The Atomic Theory of Matter

Theories of Matter
• The Greeks and Hindus appear to have developed theories on matter.
• Most of the writings are attributed to the Greeks due to the amount of recorded
information that has survived to the present.
• Greeks thought substances could be converted or transformed into other forms.
• They observed the changing of states due to heat and equated it with biological
processes.
• The Greeks were philosophers and thinkers, not experimentalists, so they did not
conduct experiments to verify their ideas.

John Dalton - Atomic Theory

– All bodies are constituted of a vast number of extremely small particles, or atoms of
matter bound together by a force of attraction
– The ultimate particles of all homogeneous bodies are perfectly alike in weight, figure,
etc.
Atoms have definite relative weights “expressed in atoms of hydrogen, each of which is
denoted by unity”
– Atoms combine in simple numerical ratios to form compounds
– Under given experimental conditions a particular atom will always behave in the same
manner
– Atoms are indestructible

1. Matter is made up of indivisible atoms.

2. All atoms of an element are identical.
3. Atoms are neither created nor destroyed.
4. Atoms of different elements have different weights and chemical properties.

Atoms of different elements combine in simple whole numbers to form compounds.

J.J. Thompson

• Found that cathode rays could be deflected by an electric field

• Showed that cathode "rays" were actually particles
• Found the charge to mass ratio of the particles to be approximately
108 Coulomb (C) per gram.
• Same charge to mass ratio regardless of metal used for cathode/anode
or gas used to fill the tube.

Thomson’s experiments used a vacuum tube. A vacuum tube has had all gases pumped
out of it. At each end of the tube is a metal piece called an electrode, which is connected
through the glass to a metal terminal outside the tube. These electrodes become
electrically charged when they are connected to a high-voltage electrical source. When
the electrodes are charged, rays travel in the tube from the negative electrode, which is

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the cathode, to the positive electrode, the anode. Because these rays originate at the
cathode, they are called cathode rays.

Thomson found that the rays bent toward a positively charged plate and away from a
negatively charged plate. He knew that objects with like charges repel each other, and
objects with unlike charges attract each other. Thomson concluded that cathode rays are
made up of invisible, negatively charged particles referred to as electrons. These
electrons had to come from the matter (atoms) of the negative electrode.
Conclusion: Particles were a universal component of matter.

• Electron - (originally called corpuscles by Thompson) particles

given off by the cathode; fundamental unit of negative electricity
• Raisin Pudding Model -
o Matter is electrically neutral and electrons are much lighter than atoms.

Raisin Pudding Model

Conclusion: There must be positively charged particles which also must carry the mass
of the atom. Dalton's model is now incorrect becauseatoms are divisible.

1899 - Ernst Rutherford

Studied absorption of radioactivity.

• Alpha radiation - positive charge - absorbed by a few hundredths of a cm or metal

foil

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 • Beta radiation - negative charge - could pass through 100x as much foil before it
was absorbed
• Gamma rays - no charge - could penetrate several cm of lead

Rutherford updated Thomson's Raisin Pudding Model of the atom.

• Studied the deflection of alpha particles as they were targeted

at thin gold foil sheets.
o Most of the alpha particles penetrated straight through.
o However few were deflected at slight angles.

Even fewer (only about 1 in 20,000) were deflected at

angles over 90 .

Diagrammatically

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The Rutherford Atom Model

The atom is mostly empty space with a dense nucleus. Protons and neutrons in are
located in the nucleus. The number of electrons is equal to the number of protons.
Electrons are located in space around the nucleus. Atoms are extremely small.
Conclusion: The positive charge and mass of an atom were concentrated in the center
and only made up a small fraction of the total volume. He named this concentrated
center the nucleus

• Rutherford was also able to estimate the charge of an atom by studying the
deflection of alpha particles. He found that the positive charge on the atom was
approximately half of the atomic weight.

Rutherford proposed the name "proton" for the positively charged particles in the
nucleus of an atom. At the same time, he also proposed that the nucleus also contained
electrically neutral particles which accounted for the remaining mass of the atom. He
called this yet unknown particle the "neutron".

The Subatomic Particles

Atomic Rules

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 • The number of protons in the nucleus of an atom is equal to the atomic number
(Z).
• In a neutral atom, the number of electrons is equal to the number of protons.
• The mass number (M) of an atom is equal to the sum of the number of
protons and neutrons in the nucleus.
• The number of neutrons is equal to the difference between the mass number (M)
and the atomic number (Z).

Symbols of Elements

Isotopes
Atoms of the same element with different masses; Isotopes have different numbers of
neutrons.

Isotopic Masses of Hydrogen and Magnesium

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 Calculation of Atomic Weights

Exercise:

Question 1:A naturally-occurring sample of element X is found to contain 81.8 per cent
X-10 (ie, element X with a mass number of 10) and 18.2 per cent X-11. Calculate the
apparent atomic mass of this naturally-occurring sample of element X.

Question 2: Copper is listed on the periodic table as having a relative atomic mass of
63.55. Reference books indicate two isotopes of copper, with relative masses of 62.93
and 64.93. Find the percent abundance of each isotope.

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Question 3: Element E occurs in two isotopes. 15% of all atoms of E have a relative
atomic mass of 51.05 and the rest a relative atomic mass of 52.05. What is the average
relative atomic mass for the element E?

The Periodic Table

In 1869, Dmitri Mendeleev discovered that if the known elements were arranged in order
of atomic number, they could be placed in horizontal rows such that the elements in the
vertical columns had similar properties.
A tabular arrangement of elements in rows and columns, highlighting the regular
repetition of properties of the elements, is called a periodic table.

Periods and Groups

A period consists of the elements in one horizontal role of the periodic table.

A group consists of the elements in any one column of the periodic table. The groups are
usually numbered.
The eight “A” groups are called main group (or representative) elements.
The two rows of elements at the bottom of the table are called inner transition elements.
Elements in any one group have similar properties.

The elements in group IA, often known as the alkali metals, are soft metals that react
easily with water.

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The group VIIA elements, known as the halogens, are also reactive elements.

Metals, Nonmetals, and Metalloids

A metal is a substance or mixture that has a characteristic luster and is generally a good
conductor of heat and electricity.
A nonmetal is an element that does not exhibit the characteristics of the metal.
A metalloid, or semi-metal, is an element having both metallic and nonmetallic
properties.

Chemical Formulas; Molecular and Ionic Substances

The chemical formula of a substance is a notation using atomic symbols with subscripts
to convey the relative proportions of atoms of the different elements in a substance.
Molecular substances

A molecule is a definite group of atoms that are chemically bonded together – that is,
tightly connected by attractive forces.
A molecular substance is a substance that is composed of molecules, all of which are
alike.
A molecular formula gives the exact number of atoms of elements in a molecule.
Structural formulas show how the atoms are bonded to one another in a molecule.
Ionic substances
Although many substances are molecular, others are composed of ions.

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An ion is an electrically charged particle obtained from an atom or chemically bonded
group of atoms by adding or removing electrons. Sodium chloride is a substance made up
of ions.

Naming simple compounds

Chemical compounds are classified as organic or inorganic. Organic compounds are
compounds that contain carbon combined with other elements, such as hydrogen, oxygen,
and nitrogen. Inorganic compounds are compounds composed of elements other than
carbon.

Naming Ions and Their Compounds

Naming Cations
1. Groups 1, 2, Al, and a few transition elements, which only form 1 valence state, (e.g.
Zn 2+ Cd2+ and Ag+) form only one kind of ion. They simply have the word "ion"
added after their name. e.g.
Na+ sodium ion
Mg2+ magnesium ion
Al3+ aluminum ion
2. Transition metals (most) can have differing charges
New Stock System uses metal name with the valence shown as a Roman
Numeral in parenthesis.
Old Greek/Latin System uses "ic" ending for the higher charge and "ous" ending for
the lower charge. These just need to be memorized!
− Fe2+ iron(II) ion ferrous ion
Fe3+ iron(III)ion ferric ion
Sn2+ tin(II) ion stannous ion
4+
Sn tin(IV)ion stannic ion
3. Polyatomic cations (only 2 common ones)
NH4+ ammonium ion
2+
Hg2 mercury (I) ion mercurous ion
Naming Anions
1. Monatomic anions have the suffix "ide added to the stem of the non-metal's name
i.e., chloride (Cl-), sulfide (S2-), bromide (Br-), oxide (O2-), etc.
Group 17 anions (of halogens) are called halides
2. Polyatomic anions most often contain oxygen and must be learned.
• ate indicates the base number of oxygens (typically 3 but sulfate and phosphate
have 4)
• CO32-, NO3-, PO43-, SO42-, ClO3-, BrO3-, IO3-, .
carbonate, nitrate, phosphate, sulfate, chlorate, bromate, iodate
− These can form a series,
• ClO4- perchlorate ion per means one more “O” than "ate"
• ClO3- chlorate ion
• ClO2- chlorite means one less “O” than “ate”

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 • ClO- hypochlorite hypo means one less “O” than "ite"
Other polyatomic ions you should know:
Ion Name Formula Ion Name Formula
Thiocyanate SCN- Hydroxide OH-
Chromate CrO42- Permanganate MnO4-
Dichromate Cr2O72- Acetate CH3COO-
aka CH3CO2-
aka C2H3O2-
Hydrogen Hydrogen phosphate HPO42-
Carbonate HCO3-
(Bicarbonate)
Oxalate C2O42- Dihydrogen H2PO4-
phosphate
Cyanide CN- Hydrogen sulfate HSO4-
(Bisulfate)

Naming Ionic Compounds

• Name of cation followed by name of anion
• Do not include the work "ion" in the name of the compound
• Do not name quantities of each polyatomic ion.

Example 1: Naming Binary Metal plus Nonmetal Compounds

• Binary implies two different elements.
• Rule: Name of cation (word ion dropped) + name of anion. The subscripts do not
affect the name of the compound!
• Examples: CaO calcium oxide Fe2S3 ferric sulfide .
exceptions - additional " -ide " endings
• OH- hydroxide ion CN- cyanide ion
• Examples: Ca(OH)2 calcium hydroxide KCN potassium cyanide

Example 2: Naming Compounds with Polyatomic Ions

• Rule: Name of cation (word ion dropped) + name of anion. The subscripts do not
affect the name of the compound!
• Examples: Na2SO4 sodium sulfate
(NH4)3PO4 ammonium phosphate .

Writing Formulas for Ionic Compounds

− For a compound, the total positive charge must equal the total negative charge.
• If the charge of the cation and the anion are the same:
1) Write the formula for the cation followed by the one for the anion.
2) Do not show charges of the ions in the final formula
3) Do not use parentheses.

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 • If the charges on the anion and cation are different:
1) Apply the charge of the cation as a subscript for the anion.
2) Apply the charge of the anion as a subscript for the cation.
3) Include polyatomic ions in parentheses.
4) Do not show charges of the ions in the final formula.

Naming Acids (Compounds Starting with H)

• Non-Oxy Acids (without water): These all start with an H and do not contain
oxygen. They are named similarly to other binary nonmetals, except without the
use of Greek prefixes.
Rule: hydrogen followed by anion name (should end in “ide”)
e.g. HCl hydrogen chloride HCN hydrogen cyanide
HBr hydrogen bromide H2S hydrogen sulfide
• Non-Oxy Acids (in water): These are named by using the prefix hydro and the
ending ic and acid. The ___ is filled in based on the root section of the anion.
Rule: hydro ________ic acid
e.g. HCl =hydrochloric acid; HBr = hydrobromic acid;
H2S = hydrosulfuric acid; HCN = hydrocyanic acid
• Common Acids with Oxygen (Oxyancids aka Oxoacids)
• Acids made from the "ate" anions are named by changing the "ate" to "ic" and
adding acid
e.g., nitrate ion (NO3-)gives nitric acid (HNO3);
sulfate ion (SO42-) gives sulfuric acid (H2SO4)
• Acids that are made from the "ite" anions are named by changing the "ite" to
"ous" and adding acid
e.g., chlorite ion (ClO3-) gives chlorous acid (HClO3)
sulfite ion (SO32-) gives sulfurous acid (H2SO3)
• The prefixes "per" and "hypo" do not change the rules above.
e.g., hypochlorite ion (ClO-) gives hypochlorous acid (HClO);
perchlorate ion (ClO4-) gives perchloric acid (HClO4)

Oxyacid/Oxyanion Memory Framework

− Inorganic nomenclature would be a lot simpler if it weren’t for the oxyacids and
the oxyanions they form. An acid that contains oxygen in addition to hydrogen and
another nonmetal is an oxyacid. When hydrogen ions are removed from an oxyacid, the
oxygen stays with the nonmetal as part of an oxyanion Here’s a few matrices I hope will
help you in remembering how they go together and are named. Once you’ve mastered
this you will be able to name 23 oxyacids and the associated ion.
− Remember these seven “ic” acids:

Acid (Group) Formation Equation Ion Name

Carbonic acid (4A) H2CO3
2H+ + CO32- Carbonate
Nitric acid (5A) HNO3
H+ + NO3- Nitrate
Phosphoric acid (5A) H3PO4
3H+ + PO43- Phosphate
Sulfuric acid (6A) H2SO4
2H+ + SO42- Sulfate

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Chloric acid (7A) HClO3
H+ + ClO3- Chlorate
Bromic acid (7A) HBrO3
H+ + BrO3- Bromate
Iodic acid (7A) HIO3
H+ + IO3- Iodate

− Got that down? Notice that there are five ions with three oxygens and two ions
with four oxygens, so the ic/ate relationship for naming oxyacids/oxyanions doesn’t
relate to the same number of oxygens (How ‘bout the charge number?).
− Now, let’s look at the cousins of these “ic” acids. The most complicated first,
those formed by the Group 7A elements Cl, Br, and I (excluding fluorine).

