ATOMIC STRUCTURE AND THE PERIODIC TABLE Theoretical change with respect to Daltons atomic theory 1.

In 1803, atomic theory was revived by John Dalton a) matter is made up of tiny particles called atoms which cannot be created, destroyed or split b) all atoms of one element are identical:- same mass and same chemical properties c) a chemical reaction consists of rearranging atoms from one combination to another. d) When elements combine to form compounds, small whole numbers of atoms form molecules. However this was proved to be not entirely correct. Atoms have been split as well as created i.e. nuclear reactions. Also there are isotopes, meaning that not all atoms of an element are identical. Therefore theory was forced to CHANGE in regards to these observations contradicting to the theory put forward by Dalton. The distribution of charge and mass in an atom Particle Electron Proton Neutron Location Orbitals Nucleus Nucleus Mass 1/1837 unit 1 unit 1 unit Charge -1 unit +1 unit 0

A unit is one atomic mass unit = 1.67 x 10-27 kg

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Terminology Term Atomic/proton number Nucleon/mass number Nuclide Isotopes Definition Number of protons in a nucleus of an atom Sum of the number of protons and neutrons in the nucleus of an atom Any atomic species of which the proton number and nucleon number are specified e.g. 126C and 94B are nuclides Nuclides of the same element or atoms of the same element with different mass numbers NB isotopes have the same chemical properties but different physical properties Mass of an atom based on a scale such that the C-12 isotope has a mass of 12.00 units relative atomic mass = mass of 1 atom of an element x 12 mass of 1 atom of carbon-12

Relative atomic mass

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Phenomenon of radioactivity Radiation is the spontaneous decay of unstable atoms with the emission of either alpha, beta or gamma radiation. Alpha decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle (two protons and two neutrons bound together into a particle identical to a helium nucleus) and transforms (or 'decays') into an atom with a mass number 4 less and atomic number 2 less. For example: although this is typically written as: Beta decay is a type of radioactive decay in which a fast moving electrons is emitted. The new atom has no change in mass number but an atomic number increases by 1. Gamma rays or gamma-ray (denoted as ) are forms of electromagnetic radiation (EMR) or light emissions of a specific frequency produced from subatomic particle interaction, such as electron-positron annihilation and Most elements have isotopes. For stable radioactive decay. There is no change in atomic or mass number of the atom. isotopes, an interesting plot arises when
the number of neutrons is plotted versus the number of protons.

Band of stability (n/p ratio)

Because the plot shows only the stable isotopes, this graph is often called the Nuclear Belt of Stability. The plot indicates that lighter nuclides (isotopes) are most stable when the neutron/proton ratio is 1/1. This is the case with any nucleus that has up to 20 protons. As the atomic number increases beyond 20, a different trend becomes apparent. In this range, it appears that a stable nucleus is able to accommodate more neutrons. Stable isotopes have a higher neutron to proton ratio, rising to 1.5/1 for elements having atomic numbers between 20 and 83.

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Uses of radioisotopes 1. 3. 5. radiocarbon dating 2. smoke detectors pacemakers 4. medical uses i.e. tracers or chemotherapy irradiation in pest control

Calculations of relative atomic mass from isotopic data Ar of an element = sum of (abundances x mass number of all of the isotopes of an element) e.g. zirconium-90 51.5% zirconium-91 11.2% zirconium-92 17.1% zirconium-94 17.4 % zirconium-96 2.8% Ar zirconium = (51.5 x 90) + (11.2 x 91) + (17.1 x 92) + (17.4 x 94) + (2.8 x 96) = 9131.8 The average mass of these 100 atoms would be 9131.8 / 100 = 91.3 (to 3 significant figures). 91.3 is the relative atomic mass of zirconium.

