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IB Chemistry

ATOMIC THEORY
Atomic Structure
Atomic Structure
Atoms are very small ~ 10-10 meters
All atoms are made up of three sub-
atomic particles: protons, neutrons and
electrons

The protons and neutrons form a small


positively charged nucleus
The electrons are in energy levels outside the
nucleus
Atomic Structure
The actual values of the masses and charges
of the sub-atomic particles are shown below:

A meaningful way to consider the masses of the sub-


atomic particles is to use relative masses
Atomic Structure -
Definitions
Atomic number (Z) is the number of
protons in the nucleus of an atom. The
number of protons equals the number of
electrons in a neutral atom
N.B. No. of protons always equals the no.
of electrons in any neutral atom of an
element.
Mass number (A) is the sum of the
number of protons and the number of
neutrons in the nucleus of an atom.

So how can you work out the number of neutrons in an atom?


No. of neutrons = Mass number atomic number
Atomic Structure - Example

So how can you work out the number of neutrons in


an atom?
Example

No. of neutrons = Mass number atomic number

No. of neutron = Mass No. Atomic No.


= 23 11
= 12
Atomic Structure - Questions
1. What are the three sub atomic particles that
make up the atom?
2. Draw a representation of the atom and
labelling the sub-atomic particles.
3. Draw a table to show the relative masses
and charges of the sub-atomic particles.
4. State the atomic number, mass number and
number of neutrons of: a) carbon, b) oxygen
and c) selenium.
5. Which neutral element contains 11 electrons
and 12 neutrons?
Atomic Structure - Questions
5. Copy and complete the following table:
Summary Slide
All atomic masses are relative to
the mass of carbon-12.

Eg one hydrogen atom weighs 1/12


the mass of a carbon-12 atom.
Isotopes
Isotopes are atoms of the same element with
the same atomic number, but different mass
numbers, i.e. they have different numbers of
neutrons.
Each atom of chlorine
contains the following:
35 Cl 37 Cl
17 17

17 protons 17 protons
17 electrons 17 electrons
18 neutrons 20 neutrons
The isotopes of chlorine are often referred to as
chlorine-35 and chlorine-37
Isotopes
Isotopes of an element have the same chemical
properties because they have the same number
of electrons. When a chemical reaction takes
place, it is the electrons that are involved in the
reactions.
However isotopes of an element have the
slightly different physical properties because
they have different numbers of neutrons, hence
different masses.
The isotopes of an element with fewer neutrons
will have:
Lower masses faster rate of diffusion
Lower densities lower melting and boiling points
Isotopes - Questions
1. Explain what isotopes using hydrogen as an
example.
2. One isotope of the element chlorine, contains
20 neutrons. Which other element also
contains 20 neutrons?

3. State the number of protons, electrons and


neutrons in:
a) one atom of carbon-12
b) one atom of carbon-14
c) one atom of uranium-235
d) one atom of uranium-238
Mass Spectrometer
The mass spectrometer is an instrument used:
To measure the relative masses of isotopes
To find the relative abundance of the isotopes
in a sample of an element

When charged particles


pass through a magnetic
field, the particles are
deflected by the magnetic
field, and the amount of
deflection depends upon
the mass/charge ratio of
the charged particle.
Mass Spectrometer 5
Stages

Once the sample of an element has


been placed in the mass spectrometer,
it undergoes five stages.
Vaporisation the sample has to be in
gaseous form. If the sample is a solid or
liquid, a heater is used to vaporise some
of the sample.
X (s) X (g)

or X (l) X (g)
Mass Spectrometer 5
Stages
Ionization sample is bombarded
by a stream of high-energy
electrons from an electron gun,
which knock an electron from an
atom. This produces a positive
ion: X (g) X +
(g) + e-

Acceleration an electric field is used to accelerate


the positive ions towards the magnetic field. The
accelerated ions are focused and passed through a
slit: this produces a narrow beam of ions.
Mass Spectrometer 5
Stages
Deflection
The accelerated ions are deflected into
the magnetic field. The amount of
deflection is greater when:

the mass of the positive ion is less


the charge on the positive ion is greater
the velocity of the positive ion is less
the strength of the magnetic field is
greater
Mass Spectrometer
If all the ions are travelling at the same
velocity and carry the same charge, the
amount of deflection in a given magnetic
field depends upon the mass of the ion.
For a given magnetic field, only ions with
a particular relative mass (m) to charge
(z) ration the m/z value are deflected
sufficiently to reach the detector.
Mass Spectrometer
Detection ions that reach the detector
cause electrons to be released in an ion-
current detector
The number of electrons released, hence
the current produced is proportional to
the number of ions striking the detector.
The detector is linked to an amplifier and
then to a recorder: this converts the
current into a peak which is shown in the
mass spectrum.
Atomic Structure Mass
Spectrometer

