Atomic Structure & the Periodic Table

B) Atomic Theory
CHE101 Chemistry Unit 1
2015 2016
Ms. T. Jackson

Topics
The Scientific Process & Theoretical Change
Atomic Theory

Dalton 1807
Thomson 1897
Rutherford 1909
Bohr 1913

Atomic Structure

Atomic Theory
An atom is the smallest unit of matter
From the Greek atomos meaning cannot be split
Atoms are basic building blocks of chemistry

H
O

Atomic Models / Theories

Dalton
Thomson
Rutherford
Bohr

1807
1897
1909
1913

For each model/theory, describe:

The model
Experiments that produced the model
Limitations of the model
How the limitations were resolved by the next model/theory
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Atomic Theory Development Timeline

1913
Mosely
neutron existence
hypothesised

1900
Goldstein
protons detected

1800

1807
Dalton
theorised
atoms are
hard spheres

1924
deBroglie
theorised wave-particle
duality

1900

1897
Thomson
electrons detected
plum pudding model
with embedded electrons

1909
Rutherford
planetary model
electrons orbit nucleus

1932
Chadwick
neutrons detected

2000

1913
Bohr
quantum theory model
electron energy levels
quantised

1926
Schroedinger
wave equation
for electron orbitals

Dalton 1807
Hard Spheres
Conceptualized atoms as hard spheres
Assumptions of Daltons atomic theory:
1. Matter consists of tiny particles called atoms, which are
indestructible & indivisible (i.e. cannot be split)
2. All atoms of the same element are identical in mass and
chemical properties. They differ from the atoms of all other
elements.
3. Atoms can combine in simple whole number ratios to form
compounds
4. A chemical reaction consists of rearranging atoms from one
combination into another. Atoms are not created, destroyed,
or broken into smaller pieces by any chemical reaction. i.e.the
indidvidual atoms remain intact
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Dalton 1807

Hard spheres with

different masses &
chemical properties

Dalton 1807
Evidence for Daltons Model
1. a) The particulate theory of matter explains the observed
differences in behaviour of solids, liquids, and gases in terms
of packing, motion, etc.

solid

liquid

gas
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Dalton 1807
Evidence for Daltons Model
b) Diffusion experiments support the particulate nature of
matter. E.g.
purple KMnO4 crystals placed into a beaker of water purple
solution
ii. chlorine mixing with air in a gas jar although it is denser than
air
iii. random (Brownian) motion of smoke particles observed in a
smoke cell
i.

Dalton 1807
Evidence for Daltons Model
2. The previously theorised law of conservation of mass: the
total mass remains constant during a chemical reaction
was supported by Daltons atomic theory.
Since every atom has a definite mass (according to postulate
2) & a chemical reaction should only rearrange the chemical
combinations of atoms (postulate 4), the mass must remain
constant.
E.g. mercury + oxygen product
2.53 g + 0.20 g 2.73 g

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Dalton 1807
Evidence for Daltons Model
3. The previously theorised law of definite proportions (or
constant composition): a pure compound, whatever its
source, always contains definite or constant proportions of
the elements by mass
From postulate 3, a compound is a type of matter containing
the atoms of two or more elements in definite proportions.
Because atoms have definite mass, compounds must have
the atoms in definite proportions by mass.

E.g. 1.0000 g of sodium chloride always contains

0.3934 g sodium and 0.6066 g chlorine
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Dalton 1807
Evidence for Daltons Model
4. Daltons atomic theory predicted the law of multiple
proportions: when two elements form more than one
compound, the masses of one element in these compounds
for a fixed mass of the other element are in ratios of small
whole numbers
Deducing this law from atomic theory helped to convince
chemists of the validity of the theory.
E.g. carbon + oxygen compound 1 + compound 2
1.000 g excess
1.000 g C :
1.000 g C :
1.3321 g O
2.664 O
CO
+
CO2
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Dalton 1807
Inaccuracies/Problems with DaltonsModel
Atoms were later found to consist of further particles i.e. they
could be divided into smaller parts
Atoms can be destroyed by nuclear reactions
Atoms of the same element can have different masses isotopes

