40 CHAPTER 2 Atoms, Molecules, and Ions

2.1 | THE ATOMIC THEORY OF MATTER

Philosophers from the earliest times speculated about the nature of the fundamental
“stuff ” from which the world is made. Democritus (460–370 BC) and other early Greek
philosophers described the material world as made up of tiny indivisible particles they
called atomos, meaning “indivisible or uncuttable.” Later, however, Plato and Aristotle
formulated the notion that there can be no ultimately indivisible particles, and the
“atomic” view of matter faded for many centuries during which Aristotelean philosophy
dominated Western culture.
The notion of atoms reemerged in Europe during the seventeenth century. As
chemists learned to measure the amounts of elements that reacted with one another to
form new substances, the ground was laid for an atomic theory that linked the idea of el-
ements with the idea of atoms. That theory came from the work of John Dalton during
the period from 1803 to 1807. Dalton’s atomic theory was based on the four postulates
given in 쑼 FIGURE 2.1.
Dalton’s theory explains several laws of chemical combination that were known
during his time, including the law of constant composition •(Section 1.2),* based on
postulate 4:
In a given compound, the relative numbers and kinds of atoms are constant.

It also explains the law of conservation of mass, based on postulate 3:

The total mass of materials present after a chemical reaction is the same as the total mass
present before the reaction.

A good theory explains known facts and predicts new ones. Dalton used his theory
to deduce the law of multiple proportions:
If two elements A and B combine to form more than one compound, the masses of B that
can combine with a given mass of A are in the ratio of small whole numbers.

Dalton’s Atomic Theory

1. Each element is composed of extremely small particles called atoms.

An atom of the element oxygen An atom of the element nitrogen

2. All atoms of a given element are identical, but the atoms of one element
are different from the atoms of all other elements.

Oxygen Nitrogen

3. Atoms of one element cannot be changed into atoms of a different element

by chemical reactions; atoms are neither created nor destroyed in chemical
reactions.
Oxygen Nitrogen

4. Compounds are formed when atoms of more than one

씰 FIGURE 2.1 Dalton’s atomic theory. element combine; a given compound always has the
John Dalton (1766–1844), the son of a poor same relative number and kind of atoms.
English weaver, began teaching at age 12.
He spent most of his years in Manchester,

where he taught both grammar school and N O NO
college. His lifelong interest in meteorology
led him to study gases, then chemistry, and Elements Compound
eventually atomic theory. Despite his humble
beginnings, Dalton gained a strong scientific
reputation during his lifetime.

*The short chainlike symbol that precedes the section reference indicates a link to ideas presented earlier in
the text.
 SECTION 2.2 The Discovery of Atomic Structure 41

We can illustrate this law by considering water and hydrogen peroxide, both of which
consist of the elements hydrogen and oxygen. In forming water, 8.0 g of oxygen combine
with 1.0 g of hydrogen. In forming hydrogen peroxide, 16.0 g of oxygen combine with
1.0 g of hydrogen. Thus, the ratio of the mass of oxygen per gram of hydrogen in the two
compounds is 2:1. Using Dalton’s atomic theory, we conclude that hydrogen peroxide
contains twice as many atoms of oxygen per hydrogen atom as does water.

GIVE IT SOME THOUGHT

Compound A contains 1.333 g of oxygen per gram of carbon, whereas com-
pound B contains 2.666 g of oxygen per gram of carbon.
a. What chemical law do these data illustrate?
b. If compound A has an equal number of oxygen and carbon atoms, what can
we conclude about the composition of compound B?

