Chapter PERIODIC CLASSIFICATION OF ELEMENTS AND PERIODICITY INTRODUCTION: “A table obtained by the arrangement of elements into periods and groups is called periodic table.” The development of periodic table is one of the most significant achievement in the history of chemistry “The periodic table provides of basic framework to study the periodic behaviour of physical and chemical properties of elements as well as their compounds.” HISTORICAL BACKGROUND AL-Razi He organized the known elements and compounds. His classification was based upon the physical and chemical prop ies of elements and compounds, Dobereiner (Law of Triads): In 1829, Dobereiner discovered the families of elements which have same chemical properties. One family of elements consists of three elements, so he called it “triads”. In the given table each vertical column given is triad “The atomic mass of middle element is the average of atomic masses of other two elements of triads.2 ICH.1] Periodic Classification of Elements and Periodicity Table — Some Doberiner’s Triads Element of triads with their ‘Means of 1* and third element atomic masses Li, Nass, Ko CEE) Chss, Brso, Tiny 3554127 _ gy Caso, Sts, Bais7 oe? = 885 NEWLAND’S LAW OF OCTAVE In 1864, Newland, an English chei increasing atomic masses. He stated that: Every eight (8") element had similar properties as first one, if they are arranged according to their atomic masses.” Table — Newland’s octaves ist classified 62 elements on the basis of their H Be B Cc N Oo F Mg Al Si P s cl Ca Cr Ti Mn Fe DIMITRIE MENDELEEV’S PERIODIC TABLE In 1871, a Russian chemist, Dimitrie Mendeleev gave a more useful and comprehensive scheme for the classification of elements. First of all, he arranged the clements into periods and groups. Vertical columns are called groups and horizontal rows are called periods. Mendeleev’s periodic table consist of eight groups and twelve periods. He arranged the elements according to their ascending atomic masses and studied their behaviours, “If elements are arranged according to their ascending atomic masses, he found that elements with similar chemical properties appeared at regular intervals. The appearance of properties of elements afier regular intervals is called periodic law or periodicity.” Advantages of Mendeleev’s Periodic Table: Mendeleev left some gaps in his table for elements, which had not yet been discovered, and by considering their positions in the Periodic Table he predicted properties of these elements. For example, germanium was not known at that time but Mendeleev was confident that this element must exist so he predicted its properties. A few years later, germanium was discovered and its properties were same as predicted by Mendeleev. Mendeleev corrected the atomic mass of Be. It was though to be 13.5 which was wrong. He proposed the atomic mass of Be to be 9.Key to Chemistry Part-ll 3 Defects of Mendeleev’s Periodic Table: (1) The basis of Mendeleev’s periodic table was atomic ma: of structure of atom, (2) Position of hydrogen could not be decided by Mendeleev. (3) Lanthanides (85 ~ 71) and Actinides (90 ~ 103) were not placed properly, (4) Position of isotopes was not indicated (5) According to atomic masses, the position of the following pair of elements was not regular. Ar K Co Ni Te I 39.9 39 58.9 58.6 127.6 126.9 THE MODERN PERIODIC TABLE “lf elements are arranged according to their ascending order of atomic number, their chemical properties repeat in periodic mann In order to make the periodic table more usefil and accurate, a few improvements were made by Mosley in the Mendeleev’s periodic table, Improvement in Mendeleev’s Periodic Table: (1) After the discovery of x-rays, Mosley in 1913 discovered the atomic number of elements. “Atomic number is the number of protons present in the nucleus of an atom.” According to Mosley, atomic number is the fundamental property of an element while atomic mass is not a fundamental property, as one element has different atomic masses for different isotopes. Hence periodic table was rearranged according to ascending order of atomic numbers. This improvement which was made by Mosley, was called modern periodic law. According to modern periodic law: “If elements are arranged in the ascending order of their atomic numbers, their chemical properties repeat in a periodic manner. (2) Another improvement was the addition of an extra group (group VIII) at the extreme right of the Periodic Table. This group contains noble gases, which had not been discovered in Mendeleev’s time. (3) Another confusion in Mendeleev’s table was that elements like Be, Mg, Ca, Sr, Ba and Zn, Cd, Hg were placed in one vertical group, while according to their properties, they belonged to two different categories. The same was true for so many other elements placed in the same vertical group. In modern Periodic Table, the confusion was removed by introducing two types of vertical groups, A and B, In modem periodic table Be, Mg, Ca, Sr and Ba are placed in group IIA and Zn, Cd, Hg in group IIB. (4) Position of isotopes was adjusted because the periodic table was based on atomic number, (5) Position of Lanthanides and actinides was also adjusted It did not give the idea[CH.1] Periodic Classification of Elements and Periodicity « por . (gsz) | (use) | (zsv | (sz | ee (erz) | (rpc) [80 LEZJozo sezfoco iezfseo Eze] PIN | Why wy] ng }aN [A fed UL) + sozsas oprunay + 101 | oot so | v6 | 6 | co 6 [recs scion Press ogee] gen [rae prrfezony wy | aa ng | tis | wg | PN 9) | # SHias aprurque’y ol» olels|o & pojard 20 oo1q-s . 3014 . POP » Pais, (02) | on | G92] wo | com ] ger [ence [evar « SH | 4a | 3S | dd | Fa pov+] ee soi | cot | sot | sor | tor | os | 38 seen ecco i960 s|sirsos 0D JOT A a& te | & ul IIIA, £9 S Fr ¢ 6 a au ana aa FRR Sse o1WOly. I< vant so tesodoud pio —> JoquinN o1WoIy PP EEE PE ee th A elo ECE tele) é ~ w + 7 aKey to Chemistry Part-II 5 GROUPS AND PERIODS (a) Groups: “Elements with similar properties are placed in vertical columns called groups.” There are eight groups, which are usually numbered by Roman numerals I to VILL. Each group is divided into two sub-groups, designated as A and B sub-groups. The sub-groups, containing the typical or normal elements or representative elements, are labeled as A sub-groups whereas B sub-groups contain less typical elements, called transition clements and are arranged in the centre of the Periodic Table. (b) Periods: “The hori: Period 1: The period | contains only two elements, hydrogen and helium. Period 2 and 3: The period 2 and 3 contain eight elements each and are called short periods. All the clements in these periods are typical elements and belong to A sub-groups. In these periods, every eighth element resembles in properties with the first element. As lithium and beryllium in the 2™ period resemble in most of their properties with sodium and magnesium of the 3° period respectively. Similarly boron and aluminium both show oxidation state, of +3, fluorine in 2 period has close resemblances with chlorine of 3" period. Period 4 and The period 4 and 5 are called long periods. Each long period consists of eighteen elements. Out of these, cight are typical elements belonging to A sub-groups similar to second and third periods. Whereas the other ten elements, placed in the centre of the Table belong to B sub-groups and are known as Transition Elements. In these periods the repetition of properties among the elements occur after 18 elements. As after 9K (having atomic number 19), the next element with similar properties is s7Rb. Period 6: The period 6 is also a long period, which contains thirty-two elements. In this periodic there are eight typical elements, ten transition elements and a new set of fourteen clements called Lanthanides as they start after s-La, Lanthanides have remarkably imilar properties and are usually shown separately at the bottom of the Periodic Table. Period 7: The period 7 is incomplete so far. It contains only two normal elements s7Fr and ssRa, seven transition elements and fourteen inner transition elements. The inner transition elements of this period are called Actinides as they follow s»Ac. The actinides are also shown at the bottom of the Periodic Table under the Lanthanides. Due to their scarcity, the inner transition elements are also called rare earth elements. (clements after uranium) they are prepared in the laboratories. ntal rows of the periodic table are called periods. Trans-uranic elemen6 [CH.1] Periodic Classification of Elements and