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Thomson 1897
Plum Pudding Model
Plum-pudding model with
electrons embedded in a sea of positive charge

n+

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Thomson 1897
Experimental Evidence
1) 2 electrodes from
high voltage source
sealed into an evacuated
glass tube

2) high voltage current

turned on

3) beam of rays given

off by negatively charged
electrode (cathode)

4) cathode rays deflected

by electric field towards
positively charged plate

Discharging electricity through gases at low pressure

Cathode rays deflected by electric and magnetic fields
Charge/mass ratio e/m = -1.76 x 1011 Ckg-1 same regardless of type of gas or
electrode used
Same negatively charged particles (electrons) present in all matter
Atoms are not indivisible. They contain charged sub-atomic particles

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Thomson 1897
Inaccuracies/Problems with the Model
This model could not explain the deflection of (alpha)
particles by metal foil (Later discovered that most of the atom
is actually empty space with electrons orbiting the positively
charged nucleus) [see Rutherford model]

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Rutherford 1909
Planetary Model
Planetary model with negatively charged electrons orbiting
a positively charged nucleus

electron
n
n+
+

nucleus

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Rutherford 1909
Experimental Evidence
Bombarding thin metal
foils (e.g. gold) with alpha
particles
Most passed through with
no interaction
A few ~ 1 in 8000 were
scattered at large angles;
some were sent
backwards towards the
source
Atom mainly empty
space with mass &
positive charge
concentrated (>99.5%) in
tiny central nucleus while
negatively charged
electrons orbit the
nucleus (like planets
orbiting the sun)
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Rutherford 1909
Experimental Evidence (Geiger & Marsden)

Illustration of theorised
explanation for scattering
of particles by the nuclei
of metal atoms
Only particles that
collide with the positively
charged nucleus are
deflected
The vast majority pass
through the spaces
between the nuclei

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Rutherford 1909
Inaccuracies/Problems with the Model
If electrons are negatively charged, and the nucleus is
positively charged, why dont the electrons spiral into the
nucleus?
Could not explain atomic and emission spectra, i.e. why do
atoms absorb or emit light of certain frequencies? [see Bohr
model]

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Bohr 1913
Quantization of Electronic Energy Levels
Quantum theory based model
Max Planck had recently suggested that in certain systems
energy can be absorbed or emitted in certain specific
amounts i.e. in separate packets of energy called quanta
Bohr applied this to the atom & postulated the existence of
discrete energy levels within the atom, i.e. electrons can only
orbit the nucleus at certain distances depending on energy
electron
nucleus
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Bohr 1913
Features of the Bohr Model
Electrostatic force between nucleus & orbiting electrons
cancelled out by outward force due to orbital motion [so
electrons do not spiral into the nucleus]
Electron in a given orbit can only have a certain amount of
energy (i.e. the energy is quantized) & the orbit can only have
a certain radius
If the electron absorbs a quantum of energy (a photon of
light energy), it moves to an orbit with a higher energy level
that is further away from the nucleus. It is in an excited
energy state
An excited electron emits energy to return to its stable
ground state orbit
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Bohr 1913
Features of the Bohr Model
For an electron to move from an orbit E1 to one of energy E2,
the light absorbed must have a frequency given by Plancks
equation:
where = frequency
h = E2 E1
-34 Js
h
=
Plancks
constant
=
6.63
x
10
or DE = h
c = speed of light (or electromagnetic
(Also, c = l
radiation) in vacuo = 3 x 108 ms-1
So, DE = hc/l)
l = wavelength

Orbit of energy E2
Orbit of energy E1
Energy emitted = E2 E1
Frequency of light emitted
= = (E2 E1)/h

