Atoms, Molecules and Moles PDF

Foundations to Chemistry - adapted from "Chemistry, Matter and the Universe" Page 1 of 1
2. Atoms, Molecules and Moles -- Jump to --
Introduction
Hydrogen and helium occupy a special place in the chemical

world because they are the elements from which all other
elements were made.
They have another aspect that makes them useful to us now: They are the simplest of all atoms. All of the ide
atomic structure that can be illustrated with hydro
will carry directly over to the study of the heavier a
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http://www.chem.ox.ac.uk/vrchemistry/AMM/HTML/page01.htm 2006/11/27
Electrons, Nuclei, and Atomic Number
An atom is made up of a very small but heavy central nucleus with a positive
charge, surrounded by a negatively charged cloud of electrons. Because atoms
are so small, the familiar units of feet or centimeters are useless in measuring
them. A more common unit of length is the angstrom, symbolized .
There are 100,000,000 or 10 in one centimeter, or to express matters the other

way around,
1 = 1/10 cm = 10 cm = 0.00000001 cm
Most atoms are of the order of 1.0 to 2.4 in diameter, which is why
angstroms are so convenient. The nucleus of an atom is much smaller yet,
typically with a diameter of 10 cm or 10 .
If an atom were as large as a football stadium, the nucleus would be the size of
a small ladybug crawling across the 50-yard line. In spite of this size difference,
virtually an of the mass of an atom is concentrated in its nucleus. One electron,
which has a negative charge, weighs only 1/1836 as much as the lightest of all
nuclei, that of the hydrogen atom (proton).
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An atomic nucleus is built from two major kinds of particles: On this scale, a proton has a mass of 1.00728 am
protons and neutrons. A proton carries one unit of positive charge, lighter than a neutron, which has a mass of 1.0086
which balances the negative charge on an electron. The neutron and neutrons usually are thought of as having
is uncharged. The standard unit for measuring masses of atoms is amu) unless exact calculations are called for. O
the atomic mass unit (amu) defined such that the most common electron weighs only 0.00055 amu. The cha
kind of carbon atom weighs exactly 12 amu. relationships between these three fundamenta
summarized in the table to the left.
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The two simplest kinds of atoms are hydrogen (H),and helium (He), diagramed
on Page 1. Hydrogen has one proton in its nucleus and one electron around it.
Helium has two protons and hence must have two electrons, since the number
of positive and negative charges in a neutral atom must be the same. Because
electrons surround an atom, and the nucleus is small and deeply buried, the
outer part of the electron cloud is all that another atom "sees." It is the electron
cloud that gives each atom its chemical character.
Reactions leading to the making of chemical bonds involve the gain, loss, or
sharing of electrons between atoms, as we shall see in subsequent chapters.
Since the number of electrons in a neutral atom must equal the number of
protons in its nucleus, the number of protons indirectly decides the chemical
behavior of the atom. All atoms with the same number of protons are defined
as the same chemical element, and the number of protons is its atomic
number.
The atomic number sometimes is written as a subscript in front of the symbol

of the element, such as H and He. This is convenient but unnecessary,
since, for example, every atom with atomic number 2 by definition is called
helium and given the symbol He.
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The way in which electrons are arranged around a nucleus and the effect that
this has on chemical behavior are the subject of the next chapter.
At the moment, notice only the trend from metals, to nonmetals, to an inert gas,
and the beginning of a repetition of properties with the inert gas neon and the
soft metal sodium.
Chemical properties are periodic functions of the atomic number - in a listing of

elements by increasing atomic number, similar properties are encountered
again and again at regular intervals.
This is one of the most important generalizations in chemistry.
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Isotopes of Hydrogen
So far we have said nothing about neutrons. The most
common type of hydrogen has none in its nucleus
(right). Other kinds of hydrogen atoms have either one
or two neutrons, in addition to the proton that defines
their chemical character. Atoms such as these three,
with the same atomic number but with different
numbers of neutrons in their nuclei, are called isotopes
of the same chemical element. The sum of the number
of protons and neutrons is the mass number, and is
written as a superscript before the symbol of the
element: , , .
The three isotopes of hydrogen have quite different

masses: approximately 1, 2, and 3 amu. But because
the number of protons is the same, they have the same
number of electrons around the nucleus. To an
approaching atom, all hydrogen atoms look much the
same, and exhibit virtually the same chemical behavior.
The differences are important only in properties such
as rates of reaction or rates of diffusion of molecules,
for which the mass of an atom and its speed are
important.
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For heavier elements, the addition of one or two
neutrons has a less important effect on properties; thus
isotopes are not given special names.
Only for hydrogen, in which additional neutrons double

or triple the atomic mass, have special names and
symbols been developed:
= H = light hydrogen or "ordinary" hydrogen, with

one proton and no neutrons in the nucleus.
= D =deuterium (from "deutero-" or two), with one
proton and one neutron in the nucleus.
= T =tritium (from "tri-" or three), with one proton and
two neutrons in the nucleus
Ordinary water has the chemical formula . Heavy

water, , has become familiar because of its use as a
moderator or neutron absorber in certain types of
nuclear reactors. About 150 hydrogen atoms per million
on our planet are D atoms. Tritium is radioactive and
must be produced artificially.
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If protons and neutrons each weighed exactly 1 amu,
and there was no change in mass when the nucleus
was formed, then the mass number of an isotope would
equal the sum of the masses of the protons and
neutrons in amu, or its atomic weight. This is not strictly
true. Not only are protons and neutrons slightly heavier
than 1 amu, there is a small loss in mass when they
combine to form a nucleus.
This missing mass is converted to energy during the

