1 Introduction

1.1 Scientific discoveries

Timeline Important dates and discoveries The scientific method

1.2 Building the chemistry language from the Big-bang

from t=0 to t=13.7 billion years

1.3 Periodic Table

chemical families periods

1.4 Nomenclature of compounds

name of ions names of ionic compounds

1.5 Measurements and Units

SI system prefix for units derived units

1.6 Chemical quantities

the mole molar mass

1.7 Determination of the chemical formulas

mass percentage composition determining the empirical formulas determining
the molecular formulas

1.8 Reaction stoichiometry

how to use reaction stoichiometry the limits of reaction gases expressing
concentrations

Timeline
Stone Age
Broad prehistoric period during which stone
was widely used

A variety of stone tools

11000 BC

2000 000 BC
Paleolithic (Old Stone Age)
Human used stones for
hunting which was found
in nature

15000 BC
Mesolithic (Middle Stone Age)

Human started to sharpen their stone

tools for hunting

Neolithic (New Stone Age)

Human learned about
agriculture and
domesticate animals.

4000
First
civilizations
emerged

Awash river. Source of sediments in which

the oldest Stone
Age tools have been found

Timeline
Greeks
(Democratus ~450 BC)
Discontinuous
theory of matter

400 BC
Greeks
(Aristotle ~350 BC))
Continuous
theory of matter

ALCHEMY

300 AD

1000

Hermes Trismegistus
Zosimus of Panopilis
Avicenna
Roger Bacon

Galileu Galilei
(1564 - 1642)

Decline of the
Byzantine
Empire
(1204)
Issac Newton
(1642 - 1727)

Important dates and Discoveries

Johannes Kepler - laws of Planetary
Motion

1605

Miquel de Cervantes puplishes the first

part of Don Quixote

Galileo Galilei - first describes the

Principle of Relativity

1632 The inquisition convicts Galileo of heresy

Newton's Law - Universal Gravitation

1687

Venetians take Athens from the Turks

Antoine-Laurent de Lavoisier - Law of

Conservation of Mass

1789

Simon Bolivar was born (1783)

Demolition of the Bastille

John Dalton - develops his atomic theory

1805

Napoleon assembles an invasion fleet

against Britain

Michael Faraday - concludes from his

work on electromagnetism

1839

British forces capture Hong Kong

Louis Pasteurs - experiments show that

organisms such as bacteria and fungi do
not appear of their own

1861

The first battle of the American Civil War

J. J. Thomson - discovers the electron

1897

Germany claims Ruanda and Urundi as a

joint colony to German East Africa

Albert Einstein - photoelectric effect

1905

Bloody Sunday (in St Petersburg)

Important dates and Discoveries

Ernest Rutherford - planetary
model of the atom

1911

The lost Inca city of Machu Picchu is reached

by US archaeologist

Albert Einstein -Theory of Relativity

1914
1918

The Great 1st War

(8 million deads)

Alexander Oparin hypothesizes that

life on Earth

1922

Mahatma Gandhi is arrested by the British in

India as an agitator and is sentenced to six
years in prison

Erwin Schrdinger publishes his

Equation

1926

Spanish architect Antoni Gaud dies after

being hit by a tram

1927

Mussolini's treaty with Ahmed Zogu gives

Fascist Italy a dominant position in Albania

The discovery of nuclear fission

1939
1945

2nd World War

More than 80 million deads (Holocaust deaths
range between 4.9 to 6.0 million)

Francis Crick and James D. Watson

DNA structure

1953

Joseph Stalin dies

Stephen Hawking - theorems

regarding singularities in space-time

1970

Nelson Mandela condenated to life in 1968

(prisoner 46664)

Edwin Hubble shows that all the

galaxies in the universe are moving
away from us

The scientific method

Observation
Hypothesis

Repeat

Experiment
Control
group

Experimental
Group
Results

Evidence
supports
hypothesis

Inconsistent
with
hypothesis

Scientific theory

Revise
Hypothesis

Helicopter sketched by Leonardo da Vinci

Da Vinci invented so that the first theoretical

helicopter, because only in the 20th century
was the first built.
http://commons.wikimedia.org

How the elements are formed

The heaviest elements are produced in supernova explosions of

massive stars that are at least eight times the size of our Sun

The Big-Bang

Only hydrogen, some He and small amounts of Be, Li, and Bo are produced during the
big bang. Other elements that are lighter than iron are made in stellar interiors,
heavier ones are made during supernova explosions.

Making helium from hydrogen

4 H 1He + + e+ + Energy

Hydrogen

Positron

Helium
Neutrino

Proton
Neutron

Formation of light elements

Massive star near the
end has an onion
like structure just
prior to exploding as a
supernova

H, He
He, N
He, C, 22Ne
O, C
O, Ne, Mg
Si, S
Fe, Ni

Red Giant Star

Relative abundances of the principal

elements

(a) The Universe

as whole

(b) The crust of

Earth

(c) Human

Chemistry. Molecules, Matter and change. Peter Atkins, Loretta Jones. 4th ed.

