CAPE Chemistry UNIT 1 Chemical Principles and Applications I

Module 1 Fundamentals in Chemistry Lecture Notes 1

The Scientific Method

There needs to be a systematic approach to problem solving so as to achieve best results. In the sciences,
scientists use three basic steps in an attempt to study the laws of nature. These are:

1. Making observations An observation is something witnessed that can be recorded.

Observations may be qualitative (the sky is blue; water is a liquid) or
quantitative (water boils at 100 oC; a certain chemistry book weighs 2
kilograms). A qualitative observation does not involve a number. A
quantitative observation (called a measurement) involves both a number and
a unit.
2. Suggesting a possible explanation (Formulating Hypotheses) A hypothesis is a possible
explanation for an observation. Hypotheses need to be tested to see if they
are valid.
3. Doing experiments to test the possible explanations (Testing the hypothesis)
An experiment is carried out to test a hypothesis. This involves gathering
new information that enables a scientist to decide whether the hypothesis is
validthat is, whether it is supported by the new information learned from
the experiment. Experiments always produce new observations, and this
brings the process back to the beginning again.

Scientists call this process, the Scientific Method. The Scientific Method is a framework for gaining and
understanding knowledge (Zumdahl, 2010). When the steps have been repeated many times, eventually a
set of hypotheses which agree with the observations is obtained. These
hypotheses are assembled into a THEORY or MODEL a set of tested
hypotheses which explain a natural occurrence.

Theories are educated guesses of a natural phenomenon. As such,

scientists continue to conduct experiments even when a theory has been
formulated in an attempt to refine or replace existing theories. In doing
so scientists make predictions and then preforms further experiments.

However, as experiments are conducted and observations made

repeatedly in all systems, at different parts of the world, a LAW is

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formulated. A natural law is a summary of observed behaviour. Therefore, a law summaries what
happens whereas a Theory explains why it happens.

Example: Theory: Objects fall because they have mass.

Law: All things fall.

Chemical and Physical Properties

Colour Malleability Ductility Heat of combustion Hardness
Odour Reactivity with water Volume Melting point pH
Lustre Boiling point Density Electromotive force Weight
Mass Conductivity Length Heat of solution
Temperature

Chemical properties are properties exhibited as matter undergoes changes in composition. For example:
_____________________________________________________________________________________

Physical properties are properties exhibited in the absence of any change in composition. Physical
properties can be further classified as extensive or intensive. Extensive properties are dependent on the
amount of material. For example: _________________________________________________________.
Intensive properties are independent of the amount of material. For example: ______________________

_____________________________________________________________________________________

NB: A ratio of two (2) extensive properties gives an intensive property. Eg. Density, pressure and
concentration.

Units of Measurement
In 1960 and international agreement set up a system of units called the International System (Le Systme
International dunits or the SI system of units. Below shows a list of the Fundamental Quantities.
Table 1: Fundamental Quantities
Physical Quantity Name of Unit Abbreviation
Mass kilogram kg
Length meter m
Time second s
Temperature Kelvin K
Electric current ampere A
Amount of substance mole mol
Luminous intensity candela cd

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 Table 2: Derived Quantities
Derived Symbol Derivation SI unit Special
quantity Name
Area A length x length = m x m m2
Volume V length x length x length = m x m m3
Density xm kgm-3
Velocity/speed v mass/volume = kg/m3 ms-1
Acceleration a length/time = m/s ms-2
Force F velocity/time = ms-1/s kg ms-2 Newton, N
Pressure p mass x acceleration = kg x ms-2 kg m-1 s-2 Pascal, P
Work w force/area = kg ms-2 / m2 kg m2 s-2 Joule, J
force x length = kg ms-2 x m

Table 3: Prefixes used in the SI system.

Prefix Symbol Meaning Exponential
Notation
exa E 1,000,000,000,000,000,000 1018
peta P 1,000,000,000,000,000 1015
tera T 1,000,000,000,000 1012
giga G 1,000,000,000 109
mega M 1,000,000 106
kilo k 1,000 103
hecto h 100 102
deka da 10 101
- - 1 1
deci d 0.1 10-1
centi c 0.01 10-2
milli m 0.001 10-3
micro 0.000001 10-6
nano n 0.000000001 10-9
pico p 0.000000000001 10-12
femto f 0.000000000000001 10-15
atto a 0.000000000000000001 10-18

