2 Atomic Structure, Periodic Table & Chemical Nomenclature

Atomic Structure
Dalton’s Atomic Theory and the Modern

view of Atomic Structure
Early Ideas of Atoms – Democritus’ Theory
• The concept of the atom was first proposed about 2,500 years ago.
• It has always been difficult to convince people of the existence of things that are
too small to see.
• We will spend some time considering the evidence (observations) that convince
scientists of the existence of atoms.
Democritus
• Democritus (460-370 BC) and other early Greek philosophers thought that the
material world must be made up of tiny indivisible particles that they called
atomos, meaning "indivisible"
• Democritus then reasoned that changes occur when the many atomos in an
object were reconnected or recombined in different ways.
Early Ideas of Atoms – Democritus’ Theory
• He even extended his theory, suggesting that there were different varieties of
atomos with different shapes, sizes, and masses.
• He thought, however, that shape, size and mass were the only properties
differentiating the different types of atomos.
• According to Democritus, other characteristics, like colour and taste, did not reflect
properties of the atomos themselves, but rather, resulted from the different ways
in which the atomos were combined and connected to one another.
• Democritus’ theories were scoffed at, and the "atomic" view of matter faded for
many centuries.
• The notion of atoms re-emerged in Europe during the seventeenth century, when
scientists tried to explain the properties of gases.
Early Ideas of Atoms – Dalton’s Atomic
Theory
• As chemists learned to measure the amounts of elements that reacted with one
another to form new substances, the ground was laid for an atomic theory that
linked the idea of elements with the idea of atoms.
• That theory came from the work of an English school teacher, John Dalton during
the period from 1803-1807.
• Dalton's atomic theory involved the following postulates (or hypotheses).
Theory
• Dalton's theory explains several simple laws of chemical combination that were
known during his time. One of these laws was the law of constant composition:
In a given compound, the relative numbers and kinds of atoms are constant.
• This law is the basis of Dalton's Postulate 4.
• Another fundamental chemical law was the law of conservation of mass aka (also
known as) the law of conservation of matter:
The total mass of materials present after a chemical reaction is the same as the
total mass present before the reaction.
• This law is the basis for Postulate 3. Dalton proposed that atoms always retain their
identities and that atoms taking part in a chemical reaction rearrange to give new
chemical combinations.
Theory
• A good theory explains the known facts and predicts new ones. Dalton used his
theory to deduce the law of multiple proportions:
If two elements A and B combine to form more than one compound, the masses of
B that can combine with a given mass of A are in the ratio of small whole numbers.
The Modern view of Atomic Structure
• Dalton reached his conclusion about atoms based on chemical observations in the
macroscopic world of the laboratory. Neither he nor those who followed him
during the century after his work was published had direct evidence for the
existence of atoms.
• Today’s world is a microscopic one where we can use powerful instruments to
measure the properties of individual atoms and even provide images of them.
• As scientists developed methods for more detailed studying of the nature of
matter, the atom, which was supposed to be indivisible, began to show signs of a
more complex structure.
• Before we summarize the current model of atomic structure, let us briefly
consider a few of the landmark discoveries (also referred to as models) along the
following timeline that led to that model.
The Modern view of Atomic Structure
Discovery of the Electron
• In the mid-1800s, scientists were beginning to realize that the study of chemistry
and the study of electricity were actually related.
• First, a man named Michael Faraday showed how passing electricity through
mixtures of different chemicals could cause chemical reactions.
• Shortly after that, scientists found that by forcing electricity through a tube filled
with gas, the electricity made the gas glow!
• Scientists didn’t, however, understand the relationship between chemicals and
electricity until a British physicist named J. J. Thomson began experimenting with
what is known as a cathode ray tube.
• The following figures show a picture and a basic diagram of a cathode ray tube like
the one J. J. Thomson would have used. A cathode ray tube is a small glass tube
with a cathode (a negatively charged metal plate) and an anode (a positively
charged metal plate) at opposite ends.
• By separating the cathode and anode by a short distance, the cathode ray tube can
generate what are known as cathode rays – rays of electricity that flow from the
cathode to the anode.
• J. J. Thomson wanted to know what cathode rays were, where cathode rays came
from, and whether cathode rays had any mass or charge.
• Through his rigorous experiments, J. J. Thomson suggested that the small, negatively
charged particles making up the cathode ray were actually pieces of atoms.
• He called these pieces “corpuscles,” although today we know them as electrons.
• Thanks to his clever experiments and careful reasoning, J. J. Thomson is credited with
the discovery of the electron.
• In 1897 J. J. Thomson (1856–1940) studied these negatively charged particles more
• carefully. By studying the degree of deflections of cathode rays in different electric and
magnetic fields, Thomson determined the ratio of the charge (e) of the electron to its
mass (m). The modern value for this ratio is
e/m = 1.75882 x 108 coulomb (C)/gram
The oil drop apparatus
1916 – Robert Millikan

determines the mass of the
electron: 1/1840 the mass of a
hydrogen atom; has one unit of
negative charge
Mass of the electron is 9.11 x 10-28 g

• With his oil drop experiment, Robert Millikan was able to accurately measure the
charge of the electron. When combined with the charge to mass ratio, he was able to
calculate the mass of the electron.
Millikan's oil-drop experiment. A

representation of the apparatus
Millikan used to measure the
charge of the electron.
Thomson’s Plum Pudding Model
• When Thomson discovered the negative electron, he realized that atoms had to contain
positive material as well – otherwise they wouldn’t be neutral overall.
• As a result, Thomson formulated what’s known as the “plum pudding” model for the
atom.
• Thomson’s plum pudding model was much like a
chocolate chip cookie. Notice (on the next slide)
how the chocolate chips are the negatively
charged electrons, while the positive charge is
spread throughout the entire cookie.
• J.J. Thomson had measured the charge to mass
ratio of the electron, but had been unable to
accurately measure the charge on the electron.
A plum pudding in which the raisins
represent the distribution of
electrons in the atom.
Rutherford’s Nuclear Model
• Everything about Thomson’s experiments suggested the “plum pudding” model was
correct – but according to the scientific method, any new theory or model should be
tested by further experimentation and observation.
• Disproving Thomson’s “plum pudding” model began with the discovery that an element
known as uranium emits positively charged particles called alpha particles as it
undergoes radioactive decay.
• Radioactivity is the spontaneous emission of radiation by an atom. It only happens with
a few very unstable elements.
• Alpha particles themselves didn’t prove anything about the structure of the atom, they
were, however, used to conduct some very interesting experiments.
• Rutherford found from his gold foil experiment that when he fired alpha particles at a
very thin piece of gold foil, an interesting thing happened. Almost all of the alpha
particles went straight through the foil as if they’d hit nothing at all. This was what he
expected to happen.
• Rutherford decided that the only way to explain his results was to assume that the
positive matter forming the gold atoms was not, in fact, distributed like the batter in
plum pudding, but rather, was concentrated in one spot, forming a small positively
charged particle somewhere in the centre of the gold atom.
• We now call this clump of positively charged mass the nucleus.
• According to Rutherford, the presence of a nucleus explained his experiments,
because it implied that most alpha particles passed through the gold foil without
hitting anything at all. Once in a while, though, the alpha particles would actually
collide with a gold nucleus, causing the alpha particles to be deflected, or even to
bounce right back in the direction they came from.
Rutherford postulated a very

small, dense nucleus with the
electrons around the outside of
the atom.
Most of the volume of the atom
is empty space.
If an atom could be
expanded to the size of a
football stadium, the
nucleus would be the
size of a single
blueberry.
• Subsequent experimental studies led to the discovery of both positive particles
(protons) and neutral particles (neutrons) in the nucleus. Protons were discovered
in 1919 by Rutherford. In 1932 British scientist James Chadwick (1891-1972)
discovered neutrons.
Radioactivity
• In 1896 the French scientist Henri Becquerel (1852-1908) was studying a uranium
compound when he discovered that it spontaneously emits high-energy radiation.
• This spontaneous emission of radiation is called radioactivity.
• At Becquerel's suggestion Marie Curie and her husband, Pierre, began experiments to
isolate the radioactive components of the compound.
• Further study of the nature of radioactivity, principally by the British scientist Ernest
Rutherford, revealed three types of radiation:
alpha ( ), beta ( ), and gamma ( ) radiation.
• Each type differs in its response to an electric field, as shown in the following figure.
• The paths of both a and {3 radiation are bent by the electric field, although in
opposite directions; y radiation αis unaffected.
Radioactivity
Radioactivity
• Rutherford showed that both  and  rays consist of fast-moving particles, which
were called  and  particles.
• In fact,  particles are high-speed electrons and can be considered the radioactive
equivalent of cathode rays. They are attracted to a positively charged plate.
• The  particles have a positive charge and are attracted toward a negative plate.
• In units of the charge of the electron,  particles have a charge of 1- and  particles a
charge of 2+.
• Each  particle has a mass about 7400 times that of an electron.
• Gamma radiation is high-energy radiation similar to X-rays; it does not consist of
particles and carries no charge
The Bohr Model
• By 1913, the evolution of our concept of the atom had proceeded from Dalton’s
indivisible spheres idea to J. J. Thomson’s plum pudding model and then to
Rutherford’s nuclear atom theory.
• Rutherford, in addition to carrying out the brilliant experiment that demonstrated
the presence of the atomic nucleus, also proposed that the electrons circled the
nucleus in a planetary type motion.
• In 1913, the Danish physicist Niels Bohr