nucleus-forming process and is lost by the atom. The
nucleus cannot be taken apart again unless the lost
energy is resupplied to make up the full mass, that is,
the mass of the initial protons and neutrons. This
missing energy represents the binding energy of the
nucleus, or the energy that holds the nucleus together.
Nevertheless, for approximate calculations we can

think of the atomic weight of an isotope as being
approximately equal to the sum of its protons and
neutrons, or to its mass number.
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Isotopes of Helium
Helium also has isotopes. The difference between superscript and Some isotopes of an element are stable and show
subscript gives the number of neutrons in the nucleus, and this break down; others decompose spontaneously a
can be 1, 2, 3, or 4. An atom has m nuclear n particles, n radioactive. Light hydrogen and deuterium are sta
protons, and m - n neutrons. Instead of special names, the radioactive. The or T nucleus apparently has an
isotopes of helium and heavier elements are distinguished by neutrons to protons. In time it decays spontaneo
giving their name and mass number, for example, helium-3 for converting one of the neutrons into a proton and a
. All but a minute fraction of helium atoms found on Earth are
helium-4. Only one atom per million is helium-3, and helium-5 and +
-6 do not exist naturally.
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Isotopes of Helium
The reaction on the previous page was written using the A proton, which has a +1 charge and unit mass nu
notation introduced previously, with the subscript now ; a neutron, which has no charge and unit mas
representing the charge on a particle (rather than the number of electron, which has a - 1 charge and no negligib
protons in the nucleus), and the superscript giving the mass rough-counting scale, is . When a nuclear react
number, or approximate mass in amu. one is written and balanced properly, the total cha
and the total mass number (superscripts) on the
the total charge and mass on the right.
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Isotopes of Helium
When one of the two neutrons in the tritium nucleus breaks down One element is changed into another, and the elec
into a proton and an electron, then a oneproton, two-neutron from the nucleus as beta radiation. We shall no
nucleus of hydrogen is converted into a two-proton, one-neutron with radioactive decay and unstable isotopes, but
nucleus of helium: at least that atomic nuclei are stable when their ra
to protons lie within a certain range, namely, 1:1
+ excess of neutrons. With too many neutrons or to
a nucleus becomes unstable and decays spont
This reaction is illustrated above. more stable isotope of an element with an atomic
that of the original element.
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Isotopes of Helium
When one of the two neutrons in the tritium nucleus breaks down One element is changed into another, and the elec
into a proton and an electron, then a oneproton, two-neutron from the nucleus as beta radiation. We shall no
nucleus of hydrogen is converted into a two-proton, one-neutron with radioactive decay and unstable isotopes, but
nucleus of helium: at least that atomic nuclei are stable when their ra
to protons lie within a certain range, namely, 1:1
+ excess of neutrons. With too many neutrons or to
a nucleus becomes unstable and decays spont
This reaction is illustrated above. more stable isotope of an element with an atomic
that of the original element.
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Isotopes and Observed Atomic Weights

Most of the naturally occurring elements are mixtures of
several isotopes. Of the carbon found on this planet,
98.9% is carbon-12, or , which has six protons and
six neutrons. (The atomic mass scale is defined so that
an atom of carbon- 12 weighs exactly 12 amu.) 1.1% is
carbon-13, with one additional neutron. Both of these
isotopes are stable, but carbon-14 is radioactive, and is
present in minute amounts only because it is being
produced constantly by cosmic-ray bombardment of
nitrogen in the upper atmosphere. Carbon-14 is the
basis of radiocarbon dating. As long as a tree or other
organism is alive, it constantly takes in more carbon
from its surroundings, and the ratio of to equals
that in the atmosphere as a whole. Radioactive decay
and replenishment from the atmosphere are in balance.
When the tree dies, this intake stops and what little
carbon-14 it has begins to disappear. By measuring the
ratio of to in a wood or other carbon containing
relic from an archaeological site, scientists can
calculate how long in the past the specimen ceased to
be alive and thus ceased to exchange with its
surroundings.
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Isotopes and Observed Atomic Weights
The atomic weight of an element in nature is the weighted average, in terms of

natural abundance, of the atomic weights of its naturally occurring isotopes.
Boron is a good example since it has appreciable amounts of two stable
isotopes.
Because isotopes of the same element have such similar chemical properties,
the ratio of isotopes ordinarily is unchanged during chemical reactions.
If individual isotopes are wanted, they must be separated by some technique,

such as diffusion or mass spectrometry, that is sensitive to small mass
differences.
To the chemist, all isotopes of an element react in much the same way. What
is important to chemical behavior is not the number of neutrons in an atom, but
the number of protons because this determines the number of electrons, and
electrons give rise to all of the important chemical properties of the elements.
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Bonds Between Atoms
At ordinary temperatures and pressures, both hydrogen and There is one important difference, however, il
helium are gases (upper left). Individual particles move freely, are movie at the top. In helium gas the particles ar
far apart on the average, and are independent of one another atoms, but the particles in hydrogen gas are tw
except when they collide. Their energy of motion is sufficiently together in an hydrogen molecule. Why the diffe
greater than the van der Waals attractions that when they do
collide, they rebound rather than stick together. Hydrogen and
helium gases both are made up of essentially free particles.
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms

Atoms combine into molecules because by doing so
they achieve a state of lower energy. Making molecules
from atoms is a "downhill" process, and tearing
molecules apart again into atoms always requires
energy to go back up the energy hill. We usually can
think of molecules as being held together by bonds
between pairs of atoms within them. A key question in
chemistry is: Which atoms will combine with one
another, in what way, and why?
At the beginning of this century chemical bonding was

still a mystery. One of the triumphs of quantum
mechanics, a shatteringly unorthodox theory developed
between 1900 and 1926, was the successful explanation
not only of atomic structure, but of bonding between
atoms in molecules.
We can take some of the pictorial conclusions from

quantum mechanics and use them to predict the
behavior of atoms in molecules, without becoming
involved in the mathematics. This is done in Chapters 7-
9.
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Bonds Between Atoms


atoms in molecules.