Name the five stages which the


sample undergoes in the mass
spectrometer and make brief notes of
what you remember under each stage.
Complete Exercise 4, 5 and 6 in the
handbook. Any incomplete work to be
completed and handed in for next
session.
Atomic Structure Mass
Spectrometer
Isotopes of boron

m/z value 11 10
Relative 18.7 81.3
abundance
%

Ar of boron = (11 x 18.7) + (10 x 81.3)


(18.7 + 81.3)

= 205.7 + 813
100
= 1018.7 = 10.2
100
Mass Spectrometer
Questions

A mass spec chart for a sample of


neon shows that it contains:
90.9% 20Ne
0.17% 21Ne

8.93% 22Ne

Calculate the relative atomic mass of


neon
You must show all your working!
Mass Spectrometer
Questions
90.9% 20Ne
0.17% 21Ne

8.93% 22Ne

(90.9 x 20) + (0.17 x 21) + (8.93 x 22)


100

Ar= 20.18
Mass Spectrometer
Questions

52. Calculate the


3 relative atomic
mass of lead
23.
22.
6 You must show
61.5 all your
204 206 207 208 m/ working!
e
Mass Spectrometer
Questions
1.5% 204Pb
23.6% 206Pb
22.6% 207Pb
52.3% 208Pb
(1.5 x 204) + (23.6 x 206) + (22.6 x 207)+(52.3
x 208)
100
306 + 4861.6 + 4678.2 + 20724.2
10878.4 100
100
Ar= 207.24
Energy Levels
Electrons go in shells or energy
levels. The energy levels are
called principle energy levels, 1
to 4.
The energyNumber
Principle levels of
contain sub-
levels.
energy sub-levels
level
1 1 These sub-levels
are assigned the
2 2
letters, s, p, d, f
3 3
4 4
Energy Levels
Each type of sub-level can hold a
different maximum number of
electron. Maximum
Sub-level number of
electrons
s 2
p 6
d 10
f 14
Energy Levels
The energy of the sub-levels
increases from s to p to d to f. The
electrons fill up the lower energy
sub-levels first.
Looking at this table can you
work out in what order the
electrons fill the sub-levels?
Energy Levels
Lets take a look at the Periodic
Table to see how this fits in.
Electronic Structure
So how do you write it?
1s2 Example
For magnesium:
1s2, 2s2, 2p6, 3s2
Energy level Number of
Sub-level electrons
Electronic Structure
The electronic structure follows a pattern the
order of filling the sub-levels is 1s, 2s, 2p, 3s,
3p
After this there is a break in the pattern, as
that the 4s fills before 3d.
Taking a look at the table below can you work
out why this is?
This is because the 4s
sub-level is of
lower energy than the
3d sub-level.
Electronic Structure
The order in this the energy levels
are filled is called the Aufbau
Principle.
Example (Sodium 2, 8, 1)
Electronic Structure
There are two exceptions to the Aufbau
principle.
The electronic structures of chromium
and copper do not follow the pattern
they are anomalous.
Chromium 1s2, 2s2, 2p6, 3s2, 3p6, 3d5,
4s1
Copper 1s 2, 2s2, 2p6, 3s2. 3p6, 3d10, 4s1
Write the electronic configuration for the following elements:
a) hydrogen c) oxygen e) copper
b) carbon d) aluminium f) fluorine
Electronic Structure of ions

When an atom loses or gains


electrons to form an ion, the
electronic structure changes:
Positive ions: formed by the loss of e-
1s2 2s2 2p6 3s1 1s2 2s2 2p6
Na atom Na+ ion

Negative ions: formed by the gain of e-


1s2 2s2 2p4 1s2 2s2 2p5
O atom O- ion
Electronic Structure of transition
metals

With the transition metals it is the


4s electrons that are lost first
when they form ions:
Titanium (Ti) - loss of 2 e-
1s2 2s2 2p6 3s2 3p6 3d2 4s2
1s2 2s2 2p6 3s2 3p6 3d2
Ti atom Ti2+ ion

