3 Classification of elements and periodicity in properties Dobereiner’s Law of Triads: Johann Dobereiner in 1829 classified similar elements into group of three or triads such that atomic weight of the central element was the arithmetic mean of the atomic weights of the other two members of the triad. Example Li (7) Na(3) K (39) + (7 +39) +2= 23 Cal4o) Sr (88) Ba(137)_ > (40 + 137) + 88.5 €1(35.5) Br (80) 1 (127) + (35.5 + 127}: = 80 John Newland’s law of octaves: The law states that “The elements when arranged in order of their increasing atomic weights, every eight element has properties similar to the first element like eight note of the musical scale”. Example: Element Li Be B C N O F At. Wt 7 9 11 12 14 16 19 Element Na Mg Al Si P S 23° 24 «27° 28 «3132 85.5, Limitations of Newland’s law of octaves: The law was applicable for only lighter elements having atomic weights up to 40. Moreover, with the discovery of noble gases, the eight element no longer remains a similar element. Mendeleev’s Periodic table: Mendeleev’s periodic law states “The properties of elements are periodic functions of their atomic weights”, Significance of Mendeleev’s periodic table: 1. Periodic table proved very useful in systematic study of element and their ‘compounds 2. Prediction of discovery of new elements Mendeleev had left some gaps for elements yet to be discovered. He even predicted the properties of such elements. Example: the elements Scandium, Gallium and Germanium were not known at the time. He left blank spaces for the and named them as eka born, eka aluminium and eka silicon. 3. Mendeleev’s periodic table has helped in correcting the atomic weights in doubtful cases Limitations of Mendeleev’s periodic table 1. The position of hydrogen atom is undecided 2. Position of isotopes of an element could not be explained.20 Moder periodic table: In 1913, Moseley proposed that atomic number is a more fundamental property of an element that its atomic weight. The modern periodic law states “The physical and chemical properties of elements are the periodic functions of their atomic number”. Long form of the periodic table has seven horizontal rows called peri 90/176 vertical columns called groups. Number of elements in different periods: Principal | Orbitals Periodic | valence shell being — | Eeeetrans to be | Nae of oa fier gp | accommodated | elements, First i Is 2 2 Second 2 2s2p 8 8 Third is 3s3p 8 3 Fourth 4 as3d4p 18 18 Fifth 5 Ss4d5p 18 Is Sixth 6 Bs4fSd6p 32 32 Seventh 7 7s516d7p 32 32 Classification of elements into s,p,d and f blocks 1, 8 - block elements: the elements in which the last electron enters the s - subshell of their outermost energy level. Since s - subshell has only one orbital which can accommodate only two electrons; therefore there are two groups of s - block elements. a, Group -1I— alkali metals —> nst b, Group - Il — alkaline earth metals —+ ns? ¢, General outershell configuration of s - block elements is ns 1-2 4. General characteristics of s - block elements: i, They are soft metals ii, They have low melting point and boiling point iii, They show oxidation states of +1 and +2 iv. They are highly electropositive v. They are good reducing agents (give electrons for reduction) 2. p - block elements: The elements in which the last electron enters the p sub shell of their outermost energy level. Since, p sub shell can accommodate six electrons, There are six groups of p ~ block elements. These are a, Group - 13 > boron family - ns¢np! Group - 14 > carbon family - ns¢np? Group ~ 15 — oxygen family - ns?np? Group - 16 — nitrogen family - ns’np* Group ~ 17 — halogen family ~ ns2nps Group - 18 + noble gases family - ns*np* General outer shell configuration of p - block elements is ns?np *-¢ General characteristics of p - block elements: i, They contain both semi - metal and non ~ metal ii, They show variable oxidation states ili, They are highly electronegative rPemepog iv. They form ionic as well as covalent compounds2 Note: the elements s and p block are called Representative elements. 3. d- Block elements: The clements in which last electron enter the d ~ sub shell of the penultimate energy level. Since d - sub shell has five orbitals, can accommodate then electrons. General outer shell electronic configuration of d - block elements (n - 1) }-10ns0-2, Since the properties of these elements are midway between s and p block elements, they are called transition elements. a. first transition series contains ten elements from Scandium (Sc) to Zine (zn) second transit cadmium (Cd) ¢. third transition series contains ten elements from Lanthanium (La), Hafnium (Hf) to mercury (Hg) fourth transition series contains ten elements from Actinium (Ac), Rutherfordiun (RA) to Copernicium (Cn) yn series contains ten elements from Yttrium (¥) to General characteristics of d - block elements 1, They are hard, malleable (converted into sheets) and ductile (drawn into wires) They have high melting and boiling point ‘They show variable oxidation states They from coloured complexes ‘They exhibit paramagnetsim They show catalytic properties 4, £- block elements: The elements in which the last electrons enters the f — sub shell of the antipenitimate energy level. They general outermost electronic