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If an electron obtains enough energy it jumps beyond the highest energy level and becomes a free
electron: the atom itself becomes a positive ion.
This electron transition is represented as follows: n = 1 to n = . Notation n = refers to the world
outside the atom beyond the control of the nucleus; any electron outside an atom has no potential
energy (energy = 0).
With hydrogen the ionization energy can be calculated from the frequency at the point in the emission
spectrum where the lines in the Lyman series converge. (see extension in topic 2 notes)
the minimum energy needed to remove one (first/highest energy level)/most loosely held electron
electron from 1 mole of gaseous (or free/by itself) atoms to make a gaseous cations;
X (g) X+ (g) + e-
the more strongly the electron is attracted to the nucleus, the greater the amount of energy
needed
ionization energy is usually measured in kilojoules per mole Kj mol-1 of atoms;
ionization energies are positive values (endothermic process) as energy is needed to remove an
electron.
energy needed to remove second, third,... electrons from 1 mole of gaseous ions, e.g.
the lower the energy level an electron is on, the closer it is to the nucleus, the more strongly it is
attracted, the more energy is needed;
in the same atom, successive ionization energies increase as a result of a combination of the
following factors:
the electron-electron repulsion decreases (this repulsion puts electrons onto higher energy
levels) and this increases the attraction from the nucleus, but also because
the first electron is removed from an atom whilst the second and successive electrons are
removed from ions with an increasing positive charge !!!!
nucleus has greater effect on smaller number of electrons and they are held more tightly
These ionization energies provide evidence on how an atom is structured and on the number of
electrons on the energy levels.
12.1.2 Explain how successive ionization energy data is related to the electron configuration of an atom.
All the successive ionization energies for the same element can be shown on a graph of successive
ionization energies against electrons removed.
.
Notice that the scale for ionization energies is a logarithm scale so that the large differences between
the ionization energies can be shown onto the same graph.
Observations: Explanation:
1 electron has a much smaller ionization This electron must be on a much higher energy
energy than the rest which means it needs a lot level than the rest; most of the time it is the furthest
less energy for the electrons to escape to n = away from the nucleus and held less strongly.
.
8 electrons require a lot more energy than the there are 8 electrons in the same lower energy level
2 electrons at the higher energy levels closer to the nucleus.
2 electrons need an even higher amount of there are 2 electrons on an even lower energy level;
ionization energy most of the time they are closer to the nucleus than
the other electrons and are held very tightly.
Sketch graphs showing successive ionization energies for Mg, Cl, F, Al.
1 2 3 4 5 6 7 8
H 1312
He 2372 5250
Li 520 7297 11810
Be 899 1757 14845 21000
B 800 2426 3659 25020 32820
C 1086 2352 4619 6221 37820 47260
N 1402 2855 4576 7473 9442 53250 64340
O 1314 3388 5296 7467 10987 13320 71320 84070
F 1680 3375 6045 8408 11020 15160 17860 92010
Ne 2080 3963 6130 9361 12180 15240
Na 496 4563 6913 9541 13350 16600 20113 25666
Mg 737 1450 7731 10545 13627 17995 21700 25662
12.3 First ionization energies: evidence for main energy levels and sub-levels
12.1.1 Explain how evidence from first ionization energies across periods accounts for the existence of main
energy levels and sub-levels in atoms.
He; 2370
Ne; 2080
Ionisation energy (kJ/mol)
F; 1680
Kr; 1350
H; 1310 O; 1310
Cl; 1260
Br; 1140
C; 1090 Si; 1000
P; 1060 As; 966
Be; 900
Se; 941
Be; 799 Zn; 908
Fe; Co;
762Ni;
757736
Mn; 716
Mg; 736 Ti; 661
V; 648 Ge; 762
Si; 786 Sc; 632
Ca; 590 Cu; 745Ga; 577
Al; 577 Cr; 653
Li; 519 Na; 494
K; 418
There are 6 elements between Be and Ne The second level in this main energy level can hold 6
(Ne including) after which there is again a electrons
great decrease
A decrease from N to O (also P to S) Existence of sub-level:
The electron arrangement ensures that the most outer
electron in oxygen is at a higher energy level than the
most outer electron in nitrogen. This is the case
because the electron removed in O is a paired electron
(two electrons in same orbital) and this causes greater
repulsion and less attraction.