2.2 | THE DISCOVERY OF ATOMIC STRUCTURE

Dalton based his conclusions about atoms on chemical observations made in the labora-
tory. Neither he nor those who followed him during the century after his work was pub-
lished had any direct evidence for the existence of atoms. Today, however, we can measure
the properties of individual atoms and even provide images of them (씰 FIGURE 2.2).
As scientists developed methods for probing the nature of matter, the supposedly
indivisible atom began to show signs of a more complex structure, and today we know
that the atom is composed of subatomic particles. Before we summarize the current
model, we briefly consider a few of the landmark discoveries that led to that model. We
will see that the atom is composed in part of electrically charged particles, some with a 쑿 FIGURE 2.2 An image of the surface
positive charge and some with a negative charge. As we discuss the development of our of silicon. The image was obtained by a
current model of the atom, keep in mind this fact: Particles with the same charge repel technique called scanning tunneling
one another, whereas particles with unlike charges attract one another. microscopy. The color was added to the
image by computer to help distinguish its
features. Each purple sphere is a silicon
Cathode Rays and Electrons atom.
During the mid-1800s, scientists began to study electrical discharge through a glass tube
pumped almost empty of air (쑼 FIGURE 2.3). When a high voltage was applied to the
electrodes in the tube, radiation was produced between the electrodes. This radiation,
called cathode rays, originated at the negative electrode and traveled to the positive
electrode. Although the rays could not be seen, their presence was detected because they
cause certain materials to fluoresce, or to give off light.

GO FIGURE
How do we know that the cathode rays travel from cathode to anode?

Cathode Anode
(ⴚ) (ⴙ)

(a) Electrons move from the (b) The rays are deflected by a
cathode (negative electrode) to magnet.
the anode (positive electrode).
The tube contains a glass screen
(set diagonally to the electron
beam) that fluoresces, showing
the path of the cathode rays. 씱 FIGURE 2.3 Cathode-ray tube.
42 CHAPTER 2 Atoms, Molecules, and Ions

GO FIGURE
If no magnetic field were applied, would you expect the electron beam to
be deflected upward or downward by the electric field?
Fluorescent
screen
Electrically
charged plates

N
Anode (+)

+
S Electron path
씰 FIGURE 2.4 Cathode-ray tube with Cathode (–)
perpendicular magnetic and electric fields.
Evacuated tube
The cathode rays (electrons) originate at the Electron beam undeflected if
cathode and are accelerated toward the electric and magnetic field
anode, which has a hole in its center. strengths exactly balance
A narrow beam of electrons passes through Magnet each other.
the hole and travels to the fluorescent screen.
The strengths of the electric and magnetic
fields are adjusted so their effects cancel
Electric and magnetic fields
each other allowing the beam to travel a
deflect the electron beam.
straight path.

Experiments showed that cathode rays are deflected by electric or magnetic fields in
a way consistent with their being a stream of negative electrical charge. The British sci-
entist J. J. Thomson (1856–1940) observed that cathode rays are the same regardless of
the identity of the cathode material. In a paper published in
1897, Thomson described cathode rays as streams of neg-
Oil drops atively charged particles. His paper is generally accepted
Hole in plate as the “discovery” of what became known as the electron.
Thomson constructed a cathode-ray tube having a
(+) hole in the anode through which a beam of electrons passed.
Electrically charged plates and a magnet were positioned
perpendicular to the electron beam, and a fluorescent
Source of X rays Viewing screen was located at one end (쑿 FIGURE 2.4). The elec-
microscope
tric field deflected the rays in one direction, and the mag-
(–) netic field deflected them in the opposite direction.
Thomson adjusted the strengths of the fields so that the ef-
fects balanced each other, allowing the electrons to travel
Electrically
charged plates in a straight path to the screen. Knowing the strengths
that resulted in the straight path made it possible to
calculate a value of 1.76 * 108 coulombs per gram
쑿 FIGURE 2.5 Millikan’s oil-drop for the ratio of the electron’s electrical charge to its mass.*
experiment used to measure the charge Once the charge-to-mass ratio of the electron was known, measuring either quan-
of the electron. Small drops of oil were tity allowed scientists to calculate the other. In 1909, Robert Millikan (1868–1953) of the
allowed to fall between electrically charged University of Chicago succeeded in measuring the charge of an electron by performing
plates. The drops picked up extra electrons
the experiment described in 씱 FIGURE 2.5. He then calculated the mass of the electron
as a result of irradiation by X-rays and so
became negatively charged. Millikan by using his experimental value for the charge, 1.602 * 10-19 C, and Thomson’s
measured how varying the voltage between charge-to-mass ratio, 1.76 * 108 C>g:
the plates affected the rate of fall. From
these data he calculated the negative charge 1.602 * 10-19 C
on the drops. Because the charge on any Electron mass = = 9.10 * 10-28 g
1.76 * 108 C>g
drop was always some integral multiple of
1.602 * 10-19 C, Millikan deduced this value
to be the charge of a single electron.
*The coulomb (C) is the SI unit for electrical charge.
 SECTION 2.2 The Discovery of Atomic Structure 43