Periodicity SOME MORE FAMILI ome groups have their collective names called family, e.g., Elements of Alkal Metals: Elements of group IA are called alkali metals. Alkali metals are Li, Na, K, Rb, Cs and Fr. Alkaline Earth Metals: Elements of Ca, Sr, Ba and Ra. roup IIA are called alkaline earth metals. They consist of Be, Mg. Chalcogen Famil Elements of group VIA are called chalcogen or ore forming group. Most of the ores contain oxygen or sulphur in them, They consist of O, S, Se, Te and Po. Halogen Family: The elements of group VIIA are called halogens or salt forming group. They consist of F, Cl, Br, I and At. Noble Gases or Inert Gases: Elements of group O or group VIIA are called noble gases. Noble gases consist of He, Ne, Ar, Kr, Xe and Rn. 3. BLOCKS IN THE PERIOD TABLE lements in the Periodic Table can also be classified into four blocks. This classification is based upon the valence orbital of the element involved in chemical bonding. According to this classification: (1) s-Block Elements: The elements of [A and IIA sub-groups are called s-block elements because their valence electrons involve “s” orbital (2) p-Block Elements: The elements of IIIA to VIIIA sub-groups (except He) are known as p-block elements as their valence electrons are present in “p” orbital. (3) d-Block Elements: As in transition elements, electrons in orbital are responsible for their valence hence they are called d-block elements. (4) f-Block Elements: Lanthanides an Actinides, valence electrot orbital hence these elements are called f-block elements. re present in “Ff” This classification is quite useful in understanding the chemistry of elements and predicting their properties, especially the concept of valency or oxidation state.Key to Chemistry Part-ll 7 METALS, N METALS AND METALLOIDS Elements of the periodic table can also be classified as metals, non-metals and metalloids. Characters of Metals: (a) All metals have luster and good shine. (b) All metals are malleable (can be drawn into sheets) and ductile (can be drawn into wires). (c) All metals are good conductors of heat and electricity. (d) All metals form basic oxides, which give bases when dit CaO + HXO ———> Ca(OH)2 Na2O + H20 ————» 2NaOH olved in water e.g., (ec) All metals have tendency to lose ele ‘ons easily and form positive ions. M ——> M'+ le Majority of the elements of periodic table are metals, Characters of Non-metals: (a) Non-metals have no luster or shine (b) Solid non-metals are brittle can be broken down into pieces by applying pressure in nature. (c) All non-metals are poor or non-conductors of heat and electricity. (d) All non-metals form acidic oxides, which give acids when dissolved in water and they react with bases to form salt and water. N20s + H30 ———> 2HNOs Ou P30 + 3H;0 ———> 2HPO, SO: + 2NaOH ———> Na:SO; + H20 SO; + HO ———> (ec) Some non-metals gain electrons and form negative ions. All the gases are non-metals. Element from group IVA to VIIA top right of periodic table, above the stepped line are non-metals Characters of Metalloids or Semi-metals: “The elements which have intermediate properties of metals and non-metals are called metalloids or semi-metals,” Metalloids are located around the diagonal line running from boron to astatine except aluminium in the Periodic Table.8 [CH.1] Periodic Classification of Elements and Periodicity (1) Oxides of the metalloids are amphoteric in nature. (2) They have less conductivity than metals and greater than non-metals (3) Their conductivity increas s by inereasing temperature. Metals Metalloids—-Non-metals —— 4 Ti] Be B[CNIO[F] [Ne Na| Mg} AL} Si] P| S |} cL Ar Metals K [Ca Gal Ge} As | Se | Br Kr Non-metals Rb] Sr to[sa]sopte[ 1] [Xe Cs| Ba Ti| Pb| Bi} Po} At Ral ) Fr [Ra Classifying the element as metals metalloids and non-metals on the basis of their electrical conductance Generally elements on the left hand side, in the center and at the bottom of periodic table are metals. Non-metal elements are present on the upper right of periodic table. Lowers members of group VIIA, IVA and VA have the properties of both metals and non-metals. These elements are called semi-metals or metalloids. At the top right comer of group IVA to VIIIA, above the stepped line are non-metals. The elements just under the “steps” such as Si, As, and Te are metalloids. All the remaining elements except hydrogen are metals. “The gradual change in the properties of elements when they are arranged according to their ascending order of atomic numbers is called periodic trend or periodicity. In periods, physical and chemical properties change gradually due to the change in atomic sizes and the electronic configuration of elements. In a group of the periodic table, chemical properties remain almost same but physical properties change due change in the atomic size. 1. ATOMIC SIZE (a) Atomic Radius: The average distance between the nucleus of the atom and its outer most shell provided the atom is assumed to be spherical. Size of a single atom cannot be measured directly because atoms have no sharp boundaries. Radius is defined as the distance form centre to boundary. We have studied that electrons have wave nature and concentration of cloud of electrons decreases rapidlyKey to Chemistry Part-I 9 as the distance increases and it is not zero even at a large distance. It is impossible to know the boundary of an atom. Some techniques have been developed which can measure the distance between the nuclei of bonded atoms. Half of this distance is considered as atomic radius. Trend of Atomic Radius in the Periodic Table: In the periodic table, the atomic radius increases from top to bottom within a group due to increase in atomic number. This is because of the addition of an extra shell of electrons in each period. In a period, however, as the atomic number increases from left to right the atomic radius decreases. This gradual decrease in the radius is due to the increase in the positive charge in the nucleus. As the nucleus charge increases, electrons in shell are pulled closer to the nucleus. The overall size of the atom decreases. This effect is quite remarkable in the elements of longer periods in which ‘d’ and ‘f orbitals are involved. For example, gradual decrease in the size of lanthanides is called Lanthanide contraction. Atomic radii of representative elements are given in the table. IA 1A IA IVA VA VIA VITA | VITA ou re} © ®© ©@©0 © © @©xo ©@®@ ©0006 OO O©GGe@e 197 ha 109 @OQ @O9eeGoe 182 M40 ui Is 130 @@Ceoe M46 150 40 M40 Atomic radii of the ee elements and the rare gases10 [CH.1] Periodic Classification of Elements and Periodicity (b) Tonic Radius “The radius of one of the ions in an ionic compound is called ionic radius. It is the measure of the spherical region around the nucleus within which electrons are most likely to be found. Size of Cation: When a neutral atom loses one or more electrons, it becomes a positive ion or cation. The size of a cation is smaller as compared to its neutral atom. Decrease in size of cation is due to two reasons. (1) By removal of electrons usually number of shell dec shells while, Na’ has only two shells in it es. c.g., Na has three Naz ———> Nagy +e (2) By removal of electrons, the ratio of electrons to protons, do not remain balance. By removal of electron, the nuclear charge increases and remaining electrons are drawn closer to the nucleus. ¢.g., The covalent radius of Na is 157 pm and ionic radius of Na” is 95 pm (Atomic radius = 186 pm), Size of Anions: When an atom gains electron, it changes to negative ion or anion. Size of anion is always larger than its neutral atom. By addition of more electrons, the nuclear charge decreases and shell expands. For example, the covalent radius of F is 72 pm while size of ionic F is 136 pm, The radius of Cl is 99 pm and that of CI is 181 pm. Trend of Ionic Radii in the Periodic Table: Ina group, the size of similar charged ions increases from top to bottom within a period. Isoelectronic (having same number of electrons) positive ions like Na’, Mg”, AB show a decrease in the ionic radii from left to right due to increase in the nuclear charge. Same trend is observed in the negative ions. Size of anions with similar charge in a group increases from top to bottom. The size of isoelectronic negative ions (C4, N°, O*, F>) decreases from left to right. The variation in atomic and ionic metals and halogens are shown below in the tables 250 250 ' Covalent Cs 200 200 k, Ro. & Br 150 150 x cs F pl Ti x ]Re 100 100 cl Na FE Li 50 50 Covalent radius Tonie