Ar - Ca: 2 points = filling up of a sub-level with room for two electrons (4s)
Sc - Zn: 10 points = filling up of sub-level with room for ten electrons (3d)
Ga - Kr: 6 points = filling up of a sub-level with room for 6 electrons (4p)
12.1.3 State the relative energies of s, p, d and f orbitals in a single energy level.
relative energies: s p d f
This makes sense as an s electron tends to be on average more closely to the nucleus than electrons
on any of the other sub-levels. Remember that the more closely to the nucleus the more strongly an
electron is attracted, the lower its energy!
12. 5. Orbitals
Bohrs model was unable to explain the emission spectra of more complex elements so a new way of
thinking was needed.
This new thinking was based on the Heisenberg Uncertainty Principle which states that it is impossible
to pinpoint accurately both the position and the momentum of a small particle like an electron.
In simpler language, this means we can never be certain of where exactly an electron is in an atom.
To deal with this new idea, the concept of atomic orbitals was introduced.
An atomic orbital refers to a volume of space around the nucleus in which there is a high probability
(90%) (not an absolute certainty) of finding an electron of a given energy.
An orbital therefore is an area of high electron density; it is an electron charge cloud which can be
occupied by a maximum of two electrons. Atomic orbitals can have different shapes; the shape
depends on the electron distribution.
Orbitals in the same sub-level are equivalent in energy and are called degenerate orbitals.
The orbital in the s-subshell has a spherical symmetrical shape: probability of finding electron is the
same in all directions. The 3 orbitals in the p-subshell have an hourglass shape; the three orbitals are
labeled px, py and pz.
Just like the main energy levels which have been given numbers; each orbital is also given a number
depending on the main energy level it is in and its shape g 1s, 2p, 3d, 4f and so on. The larger the
principal quantum number, the larger the orbital.
s (2) 1 spherical
n=2 8
p (6) 3 hourglass
s (2) 1 spherical
n=3 p (6) 3 hourglass
18
d (10) 5 lobes
s (2) 1 spherical
p (6) 3 hourglass
n=4
d (10) 5 lobes 32
f (14) 7 lobes
http://en.wikipedia.org/wiki/Atomic_orbital
http://www.chemistry.wustl.edu/~edudev/Orbitals/movie.html
www.shef.ac.uk/chemistry/orbitron/AOs/ (best one)
12.1.6 Apply the Aufbau principle, Hunds rule and the Pauli exclusion principle to write electron configurations
for
atoms and ions up to Z = 54.
Electrons spin on their own axis which can be clockwise or anticlockwise, relative to the orbital of the
electron. Whenever a charge spins it produces a magnetic field; as a result electrons have their own
magnetic fields and they acts as magnets. The direction of the magnetic field of an electron depends
on the direction of its spin. Depending on their spin, two electrons either attract (both have opposite
spin) or repel (have same spin) each other.
Any repulsion between its electrons always increases the potential energy of an atom.
The greater the potential energy, the more unstable an atom becomes so electrons in atoms always
adopt the lowest possible energy configuration which is referred to as the ground state.
To determine the electron arrangement which achieves the lowest possible energy we need to
apply 3 principles which are described below:
When filling sub-levels with electrons, we start with the lowest level, 1s. Each sub-level is filled before
starting to fill the sub-level of the next highest energy.
Remember that two electrons can occupy the same atomic orbital but they can only do so if they have
opposite or paired spins as this reduces the repulsion between them and therefore the total amount of
potential energy in the atom.
The Pauli Exclusion Principle states that an atomic orbital can only hold two electrons if they have an
opposite spin (no repulsion caused by opposite magnetic spin of each electron).
Topic12atomicstructure 3 hours Page 6 of 17
Evidence for Pauli Principle includes the study of the magnetic effect of atoms; for instance consider
the helium atom which could have two possible electronic configurations:
in this case the magnetic effect of each electron is cancelled out; the atom is
diamagnetic and should only be slightly repelled by a magnet; or
in this case the magnetic fields of each electron reinforce each other making the atom
paramagnetic and which would cause it to be attracted by a magnet (strength of
paramagnetism indicates number of unpaired electrons);
The experimental evidence shows that a magnet has very little effect on the helium atom suggesting
that is diamagnetic and that electrons cancel out magnetic fields.