This result agrees well with the currently accepted value for the electron mass,
9.10938 * 10-28 g. This mass is about 2000 times smaller than that of hydrogen, the
lightest atom.

Radioactivity
In 1896 the French scientist Henri Becquerel (1852–1908) discovered that a compound
of uranium spontaneously emits high-energy radiation. This spontaneous emission of
radiation is called radioactivity. At Becquerel’s suggestion, Marie Curie (씰 FIGURE 2.6)
and her husband, Pierre, began experiments to isolate the radioactive components of
the compound.
Further study of radioactivity, principally by the British scientist Ernest Rutherford
(씰 FIGURE 2.7), revealed three types of radiation: alpha (a), beta (b), and gamma (g).
The paths of a and b radiation are bent by an electric field, although in opposite direc-
쑿 FIGURE 2.6 Marie Sklodowska Curie
tions; g radiation is unaffected by the field (쑼 FIGURE 2.8). (1867–1934). When Marie Curie presented
Rutherford showed that a and b rays consist of fast-moving particles. In fact, her doctoral thesis, it was described as the
b particles are high-speed electrons and can be considered the radioactive equivalent of greatest single contribution of any doctoral
cathode rays. They are attracted to a positively charged plate. The a particles have a thesis in the history of science. In 1903 Henri
positive charge and are attracted to a negative plate. In units of the charge of the elec- Becquerel, Maire Curie, and her husband,
Pierre, were jointly awarded the Nobel Prize
tron, b particles have a charge of 1- and a particles a charge of 2+ . Each a particle has in Physics for their pioneering work on
a mass about 7400 times that of an electron. Gamma radiation is high-energy radiation radioactivity (a term she introduced). In 1911
similar to X-rays; it does not consist of particles and carries no charge. Marie Curie won a second Nobel Prize, this
time in chemistry for her discovery of the
The Nuclear Model of the Atom elements polonium and radium.

With growing evidence that the atom is composed of smaller particles, attention was
given to how the particles fit together. During the early 1900s, Thomson reasoned that
because electrons contribute only a very small fraction of an atom’s mass they probably
were responsible for an equally small fraction of the atom’s size. He proposed that the
atom consisted of a uniform positive sphere of matter in which the electrons were em-
bedded like raisins in a pudding or seeds in a watermelon (씰 FIGURE 2.9). This plum-
pudding model, named after a traditional English dessert, was very short-lived.
In 1910, Rutherford was studying the angles at which a particles were deflected, or 쑿 FIGURE 2.7 Ernest Rutherford
scattered, as they passed through a thin sheet of gold foil (씰 FIGURE 2.10). He discov- (1871–1937). In 1895, Rutherford was awarded
ered that almost all the particles passed directly through the foil without deflection, with a position at Cambridge University in England,
a few particles deflected about 1 degree, consistent with Thomson’s plum-pudding where he worked with J. J. Thomson. In 1898
he moved to McGill University in Montreal,
model. For the sake of completeness, Rutherford suggested that Ernest Marsden, an un-
where he did the research on radioactivity that
dergraduate student working in the laboratory, look for scattering at large angles. To led to his 1908 Nobel Prize in Chemistry. In
everyone’s surprise, a small amount of scattering was observed at large angles, with 1907 Rutherford returned to England as a
some particles scattered back in the direction from which they had come. The explana- faculty member at Manchester University,
tion for these results was not immediately obvious, but they were clearly inconsistent where in 1910 he performed his famous
a-particle scattering experiments. In 1992 his
with Thomson’s plum-pudding model.
native New Zealand honored him by putting
his likeness on their $100 currency note.
GO FIGURE
Which of the three kinds of radiation shown consists of electrons? Negative
Why are these rays deflected to a greater extent than the others? electron