radius a poet Eg 9 17 «35 53 3 a7 85 Atomic number Atomic numberKey to Chemistry Part-II 11 IONIZATION ENERGY The amount of energy which is required to remove an electron from the outermost shell of an isolated atom in gaseous state is called ionization energy. Ionization energy of sodium atom is 496 kJ mol! Na ———> Na*+e 1) = 496 kJ mot! The amount of energy which is required to remove first electron from atom in gaseous state is also called first ionization energy.” ¢.8., Mg ————> Mg* + le 1, = 738 kJ mol! “The amount of energy required to remove second electron from monopositive ion is called second ionization energy." Mg’ ————> Mg’' + le In= 1451 kJ mol! 2" LE value is greater than 1“ LE value: When an electron is removed from an atom, it changes to monopositive ion. The nuclear charge increases due to imbalance ratio of protons and electrons. Attraction of the nucleus increase on the remaining electrons of the cation. Thus for the removal of second electron, more amount of energy is needed than the first one. OF IONIZATION ENERGY VALUES IN PERIODIC TABLE (a) Variation within the group: The factor upon which the ionization energy of an atom mainly depends are: (1) Magnitude of nuclear charge (2) Size of the atom (3) Shielding effect. (4) Nature of the orbital. The shielding effect is actually the repulsion due to electrons in between the nucleus and the outermost shell. This effect increases, as the size of the atom increases due to addition of an extra shell successively in each period hence more number of electrons “shields” the nucleus. Going down in a group, the nuclear charge increases but as the size of the atom and the number of electrons causing the shielding effect also increases therefore ionization energy decreases from top to bottom. For example, it is casier to remove an electron from cesium atom than from lithium atom. The change in ionization energies of IA elements is shown below and also given in the form of table.12 [CH.1] Periodic Classification of Elements and Periodicity Table-IE valu Li Na K Rb Cs 520 496 419 403 376 in IA group in kJ per mol (b) Variation of LE value across the period: Generally, smaller the atom with greater nuclear charge, more strongly the electrons are bound to the nucleus and hence higher the ionization energy of the atom. By moving from left to right in a period, the outer shell remains the same while the nuclear charge increases effectively that makes the removal of an electron difficult and hence the value of ionization cnergy increases. Although the number of electrons also increases in this case but the shielding is not effective within the same shell. Therefore, due to complete outermost shell in them, the removal of electron is extremely difficult. (kimole |) ol ost 1937 0 Ni Atomic number See Table-I.E value of 2" period (kJ per mole) Li Be B c N ° F Ne 520 899 801 1086 1402 1314 1681 2080 In 2™ period LE value generally increases from left to right along the period. Some abnormal values are also present between Be and B and N and O. Values of LE for B and N decreases rather than increasing. This abnormal behaviour is due to stability of Be s-orbitals. Both s-orbitals are coupled. Bes = Electronic configuration of nitrogen has three half filled p-orbitals which is more stable than the configuration of oxygen. No) = Is?, 2s*, 2px!, 2py!, 2pz! Ow) = Is’, 2s’, 2px’, 2py!, 2pz!Key to Chemistry Part-I 13 3._ ELECTRON AFFINITY “The amount of energy released or absorbed when an electron is added to an atom or gaseous ion to form gaseous negative ions.” e.g. F+e ———~+» F E.A. = -337kI mol! Cl+e ——-+> CI E.A = -349 kJ mol! Energy is usually released when electronegative elements absorb the first electron and E.A. in such cases is expressed in negative sign as in the case of halogens. When a second electron is added to a uninegative ion, the incoming electron is repelled by the already present negative charge and energy is absorbed in this process. O+e ——> 0 E.Ai = -l41 kJ mol! O +e ——> 0? E.Az = 780 kJ mol! Unlike the ionization energy, electron affinities can be either positive or negative. Energy is required to add an electron to an already stable configuration. The electron affinity values for beryllium family elements, which have ns* configuration and for the noble gases, which have ns*np® configuration are positive. All other E.A. values of representative elements are negative. Group Noble I gases H_ | Group | Group | Group | Group | Group | Group | He 3 | m | wef] v | we | vi | ey Li Be B Cc N oO F Ne 60 (240) —83 123 0.0 —141 -337 (29) Na Mg Al Si P Ss cl Ar -53 (230) (-50) 120 —14 -200 349° (35) K Ca Ga Ge As Se Br Kr 48 (156) (-36) 116 77 195, 325 (39) rb | sr | In | sn | Sb | Te i Xe -47_| cos) | -34 | -121 | -101 | -183 | -295 | ap Cs Ba Ti Pb Bi Po At Rn 46 (52) —50 —101 —101 (-170) | (-270) (41) Fr | Ra 44) Electron affinities of the representative elements14 [CH.1] Periodic Classification of Elements and Periodicity TREND OF E.A IN PERIODIC TABLE (a) Electron affinity depends upon: (i) Size of atoms (ii) Nuclear charge 400 ei (iii) Number of electrons in the 7 ; 300 valence shell. At The electron affinity generally decreases as we go down in a group due to two reasons. Firstly electrons are added to the larger orbital as compared to the first one, Secondly as we go down in a group force of attraction between the nucleus and electron decreases and they have less attraction Ind Grd ath Sth 6th 200 Po a 100 value of Row of periodic table Fluorine and oxygen have | electron affinities due to smaller size and greater repulsion for incoming electron. 400 y (klimol) H fIN|/ 4.5 6 Atomic number shown in the graph. However (bd) Itappears that there is no pattern of clectron affinity they have relation with electronic configuration. Elements such as_ helium, beryllium, nitrogen and neon which have smaller affinity for extra electrons Electronic configuration with either full filled or half filled sub-shells is stable.Key to Chemistry Part-I 15 4. METALLIC A METALLIC CHARACTERS (a) Metallic Characters: Elements of the periodic table can also be classified as metals, non-metals and metalloids. Metallic characters depend upon the size of atoms. Elements at the top right of periodic table are non-metals and the elements present at the lefi side are metals. Chemically all the elements which have a tendency to form positive ions by losing electrons are considered metals. All metals are good conductor of heat and clectricity, lustrous, malleable, ductile and forms basic oxides. Basic oxide when solved in water form hydroxides and they react with acids to form salt and water. ¢.g., NaxO + HO ———> 2NaOH O + HO ———~» 2KOH CaO + H20 ——— > Ca(OH)2 CaO + 2HCl ———> CaCh + H20 Metallic characters increases from top to bottom in groups due to increase in size of atom and ease to remove electrons. Metallic characters decreases from left to right in periods due to decrease in the atomic radii of elements. The elements of group VIIA (halogens) are least metallic in nature due to their smaller size. (b) Non-metallic Characters: The elements which gain electrons and form negative ions are called non-metals. All the gases are non-metals. Non-metals are poor conductor of heat and electricity, non- metals form acidic oxides. Acidic oxides when dissolved in water form acids. e.g., They and react with bases to form salt and water. CO: + HO ———~ H2COs 02 + HAO ———> H)SO; SOs + Hx ———> H:SOs SO; + 2NaOH ———+ NaSO; + H20 Non-metallic character of an element decreases as the atomic size increase. In a group of non-metals, like halogens, the non- = metallic characters decreases from top to 3& bottom. = Neébilicdaaor Fluorine, which is present at the top is most non-metals. This trend can also be verified in the elements of group VA and VIA. Nitrogen and oxygen are pure non-metals and exist in gaseous state. While elements present at the bottom of these groups like, bismuth, polonium etc., are fairly metallic in nature.16 [CH.1] Periodic Classification of Elements and Periodicity 5. MELTING AND BOILING POINTS Melting and boiling points of elements explains that how strong the atoms or molecules are bonded together. (a) Variation in Period: Along the short periods, the melting and boiling points of clements increase with the number of valence electrons upto group IVA and then decrease upto the noble gases. The melting points of group IA elements are low because each atom in them provides only one electron to form a bond with other atom. Melting points of group IA elements are