proposed a model of the electron
cloud of an atom in which electrons
orbit the nucleus and were able to
produce an atomic spectrum.
The Bohr Model
• Understanding Bohr’s model requires some knowledge of electromagnetic radiation
(or light).
• When gaseous atoms of a given element are heated, they emit light of only
specific
energies. When gaseous atoms of that same element absorb light, they absorb
those same energies.
• To explain these phenomena of light emission and light absorption, Niels Bohr
(1885–1962) postulated that the electrons in atoms are arranged in orbits, each
with a definite energy.
• The Bohr theory was the first to include the explanation that electrons in atoms
have discrete energy levels; that is, electrons may be found only in orbits with
specific energies.
The Bohr Model
Energy Levels
• Bohr’s key idea in his model of the atom is that electrons occupy definite orbits that
require the electron to have a specific amount of energy.
• In order for an electron to be in the electron cloud of an atom, it must be in one of
the allowable orbits and it must have the precise energy required for that orbit.
• Orbits closer to the nucleus would require smaller amounts of energy for an electron
and orbits farther from the nucleus would require the electrons to have a greater
amount of energy.
• The possible orbits are known as energy levels. One of the weaknesses of Bohr’s
model was that he could not offer a reason why only certain energy levels or orbits
were allowed.
The Bohr Model
• Bohr hypothesized that the only way electrons could gain or lose energy would be to
move from one energy level to another, thus gaining or losing precise amounts of
energy. It would be like a ladder that had rungs at certain heights, as illustrated below.
• The only way you can be on that ladder is to be on one of the
rungs, and the only way you could move up or down is to
move to one of the other rungs.
• Other rules for the ladder are that only one person can be on
a given rung and that the ladder occupants must be on the
lowest rung available.
• Suppose we had such a ladder with 10 rungs. If the ladder had
five people on it, they would be on the lowest five rungs. In
this situation, no person could move down because all the
lower rungs are full.
The Bohr Model
• Bohr worked out the rules for the maximum number of electrons that could be in
each energy level in his model.
• In its normal state (ground state), this would require the atom to have all of its
electrons in the lowest energy levels available.
• Under these circumstances, no electron could lose energy because no electron could
move down to a lower energy level.
• In this way, the Bohr model explained why electrons circling the nucleus did not
emit energy and spiral into the nucleus.
Bohr’s Model and Atomic Spectra
• The evidence used to support Bohr’s model came from the atomic spectra.
He suggested that an atomic spectrum is made by the electrons in an atom moving
energy levels.
• The electrons typically have the lowest energy possible, called ground state.
The Bohr Model
• If electrons are given energy (through heat, electricity, light, etc.), these electrons in
an atom could absorb the energy by jumping to a higher energy level or an excited
state.
• The electrons then give off the energy in the form of a piece of light, called a photon,
they had absorbed to fall back to a lower energy level.
• The energy emitted by electrons dropping back to lower energy levels would
always be precise amounts of energy because the differences in energy levels were
precise.
• This explains why we see specific lines of light when looking at an atomic spectrum
– each line of light matches a specific "step down" that an electron can take in that
atom.
• This also explains why each element produces a different atomic spectrum. Because
each element has different acceptable energy levels for their electrons, the possible
steps each element’s electrons can take differ from all other elements.
The Bohr Model
• The flames in the picture below represent (left to right) potassium, copper, cesium,
boron, and calcium.
• Each element has a characteristic spectrum from the emission of light from hot
atoms; therefore, these spectra can be used to identify elements.
• Our current understanding of the electronic structure of the atom started with the
discovery and explanation of
the spectra produced in hot
gases and flames.
The Bohr Model
The Bohr Model
The Bohr Model
ENERGY CONSERVATION AND SPECTRAL LINES
• An electron in an excited state normally returns very quickly to its ground state, either
directly or via an intermediate state.
• When the electron moves from its initial Ei to its final Ef state, a photon is emitted (or
absorbed, if Ei < Ef).
• The energy of the photon emitted (or absorbed) is given by energy conservation:
The Bohr Model
• To explain the hydrogen spectrum, Bohr suggested that in each hydrogen atom,
the electron revolves about the nucleus in one of several possible circular orbits,
each having a definite radius corresponding to a definite energy for the electron.
• An electron in the orbit closest to the nucleus has the lowest energy. With the
electron in that orbit, the atom is said to be in its lowest energy state, or ground
state.
• If a discrete quantity of additional energy were absorbed by the atom in some
manner, the electron might be able to move into another orbit having a higher
energy.
• The hydrogen atom would then be in an excited state. An atom in the excited
state will return to the ground state and give off its excess energy as light in the
process.
The Bohr Model
• In returning to the ground state, the energy may be emitted all at once, or it may be
emitted in a stepwise manner (but not continuously) as the electron drops from a
higher allowed orbit to allowed orbits of lower and lower energy.
• Since each orbit corresponds to a definite energy level, the energy of the light
emitted will correspond to the definite differences in energy between levels.
• Therefore, the light emitted as the atom returns to its ground state will have a
definite energy or a definite set of energies.
• The discrete amounts of energy emitted or absorbed by an atom or molecule are
called quanta (singular, quantum). A quantum of light energy is called a photon.
The Bohr Model
• In summary, the Bohr model is based on the following three postulates:
1. Only orbits of certain radii, corresponding to certain definite energies, are
permitted for the electron in a hydrogen atom.
2. An electron in a permitted orbit has a specific energy and is in an "allowed"
energy state. An electron in an allowed energy state will not radiate energy
and therefore will not spiral into the nucleus.
3. Energy is emitted or absorbed by the electron only as the electron changes
from one allowed energy state to another. This energy is emitted or
absorbed as a photon, E = hv.
The Bohr Model
Energy-Level Postulate
• An electron can have only certain energy values, called energy levels. Energy levels
are quantized.
• For an electron in a hydrogen atom, the energy is given by the following equation:
RH
E
n2
where RH = 2.179 x 10-18 J and n = principal quantum number
Transitions Between Energy Levels
• An electron can change energy levels by absorbing energy to move to a higher
energy level or by emitting energy to move to a lower energy level.
The Bohr Model
• For a hydrogen electron the energy change is given by
ΔE  E f  Ei
 1 1 
ΔE  RH  
n 2 n2 
 f i 
RH = 2.179 × 10-18 J, Rydberg constant

• The energy of the emitted or absorbed photon is related to DE:
E photon  ΔE electron  h
h  Planck' s constant
The Bohr Model
• We can now combine these two equations:
 1 1 
h   RH  
n 2 n2 
 f i 
• Light is absorbed by an atom when the electron transition is from lower n to higher
n (nf > ni). In this case, DE will be positive.
• Light is emitted from an atom when the electron transition is from higher n to lower
n (nf < ni). In this case, DE will be negative.
• An electron is ejected when nf = ∞.

The Bohr Model
Electron transitions for an

electron in the hydrogen
atom.
The diagram shows the
Lyman, Balmer, and
Paschen series of transitions
that occur for nf = 1, 2, and 3,
respectively.
The Bohr Model
Example 1:
What is the wavelength of the light emitted when the electron in a hydrogen atom
undergoes a transition from n = 6 to n = 3?
 1 1 
ΔE  RH  2  2 
n ni 
 f
ΔE 
hc
λ
so λ 
hc
ΔE

ΔE   2.179 x 10 18
 1 1 
J 2  2 
3 6 
  34

6.626 x 10 J  s  2.998 x 10 8 m

 s
λ 
 19
- 1.816 x 10 J 
The Bohr Model
Example 2:
Calculating the Energy and Wavelength of Electron Transitions in a One–electron
(Bohr) System
What is the energy (in joules) and the wavelength (in meters) of the line in the
spectrum of hydrogen that represents the movement of an electron from Bohr orbit
with n = 4 to the orbit with n = 6? In what part of the electromagnetic spectrum do we
find this radiation?
Solution
In this case, the electron starts out with n = 4, so n1 = 4. It comes to rest in the n = 6
orbit, so n2 = 6. The difference in energy between the two states is given by this
expression:
The Bohr Model
This energy difference is positive, indicating a photon enters the system (is absorbed) to
excite the electron from the n = 4 orbit up to the n = 6 orbit.
The wavelength of a photon with this energy is found by the expression E= hc/λ .
Rearrangement gives:
From the electromagnetic spectrum, we can see that this wavelength is found in the
infrared portion of the spectrum.
The Bohr Model
Check Your Learning
What is the energy in joules and the wavelength in meters of the photon produced when
an electron falls from the n = 5 to the n = 3 level in a He+ ion (Z = 2 for He+)?
[Answer: 6.198 × 10-19 J; 3.205 × 10-7 m]

The Bohr Model
Spectra
• When atoms or molecules absorb energy, that energy is often released as light
energy,
Fireworks, neon lights, etc.
• When that emitted light is passed through a prism, a pattern of particular
wavelengths of light is seen that is unique to that type of atom or molecule – the
pattern is called an emission spectrum.
• This light emitted can be used to identify materials through flame tests.
The Bohr Model
Exciting Gas Atoms to
Emit Light with
Electrical Energy Identifying Elements with Flame Tests
The Bohr Model
Emission Spectra
Wave-Particle Duality of Electrons
• In 1923, Louis de Broglie, a French physicist, proposed a hypothesis to explain the

theory of the atomic structure.
• By using a series of substitution de Broglie hypothesized particles to hold properties
of waves.
• Within a few years, de Broglie's hypothesis was tested by scientists shooting
electrons and rays of lights through slits.
• What scientists discovered was that the electron stream acted the same way as
light, thereby proving de Broglie correct.
• Wave-Particle Duality is the two sided nature of the electron as waves and as
particles.
• Although the duality is not very effective in large matter, the wave characteristic of
the electron implicates many of the electron's particle behaviours.
• Planck's Hypothesis of the Quantum Theory states that energy is emitted in quanta,
little packets of energy, instead of a continuous emission.
• He stated that energy emitted is related to the frequency of the light emitted.
• Planck's hypothesis states that a quantum of energy was related to the frequency by
his equation E=hν
De Broglie Wavelength
• De Broglie derived his equation using well established theories through the
following series of substitutions:
1. De Broglie first used Einstein's famous equation relating matter and energy:
where E= energy, m = mass and c = speed of light

2. Using Planck's theory which states that every quantum of a wave has a
discrete amount of energy given by Planck's equation:
where
De Broglie Wavelength
3. Since de Broglie believed that particles and waves had the same traits, the
two energies would be the same:
4. Because real particles do not travel at the speed of light, De Broglie

