As Chemistry Unit 1 Notes
As Chemistry Unit 1 Notes
refers to;
molar quantities at 298K and 1 atm pressure (1x10
5
Pa)
Enthalpy Changes
Units of H are kJ mol
1
: the mol
1
does not refer to one mole of any particular substance, but to
molar quantities in the correct proportions of the equation, and therefore the equation must always
be stated (or implied):
e.g. 0.5 N
2
+ 1.5 H
2
NH
3
H
= 46.2 kJ mol
1
The enthalpy change here refers to half a mole of nitrogen molecules reacting with 1.5 moles of
hydrogen molecules to form one mole of ammonia.
It follows that for; N
2
+ 3 H
2
2 NH
3
we multiply everything by the same factor and H
f
The enthalpy change that takes place when one mole of
substance is formed from its elements in their standard
state under standard conditions.
e.g. 0.5 N
2
+ 1.5 H
2
NH
3
Enthalpy of combustion, H
c
The enthalpy change that takes place when one mole of
substance is completely burned in oxygen under standard
conditions.
e.g. C
8
H
18
+ 12.5 O
2
8 CO
2
+ 9 H
2
O
Enthalpy of neutralisation, H
neut
The enthalpy change that takes place when one mole of
water is formed in a neutralisation reaction.
e.g. HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+ H
2
O
(l)
Enthalpy of atomisation, H
at
The enthalpy change that takes place when one mole of
gaseous atoms is formed from the element under
standard conditions.
e.g. Cl
2(g)
2Cl
(g)
Note - By definition, the
O
f
H A value for an element in its standard state must be zero.
(It takes no energy to form an element is its standard state from its constituent element in its
standard state).
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Experimental Measurements of Enthalpy
Experimental measurements of enthalpy change are generally based on knowing that the specific
heat capacity of water is 4.2Jg
-1
K
-1
. The temperature change of a given mass of water is
measured, and the energy change is found from:
Heat energy change = mass of water x 4.2 x temperature change (E = m c AT)
[Or to make sure the sign is always correct
Heat energy change = mass of water x 4.2 x (Starting temp final temp) ]
This is converted to an enthalpy change by dividing the energy change by the number of moles (of
the substance not in excess) and adding the appropriate sign; - for exothermic reactions and + for
endothermic reactions.
Example
50cm
3
of 1M HCl is placed in a polystyrene cup. 50cm
3
of 1M NaOH solution is placed in a beaker.
The temperature of each is 18
o
C. The NaOH solution is then added to the HCl in the cup. The
temperature increases to 24
o
C.
Calculate the enthalpy change for this reaction.
Heat energy change = 100 x 4.2 x (18 24) = -2520 J
Moles HCl = Moles NaOH = 50 / 1000 x 1 = 0.05 mol
H
f
(H
2
O
2
).
Chemical equation H
2(g)
+ O
2(g)
H
2
O
2(l)
This reaction does not readily occur, and so we cannot measure its enthalpy directly.
Hess's Law can be used to find the value for it using other enthalpy values by constructing a cycle,
and then equating the enthalpies from the different routes.
When 1 mole hydrogen is burnt in oxygen to form water, 285.9 kJ mol
-1
of energy are given out. This
is the enthalpy of formation of water, H
f
(H
2
O).
H
2(g)
+ O
2(g)
H
2
O
(l)
H
f
= -285.9 kJmol
-1
Hydrogen peroxide decomposes according to the equation:
H
2
O
2(l)
H
2
O
(l)
+ O
2(g)
H
R
= -98.3 kJmol
-1
These changes can be represented in an energy triangle. According to Hesss law, the energy change
to go from {H
2(g)
+ O
2(g)
} {H
2
O
2(l)
} is the same whether we go direct or via { H
2
O
(l)
+ O
2(g)
}.
So using Hesss Law;
H
f
(H
2
O
2
) = H
f
(H
2
O) - H
R
= -285.9 - -98.3 = -187.6 kJmol
-1
H
2(g)
+ O
2(g)
H
2
O
2(l)
H
f
(H
2
O
2
)
H
2
O
(l)
+ O
2(g)
H
f
(H
2
O)
H
R
The dashed arrow shows our indirect route {H
2(g)
+ O
2(g)
} to {H
2
O
2(l)
}. When the dashed arrow
points in the same direction as the energy
change arrow, the value is added in. When the
dashed arrow points in the opposite direction as
the energy change arrow, the value is
subtracted.
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Example 2 Calculating
O
f
H A from enthalpies of combustion
The enthalpies of combustion of ethene, hydrogen and carbon are 1409, 286 and
394 kJ mol
1
, respectively. Find the enthalpy of formation of ethene.
(i) Full cycle method
Construct a triangle with the elements in their standard states (including oxygen), ethene +
oxygen, and the combustion products as the three corners.
Using Hesss Law, total enthalpy change from elements to ethene must be the same by either route.