3. Hunds rule
When filling up a sub-level with 3 or more atomic orbitals, the favoured arrangement is where electrons
occupy different atomic orbitals and have the same spin (or electrons prefer to have parallel spins
which is only possible - as a result of Paulis exclusion principle - if they go into a different orbital of the
same sub-level ) (or in a sub-level with more than one orbital the electrons are spread out over these
degenerate sub-levels with their spins in the same direction).
Exercise
Draw electron-in-the boxes and show the electron configuration for the following species: B, F, Al, K,
K+, Cl-, O2-, Al3+, H-, S2-, Mg2+.
1. Electrons always fill from the lowest energy level upwards so that their total energy is kept at a
minimum. Called the Aufbau principle.
2. When one energy level is full the electrons start filling up the next highest energy level.
3. Electrons fill up the orbital in pairs. Each electron in the pair spin in opposite directions to one
another (represented by ). In the p and d orbitals the electrons fill up singularly first and then
as pairs. Called Hunds rule.
4. It is impossible for two electrons with the same spin to be in the same orbital and an orbital can
only hold a maximum of two electrons. Called the Pauli Exclusion principle.
number of electrons
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 etc
energy
level
orbital
Topic12atomicstructure 3 hours Page 7 of 17
A short hand version can be used for more than 20 electrons by using an argon, Ar core (18
electrons.
e.g. for titanium with 22 electrons the electron configuration is 1s2 2s2 2p6 3s2 3p6 4s2 3d2 or
Ar 4s2 3d2
6. The 4s orbital is lower in energy than the 3d orbital and so the 4s orbital will be filled before the
3d.
You would expect its electron configuration to be Ar 4s2 3d4 (4s __ 3d __ __ __ __ __)
This is because the energy of the 4s and 3d orbital are very similar and they almost act as one
orbital. filled orbitals or completely full orbitals are more stable than a mixture of partially
filled orbitals so the most stable configuration is Ar 4s1 3d5.
You would expect its electron configuration to be Ar 4s2 3d9 (4s __ 3d __ __ __ __ __)
Here a full 3d orbital and a filled 4s orbital is more stable than a partially filled 3d orbital.
A. 5 B. 7 C. 17 D. 23
A. Yttrium, Y, (Z = 39) is the first element in the periodic table with an electron in a f sub-level.
B. The maximum number of electrons in one d orbital is 10.
C. The maximum number of electrons in the 4th main energy level is 18.
D. In a main energy level, the sub-level with the highest energy is labeled f.
6. (N01) In which of the following ground-state electron configurations are unpaired electrons
present?
I. 1s2 2s2 2p2 II. 1s2 2s2 2p3 III. 1s2 2s2 2p4
7. (N01) Which atom or ion has the electron configuration 1s2 2s2 2p6 3s2 3p6 3d7 ?
A. Co B. Mn C. Co 2+ D. Fe3+
8. (N02) A transition metal ion X3+ has the electronic configuration [Ar] 3d4 . What is the atomic
number of element X?
A. 22 B. 24 C. 25 D. 27
9. (N02) Which of the following electronic configurations gives rise to the largest increase between
the second and third ionization energies?
10. (M99) Using the Aufbau Principle, deduce which element below has the greatest number of
unpaired electrons in its ground state.
A. Z = 13 B. Z= 14 C. Z = 15 D. Z = 16
11. (M99) Values for the first ionization energies (IE) for five successive elements in the Periodic
Table are given below. Based on these values, which statement is correct?
Element K L M N O P
A. the outermost electron in element K is in a higher energy level than that in element L
B. element M is probably a metal
C. element N is probably a non-metal
D. element P has a lower first ionization than element O
12. (specpap) An atom of which element in its ground state will have the largest number of unpaired
electrons?
A. Si B. P C. S D. Cl
13. (M00) The first 4 ionization energies (kJ mol-1 ) for a particular element are 550, 1064, 4210 and
5500 respectively. This element should be placed in the same group as
A. Li B. Be C. B D. C
14. (N98) Which ionization energy requires the greatest amount of energy?
15. (M98) All of the following effect the value of the ionization energy of an atom except the
16. (N00) A solid element, X, contains unpaired electrons in its atoms and forms an ionic chloride,
XCl2. Which electron configuration is possible for element X?
