Atoms, Molecules, and Laws of Matter

Laws of Matter
In this section, we explore the fundamental laws of chemistry.

Law of Conservation of Mass

In the 18th century, scientists thought that when things burn a substance called phlogiston
came out of them. However, by conducting experiments in closed vessels (where substances
could be accurately weighed), early scientists like Antoine Lavoisier discovered and proved that
matter could be changed but not destroyed. This is used to establish the law of conservation
of mass:
The total mass of substances present after a chemical reaction is the same as the total mass
of substances before the reaction. Matter is neither created nor destroyed in a chemical
reaction.
In the photo (left), before the reaction, a beaker with a silver nitrate solution and a graduated
cylinder with a potassium chromate solution is placed on a single-pan balance which displays
their combined mass.
When the solutions are mixed (right), a chemical reaction occurs that forms silver chromate
(red precipitate) in a potassium nitrate solution. Note that the total mass remains unchanged.

Law of Conservation of Mass. ©General Chemistry Principles and Modern Applications. 11th Edition. Petrucci R.H. et. al.
Pearson Toronto.

Law of Definite Proportions

French pharmacist Joseph Proust built on Lavoisier's ideas of extremely careful measurement
and reported that a chemical compound always contains the same proportions of elements.
This and similar observations became the basis of the law of constant composition, or the law
of definite proportions:
All samples of a compound have the same composition - the same proportions by mass of the
constituent elements.
Consider the compound water. Water is made up of two atoms of hydrogen (H) for every atom
of oxygen (O): H2 O. The two samples described below have the same proportions of the two
elements, expressed as percentages by mass.
To determine the percent by mass of hydrogen, for example, simply divide the mass of
hydrogen by the sample mass and multiply by 100%. For each sample, you will obtain the
same result: 11.19% H.

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 The point here is that the ratio between the quantities of hydrogen and oxygen in each sample will stay
the same because the composition by mass is constant, whether the weight of the substance is 27.000 g
or 10. 0 grams.

Dalton's Atomic Theory

English school teacher, John Dalton used the two fundamental laws of chemical
combination above as the basis of an atomic theory. His theory involved the following
assumptions:
1. Each element is composed of extremely small, indivisible particles called atoms. These
can neither be created nor destroyed during a chemical change.
2. All atoms of a given element are identical, but the atoms of one element are different from
the atoms of all other elements.

3. In each of their compounds, different elements combine in a simple numerical ratio, for
example, one atom of A to one of B (AB), or on atom of A to two of B (AB2 ).

If atoms of an element are indestructible (assumption 1), then the same atoms must be present
after a chemical reaction as before. The total mass remains unchanged, explaining the law of
conservation of mass.
If all atoms of an element are alike in mass (assumption 2) and if atoms unite in fixed numerical
ratios (assumption 3), the percent composition of a compound must have a unique value,
regardless of the origin of the sample analyzed. This explains the law of constant composition.
This atomic theory led to the law of multiple proportions:

Multiple Proportions
⮚ The law of multiple proportions states that two or more elements can react in different
proportions to form more than one kind of compound.

The law of multiple proportions. Carbon and Oxygen can react in two different proportions forming carbon
monoxide and carbon dioxide, a two different compounds.

Atoms: Theory and Structure

The elements from the past chapter are still made up of even smaller particles called atoms.
The idea of atoms as the building blocks of matter started with the ancient philosopher named
Democritus. He believed that all matter consists of very small, indivisible particles, which he
named atomos.
We look first at the fundamental particles, also called subatomic particles. These are the
basic building blocks of all atoms: electrons, protons, and neutrons. As shown in the table
below, the mass of an electron is very small compared with the mass of either a proton or a
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neutron. The charge of a proton is equal in magnitude, but opposite in sign, to the charge on an
electron.

