Unit 2-1

Unit 2

The Electronic Structure of Atoms and the Periodic Table

Atomic Emission Spectrum

Section 2.1
(1)

Energy associated with light

Light is a form of energy. It has dual properties : wave property and particle property.

1.Wave property Light is an electromagnetic wave. It travels with velocity c ( c = 3.00 x 108 m s-1 ). and the wavelength of the wave are related by :

The frequency

That which we call visible light is an electromagnetic wave of wavelength 400 to 700 nm (1 nm = 10-9 m ). It is a very narrow component of a large group of radiation types comprising the electromagnetic spectrum which includes radio waves, microwaves, infra-red, visible light, ultraviolet, X-rays, gamma rays and cosmic rays.

2. Particle property Light consists of discrete particles. Each discrete particle is an energy packet called photon. The energy of a photon depends on the frequency of light wave and is gives by the famous Plancks equation :

The proportionality constant h is called the Plancks constant which is equal to 6.63 x 10-34 J s. The greater the frequency the light, the shorter the wavelength, and the greater the energy of a photon. Example: Calculate the energy of 1 mole of photons with wavelength 650 nm.

Unit 2-2

(2)

The uniqueness of atomic emission spectra

Some gaseous materials emit light when they are subject to large potential differences in electric discharge tubes. Neon advertising signs work in this way and the yellow sodium street lamps are discharge tubes containing sodium vapour. If the light emitted by these substances is examined using a spectroscope, it is found not to consist of a continuous range of colours like the spectrum of white light or the colours in a rainbow. Instead, the light emitted by these substances is composed of separate lines of different colour. This kind of spectrum is called a line emission spectrum.

The atoms of each element have a unique arrangement of electrons with definite energy levels. When the atoms are excited, electrons are brought to higher energy levels. As the electrons return to lower energy levels, the atom emits radiations of definite wavelengths. This results in a unique emission spectrum which can provide useful information about the atom. The atomic emission spectra of sodium and hydrogen shown below illustrate the unique nature of the spectra. Each element has its own pattern of lines in its emission spectrum.

Unit 2-3

( 3 ) Characteristics of the atomic emission spectrum of hydrogen

When a sample of hydrogen gas is heated to a high temperature or when an electric discharge is passed through it at low pressure, the hydrogen molecules absorb energy and split into atoms. The excited hydrogen atoms contain excess energy and are unstable. Their electrons are promoted from the ground state to a higher energy level. When the excited electrons lose energy and fall back to the ground state, light of various wavelengths will be emitted to produce the atomic emission spectrum of hydrogen.

The atomic emission spectrum of hydrogen consists of coloured bright lines in dark background. The spectrum consists of several series of discrete lines which converge in different parts of the electromagnetic spectrum : Lyman series in the ultraviolet region, Balmer series in the visible region, Paschen series in the infrared region, and Brackett and Pfund series in the far infrared region.

Within each series, the lines get closer together and converge towards high frequency end of the spectrum. Finally, the lines merge into a continuum of light (light of the highest frequency). This is the convergence limits. The following figure shows the Balmer series of hydrogen :

Unit 2-4

( 4 ) Interpretation of the atomic emission spectrum of hydrogen

1. Bohrs model of hydrogen atom In 1913, Neils Bohr suggested the model of hydrogen atom with reference to quantum theory : The lowest energy state, when the hydrogen atom has least energy, is called the ground state. Hydrogen atoms with more energy than they possess in ground state are said to be excited. When a hydrogen atom is excited, the electron temporarily occupies an energy level further from the nucleus. As an electron falls back to a lower energy level, a discrete amount of energy is emitted as radiation. This produces a line in the atomic spectrum. Energy level is quantised according to quantum theory. The electrons can only exit in certain fixed energy levels. It cannot possess energy of intermediate magnitudes. When hydrogen atoms absorb or emit energy, electrons move from one energy level to another. Only transitions from one level to another are possible. Transitions of intermediate energy are not allowed. The energy of an electron can only be lost or gained in small packets called quanta. The amount of energy involved is exactly equal to a photon (a quantum of energy = h).