9.
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Bonds Between Atoms


atoms in molecules.

9.
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Bonds Between Atoms


atoms in molecules.

9.
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Bonds Between Atoms
A simple explanation of a chemical bond was given by G. N. Lewis in 1914: A

bond is formed between two atoms when a pair of electrons is shared between
them. This is the electron-pair, or covalent bond, which is the subject of
Chapter 4.
Two hydrogen atoms, each with a single electron, can share their electrons
and form a covalent bond, as shown at center left. If you were to perform a
quantum-mechanical calculation to see how the electrons in an H-H bond were
distributed, you would find that most of the time they are between the two H
nuclei.
One positive nucleus is attracted to the two electrons, which simultaneously

attract the other nucleus. At the same time, the two electrons shield or screen
the nuclei from one another and decrease the repulsion between their positive
charges.
The negatively charged electrons are the "glue" that holds the positive nuclei
together.
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Bonds Between Atoms

Chapter 4.
nuclei.

charges.
together.
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Bonds Between Atoms

Chapter 4.
nuclei.

charges.
together.
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Bonds Between Atoms

Chapter 4.
nuclei.

charges.
together.
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Bonds Between Atoms

Chapter 4.
nuclei.

charges.
together.
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Bonds Between Atoms
The energy of two hydrogen atoms can be represented in a As the atoms come closer together, little hap
diagram such as that above. The horizontal axis indicates the interatomic distance decreases to a few angst
distance between atoms in angstrom units, and the vertical axis electron of one atom begins to be "seen" by the
indicates the energy, with lower energy and greater stability other. Each electron is attracted by the othe
represented downward. The zero point of energy has been electrons become concentrated between the nuc
chosen to be that of two infinitely separated, noninteracting atoms. begins to form. The energy of the two atoms de
Two hydrogen atoms infinitely far apart obviously do not interact, attraction of each nucleus for the other ele
and thus have no bond between them. significant.
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
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Bonds Between Atoms
Energy continues to decrease as the atoms come closer and the G. N. Lewis symbolized an electron-pair bond by
screening of nuclear charges by electrons increases. If the process electrons. It is more common today to represen
is carried too far, however, the electrons are "squeezed out" from single line connecting the bonded atoms, b
between the nuclei, which have come so close together that the remember that each such bond consists of a pair o
repulsion between their positive charges becomes quite strong.
The molecule is made less stable.
At some intermediate point, screening by electrons and repulsion

of nuclei will balance: The H-H molecule will have the lowest
energy and will be most stable. If the nuclei are pushed any closer,
nuclear repulsion pushes them back again; if they are pulled apart,
electron-pair screening is lost.
This lowest-energy separation, , is the bond length of the H-H

bond, and the energy required to pull the molecule apart into
isolated atoms again, , is the bond dissociation energy or bond
energy. The atoms in a molecule oscillate about this minimum-
energy position; thus is the average bond length. In the H-H or
, molecule this distance is 0.74 .
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Electron Shells
We still have not answered the question as to why hydrogen atoms form
molecules but helium atoms do not. From what has been said so far, you might
expect that helium atoms would share two electron pairs to make two bonds
per molecule, or perhaps to make long -He-He-He-He- chains or rings of
atoms. Why doesn't this happen? To answer this question we must introduce
another idea from quantum mechanics, that of electron shells.
Electrons in atoms behave as though they were grouped into levels or shells,
with all electrons in one shell having approximately the same energies, but with
large energy differences between shells. Each shell can hold only a certain
maximum number of electrons. If one shell is filled, then an additional electron
will be forced to go into a higher-energy, less-stable shell, and this electron will
be lost easily during chemical reactions.
Conversely, if an atom lacks only one or two electrons to complete a shell, the
atom will have a strong attraction for electrons, and can take them away from
the type of atom mentioned previously. A completely filled electron shell, with
no vacancies and no extra electrons outside it, is a particularly stable situation
for an atom.
Not only can atoms gain and lose electrons, they can share them in covalent
bonds. When they do, all the shared electrons contribute toward filling
vacancies in the outer electron shell of each atom.
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Electron Shells
The innermost shell in any atom can hold a maximum of only two electrons,
and the second shell can hold eight. We will defer the reasons for this to
Chapter 8, but can use the conclusions now.
Each hydrogen atom lacks one electron of having a closed inner shell, so
when the two atoms combine to form an molecule, each atom gains an
electron and satisfies its deficiency.
Helium atoms do not combine because they already have their shells filled with
two electrons. If two helium atoms were forced together, they would have four
electrons in the vicinity of the nuclei (right). Two would be located between the
nuclei and would hold the atoms together as in . The other two would be
forced to the outside of the molecule, away from the first two. Not only
would these contribute no screening and bonding, they would attract the nuclei
and pull them away from one another. With two electrons pulling together and
two pulling apart, there would be no net bonding, and the two He atoms would
separate.
The two electrons that would tend to hold the molecule together are called
bonding electrons, and the two that would tend to pull the nuclei apart and
rupture the molecule are antibonding electrons.
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Molecules, Molecular Weight, and Moles
A molecule is a collection of atoms held together by covalent The term "organic" is a reminder that carbon compounds are the
bonds. In our simple universe of hydrogen and helium, the only basis for the most complex chemical phenomenon of all, life.
possible molecule is ; but the one-in-a-thousand heavier atoms
are the basis for a vast array of more complex molecules. The The molecular weight of any molecule is the sum of the atomic
champion of molecule-forming atoms is carbon, for reasons that weights of all its atoms. Since the atomic weight of a hydrogen
will become clear as we learn more about atomic structure. The atom is 1.008 amu (relative to carbon-12 as exactly 12 amu), the
chemistry of carbon compounds is so varied that it is given a molecular weight of the H2 molecule is twice this value, or 2.016
special name, organic chemistry. amu.
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The average atomic weight of the naturally occurring mixture of , and