Discovery of Electrons
The first cathode-ray tube (CRT) was made by Michael Faraday. It is a glass tube from which
most of the air had been evacuated. When the two metal plates inside are connected to a high-
voltage source, Faraday discovered cathode rays, a type of radiation emitted by the negative
terminal or cathode. The radiation crossed the evacuated tube to the positive terminal or
anode.
Cathode rays produced in the CRT are invisible, and they can be detected only by the light
emitted by the materials that they strike. These materials, called phosphors or fluorescent
screens, are painted on the end of the CRT so that the path of the cathode rays can be
revealed.
In the figure below, two electrically charged plates (the blue and red plates) were added to the
outside of the cathode ray tube. When only the magnetic field is on and the electric field is off, the
cathode ray strikes point A. When the electric field is on, the ray strikes point C. When both the
magnetic and the electric fields are off or when they are both on but balanced so that they cancel
each other's influence, the ray strikes point B.

Cathode-Ray Tube. ©Chemistry. Chang, R. 10th Edition. McGraw-Hill.

The cathode rays produced are deflected by electric and magnetic fields as if they are negatively
charged particles. Through that experiment conducted by J. J. Thomson, it was concluded that
cathode rays are negatively charged fundamental particles found in all atoms. Also, Thomson
established the ratio of mass to electric charge for cathode rays. Cathode rays subsequently
became known as electrons, as proposed by George Stoney in 1974.

Robert Millikan determined the electronic charge e through a series of oil-drop experiments. He
examined the motion of single tiny drops of oil that picked up static charge from ions in the air. He
suspended the charged drops in the air by applying an electric field and followed their motions
through a microscope.
From that experiment, he found the charge of an electron to be − 1.6022 x 10−19 . By combining
this value with an accurate value of the mass-to-charge ratio for an electron, we find that the mass
of an electron is 9.194 x10-28 g.

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 Millikan’s Oil-Drop Experiment Set-Up

At this point, the accepted atomic model is the one proposed by Thomson: the plum-pudding
model. He thought that the positive charge necessary to counterbalance the negative charges
of electrons in a neutral atom was in the form of a cloud.

Plum Pudding J.J. Thomson's Plum-Pudding Model of the Atom.

The Gold Foil Experiment and the Nucleus

Ernest Rutherford decided to use α particles from a radioactive source to prove the structure of
atoms. Together with Hans Geiger and Ernest Marsden, they carried out a series of
experiments using very thin foils of gold (and other metals) as targets for α particles. He
reasoned that if Thomson's model were accurate, the massive α particles should crash through
the thin foil: like cannonballs through gauze or with only minimal deflection.

Rutherford's Particle-Scattering Experiment. ©Chemistry: The Molecular Nature of Matter and Change. 9th Edition. Silberberg
M.S. McGraw-Hill.

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However, the results were very different from his proposed hypothesis: although most of the α
particles passed straight through, many of the particles were deflected at large angles.
Furthermore, some were fully reflected, never hitting the detector.
Rutherford explained the results by postulating the nuclear model of the atom, in which most of
the mass and all of its positive charge reside in a very small, extremely dense region that he
called the nucleus. Also, he postulated that most of the volume of an atom is empty space in
which electrons move around the nucleus.

Nuclear Atomic Model. Fine art america.com

Discovery of Protons

In 1886, Eugen Goldstein first observed that a cathode-ray tube also generates a stream of
positively charged particles that moves toward the cathode. These were called canal rays
because they were observed occasionally to pass through a channel or "canal" drilled in the
negative electrode. These positive rays, or positive ions, are created when the gaseous atoms
in the tube lose electrons. These will be later known as
protons.

Perforated CRT showing canal rays ©Chemistry. 9th Edition. Whitten, K. et al. Brooks/Cole CENGAGE Learning

Subsequent experiments made it possible for James Chadwick to discover and observe neutrons
in 1932.

Modern Atomic Theory

Today, an atom is defined as an electrically neutral, spherical entity composed of a positively
charged central nucleus surrounded by one or more negatively charged electrons.
Atoms are electronically neutral because every atom has an equal number of electrons and
protons.
Atoms have extremely small masses. Because it would be cumbersome to expresses such small
masses in grams, we use the atomic mass unit (amu), where
1 amu = 1.66054 x 10−24.
Each element on the periodic table differs from the preceding element by having one more
positive charge in its nucleus.