substituted v, velocity, for c, the speed of light.
5. Through the equation λ, de Broglie substituted v/λ for ν and arrived at the
final expression that relates wavelength and particle with speed.
Hence:
Practice Problems
1. The de Broglie wavelength of an electron is 2.0 x 10-16 m, find its velocity.
2. A particle with the speed of 2.1 x 107 m/s, its de Broglie wavelength is 6.5x 10-14 m.
What is the mass of the particle?
Practice Problems
3. Find the energy of a particle that weighs .000300 g and has a de Broglie wavelength
of 1.9 x 10-36 m.
4. Determine all of the following frequency, wavelengths, and energy if one is given:
a. frequency = 105 MHz
b. wavelength = 527 nm
c. energy = 3.20 x 10-17 J
d. frequency = 34.2 x 1015 Hz
Answers to Practice Problems
1. 3.6 x 10-12
2. 4.9 x 10-28 kg
3. 4.1 x 105 J
Summary of Wave-Particle Duality
Wave Equations
Frequency is inversely related to the wavelength by the speed of light.
c = 
where  = wavelength,  = frequency, and c = speed of light = 3 x 108 m/s
Dual Nature of Light
• Light also has properties of particles. These particles have mass and velocity.
• A particle of light is called a photon.
Energy
• How much energy is emitted by a photon of light can be calculated by
E = h
where
E = energy of the photon, h = Planck’s constant = 6.626 x 10-34 J s and  = frequency
Planck’s Hypothesis - energy is given off in little packets, or quanta, instead of
continuously.
Wave and Particle
To relate the properties of waves and particles, we use De Broglie’s equation:
 = h/mv
Where  = wavelength, h = Planck’s constant, m = mass and v = velocity.
Typical Units
 = waves per second (s-1)
 = meters, (m) (note: 1 m = 1 x 109 nm),
E = Joules (J),
h, Planck’s constant = Joules x Seconds, (J s)
m = kilograms
v = meters per second, m/s
• If matter has wave properties, why are they not commonly observed?
• The de Broglie relation shows that a baseball (0.145 kg) moving at about 60 mph (27
m/s) has a wavelength of about 1.7 x 10-34 m.
2
34 kgm
6.63 
  1.7 10 34
10 s
(0.145 kg )(27 m / s ) m
• This value is so incredibly small that such waves cannot be detected.
Atomic Numbers, Mass Numbers, and
Isotopes
• What makes an atom of one element different from an atom of another element? For
example, how does an atom of carbon differ from an atom of oxygen?
• The significant difference is in their subatomic compositions. The atoms of each
element have a characteristic number of protons.
Subatomic Particles
• Every atom has nearly all of its mass concentrated in a tiny region in the centre of the
atom called the nucleus.
• The nucleus is made up of particles called nucleons. There are two types of nucleon:
protons and neutrons.
• Atoms of different elements have different numbers of protons.
• Outside the nucleus, particles called electrons move around in regions of space called
orbitals.
Isotopes
Numbers of nucleons
Proton number and nucleon number
• The number of protons in the nucleus of an atom is called the proton number (Z). It
is also known as the atomic number.
• Every atom of the same element has the same number of protons in its nucleus. It is
the proton number that makes an atom what it is. For example, an atom with a
proton number of 11 must be an atom of the element sodium.
• The Periodic Table of elements is arranged in order of the proton numbers of the
individual elements.
• The nucleon number (A) is the number of protons plus neutrons in the nucleus of an
atom. This is also known as the mass number.
Isotopes
How many neutrons?
• We can use the nucleon number and proton number to find the number of neutrons
in an atom. As:
nucleon number = number of protons + number of neutrons
• Then:
number of neutrons = nucleon number – number of protons
=A–Z
• For example, an atom of aluminium has a nucleon number of 27 and a proton
number of 13. So an aluminium atom has 27 – 13 = 14 neutrons.
Isotopes
Isotopes
• All atoms of the same element have the same number of protons. However, they
may have different numbers of neutrons.
• Atoms of the same element that have differing numbers of neutrons are called
isotopes.
• Isotopes of a particular element have the same chemical properties because they
have the same number of electrons.
• They have slightly different physical properties, such as small differences in density.
• We can write symbols for isotopes. We write the nucleon number at the top left of
the chemical symbol and the proton number at the bottom left.
Isotopes
• The symbol for the isotope of boron with 5 protons and 11 nucleons is written:
• Hydrogen has three isotopes. The atomic structure and isotopic symbols for the three
isotopes of hydrogen are shown below:
Isotopes
• When writing generally about isotopes, chemists also name them by omitting the
proton number and placing the nucleon number after the name. For example, the
isotopes of hydrogen can be called hydrogen-1, hydrogen-2 and hydrogen-3.
• Isotopes can be radioactive or non-radioactive. Specific radioisotopes (radioactive
isotopes) can be used to check for leaks in oil or gas pipelines and to check the
thickness of paper. They are also used in medicine to treat some types of cancer and
to check the activity of the thyroid gland in the throat.
Atomic Mass
• Because each proton and each neutron contribute approximately one amu to the
mass of an atom, and each electron contributes far less, the atomic mass of a single
atom is approximately equal to its mass number (a whole number).
• However, the average masses of atoms of most elements are not whole numbers
because most elements exist naturally as mixtures of two or more isotopes.
Isotopes
• The mass of an element shown in a periodic table or listed in a table of atomic masses
is a weighted, average mass of all the isotopes present in a naturally occurring sample
of that element.
• This is equal to the sum of each individual isotope’s mass multiplied by its fractional
abundance.
• For example, the element boron is composed of two isotopes: About 19.9% of all
boron atoms are 10B with a mass of 10.0129 amu, and the remaining 80.1% are 11B
with a mass of 11.0093 amu.
• The average atomic mass for boron is calculated to be:
boron average mass = (0.199 × 10.0129 amu) + (0.801 × 11.0093 amu)
= 1.99 amu + 8.82 amu
= 10.81 amu
Isotopes
• It is important to understand that no single boron atom weighs exactly 10.8 amu;
10.8 amu is the average mass of all boron atoms, and individual boron atoms weigh
either approximately 10 amu or 11 amu.
Example 2:
Isotopes
Exercise:
• We can also do variations of this type of calculation, as shown in the next example.
Isotopes
• The occurrence and natural abundances of isotopes can be experimentally
determined using an instrument called a mass spectrometer.
• Mass spectrometry (MS) is widely used in chemistry, forensics, medicine,
environmental science, and many other fields to analyze and help identify the
substances in a sample of material.
• In a typical mass spectrometer (shown below), the sample is vaporized and exposed
to a high-energy electron beam that causes the sample’s atoms (or molecules) to
become electrically charged, typically by losing one or more electrons.
• These cations then pass through a (variable) electric or magnetic field that deflects
each cation’s path to an extent that depends on both its mass and charge (similar to
how the path of a large steel ball bearing rolling past a magnet is deflected to a lesser
extent that that of a small steel ball bearing).
Isotopes
• The figure below illustrates an analysis of zirconium (Zr) in a mass spectrometer
which produces a mass spectrum with peaks showing the different isotopes of Zr.
Isotopes
• The ions are detected, and a plot of the relative number of ions generated versus
their mass-to-charge ratios (a mass spectrum) is made.
• The height of each vertical feature or peak in a mass spectrum is proportional to the
fraction of cations with the specified mass-to-charge ratio.
• Since its initial use during the development of modern atomic theory, MS has evolved
to become a powerful tool for chemical analysis in a wide range of applications.
A mass spectrometer is a large and complex

instrument. A mass spectrometer can be
used to measure the mass of each isotope
present in an element. It also compares
how much of each isotope is present – the
relative abundance (isotopic abundance).
The Quantum Mechanical Model of the
Atom
• By the mid-1920s it had become apparent that the Bohr model could not be used to
explain much of the observed phenomena about electronic structure of atoms.
• A totally new approach was needed. Three physicists were at the forefront of this
effort: Werner Heisenberg (1901–1976), Louis de Broglie (1892–1987), and Erwin
Schrödinger (1887–1961).
• de Broglie originated the idea that the electron, previously considered to be a
particle, also shows wave properties (Wave-Particle Duality of Electrons).
• In 1926 the Austrian physicist Erwin Schródinger proposed an equation, now known
as Schródinger's wave equation, that incorporates both the wavelike behaviour and
the particle-like behaviour of the electron. His work opened a new way of dealing
with subatomic particles, known as either quantum mechanics or wave mechanics.
Atom
• The application of Schródinger 's equation requires advanced calculus, and we will
not be concerned with the details of his approach. We will, however, qualitatively
consider the results he obtained, because they give us a powerful new way to view
electronic structure.
• Let's begin by examining the electronic structure of the simplest atom, hydrogen.
• In the same way that a plucked guitar string vibrates as a standing wave, Schrodinger
treated the electron as a standing circular wave around the nucleus.
Atom
• The dots in this figure indicate the nodes, or points of
zero lateral (sideways) displacement, for a given
wave.
• Note that there are limitations on the allowed
wavelengths of the standing wave.
• Each end of the string is fixed, so there is always a
node at each end.
• This means that there must be a whole number of
half wavelengths in any of the allowed motions of the
string
Atom
• The hydrogen electron visualized as a standing wave around the

nucleus.
• The circumference of a particular circular orbit would have to
correspond to a whole number of wavelengths, as shown in (a)
and (b), or else destructive interference occurs, as shown in (c).
• This is consistent with the fact that only certain electron energies
are allowed; the atom is quantized.
Atom
• Solving Schrodinger's equation leads to a series of mathematical functions called
wave functions that describe the electron in an atom. These wave functions are
usually represented by the symbol Ψ (the lowercase Greek letter psi).
• AIthough the wave function itself has no direct physical meaning, the square of the
wave function, Ψ2, provides information about an electron's location when the
electron is in an allowed energy state.
• For the hydrogen atom, the allowed energies are the same as those predicted by the
Bohr model. However, the Bohr model assumes that the electron is in a circular orbit
of some particular radius about the nucleus. In the quantum mechanical model, the
electron's location cannot be described so simply.
• According to the Heisenberg’s uncertainty principle, if we know the momentum of
the electron with high accuracy, our simultaneous knowledge of its location is very
uncertain.
Atom
• Thus, we cannot hope to specify the exact location of an individual electron around
the nucleus. Rather, we must be content with a kind of statistical knowledge.
• In the quantum mechanical model, we therefore speak of the probability that the
electron will be in a certain region of space at a given instant.
• As it turns out, the square of the wave function, Ψ2, at a given point in space
represents the probability that the electron will be found at that location.
• For this reason, Ψ2 is called either the probability density or the electron density.
Electron-density distribution. This figure represents the
probability of where in the space surrounding the nucleus the
electron is to be found in a hydrogen atom in its ground
state. The regions with a high density of dots correspond to
relatively large values for Ψ2 and are therefore regions where
there is a high probability of finding the electron.
Atom
Orbitals and Quantum Numbers
• The solution to Schrodinger's equation for the hydrogen atom yields a set of wave
functions and corresponding energies. These wave functions are called orbitals.
• Each orbital describes a specific distribution of electron density in space, as given by
the orbital' s probability density.
• Each orbital, therefore, has a characteristic energy and shape. For example, the
lowest-energy orbital in the hydrogen atom has the shape illustrated in the figure
shown above.
• Note that an orbital (in the quantum mechanical model) is not the same as an orbit
(in the Bohr model). The quantum mechanical model does not refer to orbits,
because the motion of the electron in an atom cannot be precisely measured or
tracked (Heisenberg uncertainty principle).
Atom
• The Bohr model introduced a single quantum number, n, to describe an orbit. The
quantum mechanical model uses three quantum numbers, n, l, and ml, which result
naturally from the mathematics used, to describe an orbital.
• Let’s consider what information we obtain from each of these quantum numbers and
how they are interrelated.
1. The principal quantum number, n, can have positive integral values of 1, 2, 3,
and so forth. As n increases, the orbital becomes larger, and the electron
spends more time farther from the nucleus. An increase in n also means that
the electron has a higher energy and is therefore less tightly bound to the
nucleus.
Atom
2. The second quantum number – the azimuthal or angular momentum
quantum number, l – can have integral values from 0 to (n - 1) for each value
of n. This quantum number defines the shape of the orbital. The value of l for
a particular orbital is generally designated the letters s, p, d, and f
corresponding to l values of 0,1,2, and 3, respectively, as summarized here:
[The letters s, p, d, and f come from the words sharp, principal, diffuse, and
fundamental, which were used to describe certain features of spectra before
quantum mechanics was developed]
Atom
3. The magnetic quantum number, ml, can have integral values between -I
and l, including zero. This quantum number describes the orientation of
the orbital in space.
• The collection of orbitals with the same value of n is called an electron shell. All the
orbitals that have n = 3, for example, are said to be in the third shell.
• Further, the set of orbitals that have the same n and l values is called a subshell.
• Each subshell is designated by a number (the value of n) and a letter (s, p, d, or f,
corresponding to the value of l).
• For example, the orbitals that have n = 3 and l = 2 are called 3d orbitals and are in
the 3d subshell.
• The following table shows the relationship among Values of n, l, and ml . It
summarizes the possible values of the quantum numbers l, and ml for values of n
through n = 4.
Atom
Atom
• The restrictions on the possible values of the quantum numbers give rise to the
following very important observations:
1. The shell with principal quantum number n will consist of
exactly n subshells. Each subshell corresponds to a different
allowed value of l from 0 to (n - 1). Thus, the first shell (n = 1)
consists of only one subshell, the 1s (l = 0); the second shell
(n = 2) consists of two subshells, the 2s (l = 0) and 2p (l = 1); the
third shell consists of three subshells, 3s, 3p, and 3d, and so forth.
Atom
2. Each subshell consists of a specific number of orbitals. Each orbital
corresponds to a different allowed value of ml . For a given value of l, there are
(2l + 1) allowed values of ml, ranging from -l to +l. Thus, each s (l = 0) subshell
consists of one orbital, each p (l = 1) subshell consists of three orbitals, each d
(l = 2) subshell consists of five orbitals, and so forth.
3. The total number of orbitals in a shell is n2, where n is the principal quantum
number of the shell. The resulting number of orbitals for the shells – l, 4, 9, 16
– is related to a pattern seen in the periodic table: We see that the number of
elements in the rows of the periodic table – 2, 8, 18, and 32 – equals twice
these numbers.
Atom
the periodic table shows the
order in which electrons are
added to orbitals as we move
through the table from
beginning to end. The first
row 1 orbital (s), the next two
rows have 4 orbitals (1 s- & 3
p-orbitals), the next two rows
have 9 orbitals (1 s-, 5 d- & 3
p-orbitals) and the last two
rows have 16 orbitals (1 s-, 7
f-, 5 d- & 3 p-orbitals)
• The adjacent diagram shows the relative
energies of the hydrogen atom orbitals through n
= 3. Each box represents an orbital; orbitals of
the same subshell, such as the 2p, are grouped
together.
Orbital energy levels In the hydrogen