2. Plancks relationship The energy of transition can be calculated from the difference in energy between two energy levels. If the frequency of light emitted is , the difference between two energy levels is related by Plancks equation : Einitial Efinal ( E ) = quantum of energy = frequency of light (Hz, s-1) h = 6.63 x 10-34 J s (Plancks constant) c = 3.00 x 108 m s-1 (velocity of light) = wavelength of light (m)

Where

E is proportional to the frequency of radiation and is inversely proportional to wavelength. When an electron falls from a higher energy level to a lower energy level, it emits a quantum of energy E in radiation of definite frequency, . Since E for the change is always the same in a given atom, must be a constant. Therefore, radiation always has the same energy and is always of the same frequency for this particular electron transition. The atomic emission spectrum consists of discrete lines, i.e. discontinuous.

Unit 2-5

3. Balmer series The following figure shows the energy levels in a hydrogen atom and the electron transitions which produce the lines in the visible region of the atomic emission spectrum of hydrogen :

Note that : a. The electronic energy levels are numbered (n = 1, n = 2, n = 3, etc.). These numbers are sometimes referred to as the principal quantum numbers for the energy levels. The level of lowest energy is given the principal quantum number 1, the next lowest 2, and so on. b. The coloured lines in the Balmer series are caused by electron transitions from the higher level to the level n = 2. For example, transitions from n = 3 to n = 2 result in a red line (at frequency 4.568 x 1014 Hz) in the hydrogen spectrum, while transitions from n = 4 to n = 2 produce a blue line. Question : Calculate the difference in energy between energy levels of n = 3 and n = 2.

c. As the energy levels get closer and eventually come together, it follows that the spectral lines also get closer and eventually come together. This particular frequency is called the convergence limit.

Unit 2-6

4. Lyman Series, Paschen series, Brackett series and Pfund series When transition occur from the higher levels to the lowest energy level ( n = 1 ), more energy is released than with transitions to the n = 2 level. Consequently, these lines appear at higher frequencies in the spectrum. In the case of hydrogen, transitions to the n = 1 level result in lines in the ultraviolet region of the spectrum and is known as the Lyman series. Similarly, electron falls back to the third, fourth, and fifth energy levels gives the Paschen, Brackett, and Pfund series respectively.

The wavelengths and frequencies of the discrete lines of the various series was found by Rydberg experimentally to obey the following relationship : where RH = 1.0968 x 107 m-1. Spectral series Lyman Balmer Paschen Brackett Pfund Final energy level (n1) Initial energy level (n2)

5. Intensity of the spectral lines The spectral lines in the atomic emission spectrum of hydrogen are not of equal intensity because the intensity of a particular spectral line depends on the number of electrons making the electronic transition corresponding to a particular frequency. It is unlikely that the number of electrons making various electronic transitions is the same. 6. Convergence limit and ionisation energy If sufficient energy is given to an atom, it is possible to excite an electron just beyond the highest energy level. In this case the electron will escape and the atom becomes as ion. Ionisation has taken place. By determining the frequency at which the converging spectral line come together, the ionisation energy of an atom can be found. Question : An accurate value for the frequency at the convergence limit of Lyman series for hydrogen is 3.27 x 1015 Hz. Calculate the ionisation energy of hydrogen.

Unit 2-7

Section
(1)

2.2

Atomic Orbital

The wave nature of electrons

In 1924, a French Physicist Louis de Broglie postulated that matter could have both particle and wave properties. For the case of an electron, this postulate was later confirmed by the experiments performed by C. Davisson with his partner L. Germer, and by G. P. Thomson. When they passed a beam of electrons through a crystal and through a gold foil, they obtained a diffraction pattern on a screen similar to that observed when X-ray was used. This piece of evidence demonstrated that electrons did indeed possess wave properties. Following this, studies in quantum mechanics have shown that electrons are not localized in fixed orbits, and as a matter of fact, we can find only describe the location of an electron in terms of probability of finding it in a certain position at any time. The probability, considered over a period of time, gives an average picture of how the electron behaves. The picture does not show the actual location of the electron at any given time. Instead, it shows where the electron is most likely to be at any time. The total picture of the probability of finding an electron at various points in spaces is called an orbital. The following figure shows the probability distribution of the electron in a hydrogen atom :

Note that the denser the dots, the more likely the electron will be in that region. Nowhere is the probability equal to zero. Even at points at very great distances from the nucleus there is some probability, although it is small. Atomic orbital The volume of the space in which there is a 95% chance of finding the electron is called the atomic orbital. There is a 5% probability that the electron will be outside this volume of space at a given instant. An atomic orbital can be viewed as a representation of a region within which there is a high probability of finding an electron. Figure below depicts the boundary surface for the electron distribution in hydrogen atom :