Number of Oxygen Atoms Acid Prefix and/or suffix Anion Prefix and/or
Compared with –ic acid (Example) Suffix(Example)
and –ate Anion
One more Per-ic Per-ate
HClO4 (perchloric) ClO4- Perchlorate
Same ic -ate
HClO3 chloric ClO3- chlorate
One fewer -ous -ite
HClO2 chlorous ClO2- chlorite
Two fewer Hypo-ous hypo-ite
HClO hypochlorous ClO- hypochlorite
No Oxygen Hydro-ic -ide
HCl hydrochloric Cl- chloride

− Other “ic” acids and anions and how they are arrayed on the periodic table.
4A/14 5A/15 6A/16 7A/17
H2CO3/CO32- HNO3/NO3-
Carbonic/ Nitric/nitrate
Carbonate HNO2/NO2-
Nitrous/nitrite
H3PO4/PO43- H2SO4/ SO42- HClO4 / ClO4-
Phosphoric/ Sulfuric/sulfate perchloric/perchlorate
Phosphate
H2SO3/ SO32- HClO3 / ClO3-
H3PO3/PO33- Sulfurous/sulfite chloric/chlorate
Phosphorous/
H2S/S2- HClO2 / ClO2-
Phosphite
Hydrosulfuric/sulfide chlorous/chlorite
HClO / ClO-
hypochlorous/hypochlorite
HCl
hydrochloric/chloride
HBrO4 BrO4-
perbromic/perbromate
HBrO3 / BrO3-

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 4A/14 5A/15 6A/16 7A/17
bromic/bromate
HBrO2 / BrO2-
bromous/bromite
HBrO / BrO-
hypobromous/hypobromite
HBr
hydrobromic/bromide
HIO4 IO4-periodic/periodate
HIO3 / IO3-
iodic/iodate
HIO2 / IO2-
iodous/iodite
HIO / IO-
hypoiodous/hypoiodite
HI
hydroiodic/iodide
− Other acids you should know:
− H2C2O4 oxalic acid
HCN hydrocyanic acid
H2S hydrosulfuric acid
HC2H3O2 acetic acid

Naming Binary Compounds made of Two Nonmetals

(Covalent Compounds)
− Rule: Greek prefixes are used to designate the number of atoms of each
element present.
• Prefixes are mono (1), di (2), tri (3), tetra (4), penta (5), hexa (6), hepta (7), octa
(8), nona (9), deca (10)…
• The prefix mono is omitted for the first element
• The 'o' in mono and the 'a' in penta are dropped when the prefix is attached to a
name starting with the letter 'o', e.g., CO is carbon monoxide not carbon
monooxide
• The second element gets the suffix "ide"
• The IUPAC ordering scheme is:
B>Si>C>P>N>H>S>I>Br>Cl>O>F
• Examples: N2O3 dinitrogen trioxide
CO carbon monoxide
P2O5 diphospherous pentoxide
SF6 sulfur hexafluoride
CCl4 carbon tetrachloride

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Chemical Reactions: Equations
Writing chemical equations

A chemical equation is the symbolic representation of a chemical reaction in terms of

chemical formulas. For example, the burning of sodium and chlorine to produce sodium
chloride is written

2 Na + Cl2 → 2 NaCl

The reactants are starting substances in a chemical reaction. The arrow means “yields.”
The formulas on the right side of the arrow represent the products. In many cases, it is
useful to indicate the states of the substances in the equation. When you use these labels,
the previous equation becomes

2 Na ( s ) + Cl2 ( g ) → 2 NaCl ( s )

The law of conservation of mass dictates that the total number of atoms of each element
on both sides of a chemical equation must match. The equation is then said to be
balanced.
CH 4 + O 2 → CO 2 + H 2 O

Consider the combustion of methane to produce carbon dioxide and water. For this
equation to balance, two molecules of oxygen must be consumed for each molecule of
methane, producing one molecule of CO2 and two molecules of water.

CH 4 + O 2 → CO 2 + H 2O

Now the equation is “balanced.”

Visualizing a Chemical Reaction

2 Na + Cl2 → 2NaCl

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 Formation of Ammonia

• Stoichiometry
– mass relationships between substances in a chemical reaction
– based on the mole ratio
• Mole Ratio
– indicated by coefficients in a balanced equation

2 Mg + O2 → 2 MgO

Formula Weight (FW)

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 Sum of the atomic weights for the atoms in a chemical formula. So, the formula
weight of calcium chloride, CaCl2, would be
Ca: 1(40.1 amu)
+ Cl: 2(35.5 amu)
111.1 amu
These are generally reported for ionic compounds
Molecular Weight (MW)
Sum of the atomic weights of the atoms in a molecule. For the molecule ethane, C2H6,
the molecular weight would be

C: 2(12.0 amu)

+ H: 6(1.0 amu)

30.0 amu

Note:
 If the chemical formula is merely an atom, formula weight
is equal to atomic weight
 If the chemical formula is merely a molecular compound,
then formula weight is equal to molecular weight
Percent Composition

One can find the percentage of the mass of a compound that comes from each of the
elements in the compound by using this equation:

Stoichiometry
Mole Concept and Avogadro’s Constant
Describe the mole concept and apply it to substances.
The mole concept applies to all kinds of particles: atoms, molecules, ions, formula units
etc. The amount of substance is measured in units of moles. The approximate value of
Avogadro’s constant (L), 6.02 x 1023 mol-1, should be known.
A mole (often abbreviated mol) is the number equal to the number of carbon atoms in
exactly 12 grams of pure 12C. Techniques such as mass spectrometry, which count atoms
very precisely, have been used to determine this number as 6.02214 x 1023 (6.02 x 1023 is
good enough). This number is called Avogadro’s number to honor his contributions to
chemistry. One mole of something consists of 6.02 x 1023 units of that substance. Just as
a dozen eggs is 12 eggs, a mole of eggs is 6.02 x 1023 eggs.

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The mole is also defined as such that a sample of a natural element with a mass equal to
the element’s atomic mass expressed in grams contains 1 mole of atoms. This definition
also fixes the relationship between the atomic mass unit and the gram. Since 6.02 x 1023
atoms of carbon (each with a mass of 12 amu) have a mass of 12 g, then
(6.02 x 1023 atoms)(12 amu/atom)= 12 g
6.02 x 1023 amu=1 g
Calculate the number of particles and the amount of substance (in moles).
Calculate between the amount of substance (in moles) and the number of atoms,
molecules or formula units.
In order to convert from x moles of anything to how many actual atoms, multiply x by
Avagadro’s constant to find how many actual particles you have.
For example, say you are given 2.3 moles of hydrogen. In order to find how many actual
particles of hydrogen you have, you do the following calculations…
2.3 mol H x (6.02 x 1023 particles H/1 mol H) = 1.38 x 1024
Define the term molar mass (M) and calculate the mass of one mole of a species.
The molar mass of a substance is the mass in grams of one mole of the compound.
Methane is CH4, which means in a molecule of methane there is one carbon atom and
four hydrogen atoms. So, the molar mass of CH4 would be, what is the mass in grams of
one mole of methane, or what is the mass of 6.02 x 1023 CH4 molecules? The mass of 1
mole of methane can be found by summing the masses of carbon and hydrogen.
Mass of 1 mol C: 12.01 g , Mass of 4 mol H: 4 x 1.008 g Add them.
Mass of 1 mol CH4: 16.04 g
Distinguish between atomic mass, molecular mass and formula mass.
The term molar mass (in g mol-1) can be used for all of these.
Molecular Mass: The mass in grams of one mole of molecules or formula units of a
substance; the same as molar mass.
Formula Mass: The mass of a formula, including ionic compounds. Technically,
molecular mass only applies to molecules (which are defined by covalent bonding).
Formula mass can also include ionic compounds, etc.

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Atomic Mass: Atomic mass is the average atomic mass of an element, which is
determined by finding the different isotopes of an element present in nature, and how
much percent of the total amount of that element in the world they make up.

State the relationship between the amount of substance (in moles) and mass, and carry
out calculations involving amount of substances, mass and molar mass.
The relationship between moles and mass is demonstrated in the mass formula.
Number of Moles (N)= mass (m)/Molecular Mass (M)…
N=m/M
So, say you are given 40 grams of Carbon Dioxide, how many moles do you have? The
molecular mass of Carbon Dioxide (CO2) is 44 g. So, the way to solve this would be to
divide 40 grams by 44 g.
Number of Moles: 40g/44= .91 mol
Define the terms empirical formula and molecular formula.
The molecular formula is a multiple of the empirical formula.
The empirical formula is best understood by knowing its usefulness. One way scientists
find the formulas for molecules is by determining the percent of the mass each element in
the molecule takes up. For example, let us take CH5N. A scientist is attempting to find
the formula but doesn’t know what it is. He breaks it up and finds that 38.67% Carbon,
16.22% Hydrogen, and 45.11% Nitrogen. By assuming the compound weighs 100
grams, each of these percentages now becomes gram units. Then by changing them to
moles and setting them up in ratio to each other, the scientist finds that the ratio of
Nitrogen to Hydrogen to Carbon is 1:5:1. So, he knows that the formula can be CH5N.
However, the formula could also be C2H10N2, or C3H15N3. That is because all he has is a
ratio. The empirical formula is CH5N. This is the simplest form. The exact formula is
called the molecular formula, and that will be (CH5N)n where n is an integer. Sometimes
the empirical and molecular formula will be the same, other times they will not be. If
you did not understand the whole percent composition and ratios. The important part is
understanding the difference between empirical and molecular formula and how they are
related. The empirical formula is the formula for the compound that has the lowest
values possible for it to still work. The molecular formula is the formula with the actual

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values for the compound, and it will always be the empirical formula multiplied by some
integer.
Determining the empirical formula and/or the molecular formula of a given
compound.
Determine the:
• Empirical formula from the percentage composition or from other suitable
experimental data.
• Percentage composition from the formula of a compound.
• Molecular formula when given both the empirical formula and the molar mass.
1. Empirical formula from the percentage composition or from other suitable
experimental data.
When a new compound is prepared, one of the first items of interest is the formula of the
compound. This is most often determined by taking a weighed sample of the compound
and either decomposing it into its component elements or reacting it with oxygen to
produce substances such as CO2, H2O, and N2, which are then collected and weighed.
We will see how information of this type can be used to compute the formula of a
compound. Suppose a substance has been prepared that is composed of carbon,
hydrogen, and nitrogen. When 0.1156 gram of this compound is reacted with oxygen,
0.1638 gram of carbon dioxide (CO2) and 0.1676 gram of water (H2O) are collected.
Assuming that all the carbon in the compound is converted to CO2, we can determine the
mass of carbon originally present in the 0.1156-gram sample. To do this, we must use
the fraction (by mass) of carbon in CO2. The molar mass of CO2 is
C: 1 mol x 12.01g/mol=12.01 g
O: 2 mol x 16.00 g/mol=32.00 g
Added together, the molar mass of CO2 = 44.01 g/mol.
The fraction of carbon present by mass is
Mass of C/Total mass of CO2 = 12.01 g C/ 44.01 g CO2
This factor can now be used to determine the mass of carbon in 0.1638 gram of CO2:
0.1638 g CO2 x 12.01 g C/44.01 g CO2 = 0.04470 g C
Remember that this carbon originally came from the 0.1156-gram sample of unknown
compound. Thus the mass percent of carbon in this compound is

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(0.04470 g C/0.1156 g compound) x 100= 38.67% C
The same procedure can be used to find the mass percent of hydrogen in the unknown
compound. We assume that all the hydrogen present in the original 0.1156 gram of
compound was converted to H2O. The molar mass of H2O is 18.02 grams, and the
fraction of hydrogen by mass of H2O is
Mass of H/Mass of H2O = 2.016 g H/18.02 g H2O
Therefore, the mass of hydrogen in 0.1676 gram of H2O is
0.1676 g H2O x (2.016 g H/18.02 g H2O)= 0.01875 g H
And the mass percent of hydrogen in the compound is
(0.01875 g H/0.1156 g) compound x 100 = 16.22%
The unknown compound contains only carbon, hydrogen, and nitrogen. So far we have
determined that is is 38.67% carbon and 16.22% hydrogen. The remainder must be
nitrogen.
100.00% - (38.67% + 16.22%) = 45.11% N
We have determined that the compound contains 38.67% carbon, 16.22% hydrogen, and
45.11% nitrogen. Next we use these data to obtain the formula. Since the formula of a
compound indicated the numbers of atoms in the compound, we must convert the masses
of the elements to numbers of atoms. The easiest way to do this is to work with 100.00
grams of the compound in the present case, 38.67% carbon by mass means 38.67 grams
of carbon per 100.00 grams of compound, etc. To determine the formula, we must
calculate the number of carbon atoms in 38.67 grams of carbon, the number of hydrogen
atoms in 16.22 grams of hydrogen, etc. You can do that using the mass formula (found in
1.2.4.). The answers are 3.220mol C, 16.09 mol H, 3.219 mol N. Thus 100.00 grams of
this compound contains 3.220 moles of carbon atoms, 16.09 moles of hydrogen atoms,
and 3.219 moles of nitrogen atoms. We can find the smallest whole number ratio
(empirical formula) of atoms in this compound by dividing each of the mole values above
by the smallest of the three:
C: 3.220/3.219 = 1.000 = 1
H: 16.09/3.219 = 4.998 = 5
N: 3.219/3.219 = 1.000 = 1

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So, the empirical formula for the unknown compound is CH5N. Now, if you want to
know the molecular formula, you have to know the formula mass of the unknown
compound. If the formula mass of the unknown is the same as the formula mass of the
empirical formula, then the empirical formula is the molecular formula, but if the formula
mass of the unknown is say n times more then the formula mass of the empirical formula,
then the molecular formula is n times the empirical formula.