Lesson in Significant Figures

Rules for determining the number of significant figures in a value.
1. All non-zero digits are significant (23.71 4 sf)
2. Zeros before a non-zero digits are not significant (0.005 1 sf)
3. Zeros after the last non-zero digit that lie after the decimal point are significant (5.2200 5 sf)
4. Zeros in the middle of a number are significant (301.043 6 sf)
5. Zeros after the last non-zero digit that lie before the decimal point may or may not be significant.
In this case express the value in scientific notation: (50,000 1 or 5 sf; or 5 x 104 1 sf; 5.0000 x
104 5 sf)
6. Infinite significant is assigned to defined quantities ( 7 days in one week)
7. When adding or subtracting, the final answer cannot have more decimal places than any of the
original numbers (3.18 + 0.0059 = 3.19 max. number of decimal places = 2)
8. When multiplying or dividing, the final answer cannot have more significant figures than any of
the original numbers (4.50 x 0.13 = 0.58 max. number of sig. figures = 2)

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Rules for rounding numbers.
1. If the digit considered is less than 5, drop it. (3.453 = 3.45)
2. If the digit considered is more than 5, round up by 1. (531.646 = 531.65)
3. If the digit is 5, round UP for ODD numbers and round DOWN for EVEN numbers. (28.435 =
28.44 or 28.485 = 28.47)
Practice Questions
1. Report the following numbers to 3 sf:
i) 5.663105 ii) 9.276052 iii) 5.035071 iv) 607.294

2. State the number of significant figures in each of the following quantities:

(a) 3.00100 g of sugar (b) 0.0200 s (c) six thermometers (d) 0.0023 oC

3. Report the following numbers to 4 sf:

(i) 4.7475 ii) 4.7465 iii) 0.000239387 iv) 5021.

Elements: The Search for Patterns

Dbereiners Triads
As elements were being identified, chemists tried to group elements that resembles each other. They were
looking for a theory to be used to group and explain the properties of metals that resembled each other.
The first real success came in 1817 when Johann Dbereiner noted
that the metals calcium, strontium and barium were very alike. A
decade later when bromine was discovered, he saw that the non-
metals chlorine, bromine and iodine were also very similar.
He noticed that the mass of the middle element of each of the
triads was approximately equal to the average mass of the outer
two (2) elements.
However, Dbereiner could not explain why this was so, he
believed that elements could arrange in threes or triads but he
couldnt find enough triads to construct a convincing theory to
explain his classification.

Newlands octaves
John Newlands was a chief chemist in a London sugar refinery. In 1865, he noticed that if elements were
arranged according to increasing atomic mass, similar chemical properties appeared at every eight (8)
element. He related this phenomenon to the musical Law of octaves. Newlands had glimpsed the correct
underlying pattern to the recurring properties of the elements, but he did not take the idea far enough. The
real father of the modern periodic table was a Russian, Dimitri Mendeleyev.

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Mendeleyevs Periodic Table
Mendeleyev collected the elements together in a table that revealed the periodic (repeating) pattern in their
properties. He arranged the 62 element known at that time by referring to their atomic masses. Starting with
hydrogen, he wrote out the elements in horizontal rows, in order of increasing atomic mass. This gathered
elements with similar properties below one another in vertical groups. He looked at the arrangement of the
elements in his table and was then able to state his periodic law, as follows:
The elements, if arranged according to their atomic masses, show an evident periodicity of properties.
The problem with arranging the elements in strict order of atomic mass is that the pattern does match the
properties of all the elements. Mendeleyev had the courage to use his knowledge of the properties of
elements to bend his own rule; he simply exchanged some positions on the basis that the atomic masses
known at the time might be inaccurate. Mendeleyev also had the foresight to realise that some elements had
yet to be discovered.
Having suggested that there must be undiscovered elements,
Mendeleyev left gaps for them in his table in order to preserve
the principle of periodicity. Most significantly he went on to
predict in detail the chemical properties that these unknown
elements would have. For example; he predicted the properties
of the element found between silicon and tin which he called
eka-silicon. He did this by observing the properties of the other
element in the group. The properties of germanium, isolated by
Chemens Winkler in 1886, were in close agreement with
Mendeleyevs predictions for eka-silicon. It is a further
testimony to brilliance of Mendeleyevs ideas that the later
discovery of an entirely new group, the Noble gases, did not
disrupt his overall scheme.

Discovery of the Atom

The STM direct evidence for atoms?

The scanning tunnelling microscope (STM) was invented in 1981. It creates
images of surfaces with a resolution that is sufficiently high to detect individual
atoms. The STM constructs an image by using a computer to analyse the electric
current flowing between a surface and a very fine probe.
Electricity does not usually escape from the surface of conducting wires, but if
a second conducting wire is brought
close enough to the wire, electrons cross
the gap by a process called tunnelling. A
tiny but measurable current flows. The
STM uses a minute needle-like probe,
tipped with tungsten, to scan the surface being examined. A very
small potential difference (voltage) is applied across the gap between
the probe and the surface. When the probe encounters a bump on the
surface the gap becomes smaller and the current increases; when the
probe encounters a dip the gap becomes larger and the current
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decreases. When all the data have been collected the computer generates a contour map of the surface. A
very sharp probe is able to detect individual atoms in the surface being scanned.