O
f
H A = 2
O
f
H A (CO
2
) + 2
O
f
H A (H
2
O)
O
c
H A (C
2
H
4
)
= 2(394) + 2(286) (1409) = + 49 kJ mol
1
N.B. Always include the + sign in H answers for endothermic reactions.
Example 3 Finding enthalpy of reaction from
O
f
H A values
(ii) Algebraic method
*
O
r
H A (reaction) must be added to all the enthalpies of formation on the left hand side
of equation, to be equal to the total enthalpies of formation on the right hand side.
Write out this statement, then the equation, with plenty of space, and write the
enthalpies of formation underneath each substance:
O
reaction
H A + sum of
O
f
H A (reactants) = sum of
O
f
H A (products)
C
2
H
4
(g) + 3O
2
(g) = 2CO
2
(g) + 2H
2
O(l)
1409 +
O
f
H A (ethene) + 3( 0) = 2(394) + 2(286)
So
O
f
H A (ethene) = 2(394) + 2(286) (1409) = + 49 kJ mol
1
* The advantage of the algebraic method is that you are less likely to omit enthalpy
values, and each value used is directly linked to the formula in the equation above, so that the
layout is self-explanatory.
2C(s) + 2H
2
(g) + 3O
2
(g)
C
2
H
4
(g) + 3O
2
(g)
O
f
H A
2CO
2
(g) + 2H
2
O(l)
2
O
f
H A (CO
2
) + 2
O
f
H A (H
2
O)
= 2(394) + 2(286)
O
c
H A (C
2
H
4
)
= 1409
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Using the algebraic method:
O
reaction
H A + sum of
O
f
H A (reactants) = sum of
O
f
H A (products)
2 Al
2
O
3
+ 3C 4Al(l) + 3CO
2
O
reaction
H A + 2(1669) + 0 = 4(+10) + 3(394)
O
reaction
H A = 1142 (3338)
= + 2196 kJ mol
1
for 2 mol
so for 1 mol
O
reaction
H A = + 1098 kJ mol
1
Example 4 use of enthalpies of combustion directly
Occasionally, instead of enthalpies of formation, only enthalpies of combustion (or solution)
are given in a question (in Example 1, two of the enthalpies of combustion were also
enthalpies of formation). These cannot be used in exactly the same way as enthalpies of
formation, and you are less likely to make mistakes if you draw the full cycle out.
e.g. The enthalpies of combustion of ethyne(g) and benzene(l) are 1299 and
3273 kJ mol
1
, and the enthalpy of vaporisation of benzene is +30kJ mol
1
.
Find
O
reaction
H A for: 3C
2
H
2
(g) C
6
H
6
(g) (i.e. 3 ethyne benzene)
Method: construct a cycle, including the combustion products. This means adding 7.5 oxygen
molecules to both sides.
6 CO (g) + 3 H O(l)
2 2
3 C H (g) + 7.5 O (g)
2 2 2
C H (g) + 7.5 O (g)
2 6 6
3(1299)
3273
A H
From Hess' Law:
O
H A = 3 (1299) (3273) = 564 kJ mol
1
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Bond Enthalpy
When a chemical reaction takes place it involves bond breaking and bond forming.
When a bond is formed one electron from each atom enters a new electron cloud of lower
energy. As the system moves to a lower energy level, energy is given out. In order to break
the bond this energy has to be put back into the system.
The heat energy obtained when a bond is formed, and taken in when it is broken is called the
bond enthalpy.
If we considered a molecule such as methane, the energy required to break each of the
bonds is not exactly the same. So the total energy required to break up a methane molecul e
is divided by 4 to give an average bond enthalpy.
Average bond enthalpies can be used to determine approximately the enthalpy change
which will take place in a particular reaction.
O
H A
reaction
= sum of bonds broken on left sum of bonds made on right
Consider the reaction between fluorine and methane.
CH
4
+ 4F
2
CF
4
+ 4HF
For each mole
Bonds broken; C-H 4 x 412 = 1648 kJ Bonds formed; C-F 4 x -484 = -1936 kJ
F-F 4 x 158 = 632 kJ H-F 4 x -562 = -2248 kJ
Total energy used = +2280 kJ Total energy produced = -4184 kJ
Total enthalpy change for the reaction = Broken Formed = +2280 -4184 = -1904 kJ.
We can show this on an energy diagram:
In reality the reaction between methane and fluorine does not required four fluorine molecules
to collide with a methane molecule at the same instant, but actually takes place as a series of
steps (in a process called the reaction mechanism).
Bond energies are useful as a guide to the possible sequence of events.
For example in the reaction between methane and fluorine, which is the first bond to break
C-H (bond enthalpy 412) or F-F (bond enthalpy 158)?
Since the F-F bond requires less energy to break it, this will be the first bond broken.
The bond enthalpies relate to the activation enthalpy for a reaction and therefore have an
influence on how fast the reaction can go. If the bond enthalpies are low, then the activation
enthalpy will be low and the reaction can take place at a high rate.
C + 4H + 8F
CH
4
+ 4F
2
CF
4
+ 4HF
Enthalpy
4184
+2280
AH = -1904 kJ mol
1
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Reaction Mechanisms
A reaction mechanism shows which bonds are formed and broken during a reaction and
informs chemists how a reaction proceeds.