2. Percentage composition from the formula of a compound.

Say you are given the formula H2O, and you want to find out the percentage composition
of hydrogen. How you do this is you find the formula mass of water, and then find the
atomic mass of H2, and divide the latter by the former. Then multiply by 100 to get a
percent value. So, formula mass of H2O is 18, H2 is 2, so 2 g H2/ 18 g H2O=.11, x
100=11.1%.

3. Molecular formula given both the empirical formula and the molar mass.
Say you are given the empirical formula CH5N, and are told that the molar mass is 62.12
g, and are told to find the molecular formula. First you find the formula mass of CH5N,
which ends up being 31.06 g. You know that that multiplied by n equals the molecular
mass of the formula you want, and the n in this is case is 2 (you could find this by
dividing 62.12 g unknown/ 31.06 g empirical formula).
Calculating stoichiometric quantities and use these to determine experimental and
theoretical yields.
Mass is conserved in all chemical reactions. Given a chemical equation and the mass or
amount (in moles) of one species, calculate the mass or amount of another species.
The first rule to remember is mass is always conserved (at least at this point in the
syllabus). So the total mass of one side should always add up on another side. Now,
once again we will use the chemical equation from above.
2C6H14 (g) + 13O2 (g)
12CO2 (g) + 14H2O (l)
Say you are told that you have 40 grams of hexane, how many grams of oxygen do you
need to completely react with all the hexane? Well, in order to solve this you use mole
rations.

21
2 moles hexane/13 moles O2 = 40 g hexane/x moles O2. You then solve this like a
normal ratio problem (multiply diagonally then solve for x). You answer is 260 grams of
oxygen is needed to react with 40 g of hexane. Note: This is not the best example because
you normally don’t use the measurement grams for gases, but it would be the same way
for liters.
Determine the limiting reactant and the reactant in excess when quantities of reacting
substances are given.
Given a chemical equation and the initial amounts of two or more reactants:
• Identify the limiting reactant
• Calculate the theoretical yield of a product
• Calculate the amount(s) of the reactant(s) in excess remaining after the reaction is
complete.
1. Identify the limiting reactant.
There are many ways to solve for the limiting reactant, and everyone tends to like their
own way. I will show mine below but if you don’t like it feel free to ask your teacher or
someone else for another way to do it. Say you have the equation
4FeCr2O4(s) + 8K2CO3(s) + 7O2(g)
8K2CrO4(s) + 2Fe2O3(s) + 8CO2(g)
The masses are 169 kg, 298 kg, and 75 kg respectively for the reactants, and you want to
find out which one is the limiting reagent. In order to do this, you first have to find out
how many moles of each of the reactants you have (using the mass formula), we find
their to be 7.55 x 102 mol chromite ore, 2.16 x 103 mol potassium hydroxide, and 2.34 x
103 mol O2.
You then set up the mole ratios you need to react correctly and the mole ratios you have.
So, to react correctly you should 4 moles of chromite ore for every 8 moles of potassium
carbonate. That is, 4 mol FeCr2O4/8 mol K2CO3(s), which equals .5. You then take the
values that you actually have, which are 7.55 x 102 mol chromite ore/2.16 x 103 mol
potassium hydroxide, which equals .35. This is smaller then .5, and that means that the
numerator is too small (if the answer was bigger then .5, the denominator would be too
small). Whichever value is too small, that number is the limiting reagent FOR THAT
PAIR. You then have to take that reagent and compare it with the other reactant, or the
rest of the reactants if there are more then three. So, taking chromite ore we do the same

22
thing comparing it with oxygen. We have 7.55 x 102 mol chromite ore/ 2.34 x 103 mol
O2 which then equals .32. The ratio we want is 4/7, or .57, which is bigger then the
actual value we got, which means O2 is the limiting reagent of the entire reaction (you
don’t have to then compare it to the first reactant tested). So, oxygen is the limiting
reagent of the formula.
2 and 3. Calculate the theoretical yield of a product and amount of excess reagent
remaining after reaction is complete.
Theoretical yield of a product is the amount of a product formed when the limiting
reactant is completely consumed. In order to obtain it, you go through several steps, that
we will go through with the reaction 2C2H6 + 7O2
4CO2 + 6H20 starting with 20 g of
ethane and 40 grams of oxygen. So, the first step is to identify the limiting reagent.
2 mol ethane/7 mol oxygen=.29 .66 mol ethane/1.25 mol oxygen=.528. Since the
number is too big, that means the denominator is the limiting reagent, or oxygen is the
limiting reagent. We then have to find how much ethane is used up before the oxygen is
consumed. We do this by multiplying the actual amount of oxygen by the mole ratio of
the two reactants.
1.25 mol oxygen x (2 mol ethane/ 7 mol oxygen)= .36 mol ethane.
This is how much ethane is used up in the reaction, so now we know how much ethane
was used and we know how much ethane we started with, so to find how much ethane is
left over we do a simple subtraction.
.66 mol ethane started with - .36 mol ethane used = .3 mol ethane left over.
So, we have .3 mol ethane left over after the reaction. Then, to find theoretical yield, you
have two options. You can use how much oxygen use, or you can use how much ethane
you use in the reaction, either should gain you the right answer. I would recommend
using the value given to you by the problem, so that way if you made a mistake in finding
the excess reagent left over you won’t mess up your second answer. You know you used
1.25 mol oxygen, so you do another mole ratio.
1.25 mol oxygen x (4 mol carbon dioxide/7 mol oxygen)=.714 mol carbon dioxide.
So, .714 mol carbon dioxide is your theoretical yield for that product.
Note: Rarely do you ever calculate the theoretical yield, because side reactions normally
occur that decrease from the theoretical yield. The actual yield is sometimes compared to

23
the actual yield by doing the following calculations: actual yield/theoretical yield x 100=
Percent Yield.
Solutions
Define the terms solute, solvent, solution and concentration (g dm-3 and mol dm-3).
Concentration in mol dm-3 is often represented by square brackets around the substance
under consideration, eg. [CH3COOH].
Solute: A substance dissolved in a liquid to form a solution.
Solvent: The dissolving medium in a solution.
Molarity: moles of solute per volume of solution in liters. This often times written by IB
with units mol dm-3, which means moles/dm3, and a dm3 equals a liter. Same meaning,
just different ways of writing it. I recommend writing it mol dm-3 whenever your in IB
class because it gets you well practiced, but if you are working with people outside of the
IB program write it per liters, because I have found they have a hard time understanding
IB notation. This is also often times written short hand in square brackets such as
[CH3COOH]. That means the molarity of that compound. This could also be written as g
dm-3,(molality) however I have never seen it written that way, even by IB. If it is ever
written that way, I would recommend converting it to moles (by just using Avagadro’s
number), however I could see how having it in grams may help calculate it at some point.
So, if you dissolve 5 moles of HCl in 3 Liters of water, your molarity [HCl] is 5 mol/3 L,
or 1.66 mol L-1, or 1.66 mol dm-3.
Carrying out calculations involving concentration, amount of solute and volume of
solution.
These are fairly easy. Just remember that concentration equals amount of solute/volume
of solution. So say you know the concentration of a solution is 4 mol dm-3, and you
know the volume is 5 L. That means x mol/ 5 L=5 mol/L. That means x must equal 20
mol.
Note: A good rule to remember is the equation m1L1=m2L2. m stands for the molarity,
and L stands for volume. So, if you had a 2 L concentration of 5 M HCl solution (M is
often used to stand for molarity) and you wanted to dilute it to a 2 M HCl, how much
water would you need to add? Well, m1=5, L1=2, m2=2, and L2=?. So, (5 mol/L)(2
L)=(2 mol/L)(? L). By solving for the unknown, you find your final solution will be a

24
volume of 5 liters, and since you started with 2 liters, you need to add 3 liters to get to 5
liters.
Solve solution stoichiometry problems.
Given the quantity of one species in a chemical reaction in solution (in grams, moles or in
terms of concentration), determine the quantity of another species.
When it is given to you in grams or moles, it’s just like a regular stoichiometric problem.
However, if it is given to you in terms of concentration, work your way around it to find
moles or grams (so, if you have a concentration of 5 M, then you have 5 moles per liter,
and if you have 3 liters, that means you have 15 moles.)

Calculating Concentration of solutions

The concentration of a chemical solution refers to the amount of solute that is dissolved
in a solvent!

Molarity (M)

It is the number of moles of solute per liter of solution (not necessarily the same as
the volume of solvent!).

Example:
What is the molarity of a solution made when water is added to 11 g CaCl2 to make
100 mL of solution?

Solution:
11 g CaCl2 / (110 g CaCl2 / mol CaCl2) = 0.10 mol CaCl2
100 mL x 1 L / 1000 mL = 0.10 L
molarity = 0.10 mol / 0.10 L
molarity = 1.0 M

Dilutions

You dilute a solution whenever you add solvent to a solution. Adding solvent results in a
solution of lower concentration. You can calculate the concentration of a solution
following a dilution by applying this equation:

MiVi = MfVf

where M is molarity, V is volume, and the subscripts i and f refer to the initial and final
values.

25
Example:
How many millilieters of 5.5 M NaOH are needed to prepare 300 mL of 1.2 M NaOH?

Solution:
5.5 M x V1 = 1.2 M x 0.3 L
V1 = 1.2 M x 0.3 L / 5.5 M
V1 = 0.065 L
V1 = 65 mL

So, to prepare the 1.2 M NaOH solution, you pour 65 mL of 5.5 M NaOH into your
container and add water to get 300 mL final volume.

Aqueous Solution Dilutions

Concept
Most laboratories keep stock solutions of common or frequently used solutions of high
concentration. These stock solutions are used for dilutions.

Problem:
Calculate the amount of 1 M NaOH aqueous solution needed to make 100 mL of 0.5 M
NaOH aqueous solution.

Formula needed:
M = m/V
where M = molarity of solution in mol/liter
m = number of moles of solute
V = volume of solvent in liters

Step 1:
Calculate the number of moles of NaOH needed for 0.5 M NaOH aqueous solution.
M = m/V
0.5 mol/L = m/(0.100 L)
solve for m:
m = 0.5 mol/L x 0.100 L = 0.05 mol NaOH.

Step 2:
Calculate the volume of 1 M NaOH aqueous solution that gives that gives the number of
moles of NaOH from step 1.
M = m/V
V=m/M
V = (0.05 moles NaOH)/(1 mol/L)
V = 0.05 L or 50 mL

26
Answer:
50 mL of 1 M NaOH aqueous solution is needed to make 100 mL of 0.5 M NaOH
aqueous solution.
Concentration and Molarity Example Problem

Determine the molarity of a solution made by dissolving 20.0 g of NaOH in sufficient

water to yield a 482 cm3 solution.

Solution

Molarity is an expression of the moles of solute (NaOH) per liter of solution (water). To
work this problem, you need to be able to calculate the number of moles of sodium
hydroxide (NaOH) and be able to convert cubic centimeters into liters.

Step 1 Calculate the number of moles of NaOH that are in 20.0 grams.

Na is 23.0
H is 1.0
O is 16.0

Plugging these values:

1 mol NaOH weighs 23.0 g + 16.0 g + 1.0 g = 40.0 g

So the number of moles in 20.0 g is:

moles NaOH = 20.0 g × 1 mol/40.0 g = 0.500 mol

Step 2 Determine the volume of solution in liters.

1 liter is 1000 cm3, so the volume of solution is: liters solution = 482 cm3 × 1 liter/1000
cm3 = 0.482 liter

Step 3 Determine the molarity of the solution.

Simply divide the number of moles by the volume of solution to get the molarity:

molarity = 0.500 mol / 0.482 liter

molarity = 1.04 mol/liter = 1.04 M

Answer

27
The molarity of a solution made by dissolving 20.0 g of NaOH to make a 482 cm3
solution is 1.04 M

Limiting Reactant and Theoretical Yield

Example Problem for Limiting Reactant and Theoretical Yield

Problem

You are given the following reaction:

2 H2(g) + O2(g) → 2 H2O(l)

Calculate:

a. the stoichiometric ratio of moles H2 to moles O2

b. the actual moles H2 to moles O2 when 1.50 mol H2 is mixed with 1.00 mol O2
c. the limiting reactant (H2 or O2) for the mixture in (b)
d. the theoretical yield, in moles, of H2O for the mixture in (b)

Solution

a. The stoichiometric ratio is given by using the coefficients of the balanced equation.
The coefficients are the numbers listed before each formula.