atom. Each box represents an orbital.
Note that all orbitals with the same
value for the principal quantum number,
n, have the same energy.
Atom
• When the hydrogen electron occupies the lowest energy orbital (1s), the hydrogen
atom is said to be in its ground state. When the electron occupies any other orbital,
the atom is in an excited state.
• At ordinary temperatures, essentially all hydrogen atoms are in the ground state. The
electron can be excited to a higher-energy orbital by absorption of a photon of
appropriate energy.
Atom
Orbital Representation
• In our discussion of orbitals so far, we have emphasized their energies. But the
wave function also provides information about the electron's location in space
when it occupies an orbital.
• Let’s examine the ways that we can picture the orbitals. In doing so, we will examine
some important aspects of the electron-density distributions of the orbitals.
The s Orbitals
• One representation of the lowest-energy orbital of the hydrogen atom, the 1s, is
shown below.
• This type of drawing, which shows the distribution of electron density around the
nucleus, is one of the several ways we use to help us visualize orbitals.
• The first thing that we notice about the electron density for the 1s orbital is that it is
spherically symmetric – i.e., the electron density at a given distance from the nucleus
is the same regardless of the direction in which we proceed from the nucleus.
Atom
• All of the other s orbitals (2s, 3s, 4s, and so forth) are spherically symmetric as well.
• Remember that the l quantum number for the s orbitals is 0; therefore the ml
quantum number must be 0. Therefore, for each value of n, there is only one s orbital.
Atom
The p Orbitals
• The distribution of electron density for a 2p orbital is shown below.
• As we can see from this figure, the electron density is not distributed in a spherically
symmetric fashion as in an s orbital.
Atom
The p Orbitals
• Instead, the electron density is concentrated in two regions on either side of the
nucleus, separated by a node at the nucleus.
• We say that this dumbbell-shaped orbital has two Iobes.
• Remember that we are making no statement of how the electron is moving within the
orbital. The only thing Figure (a) portrays is the averaged distribution of the electron
density in a 2p orbital.
• Beginning with the n = 2 shell, each shell has three p orbitals.
• Recall that the I quantum number for p orbitals is 1. Therefore, the magnetic
quantum number ml can have three possible values: -1, 0, and +1. Thus, there are
three 2p orbitals, three 3p orbitals, and so forth, corresponding to the three possible
values of ml.
• Each set of p orbitals has the dumbbell shapes shown in Figure (a) above for the 2p
orbitals.
Atom
The p Orbitals
• For each value of n, the three p orbitals have the same size and shape but differ from
one another in spatial orientation.
• We usually represent p orbitals by drawing the shape and orientation of their wave
functions, as shown in Figure (b) above.
• lt is convenient to label these as the px, py and pz orbitals. The letter subscript
indicates the Cartesian axis along which the orbital is oriented.
• Like s orbitals, p orbitals increase in size as we move from 2p to 3p to 4p, and so forth.
The d and f Orbitals
• When n is 3 or greater, we encounter the d orbitals (for which l = 2).
• There are five 3d orbitals, five 4d orbitals, and so forth because in each shell there are
five possible values for the ml quantum number: - 2, - 1, 0, 1, and 2.
• The different d orbitals in a given shell have different shapes and orientations
in space, as shown below.
• When n is 4 or greater, there are seven equivalent f orbitals (for which l = 3).
• The shapes of the f orbitals (shown below) are even more complicated than those
of the d orbitals.
Atom
MULTI-ELECTRON ATOMS
• So far, we have seen that quantum mechanics leads to a very elegant description of
the hydrogen atom. This atom, however, has only one electron.
• How must our description of the electronic structure of atoms change when we
consider atoms with two or more electrons (a multi-electron atom)?
• To describe these atoms, we must consider the nature of orbitals and their relative
energies as well as how the electrons populate the available orbitals.
Atom
Orbitals and Their Energies
• The quantum mechanical model would not be very useful if we cannot extend what
we have leamed about hydrogen to other atoms.
• Fortunately, we can describe the electronic structure of a multi-electron atom in
terms of orbitals like those of the hydrogen atom. Thus, we can continue to designate
orbitals as Is, 2px, and so forth. Further, these orbitals have the same general shapes
as the corresponding hydrogen orbitals.
• Although the shapes of the orbitals for multi-electron atoms are the same as those
for hydrogen, the presence of more than one electron greatly changes the energies
of the orbitals.
• In hydrogen the energy of an orbital depends only on its principal quantum number,
n; the 3s, 3p, and 3d subshells all have the same energy, for instance.
• In a multi-electron atom, however, the electron-electron repulsions cause the
different subshells to be at different energies, as shown in the figure below.
Atom
• To understand why this is so, we must consider the forces between the electrons and
how these forces are affected by the shapes of the orbitals.
• In a multi-electron atom, for a given value of n, the energy of an orbital increases
with increasing value of l.
• We can see this illustrated in the figure above. Notice, for example, that the n = 3
orbitals (in red) increase in energy in the order 3s < 3p < 3d.
• The figure above is a qualitative energy Ievel diagram; the exact energies of the
orbitals and their spacings differ from one atom to another.
• Notice that all orbitals of a given subshell (such as the five 3d orbitals) still have the
same energy as one another, just as they do in the hydrogen atom.
• Orbitals with the same energy are said to be degenerate.
Atom
Electron Spin and the Pauli Exclusion Principle
• We have now seen that we can use hydrogen-like orbitals to describe multi-electron
atoms.
• What, however, determines which orbitals the electrons reside in? That is, how do
the electrons of a multi-electron atom populate the available orbitals?
• To answer this question, we must consider an additional property of the electron.
• When scientists studied the line spectra of multi-electron atoms in great detail, they
noticed a very puzzling feature: Lines that were originally thought to
be single were actually closely spaced pairs.
• This meant, in essence, that there were twice as many energy levels as there were
"supposed" to be.
• In 1925 the Dutch physicists George Uhlenbeck and Samuel Goudsmit proposed a
solution to this dilemma.
Atom
• They postulated that electrons have an intrinsic property, called electron spin, that
causes each electron to behave as if it were a tiny sphere spinning on its own axis.
• This observation led to the assignment of a new quantum number for the electron, in
addition to n, l, and ml, which we have already discussed.
• This new quantum number, the spin magnetic quantum number, is denoted ms (the
subscript s stands for spin).
• Two possible values are allowed for ms, +½ or -½ which was first interpreted as
indicating the two opposite directions in which the electron can spin.
Atom
• Spinning charge produces a magnetic field.
• The two opposite directions of spin therefore produce oppositely directed magnetic
fields, as shown in in the figure above.
• These two opposite magnetic fields lead to the splitting of spectral lines into closely
spaced pairs.
• Electron spin is crucial for understanding the electronic structures of atoms.
• In 1925 the Austrian-born physicist Wolfgang Pauli (1900-1958) discovered the
principle that governs the arrangements of electrons in multi-electron atoms.
• The Pauli exclusion principle states that no two electrons in an atom can have the
same set of four quantum numbers n, l, ml and ms.
For a given orbital (Is, 2pz, and so forth), the values of n, l, and ml are fixed. Thus, if we
want to put more than one electron in an orbital and satisfy the Pauli exclusion principIe,
our only choice is to assign different ms values to the electrons.
Atom
• Because there are only two such values, we conclude that an orbital can hold a
maximum of two electrons and they must have opposite spins.
• This restriction allows us to index the electrons in an atom, giving their quantum
numbers and thereby defining the region in space where each electron is most likely
to be found. It also provides the key to one of the great problems in chemistry-
understanding the structure of the periodic table of the elements.
• Now that we have included a fourth quantum number – the spin quantum number –
we can view a complete table of Permissible Values of the Quantum Numbers
Through n = 4
Permissible Values of the Quantum Numbers Through n = 4
Atom
ELECTRON CONFIGURATIONS
• Electron configuration is the way in which electrons are distributed among the
various orbitals of an atom .
• The electron cloud of an atom is assumed to be the superposition of charge
clouds, or orbitals, arising from the individual electrons; these orbitals resemble
the atomic orbitals of hydrogen described earlier.
• Each electron is described by the same allowed combinations of quantum
numbers (n, l, ml and ms) that we used for the hydrogen atom; however, the order
of energies of the orbitals is often different from that in hydrogen.
Atom
• Let us now examine the electronic structures of atoms of different elements.
• The electronic arrangement that we will describe for each atom is called the ground
state electron configuration.
• This corresponds to the isolated atom in its lowest energy, or unexcited, state.
• In describing ground state electron configuration, the guiding idea is that the total
energy of the atom is as low as possible.
• To determine these configurations, we use the Aufbau Principle as a guide:
Each atom is “built up” by (1) adding the appropriate numbers of protons
and neutrons as specified by the atomic number and the mass number,
and (2) adding the necessary number of electrons into orbitals in the way
that gives the lowest total energy for the atom.
The Quantum Mechanical Model of the Atom
• The orbitals increase in energy with increasing value of the quantum number n. For a
given value of n, energy increases with increasing value of l. In other words, within a
particular main shell, the s subshell is lowest in energy, the p subshell is the next lowest,
then the d, then the f, and so on.
• As a result of changes in the nuclear charge and interactions among the electrons in the
atom, the order of energies of the orbitals can vary from atom to atom.
• Two general rules help us to predict electron configurations.
1. Electrons are assigned to orbitals in order of increasing value of (n+l).
2. For subshells with the same value of (n+l), electrons are assigned first
to the subshell with lower n.
• For example, the 2s subshell has (n + l = 2 + 0 = 2), and the 2p subshell has (n + l = 2 + 1 =
3), so we would expect to fill the 2s subshell before the 2p subshell (rule 1). This rule also
predicts that the 4s subshell (n + l = 4 + 0 = 4) will fill before the 3d subshell (n + l = 3 + 2 =
5).
• Rule 2 reminds us to fill 2p (n + l = 2 + 1 = 3) before 3s (n + l = 3 + 0 = 3), because 2p has a
lower value of n.
• The usual order of energies of orbitals of an atom and a helpful device for remembering
this order are shown in the following two figures below:
An aid to remembering the usual order of filling of atomic
The usual order of filling (Aufbau order) of the orbitals. Write each shell (value of n) on one horizontal line,
orbitals of an atom. The relative energies are starting with n = 1 at the bottom. Write all like subshells
different for different elements. (same l values) in the same vertical column.
• This order of filling electrons should be considered only as a guide to predicting
electron arrangements.
• The observed electron configurations of lowest total energy do not always match
those predicted by the Aufbau guide, and we will see a number of exceptions,
especially for elements in the B groups of the periodic table.
Pauli Exclusion Principle
• The electronic structures of atoms are governed by the Pauli Exclusion Principle:
No two electrons in an atom may have identical sets of four quantum numbers.
• An orbital is described by a particular allowed set of values for n, l, ml and ms.
• Two electrons can occupy the same orbital only if they have opposite spins, ms. Two
such electrons in the same orbital are paired.
• For simplicity, we indicate atomic orbitals as just a line (__) or a box and show an
unpaired electron as __ and spin-paired electrons as __.
• By “unpaired electron” we mean an electron that occupies an orbital singly.
Hund’s Rule
• This rule deals with the filling of electrons in the equal energy (degenerate) orbitals
of the same subshell (p , d and f ).
• According to this rule ,
” Electron pairing in p ,d and f orbitals cannot occur until each orbital of a
given subshell contains one electron each or is singly occupied “.
• This is due to the fact that electrons being identical in charge, repel each other when
present in the same orbital.
• This repulsion can, however, be minimised if two electrons move as far apart as
possible by occupying different degenerate orbitals.
• When filling sublevels other than s, electrons are placed in individual orbitals
before they are paired up.
• Electrons fill like people do on a bus. You would never sit right next to someone you
did not know if there are free seats available, unless of course all the seats are taken
then you must pair up.
Working with Shells and Subshells
• Indicate the number of subshells, the number of orbitals in each subshell, and the
values of l and ml for the orbitals in the n = 4 shell of an atom.
Solution
• For n = 4, l can have values of 0, 1, 2, and 3. Thus, s, p, d, and f subshells are found in
the n = 4 shell of an atom. For l = 0 (the s subshell), ml can only be 0. Thus, there is
only one 4s orbital.
• For l = 1 (p-type orbitals), ml can have values of –1, 0, +1, so we find three 4p
orbitals.
• For l = 2 (d-type orbitals), ml can have values of –2, –1, 0, +1, +2, so we have five 4d
orbitals.
• When l = 3 (f-type orbitals), ml can have values of –3, –2, –1, 0, +1, +2, +3, and we
can have seven 4f orbitals.
• Thus, we find a total of 16 orbitals in the n = 4 shell of an atom.
Check Your Learning
• Identify the subshell in which electrons with the following quantum numbers are
found: (a) n = 3, l = 1; (b) n = 5, l = 3; (c) n = 2, l = 0.
[Answer: (a) 3p (b) 5f (c) 2s]