The weaker the bond, the more likely it is to break.
Types of bond breaking
Bonds can break in two ways.
1) The electrons in the covalent bond return to their original atoms.
The species that form have an unpaired electron they are called free radicals.
Cl Cl Cl Cl
This is known as Homolytic fission (Homo as the products formed are both free radicals).
2) The electrons in the bond both move in the same direction.
The process forms ions and is called hetrolytic fission.
Cl
+
Cl
-
Probing reaction mechanisms
Bond enthalpies allow us to postulate what happens during a reaction.
e.g. The most likely bond to break in the molecule below (bromoethane) is the C-Br bond as it
is the weakest.
H C C Br
H
H
H
H
Bond
Bond enthalpy (kJ
mol
-1
)
(kJ/mol)
C-H 413
C-C 347
C-Br 290
When bromoethane reacts the most likely mechanism for the reaction will involve the breaking
of the C-Br bond to form the carbocationic intermediate (C
2
H
5
+
) and a Br
-
ion.
H C C Br
H
H
H
H
H C C
H
H
H
H
+
Br
-
Carbocationic intermediate
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Bond enthalpies and enthalpies of Atomisation
The enthalpy of atomisation of an element is the enthalpy change when one mole of
gaseous atoms of an element is formed from an element is its standard state under standard
conditions (298K and 1 atm).
e.g. It is the enthalpy change for the following process:
1/2Cl
2
(g) Cl(g) ; enthalpy change = AH
a
[1/2Cl
2
(g)] = + 121 kJ mol
-1
During atomization all the bonds in the reactants are broken and no new bonds are formed
(as all the products are atoms).
Therefore AH
a
= The sum of all the bonds in the reactants.
For 1/2Cl
2
(g) Cl(g) the bonds broken = (Cl-Cl)
Therefore Bond enthalpy of (Cl-Cl) = 2 x 121 = + 242 kJ mol
-1
Another example
AH
a
[CH
4
(g)] = +1646 kJ mol
-1
The equation for atomisation of CH
4
is; CH
4
(g) C(g) + 4H(g)
Bonds broken = 4 (C-H)
Therefore 4 (C-H) = 1646
(C-H) = 1646 / 4 = 412 kJ mol
-1
The bond enthalpy of (C-H) in CH
4
is 412 kJ mol
-1
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Born-Haber cycles
Lattice enthalpies cannot be determined directly and are found instead by cycles, called the
Born-Haber cycles, which are similar to the cycles used for determining enthalpy changes
using Hess's law.
- Starting with the elements in their standard states, we first form gaseous atoms
(atomisation enthalpies).
- We then remove electron(s) from the metal (ionisation enthalpy), and give electron(s)
to the non-metal (electron affinity).
- The gaseous ions are now combined to form the crystal (lattice enthalpy).
- The alternative route is to form the crystal directly from the elements (enthalpy of
formation).
We can illustrate the use of a Born-Haber cycle by calculating the enthalpy of formation of
magnesium chloride (in order to compare with the observed value of 642 kJ mol
- 1
).
If there is good agreement, it is likely that the compound fits the ionic model well.
Mg
2+
(g) + 2e
+ 2Cl(g)
Mg
2+
(g) + 2Cl
(g)
Mg(g) + 2Cl(g)
Mg(g) + Cl
2
(g)
Mg(s) + Cl
2
(g)
MgCl
2
(s)
2 electron affinity of Cl
Mg: first I.E
+ second I.E.
2 atomisation
of Cl
atomisation
of Mg
enthalpy of
formation of MgCl
2
lattice enthalpy
of MgCl
2
(s)
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For the route via atoms, and gaseous ions, the values are as follows:
Process: Enthalpy Value for MgCl
2
/kJ mol
1
a) Elements to atoms Atomisation of Mg +150
2 Atomisation of Cl +242
b) metal atom to cation First ionisation E of Mg +736
+ second I.E. +1450
c) non-metal to anion 2 electron affinity Cl 728
d) ions to crystal lattice enthalpy of MgCl
2
2493
Therefore: enthalpy of formation 643 kJ mol
1
Note;
In (a) and (c) allowance is made for two Cl atoms, and in (b) the total energy needed is the
sum of the first two ionisation energies.
In (d), the lattice enthalpy is defined as the enthalpy change on formation of one mole of
crystals from the gaseous ions (see previous section), and is negative.
The Born-Haber cycle is a conventional Hesss Law cycle, following the directions of the
arrows, but the vertical heights give a rough idea of the enthalpy content (lower =
thermodynamically more stable).
Study of this Born-Haber cycle shows that although the (negative) electron affinity of the non-
metal goes some way towards compensating for the high ionisation energy, it is the large
negative value for the lattice energy which makes the whole process favourable.
Ionic compounds are likely to be formed if one element (the metal) has low ionisation energy
(or energies), the other (non-metal) has a reasonably high electron affinity, and if the lattice
energy of the compound formed is high.
