Atomic Structure

Details of the three Sub-atomic (fundamental) Particles

Particle Proton Neutron Electron Position Nucleus Nucleus Orbitals Relative Mass 1 1 1/1800 Relative Charge +1 0 -1 There are various models for atomic structure

An atom of Lithium (Li) can be represented as follows:

Mass Number Atomic Number

7 3

Li

Atomic Symbol

The atomic number, Z, is the number of protons in the nucleus. The mass number ,A, is the total number of protons and neutrons in the atom.

Number of neutrons = A - Z

Isotopes

Isotopes are atoms with the same number of protons, but different numbers of neutrons.

Isotopes have similar chemical properties because they have the same electronic structure. They may have slightly varying physical properties because they have different masses.

THE MASS SPECTROMETER

Electric field accelerates the ions Electrons ionise the sample Vaporised sample magnetic field defects the ions /ath of heavier ion Vacuum pump The mass spectrometer can be used to determine all the isotopes present in a sample of an element and to therefore identify elements.

/ath of lighter ion detector

It needs to be under a vacuum otherwise air particles would ionise and register on the detector

The following are the essential 4 steps in a mass spectrometer. 1.Ionisation A Vaporised sample is in ected at low pressure An electron gun fires high energy electrons at the sample This !noc"s out an #outer$ electron %orming positive ions with different charges E.g. Ti Ti& & e' 2. Acceleration A negative electric field accelerates the positive ions and ma"es them into a beam 3. Deflection The beam of positive ions is deflected by a strong magnetic field. The degree of deflection depends on the mass(to(charge ratio, m)*. The smaller this ratio the larger the deflection. +y varying the magnetic field ratio, ions of different m)* ratios pass through the centre.

,earn all these steps carefullyIf the sample is not vapori*ed then vapori*ing it would be the first step.

The heavier an ion the less it is deflected

. Detection The ions reach the detector and generate a small current, which is fed to a computer for analysis. The si*e of the current is proportional to the abundance of the species

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The relative atomic mass 2uoted on the periodic table is a weighted average of all the isotopes .66 76 8 abundance 46 46
25Mg+ 26Mg+

97.968
24Mg+

%ig; spectra for <agnesium from mass spectrometer %or each isotope the mass spectrometer can measure a m!" #mass!c$ar%e ratio& and an abun'ance .6..:8 If as"ed to give the species for a pea" in a mass spectrum then give charge and mass number e.g. 34<g&
Eometimes two electrons may be removed from a particle forming a 3& ion. 34<g3& with a 3& charge would have a m)* of .3

36 34

....98 34 m)*

35

R.A.M = (isotopic mass x % abundance) 100

%or above e?ample of <g >.A.< @ A#97.9 ? 34$ & #.6..: ? 35$ & #....9 ? 34$B ).66 @ 34.: R.A.M = (isotopic mass x relative abundance) total relative abundance

=se these e2uations to wor" out the >.A.< If relative abundance is used instead of percentage abundance use this e2uation

Mass s(ectra for Cl2 an' )r2

Cl has two isotopes Cl:5 #958$ and Cl:9#358$ +r has two isotopes +r9D #568$ and +r7.#568$ +r9D+r7. & +r7.+r9D & Cl:5Cl:5 &
relative abundance

These lead to the following spectra caused by the diatomic molecules

Cl:5Cl:9 & Cl:9Cl:9 & 96 93 94 m)*

relative abundance

+r9D+r9D &

+r7.+r7. &

.57

.46

.43

m)*

<ass spectrometers have been included in planetary space probes so that elements on other planets can be identified. Elements on other planets can have a different composition of isotopes

Measurin% t$e Mr of a molecule

If a molecule is put through a mass spectrometer it will often brea" up and give a series of pea"s caused by the fragments. The pea" with the largest m)*, however, will be due to the complete molecule and will be e2ual to the <r of the molecule. This pea" is called the parent ion or molecular ion

S(ectra for C H1* Mass spectrum for butane 43 <olecular ion C H1*+

29 58

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Electronic Structure
<odels of the atom
An early model of the atom was the +ohr model #1CEE model$ #3 electrons in first shell, 7 in second etc.$ with electrons in spherical orbits. Early models of atomic structure predicted that atoms and ions with noble gas electron arrangements should be stable.

T$e A,le-el mo'el

Electrons are arranged on;
/rinciple energy levels numbered .,3,:,4.. . is closest to nucleus
Eplit into Eub energy levels labelled s , p, d and f s holds up to 3 electrons ( holds up to 4 electrons ' holds up to .6 electrons f holds up to .4 electrons

Eplit into

Frbitals which hold up to 3 electrons of opposite spin

S$a(es of orbitals
/rinciple level Eub(level .s . 3 3s, 3p : :s, :p, :d 4
4s, 4p, 4d, 4f Frbitals represent the mathematical probabilities of finding an electron at any point within certain spatial distributions around the nucleus. Each orbital has its own appro?imate, three dimensional shape. It is not possible to draw the shape of orbitals precisely.