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 The structure of the atom.

All atoms of a particular element have the same atomic number, Z, and all atoms with the same
number of protons are atoms of the same element. This is shown in the nuclide symbol:

Nuclide Symbol
In the notation above, E stands for the atom symbol and it has atomic number Z and mass
number A (total number of protons and neutrons). Note that an uncharged atom has the same
number of electrons and protons.

Atoms that have the same atomic number (Z) but different mass numbers (A) are called
isotopes. Isotopes can be written as E-Z, e.g. Cl-35 or Cl-37, or by using the element symbol
with the atomic number written as a subscript and the mass number written as a superscript, both
to the left.

Isotopes.

Examples
Give the number of protons, neutrons, and electrons in each of the following species:
20
a. 11 Na : The atomic number (Z) is 11 so there are 11 protons. The mass number (A), so the number of
neutrons is 20 - 11 = 9. The number of electrons is the same as the number of protons: 11.
22
b. 11 Na : Z is 11, A is 22, so the number of neutrons is 22 - 11 - 11. The number of electrons is 11.
17
c. O : Z of oxygen is 8, so there are 8 protons. A is 17, so there are 17 - 8 = 9 neutrons. There are 8
electrons.

d. Carbon-14 : This can also be written as 14C. Its Z is 6, so there are 14 - 6 = 8 neutrons. The number of
electrons is 6.

Periodic Table: An Introduction

Recognition of periodic regularities in physical and chemical behavior and the need to organize
the large volume of available information about the structure and properties of elemental
substances led to the development of the periodic table, a chart in which elements having
similar chemical and physical properties are grouped together.
In 1869, chemists Dmitri Mendeleev and Lothar Meyer independently published arrangements
of known elements close to the periodic table we have today. Mendeleev's classification was
based primarily on the chemical properties of elements, whereas Meyer's classification was
based largely on physical properties.

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Mendeleev arranged the known elements in order of increasing atomic weight in such a way
that elements with similar chemical properties fell into the same column. It also provided for
elements that were unknown at the time. When he encountered "missing" elements,
Mendeleev left blank spaces. This helped in predicting the properties of the unknown element.

Mendeleev's Periodic Table. Origins: Mendeleev's Periodic Table

The vertical columns are referred to as groups or families, and the horizontal
rows are called periods. Elements in a group have similar chemical and physical
properties, and those within a period have properties that change progressively
across the table.

The Periodic Table as of 2021. ©Ptable.com

Elements are often referred to collectively by their periodic table group number. However,
several groups have common names that are used so frequently so they should be learned.
Group 1 elements are called alkali metals (excluding hydrogen), and Group 2 elements are
called alkaline earth metals. Group 17 are known as halogens, and elements in Group 18
are called noble gases, or rare gases.

⚠ letter
Sometimes an older system for groups is used, with the group numbers from 1 to 8 and either a
A or B. The eight A groups (Groups 1, 2, 13,14, 15, 16, 17, and 18) contain the main group
elements. The ten B groups, located from Group 3 to Group 12, contain the transition elements.
Two horizontal series of inner transition elements, the lanthanides and the actinides, fit between the
elements in Group 3 and Group 4 and are placed below the main body of the table.

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Classifying the Elements
One of the clearest ways to classify the elements is as metals, nonmetals, and metalloids.

The metals (as color-coded blue in the table) lie in the large, lower left portion of the table.
They are generally shiny solids at room temperature (excluding mercury) that conduct heat
and electricity well. They can be tooled into sheets and wires.
The nonmetals (noble gases and reactive nonmetals, yellow in the table) lie in the small,
upper right portion of the table (with the exception of hydrogen). They are generally gases
or dull, brittle solids at room temperature (excluding bromine) and conduct heat and
electricity poorly.