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ATOMIC STRUCTURE AND PERIODICITY
Basic structure of the atom.
An atom contains protons, neutrons and electrons. The protons and neutrons are found in the
nucleus of the atom while the electrons exist in the energy levels around the nucleus.
The characteristics of these basic particles are shown in the table
PARTICLE RELATIVE MASS RELATIVE CHARGE
Proton 1 +1
Electron 1/1840 -1
Neutron 1 None
The nucleus carries virtually all the mass of the atom and is positively charged.
Number of protons in the nucleus = the atomic number of that atom.
The total number of particles in the nucleus is given by the mass number.
Mass number = Protons + Neutrons
Number of neutrons in a nucleus = Mass number - Atomic number
The atomic and mass numbers can be shown with the symbol of the atom:
In a neutral atom, there will be no overall charge, so the no. of electrons = no. of protons.
The chemical nature of the atom is determined by the number of electrons it has and in
particular the electron arrangement.
So the atomic number tells us what type of atom we have.
The number of neutrons in a particular type of atom often varies.
One example of this is in hydrogen
Hydrogen-1 Hydrogen-2 Hydrogen-3
Deuterium Tritium
The atomic number for all these is 1 because they are all hydrogen atoms.
The mass number is different.
Atoms of the same type with different numbers of neutrons are called isotopes.
X
Mass number
Atomic number
1 proton 1 proton + 1 neutron 1 proton + 2 neutrons
H
1
1 H
2
1
H
3
1
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Carbon also has isotopes. C-12 is an important isotope in chemical definitions;
R.A.M. A
r
= mean* mass of 1 atom of the element
one-twelfth of the mass of 1 atom of
12
C
Relative Molecular Mass and Relative Isotopic Mass are measured on the same scale.
R.I.M. = mass of 1 atom of the isotope
one-twelfth of the mass of 1 atom of
12
C
R.M.M. M
r
= mean mass of 1 molecule of the substance
one-twelfth of the mass of 1 atom of
12
C
The term relative molecular mass should only be applied to substances which have
covalently-bonded molecules e.g. Cl
2
, SO
2
, C
8
H
18
. For ionic materials like NaCl and CuSO
4
the term relative formula mass is preferred, though it is calculated in the same way, by
adding up the R.A.M.s of all the atoms in the formula. R.F.M. can be used for molecular
substances, too.
The relative formula mass of a substance is:
R.F.M. M
r =
the mean mass of one formula unit of the substance
one twelfth of the mass of one atom of
12
C.
Relative Atomic Mass is the weighted mean of one mole of a normal sample of
the element expressed on a scale on which one mole of the atoms of the C-12
isotope has a mass of exactly 12 units.
Relative Molecular Mass is the weighted mean of one mole of a normal sample
of the substance expressed on a scale on which one mole of the atoms of the C-
12 isotope has a mass of exactly 12 units.
Relative Isotopic Mass is the mass of one mole of an isotope of the element
expressed on a scale on which one mole of the atoms of the C-12 isotope has a
mass of exactly 12 units.
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The Mass Spectrometer
The mass spectrometer is a method of determining relative atomic and molecular masses.
The main processes involved are;
1. the sample is vaporised,
2. the sample is ionised,
3. the ions are accelerated by an electric field,
4. the accelerated ions pass through a magnetic field and are deflected,
5. the ions are detected and recorded.
The vaporised sample is fed into the ionisation chamber. Here it is bombarded by a stream of
electrons which knock electrons out of the molecules in the sample.
X
(g)
+ e
-
X
+
(g)
+ 2e
-
These charged ions are then accelerated through an electric field and pass into a magnetic
field. The magnetic field deflects the ions according to their mass and charge.
For a particular setting of electric and magnetic fields only particles of a certain mass reach
the detector. Lower masses are deflected too much and higher masses too little.
The magnetic field strength is gradually altered changing the mass of particles which will
reach the detector. The detector is connected to an amplifier and recorder so the mass of
particles can be determined.
Vaporised sample
Electron gun
Accelerating field
Magnetic field
Tube under
vacuum
Ion detector
Amplifier
Recorder
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The mass spectrum of an element shows the relative isotopic mass and relative abundance of
each isotope of the element being tested. In a mass spectrum the height of each peak = the
relative abundance.
The Relative Atomic Mass of an element can be found by finding the sum of the products of
the relative abundance of each isotope and its relative isotopic mass and the dividing by the
total relative abundance.
e.g. The two sketches show the mass spectra obtained from atoms of two different elements.
In each case determine the R.A.M.
height
mass/charge ratio
50.5%
49.5%
79 81
(a)
height
mass/charge ratio
(b)
64 66 68
(a) We assume the two peaks are due to atoms of two isotopes.
Mean r.a.m. = 79
\
|
.
|
|
50.5
100
+ 81
\
|
.
|
|
49.5
100
= 79.99 = 80.0 (to 3 s.f.)