An atom fills up the sub shells in order of increasing energy #note :d is higher in energy than 4s and so gets filled after the 4s .s 3s 3p :s :p 4s :d 4p 5s 4d 5p

Writing electronic structure using letters and numbers

Number of electrons in sub-level

s sublevels are spherical

For oxygen 1s2 2s2 2p4

Number of main energy level Name of type of sub-level

p sublevels are shaped like dumbbells

Using spin diagrams

%or fluorine

2p
2s 1s

An arrow is one electron Box represents one orbital

The arrows going in the opposite direction represents the different spins of the electrons in the orbital

The periodic table is split into blocks. A s block element is one whose outer electron is filling a s-sub shell

Ghen filling up sub levels with several orbitals, fill each orbital singly before starting to pair up the electrons

2p
Electronic structure for ions Ghen a positive ion is formed electrons are lost <g is .s3 3s3 3p4 :s3 but <g3& is .s3 3s3 3p4 Ghen a negative ion is formed electrons are gained F is .s3 3s3 3p4 but F3( is .s3 3s3 3p4

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Ionisation Ener%ies
Hefinition ;%irst ionisation energy
The first ionisation energy is the enthalpy change when one mole of gaseous atoms forms one mole of gaseous ions with a single positive charge This is represented by the equation:
>emember these definitions very carefully The e2uation for .st ionisation energy always follows the same pattern. It does not matter if the atom does not normally form a &. ion or is not gaseous

H(g)

H+

(g)

e-

Always gaseous

Hefinition ;Eecond ionisation energy

The second ionisation energy is the enthalpy change when one mole of gaseous ions with a single positive charge forms one mole of gaseous ions with a double positive charge This is represented by the equation:

Ti& #g)

Ti3&#g) & e(

.actors t$at affect Ionisation ener%/

There are three main factors ..The attraction of the nucleus #The more protons in the nucleus the greater the attraction$ 3. The distance of the electrons from the nucleus #The bigger the atom the further the outer electrons are from the nucleus and the wea"er the attraction to the nucleus$ :. Ehielding of the attraction of the nucleus #An electron in an outer shell is repelled by electrons in complete inner shells, wea"ening the attraction of the nucleus$

<any 2uestions can be answered by application of these factors

Successi-e ionisation ener%ies

The patterns in successive ionisation energies for an element give us important information about the electronic structure for that element. 1$/ are successi-e ionisation ener%ies al2a/s lar%er3 The second ionisation energy of an element is always bigger than the first ionisation energy. Ghen the first electron is removed a positive ion is formed. The ion increases the attraction on the remaining electrons and so the energy re2uired to remove the ne?t electron is larger. Ho2 are ionisation ener%ies lin4e' to electronic structure3
Ionisation energy

0otice the big ump between 4 and 5.

. 3 : 4 5 0o of electrons removed 4

E0(lanation The fifth electron is in a inner shell closer to the nucleus and therefore attracted much more strongly by the nucleus than the fourth electron. It also does not have any shielding by inner complete shells of electron

E?ample; Ghat group must this element be inK

1 Ionisation energy "I mol(. 5D6 2 ..56 3 4D46 4476 5 7.36

Jere there is a big ump between the 3nd and :rd ionisations energies which means that this element must be in group 3 of the periodic table as the :rd electron is removed from an electron shell closer to the nucleus with less shielding and so has a larger ionisation energy

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The first Ionisation energy of the elements

Ionisation energy kJ mol-1 The shape of the graph for periods two and three is similar. A repeating pattern across a period is called periodicity. The pattern in the first ionisation energy gives us useful information about electronic structure You need to carefully learn the patterns
5

2000 1500 1000

500 0

Atomic number

10

15

20

Q. Why has Helium the largest first ionisation energy? A. Its first electron is in the first shell closest to the nucleus and has no shielding effects from inner shells. He has a bigger first ionisation energy than H as it has one more proton Q. Why do first ionisation energies decrease down a group? A. As one goes down a group, the outer electrons are found in shells further from the nucleus and are more shielded so the attraction of the nucleus becomes smaller Q. Why is there a general increase in first ionisation energy across a period? A. As one goes across a period the electrons are being added to the same shell which has the same distance from the nucleus and same shielding effect. The number of protons increases, however, making the effective attraction of the nucleus greater. Q. Why has Na a much lower first ionisation energy than Neon? This is because Na will have its outer electron in a 3s shell further from the nucleus and is more shielded. So Nas outer electron is easier to remove and has a lower ionisation energy. Q. Why is there a small drop from Mg to Al? Al is starting to fill a 3p sub shell, whereas Mg has its outer electrons in the 3s sub shell. The electrons in the 3p subshell are slightly easier to remove because the 3p electrons are higher in energy and are also slightly shielded by the 3s electrons Q. Why is there a small drop from P to S? With sulphur there are 4 electrons in the 3p sub shell and the 4th is starting to doubly fill the first 3p orbital. When the second electron is added to a 3p orbital there is a slight repulsion between the two negatively charged electrons which makes the second electron easier to remove. Learn carefully the explanations for these two small drops as they are different to the usual factors Many questions can be answered by application of the 3 factors that control ionisation energy

3p

3p 3s
Two electrons of opposite spin in the same orbital sulphur 1s2 2s2 2p63s23p4

3s

phosphorus 1s2 2s2 2p63s23p3

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