The metalloids, also called semimetals, lie along the staircase line (green), have
properties between those of metals and nonmetals.

Molecules and Ions

Molecules
A molecule is an aggregate of at least two atoms in a definite arrangement held together by
chemical forces, called chemical bonds. A molecule may contain atoms of the same element or
atoms of two or more elements joined in a fixed ratio, following the law of definite proportions.

⚠ A molecule is not necessarily a compound.

For example, hydrogen gas H2 is a pure element, but it consists of molecules made up of two H
atoms each. Water, on the other hand, is a molecular compound that contains hydrogen and
oxygen in a definite ratio. Like atoms, molecules are electrically neutral.
The hydrogen molecule, H2 , is called a diatomic molecule because it contains only two
atoms. Other elements that normally exist as diatomic molecules are nitrogen, oxygen, as well
as halogens.

⚠ A diatomic molecule can also contain atoms of different elements, like HCl or CO.

Molecules containing more than two atoms are called polyatomic molecules. They can be
atoms of the same elements, as in ozone O3 , or ammonia, NH3 .

Ions
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 When atoms lose or gain electrons, the species formed are called ions. These carry net charges
which could either be positive or negative. Note that an electron is negatively charged.
The atoms of metallic elements tend to lose one or more electrons when they combine with
nonmetal atoms, and the nonmetal atoms tend to gain one or more electrons. Because of that,
removing electrons from an uncharged metal atom produces a positively charged ion - a
cation. Adding electrons to an uncharged nonmetal atom produces a negatively charged ion -
an anion.

⚠ The number of protons does not change when an atom becomes an ion.

In the expression below, #± indicates that the charge is written with the number (#) before the + or
- sign. However, when the charge is 1+ or 1-, the number 1 is not included.

Ions. ©General Chemistry Principles and Modern Applications. 11th Edition. Petrucci R.H. et. al. Pearson Toronto.

Example

If Sodium (Na), which has 11 protons & 11 electrons, loses an electron, it becomes Na+ which has
11 protons and 10 electrons.
This can be shown as

Na → Na+ + e−

If Chlorine (Cl), which has 17 protons and 17 electrons, gains an electron, it becomes Cl− which
has 17 protons and 18 electrons.
This can be shown as

Cl + e− → Cl−
Sodium chloride (NaCl), ordinary table salt, is called an ionic compound because it is formed
from cations and anions. An atom can lose or gain more than one electron. Examples are Mg2+,
Fe3+, and N3−. These ions, along with Na+, are called monatomic ions because they contain
only one atom.
Polyatomic ions may also exist. These are ions in which their atoms are covalently bonded.
To indicate different polyatomic ions made up of the same elements, the name of the ion is
modified.
Click here to be redirected to a list of cations and anions.
The names of monatomic anions are formed by replacing the ending of the name of the
element with -ide. Polyatomic anions containing oxygen have names ending in either -ate or -
ite are called oxyanions. The -ate is used for the most common or representative oxyanion of
an element, and -ite is used for an oxyanion that has the same charge but one O atom fewer.

Example

nitrate ion NO3 –

nitrite ion NO2 –

sulfate ion SO4 –

sulfite ion SO3 2 –

Prefixes are used when the series of oxyanions of an element extends to four members, like with

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the halogens. The prefix per- indicates one more O atom than the oxyanion ending in -ate; hypo-
indicates one O atom fewer than the oxyanion ending in -ite.

Example
Hypochlorite ion ClO –

Chlorite ion ClO2 –

Chlorate ion ClO3 –

Perchlorate ion ClO4 –

Anions derived by adding H+ to an oxyanion are named by adding as a prefix the word hydrogen or
dihydrogen, as appropriate.
Example
carbonate ion CO3 2 –
–
hydrogen carbonate ion HCO3
phosphate ion PO4 3 –
dihydrogen phosphate ion H2PO4 –

Chemical Formulas
Chemical formulas are used to express the composition of molecules and ionic compounds
in terms of chemical symbols. In this section, we will be unpacked two types of formulas:
molecular formulas and empirical formulas.

