CHEMISTRY 12 PUNJAB CURRICULUM AND TEXTBOOK BOARD, LAHORETextbook Board, Lahore. luced or used for preparation of test helping books etc. _ AUTHORS: © Dr Jameel Anwar » © Dr. Shaukat Ali | © DrM. Akram Kashmiri © Mrs. Nasreen Batool Qasier @ Mrs. Nazeer Ahmad Chaughtai (L) © Mr. Saad Ali Khan ‘© Mr. Naseem Asghar Ginai © Mr Iftikhar Ahmad EDITORS: ° Prot. Dr. Jameel Anwar Dr. Imtiaz Ahmad Syed Ghulam-Akbar Ch. Karam Elahi (L) Mr. Tariq Ahmad Niazi Mr. Zafar Mehdi Zafar Mr. Javed Iqbal Lodhi Mr, Muhammad Shoaib Jehangir eooo0oo0o0 0 COMPOSING, DESIGNING Ex-Director, Institute of Chemistry Punjab University, Lahore. © Prof. Dr. Abid Zia Vice Principal (Rtd.), Gavernment College of Science, Lahore. © Prof. Dr. M. Akram Kashmiri airman, Chemistry Department, SUPERVISION: ¥ RS. _Dr. Saman Jamil nment College University, Lahore. _ AND ILLUSTRATIONS: © Hafiz Inam-ul-Haq © Izhar Sons Printers, 9 Rattigan Road, Lahore © Qadri Graphics,.Lahore ARTIST: @ Aisha Waheed Director (Manuscripts): © Ms. Nisar QamarChapter eer Aw YD Subject! Periodic Classification of Elements and Periodicity s-Block Elements Group IIIA and Group IVA Elements Group VA and VIA Elements The Halogens and the Noble Gases Transition Elements Fundamental Principles of Organic Chemistry Aliphatic Hydrocarbons Aromatic Hydrocarbons Alkyl Halides Alcohols, Phenols and Ethers Aldehydes and Ketones - Carboxylic Acids Macromolecules Common Chemical Industries in Pakistan Environmental Chemistry Glossary Index 20 37 56 79 118 136 169 194 211 228 250 268 291 322 328At room temperature the elements is: “YELLOw [ig EEN Compound Form Uauia TS sturat sone Elemental Form | GREEN Elemental and Eompound Form Appearance in Nature: et eee (lad Asap pps ies, iipetemwwsnen | |? Ete <8 ngad'as? [Arj304s" acnereersl res peo ie ie ue a Ae desta kysa'ss! Ri erie "txeqat'sa%es! Teolst sao? [| proyrrear7e? IRoyst'6 Pca ered s ACHAPTER 1 PERIODIC CLASSIFICATION OF ELEMENTS AND PERIODICITY In this chapter you will learn 1, To describe the periodic table in terms of groups and periods. 2. To describe and explain periodicity in physical and chemical properties. 3. To describe the position of hydrogen in the periodic table. 1.1. INTRODUCTION To achieve a thorough understanding of a complex subject like chemistry, it would be _ highly desirable to fit all the facts into a simple logical pattern. The periodic table of elements has served the purpose to systematize the properties of the elements for well over 100 years. The development of periodic table is one of the most significant achievements in the history of chemical sciences. 1 he Periodic Table provides a basic framework to study the periodic behaviour of physical and chemical properties of elements as well as their compourids, In previous classes, you have learnt about the periodic classification of elements. This chapter describes in more detail the periodic table and the periodicity of elements. 1.1.1 Historical Background The early history of ideas leading up to the Periodic classification of elements is fascinating but will not be treated in detail. Those who made memorable contributions in this field are Al-Razi, Dobereiner, Newlands and Mendeleev. Al-Razi's classifications was based on the physical and chemical properties of substances. Dobereiner, a German chemist in 1829, arranged then known elements in group called Triads, as each contained three elements with similar properties. Newlands who was an English chemist, in 1864, classified 62 elements, known at that time, in increasing order of their atomic masses. He noticed that every eighth element had some properties in common with the first one. The principle on which this Classification is based was called the Law of Octaves. In 1871, Russian Chemist, Dmitri Mendeleev, gave a more useful and comprehensive ——cheme for the classification of elements. He presented the first regular periodic table in which ~elements of similar chemical properties were arranged in eight vertical columns called Groups. ‘The horizontal rows of the table were called Periods. Mendeleev also started by arranging the elements in ascending order of their atomic masses and found that elements having similar chemical properties appeared at regular intervals, This significant observation was called Periodic Law. Mendeleev Jeft 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 indeed discovered and a remarkable agreement was found with Mendeleev's predictions. 