Maximum Number of Electrons
Calculate the maximum number of electrons that can occupy a shell with:
(a) n = 2, (b) n = 5, and (c) n as a variable.
Solution
(a) When n = 2, there are four orbitals (a single 2s orbital, and three orbitals labelled
2p). These four orbitals can contain eight electrons.
(b) When n = 5, there are five subshells of orbitals that we need to sum:
1 orbital labelled 5s
3 orbitals labelled 5p
5 orbitals labelled 5d
7 orbitals labelled 5f
+9 orbitals labelled 5g
25 orbitals total
Since each orbital holds two electrons, 50 electrons can fit in this shell.
(c) The number of orbitals in any shell n will equal n2. There can be up to two electrons
in each orbital, so the maximum number of electrons will be 2 × n2
Check Your Learning
If a shell contains a maximum of 32 electrons, what is the principal quantum number,
n?
[Answer: n = 4]
Orbital Energies and Atomic Structure

• The energy of atomic orbitals increases as the principal quantum number, n,
increases.
• In any atom with two or more electrons, the repulsion between the electrons makes
energies of subshells with different values of l differ so that the energy of the orbitals
increases within a shell in the order s < p < d < f.
• The following figure is a generalized energy-level diagram for atomic orbitals in an
atom with two or more electrons.
• The 1s orbital at the bottom of the
diagram is the orbital with
electrons of lowest energy.
• The energy increases as we move
up to the 2s and then 2p, 3s, and
3p orbitals, showing that the
increasing n value has more
influence on energy than the
increasing l value for small atoms.
• However, this pattern does not
hold for larger atoms. The 3d
orbital is higher in energy than the
4s orbital. Such overlaps continue
to occur frequently as we move
up the chart.
The Aufbau Principle

• To determine the electron configuration for any particular atom, we “build” the
structures in the order of atomic numbers.
• Beginning with hydrogen, and continuing across the periods of the periodic table, we
add one proton at a time to the nucleus and one electron to the proper subshell until
we have described the electron configurations of all the elements.
• This procedure is called the Aufbau principle, from the German word Aufbau (“to
build up”).
• Each added electron occupies the subshell of lowest energy available (in the order
shown in the figure below also called the aufbau diagram), subject to the limitations
imposed by the allowed quantum numbers according to the Pauli exclusion principle.
• A mnemonic diagram for the building-up
order (also referred to as diagonal rule)
• You obtain this diagram by writing the
subshell(s) in rows, each row having subshell(s)
of given n.
• Within each row, you arrange the subshell(s) by
increasing l. (You can stop after writing the nf
subshell(s), since no known elements contain g
or higher subshell(s).)
• Now, starting with the 1s subshell(s), draw a
series of diagonals, as shown. The building-up
order is the order in which these diagonals strike
the subshell(s).
Electron configurations using the Periodic Table
• Since the arrangement of the periodic table is based on the electron
configurations, the figure below provides an alternative method for determining
the electron configuration.
• The filling order simply begins at hydrogen and includes each subshell as you
proceed in increasing Z (atomic number) order.
• For example, after filling the 3p block up to Ar, we see the next orbital will be 4s (K,
Ca), followed by the 3d orbitals.
• Let us now construct the ground-state electron configuration and orbital diagram for
a selection of atoms in the first and second periods of the periodic table.
• Orbital diagrams are pictorial representations of the electron configuration, showing
the individual orbitals and the pairing arrangement of electrons. We start with a
single hydrogen atom (atomic number 1), which consists of one proton and one
electron.
• Referring to the aufbau diagram (pg 121) or the Periodic Table (pg 123), we
would expect to find the electron in the 1s orbital. By convention, the ms = +½ value
is usually filled first. The electron configuration and the orbital diagram are:
• Following hydrogen is the noble gas helium, which has an atomic number of 2. The
helium atom contains two protons and two electrons.
• The first electron has the same four quantum numbers as the hydrogen atom
electron (n = 1, l = 0, ml = 0, ms = +½). The second electron also goes into the 1s
orbital and fills that orbital.
• The second electron has the same n, l, and ml quantum numbers, but must have the
opposite spin quantum number, ms = −½. This is in accord with the Pauli exclusion
principle: No two electrons in the same atom can have the same set of four quantum
numbers.
• For orbital diagrams, this means two arrows go in each box (representing two
electrons in each orbital) and the arrows must point in opposite directions
(representing paired spins). The electron configuration and orbital diagram of helium
therefore are:
• The n = 1 shell is completely filled in a helium atom.

• The next atom is the alkali metal lithium with an atomic number of 3. The first two
electrons in lithium fill the 1s orbital and have the same sets of four quantum
numbers as the two electrons in helium. The remaining electron must occupy the
orbital of next lowest energy, the 2s orbital (aufbau diagram or Periodic Table).
• Thus, the electron configuration and orbital diagram of lithium are:
• An atom of the alkaline earth metal beryllium, with an atomic number of 4, contains
four protons in the nucleus and four electrons surrounding the nucleus. The fourth
electron fills the remaining space in the 2s orbital.
• An atom of boron (atomic number 5) contains five electrons. The n = 1 shell is filled
with two electrons and three electrons will occupy the n = 2 shell.
• Because any s subshell can contain only two electrons, the fifth electron must occupy
the next energy level, which will be a 2p orbital. There are three degenerate 2p
orbitals (ml = −1, 0, +1) and the electron can occupy any one of these p orbitals.
• When drawing orbital diagrams, we include empty boxes to depict any empty orbitals
in the same subshell that we are filling.
• Carbon (atomic number 6) has six electrons. Four of them fill the 1s and 2s orbitals.
The remaining two electrons occupy the 2p subshell.
• We now have a choice between filling one of the 2p orbitals and pairing the
electrons or leaving the electrons unpaired in two different, but degenerate, p
orbitals.
• The orbitals are filled as described by Hund’s rule: the lowest-energy configuration
for an atom with electrons within a set of degenerate orbitals is that having the
maximum number of unpaired electrons.
• Thus, the two electrons in the carbon 2p orbitals have identical n, l, and ms quantum
numbers and differ in their ml quantum number (in accord with the Pauli exclusion
principle).
• The electron configuration and orbital diagram for carbon are:
• Nitrogen (atomic number 7) fills the 1s and 2s subshells and has one electron in each
of the three 2p orbitals, in accordance with Hund’s rule. These three electrons have
unpaired spins.
• Oxygen (atomic number 8) has a pair of electrons in any one of the 2p orbitals (the
electrons have opposite spins) and a single electron in each of the other two.
• Fluorine (atomic number 9) has only one 2p orbital containing an unpaired electron.
• All of the electrons in the noble gas neon (atomic number 10) are paired, and all of
the orbitals in the n = 1 and the n = 2 shells are filled.
• The electron configurations and orbital diagrams of these four elements are:
Writing Shorthand (abbreviated) Electron Configuration
• The alkali metal sodium (atomic number 11) has one more electron than the neon
atom. This electron must go into the lowest-energy subshell available, the 3s
orbital, giving a 1s22s22p63s1 configuration.
• The electrons occupying the outermost shell orbital(s) (highest value of n) are
called valence electrons, and those occupying the inner shell orbitals are called
core electrons.
• Since the core electron shells correspond to noble gas electron configurations, we
can abbreviate electron configurations by writing the noble gas that matches the
core electron configuration, along with the valence electrons in a condensed
format. For our sodium example, the symbol [Ne] represents core electrons,
(1s22s22p6) and our abbreviated or condensed configuration is [Ne] 3s1.
Writing Shorthand (abbreviated) Electron Configuration
• Similarly, the abbreviated configuration of lithium can be represented as [He]2s1,
where [He] represents the configuration of the helium atom, which is identical to
that of the filled inner shell of lithium.
• Writing the configurations in this way emphasizes the similarity of the
configurations of lithium and sodium. Both atoms, which are in the alkali metal
family, have only one electron in a valence s subshell outside a filled set of inner
shells.
• The electron configurations of silicon (14 electrons), phosphorus (15 electrons),
sulphur (16 electrons), chlorine (17 electrons), and argon (18 electrons) are
analogous in the electron configurations of their outer shells to their corresponding
family members carbon, nitrogen, oxygen, fluorine, and neon, respectively, except
that the principal quantum number of the outer shell of the heavier elements
(chlorine and argon) has increased by one to n = 3.
• The following figure shows the lowest energy, or ground-state, electron
configuration for these elements as well as that for atoms of each of the known
elements.
Example
Quantum Numbers and Electron Configurations
What is the electron configuration and orbital diagram for a phosphorus atom? What
are the four quantum numbers for the last electron added?
Solution
• The atomic number of phosphorus is 15. Thus, a phosphorus atom contains 15
electrons. The order of filling of the energy levels is 1s, 2s, 2p, 3s, 3p, 4s, . . . The 15
electrons of the phosphorus atom will fill up to the 3p orbital, which will contain
three electrons:
Example
Quantum Numbers and Electron Configurations
• The last electron added is a 3p electron. Therefore, n = 3 and, for a p-type orbital, l =
1. The ml value could be –1, 0, or +1. The three p orbitals are degenerate, so any of
these ml values is correct. For unpaired electrons, convention assigns the value of +½
for the spin quantum number; thus, ms = +½.
Check Your Learning