Elements, Molecules and Ions

Pure Substances

Elements
Atoms

Ne

Compounds

Molecules

O2

Molecules

Ions

H2O

NaCl

Names of the elements

Chemists have a useful system that saves writing the full names of the
elements. Each element is represented by a chemical symbol made up of
one or two more letters

Hydrogen H
Helium He

Carbon C
aluminum Al

Nitrogen N

Oxygen O

Nickel Ni

Silicon Si

Some elements have symbols formed from the first letter of the name and
a later letter
Magnesium Mg

Chloride Cl

Zinc Zn

Plutonium Pu

Naming ionic compounds(1):

Positive Ions
Monatomic cations (a single atom with a positive charge) take the name of the element plus
the word "ion. Examples:
Na+ = sodium ion
Zn+2 = zinc ion
If an element can form more than one (1) positive ion, the charge is indicated by the Roman
numeration in parentheses followed by the word "ion. Examples:
Fe2+ = iron(II) ion
Fe3+ = iron (III) ion
Negative Ions
Monatomic anions (a single atom with a negative charge) change their ending to "-ide.
Examples:
O2- = oxide ion
Cl- = chloride ion

http://www.webelements.com/

Naming ionic compounds(2):

Oxoanions (negatively charged polyatomic ions which contain O) end in "-ATE". However, if
there is more than one oxyanion for a specific element then the endings are:
Two less oxygen
than the most
common starts
with HYPO-"
and ends with
"-ITE"
ClO- =
hypochlorite

One less
oxygen than
the most
common
ends with "ITE"

THE MOST COMMON OXOANION

ENDS WITH "-ATE"

ClO2- = chlorite

Most common
oxyanions with
four oxygens

Most common
oxyanions with
three oxygens

NO2- = nitrite

SO42- = sulfate

NO3- = nitrate

SO32- = sulfite

PO43- =
phosphate

ClO3- = chlorate

CrO42- =
chromate

CO32- = carbonate

One more
oxygen than the
most common
starts with "per" and ends with
"-ATE"
ClO4- = perchlorate

http://www.webelements.com/

Naming ionic compounds(3):

Polyatomic anions (a negatively charged ion containing more than one type of element)
often add a hydrogen atom. In this case the anion's name either adds "hydrogen-" or "bi" to the beginning
Example:
CO32- becomes HCO3"Carbonate" becomes either "Hydrogen Carbonate" or "Bicarbonate"

When combining cations and anions into an ionic compound, the cation name is always
put first and then the anion name (the molecular formulas are also written in this order
as well.)
Examples:

Na+ + Cl- NaCl

sodium + chloride sodium chloride
Cu2+ + SO42- CuSO4
copper(II) + sulfate copper(II) sulfate
Al3+ + 3NO3- Al(NO3)3
aluminum + nitrate aluminum nitrate
http://www.webelements.com/

Groups in the periodic table

The vertical groups are sometimes called chemical families and may have special names:
Alkali Metals (note: Hydrogen is normally not included in this group), Alkaline Earth Metals,
Halogens, Noble Gases.
Horizontal rows of elements are called periods. Periods are based on the electron shells for
any given atom. We will work the electronic configuration in the next point (2. Atoms).

Representation of the elements in the periodic table

Elements in the periodic Table are indicated by symbols. To the left the symbol we find
the atomic mass (A) at the upper corner and the atomic number (Z) at the lower corner

A SYMBOL
Z

1
H
1

12
C
6

23
Na
11

A = Z + neutrons

The atomic number (Z) gives the element identity.

Different forms of the same element can have different masses. They are called
isotopes. Some representation of the isotopes are:
1
H (regular hydrogen)
1

2
H (deuterium)
1

12
C or C-12
6

13
C or C-13
6

The atomic mass reported in the periodic table for a given element is actually a weight
average of the masses of its isotopes as found in nature. Thus the mass of carbon is
reported as 12.0115 rather than 12.0000 because of the contribution of the isotopes.

Fundamental variables and units

We will use the Systme International (SI) units in this course. Occasionally, we use
the English Engineering system of Units. As found in US National Institute of
Standards and Technology (NIST) documents, the important base SI units, and
corresponding English units are:
Unit of length: meter (m)
The meter is the length of the path travelled by the light in vacuum during a time
interval of 1/299 792 458 of a second
English units: foot (ft)
Unit of mass: kilogram (Kg)
The kilogram is the unit of mass; it is equal to the mass of the international
prototype of the kilogram (a platinum-iridium stored in Paris), roughly equal to
the mass of one liter of water at standard temperature and pressure.
English unitis: POUND MASS (lbm)

Chemistry. Molecules, Matter and change. Peter Atkins, Loretta Jones. 4th ed.

Fundamental variables and units

Unit of time: second (s)
The duration of 9192631770 periods of the radiation corresponding to the transition
between the two hyperfine levels of the ground state of the cesium 133 atom
English time units are identical to those of SI
Unit of temperature: kelvin (K)
The kelvin, unit of thermodynamic temperature, is the fraction 1/273.16 of the
thermodynamic temperature of the triple point of water.
Unit of electric current: ampere (A)
The ampere is that constant current which, if maintained in two straight parallel
conductors of infinite length, of negligible circular cross-section and placed 1 meter
apart in vacuum, would produce between these conductors a force equal to 2 x 10-7
newton per meter of length.
Unit of amount of substance: mole (mol)
The mole is the amount of substance of a system which contains as many elementary
entities as there are atoms in 0.012 kg of carbon 12; its symbol is mol;

Chemistry. Molecules, Matter and change. Peter Atkins, Loretta Jones. 4th ed.