(b) No scale is given, so we must use a ruler to measure the heights. Let us assume these
are (from left to right) 3.8 cm, 2.4 cm, and 1.2 cm. Total = 7.4cm
Mean r.a.m. = 64
\
|
.
|
|
3.8
7.4
+ 66
\
|
.
|
|
2.4
7.4
+ 68
\
|
.
|
|
1.2
7.4
= 65.3 (to 3 s.f.)
A very accurate version of the mass spectrometer can be used to determine relative
isotopic masses to a high degree of accuracy: e.g.
16
O = 15.99415 and
17
O = 16.99913.
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Mass Spectra of Molecules
The full mass spectrum of chlorine is more complicated than the examples shown on page 4.
This is because chlorine is made up of diatomic molecules (molecules containing two atoms).
Peaks occur at mass numbers 35, 37, 70, 72 and 74. The identity of these is as follows.
Peak at Species responsible
35
35
Cl
+
37
37
Cl
+
70
35
Cl
2
+
72
35
Cl
37
Cl
+
74
37
Cl
2
+
Peaks still occur at mass numbers 35 and 37 because molecules break up in the mass
spectrometer.
Example
Bromine has two isotopes of mass 79 and mass 81.
Predict the peaks you would expect to see in a mass spectrograph of bromine, Br
2
.
Peak 79 81 158 160 162
Species
79
Br
+
81
Br
+
79
Br
2
+
79
Br
81
Br
+
81
Br
2
+
When molecules are passed through the mass spectrometer, the peak with the highest mass
is caused by the ion formed from the whole molecule this is called the molecular ion or
parent ion.
The RFM of a compound can be found from the mass value of the molecular ion.
Molecules of a particular compound will always break up in the same way and in
the same proportion when passed through a mass spectrometer. This means that a given
compound will always produce the same pattern in a mass spectrum. This can be used to
identify the presence of compounds in analysis.
This has been used as follows.
- In sport to detect the use of anabolic steroids
- By pharmaceutical industries to identify synthesized compounds as possible potential
drugs
Independent research:
Research how the mass spectrometer used in space research.
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Electronic Structure of the atom
The electronic structure of an atom that determines its chemical properties.
Electrons can be regarded as having certain energy levels. The lower levels fill before the
higher levels are occupied.
The simple theory your learnt at IGCSE, pictures the atom as having shells, the shell of
lowest energy being closest to the nucleus. The next shell can hold up to eight electrons. The
third shell also holds up to eight electrons.
Bonding is explained in terms of atoms trying to obtain a stable electrons arrangement by;
(i) transfer from electron rich atoms(metals) to electron deficient atoms(non-metals);
(ii) sharing electrons between electron deficient atoms.
This model on its own is not sophisticated enough for understanding A level work fully and
does not explain how the atoms arrange electrons above a number of twenty.
The simple bonding theory which comes from the model cannot explain the structure of
molecules such as PCl
5
or SF
6
.
Electronic Configuration
- The shells used in the simple view of the atom are divided into subshells.
Shell Subshells
1 s
2 s p
3 s p d
4 s p d f
- The higher the energy of the shell, the more subshells it contains.
Electrons inside the atom should be thought of as waves rather than particles.
The area occupied by an electron wave is called the orbital.
An orbital has no edge: the electron density just tails off more and more. However, we can
calculate the surface which would contain a given percentage (say, 95%) of the electron
density, and use this to gain an idea of the shape of the orbital (below).
1s orbital
spherically symmetrical
2p 2p
2p
x
y z
three 2p orbitals
each pointing along
a different axis
x
y
z z
y
x
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It is important to remember that the electron density is not uniform within this shape.
The s-orbital is always spherically symmetrical, while the three 2p orbitals each point along
one particular axis, at right angles to the other two. Remember that when one electron
occupies a 2p orbital it occupies both halves; when two electrons occupy it, they both occupy
both halves.
Each electron in an atom is different from all the other electrons.
The s subshell
s orbitals can contain a maximum of two electrons.
These have the same energy value, but are said to have opposite spin values.
The p subshell
There are three p orbitals, each of which can contain a maximum of two electrons.
The d subshell
There are five d orbitals, each of which can contain a maximum of two electrons.
Electron shells
- The first shell holds two electrons in an s subshell. 1s
- The electrons have the same energy value, but are said to have opposite spin values.
- The second shell holds eight electrons.
- These are split into two energy levels;
the lower level has two electrons in the 's' subshell 2s
the higher level has six electrons in the 'p' subshell. 2p
- The electrons in the 'p' subshell are found in three different regions of the atom which
are called 'x', 'y' and 'z'.
Second shell
8 electrons
- The thrid shell holds eighteen electrons.
- These are split into three energy levels;
the lower level has two electrons in the 's' subshell 3s
the next highest level has six electrons in the 'p' subshell. 3p
the highest level has ten electrons in the 'd' subshell. 3d
Note - In the higher shells there is overlap between the energy levels of the subshells. E.g.
The 4s subshell is filled before the 3d subshell.
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Electronic configurations
Electronic Configuration can be predicted. If the following rules are followed:
- Electrons go into lower energy levels before higher ones.