is 12.011 amu, so the molecular weight of methane gas, , is
The molecular weight of water, , is
Large biological molecules can have molecular weights of several millions.
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Chemists talk about reactions between molecules, yet except for certain
extraordinary experimental conditions, no one can see a molecule. There is no
easy way to count out equal numbers of various kinds of molecules in
preparation for a chemical reaction.
There is a simple way, however, to weigh different amounts of various

molecules and to be sure that the resulting amounts each contain the same
number of molecules.
Since the molecular weights of hydrogen gas, methane, and water are 2.016
amu, 16.043 amu, and 18.015 amu, respectively, we can be sure that 2.016
tons of hydrogen gas, 16.043 tons of methane, and 18.015 tons of water each
contain the same number of molecules, although we may have no idea what
that number is.
By the same principle, if we know that walnuts weigh twice as much as

peanuts, we can be sure that two pounds of walnuts and one pound of peanuts
contain the same number of nuts, without counting them or knowing exactly
how many there are. If our only goal is to pair off walnuts with peanuts, or to
pair off molecules in chemical reactions, then this limited information is good
enough.
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Example. A hardware store clerk is told to weigh one pound of machine bolts
for a customer, and also to weigh approximately enough hexagonal nuts to go
with them. He finds that a hex nut weighs 0.40 as much as a machine bolt of
the type requested. How many nuts should he include with the order?
Answer. He should include 0.40 X 1 pound = 0.40 pound of hex nuts
Such a procedure would be good enough for most real situations, and a lot
easier and faster than sitting down and counting individual pieces. This is
exactly what the chemist does with molecules.
Example. A chemist wants to make as much methane, , as he can from

100 g of carbon. How much hydrogen will be required?
Solution. The atomic weight of hydrogen is 1.008 amu, and that of carbon is
12.011 amu. Four hydrogen atoms are required for each carbon atom, so
4x1.008 amu = 4.032 amu of hydrogen will be needed for each 12.011 amu of
carbon. The relative weights of hydrogen and carbon will be 4.032 units of
hydrogen to 12.011 units of carbon, whatever the weighing units chosen. The
problem was expressed in grams. Thus
100g carbon x (4.032g hydrogen / 12.011g carbon) = 33.6g hydrogen
will be required. Like the hardware store clerk, the chemist can weigh 100g of
carbon and 33.6g of hydrogen and assume that he has the right relative
number of atoms without counting them.
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Most chemical measurements are made in grams. An amount of Solution. The number of moles of carbon is
any substance in grams that is numerically equal to its atomic or
molecular weight in amu has been defined as one mole of that (100g carbon / 12.011 g ) = 8.33 moles of c
substance.
Four times as many hydrogen atoms are needed a
to make methane, , so four times as man
By this definition, one mole of hydrogen is 2.016 grams, one mole
required also:
of methane is 16.043 grams, and one mole of water is 18.015
grams. We can convert any gram quantity of a chemical
(4 moles H / 1 mole C) x 8.33 moles C = 33.3 mole
substance to moles by dividing by its molecular weight. Once we
have done this, we know that equal numbers of moles of all kinds
Since the atomic weight of hydrogen is 1.008, this
of substances must have equal numbers of molecules. The same
number of molecules is present in a mole of hydrogen, water,
33.3 moles hydrogen x 1.008 g = 33.6g of
methane, or any other substance. This is very useful, because
then we can measure the right amounts of starting material for This is the same answer as we obtained previous
chemical reactions, and can tell from the results how many we used moles instead of merely the ratio of atom
molecules of product were formed per molecule of reactants.
Example. How many moles of carbon are present in the 100 g of

the preceding example? How many moles of hydrogen atoms
would be needed to combine with these? How many grams of
hydrogen would be needed?
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The mole represents a scale-up from atomic mass units to grams. The number of molecules of a substance per
Instead of counting molecules, an impossible task, we can count Avogadro's number and given the symbol N.
moles. How many molecules are there in one mole of a (By the way in which a mole was defined as a
substance? We really do not need to know this to use moles in substance in grams, equal in numerical value
solving chemical problems, any more than the hardware store weight in amu, Avogadro's number also is the num
clerk needed to know how many bolts there were in a pound. But gram.)
there are situations when this knowledge is useful.
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The mole represents a scale-up from atomic mass units to grams. The number of molecules of a substance per
Instead of counting molecules, an impossible task, we can count Avogadro's number and given the symbol N.
moles. How many molecules are there in one mole of a (By the way in which a mole was defined as a
substance? We really do not need to know this to use moles in substance in grams, equal in numerical value
solving chemical problems, any more than the hardware store weight in amu, Avogadro's number also is the num
clerk needed to know how many bolts there were in a pound. But gram.)
there are situations when this knowledge is useful.
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This number can be measured experimentally by

several independent methods, using gases, liquids, and
crystals, and has been found to have the value
N = 602, 209, 430, 000, 000, 000, 000, 000

N = 6.022 x 10 molecules
As an illustration of how many molecules there are in

one mole, if each molecule were represented by an
ordinary glass marble, and these marbles were packed
as closely together as possible, one mole of marbles
would cover the entire United States with a layer
seventy miles deep!
All these molecules are contained in only 2.016 grams

of hydrogen gas (a balloon 35 cm in diameter), 18.015
grams of water (half of a one ounce shot glass), or a
cube of rock salt 3 cm on a side.
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N = 602, 209, 430, 000, 000, 000, 000, 000


seventy miles deep!

