Wednesday, February 27, 2013

Ionisation energy and electron affinity

Introduction
Ionisation Energy Ionisation energy is one of the important properties of elements . If energy is supplied to an atom , electrons are promoted to higher energy levels . If sufficient energy is supplied , an element in the outer most  shell can be completely removed from the atom , resulting in the formation of a positive ion .

The minimum energy required to remove the most loosely bound electron from an isolated gaseous atom is called ionisation energy . It is also called the first ionisation energy . ( I1 )
      M (g)    +   I1    `|->`   M+ (g)   +  e-

The minimum energy required to remove another electron affinity from the uni positive ion is called second ionisation energy ( I2 ) .
     M (g)    +   I2    `|->`   M2+ (g)   +  e-

The second ionisation energy ( I2 ) is greater than the first ionisation energy  . On removing an electron from an atom , the uni positive ion formed will have more effective nuclear charge than the number of electrons .

This decreases the repulsions between the electrons and increases the nuclear attraction on the electrons . As a result , more energy is required to remove an electron from the uni positive ion . Hence the second ionisation energy ( I2 ) is greater than the ionisation energy ( I1 )  .

Similarly the third ionisation energy ( I3 ) is greater than the second ionisation energy . An atom has as many ionisation energies as the number of electrons present in it . The order of ionization energies
     I1  <   I2   <   I3   <  ........In
where n is the number of electrons in the atoms . Ionisation energies are determined from spectral studies as well as from discharge tube experiments . They are measured in electron volts (eV) atom-1 .
    1 eV   =  1.602 * 10-19 J ,  hence 1 mol of eV has energy  1.602 *10-19 * 6.023*1023
               = 96.45 k j mol-1 .

The discharge tube is filled with gas whose ionisation energy is required . At low voltages , there is no flow of electricity . But , on increasing the voltage between anode and cathode , the gas ionizes at a particular voltage , which is indicated by sudden increase in the flow of electricity . That particular voltage is called ionization energy  .

The magnitude of ionisation of an atom depends on the following factors
  • Atomic radius
  • Nuclear charge
  • Screening or shielding effect on the outer most electrons from the attraction of the nucleus .
  • Completely filled or half filled nature of sub shells .

Ionisation potentials of some elements



Electron Affinity


Electron Affinity
Electron affinity is another important property of elements like ionisation energy is required to remove an electron from an atom . Conversely , when electron is added to an atom , energy is released .

Electron affinity of an element is the energy released when an electron is added to a neutral gaseous atom of that element .
Energy is released when only one electron is added to an  atom forming a uni negative ion . The negative ion prevents entry of further electrons due to repulsive forces between negative charges . Thus energy is needed to overcome these repulsive forces between uni-negative ion ( X- ) and electron ( e- ) and to add one more electron energy is required . Hence , second electron affinity value usually has a positive value .

Electron affinity depend on the size and the effective nuclear charge of atom . They cannot be determined directly , but are obtained indirectly using the Born-Haber cycle . Electron affinity are measured in kj mol-1 .
Halogens have high values for electron affinity due to their small atomic sizes and requirement of only one electron to get the nearest inert gas configuration . Depending on thermodynamic notation that energy liberated is shown by negative sign , the electron affinity values are mentioned with numerals carrying negative sign before them . If energy is absored during the addition of an electron to an atom , then it is shown by  positive sign .

Variation of electron affinity in a group and in a period .

Variation of Electron affinity in a group

From top to bottom as the atomic size increases , the electron affinity decreases , in a period . But the electron affinity of the second element in the group is greater than the first one . For example , in halogens , the electron affinity of fluorine is -333 kj mol-1 while the electron affinity of chlorine is -348 kj mol-1 . It is because fluorine atom is smaller in size than chlorine atom and has strong inter repulsions . During the addition of electrons of fluorine atom the electronic repulsions are overcome at the expense of some liberated energy and hence , the overall energy liberated is less than that of chlorine atom .
Similarly phosphorus has bigger electron affinity value than nitrogen and sulphur has greater electron affinity than oxygen in V and VI groups .

Variation of electron affinity in a period

In a period , as we move from left to right , the atomic size decreases and the nature of the element changes from metallic to non metallic and this results in an increase in the electron affinity values . In a given period halogen has the highest electron affinity . Since the outer shells of zero group elements are filled with electrons to attain octet structure sp2sp6 , they do not accept electron and their electron affinities are treated as zero .

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