- Electrons go into lower sub-shells before higher ones.
- Electrons occupy orbitals with 1 electron rather than 2 if possible.
- Electrons can only occupy the same orbital if they have opposite spins.
- The orbital order 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p
E
n
e
r
g
y
2s
3s
3p
3d
4s
4p
4d
4f
1s
2p
Relative energies oforbitals for elements 220
e.g.
Atom No of electrons Configuration
Si 14 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
2
K 19 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
2
Mn 25 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
2
, 3d
5
Ge 32 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
2
, 3d
10
, 4p
2
Kr 36 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
2
, 3d
10
, 4p
6
Another way of representing electronic configuration giving greater detail is as electrons in
boxes
N. 7
When writing the electron configurations of ions, it is important to take into account the
number of electrons lost or gained. Ca
2+
1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
An exactly half full or full d subshell is particularly stable. This gives chromium and copper
what is at first sight an unexpected electronic configuration.
The extra stability of the exactly half full or full d subshell means that an electron from the 4s
goes to the 3d to give a half full subshell for chromium and a full subshell for copper.
Element Initially expected but wrong Correct electron configuration
Chromium, Cr 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
2
, 3d
4
1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
1
, 3d
5
Copper, Cu 1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
2
, 3d
9
1s
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 4s
1
, 3d
10
1s 2s 2p
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Configurations and the Periodic Table
s, p and d-block elements
All s-block elements have their highest energy electrons in s-orbitals.
All p-block elements have their highest energy electrons in p-orbitals.
All d-block elements have their highest energy electrons in d-orbitals.
Evidence for Electron shells and subshells
Ionisation Energies
An electron is attracted to the positive charge in the nucleus of the atom. It is possible to
remove an electron from an atom. The process of removing an electron form an atom to form
a positive ion is called ionisation. The energy required to remove one electron from an atom
is the first ionization energy.
The size of the ionisation energy is an indication of the strength of attraction between the
outer electrons and the nucleus.
Energy changes in chemistry are generally measured as heat energy or enthalpy.
The definition of the first ionisation energy is:
or
Examples
The first ionization energy of chlorine Cl
(g)
Cl
+
(g)
+ e
-
The second ionization energy of sodium Na
+
(g)
Na
2+
(g)
+ e
-
1s
2s
3s
4s
5s
6s
3d 4p
3p
2p
5p
6p
4d
5d
The enthalpy change for the following reaction:
X
(g)
X
+
(g)
+ e
-
The energy required to remove one electron from each atom in one mole of
mole of gaseous atoms producing one mole of gaseous ions with one
positive charge.
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Successive ionisation energies
The graph of successive ionisation energies against number for potassium (At No 19) shows
electrons grouped into four energy levels or quantum shells with similar energies.
Ionisation number
To remove the second electron it is necessary to break into a complete shell, so a lot more
energy needed. Similarly with the tenth electron there is an increase in the energy required for
its removal as this has to come from a complete shell.
From successive ionization energies it is possible to tell which group of the Periodic table an
element is in. The table below shows successive ionisation energies for an element.
Energy values are given in kJmol
-1
.
1
st
2
nd
3
rd
4
th
5
th
6
th
577 1820 2740 11600 14800 18400
Notice that there is a large increase after the third ionisation energy so the fourth electron is
much more difficult to remove.
This means that there are three electrons in the outer shell, so the element is in group 3.
Example
Here are successive I.E. values in kJ mol
-1
for two elements:
element X 1010 1900 2900 5000 6300 21300 25400 29800
element Y 590 1150 4940 6480 8120 10700 12300 14600 18200 20400 57100.
In what group of the periodic table are X and Y?
For X there is a sharp rise between the 5th and the 6th values, so X must have five electrons
in its outer shell. X is a Group 5 element.
Y shows a jump between the second and third values, so it is in Group 2.
Log
Ionisation
Energy
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First ionisation energy
The first ionisation energy is energy required to remove one electron from an atom.
The factors which affect ionisation energies are:
- the nuclear charge,
- the distance away from the nucleus of the electron,
- the shielding of the nucleus by other electrons.
(Being spherical s subshells are much better at shielding than p subshells).
If first ionisation energy is plotted for a number of elements the results provide evidence for
the existence of subshells.
- Lithium has the lowest first ionisation energy of the second period.
- It is more difficult to remove an electron from Beryllium since the charge on the nucleus
has increased Beryllium having a 4+ nuclear charge, whereas lithium is only 3+.
- Although Boron also has a higher nuclear charge, it has lower first ionisation energy
because the electron is now in the 'p' subshell, and the inner s subshell shields it from
the nucleus.
- The ionisation energy increases again to Carbon and Nitrogen as the nuclear charge
increases.
- Oxygen has a higher nuclear charge, but the first ionisation energy is lower because
the extra electron now has to pair up in an orbital (in Nitrogen each p orbital has an
electron in it) so the extra electron is repelled and it is easier to remove it.
- The values increase after oxygen as the nuclear charge increases.