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N = 602, 209, 430, 000, 000, 000, 000, 000


seventy miles deep!

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N = 602, 209, 430, 000, 000, 000, 000, 000


seventy miles deep!

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Measuring Moles; The Gas Laws
There is an easier way of measuring moles when one is

dealing with gases. To a very good first approximation,
the molecules of any gas are independently moving
particles, having mass but negligible volume, and with
negligible interactions except at the instant of collision.
To the extent that this is so, all gas molecules are alike
except for mass.
At the same pressure and temperature, equal volumes of

any gases will contain equal numbers of moles and of
molecules. This is known as Avogadro's principle, after
the man who first proposed it in 1811.
It means that we do not have to weigh gases that are to

enter into a reaction, we only have to bring them to a
common temperature and pressure and measure
volumes.
Right: Apparatus and scientists associated with the

chemistry in the following pages; Robert Boyle and
Jacques Charles.
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If two molecules of hydrogen gas are to react with one
molecule of oxygen gas,
then we obtain the correct ratio of reactants by starting

with two volumes of hydrogen and one of oxygen
(right). Since the reaction produces two molecules of
water, we can predict that if the product obtained is
water vapor, there will be two volumes of vapor. The
reaction by which ammonia, , is prepared from
nitrogen and hydrogen gases is
Avogadro's principle tells us that if we want to carry out

this reaction without waste, we should begin with three
times as much hydrogen as nitrogen by volume at the
same pressure and temperature. The product,
ammonia, will have twice the volume of the starting ,
or half the volume of the entire starting gas mixture. For
gases, equal volumes at the same temperature and
pressure contain equal numbers of moles.
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We can do even better than this. Given the pressure

and temperature, we can calculate the volume that a
mole of gas should occupy, and can find out how the
volume changes as a gas is expanded or compressed,
and heated or cooled. The relationship between
pressure (P), volume (V), temperature (T), and number
of moles (n), is given by the ideal gas law,
PV = nRT
in which R is a constant. But to understand what this

gas law means and how to use it, we must back up a
step or two.
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We can do even better than this. Given the pressure

and temperature, we can calculate the volume that a
mole of gas should occupy, and can find out how the
volume changes as a gas is expanded or compressed,
and heated or cooled. The relationship between
pressure (P), volume (V), temperature (T), and number
of moles (n), is given by the ideal gas law,
PV = nRT
in which R is a constant. But to understand what this

gas law means and how to use it, we must back up a
step or two.
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In 1660, Robert Boyle published a book entitled "New original volume, and keep the temperature constant, the pressure
Experiments Physico-Mechanical, Touching [concerning] the will be doubled. If you continue to squeeze until the volume is a
Spring of the Air." In it he gave the evidence for what is known quarter of the starting volume, the pressure will be four times as
today as Boyle's law. Air does have "spring." If you compress it, it great. Conversely, if you release the constraints on a gas and
pushes back. Poke an airfilled plastic balloon chair with your allow it to expand to twice its initial volume, the pressure of the
fingertip, and you will easily make a large dent, which vanishes gas will be halved, if the temperature is kept constant. This
when you take your finger away. Yet if you sit down on the chair, behavior is illustrated in the table and PV plot above, which
the air inside pushes back with enough force to hold up your describe a hypothetical experiment beginning with 20 liters of a
weight. If you compress an enclosed body of gas until it is half its gas at 1 atmosphere pressure.
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Pressure is usually measured in atmospheres or
millimeters of mercury; 1 atm = 760 mm of Hg.
As you can see on the previous page, throughout the

experiment the volume is inversely proportional to
pressure; or to express matters another way, the
product of pressure and volume is unchanged. This can
be written as
PV = k - Boyle's law
in which k is a constant that can be evaluated for a

particular temperature from one particular set of
pressurevolume conditions. In the table at the top of the
page, this constant k is equal to 20 liter atmospheres.
If we want to compare two sets of experimental

conditions at constant temperature, designated by
subscripts 1 and 2, then Boyle's law can be written
P V =P V
Either form of Boyle's law can be used in an actual

problem.
Page 32 of 48


be written as


P V =P V

problem.
Page 32 of 48


be written as


P V =P V

problem.
Page 32 of 48


be written as


P V =P V

problem.
Page 32 of 48


be written as


P V =P V

problem.
Page 32 of 48
Example. An eight-foot diameter weather balloon is filled with 7600 liters of

hydrogen gas at sea level where the pressure is 1 atm. By the time the balloon
has ascended to an altitude at which the pressure is 0.70 atm, what is the
volume of the balloon?
Solution 1. Use Boyle's law in the form PV = k and evaluate k. At sea level,
P = 1 atm, and V = 7600 liters; thus
k = PV = (1 atm) (7600 liters) = 7600 liter atm.
This constant is equally valid for any other P and V, as long as the temperature
is unchanged. (This is a flaw in our example. The temperature actually would
change with altitude.) We can then write
(0.70 atm) V = 7600 liter atm
Page 33 of 48