Unit 2-8

( 2 ) Electron shells, subshells and number of orbitals

In quantum mechanics, the electron is treated as wave. A wave function is used to describe its motion. Solutions of the wave equation for electrons show electronic energy levels are quantized and described by quantum numbers. The most important quantum is the principal quantum number n which determines the energy and distance of electron from the nucleus. The term electron shell is used for a group of orbitals with the same principal quantum number. subshell is a group of orbitals with the same energy. For n = 1, electrons are in the lowest energy level ( K shell ) and are nearest to the nucleus. is one sub-level (subshell) and one kind of orbital : the 1s orbital. For n = 2, electrons are in the second energy level ( L shell ). and two kinds of orbitals : the 2s and 2p orbitals. For n = 3, electrons are in the third energy level ( M shell ). and three kinds of orbitals : the 3s, 3p and 3d orbitals. For n = 4, electrons are in the fourth energy level ( N shell ). and four kinds of orbitals : the 4s, 4p , 4d and 4f orbitals. A

There

There are two sub-levels (subshells)

There are three sub-levels (subshells)

There are four sub-levels (subshells)

principal quantum number n

electron shell

subshell

number of orbitals

name of orbitals

In general, the total number of orbitals for each value of principal quantum number n is n2 . Each orbital can be occupied by two electrons with opposite spins at most. n total number of orbitals maximum number of electrons

Unit 2-9

( 3 ) Shapes of s and p orbitals

s orbital The shape of an s orbital is spherically symmetrical about the nucleus. The orbital has no preferred direction. The probability of finding an electron at a distance r from the nucleus is the same in all directions. The following figures show the shapes of a 1s orbital and a 2s orbital.

p orbitals There are three p orbitals for each electron shell except n = 1. They are all dumb-bell in shape. p orbitals are directional and situated along three coordinate axes (x, y, and z). The px, py and pz orbitals are perpendicular to one another. They have the same energy and are collectively referred to as the p subshell. There is zero probability of finding a p electron at the nucleus. Figures below depict three 2p orbitals : 2px, 2py and 2pz.

d orbitals There are five d orbitals for each d subshell.

Three of them has the shapes shown below :

Unit 2-10

(4)

The relative energies of orbitals

One-electron system For a one-electron atom, such as hydrogen atom or one-electron ions, such as He+ , Li2+ , the relative energy level diagram of orbitals is shown in the following diagram. Notice that all subshells of the same energy level have the same energy.

Many-electron system For a many-electron atom, the energies of subshells increase in the order s< p< d< f . The relative energy level diagram of orbitals is shown in figure :

Unit 2-11

Section 2.3

Electronic Configuration

( 1 ) Building up principles
The distribution of electrons in an atom is called electronic configuration. configuration can be expressed in two ways : The electronic

1. notations using 1s, 2s, 2p, etc.; 2. electrons-in-boxes diagram, which tells how electrons occupy different orbitals with spins shown. In electron-in-boxes diagrams, represents an orbital, which can accommodate one electron or 2 electrons at most.

represents one electron which occupies an orbital singly.

represents two electrons having opposite spins.

Building up of electronic configurations is based on three principles. 1. Aufbau principle : electrons enter the orbitals in order of ascending energy. 1s <2s <2p <3s <3p <4s <3d <4p <5s <4d <5p <6s <4f <5d <6p <7s <5f <6d <7p <8s

2. Hunds rule : orbitals of the same energy must be occupied singly by electrons with same spins before pairing occurs. Expanation : Electrons occupying orbitals of the same energy singly with spin parallel can minimize electrical repulsion between them by exchange of same spin electrons.

3. Paulis exclusion principle : electrons occupying the same orbital must have opposite spins. Explanation : Electrons occupying the same orbitals have opposite spins such that the resulting magnetic attraction can counterbalance the electrical repulsion between them.