1.1.2 Improvementsin Mendeleev's Periodic Table * In order to make the periodic table more useful and accurate, a few improvements were made in Mendeleev’s periodic table. After the discovery ofatomic number by Moseley in 1911, it was noticed that elements could be classified more satisfactorily by using their atomic numbers, rather than their atomic masses. Hence, the periodic table was improved by arranging the elements in ascending order of their atomic numbers: instead of their atomic masses. This improvement rectified a number of confusions present in the old periodic table. The modern Periodic Law states that: “if the elements are arranged in ascending order of their atomic numbers, theirchemical properties repeat in a periodic manner”. ‘Another improvement was the addition of an extra group (group VIIA) at the extreme: right of the periodic table. This group contains noble gases, which had not been discovered in Mendeleev's time. Another confusion in Mendeleev's table was that elements like Be, Mg, Ca, Sr, Ba and Zn, Cd, Hg were placed in a single 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 dividing the elements in two types of vertical groups, A and B. In moder periodic table, Be, Mg. Ca, Srand Baare placedin group IIAand Zn, Cd, Hgin group TB. 1.2 THEMODERN PERIODIC TABLE Inmodem periodic table (see periodic table) all the elements are arranged in ascending order of their atomic numbers. Followings are the essential features of the periodic table. ih Groups and Periods Elements with similar properties are placed in v ertical columns called Groups. There are eight groups .which are usually numbered by Roman numerals | to VIII. Each group is divided into two subgroups, designated as A and B subgroup. The subgroups, containing the representative or normal elements are labelled as A subgroup, whereas B subgroups contain less typical elements, called transition elements and are arranged in the centre of the periodic table. ‘The horizontal rows of the periodic table are called Periods. The essential features of periods are as follows:Chemistry XII = 2 wn a Zz = a: u ty eae Sitesiteei w _ = | | SS ie 2 ty S 2 Sih: Bie Zs Ses 32 sileOsliews 2 2 ii S| fissile Sea: 2 BE o/ Zin Silom ite = ipese zs $ | | | ee ey eS ilees Ww 2 ~Sesieedieitead ces @ es B 4 4d -Shdibgibeihey = 2 2 oSh>uSilewafega iv — = Siiscifemtee ites i i \ [-sile> the sche id PSipouegs ai aoe fee dta Site aed ~ ” o =Le ¥ Periodic Classification of Elements and Periodicity a) _Thereare7periodsin the periodic table numbered by Arabic numerals | to7 ) _‘Theperiod I contains only two elements, hydrogen and helium. ¢) The periods 2 and 3 contain eight elements each and are called short periods. All the elements in these periods are representative elements and belong to A subgroup. In these periods, every eighth element resembles in properties with the first element. As lithium ‘and beryllium in the 2nd period resemble in most of their properties with sodium and magnesium of the 3rd period, respectively. Similarly, boron and aluminium both show ‘oxidation state of +3, fluorine in 2nd period has close resemblances with chlorine of 3rd period. @) _The periods 4 and 5 are called long periods. Each long period consists of eighteen elements. Out of these, eight are representative elements belonging to A subgroup ‘Similar to second and third periods. Whereas the other ten elements, placed in the centre ‘of the table belong to B subgroups and are known as transition elements. In these periods, the repetition of properties among the elements occurs after 18 elements. As after ,,K (having atomic number 19) the next element with similar properties is ,Rb. €) The period 6 is also a long period, which contains thirty two elements. In this period there are eight representative elements, ten transition elements and a new set of fourteen elements called Lanthanides as they start after La. Lanthanides have remarkably ‘similar properties and are usually shown separately at the bottom of the periodic table. f) ‘The period 7 is incomplete so far. It contains only two normal elements ,,Fr and ,,Ra, ten. transition elements and fourteen inner transition elements. The inner transition elements ‘of this period are called Actinides, as they follow ,,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, 2. Some More Families in the Periodic Table: ‘While studying about periods you have noticed that certain rows of elements with similar properties have assigned common names such as transition elements, Lanthanides, Actinides or Rare Earth elements. Similarly, due to their peculiar characteristics, some typical elements belonging to sub-group A, have also been assigned family names. For example, elements of the group IA are called Alkali Metals, because of their property to form strong ~ alkalies with water, 2Nay) + 2H,0(~ —> 2NaOH (a) + Hy@ Similarly, due to their presence in Barth's crust and alkaline character, the elements of PITA are known as Alkaline Earth Metals, Another important family in the periodic table is ily, The name “Halogens” is given to the elements of group VIIA, due to their salt ‘As the gases of group VIIIA are least reactive they are called “Noble Gases”. jare usefull fora quick recognition ofan elementin the periodictable.Genki eS 3. Blocks in the Periodic Table Elements 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, elements of IA and IIA subgroups are called s-block elements because their valence electrons are available in s orbital. The elements of IIIA to VIIA subgroups (except He) are known as p-block elements as their valence electrons are present in p orbital. Similarly in transition clements, clectrons in d-orbital are responsible for their valency hence they are called d-block elements. For Lanthanides and Actinides valence electrons are present in f- orbital hence these elements are called f-block elements, This classification is quite useful in understanding the chemistry of elements and predicting their properties especially the concept of valency or oxidation state. 