considerably higher than those of group IA elements because each atom in them provides two binding electrons. Since carbon has the maximum number of binding electrons, thus it has a very high melting point in diamond in which each carbon is bound to four other carbon atoms. In general, the elements which exist as giant network covalent structures have very high melting points An important change occurs when we move from group IVA to VA, VIA, VIIA as the lighter elements of these groups exist as small, covalent molecules rather than as three dimensional lattices. For instance, nitrogen, oxygen and fluorine exist as individual diatomic molecules which have very weak intermolecular force between them, Consequently their melting and boiling points are extremely low (b) Variation in Groups: ‘The melting and boiling points of IA and HA group elements decrease from top to bottom due to the increase in their atomic sizes. The binding forces present between large sized atoms are relatively weaker as compared to those between smaller atoms. For elements of group VIIA which exist in the form of molecules, the melting and boiling points increase down the group. This is because large molecules exert stronger force of attraction due to their higher polarizabilities and intermolecular forces. Fz and Ch are gas ee s, Bro is liquid and Tz and At are solids at room temperature. 1 1000 ing Points (°C) M 0 20 40 60 «680 100 0 2 40 60 Atomic number Atomic number Melting points of Group IV elements Melting and boiling point of halogensKey to Chemistry Part-II 17 state.” a) (2) GB) (4) (3) (6) OXIDATION STATE “The charge which is present on an element in a compound is called its oxidation In ionic compounds number of electrons which an atom loses or gains is its oxidation state. e.g., In NaCl, oxidation state of sodium and chlorine is +1 and —1 respectively. In covalent compounds oxidation state of an element is decided by the difference of electronegativity between two atoms. Element with greater electronegativity has negative charge. For example, SnCly is a covalent compound. The oxidation state of Sn is +4 and chlorine is — Oxidation state of an element is zero in its free state ¢ Ch, OF, Ni, $? ete. Element with maximum positive oxdiation state of representaitve elements is equal to group number. (i) Elements of group IA and IIA have oxidation states +1 and +2 respectively. (ii) Elements of group IITA B, Al, Ga etc. have oxidation state +3. (iii) Elements of group IVA C, Si, Ge, Sn, Pb have oxidation state +4. (iv) Elements of group VAN, P, As, Sb and Bi all shows oxidation state +3, and +5, +3 oxidation state is due to s-inert pair effect. e.g. 115-6 HAS 43-3 S83 25-6 HNOs, HNO», PCh, PCls, HsP Os, HsP Os (v) Elements of group VIA show maximum oxidation +6 except oxygen. However, +4 oxidation state is also common. e.g., 6 HHH SOs, H2SOs, H2S Os (vi) Elements of group VIIA show maximum oxidation state, +7 except fluorine +7, +5, +3 and +1, Oxidation states are more common is group VIIA. ¢.g.. Te 4148-6 st me HC10s, HC1Os, HCIO2, HCIO Metallic representative clements commonly show only positive oxidation state, Most negative oxidation number found in representative elements is equal to the group number minus 8. Negative oxidation states of group VA, VIA and group VIIA is -3, -2 and -1 respectively.18 [CH.1] Periodic Classification of Elements and Periodicity Group number -8 = Negative oxidation state Group 5-8 =33 Group 6-8 =-2 Group 7-8 --1 Negative oxidation state of an element is the number of electrons needed to complete the octet of valence shell (7) Oxidation state of noble gas: is zero because their outer most shell is complete. Table — Common oxidation number of representative elements (only first three periods) Period 1A TIA A IVA VA VIA VIIA 0 1 H He +1 0 -l 2 Li Be B c N F Ne +1 +2 +3 4 +5 =I 0 to to 4 1 3 3 Mg Al Si P Ss cl Ar +2 3 4 +5 +6 +7 0 4 43 +4 +5 3 -2 3 +1 -1 Transition elements, which are shown in B sub-groups of the periodic table, also show the oxidation states equal to their group number as it can be seen for Cu(1), Zn(II), V(V) and Mn(VII). But due to greater number of valence electrons available in partially filled d-orbitals, these elements usually show more than one oxidation states in their compounds. For example: 246-8 +10 -10 CwCh, ZnSOs V20s, ® Os, KMnOs, Mn OxKey to Chemistry Part-II 19 ELECTRICAL CONDUCTANCE “The capability of a substance to conduct electricity without change in composition is called conductivity Electrical conductivity of metals depend upon the movement of free electrons in solid lattice. Following trend is seen in the periodic table about conductivity. a Q) @) (4) (6) General trend in the period table is that, electrical conduc ty is high for metals on left side of each period, lower for metalloids for the centre and negligible for th non-metals of each period The electrical condu nce of metals in group IA and IIA generally increases from top to bottom. However the trend is not free from the individual variation in different atoms. Metals of group IB, which are known as coinage metals, have extraordinary high value of electrical conductance Non-metals, on the other hand, especially of groups VIA and VIIA, show such low electrical conductance that they can be considered as non-conductors In the series of transition metals the values of electrical conductance vary so abruptly that no general trend can be assigned to them, Carbon, in the form of diamond is non-conductor because all of its valence electrons are tetrahydrally bound and unable to move freely, while in the form of graphite, carbon is fairly good conductor because one of its four valence electrons is relatively free to move The lower elements of group IVA, tin and lead, are fairly good conductors and their values of electrical conductivity are comparable with those of their counterparts in group 1A. 8. HYDRATION ENERGY “The amount of heat evolved or absorbed when on mole of gaseous ions or other solute particles dissolves in water to give an infinitely dilute solution.” For example, when one mole of gaseous hydrogen ions are dissolved in water, resulting an infinitely dilute solution, a large amount of heat is liberated. Hi, + Water ———> Hoag) AH =-1075 kJ mol?20 ICH.1] Periodic Classification of Elements and Periodicity Hydration energies of a few negati ¢ and positive ions are shown in the table. Table — Hydration energies of ions Ton | AH, kJ mor! | Ion | AH, kJ mor! | fon | AH, kJ mor! | Ton | AH, kJ mor! Li 499 FE 457 Na’ 390 Mg’ -1s91 | AI" 4613. | cr 384 K -305 Ca* -1562 Br -351 r 307 ation in Group: Hydration energy depends upon the charge to size or volume ratio of the ions. In IA group, the size of ions increases but charge is same, so the hydration energy decreases. Hydration energy of VIIA group also decreases downward due to decrease in the ratio of charge to size. Variation in Period: Hydration energy in period increases trom left to right, For example, hydration energy of Mg” ion is greater than Na” due to greater ratio of charge to size. Hydration energy of Al is greater than Mg** also due to greater ratio of charge to size. PERIODIC RELAT: (a) Halides: “Binary compounds of halogens with other elements are called halides." There are three types of halides: (i) Tonic halides (ii) Polymeric halides (iii) Covalent halides (i) Tonic Halide “If ionic bond is present between the metal and halogen, the halides are called ionic halides.” All elements of group IA form ionic halides with halogens. Element of group IA also form ionic halides with halogen except beryllium. Strongly electropositive clements, having greater clectronegativity difference with halogen atom, form ionic halides. The halides of group IA are considered purely ionic compounds which have high melting points and solid in nature. Such halides have three dimensional lattices consist of discrete ions. Among the pure ionic compounds, the fluorides have the highest lattices energies due to the small size of fluoride ion. Thus for ionic halides the fluorides have the highest melting and boiling points which decrease in the order: Fluoride > Chloride > Bormide > Iodideto Chemistry Part-ll 241 i) Polymeric H: lides: “The halides which have polymeric or bridge structure are called polymeric halide: LLL SL NS SL Al Al i \ / \ JN \ 7 a NZ NG Usually electron deficient halides form such polymeric halides to complete their octet. Less electropositive elements such as Be, Ga and Al form polymeric halides having partly ionic bonding with layer