() rays are negatively charged

Lead block
rays carry no charge
rays are positively charged

Positive charge
() spread throughout
Electrically Photographic plate sphere
charged plates
Radioactive
쑿 FIGURE 2.9 J. J. Thomson’s plum-
substance
pudding model of the atom. Ernest
쑿 FIGURE 2.8 Behavior of alpha (A), beta (B), and gamma (G) rays in an electric field. Rutherford proved this model wrong.
44 CHAPTER 2 Atoms, Molecules, and Ions

GO FIGURE
What is the charge on the particles that form the beam?
Experiment Interpretation

Incoming
a particles

Beam of a particles

Source of
a particles
Nucleus

Gold foil

씰 FIGURE 2.10 Rutherford’s

A-scattering experiment. When a particles
pass through a gold foil, most pass through
undeflected but some are scattered, a few at
very large angles. According to the plum- Circular
pudding model of the atom, the particles fluorescent
should experience only very minor screen
deflections. The nuclear model of the atom A few a particles are
explains why a few a particles are deflected scattered because of
at large angles. For clarity, the nuclear atom repulsion by tiny
Most a particles positive nucleus
is shown here as a colored sphere, but
undergo no scattering
most of the space around the nucleus is
because most of
empty except for the tiny electrons
atom is empty
moving around.

Rutherford explained the results by postulating the nuclear model of the atom, a
model in which most of the mass of each gold atom and all of its positive charge reside
in a very small, extremely dense region that he called the nucleus. He postulated further
that most of the volume of an atom is empty space in which electrons move around the
nucleus. In the a-scattering experiment, most of the particles passed through the foil
unscattered because they did not encounter the minute nucleus of any gold atom. Occa-
sionally, however, an a particle came close to a gold nucleus. The repulsion between the
highly positive charge of the gold nucleus and the positive charge of the a particle was
then strong enough to deflect the particle, as shown in Figure 2.10.
Subsequent experiments led to the discovery of positive particles (protons) and
neutral particles (neutrons) in the nucleus. Protons were discovered in 1919 by Ruther-
ford and neutrons in 1932 by British scientist James Chadwick (1891–1972). Thus, the
atom is composed of electrons, protons, and neutrons.

GIVE IT SOME THOUGHT

What happens to most of the a particles that strike the gold foil in Rutherford’s
experiment? Why do they behave that way?

|
2.3 THE MODERN VIEW OF
ATOMIC STRUCTURE
Since Rutherford’s time, as physicists have learned more and more about atomic nuclei,
the list of particles that make up nuclei has grown and continues to increase. As
chemists, however, we can take a simple view of the atom because only three subatomic
particles—the proton, neutron, and electron—have a bearing on chemical behavior.
As noted earlier, the charge of an electron is -1.602 * 10-19 C. That of a proton is
equal in magnitude, +1.602 * 10-19 C. The quantity 1.602 * 10-19 C is called the
 SECTION 2.3 The Modern View of Atomic Structure 45