Chromium (Cr) - loss of 3 e-


1s2 2s2 2p6 3s2 3p6 3d5 4s1 1s2 2s2 2p6 3s2 3p6 3d3
Cr atom Cr3+ ion
Electronic Structure -
Questions

Give the full electronic structure of


the following positve ions:
a) Mg2+ b) Ca2+ c) Al3+

Give the full electronic structure of


the negative ions:
a) Cl- b) Br- c) P3-
Electronic Structure -
Questions

Copy and complete the following


table: No. of No. of No. of
Atomi Mass Electronic
proton neutron electron
c no. no. structure
s s s
1s2 2s2 2p6
Mg 12
3s2
Al3+ 27 10

S2- 16 16

Sc3+ 21 45

Ni2+ 30 26
Orbitals
The energy sub levels are made up of
orbitals, each which can hold a
maximum of 2 electrons.
Different sub-levels have different
number of orbitals:
Max. no.
Sub- No. of
of
level orbitals
electrons
s 1 2
p 3 6
d 5 10
f 7 14
Orbitals
The orbitals in different sub-levels have
different shapes:
s orbitals
1s 2s
p orbitals
Orbitals
Within a sub-level, the electrons occupy
orbitals as unpaired electrons rather
than paired electrons. (This is known as
Hunds Rule).
We use boxes to represent orbitals:

2p

2s
Electronic structure of
1s carbon, 1s2, 2s2, 2p2
Orbitals
The arrows represent the electrons in
the orbitals.
The direction of arrows indiactes the
spin of the electron.
Paired electrons will have opposite spin,
as this reduces the mutual repulsion
between the paired electrons.
2p

2s
Electronic structure of
1s carbon, 1s2, 2s2, 2p2
Orbitals
Using boxes to represent orbitals, give
the full electronic structure of the
following atoms:
a) lithium b) fluorine c)
potassium
d) nitrogen e) oxygen

2p
2s
1s
Orbitals
Using boxes to represent orbitals, give
the full electronic structure of the
following atoms:
a) lithium b) fluorine c)
potassium
d) nitrogen e) oxygen
Electronic structure of
lithium: 1s2, 2s1 2p
2s

1s
Orbitals
Using boxes to represent orbitals, give
the full electronic structure of the
following atoms:
a) lithium b) fluorine c)
potassium
d) nitrogen e) oxygen
Electronic structure of
fluorine: 1s2, 2s2, 2p5 2p

2s

1s
Orbitals
Using boxes to represent orbitals, give
the full electronic structure of the
following atoms:
a) lithium b) fluorine c)
potassium
d) nitrogen e) oxygen 4s
Electronic structure of
potassium: 1s2, 2s2, 2p6, 3s2, 3p
3p6, 4s1 3s
2p
2s
1s
Orbitals
Using boxes to represent orbitals, give
the full electronic structure of the
following atoms:
a) lithium b) fluorine c)
potassium
d) nitrogen e) oxygen
Electronic structure of
nitrogen: 1s2, 2s2, 2p3 2p

2s

1s
Orbitals
Using boxes to represent orbitals, give
the full electronic structure of the
following atoms:
a) lithium b) fluorine c)
potassium
d) nitrogen e) oxygen
Electronic structure of
oxygen: 1s2, 2s2, 2p4 2p

2s

1s
Ionization Energy
Ionization of an atom involves the loss of an
electron to form a positive ion.
The first ionization energy is defined as the
energy required to remove one mole of electrons
from one mole of atoms of a gaseous element.
The first ionization energy of an atom can be
represented by the following general equation:
X(g) X+ + e- H > 0
Since all ionizations requires energy, they are
endothermic processes and have a positive
enthalpy change (H) value.
Ionization Energy
The value of the first ionization
energy depends upon two main
factors:
The size of the nuclear charge
The energy of the electron that has
been removed (this depends upon its distance from the
nucleus)
Ionization Energy
As the size of the nuclear charge increases the
force of the attraction between the negatively
charged electrons and the positively charged
nucleus increases.
Small Large
nuclear nuclear
charge

+ + charge

Small force Large
of force of
attraction attraction

Smaller
Greater
ionization ionization
energy energy
Ionization energy
As the energy of the electron increases, the
electron is farther away from the nucleus. As
a result the force of attraction between the
nucleus and the electron decreases.
Electrons
Electrons closer further away
to positive + + from positive
nucleus nucleus

Large force of Small force
of
attraction attraction

Greater Smaller
ionizati ionizati
on on
energy energy
Ionization energy - Questions

Write an equation to represent the first


ionization of:
a) aluminium
b) lithium
c) sodium
Trends across a Period
Going across a period, the size of the 1st
ionisation energy shows a general
increase.
This is because the electron comes from
the same energy level, but the size of
the nuclear charge increases.