SI Base Units
Base Quantity

SI base unit

Name

Symbol

Name

Symbol

Length

l, x, r,

Meter

Mass

Kilogram

kg

Time, duration

Second

Electric current

I, i

Ampere

Thermodynamic temperature

Kelvin

Amount of substance

Mole

mol

Luminous intensity

Iv

candela

cd

Examples of derived units in the SI

Base Quantity

SI base unit

Name

Symbol

Name

Symbol

Area

Square meter

m2

Volume

Cubic meter

m3

Speed, velocity

Meter per second

m/s

Acceleration

Meter per second square

m/s2

Density

Kilogram per cubic meter

kg/m3

Specific volume

Cubic meter per kilogram

m3/kg

Current density

Ampere per square meter

A/m2

Magnetic field strength

Ampere per meter

A/m

Amount concentration

Mole per cubic meter

mol/m3

Mass concentration

Kilogram per cubic meter

kg/m3

The mole
The name of mole comes from the Latin word for massive heap
The unit was invented to provide a simple way of reporting huge numbers of
atoms and molecules in visible samples.
The definition of the unit is as follows:
1 mole is the number of atoms in exactly 12 g of carbon-12.
The mass of carbon-12 atom is: 1.99265 x 10-23 g, so the number of atoms in exactly
12 g of carbon-12 is:
12 =

12
= 6.0221 1023
1.992 1023

1 mol of atoms (of any element) is 6.0221 1023 atoms of the element. This occurs
for 1 mol of anything atoms, ions or molecules.
The number 6.0221 1023/mol is called Avogadro constant, NA
Example: The Junin mine is a large copper mine located in Imbabura, Province. The
Ascedent Copper Corporation estimated that the Junin mine has 9 milion of tonnes
of Cu. How many moles of Cu are there in the Junin mine? Cu atomic mass = 63.5
g/mol

Molar Mass
Of an element is the mass of the element per mole of its atoms
Molar mass

Of a molecular compound is the mass of the compound per

mole of its molecules
Of an ionic compound is the mass of the compound per mole of
its formula units

Example: The mass of fluorine atom is 3.155 x 10-23g so the molar mass of fluorine is:
(Mass of one atom) x (number of atoms per mole)=
(3.155x10-23 g)x(6.01221x1023/mol)= 19.00 g/mol
Unlike the molar mass of fluorine, molar masses of most elements cannot be calculated
from the know mass of a single isotope. For most elements we need to calculate the
average molar mass of an atom in a sample.
Example: There are two naturally occurring isotope of chlorine, chlorine-35 and chlorine37. The mass of an atom of chlorine-35 is 5.807 x 10-23g and that of an atom of chlorine-37
is 6.139 x 10-23g. In a typical natural sample of chlorine, 75.77% of the sample is chlorine35 and 24.23% is chlorine-37. What is the average molar mass of chlorine?
Average mass of a Cl atom =
[0.755 x (5.807 x 10-23g)+0.2423 x (6.139x10-23g)]=5.887x10-23g.
It follows that:
Molar mass of chlorine = average mass of a Cl atom x number of Cl atoms per mole=
(5.887x10-23g)x(6.01221x1023/mol)=35.45 g/mol

Determination of Chemical Formulas

The chemical formula of a compound is the general term for the statement of the
composition of the compound in terms of the chemical symbols of the elements
present.
We can distinguish The empirical formula and The molecular formula
The empirical formula of a compound is a chemical formula that shows the relative
numbers of atoms of each element using the smallest whole number of atoms
The molecular formula tell us the actual number of atoms of each element in a
molecule
To determine the empirical formula we begin by measuring the mass
percentage composition
The copper catalyst ensure that any CO produced is oxidized to
CO2
1 mol of C in sample gives 1 mol of CO2 as product
2 mol of H in sample gives 1 mol of H20 as product

Apparatus used for a combustion analysis

Determining an empirical formula from a mass percentage

Example: There is evidence that trypitoline may be potential neurotoxins that may
play a role in Parkinsons diseases. This compound has the mass percentage
composition 76.71% C, 7.02% H, and 16.27%N. Determine the empirical formula of
the compound.
Base of calculus: 100 g 76.71 g of C, 7.02 g of H, 16.27 g of N.
Converting to the number of moles:
1
= 76.71
= 6.387
12.01
1
= 7.02
= 6.96
1.0079
1
= 16.27
= 1.161
14.01
C 76.71 g 6.387 mol (1.161) 5.501 (x2) 11.002
H 7.02 g 6.96 mol (1.161) 5.99 (x2) 12.0
N 16.27 1.161 mol (1.161) 1.000 (x2) 2.0

C11H12N2

Gases
The molecular character of gases:
Gas fills any container it occupies
This suggests that the intermolecular forces
which holds solids and liquids together have
been largely broken in the gases
The gases are essentially free to move
Each gas molecule has a mass and a velocity
Therefore they will have a momentum

Gas container

The gases molecules will collide with a wall of

the container or another molecule
An individual molecule undergoes several
billion changes of speed and direction each
second

Conservation of momentum
Rate of change of momentum = sum of forces

Area (A)

