
very stable. Compounds in which nitrogen has oxida-
tion numbers from 23 to 15 are formed between nitro-
gen and hydrogen and/or oxygen atoms. Ammonia,
NH3, is widely used in fertilizers.
5. White phosphorus, P4, is highly toxic, very reactive,
and flammable; the polymeric red phosphorus, (P4)n, is
more stable. Phosphorus forms oxides and halides with
oxidation numbers of 13 and 15 and several oxoacids.
Key Words
Carbide, p. 921
Catenation, p. 920
Chlor-alkali
process, p. 941
Cyanide, p. 921
Hydrogenation, p. 918
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Chapter Summary
The phosphates are the most important phosphorus
compounds.
6. Elemental oxygen, O2, is paramagnetic and contains two
unpaired electrons. Oxygen forms ozone (O3), oxides
2
(O22), peroxides (O22
2 ), and superoxides (O2 ). The most
abundant element in Earth’s crust, oxygen is essential
for life on Earth.
7. Sulfur is taken from Earth’s crust by the Frasch process
as a molten liquid. Sulfur exists in a number of allo-
tropic forms and has a variety of oxidation numbers in
its compounds.
8. Sulfuric acid is the cornerstone of the chemical indus-
try. It is produced from sulfur via sulfur dioxide and
sulfur trioxide by means of the contact process.
9. The halogens are toxic and reactive elements that are
found only in compounds with other elements. Fluorine
and chlorine are strong oxidizing agents and are pre-
pared by electrolysis.
10. The reactivity, toxicity, and oxidizing ability of the
halogens decrease from fluorine to iodine. The halogens
all form binary acids (HX) and a series of oxoacids.
Electronic