electronic charge. For convenience, the charges of atomic and subatomic particles are Nucleus Volume occupied
usually expressed as multiples of this charge rather than in coulombs. Thus, the charge containing by electrons
of the electron is 1- and that of the proton is 1+ . Neutrons are electrically neutral protons and
neutrons
(which is how they received their name). Every atom has an equal number of electrons
and protons, so atoms have no net electrical charge.
Protons and neutrons reside in the tiny nucleus of the atom. The vast majority of an
atom’s volume is the space in which the electrons reside (씰 FIGURE 2.11). The elec- ~104 Å
trons are attracted to the protons in the nucleus by the electrostatic force that exists be-
tween particles of opposite electrical charge. In later chapters we will see that the 1–5 Å
strength of the attractive forces between electrons and nuclei can be used to explain
many of the differences among different elements. 쑿 FIGURE 2.11 The structure of the
atom. A cloud of rapidly moving electrons
GIVE IT SOME THOUGHT occupies most of the volume of the atom.
The nucleus occupies a tiny region at the
a. If an atom has 15 protons, how many electrons does it have? center of the atom and is composed of the
b. Where do the protons reside in an atom? protons and neutrons. The nucleus contains
virtually all the mass of the atom.
Atoms have extremely small masses. The mass of the heaviest known atom, for
example, is approximately 4 * 10-22 g. Because it would be cumbersome to express
such small masses in grams, we use the atomic mass unit (amu),* where 1 amu =
1.66054 * 10-24 g. A proton has a mass of 1.0073 amu, a neutron 1.0087 amu, and an
electron 5.486 * 10-4 amu (쑼 TABLE 2.1). Because it takes 1836 electrons to equal the
mass of one proton or one neutron, the nucleus contains most of the mass of an atom.
Most atoms have diameters between 1 * 10-10 m and 5 * 10-10 m. A convenient
non–SI unit of length used for atomic dimensions is the angstrom (Å), where
1 Å = 1 * 10-10 m. Thus, atoms have diameters of approximately 1-5 Å. The diame-
ter of a chlorine atom, for example, is 200 pm, or 2.0 Å.

SAMPLE EXERCISE 2.1 Atomic Size

The diameter of a US dime is 17.9 mm, and the diameter of a silver atom is 2.88 Å. How many
silver atoms could be arranged side by side across the diameter of a dime?
SOLUTION
The unknown is the number of silver (Ag) atoms. Using the relationship 1 Ag atom = 2.88 Å
as a conversion factor relating number of atoms and distance, we start with the diameter of the
dime, first converting this distance into angstroms and then using the diameter of the Ag atom
to convert distance to number of Ag atoms:
10-3 m 1Å 1 Ag atom
Ag atoms = (17.9 mm) ¢ ≤ ¢ -10 ≤ ¢ ≤ = 6.22 * 107Ag atoms
1 mm 10 m 2.88 Å
That is, 62.2 million silver atoms could sit side by side across a dime!

PRACTICE EXERCISE
The diameter of a carbon atom is 1.54 Å. (a) Express this diameter in picometers. (b) How
many carbon atoms could be aligned side by side across the width of a pencil line that is
0.20 mm wide?
Answers: (a) 154 pm, (b) 1.3 * 106 C atoms

The diameter of an atomic nucleus is approximately 10-4 Å, only a small fraction of

the diameter of the atom as a whole. You can appreciate the relative sizes of the atom and
its nucleus by imagining that if the hydrogen atom were as large as a football stadium,

TABLE 2.1 • Comparison of the Proton, Neutron, and Electron

Particle Charge Mass (amu)

Proton Positive (1 +) 1.0073

Neutron None (neutral) 1.0087
Electron Negative (1 -) 5.486 * 10-4

*The SI abbreviation for the atomic mass unit is u. We will use the more common abbreviation amu.
46 CHAPTER 2 Atoms, Molecules, and Ions

A CLOSER LOOK
BASIC FORCES between their centers, and k is a constant determined by the units for
Q and d. A negative value for the force indicates attraction, whereas a
Four basic forces are known in nature: (1) gravitational, positive value indicates repulsion.
(2) electromagnetic, (3) strong nuclear, and (4) weak All nuclei except those of hydrogen atoms contain two or more
nuclear. Gravitational forces are attractive forces that protons. Because like charges repel, electrical repulsion would cause
act between all objects in proportion to their the protons to fly apart if the strong nuclear force did not keep them
masses. Gravitational forces between atoms or together. This force acts between subatomic particles, as in the nu-
between subatomic particles are so small that they are of no chemical cleus. At this distance, the attractive strong nuclear force is stronger
significance. than the positive–positive repulsive electric force and holds the nu-
Electromagnetic forces are attractive or repulsive forces that act cleus together.
between either electrically charged or magnetic objects. Electric The weak nuclear force is weaker than the electric force but
forces are important in understanding the chemical behavior of stronger than the gravitational force. We are aware of its existence
atoms. The magnitude of the electric force between two charged par- only because it shows itself in certain types of radioactivity.
ticles is given by Coulomb’s law: F = kQ1Q2>d2, where Q1 and Q2 are
the magnitudes of the charges on the two particles, d is the distance RELATED EXERCISE: 2.88