Unit 2-12

( 2 ) Electronic configurations of atoms from H to Kr

The building up of electronic configurations follows the three principles. In addition, extra stability is gained by electronic configurations in which orbitals of the same energy are either exactly half-filled or full-filled. Exactly half-filled subshells (e.g. np3, nd5) attain extra stability because electrons are evenly distributed in different orbitals. This minimizes electronic repulsion. Full-filled subshells (e.g. ns2, np6, nd10) attain extra stability because extra energy is needed to break the spin paired arrangement in a full-filled subshell. Hydrogen H (Z = 1) 1s 2s 1s1 2p (1)

Helium

He (Z = 2) 1s 2s

1s2 2p

(2)

The second period elements : Lithium Li (Z = 3) 1s 2s

(2.1) 1s22s1 2p

Beryllium

Be (Z = 4) 1s 2s

1s22s2 2p

(2.2)

Boron

B (Z = 5) 1s 2s

1s22s22p1 2p

(2.3)

Carbon

C (Z = 6) 1s 2s

1s22s22p2 2p

(2.4)

Nitrogen

N (Z = 7) 1s 2s

1s22s22p3 2p

(2.5)

Note that : According to Hunds rule, the 7th electron occupies another 2p orbital and the 5th, 6th and 7th electrons have parallel spins. The 2p subshell is now exactly half-filled. Oxygen O (Z = 8) 1s 2s 1s22s22p4 2p (2.6)

Fluorine

F (Z = 9) 1s 2s

1s22s22p5 2p

(2.7)

Unit 2-13

Neon

Ne 1s

(Z = 10) 2s

1s22s22p6 2p

(2.8)

Note that : The 2s and 2p subshells of neon is completely filled. This electronic configuration is very stable. ( ns2np6 is known as the stable noble gas electronic configuration)

The third period elements : Sodium Na (Z = 11) inner shell 3s 1s22s22p63s1 3p (2.8.1)

Magnesium

Mg (Z = 12) inner shell 3s

1s22s22p63s2 3p

(2.8.2)

Aluminium

Al (Z = 13) inner shell 3s

1s22s22p63s23p1 3p

(2.8.3)

Silicon

Si (Z = 14) inner shell 3s

1s22s22p63s23p2 3p

(2.8.4)

Phosphorus

P (Z = 15) inner shell 3s

1s22s22p63s23p3 3p

(2.8.5)

Surphur

S (Z = 16) inner shell 3s

1s22s22p63s23p4 3p

(2.8.6)

Chlorine

Cl (Z = 17) inner shell 3s

1s22s22p63s23p5 3p

(2.8.7)

Argon

Ar (Z = 18) inner shell 3s

1s22s22p63s23p6 3p

(2.8.8)

Note that : The 3s and 3p subshells of argon is completely filled. stable. ( Argon is a noble gas )

This electronic configuration is very

Unit 2-14

s-block elements of the fourth period : Potassium K (Z = 19) inner shell 1s22s22p63s23p64s1 (2.8.8.1) 3d 4s

Note that : The 4s orbital has energy lower than the 3d orbitals. According to Aufbau principle, the last electron of potassium enters the 4s orbital, not the 3d orbital. Calcium Ca (Z = 20) inner shell 1s22s22p63s23p64s2 (2.8.8.2) 3d 4s

d-block elements of the fourth period : Transition elements ( Z = 21 30 ) Scandium Sc (Z = 21) inner shell 1s22s22p63s23p63d14s2 (2.8.9.2) 3d 4s

Note that : The last electron of scandium enters the 3d orbital. 4s orbital now has higher energy than 3d orbitals. Titanium Ti (Z = 22) 1s22s22p63s23p63d24s2 (2.8.10.2) inner shell 3d 4s

Vanadium

V (Z = 23) inner shell

1s22s22p63s23p63d34s2 (2.8.11.2) 3d 4s

Chromium

Cr (Z = 24) inner shell

1s22s22p63s23p63d54s1 (2.8.13.1) 3d 4s

Note that : Chromium has the electronic configuration 1s22s22p63s23p63d54s1 but not 1s22s22p63s23p63d44s2. The exactly half-filled 3d subshell and 4s subshell structures give extra stability to the chromium atom. Manganese Mn (Z = 25) inner shell 1s22s22p63s23p63d54s2 (2.8.13.2) 3d 4s