hydrogen gas at sea level where the pressure is 1 atm. By the time the balloon
has ascended to an altitude at which the pressure is 0.70 atm, what is the
Solution 1. Use Boyle's law in the form PV = k and evaluate k. At sea level,
P = 1 atm, and V = 7600 liters; thus
k = PV = (1 atm) (7600 liters) = 7600 liter atm.
This constant is equally valid for any other P and V, as long as the temperature
is unchanged. (This is a flaw in our example. The temperature actually would
change with altitude.) We can then write
(0.70 atm) V = 7600 liter atm
Page 33 of 48
Solution 2. Use Boyle's law in the form P V = P V , where conditions (1) are
at sea level and (2) are at the higher altitude:
(1atm) (7600 liters) = (0.70 atm) V
A drop in pressure to 0.70 atm has permitted the gas in the balloon to expand.
Right: Sir Robert Boyle (1627 - 1691)
Page 34 of 48
The molecular explanation of Boyle's law is simple. The

pressure exerted by a gas on the walls of its container
arises because the gas molecules strike the walls and
rebound (right).
How great the pressure is depends on how fast the

molecules are moving, and how often they rebound from
the container walls.
The speed of the molecules depends on the

temperature and does not affect Boyle's law, which
applies only at a constant temperature. But if we
squeeze the gas into half its initial volume, then each
cubic centimeter of gas has twice as many molecules
(below right). Impacts with the walls occur twice as
often, so the pressure is twice as great.
Boyle's law is simply a reflection of how often the gas

molecules bounce off the walls of the container.
Page 35 of 48
Gas Molecules and Absolute Zero
Boyle's experiments all were carried out at constant temperature. Translating his data into modern units, he found that for every
A century later, Jacques Charles, in France, studied what happens degree Celsius, or centigrade, rise in temperature, the gas volume
to the volume of a gas when the temperature is changed and the increased by 1/273 of its volume at 0 . This is easier to
external pressure is kept constant. This is the problem of heating understand from the graph of volume versus temperature shown
or cooling a balloon full of air, with a fixed outside pressure exerted above. Within the observed range of temperatures, the plot is a
by the surroundings. In every gas he studied, Charles observed a straight line. If we extend this straight line back to zero volume, it
crosses the temperature axis at -273.15 . (For simplicity in the
steady increase in volume with an increase in temperature.
discussion that follows, we often shall use -273 .)
Page 36 of 48
Page 36 of 48
Page 36 of 48
Page 36 of 48
Gas Molecules And Absolute Zero

Charles' data suggest that, if a gas continued to behave
at lower temperatures in the way that it does at room
temperature, its volume would shrink to nothing at -273
. This is the point at which, in principle, all molecules
would come to rest and gases would cease to exert
pressure or occupy volume.
This theoretically possible but experimentally

unattainable temperature is known as absolute zero. We
can define an absolute temperature scale (also known as
the Kelvin scale after the British thermodynamicist Lord
Kelvin), in which the temperature (T) in degrees absolute
or Kelvin (K) is related to the temperature in degrees
centigrade (t) by the expression
T(K) = t ( ) + 273.15
Top Right: Jacques Charles (1746 - 1823)

Bottom Right: Lord Kelvin (1824 - 1907)
Page 37 of 48

The work of Charles tells us that the volume of a gas at
constant pressure is directly proportional to its absolute
temperature, T (not to its centigrade temperature):
V = k' T
Here k' is a constant that relates V and T, and is the

slope of the lines in the plots at the top of page 36.
We also can write Charles' law as
If two sets of experimental conditions at the same

pressure are being compared, 1 and 2, then Charles' law
can be written as
It is important to remember that this equality holds only

at constant pressure.
Page 38 of 48
Example. A hot-air balloon heated by a propane burner

has a volume of 500,000 liters when the air inside is
heated to 75 . What will the volume be after the air has
cooled to 25 , if the pressure remains constant?
Solution. The first step is to convert temperature from

centigrade to absolute:
T = 75 + 273 = 348K
T = 25 + 273 = 298K
Then we can use Charles' law:
Page 39 of 48
The Ideal Gas Law
Boyle's law describes the relationship between pressure and volume, temperature, or amount of gas.
volume when temperature is fixed; Charles' law relates volume If pressure is measured in atmospheres, volume in liters, and
and temperature when the pressure is constant. We can combine temperature in degrees Kelvin, then R has the numerical value
these two laws into the ideal gas law-ideal because it is obeyed R = 0.0821 liter deg
strictly by no real gases, but is followed more and more closely as
the pressure decreases and temperature increases. For n moles The ideal gas law is much more powerful than either Boyle's or
of an ideal gas Charles' laws alone. We now can calculate how many moles of
PV = nRT hydrogen gas there were in the weather-balloon example,
The gas constant, R, is a fixed quantity, independent of pressure, assuming a temperature of 25 .
Page 40 of 48
The Ideal Gas Law
Boyle's law describes the relationship between pressure and volume, temperature, or amount of gas.
volume when temperature is fixed; Charles' law relates volume If pressure is measured in atmospheres, volume in liters, and
and temperature when the pressure is constant. We can combine temperature in degrees Kelvin, then R has the numerical value
these two laws into the ideal gas law-ideal because it is obeyed R = 0.0821 liter deg
strictly by no real gases, but is followed more and more closely as
the pressure decreases and temperature increases. For n moles The ideal gas law is much more powerful than either Boyle's or
of an ideal gas Charles' laws alone. We now can calculate how many moles of
PV = nRT hydrogen gas there were in the weather-balloon example,
The gas constant, R, is a fixed quantity, independent of pressure, assuming a temperature of 25 .
Page 40 of 48
The Ideal Gas Law

Example. An eight-foot diameter weather balloon is filled with 7600 The average molecular weight of the air mixture then is
liters of at 1atm pressure and 25 . How many moles of
hydrogen gas are present? 80 % x 28.013 g + 20 % x 32.000 g
=28.81 g
Solution. P = 1 atm, V = 7600 liters, T = 25 = 298K.
The weight of air displaced is
311 moles x 28.81 g = 8960 g
The buoyancy of the balloon is the difference in weight of air and

hydrogen:
As an interesting sidelight, we can calculate the lifting power of the
balloon.
8960 g - 627 g = 8333 g
Solution. The 311 moles of gas weigh 311 moles X 2.016 g