Empirical Formulas
An empirical formula tells us which elements are present and the simplest whole-number ratio
of their atoms,
but not necessarily the actual number of atoms in a given molecule.
As an example, consider the compound H2O2 , a substance used as an antiseptic and as a
bleaching agent for textiles and hair. It has two hydrogen atoms and two oxygen atoms. The ratio
of hydrogen to oxygen atoms in this molecule is 2:2 or 1:1. The empirical formula of hydrogen
peroxide is HO.
For many molecules, the molecular formula and the empirical formula are one and the same.
Some examples are ammonia (NH3), carbon tetrachloride (CCl4), and methane (CH4).

Empirical formulas are the simplest chemical formulas, written by reducing the subscripts in the
molecular formulas to the smallest possible whole numbers. Molecular formulas are the true
formulas of the molecules.

Molecular Formulas
A molecular formula shows the exact number of atoms of each element is the smallest unit of
a substance. O3, HCl, and H2 are some examples. The subscript numeral indicates the number
of atoms of an element present. There is no subscript for H and Cl in HCl because there is
only one atom of each in the molecule of HCl, and so the number "1" is omitted from the

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 O3 .
formula.
Formula of Molecular Compounds
A molecular compound is made up of discrete units called molecules, which usually consist
of a small number of nonmetal atoms held together by covalent bonds.
The constituent elements are denoted by their symbols. The number of atoms is indicated by
subscripts. For example, consider H2O:

Molecular Models
Molecules are too small for direct observation. Thus, molecular models are used as a means of
visualizing these substances. Either the ball-and-stick or the space-filling model is usually
used. The angles they form between atoms approximate the bond angles in actual molecules.
With the exception of the H atom, the balls are all the same size. Each type of atom is
represented by a specific color, as shown below:

Molecular Models

Formula of Ionic Compounds

An ionic compound is made up of positive and negative ions joined together by electrostatic
forces of attraction (attraction of oppositely charged objects).

empirical formulas because ionic compounds do not consist of

discrete molecular units.

In the formation of sodium chloride (NaCl), each sodium gives

up one electron to become a sodium ion, Na+, and each chlorine

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atom gains one electron to become a chloride ion, Cl−. For
sodium chloride to be electrically neutral, there must be one Na+
ion for each Cl− ion (+1 + (-1) = 0). Thus, the formula for sodium
chloride is NaCl.
On the figure right above is a portion of an ionic crystal and a
formula unit of NaCl. The ratio of chloride ions to sodium ions in
sodium chloride is 1:1, so we can select any combination of one
Na+ ion and Cl−ion as a formula unit.
The formula unit of an ionic compound is the smallest electrically neutral collection of ions.
Because it is buried in a vast network of ions, called a crystal, a formula unit of an ionic
compound does not exist as a distinct entity. Thus, it is inappropriate to call a formula unit of a
solid sodium chloride a molecule.

Example

1. Potassium Bromide. The potassium cation K+ and bromine anion Br− combine to form the
ionic compound potassium bromide. The sum of the charges is +1 + (-1) = 0, so no
subscripts are necessary. The formula is KBr.

2. Zinc Iodide. The zinc cation Zn2+ and the iodine anion I− combine to form zinc iodide. The

sum of the charges of one Zn2+ and one I− ion is +2 + (-1) = +1. To make the charges add
up to zero, we multiply the
-1 charge of the anion by 2 and add the subscript "2" to the symbol for iodine. Therefore the
formula for zinc iodide is ZnI2.

3. Aluminum Oxide. The cation is Al3+ and the oxygen anion is O2−. The following
diagram helps us determine the subscripts for the compound formed by the cation
and the anion:

The sum of the charges is 2(+3) + 3(-2) = 0. Thus, the formula for aluminum oxide is Al2O3.