2 mol H2 / mol O2

b. The actual ratio refers to the number of moles actually provided for the reaction. This
may or may not be the same as the stoichiometric ratio. In this case, it is different:

1.50 mol H2 / 1.00 mol O2 = 1.50 mol H2 / mol O2

c. Note that the actual ratio of smaller than the required or stoichiometric ratio, which
means there is insufficient H2 to react with all of the O2 that has been provided. The
'insufficient' component (H2) is the limiting reactant. Another way to put it is to say that
O2 is in excess. When the reaction has proceeded to completion, all of the H2 will have
been consumed, leaving some O2 and the product, H2O.

d. Theoretical yield is based on the calculation using the amount of limiting reactant, 1.50
mol H2. Given that 2 mol H2 forms 2 mol H2O, we get:

theoretical yield H2O = 1.50 mol H2 x 2 mol H2O / 2 mol H2

28
theoretical yield H2O = 1.50 mol H2O

Note that the only requirement for performing this calculation is knowing the amount of
the limiting reactant and the ratio of the amount of limiting reactant to the amount of
product.

Answer

a. 2 mol H2 / mol O2
b. 1.50 mol H2 / mol O2
c. H2
d. 1.50 mol H2O

Gravimetric analysis

Gravimetric analysis, which by definition is based upon the measurement of mass, can be
generalized into two types; precipitation and volatilization. The quantitative
determination of a substance by the precipitation method of gravimetric analysis involves
isolation of an ion in solution by a precipitation reaction, filtering, washing the precipitate
free of contaminants, conversion of the precipitate to a product of known composition,
and finally weighing the precipitate and determining its mass by difference. From the
mass and known composition of the precipitate, the amount of the original ion can be
determined.

Worked Example
A certain barium halide exists as the hydrated salt BaX2.2H2O, where X is the halogen.
The barium content of the salt can be determined by gravimetric methods. A sample of
the halide (0.2650 g) was dissolved in water (200 cm3) and excess sulfuric acid added.
The mixture was then heated and held at boiling for 45 minutes. The precipitate (barium
sulfate) was filtered off, washed and dried. Mass of precipitate obtained = 0.2533 g.
Determine the identity of X.
Answer:
The precipitate is barium sulfate. The first stage is to determine the number of moles of
barium sulfate produced, this will, in turn give us the number of moles of barium in the
original sample.
Relative Molecular Mass of barium sulfate

29
= 137.34 (Ba) + 32.06 (S) + (4 x 16.00) (4 x O)
= 233.40
Number of moles
= mass / RMM
= 0.2533 / 233.40
= 1.09 x 10 -3
This is the number of moles of barium present in the precipitate and, therefore, the
number of moles of barium in the original sample. Given the formula of the halide, (i.e. it
contains one barium per formula unit), this must also be the number of moles of the
halide. From this information we can deduce the relative molecular mass of the original
halide salt:
RMM = mass / number of moles
= 0.2650 / 1.09 x 10-3
= 244.18
The relative atomic mass of 2 X will be given by the RMM of the whole salt - that of the
remaining components; So RAM of 2 X = 244.18 - 173.37 = 70.81
2 X = 70.81, so X = 35.41.
The RAM of chlorine is 35.45 which is in good agreement with the result obtained and
hence the halide salt is hydrated barium chloride and X = Chlorine
Problems
1. A sample (0.203 g) of hydrated magnesium chloride (MgClm.nH2O) was dissolved in
water and titrated with silver nitrate solution (0.100 mol dm-3), 20.0 cm3 being required.
Another sample of the hydrated chloride lost 53.2 % of its mass when heated in a stream
of hydrogen chloride, leaving a residue of anhydrous magnesium chloride. Calculate the
values of m and n
(Answer: m = 2, n = 6)
2. When an sample of impure potassium chloride (0.4500g) was dissolved in water and
treated with an excess of silver nitrate, 0.8402 g of silver chloride was precipitated.
Calculate the percentage KCl in the original sample.
(Answer: 97.12 %)
Exercise

30
1. A compound contains 18.8% sodium, 29.0% chlorine, and 52.2% oxygen, by mass. If
the molar mass of the compound is 122.44 g/mol, determine the empirical and
molecular formulas. (Answer: Empirical and molecular formula - NaClO4)
2. A 4.99 gram sample of a compound contains 1.52 grams of nitrogen atoms and 3.47
grams of oxygen atoms. The molar mass of the compound is between 90.0 g and 95.0
g. Determine the empirical and molecular formulas. Also, calculate the actual molar
mass of this compound. (Answer: Empirical formula - NO2. Molecular formula -
N2O4. Molar mass = 92.04 g/mol)
3. Ascorbic acid is another name for Vitamin C. It is composed of 40.92% carbon, 4.58%
hydrogen, and 54.50% oxygen, by mass. Determine the empirical formula for
ascorbic acid. (Answer: Empirical formula - C3H4O3)

Classes of Reactions

31
 Chemical reactions

Precipitation Oxidation-Reduction Acid-Base

Reactions Reactions Reactions

Combustion Synthesis Decomposition

Reactions Reactions reactions

Oxidation Numbers and Redox Reactions

What is meant by a “redox” reaction?

A reaction that involves the transfer of electron density from one atom to another
(REDOX = REDuction/OXidation reaction)
A loss of electrons is oxidation (leo). A gain of electrons is reduction (ger).
Redox reactions involve both an oxidizing agent and reducing agent. An oxidizing agent
is a substance that causes oxidation (by taking electrons). Thus, an oxidizing agent is
itself reduced. Similarly, a reducing agent is oxidized in a reaction.

Mg + S→ MgS

The magnesium atom (which has zero charge) changes to a magnesium ion by losing 2
electrons, and is oxidized to Mg2+
The sulfur atom (which has no charge) is changed to a sulfide ion by gaining 2 electrons,
and is reduced to S2-

0 0 +1 −1
2 Na + Cl 2 → 2 Na Cl

0 +1
Na → Na + e −

32
Each sodium atom loses one electron:
0 −1
Each chlorine atom gains one electron: Cl + e − → Cl

Further Examples

+1 +5 −2 +1 −1 +1 −1 +1 +5 −2
Ag N O 3 (aq ) + Na Cl (aq ) → Ag Cl ( s ) + Na N O 3 (aq )

+1 −2 +1 +1 +6 −2 +1 +6 −2 +1 −2
2 Na O H (aq ) + H 2 S O 4 (aq ) → + Na 2 S O 4 (aq ) + H 2 O (l )

Rules:

1. Pure elements have an oxidation number of 0

2. If the compound is an ionic compound, the oxidation number for each element is the
ion’s charge
3. The oxidation number of hydrogen in a compound is +1
4. The oxidation number of oxygen in most compounds is –2 (peroxides are the
exception; in peroxides oxygen has an oxidation number of –1)
5. The sum of the oxidation numbers in a compound is zero.
6. The sum of the oxidation numbers in a polyatomic ion is equal to the ion charge.

For each element or molecule that is involved in a reaction we need to follow these
simple rules.
Rule 1. All pure substances have an oxidation number of zero. This applies to any pure
substance whether it is a diatomic gas like O2 or a piece of pure metal like Iron (Fe).
Rule 2. In compounds, elements that usually have an ionic charge imparted by their
position in a particular group have that same oxidation number. An example is Cl which
is usually in the form Cl- in compounds; this will have an oxidation number of -1 in
compounds.
Rule 3. When two or more usually negatively charged ions are involved in a compound,
the one with the highest electronegativity value is given its ionic charge as the oxidation
number; the others are worked out normally. An example is OF2. F is more
electronegative, and so it is assigned the value of -1. Here is a good table of
electronegativity values.

33
Rule 4. Oxygen in a compound always has an oxidation number of -2
Rule 5. Hydrogen in compounds always has an oxidation number of +1 except in the rare
case of Metal Hydrides where it has a value of -1.
Rule 6. The oxidation numbers in the compound or molecule must total to the overall
charge of that compound or molecule. For example CO2 has no overall charge and so the
oxidation numbers must tally to zero. The sulfate ion, SO42-, has an overall charge of -2,
so the oxidation numbers must tally to -2
Example 1: Carbon Dioxide
Let's start with the very familiar Carbon Dioxide, CO2.
Carbon Dioxide contains one carbon atom and two oxygen atoms bound together in a
discreet molecule. It is an uncharged molecule, meaning its overall charge value is zero.
First we draw each atom involved. Since there are two oxygen atoms in CO2, we put two
of them in the drawing. We then make that collection of atoms equal to the overall charge
which in this case is zero.
Next we go through the rules from 1 to 6, skipping any that are not relevant.
Rule 1: not relevant: CO2 is a compound and not a pure substance.
Rule 2: Oxygen is the most electronegative element and so it gets its standard charge of -
2 for each oxygen atom.
Rule 3: not relevant: Carbon never forms negatively charged ions and even if it did it it is
less electronegative than oxygen so what we have done is still good.
Rule 4: this has already been taken care of in Rule 2.
Rule 5: not relevant: there are no Hydrogen atoms involved.
Rule 6: In order to tally to zero, we MUST assign Carbon the oxidation number of +4.
Therefore we can confidently state that after following the oxidation number rules,
Carbon has an oxidation number of +4 in this compound.
Eg
+2 −2 +1 +1 −2
Ca (O H ) 2 H2O

Balancing Redox Equations

34
As a summary, here are the steps to follow to balance a redox equation in acidic medium
(add the starred step in a basic medium):

1. Divide the equation into an oxidation half-reaction and a reduction half-reaction

2. Balance these
o Balance the elements other than H and O
o Balance the O by adding H2O
+
o Balance the H by adding H
-
o Balance the charge by adding e
3. Multiply each half-reaction by an integer such that the number of e- lost in one
equals the number gained in the other
4. Combine the half-reactions and cancel
5. **Add OH- to each side until all H+ is gone and then cancel again**

Give atleast 2 Examples

Balance the following redox reactions in acidic (or basic) solution:

a) I2 (s) + NO3- (aq) → IO3- (aq) + NO2 (g)
b) H2O2 + ClO2 → ClO2- + O2

35
 Atomic Structure

Quantum theory: is a theory needed to describe physics on a microscopic / nanoscopic

scale such as atoms, molecules, electrons protons etc.

Atomic Structure: Atomic Spectra

Absorption Spectrum - The spectrum of dark lines against a light background those
results from the absorption of selected frequencies of the electromagnetic radiation by an
atom or molecule.

Emission Spectrum - The spectrum of bright lines against a dark background obtained
when an atom or molecule emits radiation when excited by heat or an electric discharge.
Interaction of Atoms with Electromagnetic Radiation

The realization that radio waves, infrared radiation, visible light, ultraviolet radiation, X-
rays and gamma rays were all forms of ELECTROMAGNETIC WAVES with different
wavelengths led to a further understanding of the atom.

Electromagnetic Spectrum

The Wave – Particle Nature of Light

These waves can be described by their wavelength, lambda, λ, amplitude and frequency,
nu, υ . Frequency is the number of cycles of a moving wave that pass a given point per
unit time. Units for frequency are given in cycles/second or Hertz (Hz) The units for
wavelength are in length, the common units being meters, nanometers and Å, angstrom.

36
The relationship between wavelength and frequency is given by the equation

c=λυ

The Photoelectric Effect

This is an effect that is best explained by Einstein's photon model of electromagnetic

radiation. When light is shone on metal, the surface may become positively charged. This
is because electrons gain energy from the light waves, and are able to leave the metal's
surface. However, there were some strange effects that could not be explained by
considering light as a wave. The frequency of the light must be above a certain threshold
value for that metal for electrons to be emitted. For example blue light causes sodium to
emit electrons but red light does not. If light was a wave the electrons would eventually
absorb enough energy to be emitted, regardless of frequency. Also, incredibly weak
beams of light can cause electrons to be emitted. If light was a wave and spread out you
would not expect any electrons to obtain the energy to escape. Finally it was discovered
that the kinetic energy of the electrons depends not on the intensity of the light but on its
frequency. A very weak ultraviolet beam will give electrons a higher kinetic energy than
a very bright blue beam of light. Einstein explained this by saying that the light arrived in
photons. One photon gave all its energy to one electron. The electron must gain a certain
amount of energy to overcome the forces that hold it inside the metal. It appears that one
electron can only accept one photon of energy, so this must have the required frequency
to have the necessary escape energy, so the intensity will not make any difference to this.
Brighter light means there are more photons, so more electrons can be emitted, but it is
the frequency of the light that decides the energy of the photon and so the electron's
kinetic energy. Electrons can also be emitted very quickly because it only requires one
photon for emission to occur, not the gradual build up of wave energy.

From the above we see that atoms absorb or emit light of certain frequencies. How can
we relate frequency, energy and wavelength.

λ and υ are related by the equation c = λ υ ……………….Equation (1)

37
Energy of a photon is given by the equation E = h υ ………….. Equation (2)

Combine equations 1 And 2

Since υ = c/λ

Then E = h c/λ ……………………………….Equation (3)

Equation 3 can be expressed as ∆E = h c/λ this equation is used to calculate the

energy of a photon in transition. ∆E is a change in energy.