the nucleus would be the size of a small marble. Because the tiny nucleus carries most of
the mass of the atom in such a small volume, it has an incredibly high density—on the
order of 1013 –1014 g>cm3. A matchbox full of material of such density would weigh
over 2.5 billion tons!
An illustration of the atom that incorporates the features we have just discussed is
shown in Figure 2.11. The electrons play the major role in chemical reactions. The sig-
nificance of representing the region containing the electrons as an indistinct cloud will
become clear in later chapters when we consider the energies and spatial arrangements
of the electrons.

Atomic Numbers, Mass Numbers, and Isotopes

What makes an atom of one element different from an atom of another element is that
the atoms of each element have a characteristic number of protons. Indeed, the number of
protons in an atom of any particular element is called that element’s atomic number.
Because an atom has no net electrical charge, the number of electrons it contains must
equal the number of protons. All atoms of carbon, for example, have six protons and six
electrons, whereas all atoms of oxygen have eight protons and eight electrons. Thus, car-
bon has atomic number 6, and oxygen has atomic number 8. The atomic number of
each element is listed with the name and symbol of the element on the inside front cover
of the text.
Atoms of a given element can differ in the number of neutrons they contain and,
consequently, in mass. For example, most atoms of carbon have six neutrons, although
some have more and some have less. The symbol 126C (read “carbon twelve,” carbon-12)
represents the carbon atom containing six protons and six neutrons. The atomic num-
ber is shown by the subscript; the superscript, called the mass number, is the number
of protons plus neutrons in the atom:
Mass number (number of
protons plus neutrons)
12
6 C Symbol of element

Atomic number (number

of protons or electrons)

Because all atoms of a given element have the same atomic number, the subscript is
redundant and is often omitted. Thus, the symbol for carbon-12 can be represented
simply as 12C. As one more example of this notation, carbon atoms that contain six
protons and eight neutrons have mass number 14, are represented as 146C or 14C, and are
referred to as carbon-14.
 SECTION 2.4 Atomic Weights 47

TABLE 2.2 • Some Isotopes of Carbon*

Symbol Number of Protons Number of Electrons Number of Neutrons

11
C 6 6 5
12 6 6 6
C
13 6 6 7
C
14 6 6 8
C

*Almost 99% of the carbon found in nature is 12C.

Atoms with identical atomic numbers but different mass numbers (that is, same
number of protons but different numbers of neutrons) are called isotopes of one
another. Several isotopes of carbon are listed in 쑿 TABLE 2.2. We will generally use the
notation with superscripts only when referring to a particular isotope of an element.

SAMPLE EXERCISE 2.2 Determining the Number of Subatomic Particles

in Atoms
197
How many protons, neutrons, and electrons are in (a) an atom of Au, (b) an atom of
strontium-90?
SOLUTION
(a) The superscript 197 is the mass number (protons + neutrons). According to the list of
elements given on the inside front cover, gold has atomic number 79. Consequently, an atom
of 197Au has 79 protons, 79 electrons, and 197 - 79 = 118 neutrons. (b) The atomic number
of strontium (listed on inside front cover) is 38. Thus, all atoms of this element have 38 pro-
tons and 38 electrons. The strontium-90 isotope has 90 - 38 = 52 neutrons.
PRACTICE EXERCISE
How many protons, neutrons, and electrons are in (a) a 138Ba atom, (b) an atom of
phosphorus-31?
Answer: (a) 56 protons, 56 electrons, and 82 neutrons, (b) 15 protons, 15 electrons, and
16 neutrons