4. Ammonium Arsenate. The cation is ammonium (NH4 +) and the anion is arsenate (AsO4−).
Using the same method as number 3, we end up with
4 the formula (NH 4)3AsO4.

Naming Inorganic Compounds

To begin with chemical nomenclature - the naming of chemical compounds, we must
distinguish between inorganic and organic compounds. Organic compounds contain carbon,
usually in combination with elements such as hydrogen, oxygen, nitrogen, and sulfur. All other
compounds are classified as inorganic compounds.

⚠ dioxide
For convenience, some carbon-containing compounds, such as carbon monoxide (CO), carbon
(CO2), carbon disulfide (CS2 ), compounds containing the cyanide group (CN−), and
carbonate (CO2−) and bicarbonate (HCO−) groups are considered to be inorganic compounds.

Compounds of Metals and Nonmetals

Binary compounds are those formed between two elements. If one element is a metal and
the other a nonmetal, the binary compound is usually made up of ions; that is, it is a binary
ionic compound. To name a binary compound of a metal and a nonmetal,
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 write the unmodified name of the metal

then write the name of the nonmetal, modified to end in -ide.

Example

NaCl = Sodium chloride

MgI2 = Magnesium iodide
Al2O3 = Aluminum oxide

Some metals are capable of forming several ions. It is important to distinguish between them
in naming compounds. The metal iron, for example, forms two common ions: Fe2+ and Fe3+.
The first is called iron(II) ion, and the second is the iron(III) ion. The roman numeral following
the name of the metal indicates its oxidation state. Thus, FeCl2 is iron(II) chloride, while FeCl3
is iron(III) chloride.

There is an older system of naming that is still used. The idea is to use the suffix -ous for the
lower oxidation state, of the metal and -ic for the higher oxidation state.
For example,
In Cu2O, the oxidation state of copper is +1

and it is assigned the name cuprous oxide or copper(I) oxide.

In CuO, it is +2
and is assigned the name cupric oxide or copper(II) oxide.

Binary Compounds of Two Nonmetals

If two elements in a binary compound are both nonmetals instead of metal and nonmetal, the
compound is a molecular compound. The naming method is similar to the one discussed above.
For example,
HCl = Hydrogen chloride

Generally, the name of the element farther to the left in the periodic table is usually written
first. Except when the compound contains oxygen and chlorine, bromine, or iodine, in
which case oxygen is written last.

If both elements are in the same group, the one closer to the bottom of the table is

named first. The name of the second element is given an -ide ending.

Some pairs of nonmetals form more than one binary molecular compound, and we need to
distinguish among them. Generally, we indicate relative numbers of atoms through prefixes:

mono- 1 hexa- 6
di- 2 hepta- 7

tri- 3 octa- 8
tetra- 4 nona- 9
penta- 5 deca- 10

Example

SO2 = sulfur dioxide SO3 = sulfur trioxide B2Br4 = diboron

tetrabromide.

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 ⚠ nitrogen
Note that we do not use the prefix mono- for the first-named element. For example, NO is called
monoxide, and not mononitrogen monoxide.

Binary Acids
An acid is a substance that dissociates into hydrogen ions (H+) and anions in water. A quick way to identify
acids is to see if there is an H (denoting hydrogen) in front of the molecular formula of the compound.

1. To name acids containing anions whose names end in -ide, add the prefix hydro- to this anion name, and
then follow with the word acid.

Example

Cl− chloride HCl hydrochloric acid

F− fluoride HF hydrofluoric acid

Br− bromide HBr hydrobromic acid

sulfide H2 S hydrosulfuric acid

S2−

2. Acids containing anions whose names end in -ate or -ite are named by changing -ate to -ic and -ite to -ous
and then adding the word acid. Prefixes in the anion name are retained in the name of the acid.

Example

ClO−4 perchlorate HClO4 perchloric acid

ClO−3 chlorate chloric acid

HClO3

ClO−2 chlorite chlorous acid

HClO2
hypochlorous acid hypochlorous acid
ClO−
HClO

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