Time=t

wall of the container

The pressure on a wall off the container will be equal to the total force divide by
the area. All gas molecules are colliding the wall of the container. They will
experiment a change in the momentum (p). At the end all those molecules will
have a combined force F (total force). The total force can be represented the
change in the momentum divided by the time (the time that the gas molecule
expend to collide the wall again):

That is why a gas container has a pressure (P = /). It has pressure because the
molecules are colliding to the sides of the container and therefore changing the
momentum.
Force is the rate of change of momentum

Pressure
measurer
Water
bath

Gas
container

V constant

The gas laws

m

Experiment:
Heat up (Different
temperatures). Read the
related related pressure
P

P constant

T constant

1 2
=
1 2

1 2
=
1 2

1 1 = 2 2
T

Pressure Law

piston

Experiment:
Heater plate
Use different mass. Measure
Experiment:
the volume at the container
Heat up. Measure the
correspondent to the different
correspondent volume
pressures (P=F/A=mg/A)
of the container

Heater plate

-2730C

m constant

Boyles Law

0
1/V -273 C

Charles Law

Avogadros principle
Adding more gas to a flexible container (a balloon) increases its volume. The Italian scientist
Amadeo Avogadro discovered that, at constant temperature and pressure, the volume of the
gas is proportional to the amount of the gas

=
In addition, measurements of the molar volumes of five gases at the same pressure and
temperature shows that regardless of the identity of the gases, the molar volumes are all
very similar. This suggests that under the same conditions of temperature and pressure a
given number of molecules occupy the same volume, regardless of their chemical identity.
This observation is know as Avogadro Principle.
Ideal gas

argon
carbon dioxide
nitrogen
oxygen
Hydrogen

22.41
22.09
22.26
22.40
22.40
22.43

The molar volume (in liters per mole) of various gases at

0 0C, and 1 atm; all are very similar

The difference are small under normal conditions and

become smaller as the pressure of the gas is reduced

The ideal gas law

Charles law and Avogadros principle have told us that the volume of a gas is
directly proportional to its absolute temperature (VT) and the number of moles
(Vn), respectively.
Boyles law has told to us that the volume is inversely proportional to the pressure
(V1/P)
When we combine these three relations we obtain:
From Avogadro

From Charles

From Boyle

The constant of proportionality in PV nT is denoted R and called gas constant, R:

The molar volume (Vm):

=
= 0.0820578

.
(0.082058
) (273.15)
.

=
= 22.41 /
1.00
=

Real gases (1)

The difference between ideal and real gases is

expressed strikingly by plotting the
compression factor Z=PV/nRT as a function of P.
For an ideal gas PV/nRT =1

Compressibility factor, Z

Real gases are only nearly ideal. Gases can be condensed to

liquid or solids, whereas ideal gas never condenses to a
liquid, regardless low temperatures or high pressures.
When an ideal gas is compressed or cooled, its volume
decreases without limit and may approach zero.

hydrogen

CH4

Ideal gas
Pressure, P

ethane

ammonia

We can explain this behavior if we suppose that molecules interact with one
another. As a gas is compressed, the average separation of the molecules
decreases and the attractions become more important. Because the molecules
move less freely, the pressure is less than predicted by the ideal gas law.

Real gases (2)

Johannes van der Waals suggested a way to change the ideal gas law taking in account
the effect of intermolecular forces in the gases molecules:
Effect of attractions

2
+ 2

Effect of repulsion

Van der Waalss forces are feeble; but without them, life as we know it would be
impossible. Van der Waals forces include all intermolecular forces that act between
electrically neutral molecules.
a, L2.atm/mol

b, L/mol

Air

1.4

0.039

Ammonia

4.17

0.037

Argon

1.35

0.032

Carbon dioxide

3.59

0.043

Helium

0.034

0.024

Hydrogen

0.244

0.027

Oxygen

1.36

0.032

The stoichiometry of reacting gases

A balanced equation of a chemical reaction shows, in terms of moles how much each
substance is involved in the reaction. Stoichiometry is the study of the relationships of
quantities of substances in a chemical reaction. Consider the reaction:
(1)

2() + 22() 22()

This balanced equation tell us: one mole of nitrogen reacts with two moles of oxygen to
produce 2 moles of nitrogen dioxide. Several mole ratio are possible:

(2)

1 2
2 2
1 2
2 2
2 2
2 2

2 2
1 2
2 2
1 2
2 2
2 2

No matter how much of each reactant there is to start with, they will react only in the
ratio of 1 mol N2/2 mol O2. If exactly 1 mole of N2 and 2 moles of O2 are brought together,
both reactants will completely consumed. If 1 mole of N2 and 5 moles of O2 are bought
together, only 2 moles of O2 will react; 3 moles will left unreacted. If 3 moles of N2 and 2
moles of O2 are brought together, 2 moles of N2 will remain unreacted.