The Discovery of the Electron

Following Daltons work it was believed that atoms could not be broken down into anything simpler. The
first indication that atoms have an internal structure came with the discovery of the electron. During the
1870s, physicists carried out experiments into the electrical conductivity of gases. They used a piece of
apparatus called a discharge tube, which was a long glass tube fitted with metal electrode at each end.
When the gas inside was at very low pressure, a green glow appeared in the glass at the end of the tube
furthest from the cathode (the negative electrode). Scientists proved that the glow was caused by invisible
rays originating from the cathode and travelling away from it in straight lines. In 1895 the French physicist
Jean Perrin placed a metal cylinder in the tube to collect the cathode rays. The charge in the cylinder
showed that cathode rays are negatively charged. In
1897, J. J. Thompson deflected cathode rays with
both electric and magnetic fields, and used his
results to measure the ratio of their charge to their
mass. He reasoned that, if cathode rays have mass,
then they must be composed of streams of particles.
These particles are now called electrons. He
calculated the mass of an electron to be nearly 2000
times smaller than the mass of a hydrogen atom.
A cathode ray tube

The Geiger- Marsden Experiment

Ernest Marsden, a student of Hans Geiger carried out experiments which involved the deflection of alpha
particles (which were known at that time to be positively charged) as they struck a thin sheet of gold foil (<
1 m thick). From these experiments Geiger and Marsden observed that, the majority of alpha particles were
deflected by less than one (1) degree. This suggests that these particles would have passed through
seemingly empty space. Another observation that the duo made was that a very, very small fraction of the
alpha particles bounced back towards the source meaning that within the atom, there must be a positively
charged body present that would repel the positively charged alpha particles. This led to the discovery of
the proton.

With the results from the Geiger-Marsden experiment, Ernes9t Rutherford, in 1911 proposed a new model
of the atom that has at its centre a very small positively charged nucleus with enough electrons surrounding
the nucleus to balance the positive charge of the nucleus.

Discovery of the Neutron

In 1932, James Chadwick bombarded the element beryllium with alpha particles. He observed that this
bombardment produced a highly penetrating stream of particles which could pass through many centimetres
of solid lead but which however, was not deflected by electric or magnetic fields. Therefore, this new
particle has mass but has no charge, and this was Chadwicks conclusion. Chadwick had discovered the
neutron theorised by Rutherford in his earlier studies.

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 Mass Spectrometry

The relative atomic mass of an element is the average mass of one atom of the element relative to 1/12th the
mass of one atom of carbon-12. In order to calculate the average mass, the masses of the isotopes of the
elements must be known, together with their relative abundances. These values are found using an
instrument called the mass spectrometer.
Mass spectrometry is an analytical technique that uses a mass
spectrometer to determine the relative atomic mass (Ar) and the relative
abundance of isotopes of an element. This technique is also used to
determine the structure of organic molecules based on fragmentation
patterns. The diagram below illustrates the operating principles of a
mass spectrometer.

There are four main steps:

1. Ionization:

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 A sample of an element is introduced as a vapour (the element may need to be heated if it is a solid).
In the ionization chamber, an electron gun (a heated wire filament) gives off electrons which are
attracted to the positively charged plate called the electron trap. This produces a beam of high energy
electrons. The vaporized sample is bombarded with the electron beam. When hit by the electron
beam, an atom in the chamber can lose an electron to form a positive ion.

2. Acceleration:

The positive ions are repelled away from the very positive ionization chamber and pass through three
slits, the final one of which is at 0 volts. The middle slit carries some intermediate voltage. The
positive plates creates an electric field to accelerate the positive ions to high speed.

3. Deflection:

The stream of fast-moving ions is deflected sideways as it passes through a magnetic field. Lighter ions are
therefore deflected more that heavier ions. Different ions are deflected by the magnetic field by different
amounts. The amount of deflection depends on:

The mass of the ion. Lighter ions are deflected more than heavier ones.
The charge on the ion. Ions with 2 (or more) positive charges are deflected more than ones with
only 1 positive charge.

These two factors are combined into the mass/charge ratio. (m/z or m/e).

4. Detection: Ions of the same charge and mass will all follow one particular path. This stream of ions
is detected by an instrument, such as an electrometer, that can detect charged particles.

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 The Mass Spectrum
Analysis of a sample using a mass spectrometer produces a mass spectrum. The mass spectrum contains
several lines whose height is proportional to the number of electrons hitting the detector. It is a graph of
relative abundance on the x-axis and mass to charge ratio on the y axis.

Example of a mass spectrum

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