= 627 g. The lifting power of the balloon is the difference The balloon therefore can lift slightly more than 8 kilograms, or 18
between this and the weight of the air that the balloon displaces. pounds, of payload. We now can take into account the
simultaneous change of pressure and temperature, and correct
The same volume of air also would contain 311 moles (Avogadro's the flaw in the weather balloon example first used to illustrate
principle), and air can be considered a mixture of 80% nitrogen gas Boyle's law.
and 20% oxygen gas.
Page 41 of 48
The Ideal Gas Law

gas at 1 atm. pressure and 25 . As the balloon rises to an altitude where the
pressure is only 0.70 atm, the temperature drops to -20 . What then is the
Solution. Let sea-level conditions be denoted by subscript 1, and high altitude

conditions, by 2. The number of moles of gas does not change, so we can use
the ideal gas law in the form
or
The decrease in pressure to 0.70 atm causes an increase in volume by a factor

of 1.00/0.70, but the simultaneous drop in temperature causes a shrinkage by
a factor of 253/298. The balloon does not expand as much as it would have if
the temperature had remained constant.
Page 42 of 48
The Ideal Gas Law
At the beginning of the section on gas laws, we said that all gases have the
same volume per mole at constant pressure and temperature. We now can
calculate what this molar volume is. Scientists refer to 1 atm pressure and
0 (273.15K) as "standard temperature and pressure," or STP. At STP, the
volume per mole of a gas is
A 22.4-liter sphere has a diameter of 35 cm, and this was the calculation that
produced the figure quoted previously in this chapter. One mole of any gas at
STP fills a flask fourteen inches in diameter (right).
Page 43 of 48
The Ideal Gas Law
The ideal gas law describes the behavior of a fictional gas. This is close to being true at room temperature and 1 atm
pressure.
Real gases act at room temperature as if they would shrink to
nothing at absolute zero, when in fact they condense first. Before At lower temperatures and slower speeds, the attractive forces
reaching absolute zero, all real gases liquefy or solidify, behavior between molecules no longer can be ignored.
for which the ideal gas law cannot account.
At higher pressures, at which molecules are closer together, the
No gas obeys the conditions PV = nRT perfectly, but all gases volume occupied by the molecules themselves becomes an
come close at room temperatures and low pressures. This is the appreciable part of the volume filled by the gas. The ideal gas law
reason that we can apply the gas law to any gas, including an begins to fail badly.
atmospheric mixture of and , without worrying about the
composition of the mixture. One molecule is the same as any Nevertheless, under ordinary conditions the expression PV=nRT
other in an ideal gas. is a surprisingly good description of real gas behavior.
The ideal gas law assumes that attractions between molecules

are negligible when compared with their energies of motion, and
that the actual volumes of gas molecules are negligible in
comparison with the total volume occupied by the gas.
Page 44 of 48
A Chemical World in Miniature: A Summary

We began these first two chapters with the statement that ours was a universe
mainly of hydrogen and helium, which at the same time are the simplest and
the oldest two elements. These two elements illustrate in miniature most of the
chemical principles that we will encounter with the heavier elements. The other
elements, like hydrogen and helium, are built from positively charged nuclei
containing protons and neutrons, surrounded by enough negatively charged
electrons to neutralize the positive charge of the protons.
The number of protons, or the atomic number, determines the chemical

behavior of an atom because it determines the number of electrons that
surround a neutral atom; and the gain, loss, and sharing of electrons is
responsible for an atom's chemical properties.
The number of neutrons usually is equal to or slightly greater than the number
of protons. Neutrons have little effect on chemical properties of an atom,
except for those that are influenced by mass.
Atoms with the same atomic number but different numbers of neutrons are
called isotopes. The total number of neutrons and protons in the nucleus is the
mass number of the atom, and the actual mass in amu is the atomic weight
relative to that of carbon-12 as exactly 12 amu. Observed atomic weights
usually are averages of the weights of several naturally occurring isotopes.
Page 45 of 48

Electrons in atoms surround the nucleus in a series of shells, with similar
energies within one shell and different energies from one shell to the next. The
innermost shell can hold two electrons and the next, eight. A completely filled
shell is a particularly stable arrangement for an atom.
Helium atoms will not combine with one another, for each already has the two
electrons necessary to fill its inner electron shell. Hydrogen atoms lack one
electron of having a completely filled shell, and two H atoms can share a pair
of electrons to form an molecule. In this way each of the atoms in the
molecule has two electrons in its immediate vicinity, and thereby attains a full-
shell structure. The bond in the H-H molecule can be thought of as the
prototype of the electron-pair or covalent bond in larger molecules.
An amount of any compound in grams, numerically equal to its atomic or

molecular weight in amu, is one mole of that substance. The mole concept
allows one to measure equal numbers of atoms or molecules of various
material, even without a knowledge of how many molecules there are. The
actual number of molecules in one mole, Avogadro's number, has been
measured as N = 6.022 X 10 .
From the way in which the mole is defined, this value is also the conversion
factor between amu and grams as units of mass: 1 g = 6.022 X 10 amu. One
mole of molecules weighs 2.016 grams, and one mole of He atoms, 4.003
g.
Page 46 of 48
All atoms and molecules have a very weak, short-range attraction for one
another known as van der Waals attraction. They also have finite though tiny
molecular volumes.
At ordinary temperatures, where the molecules of a gas are moving rapidly,

and at moderate pressures, where on the average they are far apart, both van
der Waals attractions and molecular volumes can be neglected, and molecules
can be treated as freely moving, nonattracting point particles.
Under these conditions the behavior of all gases is described by the ideal gas
law, PV = nRT, in which T is the absolute temperature, obtained by adding
273.15 to the centigrade temperature.
The speed with which molecules move in a gas depends on its temperature;
and in principle, if ideal gas behavior were followed all the way to absolute
zero, all molecular motion would stop at that point and both pressure and
volume would fall to zero.
Right: Johannes Diderik van der Waals (1837 - 1923)
Page 47 of 48