Max Planck hypothesized that substances were surrounded by oscillating "resonators"

which emitted energy that was quantized, or countable, because he assumed that there
were only a limited number of energies at which these oscillators could exist.
Albert Einstein extended Planck's work to include light; hypothesizing that light was
also quantized. He assumed that:

1. Light was made up of small, discrete particles of energy called photons.

2. The energy (E) of a photon is proportional to its frequency (v):

where h is Planck's constant = 6.626 x 10-34 J-s.

Jacob Balmer analyzed the hydrogen spectrum and found that hydrogen emitted four
bands of light within the visible spectrum:

Wavelength (nm) Color

656.2 red
486.1 blue
434.0 blue-violet
410.1 violet

• He found that the data fit to the following equation:

38
 = wavelength (nm)

RH = Rydberg's constant = 1.09678 x 10-2 nm-1

n1 = the lower energy level

n2 = the higher energy level

For example, to calculate the wavelength of light emitted when the electron in a hydrogen
atom falls from the fourth energy level to the second energy level:

Emission Spectrum of a Hydrogen Atom

Each series is named after its discoverer.

The Lyman series is the wavelengths in the ultra violet (UV) spectrum of the hydrogen
atom, resulting from electrons dropping from higher energy levels into the n = 1 orbit.
The Balmer series is the wavelengths in the visible light spectrum of the hydrogen atom,
resulting from electrons falling from higher energy levels into the n = 2 orbit. The

39
Paschen series is the wavelengths in the infrared spectrum of the hydrogen atom,
resulting from electrons falling from higher energy levels into the n = 3 orbit. The
Brackett series is the wavelengths in the infrared spectrum of the hydrogen atom,
resulting from electrons falling from higher energy levels into the n = 4 orbit. The Pfund
series is the wavelengths in the infrared spectrum of the hydrogen atom, resulting from
electrons falling from higher energy levels into the n = 5 orbit.

Niels Bohr proposed a model for the hydrogen atom which explainedthe spectrum of a
hydrogen atom based upon the following assumptions:

Bohr Model for the Hydrogen Atom

1. The electron in a hydrogen atom travels around the nucleus is a circular orbit.
2. The energy of the electron is directly proportional to its distance from the nucleus.
3. There are a limited number of specific allowed energy levels, i.e., the orbitals are
quantized.
4. The angular momentum of the electron in any orbital is an integral multiple of
Planck's constant divided by 2 .
5. When light is absorbed, the electron jumps from a lower energy level to a higher
energy level. When light is emitted, the electron falls from a higher energy level
to a lower energy level.

The energy of light absorbed or emitted is equal to the difference in the energy levels of
the orbits between which the electron jumps of falls.

To simplify these assumptions, remember these key words and concepts:

1. CIRCULAR ORBIT: in which the electron travels around the nucleus.

2. Energy ∞Distance: energy of an orbital is directly proportional to the distance
from the nucleus.
3. QUANTIZED: limited number of countable allowed energy levels.
4. ANGULAR MOMENTUM: fixed for each energy level.
5. Absorption is Low E to High E & Emission is High E to Low E

Energy of absorption/emission = E difference of energy levels.

40
Problems with the Bohr Model

1. The model is only valid for the hydrogen atom (with one electron).
2. The first assumption concerning the electrons in fixed circular orbits violates the
laws of classical mechanical physics.
3. The ANGULAR MOMENTUM assumption violates the Heisenberg uncertainty
principle.

Louis de Broglie studied the wave-particle duality of light as suggested by Albert

Einstein and extended this idea to include other objects such as the electron.

The energy of an object (E) in motion is equal to its mass (m) times the square of its
speed (c):

E = mc2

The energy of a wave (E) is proportional to its frequency (v) which is proportional to its
speed (s) and inversely proportional to its wavelength ( ) where h is Planck's constant:

E = hv = hc/λ

If an object acts as both a particle in motion and a wave, then the two equations can be
combined:

mc2 = hc/λ

41
Cancelling like terms and rearranging the equation to solve for the wavelength results in
the following:

λ = h/mc

By defnition, momentum (p) of an object is equal to the product of its mass (m) times its
speed (c), so p can be substituted for ms to get the de Broglie equation.

de Broglie equation - The wavelength ( ) of an object in motion is inversely

proportional to its momentum (p) where h is Planck's constant (6.626 x 10-34 J-s):

ie λ = h/mc

With this equation, if the mass of an object is too large (as it is with most objects), the
wavelength would be negligible. Very small particles such as electrons, however, are
small enough to exhibit the properties of both waves and particles.

Since electrons act as waves as well as particles, they cannot be restricted to circular
orbits, but rather must exist in three-dimensional space. Atoms or ions with a single
electron are simple enough to be explained using the Bohr model which assumes that
electrons travel in circular orbits around the nucleus. An atom or ion with any more
electrons, however, is too complex to be explained by the Bohr model.

• Heisenberg Uncertainty Principle - It is impossible to determine

the position (x) and the momentum (mv) of a particle simultaneously with
certainty.

In the Bohr model, it is assumed that there are fixed angular momentums for each
quantized orbital.

• Erwin Schrödinger developed a model of the atom which accounted for the
wave and particle-like behavior of electrons. Instead of restricting electrons to
limited circular orbits, he developed a new idea of orbitals:

• Orbitals - regions in space where electrons are most likely to be found

This no longer violated the Heisenberg Uncertainty Principle as the Bohr model did
since the exact location of an electron at any moment in time is not known.

42
 • Bohr's one-dimensional model required only one coordinate to describe the size of
the circular orbit in which an electron could be found. Schrödinger's three-
dimensional model requires three coordinates, or quantum numbers, which
describe the orbitals where electrons can be found.

Quantum Numbers

• Principle quantum number (n) - describes the SIZE of the orbital. Since the
distance from of an electron from the nucleus is directly proportional to the
energy of the electron (as described in the Bohr model), the principle quantum
number is also a measure of the orbital.
• Angular quantum number (l) - describes the SHAPE of the orbital.
o The s orbitals are spherical (l = 0).
o The p orbitals are polar (l = 1).
o The d orbitals are clover-leaf shaped (l = 2).

• Magnetic quantum number (m) - describes an orbital's ORIENTATION in

space.
o For s orbitals (l = 0), there is only one orientation possible, so m must
equal 0.
o For p orbitals (l = 1), there are three possible orientations, so m can be -1,
0, or 1.
 (see picture below)
o For d orbitals (l = 2), there are five possible orientations, so m can be -2, -
1, 0, 1, or 2.


43
 • Spin quantum number (s) - describes the SPIN or direction (clockwise or
counter-clockwise) in which an electron spins. If there are two electrons in any
one orbital, they will have opposite spins, that is, one will have a + spin and the
other will have a - spin. The maximum number of electron in any one orbital is
two.

Shells and Subshells

• Shell - A group of orbitals with the same principal quantum number

e.g. The 2s and 2p orbitals.

• Subshell - A group of orbitals with the same angular quantum number

e.g. The three 2p orbitals: 2px, 2py, and 2pz

Rules for Allowable Combinations of Quantum Numbers

• The three quantum numbers (n, l, and m) that describe an orbital must be integers.
• "n" cannot be zero. "n" = 1, 2, 3, 4...
• "l" can be any integer between zero and (n-1).

e.g. If n = 4, l can be 0, 1, 2, or 3.

• "m" can be any integer between -l and +l.

e.g. If l = 2, m can be -2, -1, 0, 1, or 2.

"s" is arbitrarily assigned as + or - , but for any one subshell (n, l, m combination),
there can only be one of each.

Graphical Representation of Allowable Combinations of Quantum Numbers

44
 Shell Subshell Subshell Orientation Number of
n l Notation m Orbitals
1 0 1s 0 1
2 0 2s 0 1
1 2p -1 0 +1 3
3 0 3s 0 1
1 3p -1 0 +1 3
2 3d -2 -1 0 +1 +2 5
4 0 4s 0 1
1 4p -1 0 +1 3
2 4d -2 -1 0 +1 +2 5
3 4f -3 -2 -1 0 +1 +2 +3 7

Example Quantum Number Problem

List the quantum numbers of all the electrons in a neon atom.

1s {
100 2 1 -1
2s {
200 210

211
2p

Electron Configurations

Electron Configuration - Describes the distribution of electrons in atomic orbitals

according to specific rules.

Electron Diagram - Illustrates the distribution of electrons in atomic orbitals according

to specific rules.

Aufbau Principle

Electrons are added one at a time, starting with the lowest energy orbital until all the
electrons have been accounted for.

45
 Relative Energies of Atomic Orbitals

Pauli Exclusion Principle

• An orbital can hold a maximum of 2 electrons.

• 2 electrons in the same orbital must have opposite spins.
• An electron is "paired" if it is sharing an orbital with another electron with an
opposite spin.
• An electron is "unpaired" if it is alone in an orbital

A H atom has one electron which is unpaired in the lowest energy orbital, 1s.

H: 1s1

A He atom has two electrons; the second one fills the 1s orbital with a spin opposite that
of the first electron. These two electrons are now paired.

He: 1s2

A Li atom has 3 electrons; the third one is added to the next lowest energy orbital, 2s and
is unpaired.

Li: 1s22s1

46
A Be atom has 4 electrons; the fourth one is fills the 2s orbital with a spin opposite that of
the first electron in the orbital. These two electrons are now paired.

Be: 1s22s2

A B atom has 5 electrons; the fifth one is added unpaired to the next lowest energy
orbital, 2p.

B: 1s22s22p1

The p subshells have 3 orbitals, each which can hold two electrons. Orbitals within the
same subshell (e.g. 2px, 2py, and 2pz) have identical sizes and shapes, and only their
orientation differs. Therefore, these orbitals are called degenerate orbitals because they
have the same energy.

Hund's Rule

Electrons are added to degenerate, equal energy, orbitals so that a maximum number of
unpaired electrons results.

O: 1s22s22p4

B: 1s22s22p1
F: 1s22s22p5

C: 1s22s22p2
Ne: 1s22s22p6

N: 1s22s22p3

An atom is diamagnetic if all of its electrons are paired.

e.g. Of the atoms listed directly above, only Ne is diamagnetic. Atoms ending with xs2,
xp6, xd10, and xf14 are diamagnetic.

An atom is paramagnetic if it has one or more unpaired electrons

e.g. B, C, N, O, and F above are all paramagnetic because they all have at least one
unpaired electron.

47
 Electron configurations are often abbreviated by naming the last element with a filled
shell (e.g. He and Ne) in brackets and listing only the orbitals after the filled shell. This
outermost shell is called the valence shell and the electron in the valence shell are called
valence electrons.

Li: 1s22s1 shorthand Li: [He] 2s1

Na: 1s22s22p63s1 shorthand Na: [Ne] 3s1

Atomic Symbol Electron Electron

Number Configuration Diagram
1 H 1s1

2 He 1s2

3 Li [He] 2s1

4 Be [He] 2s2

5 B [He] 2s22p1

6 C [He] 2s22p2

7 N [He] 2s22p3

8 O [He] 2s22p4

9 F [He] 2s22p5

10 Ne [He] 2s22p6

11 Na [Ne] 3s1

48
12 Mg [Ne] 3s2

13 Al [Ne] 3s23p1

14 Si [Ne] 3s23p2

15 P [Ne] 3s23p3

16 S [Ne] 3s23p4

17 Cl [Ne] 3s23p5

18 Ar [Ne] 3s23p6

19 K [Ar] 4s1

20 Ca [Ar] 4s2

21 Sc [Ar] 4s23d1

22 Ti [Ar] 4s23d2

23 V [Ar] 4s23d3

24 Cr [Ar] 4s13d5

25 Mn [Ar] 4s23d5

26 Fe [Ar] 4s23d6

27 Co [Ar] 4s23d7

28 Ni [Ar] 4s23d8

49
29 Cu [Ar] 4s13d10

30 Zn [Ar] 4s23d10

31 Ga [Ar] 4s23d104p1

32 Ge [Ar] 4s23d104p2

33 As [Ar] 4s23d104p3

34 Se [Ar] 4s23d104p4

35 Br [Ar] 4s23d104p5

36 Kr [Ar] 4s23d104p6

Exceptions to the predicted electron configurations

Two elements of the first 40 elements have electron configurations different from what
would be normally predicted.

Predicted: Cr: [Ar] 4s23d4

Actual: Cr: [Ar] 4s13d5

Predicted:
Cu: [Ar] 4s23d9

Actual: Cu: [Ar] 4s13d10

Relationship between electron configurations and the periodic table

50
 1s 1s
2 s 2 p
3 s 3 p
4 s 3 d 4 p
5 s 4 d 5 p
6 s 5 d 6 p
7 s 6 d 7 p

4 f
5 f

• The shell number of the s and p orbitals is the same as the period, or row, in
which they are located.
o e.g. the 2s orbital is in the 2nd period and the 3p orbitals are in the 3rd
period.
• The shell number of the d orbitals is one number lower than the period in which
they are located.
o e.g. the 3d orbitals are in the 4th period.
• The shell number of the f orbitals is one two numbers lower than the period in
which they are located. To consolidate space, the atoms with f-orbital electrons
(Lanthanide and Actinide series) are listed separate from the rest of the periodic
table.
o e.g. the 4f orbitals are considered to be in the 6th period.

Development of Elements and the Periodic Table

Dmitri Ivanovitch Mendeléev - Created the first accepted version of the periodic table.

• Grouped elements on the basis of similar chemical properties.

• Left blank spaces open to add new elements where he predicted they would occur.
• Accepted minor inversions when placing the elements in order of increasing
atomic mass.