4. Metals, Non-metals and Metalloids Another basis for classifying the elements in the periodic table is their metallic character, Generally, the elements on the left hand side, in the centre and at the bottom of the periodic table are metals, while the non-metals are in the upper right corner of the table. Some elements, especially lower members of groups, IIIA, IVA and VA (as shown in Table 1.1) have properties of both metals as well as non-metals. These elements are called semi-metals or metalloids. In the periodic table elements of groups IVA to VIIIA, at the top right hand corner above the stepped line, are non-metals. The elements just under the “steps' such as Si, As, and Te are the metalloids. All the remaining elements, except hydrogen, are metals. 1.3 PERIODIC TRENDS IN PHYSICAL PROPERTIES ‘As you have studied so far that in modem periodic table the elements are arranged in ascending order of their atomic numbers and their classification in groups and periods is based on the similarity in their properties. Yet, due to the gradual increase in the number of protons in the nucleus and electrons in outer shells the physical and chemical properties of the elements steadily vary within a group ora period. Here, we study some trends in physical properties. 1. ATOMIC SIZE a) Atomic Radius: ‘Atoms are so small that it is impossible to see an atom even with a powerful optical microscope. The size of a single atom therefore cannot be directly measured, However, techniques have been developed which can measure the distance between the centres of two bonded atoms ofany element. Half of this distance is considered to! be: the radius of the atom. Inthe 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, Ina period, however, as the atomic number increases from left to right, the atomic radius. decreases. This gradual decrease in the radius is due to increase in the positive charge in the nucleus, As the positive nuclear charge increases, the negatively charged electrons in the shells -are pulled closer to the nucleus, Thus, the size of the outermost shell becomes gradually smaller. _=a ication of Elements and Periodicity This effect is quite remarkable in the elements of longer periods in which “a” and “f” subshells are inyolved. For example, the gradual decrease in the size of Lanthanides is significant and called Lanthanide Contraction. b) tonic Radius: ‘When a neutral atom loses one or more electrons, it becomes a positive ion. The size of the atom is decreased in this process because of the two reasons. First the removal of one or more electrons from a neutral atom usually results in the loss of the outermost shell and second, the removal of electrons causes an imbalance in proton-electron ratio, Due to the greater attraction of the nuclear charge, the remaining electrons of the ion are drawn closer to the nucleus. Thus, a positive ion is always smaller than the neutral atom from which it is derived. ‘Theradius of Nais 186 pm and the radius of Na is 102 pm. On the contrary, a negative ion is always bigger than its parent atom. The reason is that addition of one or more electrons in the shell of a neutral atom enhances repulsion between the electrons causing expansion of the shell. Thus, the radius of fluorine atom is 72 pm and that of the fluoride ion (F) is 133 pm. Tn a‘group of the periodic table, similar charged ions increase in size from top to bottom. Whereas within a period, isoelectronic Positive ions show a decrease in ionic radius from left to right, because of the increasing nuclear charge, The same trend is observed for the isoelectronic negative ions ofa period; ionic ‘size decrease from left to right. The variations ‘in atomic and ionic radii of alkali metals and halogens are shown in Fig 1. Land Fig.1.2. Tonization Energy SESE nates pee eae 250, Atomic and ionic radii (pm) See lj pesim toy, 55 Atomic number a e .1 Atomic and ionic radii of alkali metals g 3 8 8 a 3 S 8 g 3 ‘Atomic and ionic radii (pm) 9 17 35 53 Atomic number Fig. 1.2 Atomic and ionic radii of halogensChemistry XI ay energy.So for magnesium, the first ionization cnergy value is the energy required to remove the firstelectron: Mgw —> Me’) + © 1.E,=738 kJ mol" Similarly, the second ionization energy value is the cnergy required to remove the second electron from a positively charged ion. Mg'@) —> Mg"@+ ¢ a) _ Variation Withina Group: The factors upon which the ionization energy ofan atom mainly depends are magnitude of nuclear charge, size of the atom, and the “shielding effect”, 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 Ne 600] shell successively in cach period hence more aa Kear number of electrons shields the nucleus. Going © 400 cs down in a group, the nuclear charge increases butas — the size of the atom and the number of electrons “jz 300 causing the shielding effect also increases therefore 2 ionization energy decreases fromtop to bottom. That § 20 is why in alkali metals, for example, it is easier to § | remove an electron from caesium atom than from 8 1°) lithium atom. The change in ionization energies of i i aah 3 1 19. 