or chain lattices. Covalent Halides: “The halides in which halogens form covalent bond with other elements are called covalent halides.” Elements with high electronegativity form covalent halides. Elements of group IVA, VA and VIA form covalent halides. Some metalloids also form covalent halides Some characters of covalent halides are given below, (a) Bond Polarity and Melting Points of Halides: The lattice of SiC consists of discrete molecules, which are highly polar, The bond in PCl; and $:Ch: are less polar than those of SiCls. On moving from left to right, the clectronegativity difference reduces and the trend shifts towards covalent halides. The gradual change in bond type and melting points of the chlorides on moving across period 3 of the periodic table in shown in the following table. ‘Table — Melting points of chloride of period 3 elements and their bonding character Property Nacl | MgCh | AIC SiC PC S2Ch M.Point (°C) | 801 715 192 68 -93 80 Bonding Ionic Partly | Partly Polar Polar Polar ionic ionic} covalent | covalent | covalent (6) Intermolecular Forces and Physical State of Halides: As the intermolecular forces in covalent halide molecules are weak van der Waals’ forces so they are often gases, liquids or low melting point solids. Physical properties of covalent halides are influenced by the size and polarizability of the halogen atom, lodides, as being the largest and more polarizable ions possess the strongest van der Waals’ forces and therefore have higher melting and boiling points than those of other covalent halides.22 (©) Nature of Halogens and Ionic Character of Halides The variation in bonding character is also present in descending fom top to bottom in the halogen group. In general, for a metal, the order of decreasing ionic character of the halides is: fluoride > chloride > bromide > iodide. For example AIF; is purely ionic compound having melting point 1290°C and fairly a good conductor whereas Alb is predominantly covalent with melting point 198°C and electrically a non- conductor. (4) Oxidation State and Ionic Characters of Halides: In case of an element forming more than one halides, the metal halide in its lower oxidation state tends to be ionic while that in the higher oxidation state is covalent. For example, PbCl: is mainly ionie and PbCL is fairy covalent. This can be explained by the high polarizing power of Pb“ as compared to that of Pb”. (b) Hydrides: The binary compounds of hydrogen with other elements are called hybrides.” According to the nature of bonding, hydrides may be broadly classified into three classes: ionic, covalent and intermediate. Tonic Hydrid The elements of group IA and the heavier members of group ILA. form ionic hydrides which contain H (hydride) ion. These hydrides are crystalline solid compounds, with high melting and boiling points and which conduct electricity in molten state. These hydrides are basic in nature. The tendency towards covalent character increases from left to right in the periodic table. Intermediate Hydrides: Hydrides of beryllium and magnesium represent the class of intermediate hydrides. Their properties are in between the ionic and covalent hydrides. They have polymeric structures and covalent nature. Table — Hydrides of the elements of IA to VILA and IIB sub-groups. IA HA mB OMIA IVA) VASA LiH = | BeH> BH; CH; NH; H,0 HF NaH MgH2 AIH SiHy PH3 HS HCL KH CaH, |ZnH, |GaH; GeHy AsH; H2Se HBr RbH SrH2 CdH2 — InH3 SnHs — SbH3 HoTe — HI CsH Bal PbH; Bis Tonic Intermediate CovalentKey to Chemistry Part-ll 23 (5) (6) a (8) The covalent hydrides are usually gases or volatile liquids. They are usually non-conduetors and dissolve in organic solvents. Their bond energies depend on the size and the electronegativity of the element. Stability of covalent hydrides increases from left to right in a period and decreases from top to bottom in a group. Fluorine forms the most stable hybride and the least stable are those of thallium, lead and bismuth. These hybrides are formed by elements with clectronegativity value greater than 1.8 (Pauling scale). Since the electronegativity of hydrogen is 2.1, most of these hybrides have polar covalent bonds in which hydrogen is carrying a slight positive charge On moving from left to right along a period the electronegativity of the other element increases and the hydrogen-element bond becomes more polar. Due to high polarity the hydrides H2O and HF are capable of forming hydrogen bonds between their molecules. The boiling points of covalent hydrides generally increase on descending a group as shown in the table, except the hydrides like H2O, HF and NHs which due to hydrogen bonding have higher boiling points than might be expected. Covalent hydrides are acidic in nature except CH, which is neutral and NH which is basic. Table — Melting and boiling points of hydrides of groups IVA and VIA Hydrides cH, SiH, Gel, Snly (Group IVA) M.P. °C) -184 =185 165 =150 BP.@C) 164 112 90 -52 Hydrides 120 HLS Se W:Te (Group VIA) M.-P. °C) 0.00 82.9 65.7 48 B.P. °C) 100 -59.6 41.3 -1824 [CH.1] Periodic Classification of Elements and Periodicity (©) Oxides: The compounds of oxygen with other e ments are called oxides." Oxides of representative elements are classified in many ways e.g, (i) Types of bond present in oxides (ii) Acidic or basic nature of oxides. (iii) Oxidation state of oxygen in oxides. We know that metal forms basic oxides and non-metal forms acidic oxides. These acidic and basic oxides combine to form salts. For example: Na,O + CO? ———> NarCOs Na2O + SO; ———> NarSOs “The oxides which show both acidic as well as basic properties are called amphoteric oxides.” Basic Oxi Oxides of IA and TIA group clements from basic oxides except the oxide of beryllium which forms intermediate or amphoteric oxide. Oxide of d-block transition elements are also basic but mostly insoluble in water. Oxide of IA and IIA have high affinity for proton and cannot exist alone in aqueous solution, Therefore, they accept proton and changes to hydroxide ions OH NaxO + H»O ———> 2NaOH CaO + H20 ———> Ca(OH) Amphoteric Oxides: Oxides of relatively less electropositive elements are amphoteric in nature. For example, BeO, AlOs, ZnO, PbO etc., are amphoettic oxides. Amphoteric oxides behave as acid when react with strong base and behave as base when react with strong acids. ¢.g., ZnO + H2SO4 ———> ZnSO4 + 20 ZnO + 2NaOH + HO ———> Na2[Zn(OH)4] ALO3 + 6HCL ———> 2AICh + 3H20 ALO; + 2NaOH ———> 2NaAlO> + H20 (i) (ii) Acidic Oxides: Oxides of non-metals such as C, N, P, S, Cl, F, Br ete. are acidic. When acidic oxides are dissolved in water, they form acids. ¢.g., Co: SO; + H10 ———> H2SOx N2Os + H20 ———» 2HNOs + H:0 ———> H2CO;Key to Chemistry Part-I 25 Trend in Periodic Table: In a period, acid-base characters change from basic (left hand side) to amphoteric and then acidic at right hand side. Example of oxides of third period is given below Na0,MgO — ALOs_—_ SiO», PsO10, SOs, CLOr KY pan, Basic Amphoter Acidic The basic characters of IA and IIA metal oxides increase downward in a group BeO < MgO < SrO < BaO. less basic while BaO In IIB group ZnO i more basic. The same nphoteric while Cd and In oxides of A group, BeO trend is found in transition metal oxid Hg oxides are basic. Oxidation State of Metal and Nature of Oxides: Acid-base characters of oxides also depend upon the oxidation state of metal. The basic characters decrease and acidic characters increase by increasing the oxidation state of metal ions. For example, in MnO, Mn2Os, MnO: and Mn20>, the oxidation state of manganese #3, +4 and +7 respectively. The acidic character increases and basic character decreases as MnO < Mn:O3 < MnO: < Mn20>. In this way Fe:Os is less basic than FeO. Table — Classification of oxide based on acid-base characters Group | 1A | WA | mB | ma | iva | va | via | vA Valence shell] <; 2 opt Isp: Isp? sept [S208 configuration] > B Spi [Sp [Sp |S" |S’ (General laco2 Iwo2 Inno, [MO [Mos [Mo: [mss formula |(M2O°|MO* |M"O™ |MLOs Tu, {M04 |MO: _|M20> ui |p - |B oc oN -~ PF Na Me |- al |si Po oS a K ca {zn Ga Ge As.