Evidence of discrete energy levels using emission spectra

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An element's emission spectrum is the relative intensity of electromagnetic radiation of each frequency it emits when it is heated (or more generally when it is excited). When the electrons in the element are excited, they jump to higher energy levels. As the electrons leave the excited state and fall back down, energy is emitted, the wavelength of which refers to the discrete lines of the emission spectrum. If discrete energy levels were NOT present, no lines could EVER be formed in an emission spectrum. e.g. emission spectrum of hydrogen

Emission spectrum of hydrogen When a gaseous hydrogen atom in its ground state is excited by an input of energy, its electron is 'promoted' from the lowest energy level to one of higher energy. The atom does not remain excited but re-emits energy as electromagnetic radiation. This is as a result of an electron 'falling' from a higher energy level to one of lower energy. This electron transition results in the release of a photon from the atom of an amount of energy (E = h) equal to the difference in energy of the electronic energy levels involved in the transition. In a sample of gaseous hydrogen where there are many trillions of atoms all of the possible electron transitions from higher to lower energy levels will take place many times. A prism can now be used to separate the emitted electromagnetic radiation into its component frequencies (wavelengths or energies). These are then represented as spectral lines along an increasing frequency scale to form an atomic emission spectrum.

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Lyman series occurs when electrons drop from higher energy levels to the ground state (n = 1), in this series, the most amount of energy is released and thus the smallest wavelength and highest frequency. In the Balmer series, all electrons drop to the n= 2 level, here energies released are not as high as in the Lyman series. Remember energy is directly proportional to frequency but indirectly proportional to wavelength.
Lyman series occurs when electrons drop from higher energy levels to the ground state (n = 1), in this series, the most amount of energy is released and thus the smallest wavelength and highest frequency. In the Balmer series, all electrons drop to the n= 2 level, here energies released are not as high as in the Lyman series. Remember energy is directly proportional to frequency but indirectly proportional Note that within each series, the spectral lines get closer together with increasing frequency. This suggests that the electronic energy levels get closer the more distant they become from the nucleus of the atom. No two elements have the same atomic emission spectrum; the atomic emission spectrum of an element is like a fingerprint.

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Atomic orbitals Quantum number First principal quantum number (n) Definition This corresponds to the shell number e.g. the 1st shell has n=1, 2nd shell has n=2

1. 2. 3.

Orbital volume of space in which there is a 95% chance of finding an electron Subshell a group of orbitals with the same energy i.e. they are degenerate e.g. 3p subshell which has 3 orbitals of the same energy Shell a group of orbitals and/or subshells with the same principal quantum number. n =1 shell is called the K shell, n=2, the L shell, n=3 the M shell etc. Types of orbitals/subshells present in the shell 1s orbital 2s orbital and 2p subshell (which contain THREE 2p orbitals) 3s orbital, 3p subshell (THREE p orbitals) and 3d subshell (FIVE d orbitals)

Principal quantum number n=1 n=2 n=3

The relative energies of s, p and d orbitals up to principal quantum number 4

Note: The 4s orbital is LOWER than the 3d orbital. Therefore electrons will enter the 4s orbital first before the 3d

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Shapes of atomic orbitals (s orbital and p orbital respectively) Remember for each p subshell, there are 3 p orbitals in x, y and z axis called px, py and pz. They are perpendicular to each other. They are of the same energy level and are called degenerate.

Order of filling electrons in orbitals & sub-shells (electronic configuration) 1s 2s 2p 3s 3p 4s 3d Each orbital can hold only TWO electrons. Electrons entering sub-shells containing 2 or more orbitals enter and occupy the orbitals SINGLY before pairing. An orbital of lower energy must be filled FIRST before electrons enter an orbital of a higher energy level.