Reaction yield
The yield of a product would be 100% if no competing reactions were taking place.
However, if a reactant can take part in one more than one reaction at the same
time, then the yield of a particular product will be less than 100% because other
products will also form.
Product 2
Reactants

Product 1

Reactants

=
100%

Product 1
Product 3

The theoretical yield of a product is the maximum mass that can be expected on
the basis of the stoichiometry of a chemical reaction. The percentage yield is the
percentage of the theoretical yield actually achieved.
Example: In a study of old mining lanterns, an excess amount of water was poured on
100 g of calcium carbide and 28.3 g of acetylene (C2H2) was produced. Calculate the
reaction yield of acetylene for the reaction.
2 + 22

+ 2 2 ()

Limiting reactants
The limiting reactant in a reaction is the species supplied in an amount smaller that
that required by the stoichiometric relation between the reactants.
Suppose that (nA)feed is the number of moles of reactant A in excess present in the
feed of a reactor and (nA)esteq the amount needed to fully react with the limiting
reagent. Then (nA)feed - (nA)esteq is the amount by which A in the feed exceeds the
quantity needed to be fully consumed if the reaction is complete. The excess fraction
of A is:

=
( )
Example: Consider for example the hydrogenation of acetylene to form ethane
C2H2 + 2H2 C2H6
Suppose that 20 kmol/h of C2H2 and 50 kmol/h of H2 is entering in the reactor. The
stoichiometric ratio of H2 to C2H2 is 2: 1 (the relationship between the coefficients in the
stoichiometric equation). Since the relationship between H2 and C2H2 in the feed is 2.5: 1
(50:20), H2 is fed into a higher proportion compared to the stoichiometric C2H2.
Consequently, C2H2 is the limiting reagent. It would be required 40 kmol H2/h to be
completely consumed. 25% of H2 is in the excess in the feeding.

Chemistry. Molecules, Matter and change. Peter Atkins, Loretta Jones. 4th ed.

Expressing concentration
Concentration
expression

Measurements
required

Temperature
Dependent?

Percentage
composition
(by mass)

Mass of solute
Mass of
solution

No
Mass does not change with
temperature

Molarity

Mass of solute
Volume of
solution

Yes
Volume changes with
temperature

Molality

Mass of solute
Mass of solvent

No
Neither mass nor moles
changes with temperature

Moles of solute
Moles of
solvent

No
moles does not change
with temperature

Mole fraction

Equation


=
100

+ + + .

2. Atomic structure
2.1 Bohr atomic model and previous history of
atomic models
2.1 Electromagnetic radiation
The characteristic of light Quanta and photons (photoelectric effect) Atomic
spectra and energy levels

2.3 Modern Quantum Model

2. Atom
1
9
1
1

1
8
9
7

4
0
0
B
C

Thomson
Democritus

Bohr

1
9
0
7

1
8
0
9

Dalton

Modern Quantum
model post 1930

Rutherford

Early Greek theories

400 BC

What is make the matter?

Can we divide infinitely the matter?
Democritus

Democritus considered that when can cut

a particle until to reach a point where the
particles is indivisible. This smallest build
block was called atom

Aristotele

Aristoteles believed that the matter ca be

divided infinititely.
His theory prevails until 18th - 19th
centuries

Daltons theory (1805)

The Democrituss theory prevails back.
The matter was contituted by indivisable building blocks called ATOMO (indivisible
particles)
All elements are composed of atoms.
All atoms of the same element are identical in particular they have the same
mass
The atoms of one kind of element are different from the atoms of all other
elements
Atoms are indestructible and retain their identity in chemical reactions
Compounds are formed by joining atoms in specific whole number ratios

J. J. Thomson The electron

Thomsons illustration of the Crookes tube by which he observed the deflection of cathode
rays by an electric field
The cathode ray tube is a glass tube from which most of the air has been
evacuated;
When two metal plates are conected to a high voltage source the negatively charge
plate (cathode) emits an ray;
The cathode ray is drawn to the positively charge plate (anode) where it passes
through a hole and continues traveling to the other end of the tube;
When the rays strikes the specially coated surface the cathod ray produce strong
fluorescence, or bright light;

J. J. Thomson experiments
Applied Electric field
When an electric field is applied across the cathode ray, the cathode ray is attracted
by the plate bearing positive charges.

Applied Magnetic field

A moving charge body can interact with an external magnetic field. The electrons are
deflected by the magnetic field
Determine charge to mass ratio
Thomson adjusted the electron field so that the electrotatic deflection was the same
as the magnetic deflection, and he was able to calculate the charge to mass ratio of
an electron. Thomson determined the charge to mass ratio of an electron to be -1.76
x 108 coulombs per gram

J.J Thomson experiment

Cathode rays must be negatively charged
What constitutes the X-rays must be 1000 times smaller than an hydrogen atom
All different metals he used as cathode and anode give off cathode rays
Based on these three conclusions he was able to propose the plum-pudding model of
the atom:

----Electron

---

-----

-----

Positively
charged
pudding

The discovery of the nucleus

RaBr
Experimental arrangement used by Ernest Rutherford and his two students (Hans
Geiger and Ernest Marsden) in the discovery of the nucleus

What does Rutherford expected?