Predicted properties for undiscovered elements, allowing for his theories to be tested.

51
A version of Mendeléev's periodic table published in the journal Annalen der Chemie in
1871.

The Modern Periodic Table

52
Period - A horizontal row in the periodic table.

• The energy levels of the s and p orbitals are numbered by the row in which they
are located.
o e.g. The 2s orbital is in the second row (Li and Be) and the 3p orbitals are
in the third row (Al, Si, P, S, Cl, Ar)
• The d orbitals are placed one row below their energy level.
o e.g. The 3d orbitals are in the fourth row

Group - A vertical column, or family, in the periodic table.

• Numbered in two ways:

1 1
1 2 3 4 5 6 7 8 9 12 13 14 15 16 17 18
0 1

I II III IV V VI VII I II III IV V VI VII VIII

VIIIB
A A B B B B B B B A A A A A A

H
H
e
N
Li Be B C N O F
e
N M
Al Si P S Cl Ar
a g
G G A B
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Se Kr
a e s r
R P A T X
Sr Y Zr Nb Mo Tc Ru Rh Cd In Sn Sb I
b d g e e
A H P A R
Cs Ba La Hf Ta W Re Os Ir Pt Tl Pb Bi
u g o t n
A Un Un Un Un Un Un
Fr Ra
c q p h s o e

Group 1 (IA) - Alkali Metals (excluding H)

53
 • Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), and Fr
(francium)
• All form hydroxides (e.g. NaOH)
• All are active metals
o Activity increases as you move down the column
o React violently when they come into contact with water
• All have one valence electron

Li: [He] 2s1 Rb: [Kr] 5s1

Na: [Ne] 3s1 Cs: [Xe] 6s1
K: [Ar] 4s1 Fr: [Rn] 7s1

• All lose one electron to form cations with a charge of +1

e.g. Li+, Na+, and K+

Group 2 (IIA) - Alkaline Earth Metals

• Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), and

Ra (radium)
• All but Be and Mg are active metals
o Activity increases as you move down the column
o Ca, Sr, and Ba react violently when they come into contact with water
• All have two valence electrons

Be: [He] 2s2 Sr: [Kr] 5s2

Mg: [Ne] 3s2 Ba: [Xe] 6s2
Ca: [Ar] 4s2 Ra: [Rn] 7s2

• Tend to lose two electrons to form cations with a charge of +2

e.g. Be2+, Mg2+, and Ca2+

• Alkaline earth metals are less active than their adjacent alkali metals

e.g. Be is less active than Li; Mg is less active than Na

Groups 3-12 (IIIB - VIIIB, IB & IIB) - Transition Metals

• All have valence electrons in the d orbitals

• Form compounds in which they have various oxidation numbers
+
o Ag (silver) generally forms Ag (+1 oxidation state)
2+
o Zn (zinc) generally forms Zn (+2 oxidation state)
 Brass is an alloy of copper and zinc

Group 13 (IIIA)

54
 1. B (boron) - only element in the group that is not a metal; has semimetal and
nonmetal characteristics.
2. Al (aluminum) - fairly active metal, third most abundant in the earth's crust.
3+
o Loses three electrons to form Al
o Forms compounds in which it has an oxidation state of +3
3. Other metals - Ga (gallium), In (indium), and Tl (thallium) - very scarce active
metals

Group 14 (IVA)

1. C (carbon) - nonmetal
o Elemental forms of carbon include:
 Graphite (crystalline) - Strong bonds between atoms within planes
resulting in extremely high melting and boiling points. Weaker
bonds connecting the planes which account for the soft texture of
graphite.
 Diamond (crystalline) - Hardest naturally occurring substance
with extremely high melting and boiling points. Atoms arranged
in a tetrahedral array with strong C-C bonds.
 Charcoal - Results from heating wood without oxygen present
 Coke (amorphous) - More structured than other amorphous forms
of carbon; made from coal.
 Carbon Black (amorphous) - Formed by burning natural gas or
other carbon compounds in a limited amount of air
o Has strong C-C single bonds, C=C double bonds, and C C triple bonds.
o Forms covalent bonds with other elements
o Can form double and triple bonds with other nonmetals
2. S (silicon) and Ge (germanium) - semimetals
o Silicon is the second most abundant element in the earth's crust
3. Sn (tin) and Pb (lead) - less reactive metals
o Both form compounds in which their oxidation states are +2 or +4
o Bronze is an alloy of tin and copper

Group 15 (VA)

1. N (nitrogen) and P (phosphorus) - nonmetals

o Nitrogen is found in its elemental form at room temperature as a diatomic
gas (N2).
o Nitrogen makes up approximately 80% of earth's atmosphere by volume.
o In compounds, the oxidation of nitrogen can range from -3 to +5.
o Haber process - mixing N2 and H2 gases at 200 to 300 atm and 400 C to
600 C over a finely divided iron catalyst to produce NH3
o Pure elemental phosphorus is white phosphorus (P4). It is highly reactive
and combusts with air at room temperature but is unreactive with water.
o Red phosphorus is formed when white phosphorus is heated and is much
less reactive than white phosphorus.

55
 o Phosphorus can expand its valence (outermost) shell to hold more than
eight electrons (can store extra electrons in the 3d orbitals).
o N N triple bonds are much stronger than P P.
o P-P single bonds are stronger than N-N single bonds.
2. As (arsenic) and Sb (antimony) - semimetals
3. Bi (bismuth) - metal

Group 16 (VIA)

1. O (oxygen), S (sulfur), and Se (selenium) - nonmetals

o Oxygen is the most abundant element on earth, making up approximately
45% of the earth's crust (by weight), 85% of the oceans (by weight) and
20% of the atmosphere (by volume).
o Oxygen is generally diatomic (O2) in its elemental form, but ozone (O3) is
an allotrope of O2.
 At concentrations above 1 ppm, ozone is toxic.
 Ozone can absorb ultraviolet (UV) radiation from the sun, and
serves as a filter in the atmosphere.
o Oxygen is a very strong oxidizing agent, weaker only to fluorine.
o Oxygen generally takes on a -2 oxidation number in compounds.
2-
 In peroxide (O2 ), oxygen has a -1 oxidation number, e.g. H2O2,
hydrogen peroxide.
o Elemental sulfur is a yellow solid at room temperature with a cyclical
molecular structure (S8).
o O=O double bonds are much stronger than S=S double bonds.
o S-S single bonds are stronger than O-O bonds.
o Sulfur can expand its valence (outermost) shell, to hold more than eight
electrons (can store extra electrons in the 3d orbitals).
o In compounds, sulfur can have oxidation numbers ranging from -2 to +6.
o The prefix thio- is given to compounds in which an S atom replaces an O
atom.
2. Te (tellurium) and Po (polonium) - semimetals

Group 17 (VIIA) - Halogens

• F (fluorine), Cl (chlorine), Br (bromine), I (iodine), and At (astatine)

• All are nonmetals except for At which is a semimetal
• All are diatomic in their elemental form
• All gain one electron to form anions with a charge of -1.

e.g. F-, Cl-, and Br-

• In compounds, their oxidation numbers range from -1 to +7.

• None are found in nature in their elemental forms; instead they are found as salts
of the halide ions.
• Properties (at room temperature)

56
 o F2 - highly toxic, colorless gas, most reactive element known.
 So reactive that it can even form compounds with noble gases
(once thought to be inert)
 Used in manufacturing Teflon, (C2F4)n
 Used to make freons which are used in refrigerators
o Cl2 - highly toxic, pale yellow-green gas, strong oxidizing agent
 Used commercially as a bleaching agent an as a disinfectant
o Br2 - reddish-orange liquid with a bad odor
 Its name, bromine, is derived from the Greek bromos which means
"stench"
 Used in preparing fire-extinguishing agents, sedatives, insecticides,
and antiknock agents for gasoline
o I - deep purple solid with a metallic-like luster
 Sublimes directly into a violet gas (I2) from the solid phase when
heated without passing through the liquid phase
 Used as a disinfectant, catalysts, drugs, and dyes
 AgI (silver iodide) is used in photography
 Iodine deficiency in the human body can lead to a goiter, a
swelling of the thyroid gland.

Group 18 (VIIIA) - Noble (Rare) Gases

• He (helium - "sun"), Ne (neon - "new one"), Ar (argon - "lazy one"), Kr (krypton

- "hidden one"), Xe (xenon - "stranger"), and Rn (radon)
• Mistakenly labeled as "inert gases" until about 30 years ago because it was
thought that these gases did not react with anything.
• In 1962, Neil Barlett isolated the first compound containing a noble gas:
[Xe+][PtF6-]
o Since then, compounds containing Kr, Xe, and Rn have been isolated, but
none containing He, Ne, or Ar.
o The oxidation numbers of the rare gases in compounds include +1, +2, +4,
+6, and +8.
• Noble gases have filled valence (outermost) shells.

Periodic Trends

Atomic Radii
1) As you move down a group, atomic radius increases.

• WHY? - The number of energy levels increases as

you move down a group as the number of electrons
increases. Each subsequent energy level is further
from the nucleus than the last. Therefore, the atomic
radius increases as the group and energy levels
increase.

57
2) As you move across a period, atomic radius decreases.

• WHY? - As you go across a period, electrons are added to the same energy level.
At the same time, protons are being added to the nucleus. The concentration of
more protons in the nucleus creates a "higher effective nuclear charge." In other
words, there is a stronger force of attraction pulling the electrons closer to the
nucleus resulting in a smaller atomic radius.

Ionic Radii

1) Anions (negative ions) are larger than their respective atoms.

• WHY?
1. Electron-electron repulsion forces them to spread further apart.
2. Electrons outnumber protons; the protons cannot pull the extra electrons as
tightly toward the nucleus.

2) Cations (positive ions) are smaller than their respective atoms.

• WHY?
1. There is less electron-electron repulsion, so they can come closer together.
2. Protons outnumber electrons; the protons can pull the fewer electrons
toward the nucleus more tightly.
3. If the electron that is lost is the only valence electron so that the electron
configuration of the cation is like that of a noble gas, then an entire energy
level is lost. In this case, the radius of the cation is much smaller than its
respective atom.

First Ionization Energy

• Definition: The energy required to remove the outermost (highest energy)

electron from a neutral atom in its ground state.

1) As you move down a group, first ionization energy decreases.

• WHY?
1. Electrons are further from the nucleus and thus easier to remove the
outermost one.
2. "SHIELDING" - Inner electrons at lower energy levels essentially block
the protons' force of attraction toward the nucleus. It therefore becomes
easier to remove the outer electron

2) As you move across a period, first ionization energy increases.

• WHY? - As you move across a period, the atomic radius decreases, that is, the
atom is smaller. The outer electrons are closer to the nucleus and more strongly

58
 attracted to the center. Therefore, it becomes more difficult to remove the
outermost electron.

Exceptions to First Ionization Energy Trends

1) Xs2 > Xp1 e.g. 4Be > 5B

• WHY? - The energy of an electron in an Xp

orbital is greater than the energy of an
electron in its respective Xs orbital.
Therefore, it requires less energy to remove
the first electron in a p orbital than it is to
remove one from a filled s orbital.

2) Xp3 > Xp4 e.g. 7N > 8O

• WHY? - After the separate degenerate

orbitals have been filled with single
electrons, the fourth electron must be paired.
The electron-electron repulsion makes it
easier to remove the outermost, paired
electron.

(See Hund's Rule)

Second and Higher Ionization Energies

• Definition: Second Ionization Energy is the energy required to remove a second

outermost electron from a ground state atom.
• Subsequent ionization energies increase greatly once an ion has reached the state
like that of a noble gas. In other words, it becomes extremely difficult to remove
an electron from an atom once it loses enough electrons to lose an entire energy
level so that its valence shell is filled.

Ionization Energies (kJ/mol)

Element 1st IE 2nd IE 3rd IE 4th IE

Na 495.8 4562.4 6912 9543
Mg 737.7 1450.6 7732.6 10,540
Al 577.6 1816.6 2744.7 11,577

Electron Affinity

59
 • Definition: The energy given off when a neutral atom in the gas phase gains an
extra electron to form a negatively charged ion.

1) As you move down a group, electron affinity decreases.

2) As you move across a period, electron affinity increases.

Exceptions

• Among nonmetals, however, the elements in the first period have lower electron affinities
than the elements below them in their respective groups.
• Elements with electron configurations of Xs2, Xp3, and Xp6 have electron affinities less
than zero because they are unusually stable. In other words instead of energy being given
off, these elements actually require an input of energy in order to gain electrons. e.g. Be,
N, Ne
o WHY? - Electron affinities are all much smaller than ionization energies.
1. Xs2 < 0: Stable, diamagnetic atom with no unpaired electrons.
2. Xp3 < 0: Stable atom with 3 unpaired p-orbital electrons each occupying its
own subshell.
3. Xp6 < 0: Stable atom with filled valence (outermost) shell.