—s«dSe Br Rb sr Gd-—sd|n Sn Sse Cc Ba He =o Po Basic ‘Amphoterie Acidic Nitrogen forms other oxides like NxO, NO, NO2 and N20Os fluorine form OF2, 2, but not Fs or F20r. Bromine form various oxides as Br>O and BrO2 but BrO; and Br:Os are not known.26 [CH.1] Periodic Classification of Elem THE PERIODIC TABLE ts and Periodicity POSITI OF HYDROGEN Hydrogen is not a metal but in most of versions of the periodic tables, hydrogen is present at the top of group IA. Hydrogen has some similarities and dissimilarities with group IA, IVA and VIIA. (a) Similarities of Hydrogen with Group LA: (1) Hydrogen has one electron in its outermost shell and its electronic configuration is 1s!, Alkali metals also have electronic configuration ns' e.g., Li = Is’,2s! Na = Is?, 2s’, 2p®, 3s! (2) Hydrogen loses one electron like alkali metals and form H H ——> H'+e Na ———> Nav te (3) Both hydrogen and alkali metals have strong tendency to combine with highly electronegative elements such as halogens. H2 + Ck ———> 2HCI 2Na + Cl ———> 2NaCl (4) Like alkali metals, hydrogen can also form ionic bond by transfer of electrons. These ionic compounds dissociate in water. ¢.g., Na‘H", Ca Dissimilarities of Hydrogen with Alkali Metal (1) Hydrogen is a gas whereas alkali metals are solids (Cesium and Francium are liquids above 30°C). (2) Hydrogen needs only one electron to complete its valence shell whereas alkali metals need seven electrons to complete the outermost shell. 3) HY ion cannot exist independently in aqueous solution unlike alkali metals ions, e.g., Na’, K’ ete., H” associates with H:O to form H30) H’ +H,O ——> H30 (4) Alkali metals do not exist in diatomic state like H2 (5) Hydrogen is non-metal while the elements of IA group are metals.Key to Chemistry Part-I 27 (b) qd) (5) Dissimilarities of Hydrogen with Haloge: a (4) (©) a) Q) @) Similarities of Hydrogen with Halogens: Hydrogen requires one electron to complete its outermost shell while elements of group VIIA also require one electron to attain the nearest noble gas configuration, Fi = Clay = Hydrogen is a gas like mos of the halogens. Hydrogen and halogens exist in diatomic state. e.g., lb, Brz and I> By accepting one electron hydrogen and halogens form negative ions. H+le ———> H- (Hydride ion) Cl+ le ———> Cr (Chloride ion) Both hydrogen and halogens form stable ionic compounds with alkali metals. e.g., Nall, NaCl ven electrons Hydrogen has one electron in the valence shell and halogens havi in the valence shell. By losing electron, hydrogen form H” ions while halogens do not form positive ions. Hydrogen combine with oxygen to form very stable oxide (H20) while halogen does not form such stable oxides. Halide ions (F, Cl, Br, T) are stable in aqueous form while H~ is unstable in water. H-+H,0 ———> OH +H) rities of Hydrogen with Group IVA (Carbon Famil Valence shell of hydrogen is filled like those of group IVA, outer most shell of both hydrogen and carbon family is half filled Co = Pr 2p, Hydrogen and carbon combine with other elements with covalent bond. In majorities of reactions of carbon and hydrogen, they act as reducing agents. CuO + Hy ————> Cu+IO SnO2 +C ———> Sn+ CO;Dissimilarit (a) Q) QB) (4) (5) groups, as discus properties do not match exa [CH.1] Periodic Classification of Elements and Periodicity ies of Hydrogen with Group IVA: Carbon and silicon combine with each other or with other elements to form chain type compounds while hydrogen does not show this property. Hydrogen requires one electron to complete its outermost shell while elements of group IVA require four electrons. Carbon can form bond with more than one elements at a time but hydrogen can only form one bond with an element. H | H—cl H—o cl—C—H I | H H Hydrogen exist in diatomic state (H2) while elements of group IVA do not exist in diatomic state. Hydrogen is gas while group IVA elements are all solids. Hydrogen is s-block while carbon in p-block element. Some of the properties of hydrogen are similar to those of the elements of certain above, but this is a fact that hydrogen is a unique element whose tly with any of the groups in the periodic table, However due to partial resemblance in properties with alkali metals and monovalent nature, hydrogen is usually placed at the top of elements in group IA.Key to Chemistry Part-I 29 Qi @ i) EXERCISE Mendeleev in his periodic table, arranged the elements according to their atomic Fill in the blanks: Vertical columns in modern periodic table are called ————— and horizontal rows are called Members of group VIIA are called ————and alkali metals is the family name of group member (iv) Metals form ———— oxides and non-metals form ———— oxides. (¥) Hydrogen can be placed above the groups of the periodic table. (vi) Shielding effect is actually the ———— due to electrons in between the nucleus and the outermost shell. (vii) Noble gases have the ———— values of ionization energy due to their complete outermost shells (viii) When a second electron is added to a uninegative ion, the incoming electron is by the already present negative charge. (ix) Due to having partly filled d-orbitals ———— metals usually show variable valency. (x) Melting and boiling points of halogens ———— down the group. (i) (ii) group, period Halogens, IA (iv) basic, acidic @ | tAtva.via | wi repulsion’ high (viii) repelled (ix) transition @) increase Q.2__ Indicate True or False: (i) InMendeleev’s periodic table elements Be, Mg, Zn and Cd are placed in the same group. (i) The second and third periods contain eighteen elements each30 (iii) (iv) Metals are present in the top right corner of the periodic table. (¥)_ Metalloids are present in the lower half of Groups IVA, VA and VIA. (vi) Hydrogen forms uninegative ion like halogens. (vii) Oxidation state of an clement is related to the number of period it belongs. (viii) Diamond is a good conductor of electricity. (ix) Melting points of halogens decrease down the group. (x) Zinc oxide is an example of amphoteric oxide. (i) | True | Gi) | False True_| (iv) | False | (v) | True (vi) | True _| (vii) | False False | (ix) | False | (x) | True Q.3 Multiple choice questions. Encircle the correct answer: (i) Keeping in view the size of atoms, which orders is the correct one: (a) (b) Ba>Mg (© @ cll (ii) Mark the correct statement: (a) Na’ is smaller than Na atom —(b) Na‘ is larger than Na atom (©) Cl issmaller than Clatom — (d)_ CI (ion) and Cl (atom) are equal in size (iii) | Mark the correct statement: (a) All lanthanides are present in the same group (b) All halogens are present in the same period (c) All the alkali metals are present in the same group (a) All the noble gases are present in the same period (iv) Which statement is incorrect: (a) All the metals are good conductor of electricity (b) All the metals are good conductor of heat (©) All the metals form positive ions (d) All the metals form acidic oxides.Key to Chemistry Part-I 31 (vy) (vi) (wii) (ix) «&) Which statement is correct: (a) (b) (©) (d) Hydrogen resembles in properties with IA, IVA and VIIA elements Hydrogen resembles in properties with IIIA, IVA and VA elements Hydrogen resembles in properties with ITA, IVA and VIA elements Hydrogen resembles in properties with IIA, IIIA and VITA elements Mark the correct statement: (a) (b) ©) (d) The ionization energy of calcium is lower than that of barium The ionization energy of calcium is lower than that of magnesium The ionization energy of calcium is higher than that of beryllium The ionization energy of calcium is lower than that of strontium Mark the correct statement: (a) (d) Electron affinity is a measure of energy required to remove the electron Electron affinity is a measure of energy released by adding an electron Electron affinity is a measure of energy required to excite an electron Electron affinity is measure of energy released by removing an electron Mark the correct statement: (a) (b) (©) (d) Metallic character increases down the group Metallic character increases from left to right along a period Metallic character remains the same from left to right along a period Metallic character remains the same down the group Mark the correct statement: (a) (b) (©) (d) Melting points of halogens decrease down the group Melting points of halogens increase down the group Melting points of halogens remain the same throughout the group Melting points of halogens first increase and then decrease down he group Mark the correct statement: (a) (b) (ce) (d) Covalent character of metal halides increases from left to right in a period Boiling points of group IVA hydrides decrease down the group Tonic character of hydrides increases from left to right in a period The bai ity of group ITA oxides decreases on descending the group32 [CH.1] Periodic Classification of Elements and Periodicity ANSWERS @ (b) (ii) (a) di) | © |i] @ ww) (a) wi) |) | wi) |) 6 @ |} © (3) (a) Q.4 What are the improvements made in the Mendeleev’s periodic table? EH The improvements in Mendeleev’s periodic table are as