In practice, before this point is reached, van der Waals attractions and
molecular volumes become too important to be ignored, and gases deviate
from ideal behavior. The most striking deviation occurs when slowly moving
molecules "stick" to one another, and a gas condenses into a liquid. At still
lower temperatures, the liquid freezes into a crystalline solid.
The boiling point of a liquid is a useful measure of the strength of van der
Waals forces between molecules, because the smaller the molecules and the
weaker these forces are, the lower the temperature can be before the gas
molecules stick together and condense as a liquid. Of the two elements in our
simple universe, molecules must be cooled to -253 , or 20K, before they
condense. This is the boiling point of liquid hydrogen at a pressure of
1 atm.
The single atoms of helium gas are smaller, with less surface area. They must
be cooled to 4K before their attractive forces cause them to condense.
Hydrogen and helium illustrate many chemical properties, but by themselves

they are a dead end. They are not capable of the great variation seen in the
chemistry of the heavier elements. If stellar syntheses had gone no farther than
hydrogen fusion, the universe would have been stillborn. To continue, we must
turn to the elements heavier than helium, and this is the subject of the next
chapters.
Page 48 of 48

1 atm.

chapters.
Page 48 of 48

1 atm.

chapters.
Page 48 of 48

1 atm.

chapters.
Page 48 of 48
Questions
1. A common model-building kit has a scale of 2 cm to the angstrom unit. What

magnification factor would this be over the actual atomic sizes? Roughly how
big would atoms be in these models? If nuclei were shown, how big would they
be on the same scale?
2. Which are heavier, neutrons or electrons? Which are more highly charged?
What counterbalances the charge on the protons in a neutral atom? Where is
the proton charge located in the atom, and where is the counterbalancing
charge?
3. What is the difference between the nuclei of hydrogen and helium atoms?
How does this affect the number of electrons in each atom?
4. What is the difference between the various kinds of hydrogen atoms? What
are such variations in the same type of atom called?
5. If you know that an atom is a carbon atom, what can you tell about the
number of electrons, neutrons, and protons? What new information do you
have if you know that it is carbon-13?
Page 01 of 02
http://www.chem.ox.ac.uk/vrchemistry/AMM/HTML/ques01.htm 2006/11/27
Questions
6. Which is more important in determining the chemical behavior of an atom,

the number of neutrons or the number of protons? Why?
7. What holds two hydrogen atoms together in a molecule? Why do two helium
atoms not form a stable molecule?
8. Why do two hydrogen atoms become more stable if they are brought
together, but then become less stable again if they are brought too close?
9. How is the molecular weight of a molecule related to the atomic weights of

the atoms from which it is made?
10. What is a mole of a chemical substance? How is the mole concept useful in
chemistry?
11. How many molecules are present in one mole of water vapor? Of liquid
water? Of ethyl alcohol?
12. What is the molecular explanation for the phenomenon of pressure?
Page 02 of 02
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Foundations to Chemistry - adapted from "Chemistry, Matter and the Universe" Page 1 of 1

2. Atoms, Molecules and Moles -- Jump to --

Hydrogen and helium occupy a special place in the chemical

2. Atoms, Molecules and Moles -- Jump to --

Electrons, Nuclei, and Atomic Number

There are 100,000,000 or 10 in one centimeter, or to express matters the other

2. Atoms, Molecules and Moles -- Jump to --

Electrons, Nuclei, and Atomic Number

2. Atoms, Molecules and Moles -- Jump to --

Electrons, Nuclei, and Atomic Number

The atomic number sometimes is written as a subscript in front of the symbol

2. Atoms, Molecules and Moles -- Jump to --

Electrons, Nuclei, and Atomic Number

Chemical properties are periodic functions of the atomic number - in a listing of

This is one of the most important generalizations in chemistry.

2. Atoms, Molecules and Moles -- Jump to --

The three isotopes of hydrogen have quite different

2. Atoms, Molecules and Moles -- Jump to --

Only for hydrogen, in which additional neutrons double

= H = light hydrogen or "ordinary" hydrogen, with

Ordinary water has the chemical formula . Heavy

2. Atoms, Molecules and Moles -- Jump to --

This missing mass is converted to energy during the

Nevertheless, for approximate calculations we can

2. Atoms, Molecules and Moles -- Jump to --

2. Atoms, Molecules and Moles -- Jump to --

2. Atoms, Molecules and Moles -- Jump to --

2. Atoms, Molecules and Moles -- Jump to --

2. Atoms, Molecules and Moles -- Jump to --

Isotopes and Observed Atomic Weights

2. Atoms, Molecules and Moles -- Jump to --

Isotopes and Observed Atomic Weights

The atomic weight of an element in nature is the weighted average, in terms of

If individual isotopes are wanted, they must be separated by some technique,

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

At the beginning of this century chemical bonding was

We can take some of the pictorial conclusions from

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

At the beginning of this century chemical bonding was

We can take some of the pictorial conclusions from

2. Atoms, Molecules and Moles -- Jump to --

Bonds Between Atoms

At the beginning of this century chemical bonding was

We can take some of the pictorial conclusions from

2. Atoms, Molecules and Moles -- Jump to --