Element 1H 2He 3Li 4Be 5B 6C 7N 8O 9F 10Ne 11Na 19K 20Ca

1s 1 2 2 2 2 2 2 2 2 2 2 2 2

2s 1 2 2 2 2 2 2 2 2 2 2

2px

2py

2px

3s

3px

3py

3pz

4s

3d

1 1 1 2 2 2 2 2 2

1 1 1 2 2 2 2 2

1 1 1 2 2 2 2

1 2 2

2 2

2 2

2 2

1 2

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Element 21Sc 22Ti 23V 24Cr* 25Mn 26Fe 27Co 28Ni 29Cu* 30Zn

1s 2 2 2 2 2 2 2 2 2 2

2s 2 2 2 2 2 2 2 2 2 2

2px 2 2 2 2 2 2 2 2 2 2

2py 2 2 2 2 2 2 2 2 2 2

2pz 2 2 2 2 2 2 2 2 2 2

3s 2 2 2 2 2 2 2 2 2 2

3px 2 2 2 2 2 2 2 2 2 2

3py 2 2 2 2 2 2 2 2 2 2

3pz 2 2 2 2 2 2 2 2 2 2

4s 2 2 2 1 2 2 2 2 1 2

3d 1 2 3 5 5 5 7 8 10 10

* Indicates that the electronic configuration is not what is expected . For Cr what would have been expected would be 3d4 4s2, however, half filled and totally filled shells/orbitals are very stable and thus more preferred than any other configuration. Therefore the electrons half fill the 3d subshell with 5 electrons and half fill the 4s orbital with 1 electron. For Cu, what would be expected was 3d9 4s2, again the combination of a totally filled subshell and a half filled orbital is more stable than just a filled orbital and a partly filled subshell. Therefore the electrons adopt the more stable configuration.

Evidence of discrete energy levels using emission spectra

Based on information given above, it is shown that energy occupy different orbitals or even-subshells and in essence occupy discrete energy levels. When elements undergo emission spectroscopy and produce an emission spectrum, a series of lines are shown like the emission spectrum of hydrogen shown below.

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But how are these lines explained and how do they show evidence of discrete energy levels?
When the electrons in the element absorb energy, they move to higher energy levels and are no longer in the ground state (lowest energy state), they are now in an excited state (state of higher energy). As the electrons release the energy absorbed and leave the excited state to return to the ground state, the excess energy is emitted, the wavelength of which refers to the discrete lines of the emission spectrum. If discrete energy levels were NOT present, no lines could EVER be formed in an emission spectrum.

Emission spectrum of hydrogen When a gaseous hydrogen atom in its ground state is excited by an input of energy, its electron is 'promoted' from the lowest energy level to one of higher energy (similar from moving from a lower rung in a ladder to a higher rung). The atom does not remain excited but re-emits the excess energy as electromagnetic radiation. This is as a result of an electron 'falling' from a higher energy level to one of lower energy. This electron transition results in the release of a photon from the atom of an amount of energy (E = hv) equal to the difference in energy of the electronic energy levels involved in the transition. Note E = energy, h = Plancks constant and v = frequency of wavelength of radiation emitted In a sample of gaseous hydrogen where there are many trillions of atoms all of the possible electron transitions from higher to lower energy levels will take place many times. A prism can now be used to separate the emitted electromagnetic radiation into its component frequencies (wavelengths or energies). These are then represented as spectral lines along an increasing frequency scale to form an atomic emission spectrum.

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In each spectra a group of lines are see together which is classified as a series. There are 3 series which are of significance. The Lyman series occurs when electrons drop from higher energy levels to the ground state (n = 1), in this series, the most amount of energy is released and thus the smallest wavelength and highest frequency. This is why Lyman series corresponds to the ultra-violet region (high energy) The Balmer series occurs when electrons drop from higher energy levels to the n = 2 level, here energies released are not as high as in the Lyman series. This corresponds to the visible region of electromagnetic (EM) spectrum. The Paschen series occurs when electrons drop from higher energy levels to the n = 3 level. This corresponds to the infra-red region of electromagnetic (EM) spectrum.