followings: Qs a) (ii) (iii) How their The periodic table was improved by arranging the elements in ascending order of their atomic numbers instead of their atomic masses. The addition of an extra group (VIII-A) at the extreme right of the periodic table. This group contains noble gases which had not been discovered in Mendeleev’s time. In modem periodic table the elements of single vertical group of Mendeleev’s periodic table is divided into two types of vertical groups, A and B. e.g., In Mendeleev’s periodic table Be, Mg, Ca, Sr, Ba and Zn, Cd, Hg were placed in a single group but in modem periodic table Be, Mg, Ca, Sr and Ba are placed in group II-A and Zn, Cd, Hg in II-B group. the classification of elements in different blocks helps in understanding chemistry? GES This classification is based upon the valence orbital of the element involved in chemical bonding. So this classification is quite useful in understanding the chemical properties of elements especially the concept of valency as oxidation Q6 state, How do you justify the position of hydrogen at the top of various groups? Descriptive question. See text book for details, Q. Qs Why the ionic radii of negative ions are larger than the size of their parent atoms? Why perio Q.1 of Short Question. ionization energy decreases down the group and increases along a a? (ES As we know that: 1 on energy « Nuclear force « 37 Ionization energy « Nuclear force ionic sizeKey to Chemistry Part-I 33 (i) As we go down the group the atomic size increases which results as the decrease nuclear force due to which ionization energy decreases down the group. (ii) While moving from left to right in a period, the nuclear force increases and atomic size decreases which makes the removal of electron difficult and hence the value of ionization energy increases. Q.9 Why the second value of electron affinity of an clement is usually shown with a positive sign? When a second electron is added to a uni-negative ion, the incoming electron is repelled by the already present negative charge and energy is absorbed in this process so, it is usually shown with a positive sign, Q.10) Why metal ic character increases from top to bottom a group of metals? Metallic character increases from top to bottom in groups due to increase in size of atom and e: s¢ to remove electrons having low ionization energy Q.11 Explain the variation in melting points along the short periods. FTTH Melting points in short periods increase upto the middle and than decreases. (i) Increase in melting point is due to decrease in atomic size and increase in inter-atomic forces. (ii) After group IV-A lighter elements of these groups exist as small, covalent molecules and have weak inte! due to which melting points also d -molecular forces creases Q.12. Why the oxidation state of noble gases is usually zero? CE Noble gases consist of He, Ne, Ar, Kr, Xe and Rn. Their atomic numbers are 2, 10, 18, 36, 54 and 86 respectively, As the oxidation state of an element usually depends on the number in bond formation. Noble \ses have completely filled outermost shell and they have zero oxidation state, of electrons which it contribut Q.13 Why diamond is a non-conductor and graphite is fairly a good conductor? EES) Electrical conductance depends upon the number of free electrons. In case of diamond all the valence electrons are used for covalent bond formation and no fiee electrons are available for conduction of electricity and hence diamond is a non-conductor. In case of graphite carbon is fairly good conductor beca its four valence electro electr use one of is relatively free to move and hence can conduct ity34 [CH.1] Periodic Classification of Elements and Periodicity Q.14 Give brief reason for the following: (a) (b) (c) (d) (a) d and f-block elements are called transi n elements? (b) Lanthanide contraction controls the atomic sizes of elements of 6" and 7" periods. (©) The melting and boiling points of the elements increase from left to right up to the middle of p-block elements and decrease onward. (d) The oxidation states vary in a period but remain almost constant in a group. (e) The hydration energies of the ions are in the following order: ABY > Mg** > Na* (f) Ionic character of halides decreases from left to the right in a period. (g)_ Alkali metals give ionic hydrides. (h) Although both sodium and phosphorus are present in the same period of the periodic table yet their oxides are different in nature, Na2O is basic while P2Os is acidic in character, d and f-block elements are less electropositive than alkali and alkaline earth metals. They have intermediate characters between s and p-block elements and hence are called transition elements. In case of Lanthanide and Actinide series there is a gradual decreas size from left to right due to increase in nuclear charge. This gradual decrease in atomic size in these series is known as lanthanide contraction and it controls the size or 6" and 7 period elements. in the atomic Elements of I-A to [V-A group exist as three dimensional, giant structures and number of valence electrons increases up to group IV-A due to which melting points and boiling points increases up to IV-A group. On the other hand elements of V-A up to VII- A group exist as non-polar, small and diatomic molecules having weak intermolecular forces fore melting and boiling points of V-A to onward elements decreases from left to right As the oxidation states of elements is based upon the electronic configuration of elements. In a period of periodic table, the electronic configuration changes but in a group the clectronic configuration remains constant. Therefore due to same electronic configuration in elements of same group, they have same oxidation statesKey to Chemistry Part-II 35. (©) (0) (g) (h) Hydration energy of an ion depends upon the charge and the size of ion. It is directly proportional to ionic charge and inversely proportional to its size. Al’, Mg® and Na” ions are iso-electronic and their size decreases in the following order: Na* > Mg* > AP So hydration energy of AP* will be maximum among these ions. Hydration energies of these ions are given below: Na’ = -390 KJ/mol Mg?! = ~1891 KJ/mol AL’ = -4613 KI/mol Ionic character of halides decreases along a period due to decrease in difference of electro negativity. ¢.g., In 3" period: (i) NaCl and MgCh are ionic halide. (ii) AICh is polymeric halide. (iii) SiC, PCh, S Alkali metals are electropositive elements and loose electron easily. j2 are covalent in nature. M ——> M'+e These metals have low ionization energies. Hydrogen atom accepts one electron and form hydride ion. H+e ——> These metal ions and hydride ion combine to form ionic hydrides. e.g.. 2Na + H2 ————> 2NaH Na is a metal while P is a non-metal. Metals form basic oxides while non-metals form acidic oxides. NaxO when dissolved in water form NaOH Na2O + H10 ———> 2NaOH(base) Base oxide while P20s when dissolved in water form H3POs. P20s + 3H20 ————> 2H5POs (acid) Acidic oxide36 [CH.1] Periodic Classification of Elements and Periodicity (dy Q) (3) (4) 6) (6) a (8) 0) (10) (ay (2) 3) (4) (1s) (16) (7) (18) a9) 20) a1) (22) (23) (24) 25) 26) DO YOU KNOW? fied the elements on the basis of physical and chemical properties of ALRazi the sul ances. Dobreni German chemist in 1929 gave the law of triads, Mendleev corrected the atomic mass of Be and placed it in the II group above Mg, Ca, Sr, Ba. The elements from Cesx — Lun, are called Lanthnides. The elements from Thoo — Lrio3 are called actinides. Cu, Ag, Au of group I-B are called coinage metals. The elements after Us? are called transuranic elements. The elements of group VII are called halogens. The elements of group VI are called chalcogens (ore forming). Oxidation state of O in OF: is +2. AIFs is ionic compound (M.P = 1290°C) but Alls is covalent in nature (M.P = 198°C). PbCh is ionic while PbCl; is covalent. than Be (899 kJ mot"). Ionization energy of O (1314 kJ mol") is less than N (1402 kJ mol"). than Ca (590) (Units of LE = ki/m) The oxides of Be, Zn, Al, Pb are amphoteric. Ionization energy of B (801 kJ mol"') is le: Ionization energy of K (419) is les CHy is neutral hydride. NI Cesium is most reactive metal. is basic hydride. Fluorine is most reactive non-metal. Highest oxidation state (Mn‘”). Helium has highest ionization enei Cesium is strong reducing agent. Heaviest solid is osmium. Lightest gas is hydrogen. Lanthanides and actinides are called rare earth elements.fe as PERIODIC CLASSIFICATION OF 1 ELEMENTS AND PERIODICITY MULTIPLE CHOICE QUESTIONS 7" period of the periodic table contains normal elements: (a) 2 (b) 3 © 4 (@ 8 Periodic table has been divided into four blocks, which blocks contain highest ¢ (a) s (b) p @ d q@) f The division of elements into blocks in the modern periodic table is based on: (a) Shell (b) Sub-shell (©) Orbital (d) All Keeping in view the size of atoms, which order is the correct one: (a) Mg> Sr (b) Ba> Mg (©) Lu>Ce @ cI Mosley concluded by the X-ray studies of the elements that physical and chemical properties of elements depend upon: (a) Atomic mass (b) Atomic no. (©) Mass no. (@) All Which one of the following is not ionic hydride: (a) CsH (b) Lilt (©) HCL (d) NaH 1ICH.1] PERIODIC CLASSIFICATION OF ELEMENTS AND PERIODICITY 10. 