SAMPLE EXERCISE 2.3 Writing Symbols for Atoms

Magnesium has three isotopes with mass numbers 24, 25, and 26. (a) Write the complete
chemical symbol (superscript and subscript) for each. (b) How many neutrons are in an atom
of each isotope?
SOLUTION
(a) Magnesium has atomic number 12, so all atoms of magnesium contain 12 protons and
12 electrons. The three isotopes are therefore represented by 24 25 26
12Mg, 12Mg, and 12Mg. (b) The
number of neutrons in each isotope is the mass number minus the number of protons.
The numbers of neutrons in an atom of each isotope are therefore 12, 13, and 14, respectively.
PRACTICE EXERCISE
Give the complete chemical symbol for the atom that contains 82 protons, 82 electrons, and
126 neutrons.
Answer: 208
82 Pb

2.4 | ATOMIC WEIGHTS

Atoms are small pieces of matter, so they have mass. In this section we discuss the mass
scale used for atoms and introduce the concept of atomic weights.

The Atomic Mass Scale

Scientists of the nineteenth century were aware that atoms of different elements have dif-
ferent masses. They found, for example, that each 100.0 g of water contains 11.1 g of hy-
drogen and 88.9 g of oxygen. Thus, water contains 88.9>11.1 = 8 times as much oxygen,
48 CHAPTER 2 Atoms, Molecules, and Ions

by mass, as hydrogen. Once scientists understood that water contains two hydrogen
atoms for each oxygen atom, they concluded that an oxygen atom must have 2 * 8 = 16
times as much mass as a hydrogen atom. Hydrogen, the lightest atom, was arbitrarily
assigned a relative mass of 1 (no units). Atomic masses of other elements were at first
determined relative to this value. Thus, oxygen was assigned an atomic mass of 16.
Today we can determine the masses of individual atoms with a high degree of accu-
racy. For example, we know that the 1H atom has a mass of 1.6735 * 10-24 g and the
16
O atom has a mass of 2.6560 * 10-23 g. As we noted in Section 2.3, it is convenient to
use the atomic mass unit (amu) when dealing with these extremely small masses:

1 amu = 1.66054 * 10-24 g and 1 g = 6.02214 * 1023 amu

The atomic mass unit is presently defined by assigning a mass of exactly 12 amu to an
atom of the 12C isotope of carbon. In these units, an 1H atom has a mass of 1.0078 amu
and an 16O atom has a mass of 15.9949 amu.

Atomic Weight
Most elements occur in nature as mixtures of isotopes. We can determine the average
atomic mass of an element, usually called the element’s atomic weight, by using the
masses of its isotopes and their relative abundances:

Atomic weight = a [(isotope mass) * (fractional isotope abundance)]

over all isotopes of the element [2.1]

Naturally occurring carbon, for example, is composed of 98.93% 12C and 1.07% 13C.
The masses of these isotopes are 12 amu (exactly) and 13.00335 amu, respectively, mak-
ing the atomic weight of carbon
(0.9893)(12 amu) + (0.0107)(13.00335 amu) = 12.01 amu
The atomic weights of the elements are listed in both the periodic table and the table of
elements inside the front cover of this text.

GIVE IT SOME THOUGHT

A particular atom of chromium has a mass of 52.94 amu, whereas the atomic
weight of chromium is 51.99 amu. Explain the difference in the two masses.

SAMPLE EXERCISE 2.4 Calculating the Atomic Weight of an Element

from Isotopic Abundances
Naturally occurring chlorine is 75.78% 35Cl (atomic mass 34.969 amu) and 24.22% 37
Cl
(atomic mass 36.966 amu). Calculate the atomic weight of chlorine.

SOLUTION
We can calculate the atomic weight by multiplying the abundance of each isotope by its atomic
mass and summing these products. Because 75.78% = 0.7578 and 24.22% = 0.2422, we have
Atomic weight = (0.7578)(34.969 amu) + (0.2422)(36.966 amu)
= 26.50 amu + 8.953 amu
= 35.45 amu
This answer makes sense: The atomic weight, which is actually the average atomic mass, is
between the masses of the two isotopes and is closer to the value of 35Cl, the more abundant
isotope.

