Today’s Lecture

Atoms, Molecules and Ions

2.1 The Early History of Chemistry

2.2 Fundamental Chemical Laws
2.3 Dalton’s Atomic Theory
2.4 Cannizzaro’s Interpretation
2.5 Early Experiments to Characterize the Atom
2.6 The Modern View of Atomic Structure

The Scientific Method

Observation

Hypothesis

Experiment

Theory Law
(model)

Theory
modified
Prediction
as needed
Figure 1.4
Experiment
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 The Early History of Chemistry
„ Democritus proposed the existence of atoms as the
smallest indivisible unit (~400 B.C.)

„ Joseph Proust showed that a given compound always

contains exactly the same proportion of elements by mass
(~early 19th century)
„ now known as the law of definite proportions

„ e.g. carbon dioxide always contains 2.66g of O for

every 1 g of C

„ John Dalton reasoned that if elements were composed of

tiny individual particles (i.e. atoms), a given compound
should always contain the same combination of these
particles
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Fundamental Chemical Laws (cont’d)

„ Dalton discovered another principle that could be

explained in terms of atoms
„ e.g. consider two compounds that contain different
relative amounts of carbon and oxygen
„ compound I: 1.33 g of O for every 1 g of C
„ compound II: 2.66 g of O for every 1 g of C

„ how could this fact be explained in terms of atoms?

„ this principle could be readily applied to compounds of

other elements as well and is now known as the law of
multiple proportions
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 Dalton’s Atomic Theory

„ in 1808, Dalton formally published his theory of atoms

(below is a modern paraphrasing of Dalton ideas)
„ Each element is made up of tiny particles called atoms.
„ The atoms of a given element are identical; the atoms
of different elements are different in some
fundamental way or ways.
„ Chemical compounds are formed when atoms combine
with each other. A given compound always has the same
relative numbers and types of atoms.
„ Chemical reactions involve reorganization of the atoms -
changes in the way they are bound together. The atoms
themselves are not changed in a chemical reaction. 5

Dalton’s Incorrect Atomic Masses

„ If atoms existed, what were the relative masses of the

atoms of the various elements?
„ Dalton attempted to determine atomic masses:
„ at the time, water was known to contain 8 g of
oxygen for every 1 g of hydrogen
„ he assumed that water had the chemical formula OH
and assigned hydrogen a mass of 1 and oxygen a mass
of 8

„ Dalton’s list of atomic masses were incorrect because his

assumptions about chemical formulas of certain compounds
were incorrect
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 Absolute Formulas for Compounds
„ Joseph Gay-Lussac measured (under the same conditions
of temperature and pressure) the volumes of gases that
reacted with each other (1809)
„ e.g. 2 volumes of hydrogen react with 1 volume of
oxygen to form 2 volumes of water vapor

„ Amedeo Avogadro interpreted these results by proposing

that, at the same temperature and pressure, equal volumes
of different gases contain the same number of particles
„ this assumption is now known as Avogadro’s hypothesis
(1811)
„ the observations can best be explained by assuming
that gaseous hydrogen and oxygen are diatomic (two-
atom) molecules, H2 and O2 respectively 7

Cannizzaro’s Interpretation

„ Stanislao Cannizzaro’s work led to approximate values of

relative atomic masses

„ he applied Avogadro’s hypothesis to Gay-Lussac’s results

and was convinced that hydrogen gas consisted of H2
molecules
„ arbitrarily assigned the relative molecular mass of H2 to
be 2
„ he then measured the relative molecular masses for
other gaseous substances and from that he determined
the relative atomic masses

„ how?
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 Characterizing the Atom
„ in the late 19th century and early 20th century, J. J.
Thomson experimented with electrical discharges in
partially evacuated tubes called cathode-ray tubes
„ upon application of a high
voltage to the tube, a “ray”
was emitted from the
negative electrode
Figure 2.7
„this “ray” was repelled by the negative
pole of an applied electric field -
proposed that the “ray” was a stream
of negatively charged particles, now
called electrons
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Characterizing the Atom (cont’d)

„ Thomson measured the deflection of the “ray” of
electrons and determined the charge-to-mass ratio of an
electron: e
= − 1.76 x 10 8 C/g
m