Iron

Fe (Z = 26) inner shell

1s22s22p63s23p63d64s2 (2.8.14.2) 3d 4s

Cobalt

Co (Z = 27) inner shell

1s22s22p63s23p63d74s2 (2.8.15.2) 3d 4s

Unit 2-15

Nickel

Ni (Z = 28) inner shell

1s 2s 2p 3s 3p 3d 4s (2.8.16.2) 3d 4s

Copper

Cu (Z = 29) inner shell

1s22s22p63s23p63d104s1 (2.8.18.1) 3d 4s

Note that : Copper has the electronic configuration 1s22s22p63s23p63d104s1 but not 1s22s22p63s23p63d94s2. The full-filled 3d subshell and half-filled 4s subshell structures give extra stability to the copper atom. Zinc Zn (Z = 30) inner shell 1s22s22p63s23p63d104s2 (2.8.18.2) 3d 4s

p-block elements of the fourth period : ( Z = 31 36 ) Gallium Ga (Z = 31) inner shell 1s22s22p63s23p63d104s24p1 3d 4s (2.8.18.3) 4p

Germanium

Ge (Z = 32) inner shell

1s22s22p63s23p63d104s24p2 3d 4s

(2.8.18.4) 4p

Arsenic

As (Z = 33) inner shell

1s22s22p63s23p63d104s24p3 3d 4s

(2.8.18.5) 4p

Selenium

Se (Z = 34) inner shell

1s22s22p63s23p63d104s24p4 3d 4s

(2.8.18.6) 4p

Bromine

Br (Z = 35) inner shell

1s22s22p63s23p63d104s24p5 3d 4s

(2.8.18.7) 4p

Krypton

Kr (Z = 36) inner shell

1s22s22p63s23p63d104s24p6 3d 4s

(2.8.18.8) 4p

Note that : The 4s and 4p subshells of krypton is completely filled. stable. ( Krypton is a noble gas )

This electronic configuration is very

Unit 2-16

( 3 ) Electronic configurations in relation to the Periodic Table

In the Periodic Table, the elements are arranged in order of increasing atomic number. A new row (period) is started when electrons start to enter a new principal energy level. Elements whose atoms have a similar outer electronic configuration are placed in a vertical column (group). Within any block of elements in the Periodic Table, the final electron to be added to an atom enters a subshell of the type shown by the block letter (s, p, d or f).

Elements
s-block

Description

p-block

d-block

f-block

Group I (alkali metals) 1. All the elements are active metals. 2. Group similarities and trends within the groups are generally Group II (alkaline clear. earth metals) Group III to Group VI 1. Chemical behaviour in this block varies widely with the reactivity of the metals, metalloids and non-metals, and the Group VII (Halogens) comparative lack of reactivity of noble gases. Group O (Noble gases) 2. Similarities within a group are shown by halogens and noble gases. 3. Group IV elements carbon to lead show a dramatic change in chemical properties within a group (a transition from non-metal to metal). 1. Transition elements are defined as elements which have Transition elements incomplete d subshell when combined in compounds. 2. They frequently have coloured compounds and complex ions in various oxidation states. 3. They have higher melting points, and are denser and harder than non-transition metals. 1. Lanthanoids are widely spread throughout the earths crust. Lanthanoids and They are also known as rare earth. Actinoids 2. Actinoids are all radioactive metals.

Unit 2-17

Section

2.4

Electronic Structure and Ionisation Enthalpy

( 1 ) Ionisation enthalpy
Ionisation enthalpy is the energy absorbed when a mole of electron is removed from a mole of the element in the gaseous state to give positively charged ions. Energy is always absorbed in this process because work has to be done in overcoming the attractive force of the positively charged nucleus for the negatively charged electrons. The energy is measured in kJ mol-1. The first ionisation enthalpy of an element is defined as the energy required for the removal of one mole of electrons from one mole of isolated atoms of the element in the gaseous state :

The second ionisation enthalpy is defined as the energy needed for the removal of a second mole of electrons from one mole of isolated unipositive ions : Thus, the nth ionisation enthalpy is

Higher ionisation enthalpy may be defined in a similar way. the energy required for the process :

Example: sodium magnesium aluminium Discussions: 1. I.E.3 > I.E.2 > I.E.1

kJ mol-1 at 298 K I.E.1 I.E.2 500 4560 742 1450 583 1820

I.E.3 6940 7740 2740

The positive charge on an ion increases as more electrons are removed. Also, as the charge on a cation increases, its radius decreases. The nucleus then exerts a stronger electrostatic attractive force on the subsequent electron to be removed. 2. For the alkali metals (e.g. sodium), the jump from I.E.1 to I.E.2 is particularly large. The second electron to be removed originates from a lower electron shell with stable noble gas electronic configuration. It is closer to the nucleus and is very strongly held.