+ + + +

Going across a Period


Trends across a Period (2
exceptions)

The first ionisation of Al is less than that of Mg,


despite the increase in the nuclear charge.
The reason for this is that the outer electron
removed from Al is in a higher sub-level: the
electron removed from Al is a 3p electron,
whereas that removed from Mg is a 3s.
Ionisation energy/kJ mol-
Electronic structure 1

Na 1s2, 2s2, 2p6, 3s1 494


Mg 1s2, 2s2, 2p6, 3s2 736
Al 1s2, 2s2, 2p6, 3s2, 3p1 577
Si 1s2, 2s2, 2p6, 3s2, 3p2 786
P 1s2, 2s2, 2p6, 3s2, 3p3 1060
S 1s2, 2s2, 2p6, 3s2, 3p4 1000
Cl 1s2, 2s2, 2p6, 3s2, 3p5 1260
Ar 1s2, 2s2, 2p6, 3s2, 3p6 1520
Trends across a Period (2
exceptions)

The first ionisation energy of S is less than that of


P, despite the increase in the nuclear charge.
In both cases the electron removed is from the 3p
sub-level. However the 3p electron removed from
S is a paired electron, whereas the 3p electron
removed from P is an unpaired electron.
When the electrons are paired the extra mutual
repulsion results in less energy being required to
remove an electron, hence a reduction in the
ionisation energy.
Phosphorus Sulphur
3p 3p
3s 3s
Trends across a Period -
Questions
There is a break in this general trend going across
a Period.
Look at the table below and point out where the
break in the the trend is and try to give an
explanation.Electronic Ionisation energy/kJ
structure mol-1
Na 1s2, 2s2, 2p6, 3s1 494
Mg 1s2, 2s2, 2p6, 3s2 736
1s2, 2s2, 2p6, 3s2,
Al 577
3p1
1s2, 2s2, 2p6, 3s2,
Si 786
3p2
1s2, 2s2, 2p6, 3s2,
P 1060
3p3
1s2, 2s2, 2p6, 3s2,
S 1000
3p4
1s , 2s , 2p , 3s ,
Clue: which
Cl sub-level (s, p, d or f is the outer electron in?
2 2 6 2
1260
3p 5
Trends across a Period -
Questions

Now take a look at the graph below:


3000
He
-1

2500 Ne
First ionisation
energy/kJ mol

2000 F
N Ar
1500 C Cl
Be P
1000 H O Mg Ca
500 S
B Si
Li Na Al K
0
0 5 10 15 20 25
Atomic number (Z)

a) Explain what the graph shows in as much detail as


possible
b) There is one other break in the general pattern
going across a Period. What is it and explain why
Trends down a Group
+
Ionization energy decreases
going down a Group.
Going down a Group in the +

Down the Group


Periodic Table, the electron
removed during the first
ionization is from a higher
energy level and hence it is +
further from the nucleus.
The nuclear charge also
increases, but the effect of the
increased nuclear charge is +
reduced by the inner electrons
which shield the outer electrons.
Ionization energy - Questions

1. Explain why sodium has a higher first


ionization energy than potassium.
2. Explain why the first ionization
energy of boron is less than that of
beryllium.
3. Why does helium have the highest
first ionisation energy of all the
elements?
4. Complete Tasks
Successive Ionization
energy
Definition: 2nd i.e.
The energy per mole for the process
X+(g) X2+(g) +e-
And so on for further successive ionisation energies
Successive Ionization
energy
Successive i.es increases because
electrons are being removed from
increasingly positive ions.
Therefore, nuclear attraction is
greater.
Large jumps seen when electron
is removed form a new sublevel
closer to the nucleus
Successive Ionization
energy
Large increase between
4th and 3rd shells
electron closer to
nucleus

2nd i.e higher than


first electron has
greater pull from
nucleus
Electron Affinity
Energy Change per mole for:

X (g) + e- X-(g)

That is, for the gaseous atoms to


gain an electron to form anions
Electron Affinity

The first e.a is negative (exothermic) because


the electron is attracted to the positive charge
on the atoms nucleus.

The second e.a is positive (endothermic)


because an electron is being added to an ion
which is already negative : repulsion occurs