PRACTICE EXERCISE
Three isotopes of silicon occur in nature: 28Si (92.23%), atomic mass 27.97693 amu; 29Si
(4.68%), atomic mass 28.97649 amu; and 30Si (3.09%), atomic mass 29.97377 amu. Calculate
the atomic weight of silicon.
Answer: 28.09 amu
 SECTION 2.5 The Periodic Table 49

A CLOSER LOOK
THE MASS SPECTROMETER A graph of the intensity of the detector signal versus particle
atomic mass is called a mass spectrum (쑼 FIGURE 2.13). Analysis
The most accurate means for determining atomic of a mass spectrum gives both the masses of the charged particles
weights is provided by the mass spectrometer reaching the detector and their relative abundances, which are ob-
(쑼 FIGURE 2.12). A gaseous sample is introduced tained from the signal intensities. Knowing the atomic mass and the
at A and bombarded by a stream of high-energy abundance of each isotope allows us to calculate the atomic weight of
electrons at B. Collisions between the electrons an element, as shown in Sample Exercise 2.4.
and the atoms or molecules of the gas produce positively charged Mass spectrometers are used extensively today to identify chem-
particles that are then accelerated toward a negatively charged grid ical compounds and analyze mixtures of substances. Any molecule
(C). After the particles pass through the grid, they encounter two slits that loses electrons can fall apart, forming an array of positively
that allow only a narrow beam of particles to pass. This beam then charged fragments. The mass spectrometer measures the masses of
passes between the poles of a magnet, which deflects the particles these fragments, producing a chemical “fingerprint” of the molecule
into a curved path. For particles with the same charge, the extent of and providing clues about how the atoms were connected in the orig-
deflection depends on mass—the more massive the particle, the less inal molecule. Thus, a chemist might use this technique to determine
the deflection. The particles are thereby separated according to their the molecular structure of a newly synthesized compound or to iden-
masses. By changing the strength of the magnetic field or the acceler- tify a pollutant in the environment.
ating voltage on the grid, charged particles of various masses can be
selected to enter the detector. RELATED EXERCISES: 2.33, 2.34, 2.35(b), 2.36, 2.92, and 2.93

35
Accelerating grid Magnet Cl

Signal intensity
() N 37
Cl Detector
Heated ()
filament
37
A Cl
C Beam S
35
Cl
Sample B of positive Slit
() ions
Ionizing To vacuum Separation of
electron pump ions based on 34 35 36 37 38
beam mass differences Atomic mass (amu)
쑿 FIGURE 2.12 A mass spectrometer. Cl atoms are introduced 쑿 FIGURE 2.13 Mass spectrum of atomic chlorine. The
at A and are ionized to form Cl+ ions, which are then directed fractional abundances of the isotopes 35Cl and 37Cl are indicated by
through a magnetic field. The paths of the ions of the two Cl the relative signal intensities of the beams reaching the detector of
isotopes diverge as they pass through the field. the mass spectrometer.

2.5 | THE PERIODIC TABLE

As the list of known elements expanded during the early 1800s, attempts were made to
find patterns in chemical behavior. These efforts culminated in the development of the
periodic table in 1869. We will have much to say about the periodic table in later chap-
ters, but it is so important and useful that you should become acquainted with it now.
You will quickly learn that the periodic table is the most significant tool that chemists use
for organizing and remembering chemical facts.
Many elements show strong similarities to one another. The elements lithium (Li),
sodium (Na), and potassium (K) are all soft, very reactive metals, for example. The ele-
ments helium (He), neon (Ne), and argon (Ar) are all very nonreactive gases. If the ele-
ments are arranged in order of increasing atomic number, their chemical and physical
properties show a repeating, or periodic, pattern. For example, each of the soft, reactive
metals—lithium, sodium, and potassium—comes immediately after one of the non-
reactive gases—helium, neon, and argon—as shown in 씰 FIGURE 2.14.