Identify the atoms from the electron configurations given:
(a) [Ar]4s23d5
(b) [Kr]5s24d105p6
[Answer: (a) Mn (b) Xe]

Exceptions to the Aufbau (Building-Up) Principle
• The aufbau principle reproduces most of the ground-state configurations correctly.
• There are some exceptions, however, and chromium (Z = 24) is the first we encounter.
• The building-up principle predicts the configuration [Ar] 3d44s2, though the correct
one is found experimentally to be [Ar] 3d54s1. These two configurations are actually
very close in total energy because of the closeness in energies of the 3d and 4s
orbitals.
• For that reason, small effects can influence which of the two configurations is actually
lower in energy. Copper (Z = 29) is another exception to the building-up principle,
which predicts the configuration [Ar] 3d94s2, although experiment shows the ground-
state configuration to be [Ar] 3d104s1.
• This violation of the Aufbau Principle is based on the sublevel stability – half-filled
sublevels are not as stable as fully-filled sublevels, but they are more stable than
other configurations. The order of stability for these sublevels is:
Fully-filled>Half-filled>other-filled
• Hence, in copper, the theoretical filling of the two sublevels 3d and 4s (other-filled +
fully-filled) yields less stability than the actual (experimental) filling where both
sublevels are half-filled while in chromium the theoretical filling is even much less
stable than the actual (fully-filled + half-filled).
• To illustrate this point, let us put numerical value to sublevel stability as follows:
Fully-filled>Half-filled>other-filled
3.0 2.8 2.5
 Fully-filled + fully-filled = 3 + 3 = 6 most stable combination
 Fully-filled + half-filled = 3 + 2.8 = 5.8 second most stable combination
 Half-filled + half-filled = 2.8 + 2.8 = 5.6 third most stable combination
 Fully-filled + other-filled = 3 + 2.5 = 5.5 fourth in stability
 Other-filled + other-filled = 2.5 + 2.5 = 5.0 least stable combination
Introduction to Periodic Table
Introduction
• During the 1800s, when most of the elements were being discovered, many chemists
tried to classify the elements according to their similarities.
• By 1869, a total of 63 elements had been discovered. As the number of known
elements grew, scientists began to recognize patterns in the way chemicals reacted
and began to devise ways to classify the elements.
• Dmitri Mendeleev, a Siberian-born Russian chemist, was the first scientist to make a
periodic table much like the one we use today.
• Mendeleev’s table listed the elements in order of increasing atomic mass. Then he
placed elements underneath other elements with similar chemical behaviour.
• He also left holes for missing elements and used the patterns of his table to make
predictions of properties of these undiscovered elements.
• The modern periodic table now arranges elements in order of increasing atomic
number.
• Additionally, more groups and elements have been added as they have been
discovered.
• In the periodic table, the elements are arranged according to similarities in their
properties.
• The elements are listed in order of increasing atomic number as you read
from left to right across a period and from top to bottom down a group or family.
Metals, Non-metals, and Metalloids
• There is a progression from metals to non-metals across each row of elements in the
periodic table.
• The diagonal line at the right side of the table separates the elements into two groups:
the metals and the non-metals.
• The elements that are on the left of this line tend to be metals, while those to the right
tend to be non-metals (with the exception of hydrogen which is a non-metal).
• The elements that are directly on the diagonal line are metalloids, with some
exceptions. Aluminum touches the line, but is considered a metal.
• Metallic character generally increases from top to bottom down a group and right to
left across a period, meaning that francium (Fr) has the most metallic character of all
of the discovered elements.
• Most of the chemical elements are metals. Most metals have the common properties
of being shiny, very dense, and having high melting points. Metals tend to be ductile
(can be drawn out into thin wires) and malleable (can be hammered into thin sheets).
• Metals are good conductors of heat and electricity. All metals are solids at room
temperature except for mercury.
• In chemical reactions, metals easily lose electrons to form positive ions. Examples
of metals are silver, gold, and zinc.
• Non-metals are generally brittle, dull, have low melting points, and they are generally
poor conductors of head heat and electricity.
• In chemical reactions, they tend to gain electrons to form negative ions. Examples of
non-metals are hydrogen, carbon, and nitrogen.
• Metalloids have properties of both metals and non-metals. Metalloids can be shiny or
dull. Electricity and heat can travel through metalloids, although not as easily as they
can through metals.
• They are also called semimetals. They are typically semi-conductors, which means that
they are elements that conduct electricity better than insulators, but not as well as
conductors. They are valuable in the computer chip industry. Examples of metalloids
are boron, silicon and germanium.
Periodic Trends in Atomic Properties of Elements
• The electron configurations of the atoms display a periodic variation with increasing
atomic number (nuclear charge).
• As a result, the elements show periodic variations of physical and chemical behaviour.
• The periodic law states that when the elements are arranged by atomic number, their
physical and chemical properties vary periodically.
• We will look at trends in four physical properties of an atom namely, atomic radius,
ionic radius, ionization energy, and electron affinity. These quantities, especially
ionization energy and electron affinity, are important in discussions of chemical
bonding.
Atomic Radius
• An atom does not have a definite size, because the statistical distribution of electrons
does not abruptly end but merely decreases. The quantum mechanical picture makes
it difficult to establish a definite size of an atom.
• However, there are several practical ways to define the radius of atoms and, thus, to
determine their relative sizes that give roughly similar values.
Atomic Radius
• We will use the covalent radius which is defined as one-half the distance between the
nuclei of two identical atoms when they are joined by a covalent bond as shown below.
• This measurement is possible because atoms within molecules still retain much of
their atomic identity).
• The distance between the two nuclei of the same type of atom is determined and then
divided by two to arrive at the atomic (single covalent) radius.
• There are other measures of atomic radii, such as metallic radii and van der Waals’
radii. However, covalent radii can be obtained for most elements, so these provide the
best data for comparison purposes across a period.
Atomic Radius
• Atomic radius decreases across a period. This is so because as we move across a
period, the number of protons (and hence the nuclear charge), and the number of
electrons, increases by one with each successive element.
• The extra electron added to the atoms of each successive element occupies the same
principal quantum shell (energy level). This means that the shielding effect remains
roughly constant.
• So the greater attractive force exerted by the increasing positive nuclear charge on the
outer (valence) shell electrons pulls them in closer to the nucleus. Hence the atomic
radius decreases across the period.
• This can be explained further with the concept of effective nuclear charge, Zeff . This is
the pull exerted on a specific electron by the nucleus, taking into account any
electron–electron repulsions.
• For hydrogen, there is only one electron and so the nuclear charge (Z) and the
effective nuclear charge (Zeff) are equal.
Atomic Radius
• For all other atoms, the inner electrons partially shield or screen the outer electrons
from the pull of the nucleus, and thus:
Zeff = Z − S where S is shielding or Screening
• Shielding or screening is determined by the probability of another electron being
between the electron of interest and the nucleus, as well as by the electron–electron
repulsions the electron of interest encounters. It represents the portion of the nuclear
charge that is screened from the valence electron by the other electrons in the atom.
• Core electrons are very efficient at shielding, while electrons in the same valence
shell do not block the nuclear attraction experienced by each other as efficiently.
• Thus, each time we move from one element to the next across a period, Z increases by
one, but the shielding increases only slightly.
• Thus, Zeff increases as we move from left to right across a period. The stronger pull
(higher effective nuclear charge) experienced by electrons on the right side of the
periodic table draws them closer to the nucleus, making the covalent radii smaller.
Atomic Radius
• Because the core electrons are most effective at screening a valence electron from the
nucleus, the value of S is usually close to the number of core electrons in an atom.
• Let's take a look at a Na atom to see what we would expect for the magnitude of Zeff .
• Sodium (atomic number 11) has a condensed electron configuration of [Ne]3s1. The
nuclear charge of the atom is +11, and the Ne inner core consists of ten electrons
(1s22s22p6).
• Very roughly then, we would expect the 3s valence electron of the Na atom to
experience an effective nuclear charge of about 11 - 10 = +1, as pictured in a simplified
way below:
Atomic Radius
• Atomic radius increases down a group. This is so because as we go down a group, the
principal quantum number, n, increases by one for each element.
• Thus, the electrons are being added to a region of space that is increasingly distant
from the nucleus.
• Consequently, the size of the atom (and its covalent radius) increases as we increase
the distance of the outermost electrons from the nucleus. This trend is illustrated for
the covalent radii of the halogens in the figure below:
Atomic Radius
• Going down a group, the effective nuclear charge experienced by valence electrons
changes far less than it does across a row.
• For example, we would expect the effective nuclear charge for the outer electrons in
Atomic Radius
Problem 1:
Rank the following set of main group elements in order of decreasing atomic size:
Br, Rb, Kr, Ca, Sr
Solution:
Elements with n = 4: Br, Kr, Ca; Size increases going L->R, so big to small is Ca > Br > Kr
Elements with n = 5: Rb, Sr; Size increases going L->R, so big to small is Rb > Sr
Is Sr > Ca or is Ca > Sr?
Sr > Ca, so the final ranking is Rb > Sr > Ca > Br > Kr
Ionic Radius
• Ionic radius is the measure used to describe the size of an ion.
• A cation always has fewer electrons and the same number of protons as the parent
atom; it is smaller than the atom from which it is derived .
• For example, the covalent radius of an aluminum atom (1s22s22p63s23p1) is 118 pm,
whereas the ionic radius of an Al3+ (1s22s22p6) is 68 pm.
• As electrons are removed from the outer valence shell, the remaining core
electrons occupying smaller shells experience a greater effective nuclear charge
Zeff (as discussed earlier) and are drawn even closer to the nucleus.
• Cations with larger charges are smaller than cations with smaller charges (e.g., V2+
has an ionic radius of 79 pm, while that of V3+ is 64 pm).
Ionic Radius
• Going down the groups of the periodic table, we find that cations of successive
elements with the same charge generally have larger radii, corresponding to an
increase in the principal quantum number, n.
• An anion (negative ion) is formed by the addition of one or more electrons to the
valence shell of an atom.
• This results in a greater repulsion among the electrons and a decrease in Zeff per
electron.
• Both effects (the increased number of electrons and the decreased Zeff) cause the
radius of an anion to be larger than that of the parent atom.
• For example, a sulphur atom ([Ne]3s23p4 ) has a covalent radius of 104 pm, whereas
the ionic radius of the sulphide anion ([Ne]3s23p6) is 170 pm.
Ionic Radius
• For consecutive elements going down any group, anions have larger principal
quantum numbers and, thus, larger radii.
• Atoms and ions that have the same electron configuration are said to be
isoelectronic.
• Examples of isoelectronic species are N3–, O2–, F–, Ne, Na+, Mg2+, and Al3+ (1s22s22p6).
Another isoelectronic series is P3–, S2–, Cl–, Ar, K+, Ca2+, and Sc3+ ([Ne] 3s23p6).
• For atoms or ions that are isoelectronic, the number of protons determines the size.
The greater the nuclear charge, the smaller the radius in a series of isoelectronic
ions and atoms.
Ionization Energy (IE)
The amount of energy required to remove the most loosely bound electron from a
gaseous atom in its ground state is called its first ionization energy (IE1).
• The first ionization energy for an element, X, is the energy required to form a cation
with +1 charge:
• The energy required to remove the second most loosely bound electron is called the
second ionization energy (IE2).
• The energy required to remove the third electron is the third ionization energy, and
so on.
• Energy is always required to remove electrons from atoms or ions, so ionization
processes are endothermic and IE values are always positive.
Ionization Energy (IE)
• For larger atoms, the most loosely bound electron is located farther from the
nucleus and so is easier to remove.
• Thus, as size (atomic radius) increases, the ionization energy should decrease.
• Relating this logic to what we have just learned about radii, we would expect first
ionization energies to decrease down a group and to increase across a period.
• The figure below graphs the relationship between the first ionization energy and the
atomic number of several elements.
• The values of first ionization energy for the elements are given in the periodic table
after the graph.
• Within a period, the IE1 generally increases with increasing Z. Down a group, the IE1
value generally decreases with increasing Z.
The first ionization