If the atoms were indeed like blobs of positively charged jelly. Then all the
particles would easily pass through the foil, while only occasional slight deflection
in their paths;

particles

particles
Daltons model

J. J. Thomsons model

(1803)

(1897)

What Geiger and Marsden observed

Although almost all the particles did pass through and were deflected only very
slightly, about 1 in 20 000 was deflected through more than 90, and a few
particles bounced straight back in the direction from which they had come
1 dot
20 000 dots
particles

200 dots

Ernest Rutherfords model

Atoms are not blobs of positively charged jelly with electrons suspended in it like
raisins. Instead, atoms had to contain dense point like centers of positive charge
surrounded by a large volume of mostly empity space.
Rutherford called the pointlike, positively charged region of atomic nucleus
1 dot
20 000 dots
particles

200 dots

Rutherford conclusions

Discovery of the nucleus

The nucleus is positively charged
Most of the mass is concentrated in the nucleus
The positively charged nucleus, in which contains the majority of the atomic mass, is
surrounded by orbiting electrons
The nucleus is tiny compared to the atom as a whole
The atom is most empity space
What is the density of the nucleus?
The nucleus of an atom has no sharply defined boundaries. It can be considered
spherical in form but care must be taken when speaking on its radius. The value
observed depends on the method used to determine it.
By Fermi model:

= 0 1/3 = 1.21/3

1 1015

0 = 1.2 1015 = 1.2;

43 403
=
=
= 1.12 1044
3
3
The volume of the nucleus is therefore approximately proportional to the number of
particles in the nucleus (protons and neutrons).

Information about the nuclear sizes

The density of the atomic material varied as a function of the distance from the center. It
is approximately constant up from certain distance from the nucleus decreasing gradually
becoming zero at the nuclear surface
The most definitive information about the nuclear sizes come from electron scattering

The density of a nuclear material is a constant

43

=
; =
3

4 3
=
3
43
=
3
=

A= mass number=
number of protons + number of
neutrons mass of nucleus (amu)
1
1
1 = =
6.023 10+23

1 = 1.66 1024

= 0 1/3 3 = 03
403
403
=
=
3
3
3
=
403
The density of a nucleus is a constant value

The limitation of the Rutherford model

ee- +
ee-

10-14 s

Two fundamental questions:

(I) An electron accelerating around the nucleus would continuously emit
electromagnetic radiation and lose energy. Therefore it would eventually fall into
the nucleus and the atom would disintegrate. Therefore we could not exist.
Why electrons doesnt spire into the nucleus? It is essentially the reason we
have quantum mechanics
(II) Protons in the nucleus should repeal each other and the nucleus should self
destroy.
Why the nucleus do not self destroy? It is essentially the reason we have
nuclear physics

Sir James Chadwick

Noble prize in physics (1935) for the discovery of the neutron in 1932
Properties of the subatomic particles:

Particle

Symbol

Charge*

Mass,g

Electron

e-

-1

9.109x10-28

Proton

+1

1.673x10-24

Neutron

1.675x10-24

* Charges are given as multiples of the charge on a proton, which in SI units is

1.602 x 10-19 coulombs

Protons & Neutrons & Electrons

Are these the indivisible
building blocks of the matter like Democritus was thinking?

What we now know

Electron ~ 10-16 cm

Matter

Atom ~ 10-8 cm

Proton
(neutron)
~ 10-13 cm
Nucleous
~ 10-12 cm

quark
< 10-16 cm

What quarks are made of?

The nuclear atom

Atoms are made of subatomic particles called electrons, protons and neutrons;
The protons and neutrons form a compact, central body called the nucleus of the
atoms;
The electrons are distributed in space like a cloud around the nucleus;

Electron cloud

Nucleus
(greatly
enlarged)

Pyramid of Egypt in the center of the

earth representing the relative size of
the nucleus in an atom

Bohrs hypothesis
Nucleus exist consisting of all the protons and neutrons. It is negligible in size
compared to the atom

Electron moves around the nucleus in fixed orbits of fixed radius. The electron has
fixed velocity and fixed energy. That orbits were called stationary states, in which no
electromagnetic radiation was emitted.
Angular momentum of electron in any orbit is integral multiple of = h/2
(quantization of angular momentum)
Electron can make transition from lower orbit to higher orbit from the absorption of
energy radiation (excitation)
Electron can make transition from higher orbit to lower orbit by emitting energy
radiation and it is termed as de excitation

The characteristic of light

Light is a electromagnetic radiation a wave of electric and magnetic fields

Energy (E) and frequency () are directly proportional

E=h
c=

All electromagnetic radiation travels through empty space at 3.00x108 m/s. This is
denoted as c and is called the speed of light

Emission spectrum of hydrogen

The Balmer Series (visible) for Hydrogen

Allowed radii for electrons in circular orbits of the hydrogen atom

Electron with mass me and
charge e moving in a circular
orbit of radius r with constant
tangential velocity, v

nth orbit :

v
F
+e

rn

Nucleus charge is +Ze

where Z is the number
of protons and e is the
electron charge
e 1.602 x 10-19 C
me 9.1x10-31 kg
and Plancks Constant (h)
6.62 x10-34 m2kg/s

The attractive Coulomb force provides the centripetal acceleration v2/r to maintain the orbital
1
2
=
=
40 2

Quantization of angular momentum

=
2

2
1

8.9 109 2
40

Allowed radii for electrons in circular orbits of the hydrogen atom

1 2 2
=
40 2

1

1
( )()
2 2
=

=
=

40 2

40 2


2

2 2

2 2
40
40 4 2 2
1
2 6.62 1034
2
4 2
0
=
=
=
2
2
4 2 2
9 109 4 3.142 9.1 1031 1.6 1019