configuration is (n - 2)f 1-1 (nm - 1)4°-1 ns? They consist of two series of elements, each contain fourteen elements. In the first series, the filling of electron takes place in the 4f sub shell. The elements of first series follow Lanthanum, hence they are called Lanthanoids [cerium to lutetium). The elements of second series follow Actinium, hence they are called actinoids. In the second series the filling of electrons takes place in the 5f sub shell. The two series of elements are called inner transition elements. Oaeon General characteristics of f - block element: They are heavy metals They have generally high melting and boiling points ‘They show variable oxidation states Their compounds are generally coloured They have high tendency to form complexes. Ase Periodicity: the periodical repetition of elements with similar properties after certain regular intervals when the elements are arranged in order of increasing atomic number is called periodicity. Cause of periodicity: The physical and chemical properties are related to the arrangement of electrons in their atom. The cause of periodicity in properties is due to the repetition of similar outer most shell electronic configuration after certain regular intervals. The important periodic properties are2 Atomic radius Ionisation enthalpy Electron gain enthalpy Electronegativity. BORE Atomic radius: It is defined as the distance between the centre of the mi rae nucleus and outer most shell of electrons. Covalent radius: It is defined as the half of the distance between the nuclei of two covalently bonded atoms of the same elements in a molecule. Example: the bond length between two atoms in a hydrogen molecule is 74pm. therefore the covalent radius of hydrogen atom is 74/2 = 37pm. Metallic radius: It is defined as half of the inter nuclear distance between two adjacent atoms in a metallic lattice. Cation and anion: the removal of electron from an atom results in the formation of cation whereas gain of an electron leads to an anion. Tonic radius: It is defined as the distance between the nucleuses of an ion at a point up to which the nucleus has influence on its electron cloud. Radius of cation is always smaller than that of atom - give reason: a cation is smaller than its parent atom because it has less number of electrons while its muclear charge remains the same. Hence size decreases due to greater force of attraction by the nucleus on the electron, Example atomic radius of Na is 186pm where as its ionic radius Na’ is 95pm. Radius of anion is always larger than that of the atom ~ give reason: The size of an anion will be larger that that of the parent atom because anion is formed by the addition of electrons. Since the nuclear charge remains unchanged size of ion increases due to less force of attraction by the nucleus on the electrons. Example atomic radius of fluorine (F) is 64pm where as fluoride ion (F-) is 136pm. Isoelectronic species: Some atoms and ions which contain the same number of electrons. Example N?-, 0 2 -,F -Ne,Na‘,Mg,Al these species will have 10 electrons. Among isoelectronic species, cation with greater positive charge will have smaller radius and anion with greater negative charge will have the larger radius. Therefore in isoelectronic species in the increasing order of their radii is Als*< Mg < Nav < F- < O2- Variation of atomic radius in the periodic table: ‘The atomic radius increases down the group because the number of principle shells increases on moving down in the group and the distance between nucleus and outermost shell increases. As a result the effective nuclear charge on the outermost electron decreases and size of atom increases. The size of atoms decreases along the period because electrons are added to the orbitals of same shell. As a result the effective nuclear charge on the outermost electron increases and size of atom decreases2B Ionization enthalpy: It is defined as “the amount of energy required in removing an outermost electron from an isolated gaseous atom in its ground state”. This energy is measured in the units of kJ/mol. X + LE — X+ +e- Factors affecting ionisation enthalpy: 1, Atomic radius: the larger the atomic size, lesser the ionization enthalpy and vice versa. 2. Effective nuclear charge: ionization enthalpy increases with increases in the effective nuclear charge. 3. Screening or shielding effect: In multi - electron atoms, the electrons in the valence shell experience an attractive force from the nucleus and a repulsive force from the electrons in the inner shells. The electrons in the inner shells tend to shield outer electrons from the attractive force of the nucleus. This repulsive force left by the valence electrons from the electrons present in the inner shells is called screening or shielding effect. As the screening effect increases, the LE decreases. 