„ Thomson postulated that an atom consisted of a diffuse

cloud of positive charge with the negative electrons
embedded randomly within the cloud - called the plum
pudding model

Figure 2.8
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 Characterizing the Atom (cont’d)

„ in 1909, Robert Millikan conducted experiments involving

charged oil drops
„ Millikan’s experiments
showed that the charge
on an oil droplet is always
a whole number multiple
of 1.60 x 10-19 C (i.e. the
charge of one electron is
1.60 x 10-19 C)
Figure 2.9

„ using the charge-to-mass ratio determined by Thomson, he

calculated the mass of the electron as 9.11 x 10-31 kg

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The Nuclear Atom

„ in 1911, Ernest Rutherford carried out an experiment to
test Thomson’s plum pudding model (using α particles)
Some alpha Most particles
particles are pass straight
Uranium source of scattered through foil
alpha particles (embedded

Figure 2.11
in a lead block to absorb
most of the radiation)

Thin
Beam of
metal foil
alpha particles Luminescent screen
t d t t tt d

expected
results
actual
results
Figure 2.12 12

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 “Seeing” Atoms
„ some of the most compelling evidence regarding the
existence of atoms comes from scanning probe microscopy

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Modern View of Atomic Structure

„ the simplest view of the atom:

„ consists of a tiny nucleus with a

diameter of ~ 10-13 cm
„ electrons move about the nucleus at an
average distance of about ~ 10-8 cm

Figure 2.13

„ the nucleus is assumed to contain protons (positively

charged particles) and neutrons (neutral particles)

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 Atomic Structure (cont’d)
„ the mass and charge of the electron, proton and neutron
Particle Mass Charge
Electron 9.11 x 10-31 kg -1
Proton 1.67 x 10-27 kg +1
Neutron 1.67 x 10-27 kg 0
„ note that the magnitude of the electron and the proton
charge is 1.60 x 10-19 C

„ summary:
„ the nucleus is small relative to the overall size of the

atom but it has a huge mass relative to the total mass

of the atom (i.e. the nucleus has an extremely high
density) 15

Atomic Structure (cont’d)

„ chemists are generally satisfied with a relatively crude
picture of the nucleus
„ why?

„ another question
„ “if all atoms are made up of these same components
(electrons, protons and neutrons), why do different
atoms have different chemical properties?”
Because the
have different
amounts of
electrons
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 Notation for Atoms
A
Z X
„ where
„ X = element symbol (e.g. H, He, Li, etc.)

„ Z = atomic number = # of protons = # of electrons

„ A = mass number = (# of protons + # of neutrons)
„ # of neutrons = (A - Z)

e.g. 4
2 He
„

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Isotopes
„ all atoms of the same element have the same number of
protons and electrons but they can have different
numbers of neutrons

„ atoms of the same element with different number of

neutrons are called isotopes

„ e.g. there are 3 isotopes for hydrogen

1
„ protium 1 H

2
„ deuterium 1H

3
tritium
1H
„

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 Isotopes (cont’d)
„ in nature, most elements contain a mixture of isotopes:
„ e.g. Carbon (C)

„ carbon-12 (98.892%)

„ carbon-13 (1.108)

„ carbon-14 (negligible) Why do isotopes of a

particular element show
„ e.g. Silicon (Si)
almost identical chemical
„ silicon-28 (92.23%)
properties?
„ silicon-29 (4.67%)
Because they have the
„ silicon-30 (3.10%) same number of
electrons
„ e.g. Rubidium (Rb)

„ rubidium-85 (72.17%)

„ rubidium-87 (27.83%) 19

Isotopes (cont’d)

„ for some elements, several isotopes exist (e.g. platinum)

Pt (atomic number 78) Tc (atomic number 43)

„ mass number 190 (0.014%) „ many isotopes but no
„ mass number 192 (0.782%) stable isotopes
„ mass number 194 (32.967%) „ in these cases the mass

„ mass number 195 (33.832%)

number of the most stable
isotope is reported, often
„ mass number 196 (25.242%)
in brackets
„ mass number 198 (7.163%)
„ e.g. technetium (98)

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