3. Similar effect is observed with elements of other groups where electrons are removed from a lower electron shell. For example, a particularly large jump from I.E.2 to I.E.3 is observed for group II elements (e.g. magnesium). The third electron to be removed originates from a lower electron shell with stable noble gas electronic configuration.

Unit 2-18

( 2 ) Successive ionisation enthalpies for a particular element

The variation in the successive ionisation enthalpies for an element indicates the existence of electron shells and subshells. Figure below shows the plots of successive ionisation enthalpies of a potassium atom :

Interpretation of the plot : 1. The energy required to removed the 2nd to the 9th electrons, and the 10th to the 17th electrons, increases steadily. Interpretation : Each successive ionisation enthalpy is higher than the previous one because the positive charge on an ion increases as more electrons are removed. The nucleus then exerts a stronger electrostatic attractive force on the subsequent electron to be removed. 2. There are sharp and abrupt rises between the 1st and 2nd, 9th and 10th, and 17th and 18th ionisation enthalpies. Interpretation : Initially, the outer electrons which are loosely attracted to the nucleus are removed. The electrons which are removed later are from lower energy levels and closer to the nucleus. The last electrons are very strongly held to the nucleus. Existence of electron shells : 1. In a potassium atom, the two electrons in the lowest energy level are closest to the nucleus. They are most strongly attracted by the positive nucleus electrostatically. These two electrons are said to occupy the first electron shell (n = 1). 2. The following 8 electrons occupy the second electron shell (n = 2). They have higher energy level than the first 2 electrons do. They are also more distant from the nucleus. 3. Another 8 electrons, which are at a higher energy level, occupy the third electron shell (n = 3). 4. The last (outermost) electron occupies the fourth electron shell (n = 4). and is most distant from the nucleus. It has the highest energy level

Unit 2-19

Section
(1)

2.5

The Periodic Table and atomic properties of elements

Trends of atomic radii of the elements in the Periodic Table

Figure below illustrates the variation of the atomic radius for the first 56 elements in the Periodic Table :

The following trends can be observed : 1. On passing from left to right across a period, atomic radius of the elements decreases. As the nuclear charge increases with atomic number, the additional electrons enter the same electron shell. Within a period, the outermost electrons are poorly shielded from the attraction of increasing nuclear charge by the outer electrons in the same shell. The effective nuclear charge of successive elements increases and the electrostatic attraction between outer electrons and positive nucleus increases. Therefore, the outer electrons are drawn closer towards the nucleus, resulting in a reduction in atomic radius. Within a period, alkali metal atom has the largest size because the outer electron is in a new electron shell, which is further away from the nuclear attraction. The atom of noble gas has the smallest size because the electrons in the same shell do not shield each other from the nuclear charge effectively while the effective nuclear charge is large. 2. The atomic radius increases down a group Element has one more filled electron shell than the previous element in the same group. As the electron occupy electron shells of greater quantum number in successive period, they become further away from the nucleus. Besides, the inner shell of electrons can shield the outer electrons effectively from the nuclear charge. This decreases the attractive force between the positive nucleus and the electrons. 3. Across a period, the atomic radius of elements decrease abruptly at first but to the end of the period, the extent of decrease becomes smaller. At the beginning of each period, the added electrons experiences great effective nuclear charge and the electron cloud contracts quickly. Towards the end of a period, the effective nuclear charge increases comparatively slowly and the corresponding decrease in atomic size is smaller.

Unit 2-20

(2)

Trends of the first ionisation enthalpies of the elements in the Periodic Table

The following figure illustrates the variation of the first ionisation enthalpy for the first 56 elements in the Periodic Table :