energy of the
elements in the first
five periods plotted
against their atomic
number.
• There are some systematic deviations from this trend, however. Note that the
ionization energy of boron (atomic number 5) is less than that of beryllium (atomic
number 4) even though the nuclear charge of boron is greater by one proton.
• This can be explained because the energy of the subshells increases as l increases,
due to penetration and shielding (as discussed previously).
• Within any one shell, the s electrons are lower in energy than the p electrons. This
means that an s electron is harder to remove from an atom than a p electron in the
same shell.
• The electron removed during the ionization of beryllium ([He]2s2) is an s electron,
whereas the electron removed during the ionization of boron ([He] 2s22p1) is a p
electron; this results in a lower first ionization energy for boron, even though its
nuclear charge is greater by one proton.
• Thus, we see a small deviation from the predicted trend occurring each time a
new subshell begins.
• Another deviation occurs as orbitals become more than one-half filled. The first
ionization energy for oxygen is slightly less than that for nitrogen, despite the trend
in increasing IE1 values across a period.
• Looking at the orbital diagram of oxygen, we can see that removing one electron
will eliminate the electron–electron repulsion caused by pairing the electrons in the
2p orbital and will result in a half-filled orbital (which is energetically favourable).
• Analogous changes occur in succeeding periods (note the dip for sulphur after
phosphorus in the graph shown above).
• Removing an electron from a cation is more difficult than removing an electron
from a neutral atom because of the greater electrostatic attraction to the cation.
• Likewise, removing an electron from a cation with a higher positive charge is
more difficult than removing an electron from an ion with a lower charge.
• Thus, successive ionization energies for one element always increase.
• As shown in the Table above, there is a large increase in the ionization energies for
each element. This jump corresponds to removal of the core electrons, which are
harder to remove than the valence electrons.
• For example, Sc and Ga both have three valence electrons, so the rapid increase in
ionization energy occurs after the third ionization.
Electron Affinity [EA]

• The electron affinity [EA] is the energy change for the process of adding an electron
to a gaseous atom to form an anion (negative ion).
• This process can be either endothermic or exothermic, depending on the element.

• The EA of some of the elements is given in figure below. You can see that many of
these elements have negative values of EA, which means that energy is released
when the gaseous atom accepts an electron.
• However, for some elements, energy is required for the atom to become negatively
charged and the value of their EA is positive.
• Just as with ionization energy, subsequent EA values are associated with forming
ions with more charge. The second EA is the energy associated with adding an
electron to an anion to form a –2 ion, and so on.
• As we might predict, it becomes easier to add an electron across a series of atoms
as the effective nuclear charge of the atoms increases.
• We find, as we go from left to right across a period, EAs tend to become more
negative.
• The exceptions found among the elements of group 2 (2A), group 15 (5A), and
group 18 (8A) can be understood based on the electronic structure of these
groups.
• The noble gases, group 18 (8A), have a completely filled shell and the incoming
electron must be added to a higher n level, which is more difficult to do. Group 2
(2A) has a filled ns subshell, and so the next electron added goes into the higher
energy np, so, again, the observed EA value is not as the trend would predict.
• Finally, group 15 (5A) has a half-filled np subshell and the next electron must be
paired with an existing np electron.
• In all of these cases, the initial relative stability of the electron configuration
disrupts the trend in EA.
• It is important to understand the difference between ionization energy and
electron affinity: Ionization energy measures the ease with which an atom loses
• an electron, whereas electron affinity measures the ease with which an atom
• gains an electron.
• The greater the attraction between a given atom and an added electron, the
more negative the atom's electron affinity will be.
• For some elements, such as the noble gases, the electron affinity has a positive
value, meaning that the anion is higher in energy than are the separated atom
and electron. This means that an electron will not attach itself to a noble gas
atom; the resulting anion is unstable and does not form.
Chemical Nomenclature (Formulae & Names) of
Molecular and Ionic compounds
• To obtain information about a particular substance, we must know its chemical
formula and name. The names and formulas of compounds are essential vocabulary
in chemistry.
• The system used in naming substances is called chemical nomenclature from !he
Latin words nomen (name) and calare (to call).
• There are now more than 19 million known chemical substances. Naming them all
would be a hopelessly complicated task if each had a special name independent of
all others.
• Many important substances that have been known for a long time, such as water
(H20) and ammonia (NH3),do have individual, traditional names (so-called
"common" names).
• For most substances, however, we rely on a systematic set of rules that leads to an
informative and unique name for each substance, a name based on !he
composition of the substance.
• The rules for chemical nomenclature are based on the division of substances into
categories.
• The major division is between organic and inorganic compounds. Organic
compounds contain carbon, usually in combination with hydrogen, oxygen,
nitrogen, or sulphur AII others are inorganic compounds.
Names and Formulae of lonic Compounds
• Ionic compounds usually consist of metal ions combined with non-metal ions. The
metals form the positive ions, and the non-metals form the negative ions.
• Let's deal with the naming of positive ions, then the naming of negative ones. After
that, we will consider how to put the names of the ions together to identify the
complete ionic compound.
1. Positive Ions (Cations)
(a) Cations formed from metal atoms have the same name as the metal:
Na+ sodium ion Zn2+ zinc ion Al3+ aluminum ion
Ions formed from a single atom are called monatomic ions.
(b) If a metal can form different cations, the positive charge is indicated by a
Roman numeral in parentheses following the name of the metal:
Fe2+ iron(II) ion Cu+ copper(I) ion
Fe3+ iron(III) ion Cu2+ copper(II) ion
• Ions of the same element that have different charges exhibit different
properties, such as different colours.
• Most of the metals that can form more than one cation are transition metals,
elements that occur in the middle block of elements, from group 3B to group 2B
in the periodic table.
• An older method still widely used for distinguishing between two differently
charged ions of a metal is to apply the ending -ous or -ic.
• These endings represent the lower and higher charged ions, respectiveIy. They
are added to the root of the element's Latin name:
(c) Cations formed from non-metal atoms have names that end in -ium:
NH4+ ammonium ion H30+ hydronium ion
• These two ions are the onIy ions of this kind that we will encounter frequently.
They are both polyatomic. The vast majority of cations are monatomic metal
ions.
• The names and formulas of some common cations are shown in the following
table.
• The Hg22+ ion is unusual because this metal ion is not monatomic. It is called the
mercury(I) ion because it can be thought of as two Hg+ ions bound together. The
cations that you will The cations that you will encounter most frequently are
shown in boldface. You should learn these cations first.
2. Negative lons (Anions)
(a) The names of monatomic anions are formed by replacing the ending of the
name of the element with –ide:
H- hydride ion 02- oxide ion N3- nitride ion
• A few simple polyatomic anions also have names ending in -ide:
OH- hydroxide ion CN- cyanide ion O22- peroxide ion
(b) Polyatomic anions containing oxygen have names ending in -ate or -ite.
These anions are called oxyanions. The ending -ate is used for the most common
oxyanion of an element. The ending -ite is used for an oxyanion that has the same
charge but one O atom fewer:
NO3- nitrate ion SO42- sulphate ion
NO2- nitrite ion SO32- sulphite ion
• Prefixes are used when the series of oxyanions of an element extends to four
members, as with the halogens. The prefix per- indicates one more O atom than the
oxyanion ending in -ate; the prefix hypo- indicates one O atom fewer than the
oxyanion ending in -ite:
• The following scheme is a summary of the procedure for naming anions. The root of
the name (such as "chlor" for chlorine) goes in the blank.
• The following table presents some important oxyanions in a format designed to make
their names easier to learn.
Example: Determining the Formula of an Oxyanion from Its Name
Based on the formula for the sulphate ion, predict the formula for
(a) the selenate ion and
(b) the selenite ion. (Sulphur and selenium are both members of group 6A and form
analogous oxyanions.)
Solution:
(a) The sulphate ion is SO42-. The analogous selenate ion is therefore SeO42-.
(b) The ending -ite indicates an oxyanion with the same charge but one O atom fewer
than the corresponding oxyanion that ends in -ate. Thus, the formula for the selenite
ion is SeO32-.
Exercise:
The formula for the bromate ion is analogous to that for the chlorate ion. Write the
formula for the hypobromite and perbromate ions.
(c) Anions derived by adding H+ to an oxyanion are named by adding as a prefix the
word hydrogen or dihydrogen, as appropriale:
CO32- carbonate ion PO43- phosphate ion
HCO3- hydrogen carbonate ion H2PO4- dihydrogen phosphate ion
• Notice that each H+ reduces the negative charge of the parent anion by one.
• An older method for naming some of these ions is to use the prefix bi-. Thus, the
HCO3- ion is commonly called the bicarbonate ion, and HSO4- is sometimes called the
bisulphate ion.
• The names and formulae of the common anions are listed in the following table.
3. lonic Compounds
• Names of ionic compounds consist of the cation name followed by the anion name:
CaCl2 calcium chloride
Al(NO3)3 aluminium nitrate
Cu(ClO4)2 copper(II) perchlorate (or cupric perchlorate)
• In the chemical formulae for aluminium nitrate and copper(II) perchlorate,
parentheses followed by the appropriate subscript are used because the compounds
contain two or more polyatomic ions.
• Example 1: Determining the Names of lonic Compounds from Their Formulae
Name the following compounds: (a) K2SO4, (b) Ba(OH)2 (c) FeCI3
Solution
• Each compound is ionic and is named using the guidelines we have already discussed.
• In naming ionic compounds, it is important to recognize polyatomic ions and to
determine the charge of cations with variable charge.
(a) The cation in this compound is K+, and the anion is SO42-. (If you thought the
compound contained S2- and O2- ions, you failed to recognize the polyatomic
sulphate ion.) Putting together the names of the ions, we have the name of the
compound, potassium sulphate.
(b) In this case the compound is composed of Ba2+ and OH- ions. Ba2+ is the bariumion
and OH- is the hydroxide ion. Thus, the compound is called barium hydroxide.
(e) You must determine the charge of Fe in this compound because an iron atom can
form more than one cation. Because the compound contains three Cl- ions, the
cationmust be Fe3+ which is the iron(III), or ferric, ion.
Solution
The Cl- ion is the chloride ion. Thus, the compound is iron(III) chloride or ferric chloride.
PRACTICE EXERCISE
Name the following compounds: (a) NH4Br, (b) Cr2O3, (e) CO(NO3)2
Answers: (a) ammonium bromide, (b) chromium(III) oxide, (e) cobalt(Il) nitrate
Example 2: Determining the Formulae of lonic Compounds from Their Names