37 55 TAclements is shown in Fig. 1.3 Konia b) Variation Across a Period: Fig. 1.3 Ionization energies of alkali metals 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 energy increases, Although, the number of electrons also increases in this case but the shielding is not very effective within the same shell. The trend of ionization energies of short periods is shown in Fig.1.4. The figure also reveals that inert gases have the highest values of ionization energy because due Fig. 1.4 lonization energies of tocomplete outermost shell in them, the removal of Slemrots of short periead clectronis extremely difficult. He g Ss 3 = 8 Tonization energies (kJmol') 8 s ° 0 5 10 15 20 Atomic number3. _ Electron Affinity (E.A.) The electron affinity is the energy released or absorbed, when an electron is added toa ‘gaseous atom to form a negative ion. Fe + © —> Fie E,A=~328 kJ mol! Energy is usually released when electronegative elements absorb the first electron and E.A. in such cases is expressed in negative figures, 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. Om + & -—> OW E.A,= -141kJ mol Ow + ec —> OW E.A,= +744kJ mol" The absorbed energy is expressed as the electron affinity in positive figures. Electron affinity depends upon size of the atom, nuclear charge and vacancies in the outermost shell. Relatively smaller atoms with one or two vacancies in the outermost shell show large values of electron affinity. Electron affinity generally increases with increasing atomic number within a period and decreases from lighter to heavier elements in a given group of the periodic table. Knowledge of electron affinities can be combined with the knowledge of ionization energies to. predict which atoms can easily lose electrons and which can accept electrons more readily. 4. Metallic and Non-Metallic Character It has already been discussed in this chapter that elements of periodic table can be divided into metals, non-metals and metalloids. 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 electricity. A characteristic property of metals is that they form basic ‘oxides which give bases when dissolved in water. Na,0«) a+ 1,0 —> —-2NaOH (aq) Classification of Ele As it becomes easier to remove the electron of an atom bigger in size, therefore metallic character increases from top to bottom ina given group of elements. On the contrary, it decreases from left to right across a period. The elements of group VIIA (the halogens) are least metallic in nature. 1 ‘The elements which gain electrons and form negative ions are called non-metals. All the gases are non-metals. The non-metals are normally poor conductor of heat and electricity. Non- metals form acidic oxides which yield acids on dissolving in water. SO, + HOW a H,SO, (ag) = ‘Non-metallic character of an element, decreases as the atomic size increases. Therefore ina group ofnon-metals like halogens, thenon-metallic character decreases from top to bottom. Thememberat the top, fluorine, i isthe mostnon-metallic element of the periodic table. This trend -also be verified inthe elements of groups VA and VIA. Nitrogen and oxygen are pure non- ‘exist in gaseous state while bismuth and polonium, the members atthe bottom:Chemistry XI aa of 5. Melting and Boiling Points Melting and boiling points of elements tell us something about how strong the atoms or molecules in them are bound together. (a) _Variationin a Period Gn Across the short periods, the melting 2 so9 and boiling points of elements inerease with the # number of valence electrons upto groupIVAand © 2900 then decrease upto the noble gases. The melting points of group IA elements are low because. S 1000 each atom in them provides only one electron to form a bond with other atom. Melting points of group ITA clements are considerably higher than 0 those of group IA elements because each atom in Period2 Period them provides two binding electrons. /tamieparaies eS Fig. 1.5 Variation of melting points with atomic number 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 covalent structures have very high melting points, Fig. 1.5. An important change occurs when we move from group IVA to groups VA, VIA, VITAas 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 molecules which have very weak intermolecular forces between them. Consequently, their melting and boiling points are extremely low. (b) VariationinaGroup The melting and boiling points of IA and Be IIA 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, Fig. 1.6. 2 For elements of group VIIA, which exist in the form of molecules, the melting and boiling, points increase down the group, Fig. 1.7. This is Melting Points (°C) ° because large molecules exert stronger force of 0 20 40 60 «BO, (100 attraction due to their higher polarizabilities. 