The following trends can be observed : 1. On passing from left to right across each period, there is a general increase in the first ionisation enthalpy. As the nuclear charge increases with atomic number, the additional electrons enter the same electron shell. In the same shell, electrons do not shield each other effectively from the positive nuclear attraction. This results in an increase in effective nuclear charge. The outer electrons are therefore attracted more tightly towards the nucleus. More energy is needed to remove an electron from the atom. 2. Across each period, ionisation enthalpy peaks at Group O (Noble gases). Noble gas electronic configurations are extremely stable because the ns and np subshells are completely filled (ns2 np6). As the atomic radius of a noble gas is the smallest in a period, the electrons are closet to the nucleus. Besides, the effective nuclear charge is highest and holds the electrons tightly. More energy is needed to disturb the stable electronic structure and first ionisation enthalpy is therefore extremely high. 3. There is a large drop in the first ionisation enthalpy in moving from one period to another. At the beginning of each period, the additional s electron is added to a new electron shell further away from the nucleus. Also, this s electron is effectively shielded from the attraction of nuclear charge by the full inner shell of electrons. As a result, the outermost s electron is less firmly attracted and easily removed, leading to a particular low first ionisation enthalpy in Group I elements. 4. The first ionisation enthalpy decreases down a group. The outer electrons are located one quantum shell further from the nucleus. As there are more inner shell electrons, the outermost shell electrons are better shielded from the attraction of the nuclear charge. Therefore, there is weaker attraction between the outer shell electrons and the nucleus. This accounts for the decrease in first ionisation enthalpy down a group.

Unit 2-21

5. There is a drop in the first ionisation enthalpy between Group II and Group III ( Be and B; Mg and Al).

Be has a fully-filled outermost 2s subshell. It is a stable electronic configuration and more energy is required to remove an electron from it. B has an additional 2p electron beyond the full 2s subshell. It is easier to remove an outermost 2p electron because this electron is further from the nucleus and is shielded from the attraction of the nucleus by a full 2s subshell. Mg has a fully-filled outermost 3s subshell. It is a stable electronic configuration and more energy is required to remove an electron from it. Al has an additional 3p electron beyond the full 3s subshell. It is easier to remove an outermost 3p electron because this electron is further from the nucleus and is shielded from the attraction of the nucleus by a full 3s subshell.

6. There is a drop in the first ionisation enthalpy between Group V and Group VI ( N and O; P and S). N has an exactly half-filled outermost 2p subshell. This is a stable electronic structure because the 2p orbitals are singly occupied and electronic charge is evenly distributed. Therefore electrostatic repulsion is minimized. More energy is needed to remove a electron from this stable electronic structure. O has four electrons in the outermost 2p subshell. The fourth electron goes into an 2p orbital which has already been occupied by an electron. The increased repulsion causes this electron to be less tightly held. Therefore, less energy is required to remove an outermost electron from O. P has an exactly half-filled outermost 3p subshell. This is a stable electronic structure because the 3p orbitals are singly occupied and electronic charge is evenly distributed. Therefore electrostatic repulsion is minimized. More energy is needed to remove a electron from this stable electronic structure. S has four electrons in the outermost 3p subshell. The fourth electron goes into an 3p orbital which has already been occupied by an electron. The increased repulsion causes this electron to be less tightly held. Therefore, less energy is required to remove an outermost electron from S.

Unit 2-22

(3)

Trends of electron affinities of the elements in the Periodic Table

1. Electron affinity is the energy change when a mole of gaseous atoms acquires a mole of electrons to give a mole of negatively charged ions.

2. The general trend is for electron affinity to increase from left to right across the periodic table. This is because, as the nuclear charge increases, the extra electrons enter the same electron shell and so are attracted more strongly. Thus, atoms have progressively greater attraction for electrons as the group number increases. Some electron affinities are given below, the values being in kJ mol-1. C -120 N 0 O -142 S -200 F -333 Cl -348

Most electron affinities are exothermic because the orbitals of an electron theoretically extend to infinity and so the nuclear charge is never completely balanced. However, when an electron is added to an atom with a full or exactly half-filled outer subshell (e.g. nitrogen ), the electron affinity is low or endothermic since these structures show enhanced stability. These values reinforce the deductions made about stability from ionisation enthalpies. 3. The value usually decreases down a group of the Periodic Table as the atomic radii of the elements increase. The reason is that the smaller the atom the closer is the outer electron shell to the nucleus and the more strongly are electrons attracted into it. F -333 Cl -348 Br -324 I -295 The value for fluorine is anomalous because it includes a high repulsion electron cloud. a consequence of a low atomic radius and a compact outer electron shell. This is

4. The second electron affinity of an element relates to the uptake of a second electron, and is defined as the enthalpy required adding one mole of electrons to one mole of isolated uninegative ions.

The change is endothermic, because the repulsion component is greater than the attraction component. O -142 +791 S -200 +649

First electron affinity Second electron affinity

Electron affinities are generally obtained indirectly from thermochemical cycles because direct measurement is difficult.