= 0.529 2 1010 = 0.529 2

Electrons are only allowed to occupy orbits with certain discrete radii

This places constraints to the allowed velocity, momentum and the total energy of
the electron in the atom
1 2 2
1
=
= 2.18 106 /
40

Allowed radii for electrons in circular orbits of the hydrogen ion

The treatment of hydrogen atoms prescribed
by Bohr can be generalized to describe the
energy level structure and electromagnetic
radiation spectra of hydrogen-like ions, i.e. a
positive nucleus with charge Ze (Z the integer
number of protons in the nucleus) orbited by
a single electron. The nuclear charge comes
into the Bohr model in only one place

v
F
+Ze

rn

nth orbit :
Nucleus charge is +Ze
where Z is the number
of protons and e is the
electron charge
e 1.602 x 10-19 C
me 9.1x10-31 kg
and Pancks Constant (h)
6.62 x10-34 m2kg/s

The attractive Coulomb force provides the centripetal acceleration v2/r to maintain the orbital
1
2
=
=
40 2

Quantization of angular momentum

=
2

2
1

8.9 109 2
40

Allowed radii for electrons in circular orbits of the hydrogen ion

1 2 2
=
40 2

2 2

2
2
2
1

( )()
40 2 2
2 40
2 2
4
=
=
=
=
= 2
40 2



2
4 2

2
2

= 0.529 1010 = 0.529

Electrons are only allowed to occupy orbits with certain discrete radii
This places constraints to the allowed velocity, momentum and the total energy of
the electron in the atom
1 2 2

=
= 2.18 106 /
40

Energy levels
= +
1
1
= 2 +

2
40
1
1 2
1 2
=

2 40
40
1 2
1
1
=
40
2 40

1
=
1
2

1
=
40
12 = 13.6

1
12

2
40 2 2
4 2 2

1
2 2 2 4
2

= 13.6 2

2
2
2 2

2 2 12 = 10.2 = 10.2
2

10.2 1.6 1019 /

=
1.2 105 ; 1 = 1.602 1019
23
1.38 10 /
( )

Permitted energy levels of a hydrogen atom

E1= 0 eV

n=
n=8
n=7
n=6
n=5
n=4

P
O
N

E1= -0.34 eV

n=3

E1= -1.56 eV

n=2

E1= -3.4 eV

n=1

E1= -0.53 eV
E1= -0.83 eV

E1= -13.6 eV
K
Lyman Balmer Paschen Brackett Pfund Humphreys
series
series series
series series
series
(IR)
(IR)
(UV) (visible)
(IR)
(IR)

The Bohr model then predicts that the wavelengths of hydrogen atomic transitions (Rydberg formula):
1
1
1
4
1
1
= =

12 22
802 3 12 22
107 1 ; 1 = 13.6

Hydrogen lamp

n=
n=5
n=4
n=3
n=2
n=1

122 nm
103 nm
97.3 nm

Lyman
series
(UV)

Emission spectrum of hydrogen

Transition from the first excited state to the ground state

The Balmer Series (visible) for Hydrogen

Quantized, not continuous
We can use the emission spectrum to determine the
energy levels for the hydrogen atom
When an electric current is passed through a glass
tube that contains hydrogen gas at low pressure the
tube gives off blue light. The light emitted pass
through a slit that reduced it to a narrow beam. Finally
the light pass through a prism, four narrow bands of
bright light are observed against a background (Violet,
Blue violet, Blue green and Red)

source:
http://www.atnf.csiro.au/outreach//education/senior/astrophys
ics/images/spectra/bohrhydrogen.gif

Deficiencies of the Bohr model

Cannot be applied to multi-electron atoms.

Does not predict fine structure of atomic spectral lines
Does not provide a method to calculate relative intensities of spectral lines
Predicts the wrong value of angular momentum for the electron in the atom
Violates the Heisenberg uncertainly principle (although Bohrs model preceded this
by more than a decade)

Heisenbergs uncertainty principle

Particles have well defined positions, but waves do not. Our ability to observe the
electron simultaneously as both a particle and a wave means that we cannot
simultaneously measure its position and its velocity.
Heisenbergs formalized this idea with this equation:

x in the uncertainty in the position, mv is the uncertainty in the velocity, m is the

mass of the particle, and h is Plancks constant.
Heisenbergs uncertainty principle states that the product of x and mv must be
greater than or equal to a finite number (h/4). The more accurately we know the
position of an electron (the smaller x) the less accurately you can know its
velocity (the bigger v) and vice versa. The complementarity of the wave nature
and particle nature of the electron results in the complementarity of velocity and
position. An electron is observed as either a particle or a wave, but never both at
once.