No two elements have the same atomic emission spectrum; the atomic emission spectrum of an element is like a fingerprint. Ionisation energy It can be quoted more accurately as either 1 st, 2nd, 3rd, 4th etc ionisation energy. For our purposes, we will deal with the 1st ionisation energy. The 1st ionisation energy is the energy required to remove a mole of electrons from a mole of gaseous atoms to form a mole of gaseous univalent ions. A (g) A+ (g) + eTrend of 1st ionisation energies Ionisation energies generally increase going across a period Remember two factors must be considered: (1) proton number increases sequentially going across a period i.e. greater nuclear attraction for the outermost electron(s) and (2) number of electrons are also increasing. Although the addition of electrons into the shell causes repulsion and thus would increase the atomic radius, the predominant factor is the increased effective nuclear charge (which is the residual attraction of the nucleus and the outermost electron(s) after shielding of the inner electrons) i.e. more energy would be needed to remove the outermost electron(s). Thus ionisation energy increases from left to right of a period

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Ionisation energies decreases going down a group Although nuclear charge increases, the dominant factor is the increasing number of shells between the nucleus and the outermost electron(s). This results in increased shielding of the nuclear charge, therefore less attraction of the nucleus and the outermost electron(s) i.e. less energy needed to remove an outermost electron. Thus ionisation energy decreases down a group. Atypical behaviour seen in period 3 for Mg & Al AND P & S (period 3) In period 3, Mg has E.C. of [Ne] 3s2, while Al has E.C. of [Ne] 3s2 3px1, in Al the outermost electron (3p) is at a higher energy level than the outermost electron in Mg (3s), therefore less energy is needed to remove it. Or using a different explanation, the valence electron in Al experiences more shielding i.e. less nuclear attraction than one of the valence electrons in Mg i.e. less energy needed to remove it from Al than for Mg. In period 3 for P and S, the explanation needed is somewhat different. For P, the E.C. is [Ne] 3s2 3p3, while for S the E.C. is [Ne] 3s2 3p4. In the 3p subshell of P, the half-filled subshell represents a very stable configuration since it represents a system of minimum repulsion as each electron occupies one orbital singly. A lot of energy would be needed to disrupt this configuration. While in S, 3p subshell experiences electron-electron repulsion in one of its orbital which raises the energy of the system, therefore it is LESS stable and LESS energy would be needed to remove one of the valence electrons.

Below is a diagram for the 1st ionisation energy of period 3 elements. Note the circles show the areas of atypical behaviour

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Evidence of sub-shells using ionization data The graph below shows the successive ionization energies for an atom of sodium:

The electronic structure for sodium is 1s2 2s2 2p6 3s1. The energy required to remove the first electron is relatively low. This corresponds to the loss of one 3s electron. To remove the second electron needs a much greater energy because this electron is closer to the nucleus in a 2p orbital. There is a steady increase in energy required as electrons are removed from 2p and then 2s orbitals. The removal of the tenth and eleventh electrons requires much greater amounts of energy, because these electrons are closer to the nucleus in the 1s orbital. Large jumps in energy shown by the circles, indicate moving from one principal quantum number to another. The smaller, more gradual increases indicate going moving within subshells as the energies of the electrons will slowly decrease resulting in more and more energy needed to remove them.

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How to derive group number of an element from successive ionization energies A large jump (usually an increase of 3 or more times the amount) between two successive ionisation energies is typical of suddenly breaking in to an inner level. You can use this to work out which group of the Periodic Table an element is in from its successive ionisation energies. Example 1 Magnesium (1s22s22p63s2) is shown with the following successive ionisation energies:

Here the big jump occurs after the second ionisation energy. It means that there are 2 electrons which are relatively easy to remove (the 3s2 electrons), while the third one is much more difficult (because it comes from an inner level - closer to the nucleus and with less screening). Mg is therefore in group II Example 2 Silicon (1s22s22p63s23px13py1) is shown with the following successive ionisation energies:

Here the big jump comes after the fourth electron has been removed. The first 4 electrons are coming from the 3rd shell orbitals; the fifth from. Silicon is therefore in group IV To try on your own Decide which group an atom is in if it has the following successive ionisation energies:

END OF ATOMIC STRUCTURE

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Worksheet 1.
Write the electronic configurations of the following atoms or ions a) 20Ca.. b) 7N3-.. c) 26Fe2+.. d)29Cu.. 2.

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3.

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 .. .. . . . . .. .. . . . . .. .. . . . . Atomic Structure page 19 of 20

.. .. . . . . .. .. . .

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