12, 13. 14, ‘The element with highest first ionization energy @ B ) Cc @ 0 (@) N Mark the correct statement: (a) Na’ is smaller than Na (b) Na’ is larger than Na (©) Cl is smaller than CL (@) Ch ion and Clare equal The element with atomic number 9 is closest in chemical properties with element of atomic-number: (a) 27 b) 11 (17 (@) 8 Period six in periodic table contain which “block” elements: (a) sp (b) s,p,d © spf (@) sped Who introduced the zero group: (a) Lother Mayer (b) Mendeleev (©) Ramsay (d) Mosley Elements of group II-B are called: (a) Representative elements (b) Transition elements (©) Non-typical transition elements (d) Coinage metal group The elements with lowest M. Pt: (a) Be (b) Mg () Cd (d) Cr Which of the following sets of atoms are arranged in order of decreasing electronegativity? (a) N,O,F (b) Si,P,S (©) F,O,N (@) i, P When hydrogen loses its electron to form H” ion then it resemble: (a) Transition metals (b) Halogen (©) Alkali metals (d)_ Noble gasesOBJECTIVE CHEMISTRY PART-II 3 16. Which of the halides show bridge type structure: (a) NaCl (b) AICh (©) CCh (@) 10 17. Which element of the following shows max, oxidation state: (a) P (b) S (©) Mn (@) Cr 18. M.Ptis highest for the elements of group: (a) IA (b) HA (co) TIA (@) IVA 19. Amphoteric oxide is formed by: (a) Ca (b) Fe (©) Cu (a) Zn 20. In the long form of the periodic table, the most electropo: occupy: (a) Bottom right position (b) Bottom left position (©) Top right position (a) Top left position ela TES) LL (a) 2. (©) 3. (b) 4. (b) 5. (b) 6. () 1. @) 2. @ 9. © 10. | (dd) i (d) 12. (c) 13. (b) 14. (c) 15. (c) 16. (b) 17. (c) 18. (d) 19. (d) 20. (b)[CH.1] PERIODIC CLASSIFICATION OF ELEMENTS AND PERIODICITY Qu i) (ii) SOLVED EXERCISE Fill in the blanks: Mendeleev in his periodic table, arranged the elements according to their atomic Vertical columns in modern periodic table are called ———— and horizontal rows are called Members of group VIIA are called ———— and alkali metals is the family name of group member Metals form ——— oxides andnon-metals form ——— oxides. Hydrogen can be placed above the groups of the periodic table. Shielding effect is actually the ——— due to electrons in between the nucleus and the outermost shell. Noble gases have the ———— values of ionization energy due to their complete outermost shells. When a second electron is added to a uninegative ion, the incoming electron is by the already present negative charge. (ix) Due to having partly filled d-orbitals — metals usually show variable valency (x) Melting and boiling points of halogens ————down the group. elas @ masses (ii) group, period Halogens, IA (iv) basic, acidic @ | tava, via | wi repulsion (vii) high repelled (ix) transition @ rease Q.2__ Indicate True or False: (i) In Mendeleev’s periodic table elements Be, Mg, Zn and Cd are placed in the same group.OBJECTIVE CHEMISTRY PART-Il 5 (ii) iw w) wi The second and third periods contain eighteen elements each. Alkal arth metals are present in Group IIA. Metals are present in the top right corner of the periodic table Metalloids are present in the lower half of Groups IVA, VA and VIA. Hydrogen forms uninegative ion like halogens. Oxidation ate of an element is related to the number of period it belongs. (viii) Diamond is a good conductor of electricity. (ix) Melting points of halogens decrease down the group, (x) Zine oxide is an example of amphoteric oxide. @ | True | Gi) | False | Git) | True | (ivy | False [| (wy) | True (vi) | True | wit) | False | ¢ False | (ix) | False | ( | True Q.3. Multiple choice questions. Encircle the correct answer: (i) Keeping in view the size of atoms, which orders is the correct one: (a) Mg> Sr (b) Ba>Mg (©) Lu>Ce @ cet (i) Mark the correct statement: (a) Na’ is smaller than Na atom —(b) Na’ is larger than Na atom (©) Cl issmalter than Clatom — (d) Cl (ion) and Cl (atom) are equal in size (iii) Mark the correet statement: (a) All lanthanides are present in the same group (b) All halogens are present in the same period (©) All the alkali metals are present in the same group (@) All the noble gases are present in the same period (iv) Which statement is incorrect: (a) All the metals are good conductor of electricity (b) All the metals are good conductor of heat (c) All the metals form positive ionsICH.1] PERIODIC CLASSIFICATION OF ELEMENTS AND PERIODICITY (vy) (vi) (vii) (iii) (ix) () (d) All the metals form acidic oxides Which statement is correct: (a) Hydrogen resembles in properties with IA, IVA and VIIA elements (b) Hydrogen resembles in properties with IIIA, IVA and VA elements () Hydrogen resembles in properties with ITA, IVA and VIA elements. (a) Hydrogen resembles in properties with IIA, IIIA and VIIA elements Mark the correct statement: (a) The ionization energy of calcium is lower than that of barium (b) The ionization energy of calcium is lower than that of magnesium (©) The ionization energy of calcium is higher than that of beryllium (a) The ionization energy of calcium is lower than that of strontium Mark the correct statement: (a) Electron affinity is a measure of energy required to remove the electron (b) Electron affinity is a measure of energy released by adding an electron (©) Electron affinity is a measure of energy required to excite an electron (d) Electron affinity is measure of energy released by removing an electron Mark the correct statement: (a) Metallic character increases down the group (b) Metallic character increases from left to right along a period (©) Metallic character remains the same from left to right along a period (d) Metallic character rem: the same down the group Mark the correct statement: (a) Melting points of halogens decrease down the group (b) Melting points of halogens increase down the group (©) Melting points of halogens remain the same throughout the group (d)_ Melting points of halogens first increase and then decrease down he group Mark the correct statement: (a) Covalent character of metal halides increases from left to right in a period (b) Boi (©) Tonic character of hydrides increas ing points of group IVA hydrides decrease down the group from left to right in a periodOBJECTIVE CHEMISTRY PART-II 7 (d)_ The basicity of group ITA oxides decreases on descending the group Se @ | © @ | © |@wl] @ |o] @ (vi) (b) (vii) (b) ¢ (a) (ix) (b) @) fa) Q.4 What are the improvements made in the Mendeleev’s periodic tab! (EBV The improvements in Mendeleev’s periodic table are as followings: (i) The periodic table was improved by arranging the elements in ascending order of their atomic numbers instead of their atomic masses (ii) The addition of an extra group (VIII-A) at the extreme right of the periodic table. This group contains noble gases which had not been discovered in Mendeleev’s time. (iii) In modern periodic table the elements of single vertical group of Mendeleev’s periodic table is divided into two types of vertical groups, A and B. e.g., In Mendeleev’s periodic table Be, Mg. Ca, Sr, Ba and Zn, Hg were placed in a single group but in moder periodic table Be, N Sr and Ba are placed in group II-A and Zn, Cd, Hg in II-B group. Q.5 How the classification of elements in different blocks helps in understanding their chemist (GESB This classification is based upon the valence orbital of the element involved in chemical bonding. So this classification is quite usefull in understanding the chemical properties of elements especially the concept of valency as oxidation state. Q.6 How do you justify the position of hydrogen at the top of various groups? (GEA Descriptive question. See text book for details. Q.7_ Why the ionic radii of negative atoms? GES see Q.1 of Short Question. Qs (ESB As we know that: ns are larger than the size of their parent ion energy decreases down the group and increases along a