- The pattern repeats itself for the next period of the periodic table First ionization
energy is a periodic property.
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Periodicity
Periodicity is the regular occurrence of a trend across a period (or down a group).
Many periodic properties can be explained in terms of structure and bonding.
e.g. Explaining trends physical properties in period 3 from sodium to argon.
Na Mg Al Si P S Cl Ar
atom* radius / nm 0.157 0.140 0.126 0.117 0.110 0.104 0.099
ion radius / nm 0.098 0.065 0.054 no ion 0.212 0.184 0.181
ion charge +1 +2 +3 3 2 1
structure metal metal metal diamond P
4
S
8
Cl
2
atomic
melting point / K 371 923 932 1683 317
392 172 84
boiling point / K 1163 1390 2720 2630 553
718 239 87
relative conductivity 1 1.23 1.96 semi 0 0 0 0
first I.E / kJ mol
-1
500 740 580 790 1010 1000 1260 1520
r r
z z
i.e. [product of charges] [sum of radii]
Here, the constant depends on the type of structure (the way in which the ions pack together).
z
+
and z
C
2
H
6
The overall mechanism is called free radical substitution.
Note that in the propagation stage the Cl at the end can go on to attack another CH
4
and so
the chain can go on for several thousand reactions from one initiation.
The presence of traces of C
2
H
6
in the products shows that CH
3
radicals must have been
formed.
Of course, the Cl atoms can remove a hydrogen atom from CH
3
Cl, and so the reaction can
go on to CH
2
Cl
2
, then CHCl
3
and finally CCl
4
.
Cl Cl
Cl Cl
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The Alkenes
Alkenes are hydrocarbons that contain one double bond.
They are unsaturated compounds: compounds which are able to undergo addition
reactions.
They have the general formula : C
n
H
2n
The double bond in alkenes does not consist of two identical bonds.
One of the bonds is a normal bond with the electron cloud lying between to two atoms. This
is called a sigma, , bond.
The other bond has an electron cloud which is placed above and below the two atoms. This
is called the pi, , bond.
The electron clouds in ethene can be represented as shown below.
Isomers of alkenes (E-Z Isomerism)
The geometry of the C=C bond is determined by the -bond, and means that ethene is a
rectangular, flat molecule.
C C
H
H H
H
The bond angles are at about 120
o
, and rotation about the C=C axis is restricted, since
twisting through 90
o
would mean the p-orbitals would no longer overlap and the -bond would
be broken.
The restriction of rotation produces isomers called E-Z isomers (geometric isomers or cis-
trans isomers).
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For E-Z isomerism (cis-trans isomerism) to occur there must be a double bond and two
different groups on each of the double bonded carbon atoms.
C
C
H R
H R
C
C
R H
H R
.
E-Z and cis-trans are different terms for the same type of isomerism.
Trans refers to the isomer where the R groups are on opposite sides of the C=C.
Cis refers to the isomer where the R groups are on the same side of the C=C.
Isomers of butane
C C
H
H
3
C H
CH
3
C C
H
H
3
C CH
3
H
C C
H
3
C
H
3
C H
H
2E but-2-ene 2Z but-2-ene 2methylpropene
trans but-2-ene cis but-2-ene
The E-Z (cis / trans) isomers will be chemically very similar, though not quite identical, and will
have slightly different melting and boiling points.
[Note that a third isomer, 2methylpropene, which has two methyl groups attached to the
same carbon atom, is a structural isomer of these, as is but-1-ene]
E- and Z- vs cis-trans nomenclature
The cis trans system breaks down with examples like;
F
Cl
F
Cl
The E-Z naming system is more useful than the cis-trans system.
- The naming of the isomer is determined by priorities.
- Each atom on the double bond is given a priority determined by its atomic number.
- The smaller the atomic number the lower the priority hydrogen in the example above.
- If atoms with the lowest priority are on the same side on each end of the C=C the
isomer is called the Z-isomer. (Z=Zusammen (together)).
- If atoms with the lowest priority are on the same side on each end of the C=C the
isomer is called the E-isomer. (E=Entgegen (opposite)).
E- isomer (trans) Z- isomer (cis)
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Reactions of alkenes
The alkenes are more reactive than the alkanes because of the C=C bond.
It is possible for the double bond to break, allowing each carbon to form a new bond, which is
often energetically favourable. Halogens, hydrogen halides, hydrogen and potassium
manganate(VII) will produce addition reactions with alkenes.
Addition of hydrogen (hydrogenation)
Alkenes react with hydrogen in the presence of a nickel catalyst at150
o
C.
This is important in the hydrogenation of vegetable fats to make margarine.
An unsaturated vegetable oil is mixed with a nickel catalyst at 50
o
C,and hydrogen gas
bubbled through. The saturated product has a higher melting point, and is less easily oxidised
(longer shelf life).
Addition of bromine
Alkenes will decolorise bromine immediately:
The decolorisation of bromine water is used as a test for the C=C double bond.
This reaction occurs in an inert solvent like volasil.