A. [Ne] 3s2 B. [Ar] 3d2 4s2 C. [He] 2s2 2p2 D. [Ne] 3s2 3p4
PAPER 2
1. (N05) A sample of germanium is analyzed in a mass spectrometer. The first and last
processes in mass spectrometry are vaporization and detection.
(a) (i) State the names of the other three processes in the order in which they occur in a
mass spectrometer. [2]
(ii) For each of the processes named in (a) (i), outline how the process occurs. [3]
(ii) Calculate the relative atomic mass of this sample of germanium, giving your answer to
two decimal places. [2]
Topic12atomicstructure 3 hours Page 10 of 17
(c) Use the Aufbau principle to write the electron configuration of an atom of germanium. [1]
(d) The successive ionization energies of germanium are shown in the following table:
(i) Identify the sub-level from which the electron is removed when the first ionization
energy of germanium is measured. [1]
(ii) Write an equation, including state symbols, for the process occurring when measuring
the second ionization energy of germanium. [1]
(iii) Explain why the difference between the 4th and 5th ionization energies is much greater than
the difference between any two other successive values. [2]
2. (N06) Some vaporized magnesium is introduced into a mass spectrometer. One of the ions that
reaches the detector is 25Mg+
(a) Identify the number of protons, neutrons and electrons in the 25Mg+ion. [1]
(b) State how this ion is accelerated in the mass spectrometer. [1]
(c) The 25Mg 2+ion is also detected in this mass spectrometer by changing the magnetic field.
Deduce and explain, by reference to the m/z values of these two ions of magnesium,
which of the ions 25Mg+ and 25Mg 2+ is detected using a stronger magnetic field. [2]
3. (N01)
(a) The isotopes of sulfur occur naturally in the following percentages:
(i) Calculate the relative atomic mass of sulfur to three significant figures. [2]
(ii) Determine the number of neutrons in the atom of the least abundant sulfur isotope. [1]
(b) (i) Describe how the first four ionization energies of aluminium vary. (You may wish to
sketch a graph to illustrate your answer.) [2]
(ii) State the electronic configurations of aluminium, boron and magnesium. Explain how
the first ionization energy of aluminium compares with the first ionization energies of
boron and magnesium. [5]
(c) When hydrogen gas is placed in an electric discharge tube, an emission spectrum is obtained.
Sketch the spectrum, labeling its high energy end. Explain why such a spectrum is obtained. [3]
4. (N98) The successive ionization energies for boron are given below in kJ mol-1.
(a) Explain the reason why there is a large increase between the third and fourth values.
(c) State, with reasons, how the value for the second ionization energy of carbon would
compare with that of the second ionization energy of boron. [6]
5. (M99) Use the modern theory of the atom to answer each of the following.
(a) List the d, f, p and s orbitals in order of increasing relative energy. [2]
(b) Give the number of each type of orbital, d, f, p and s ate ach energy level. [2]
(c) Describe the changes which occur when hydrogen produces a line spectrum. [2]
(d) Explain why the electron configuration of the nitrogen atom is written as N:
1s22s22p12p12p1 rather than 1s22s22p22p12p0. Write the electron configuration of titanium.
[3]
(e) (i) name the instrument used to determine the atomic masses of the two naturally
occurring isotopes of gallium. Briefly describe each step involved in the operation of the
instrument. [3]
(ii) A certain sample of gallium contains 60% Ga-69 and 40% Ga-71. Give the nuclear
structures of these isotopes and calculate the relative atomic mass of gallium in this
sample.
(f) Explain the difference in the two values of ionization energy for each of the following
pairs: [6]
i. The 1st ionization energy of beryllium is 900 kJ mol-1 whereas the 2n ionization energy of
beryllium is 1757 kJ mol-1.
ii. The 1st ionization energy of aluminium is 577 kJ mol-1 whereas the 1st ionization energy
of magnesium is 736 kJ mol-1.
iii. The 1st ionization energy of aluminium is 577 kj mol-1 whereas the 1st ionization energy
of boron is 799 kJ mol-1.
Paper 1
1 B 7 C 13 B 19 25
2 B 8 D 14 B 20 26
3 D 9 A 15 A 21 27
4 B 10 C 16 B 22 28
5 C 11 C 17 23 29
6 D 12 B 18 24 30
Paper 2.
1. (N05)
3. (N01)