Write the chemical formulae for the following compounds:
(a) potassium sulphide,
(b) calcium hydrogen carbonate,
(c) nickel(II) perchlorate.
Solution
• In going from the name of an ionic compound to its chemical formula, you must
know the charges of the ions to determine the subscripts.
(a) The potassium ion is K+, and the sulphide ion is S2-. Because ionic compounds are
electrically neutral, two K+ ions are required to balance the charge of one S2- ion,
giving the empirical formula of the compound, K2S.
(b) The calcium ion is Ca2+ The carbonate ion is CO3-, so the hydrogen carbonate ion is
HC03- . Two HCO3- ions are needed to balance the positive charge of Ca2+, giving
Ca(HCO3)2.
(c) The nickel(II) ion is Ni2+. The perchlorate ion is ClO4- . Two ClO4- ions are required
to balance the charge on one Ni2+ ion, giving Ni(ClO4)2.
Exercise
Give the chemical formula for (a) magnesium sulphate, (b) silver sulphide, (e) lead(II)
nitrate.
[Answers: (a) MgSO4 (b) Ag2S, (e) Pb(N03)2]
Names and Formulae of Acids
• Acids generally do not have the word “hydrogen” in their names. They are named by
replacing the ending of the related anion by an ending including the word acid, as
follows:
• The name of an acid is related to the name of its anion, as summarized in the figure
below.
Relating names of anions and

acids. Summary of the way
in which anion names and acid
names are related. Take note that
the prefixes per- and hypo- are
retained in going from the anion
to the acid.
• If the acid is a binary hydrogen compound, including HF, HCl, HBr, HI, and H2S , the
pure compound is named as if hydrogen were an alkali metal. For example, pure HCl
is named hydrogen chloride, and H2S is named hydrogen sulphide, with no prefixes
for either element in either case.
• When the hydrogen halides are dissolved in water, they are usually named as acids.
Thus HCl in water is referred to as hydrochloric acid.
• H2S is one of very few acids usually named like an alkali metal-nonmetal compound
even when dissolved in water. It is called hydrogen sulphide, but the name
hydrosulphuric acid (analogous to
hydrochloric acid) may be used for its aqueous solution.
1. Acids containing anions whose names end in -ide are named by changing the -ide
ending to -ic, adding the prefix hydro- to this anion name, and then following with
the word acid, as in the following examples:
Anion Corresponding Acid
Cl- (chloride) HCl (hydrochloric acid)
S2- (sulphide) H2S (hydrosulphuric acid)
2. Acids containing anions whose names end in -ate or -ite are named by changing -ate
to -ic and -ite to -ous, and then adding the word acid. Prefixes in the anion name are
retained in the name of the acid. These rules are illustrated by the oxyacids of
chlorine as follows:
Example: Relating the Names and Formulas of Acids

Name the following acids: (a) HCN, (b) HNO3, (e) H2SO4, (d) H2SO3.
Solution
(a) The anion from which this acid is derived is CN- , the cyanide ion. Because this
ion has an -ide ending, the acid is given a hydro- prefix and an -ic ending: hydrocyanic
acid. Only water solutions of HCN are referred to as hydrocyanic acid: The pure
compound, which is a gas under normal conditions, is called hydrogen cyanide. Both
hydrocyanic acid and hydrogen cyanide are extremely toxic.
(b) Because NO3- is the nitrate ion, HNO3 is called nitric acid (the -ate ending of the anion
is replaced with an -ic ending in naming the acid).
(e) Because SO42- is the sulphate ion, H2SO4 is called sulphuric acid.
(d) Because SO32- is the sulphite ion, H2SO3 is sulphurous acid (the -ite ending of the
anion is replaced with an -ous ending).
Exercise
1. Give the chemical formulae for (a) hydrobromic acid, (b) carbonic acid.
[Answers: (a) HBr, (b) H2C03]
2. Name the following acids:
(a) HNO3 (b) H3PO3 (c) H2SO3
(d) HBrO (e) HClO4 (f ) HI
Solution
(a) Nitric acid. The ending -ate of the nitrate ion is changed to -ic acid.
(b) Phosphorous acid. The ending -ite of the phosphite ion is changed to –ous acid. In
this case, the stem is also changed to phosphor.
(c) Sulphurous acid. The ending -ite is changed to -ous acid, and the stem is changed
from sulph to sulphur.
(d) Hypobromous acid. The ending -ite is changed to -ous acid. The prefix hypo- on the
anion makes no difference to the suffix; the prefix is include in the acid name.
(e) Perchloric acid. The ending -ate of perchlorate ion is changed to -ic acid; the prefix
per- is not changed.
(f) Hydroiodic acid. The prefix hydro- distinguishes this binary acid from HIO3.
Practice Problem
Name the following acids:
(a) HIO3 (b) H2SO4 (c) HClO2
• Formulas for acids can be written by replacing every negative charge on the
corresponding anion with one hydrogen atom.
• For example, SO42- has two negative charges; therefore, sulphuric acid has two
ionizable hydrogen atoms (and no charge): H2SO4. If the ion is an oxyanion, the acid is
an oxyacid.
Practice Problem
Write the formula for each of the following acids:
(a) Hypophosphorous acid (b) Chloric acid (c) Perbromic acid
(d) nitrous acid and (e) sulphuric acid.
Exercise
Give the chemical formulae for (a) hydrobromic acid, (b) carbonic acid.
[Answers: (a) HBr, (b) H2C03]
Names and Formulas of Binary Molecular Compounds

• A binary compound is a compound composed of only two elements.
• Binary compounds composed of a metal and a non-metal are usually ionic
and are named as ionic compounds, as we have just discussed. (For example,
NaCl, MgBr2, and Al2N3 are all binary ionic compounds.)
• Binary compounds composed of two non-metals or metalloids are usually
molecular and are named using a prefix system.
Rules for Naming Binary Molecular Compounds
• Now let us look at the rules for naming binary molecular compounds by the prefix
system.
1. The name of the compound usually has the elements in the order given in the
formula.
2. You name the first element using the exact element name.
3. You name the second element by writing the stem name of the element with the
suffix -ide (as if the element occurred as the anion).
4. You add a prefix, derived from the Greek, to each element name to denote the
subscript of the element in the formula. (The Greek prefixes are listed in the table
below).
• Generally, the prefix mono- is not used, unless it is needed to distinguish two
compounds of the same two elements.
4. Greek prefixes (given in the Table) are used to indicate the number of atoms of each
Element. The prefix mono- is never used with the first element. When the prefix ends
in a or o and the name of the second element begins with a vowel (such as oxide), the
a or o of the prefix is often dropped.
• Let us consider N2O3. This is a binary molecular compound, as

you would predict because N and O are non-metals.
• According to Rule 1, you name it after the elements, N before
O, following the order of elements in the formula.
• By Rule 2, the N is named exactly as the element (nitrogen),
and by Rule 3, the O is named as the anion (oxide).
• The compound is a nitrogen oxide.
• Finally, you add prefixes to denote the subscripts in the formula (Rule 4). As the prefix
table above shows, the prefix for two is di-, and the prefix for three is tri-.
• The name of the compound is dinitrogen trioxide.
Here are some examples to illustrate how the prefix mono- is used.
• There is only one compound of hydrogen and chlorine: HCl. It is called hydrogen
chloride, not monohydrogen monochloride, since the prefix mono- is not generally
written.
• On the other hand, there are two common compounds of carbon and oxygen: CO and
CO2. They are both carbon oxides. To distinguish one from the other, we name them
carbon monoxide and carbon dioxide, respectively.
Here are some other examples of prefix names for binary molecular compounds.
• The final vowel in a prefix is often dropped before a vowel in a stem name, for ease
in pronunciation. Tetraoxide, for instance, becomes tetroxide.
• A few compounds have older, well-established names. The compound H2S would be
named dihydrogen sulphide by the prefix system, but is commonly called hydrogen
sulphide. NO is still called nitric oxide, although its prefix name is nitrogen monoxide.
• The names water and ammonia are used for H2O and NH3, respectively.
SF4 sulphur tetrafluoride SF6 sulphur hexafluoride
ClO2 chlorine dioxide Cl2O7 dichlorine hept(a)oxide

2 Atomic Structure, Periodic Table & Chemical Nomenclature

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2 Atomic Structure, Periodic Table & Chemical Nomenclature

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Atomic Structure

Dalton’s Atomic Theory and the Modern

1916 – Robert Millikan

Mass of the electron is 9.11 x 10-28 g

Millikan's oil-drop experiment. A

Rutherford postulated a very

• In 1913, the Danish physicist Niels Bohr

RH = 2.179 × 10-18 J, Rydberg constant

• An electron is ejected when nf = ∞.

Electron transitions for an

[Answer: 6.198 × 10-19 J; 3.205 × 10-7 m]

• In 1923, Louis de Broglie, a French physicist, proposed a hypothesis to explain the

where E= energy, m = mass and c = speed of light

4. Because real particles do not travel at the speed of light, De Broglie

Answers to Practice Problems

A mass spectrometer is a large and complex

• The hydrogen electron visualized as a standing wave around the

Orbital energy levels In the hydrogen

[Answer: (a) 3p (b) 5f (c) 2s]

Orbital Energies and Atomic Structure

The Aufbau Principle

• The n = 1 shell is completely filled in a helium atom.

Check Your Learning

[Answer: (a) Mn (b) Xe]

The first ionization

Electron Affinity [EA]

• This process can be either endothermic or exothermic, depending on the element.

Example 2: Determining the Formulae of lonic Compounds from Their Names

Relating names of anions and

Example: Relating the Names and Formulas of Acids

Names and Formulas of Binary Molecular Compounds

• Let us consider N2O3. This is a binary molecular compound, as

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