Energy absorbed = E2 E1
Frequency of light emitted
= = (E2 E1)/h
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Bohr 1913
Features of the Bohr Model
Bohr assigned quantum numbers to the orbits
Orbit of lowest energy (closest to the nucleus) n = 1
Next E level
n=2
etc.
n=5
n=4
n=3
n=2

Energy Level Diagram

ionized

n=1

n=4
n=3
Energy

n=2
n=1
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Bohr 1913
Experimental Evidence
Atomic Absorption and Emission Spectra
If white light is shined through a prism, a continuous spectrum is
produced containing all visible wavelengths or frequencies
In contrast if the light is shined through the sample of an element,
radiation is absorbed at certain frequencies producing a discontinuous
coloured spectrum (an atomic absorption spectrum)
The fact that the same discontinuous absorption spectrum is obtained
for a particular element supports the theory that electronic energy
levels are quantized
Similarly, if electrical or thermal energy is passed through a gaseous
sample of an element e.g. if the sample is heated to a sufficiently high
temperature and then allowed to cool, radiation is emitted only at
certain frequencies producing a discontinuous discrete line spectrum
(an atomic emission spectrum)
The fact that the same discrete lines are seen in the atomic emission
spectra for a particular element supports the theory that electronic
energy levels are quantized
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Bohr 1913
Experimental Evidence White Light

continuous spectrum
all colours seen
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Bohr 1913
Experimental Evidence Atomic Absorption Spectra

Sample
Discontinuous

absorption spectrum
black lines on a
bright background

27

Bohr 1913
Experimental Evidence Atomic Emission Spectra

E.g. Na in a flame yellow flame

E.g. H2 gas tube excited with
electric discharge reddish-pink
glow

emission spectrum
coloured lines on a
black background

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Hydrogen Emission Spectrum

Hydrogens emission spectrum has been extensively studied

Lines in different regions of the electromagnetic spectrum
Lines named after discoverers [note: some series overlap]
In each series, lines become closer together as frequency
increases until at high frequencies the lines coalesce or
converge to form a continuum of light

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Hydrogen Emission Spectrum

Energy Level Diagram

Hydrogen emission spectrum

transitions:
Lyman: UV
transitions to n = 1 (ground state)
from any other orbital
Balmer: visible light
transitions to n = 2
Paschen, Brackett, Pfund, IR
to n = 3, n = 4, n = 5 respectively

n=5
n=4
n=3
E

n=2

n=1

Emission
Spectrum

Lyman
series

Balmer
series

DE = h
for each line

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Bohr 1913
Inaccuracies/Problems with the Bohr Model
Explained the emission spectrum of a simple atom like
hydrogen, but failed to explain the spectra of more advanced
atoms. (Resolved by Schroedingers wave equations in 1926)
[ See later]

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Other Contributions
Goldstein (1900) & Moseley (1913)
detected protons as separate entities
theorised that since atoms are neutral # protons = # electrons
theorised that since the mass of the electron is negligible and the
mass of the protons adds up to less than the total mass of the atom
neutrally (zero) charged particles (i.e. neutrons) must exist

Chadwick (1932)
experimental detection of the neutron
bombarded Be with alpha particles
produced a stream of neutrally charged particles that had enough
mass to pass through several cm of solid lead neutrons detected

Schroedinger (1926) [see later]

applied deBroglies wave-particle duality theory to electrons
atomic orbitals described in terms of probability densities
suborbitals of electrons theorised

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References
Chemistry for CAPE by Susan Maraj and Arnold Samai. Caribbean
Educational Publishers 2011
A-Level Chemistry by E. N. Ramsden. Nelson Thornes Ltd 2000
CAPE Chemistry: A Caribbean Examinations Council Study Guide Unit 1
by Norris et al. Nelson Thornes Ltd 2012
Oxford Revision Guides AS & A Level Chemistry Through Diagrams by
Michael Lewis. Oxford University Press 2012
General Chemistry by Ebbing and Gammon. Houghton Mifflin Company
2005

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