Metals, Nonmetals, and Semimetals

Metals

Common characteristics:

• Metallic luster (shine)

• Generally solids at room temperature

60
 • Malleable
• Ductile
• Conduct heat and electricity
• Exist as extended planes of atoms
• Combine with other metals to form alloys which have metallic characteristics
• Form positive ions, e.g. Na+, Mg2+, and Al3+

Nonmetals

Common characteristics:

• Rarely have metallic luster (shine)

• Generally gases at room temperature
• Neither malleable nor ductile
• Poor conductors of heat and electricity
• Usually exist as molecules in thier elemental form
• Combine with other nonmetals to form covalent
• Generally form negative ions, e.g. Cl-, SO42-, and N3-

The differences in the characteristics of metals and nonmetals can be explained by the
following:

1. Metals have relatively few electrons in their valence shells.

2. Metals have lower ionization energies than nonmetals.
3. Metals have smaller electron affinities than nonmetals.
4. Metals have larger atoms than nonmetals.

1) As you move across a period, metallic character decreases and nonmetallic

character increases.

2) As you move down a group, metallic character increases and nonmetallic

character decreases.

Semimetals (Metalloids)

• A class of 8 elements that have properties of both metals and nonmetals.

B Si Ge As Sb Te Po At

Common characteristics:

• Generally look metallic but are brittle (not malleable or ductile)

• Neither good conductors or insulators; instead they are semiconductors.

61
Radioactivity

The nucleus

A nucleus consists of a bunch of protons and neutrons; these are known as nucleons.
Each nucleus can be characterized by two numbers: A, the atomic mass number, which is
the total number of nucleons; and Z, the atomic number, representing the number of
protons. Any nucleus can be written in a form like this:

where Al is the element (aluminum in this case), the 27 is the atomic mass number (the
number of neutrons plus the number of protons), and the 13 is Z, the atomic number, the
number of protons.

How big is a nucleus? We know that atoms are a few angstroms, but most of the atom is
empty space. The nucleus is much smaller than the atom, and is typically a few
femtometers. The nucleus can be thought of as a bunch of balls (the protons and
neutrons) packed into a sphere, with the radius of the sphere being approximately:

The strong nuclear force

What holds the nucleus together? The nucleus is tiny, so the protons are all very close
together. The gravitational force attracting them to each other is much smaller than the
electric force repelling them, so there must be another force keeping them together. This
other force is known as the strong nuclear force; it works only at small distances. The
strong nuclear force is a very strong attractive force for protons and neutrons separated by
a few femtometers, but is basically negligible for larger distances.

The tug-of-war between the attractive force of the strong nuclear force and the repulsive
electrostatic force between protons has interesting implications for the stability of a
nucleus. Atoms with very low atomic numbers have about the same number of neutrons

62
and protons; as Z gets larger, however, stable nuclei will have more neutrons than
protons. Eventually, a point is reached beyond which there are no stable nuclei: the
bismuth nucleus with 83 protons and 126 neutrons is the largest stable nucleus. Nuclei
with more than 83 protons are all unstable, and will eventually break up into smaller
pieces; this is known as radioactivity.

Why Atoms are Radioactive

Not all atoms are radioactive. This is a good thing, because the high energy particles that
result from radioactive decay aren't good for living things. However, this raises the
question of why some atoms are radioactive and some are not.
The simple answer is that radioactive atoms have an unstable nucleus. So when we say
that an atom is radioactive, we mean that its nucleus is unstable, and prone to radioactive
decay.
What makes an atom stable or unstable? There are two important factors: the size of the
nucleus, and the ratio of protons to neutrons.
Once a nucleus gets past a certain size, it is unstable. The largest stable nucleus is
bismuth-209. All isotopes larger than this are unstable, while nearly all elements smaller
than this have at least one stable isotope (exceptions are technetium and promethium).

Notice that the elements that don't have any stable isotopes aren't exactly the same ones
as the ones we've previously referred to as “artificial,” or not naturally occurring.
Uranium, as it turns out, doesn't have any stable isotopes, but it does have some that last
quite a long time before undergoing radioactive decay, so we can still find it around. And

63
when it decays, it turns into some smaller elements like thorium, francium, and so on, so
that even though they are unstable and don't last long, a little more of them are being
generated, so we can find small amounts in nature.
Large nuclei are unstable because the strong force that holds the nucleus together only
works over short distances. In a very large nucleus, the protons on opposite sides are too
far apart to be held together by the strong force, so they begin to repel each other. This
makes the edges of the nucleus want to come off from the rest of it.

To look at the ratio of protons to neutrons, it is helpful to make a chart with the number
of protons going up, and the number of neutrons going across (this is often called a
nuclide chart). In the chart below, the stable isotopes are shown in green, while unstable
isotopes are shown in yellow.

The red line shows where the number of protons is equal to the number of neutrons. For
small atoms, this is the most stable ratio (1:1). For example, oxygen-16, magnesium-24,
silicon-28, and calcium-40 are all stable atoms. As the atoms get larger, they diverge

64
from this line, and are stable with more neutrons than protons (the maximum ratio is
1.3:1). Larger stable atoms include gold-197, tungsten-184, and indium-115, all of which
have more neutrons than protons. The most logical explanation for this is that since
neutrons are neutral, they don't repel each other, but are attracted by the strong force, so
they held offset the repulsion of the protons.
Types of Radioactive Decay
When an atom is unstable, it undergoes radioactive decay in order to become more stable.
If it is too big, then it needs to become smaller. If the proton/neutron ratio is too far from
the stable range, then it needs to change.
There are three types of radioactive decay that we will study. They are named after the
particle that comes out of the nucleus during the reaction. They are called alpha decay,
beta decay, and positron emission. What are these particles, and what new isotope
results when they are emitted? Let's analyze some examples and find out.
Alpha decay
Alpha decay is relatively straightforward. An example of alpha decay is radium-224,
which emits an a particle and becomes radon-220.
224
Ra --> 220Rn + a
The atomic mass goes from 224 to 220 – a loss of 4 amu. Two protons are lost – radium's
atomic number is 88 and radon's is 86. Finally, two neutrons are also lost – radium-224
has 136 neutrons and radon-220 has 134. The lost mass, protons, and neutrons make up
the a particle – a 4He nucleus. Other isotopes that undergo alpha decay also lose 4 amu,
two neutrons and two protons, and therefore you can recognize alpha decay if given the
starting nucleus and what is produced. Here are two more examples.
239
Pu --> 235U + a
241
Am --> 237Np + a
Beta decay
Tritium undergoes beta decay. It gives off a b particle and turns into a helium-3 nucleus.
3
H --> 3He + b
b particles were found to have the same charge and mass as electrons – in fact, they are
electrons. However, a question arises because an electron came out of the nucleus of an
atom, where no electrons are supposed to be. The answer is found in the change in the

65
number of protons and neutrons. Tritium has the same mass as helium-3, but a proton
was lost, and a neutron was gained. It turns out that a neutron turns into a proton plus an
electron: no --> p+ + e-.

The electron is ejected as radiation, and the presence of the new proton causes the atomic
number to increase by one. Another isotope that undergoes beta decay is carbon-14. It
14
gives off a b particle (an electron) and becomes nitrogen-14: C --> 14N + b. Cobalt-61
emits a beta particle and becomes nickel-61: 61Co --> 61Ni + b.
Positron emission
The last kind of radioactive decay is positron emission. An example is when fluorine-18
emits a positron and becomes an oxygen-18 atom.
18
F --> 18O + e+
What is a positron? It is a positively charged electron – a particle of antimatter. It is
formed when a proton changes to a neutron plus a positron: p+ --> no + e+.

The positron comes flying out of the nucleus, leaving it with the same mass, but one
atomic number less. Other examples include: 15O --> 15N + e+, and 11C --> 11B + e+.
To summarize:

66
 charge change in change in
atomic mass of change in number
type on the atomic mass number of
the particle of neutrons
particle of isotope protons

alpha (a) 4 amu +2 lose 4 amu lose 2 lose 2

beta (b) negligible -1 no change gain 1 lose 1

Positron (e+) neg +1 no change lose 1 gain 1

You should be able to determine the product of an alpha decay, a beta decay, and a
positron emission, determine the parent isotope if the product is given, or to tell what
type of reaction has occurred if you are given both the reactant and product nuclei.

Predicting radioactive decay

We can often predict what kind of radioactive decay will occur by looking at what the
change does to the size of the nucleus and the ratio of protons to neutrons.
When an atom undergoes alpha decay, it loses two protons and two neutrons. This
reduces the mass of the nucleus without changing the proton/neutron ratio. So atoms that
have an appropriate ratio, but are too big, are likely to undergo alpha decay.

When an atom undergoes beta decay, it gains a proton but loses a neutron. This doesn't
change the mass, but it alters the proton/neutron ratio so that there are fewer neutrons
than there were before. Atoms that have too many neutrons, or in other words, isotopes
that are unusually heavy for that element, are likely to undergo beta decay.

67
When an atom undergoes positron emission, it loses a proton but gains a neutron. This
also doesn't change the mass, but it alters the proton/neutron ratio in the opposite
direction as beta decay, so that there are more protons than there were before. Atoms that
have too many protons, or in other words, isotopes that are unusually light for that
element, are likely to undergo positron emission. This isn't as common as beta decay, but
it does happen.

If we look again at the nuclide chart showing stable and unstable nuclei, we can predict
the most likely radioactive decay reaction that different kinds of unstable nuclei will
undergo. Atoms that are above the stable ones will undergo positron emission to get
closer to the stable ratio, while atoms that are below the line will undergo beta decay to
get closer to the stable ratio. Atoms that are along the line but too big will undergo alpha
decay so that they can become smaller without changing the proton/neutron ratio.

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The most common isotope of carbon has a mass of 12, as we can see from the atomic
mass given on the Periodic Table. Carbon-11 is therefore unusually light, and will likely
undergo positron emission to get rid of a proton and be a smaller element which will be
more stable with a mass of 11. Carbon-14, on the other hand, is unusually heavy, and will
likely undergo beta decay to get rid of a neutron and be a larger element which will be
more stable with a mass of 14. Plutonium-241, on the other hand, is simply too big to be
stable, and is likely to undergo alpha decay so that it can be smaller.

Radioactive decay series

Even though radioactive decay can help an atom become more stable, many times one
radioactive decay reaction isn't enough. The product of a radioactive decay may not be
stable either.
When this happens, the atom will undergo more than one radioactive decay, forming a
radioactive decay series. One isotope decays to another, then to another, and another,
until finally a stable isotope is reached.
Here is an example of a decay series:
thorium-232 --> radium-228 + a
radium-228 --> actinium-228 + b
actinium-228 --> thorium-228 + b
thorium-228 --> radium-224 + a

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radium-224 --> radon-220 + a
radon-220 --> polonium-216 + a
polonium-216 --> lead-212 + a
lead-212 --> bismuth-212 + b
bismuth-212 --> polonium-212 + b
polonium-212 --> lead-208 + a
Lead-208 is a stable isotope, so the series ends there.
A decay series can also be shown on a nuclide chart, like the one below. It shows the path
followed across the nuclide chart until a stable isotope is reached (this is a different series
than the one described above).

Uses of Radioactivity/Radiation
There are many practical applications to the use of radioactivity/radiation. Radioactive
sources are used to study living organisms, to diagnose and treat diseases, to sterilize
medical instruments and food, to produce energy for heat and electric power, and to
monitor various steps in all types of industrial processes.

70
Tracers
Tracers are a common application of radioisotopes. A tracer is a radioactive element
whose pathway through which a chemical reaction can be followed. Tracers are
commonly used in the medical field and in the study of plants and animals. Radioactive
Iodine-131 can be used to study the function of the thyroid gland assisting in detecting
disease.
Nuclear reactors
Nuclear reactors are devices that control fission reactions producing new substances from
the fission product and energy. Recall our discussion earlier about the fission process in
the making of a radioisotope. Nuclear power stations use uranium in fission reactions as a
fuel to produce energy. Steam is generated by the heat released during the fission process.
It is this steam that turns a turbine to produce electric energy.
Other uses of radioactivity
Sterilization of medical instruments and food is another common application of radiation.
By subjecting the instruments and food to concentrated beams of radiation, we can kill
microorganisms that cause contamination and disease. Because this is done with high
energy radiation sources using electromagnetic energy, there is no fear of residual
radiation. Also, the instruments and food may be handled without fear of radiation
poisoning.

Radiation sources are extremely important to the manufacturing industries throughout the
world. They are commonly employed by nondestructive testing personnel to monitor
materials and processes in the making of the products we see and use every day. Trained
technicians use radiography to image materials and products much like a dentist uses
radiation to x-ray your teeth for cavities. There are many industrial applications that rely
on radioactivity to assist in determining if the material or product is internally sound and
fit for its application.
Summary
1. Radioactivity tracers are commonly used in the medical field and also in the study
of plants and animals.

71
 2. Radiation is used and produced in nuclear reactors, which controls fission
reactions to produce energy and new substances from the fission products.
3. Radiation is also used to sterilize medical instruments and food.
4. Radiation is used by test personnel who monitor materials and processes by
nondestructive methods such as x-rays.

Organic chemistry

Naming Organic Compounds

The increasingly large number of organic compounds identified with each passing day,
together with the fact that many of these compounds are isomers of other compounds,
requires that a systematic nomenclature system be developed. Just as each distinct
compound has a unique molecular structure which can be designated by a structural
formula, each compound must be given a characteristic and unique name.
As organic chemistry grew and developed, many compounds were given trivial names,
which are now commonly used and recognized. Some examples are:

Name Methane Butane Acetone Toluene Acetylene Ethyl Alcohol

Formula CH4 C4H10 CH3COCH3 CH3C6H5 C2H2 C2H5OH

Such common names often have their origin in the history of the science and the natural
sources of specific compounds, but the relationship of these names to each other is
arbitrary, and no rational or systematic principles underly their assignments.