Photoelectric effect
Bohr Model of Atom
X-ray photon

Core-hole

Continuum
Exited
electron

eK-shells

Work function can be

defined as the work required
to move an electron from
the Fermi Level to the
vacuum level

Photoelectric effect:

L-shells
M-shells

Photon
E=h

KE = h -

(Package of energy)

Einstein concluded: The

light what we always taught
that it was a wave could
also behave like a particle.

e-

e-

Work function ()

e76

metal

Threshold frequency condition

The emission of an electron from the metal depends on the energy of a single
photon (h). If it has sufficient energy it will eject the electron from the atom.
For an electron bound to the metal with binding energy , the threshold frequency
is reached when the energy of the photon is equal to :
Threshold frequency condition

=
Energy of photon

Binding energy of the emitted electron

Low frequency light will not eject electron because no single photon has the
minimum energy necessary to eject the electron. The light used to be UV. If you
shine the light and measure the kinetic energy of the electrons and plot the kinetic
energy against frequency we find:
KE

KE = h -

Light below a frequency of 4.39 x1014 Hz or wavelength longer

than 683 nm would not eject electrons

The straight line obeys a simple equation where gradient is h

(Planck constant=6.63x10-34 Js)

Wave-particle duality
=

= 2

=
=
2

=
Now enter in the scene Louis de Broglie (1924) He provides a new concept
regarding the behavior of quantum systems in his PhD thesis.
de Broglie questioned whether this dual particle-wave nature is property of light
only, but rather applies to all physical systems as well?
=

After this contribution, Louis de Broglie got his PhD and a Nobel Prize

de Broglie waves and the Bohr model

If we examine the resulting effects of Broglies hypothesis has on the Bohr model
of hydrogen, we first recall that the allowed radii for the Bohr model are given by:
= 0.529 2
The momentum of the photon in state n is given by:
=

; =
=
=
= 2
2

2
2
The de Broglie wavelength for
everyday objects is extremely small.
For example Usain Bolt (m=92 kg and
velocity v=45km/h 12m/s) has the
Broglie wavelength:

6.626 1034
=
=

92 12/
37
6 10

http://courses.chem.indiana.edu

Energy levels
Erwin Schrdinger enters in the scene
By solving the Schrdinger equation (H=E), it is obtained a set of mathematical equations
called wave functions () that enable to describe the probability of finding electrons at
certain energy levels within the atom
The symbol H stands for the Hamiltonian operator, a set of mathematical operations the
represent the total energy (kinetic and potential) of the electron within the atom. The
symbol E is the actual energy of the electron.
The wave function for an electron in an atom is receives an special name: an atomic orbital
To visualize an atomic orbital, we think of a cloud surrounding the nucleus, with the density
of the cloud presenting the probability of finding an electron at each point
Denser regions of the cloud represent locations where the electron is more likely to be
found.
Atomic orbitals have characteristic energies and shapes
A plot of the wave function squared (2) represents an orbital, a position probability
distribution map of the electron
Each orbital has a characteristic energy.

Representation of the 1s, 2s, and 3s orbitals

the probability of finding the electron at a
certain point in space
2

Source: ChemWIKI

Zumdahl, Chemistry, Chap 7, Atomic structure and

periodicity ,6thed

Here is one of the most fascinating points in the quantum

chemistry. The electron can exist partly in all its
probable states at the same time. This follows from
Heisenberg's uncertainty principle.
The electron can not be in the in the node region

Quantum numbers (1)

n=
n=8
n=7
n=6
n=5
n=4

E1= 0 eV

n=3
n=2
n=1

E1= -13.6 eV

n, Principal quantum number

From the Schrdinger equation two more quantum numbers were found:
l, Orbital angular momentum
m, Magnetic quantum number

Schrdinger's calculation of the orbitals and energies of the hydrogen atom was a
milestone in the development of modern atomic theory. Nether less the spectral
lines did not have exactly the lines predicted.
The Stern-Gerlach experiment An electron has property of spin; the spin is
described by the quantum number S, which my have two values

Quantum numbers (2)

Quantum numbers for electrons in atoms
Name

Symbol

Values

Meaning

Indicates

1,2,.

Labels shells, specify energy

Size

Orbital angular momentum

0,1,,n-1

Labels subshell

Shape

Magnetic

Labels orbits of subshell

Direction

Spin magnetic

Labels spin state

Spin direction

Energy

Principal

n=3

l, l-1,,-l
+1/2, -1/2

l=2

+2

+1

-1

l=1

+1

-1

3p

l=0

l=0 3s

l=1

+1

l=0

2s

n=1

l=0

1s

n=2

-1

2p

-2

3d

How the electrons fill up these states

The Pauling exclusion principle: No more than two electrons may occupy any given
orbital. When two electron do occupy one orbital, their spins must be paired

Energy

Hunds rule: If more than on orbital in a subshell is available, electron will fill empty
orbitals before pairing in one of them

2p

1s

1 H 1s1

1s
2 He 1s2

2p

2s

2s

2s

2s

1s

1s

1s

1s

3 Li 1s22s1

4 Be 1s22s2 5 B 1s22s22p1

6 C 1s22s22p2

The order in which atomic orbitals are

occupied according to the building
Elements with
uncompleted
shells
Capability for
chemistry

Chemical
Bond

Nobel gases,
no capability
for chemistry

Zumdahl, Chemistry, Chap 7, Atomic structure and periodicity , 6th ed

-There are 7 separate s orbitals (1s, 2s, 3s, 4s, 5s, 6s, 7s) that can hold a maximum of 2 electrons each
-There are 6 separate p orbitals (2p, 3p, 4p, 5p, 6p, 7p) that can hold a maximum of 6 electrons each
-There are 4 separate d orbitals (3d, 4d, 5d, 6d) that can hold a maximum of 10 electrons each
-There are 2 separate f orbitals (4f, 5f) that can hold a maximum of 14 electrons each