Addition of chlorine
+
H
H
H
R
H
C C R R
H H
C C
R
H H
+
Cl
Cl
H
R
H
C C R
R
H H
C C
R
Cl Cl
H
R
H
C C R +
Br
Br R
H H
C C
R
Br Br
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Addition of Hydrogen chloride*
Addition of Hydrogen bromide*
* When addition of a hydrogen halide takes place, if the alkene is not symmetrical, the
hydrogen adds to the carbon that already has the most hydrogen. This is called
Markovnikoff's rule
Reaction with Potassium manganate(VII)
Acidified potassium managanate(VII) is decolourised (from purple to colourless) by an alkene
and a diol is formed.
[O] is a shorthand for the oxidizing agent potassium manganate(VII).
+
H
R
H
C C R Br
H
R
H H
C C
R
Br H
+
H
R
H
C C R
Cl
H
R
H H
C C
R
Cl H
H
H
C C C
H
H
H
H Br
H +
H
C C
H
H
H
H
C H
H
Br
H
R
H
C C R + [O]
H
2
O +
R
H H
C C
R
OH OH
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Addition Reactions of Alkenes
The addition reactions have a mechanism which we need to study.
It is the electron rich area in the double bond which causes the initial attack.
A molecule attacking such an area is called an electrophile (electron loving). This reaction
results in addition, so this type of reaction is called electrophilic addition.
A definition of the term electrophile is;
An electrophile is a species attracted to an area of negative charge and is an electron pair
acceptor.
Mechanism for the reaction of hydrogen bromide with ethane.
Looking at dot and cross diagram for the reaction.
This is not the way a mechanism is shown.
H
H H
H
C C
H
Br
1. The hydrogen in the hydrogen bromide
has a partial positive charge. It is attracted to
the high electron density in the double bond.
2. The hydrogen draws an electron pair out
of the double bond and forms a bond to the
hydrogen.
H
H H
H
C C
H
Br
3. The bond between the bromine and the
hydrogen weakens and breaks, both the
electrons going to the bromine.
H
H H
H
C C
H
Br
-
+
4. The carbon on the right now has only
three of its original four electrons, so it has
a positive charge. This intermediate is
called a carbocation ion.
5. The bromine has gained an electron
making it a bromide ion with a negative
charge.
6. The bromide donates an electron pair to
the positively charged carbon forming a bond.
H
H H
H
C C
H
Br
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The reaction mechanism for this is shown as follows.
The mechanism for the attack of bromine on ethane is almost identical, but as bromine is not
a polar molecule it has no partial charge.
As a bromine molecule approaches the ethane, the high electron density in the double bond
repels electrons in the nearest bromine so causing an induced partial positive charge.
H
H H
H
C C
H
Br
H
H H
H
C C
H
Br
+
-
H
H H
H
C C H
Br
H
H H
H
C C
Br
H
H H
H
C C
Br
+
-
H
H H
H
C C Br
Br
Br Br
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Asymmetric Additions (Markovnikoff's rule)
The addition of hydrogen bromide to propene could lead to two possible intermediates.
The carbocation ion with the charge on the central carbon is formed as the charge is
stabilised by the two carbons on each side of it. So the mechanism is as follows
Markovnikoff's rule states that;
When addition of a hydrogen halide takes place, if the alkene is not symmetrical, the
hydrogen adds to the carbon that already has the most hydrogen.
H
H H
H
C C
H
Br
H
H
C
H
H H
H
C C
H
H
C
H
H H
H
C C
H
H
C
H
H
+
+
If the hydrogen joins the central carbon the ion on the left will be formed.
If the hydrogen joins the end carbon the ion on the right will be formed.
H
H H
H
C C
H
Br
H
H
C
H
H H
H
C C
H
H
C
H
+
Br
-
H
H H
H
C C
H
H
C
H
Br
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Test for alkenes
The addition reactions are used to test for the presence of a double bond.
If bromine water is added to an unsaturated compound, an addition reaction occurs fairly
rapidly and the bromine water changes from orange to colourless.
In this test the product contains a Br and an OH.
This is because the bromine water contains hydroxide ions from water.
The reaction mechanism for the test on ethene shows why this product is formed.
Addition Polymers
An addition polymer is formed when monomers containing double bonds are polymerised.
In the process of polymerisation the double bond breaks and the molecules join to form
molecules of thousands or millions of units.
Polymer structure of structure of
Monomer polymer
Ethene
Propene
Chloroethene
Tetrafluoroethene
Independent research: Consider the uses of energy and resources over the life cycle of a
polymer in the context of how renewable resources, recycling and energy recovery can lead
to a more sustainable use of materials.
H
H H
H
C C
Br
H
H H
H
C C
OH
+
-
H
H H
H
C C OH
Br
Br Br
OH- from the water takes place
in the second step.
C C
H H
H H
C C
F F
F F
C C
H H
H H n
C C
H CH
3
H H
C C
H
CH
3
H H n
C C
F F
F F n
C C
H Cl
H H
C C
H Cl
H H
C C
H
Cl
H H n