The IUPAC Systematic Approach to Nomenclature

A rational nomenclature system should do at least two things. First, it should indicate
how the carbon atoms of a given compound are bonded together in a characteristic lattice
of chains and rings. Second, it should identify and locate any functional groups present in
the compound. Since hydrogen is such a common component of organic compounds, its
amount and locations can be assumed from the tetravalency of carbon, and need not be
specified in most cases .The IUPAC nomenclature system is a set of logical rules devised

72
and used by organic chemists to circumvent problems caused by arbitrary nomenclature.
Knowing these rules and given a structural formula, one should be able to write a unique
name for every distinct compound. Likewise, given a IUPAC name, one should be able to
write a structural formula. In general, an IUPAC name will have three essential features:

• A root or base indicating a major chain or ring of carbon atoms found in the
molecular structure.
• A suffix or other element(s) designating functional groups that may be present
in the compound.
• Names of substituent groups, other than hydrogen, that complete the molecular
structure.

As an introduction to the IUPAC nomenclature system, we shall first consider

compounds that have no specific functional groups. Such compounds are composed only
of carbon and hydrogen atoms bonded together by sigma bonds

Alkanes

Hydrocarbons having no double or triple bond functional groups are classified as alkanes
or cycloalkanes, depending on whether the carbon atoms of the molecule are arranged
only in chains or also in rings. Although these hydrocarbons have no functional groups,
they constitute the framework on which functional groups are located in other classes of
compounds, and provide an ideal starting point for studying and naming organic
compounds. The alkanes and cycloalkanes are also members of a larger class of
compounds referred to as aliphatic. Simply put, aliphatic compounds are compounds that
do not incorporate any aromatic rings in their molecular structure.
The following table lists the IUPAC names assigned to simple continuous-chain alkanes
from C-1 to C-10. A common "ane" suffix identifies these compounds as alkanes.
Longer chain alkanes are well known, and their names may be found in many reference
and text books. The names methane through decane should be memorized, since they
constitute the root of many IUPAC names. Fortunately, common numerical prefixes are
used in naming chains of five or more carbon atoms.

73
 Examples of Simple Unbranched Alkanes
Molecular Structural Molecular Structural
Name Isomers Name Isomers
Formula Formula Formula Formula
methane CH4 CH4 1 hexane C6H14 CH3(CH2)4CH3 5
ethane C2H6 CH3CH3 1 heptane C7H16 CH3(CH2)5CH3 9
propane C3H8 CH3CH2CH3 1 octane C8H18 CH3(CH2)6CH3 18
butane C4H10 CH3CH2CH2CH3 2 nonane C9H20 CH3(CH2)7CH3 35
pentane C5H12 CH3(CH2)3CH3 3 decane C10H22 CH3(CH2)8CH3 75

Some important behavior trends and terminologies:

(i) The formulas and structures of these alkanes increase uniformly by a CH2
increment.
(ii) A uniform variation of this kind in a series of compounds is called
homologous.
(iii) These formulas all fit the CnH2n+2 rule. This is also the highest possible H/C
ratio for a stable hydrocarbon.
(iv) Since the H/C ratio in these compounds is at a maximum, we call them
saturated (with hydrogen).

Beginning with butane (C4H10), and becoming more numerous with larger alkanes, we
note the existence of alkane isomers. For example, there are five C6H14 isomers, shown
below as abbreviated line formulas (A through E):

Although these distinct compounds all have the same molecular formula, only one (A)
can be called hexane. How then are we to name the others?

The IUPAC system requires first that we have names for simple unbranched chains, as
noted above, and second that we have names for simple alkyl groups that may be attached
to the chains. Examples of some common alkyl groups are given in the following table.

74
 Note that the "ane" suffix is replaced by "yl" in naming groups. The symbol R is used to
designate a generic (unspecified) alkyl group.

CH3
Gro CH3 CH2 (CH3)2 CH3CH2C (CH3)2C CH3CH2C (CH3)
C2H5– R–
up – CH2 CH– H2CH2– HCH2– H(CH3)– 3C–

tert-
Na Met Pro Isopro
Ethyl Butyl Isobutyl sec-Butyl Butyl Alkyl
me hyl pyl pyl

IUPAC Rules for Alkane Nomenclature

1. Find and name the longest continuous carbon chain.

2. Identify and name groups attached to this chain.
3. Number the chain consecutively, starting at the end nearest a substituent group.
4. Designate the location of each substituent group by an appropriate number and name.
5. Assemble the name, listing groups in alphabetical order.
The prefixes di, tri, tetra etc., used to designate several groups of the same kind, are not
considered when alphabetizing.

For the above isomers of hexane the IUPAC names are: B 2-methylpentane C 3-
methylpentane D 2,2-dimethylbutane E 2,3-dimethylbutane

Name the following molecule

The correct name is: 2,7,8 - Trimethyldecane and not 3,4,9 - Trimethyldecane

75
 Halogen substituents are easily accommodated, using the names: fluoro (F-), chloro (Cl-
), bromo (Br-) and iodo (I-). For example, (CH3)2CHCH2CH2Br would be named 1-
bromo-3-methylbutane. If the halogen is bonded to a simple alkyl group an alternative
"alkyl halide" name may be used. Thus, C2H5Cl may be named chloroethane (no locator
number is needed for a two carbon chain) or ethyl chloride.

Cycloalkanes

Cycloalkanes have one or more rings of carbon atoms. The simplest examples of this
class consist of a single, unsubstituted carbon ring, and these form a homologous series
similar to the unbranched alkanes. The IUPAC names of the first five members of this
series are given in the following table. The last (yellow shaded) column gives the general
formula for a cycloalkane of any size. If a simple unbranched alkane is converted to a
cycloalkane two hydrogen atoms, one from each end of the chain, must be lost. Hence the
general formula for a cycloalkane composed of n carbons is CnH2n. Although a
cycloalkane has two fewer hydrogens than the equivalent alkane, each carbon is bonded
to four other atoms so such compounds are still considered to be saturated with
hydrogen.

Examples of Simple Cycloalkanes

Name Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane Cycloalkane

Molecular
C3H6 C4H8 C5H10 C6H12 C7H14 CnH2n
Formula

Structural (CH2)n
Formula

Line
Formula

Substituted cycloalkanes are named in a fashion very similar to that used for naming
branched alkanes. The chief difference in the rules and procedures occurs in the

76
numbering system. Since all the carbons of a ring are equivalent (a ring has no ends like a
chain does), the numbering starts at a substituted ring atom.

IUPAC Rules for Cycloalkane Nomenclature

1. For a monosubstituted cycloalkane the ring supplies the root name (table above) and
the substituent group is named as usual. A location number is unnecessary.
2. If the alkyl substituent is large and/or complex, the ring may be named as a
substituent group on an alkane.
3. If two different substituents are present on the ring, they are listed in alphabetical
order, and the first cited substituent is assigned to carbon #1. The numbering of ring
carbons then continues in a direction (clockwise or counter-clockwise) that affords the
second substituent the lower possible location number.
4. If several substituents are present on the ring, they are listed in alphabetical order.
Location numbers are assigned to the substituents so that one of them is at carbon #1 and
the other locations have the lowest possible numbers, counting in either a clockwise or
counter-clockwise direction.
5. The name is assembled, listing groups in alphabetical order and giving each group (if
there are two or more) a location number. The prefixes di, tri, tetra etc., used to designate
several groups of the same kind, are not considered when alphabetizing.

Hydrocarbons having more than one ring are common, and are referred to as bicyclic
(two rings), tricyclic (three rings) and in general, polycyclic compounds. The molecular
formulas of such compounds have H/C ratios that decrease with the number of rings. In
general, for a hydrocarbon composed of n carbon atoms associated with m rings the
formula is: CnH(2n + 2 - 2m). The structural relationship of rings in a polycyclic compound
can vary. They may be separate and independent, or they may share one or two common
atoms. Some examples of these possible arrangements are shown in the following table.

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 Examples of Isomeric C8H14 Bicycloalkanes

Isolated Rings Spiro Rings Fused Rings Bridged Rings

No common One common One common Two common

atoms atom bond atoms

Alkenes and Alkynes

Alkenes and alkynes are hydrocarbons which respectively have carbon-carbon double
bond and carbon-carbon triple bond functional groups. The molecular formulas of
these unsaturated hydrocarbons reflect the multiple bonding of the functional groups:

R–CH2– This is the maximum H/C ratio for a given number of

Alkane CnH2n+2
CH2–R carbon atoms.
R–
Each double bond reduces the number of hydrogen
Alkene CH=CH– CnH2n
atoms by 2.
R
R–C≡C– Each triple bond reduces the number of hydrogen atoms
Alkyne CnH2n-2
R by 4.

As noted earlier in the Analysis of Molecular Formulas section, the molecular formula of
a hydrocarbon provides information about the possible structural types it may represent.
For example, consider compounds having the formula C5H8. The formula of the five-
carbon alkane pentane is C5H12 so the difference in hydrogen content is 4. This difference

78
suggests such compounds may have a triple bond, two double bonds, a ring plus a double
bond, or two rings. Some examples are shown here, and there are at least fourteen others!

IUPAC Rules for Alkene and Cycloalkene Nomenclature

1. The ene suffix (ending) indicates an alkene or cycloalkene.

2. The longest chain chosen for the root name must include both carbon atoms of the
double bond.
3. The root chain must be numbered from the end nearest a double bond carbon atom. If
the double bond is in the center of the chain, the nearest substituent rule is used to
determine the end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double bond is
used as the double bond locator. If more than one double bond is present the compound is
named as a diene, triene or equivalent prefix indicating the number of double bonds, and
each double bond is assigned a locator number.
5. In cycloalkenes the double bond carbons are assigned ring locations #1 and #2.
Which of the two is #1 may be determined by the nearest substituent rule.
6. Substituent groups containing double bonds are:
H2C=CH– Vinyl group
H2C=CH–CH2– Allyl group

IUPAC Rules for Alkyne Nomenclature

1. The yne suffix (ending) indicates an alkyne or cycloalkyne.

2. The longest chain chosen for the root name must include both carbon atoms of the
triple bond.
3. The root chain must be numbered from the end nearest a triple bond carbon atom. If
the triple bond is in the center of the chain, the nearest substituent rule is used to
determine the end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the triple bond is

79
used as the triple bond locator.
5. If several multiple bonds are present, each must be assigned a locator number.
Double bonds precede triple bonds in the IUPAC name, but the chain is numbered from
the end nearest a multiple bond, regardless of its nature.
6. Because the triple bond is linear, it can only be accommodated in rings larger than
ten carbons. In simple cycloalkynes the triple bond carbons are assigned ring locations #1
and #2. Which of the two is #1 may be determined by the nearest substituent rule.
7. Substituent groups containing triple bonds are:
HC≡C– Ethynyl group
HC≡CH–CH2– Propargyl group

Nomenclature of compounds containing functional group or multiple bonds:

• In naming the organic compounds containing one functional group a suffix known
as secondary suffix is added to the primary suffix (giving number of carbon atoms
in the chain) to indicate the nature of the functional group. A few important
secondary suffixes are:

Secondary Secondary
Functional group Functional group
suffix suffix

Alcohols (-OH) -ol Aldehydes (-CHO) -al

Carboxylic acids (-
Ketones (>C=O) -one -oic acid
COOH)

Amines (-NH2 ) -amine Acid amides (-CONH2 ) -amide

Acid chlorides (-
-oyl chloride Esters (-COOR) -oate
COCL)

Nitrites (-C=N) -nitrite Thioalcohols (-SH) -thiol

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Benzene Derivatives

The nomenclature of substituted benzene ring compounds is less systematic than that of
the alkanes, alkenes and alkynes. A few mono-substituted compounds are named by
using a group name as a prefix to "benzene", as shown by the combined names listed
below. A majority of these compounds, however, are referred to by singular names that
are unique. There is no simple alternative to memorization in mastering these names.

Two commonly encountered substituent groups that incorporate a benzene ring are
phenyl, abbreviated Ph-, and benzyl, abbreviated Bn-. These are shown here with
examples of their use. Be careful not to confuse a phenyl (pronounced fenyl) group with
the compound phenol (pronounced feenol). A general and useful generic notation that
complements the use of R- for an alkyl group is Ar- for an aryl group (any aromatic
ring).

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When more than one substituent is present on a benzene ring, the relative locations of the
substituents must be designated by numbering the ring carbons or by some other notation.
In the case of disubstituted benzenes, the prefixes ortho, meta & para are commonly used
to indicate a 1,2- or 1,3- or 1,4- relationship respectively. In the following examples, the
first row of compounds show this usage in red. Some disubstituted toluenes have singular
names (e.g. xylene, cresol & toluidine) and their isomers are normally designated by the
ortho, meta or para prefix. A few disubstituted benzenes have singular names given to
specific isomers (e.g. salicylic acid & resorcinol). Finally, if there are three or more
substituent groups, the ring is numbered in such a way as to assign the substituents the
lowest possible numbers, as illustrated by the last row of examples. The substituents are
listed alphabetically in the final name. If the substitution is symmetrical (third example
from the left) the numbering corresponds to the alphabetical order.

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83