4. Half filled or completely filled orbitals: The half filled and completely filled orbitals give extra stability to an atom, As a result, ionisation enthalpy is high. 5. Penetration effect of electrons: In multi - electron atom, the electron of the s ~ orbital has the maximum probability of being found near nucleus and this probability goes on decreasing in case of p,d and f orbitals of the same shell ‘Thus, within the same shell the penetration effect decrease in the order s > p > d > f. Therefore, ionisation enthalpy is maximum to remove an electron from s ~ orbital and minimum for f= orbital Variation of ionization enthalpy: Ionization enthalpy increases across a period due to decrease in atomic size and decrease on moving down in a group due to increase in atomic size. Nitrogen has greater ionization enthalpy than oxygen. Give reason: this is because nitrogen has half filled electronic configuration which is more stable. Therefore nitrogen is have more ionization enthalpy than oxygen. Electron gain enthalpy: It is defined as “the amount of energy released when an electron is added to the outermost orbit of an isolated gaseous atom. X + ¢- — X- Electron gain enthalpy decreases down the group due to increase in atomic size and increases along a period from left to right due to decreases in atomic size and effective nuclear force on the additional electron increases, as a result attraction by the nucleus for an additional electron increases. Fluorine has less electron gain enthalpy than chlorine: due to small size of fluorine atom, adding an electron to the 2p orbital leads to a greater repulsion, hence less energy is released compared to chlorine, The element with highest gain enthalpy is chlorine. Electronegativity: it is the measure of the ability of an atom in a chemical compound to attract shared electrons to itself, Fluorine is the most electronegative element. Variation of electronegativity in the periodic table: It decreases down the group due to increase in atomic size. This is due to decrease in effective nuclear charge. As a result, the capacity of attracting the electrons pair decreases. Electronegativity increase across a period due to decrease in atomic size.24 Periodic trends in chemical properti Periodicity of valence: Valence is the most characteristic property of the elements. The electrons present in the outermost shell of an atom called valence electrons and the number of these electrons determine the valence. In case of s and p block elements, the valance of an atom is generally equal to either the number of valence electrons or equal to 8 ~ number of valence electrons. Group 1 2 13 14 15 16 17 18 Valenceelectrons 1 2 3 4 5S 6 7 8 Valence 1 2 3 4 53 62 7,1 80 Periodic trends in valence of elements as shown by the formulas of their compounds Group 1 2 13 14 15 16 17 18 Formula of hydrides LiH CaH, BsHe CHs NH; H,O HCI there are already stable NaH AlHy SiHy PH; aS HBr BH is not formed because it is an abnormal bond. Formula of oxides LigO MgO B20; CO; N20; SO; ClO; NaO CaO ALO; SiO. N2Os P203 Anomalous properties of second period elements: Some elements of the second period show similarities with the elements of the third period diagonally to each other. This similarity in property of elements placed diagonally to each other is called diagonal relationship. Example group] group2_—s group 13_—group 14 Second period Li Be. B c ‘Third period i, a OSS Lithium resembles magnesium, beryllium resembles aluminium, boron resembles silicon, The anomalous behaviour of these elements is due to their small size, large charge/radius (also known as polarising power) high electronegativity, absence of d - orbitals, Metals: Elements of group ~ 1, group ~ 2, d - block elements and f - block elements are metallic in nature. They have low ionization enthalpy and lose electrons easily to form cation. They are electropositive in nature. They have high melting and boiling points. They are good conductors of heat and electricity. They are malleable and ductile. They25, are solid at room temperature except mercury. Metallic property increases down the group and decreases across a period. Non - metals: Elements of group 13 to 18 are mostly non ~ metals. They have high ionisation enthalpy and high electronegativity. They are poor conductors of heat and electricity. Non ~ metals are solids or gases at room temperature. Most non ~ metals solids are brittle, non ~ metallic property or character increases across a period and decreases down the group. Metalloids: A few elements like silicon, germanium, arsenic, antimony, tellurium, shows properties of metals as well as non ~ metals. They are called metalloids or semi ~ metals. Notation of IUPAC nomenclature of element: Digit oi j2]3 [4s [6 [7 [a [9 Name Nil | Un | bi | tri | Quad | pent | hex | spet | oct | Enn Abbreviation[N [U [> |[t [Q |p [h [so le Nomenclature of elements with atomic number above 100 ‘Atomic TUPAC official | TUPAC number| Name Symbol | "name symbol 101 |Unnilunium | Unu_|Mendelevium [Md 102 | Unnilbium Unb__| Nobelium No. 103 | Unniltrium Unt_| Lawrencium Lr 104 | Unnilquadium [Ung __| Rutherfordium [RF 105 | Unnilpentium |~Unp | Dubnium Db 106 | Unnilhexium | Unh | Seaborgium Sg 107 | Unnilseptium | Uns | Bobrium, Bh 108 | Unniloctium [Uno | Hassium Hs. 109 [Unnilennium | Une | Meitnerium Mt 110 |{Ununnillium | Unn_ | Darmstadtium [Ds 111__|Unununnium | Uuu_ | Rontgenium Rg 112 | Ununbium Unb | Copernicium [Cn 113 { Ununtrium ‘Uut | Nihonium, Nh 114__|Ununquadium | Uug__| Flerovium Fl 115 | Ununpentium | Uup | Moscovium Mc 116 | Ununhexium |" Uuh_ | Livermorium Ly 117 | Ununseptium | Uus | Tennessine Ts 118 [Ununoctium | Uuo | Oganesson Og