6. Oxidation State ‘The oxidation state ofan atom in a compounds defined as the apparent charge (withthe Atomic number é Fig.1.6 Melting points of Group IIA elements Sasi“10 sign), which it would carry in the compound. In ionic compounds, it is usually the number of electrons gained or lost by the atom, As in the case of sodium chloride, the oxidation states of sodium and chlorine are + 1 and-l, respectively. In covalent compounds, it is decided on the basis of the difference in their relative electronegativities. For example, SnCl, is a covalent compound. The oxidation state of tin is + 4 and that of chlorine is -1. The oxidation state of an elements zero ints free state. ing Points (°C) 3 s Boiling and M & 3 Oo 20 40 60 Atomic number Fig.1.7 Boiling (————-) and melting points ( ) of halogens The oxidation state of a typical element is directly or indirectly related to the group number to which the element belongs in the periodic table. The elements of group IA to IVA have the same oxidation siates as their group numbers are, Just as B, ‘Al and Ga belong to group IIIA, hence, they always show oxidation state of +3. So, for the elements of these groups, the oxidation state is same as the number of electrons present in the valence shells of the elements. However, for the elements of group WA, the oxidation states are either the number of electrons present in the valence shell (which is same as their group number) or the number of vacancies available in these shells. For example, N, P, As and Sb frequently show +3 as well as +5 oxidation states. Elements of group VIA show almost similar behaviour. In H,SO,, sulphur shows the oxidation state of +6, which is the number of electrons in its outermost shell whereas its oxidation state is -2 in H,S, which is the number of vacancies in the shell. In group VIIA elements oxidation state is mostly —1, which is again the number of ‘vacancies in their outermost shells, Group VITTA elements, which are also called zero group elements, usually show zero oxidation state because there is no vacancy in their outermost: shells. Transition elements, which are shown in B subgroups of the periodic table, also show the oxidation states equal to their group number as it can be seen for Cu(1), Zn(11), V(V), Cr(V1) and Mn (VII). But due to greater number: of valence electrons available in partly filled d-orbitals these elements usually, show more than one oxidation states in their compounds. % Electrical Conductance One of the most familiar properties of metals is their ability to conduet electricity. This property is mainly due to the presence of relatively loose electrons in the outermost shell of the element and ease of their movement in the solid lattice. The electrical conductance of metals in groups 1A and ILA, generally increases from top to bottom. However, the trend is not free fromthe individual variation in different atoms. Metals of group IB, which are known as coinage metals, have extraordinary high values 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 bad conductors or insulators. aeChemisty 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 ofits valence electrons are tetrahedrally 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 groupIA. 8. __ Hydration Energy The hydration energy is the heat absorbed or evolved when one Table 1.2 Hydration mole of gaseous ions dissolve in water to give an infinitely dilute solution, —~2“#<2ettons For example, when one mole of gaseous hydrogen ions are dissolved in | 10" | Hs. water resulting an infinitely dilute solution, a large amount of heat is liberated: beef ot Hiw+H,Om —> H,O%q AH, =-1075k mol" abd lat, Hyzdration energies of a few negative and positive ions are shown 3 ae eee inthe Table 1.2. cea eat Itis evident from the table that hydration energies highly depend | am | _4gr3 upon charge to size ratio of the ions. Fora givenset ofions,forexampleof | — | _4ay group IA, charge to size ratio decreases from top to bottom inagroup,the | co, | 443 hydration energy also decreases in the same fashion. On the contrary, the | p- | 594 hydration energy increases significantly on moving from lefttorightina | ~ | 549 period as the charge to size ratio increases, as found in the metal ions of third period. 1.4 PERIODIC RELATIONSHIP IN COMPOUNDS a) Halides: ? Halides are the binary compounds which halogens form with other elements. The physical properties of halides are largely determined by the nature of bonding present in them. On this basis, halides can be classified into two general classes: ionic and covalent. In between the two, there is another class of halides in which the halogen atom acts as a bridge between the two atoms of the other element, such halides are termed as “Polymeric” halides. Strongly electropositive elements, having greater electronegativity difference with halogen atom, form ionic halides, The halides of group IA are considered purely ionic compounds, which are high melting point solids, Such halides have three-dimensional lattices consisting of discrete ions. ‘Among the pure ionic compounds, the fluorides have the highest lattice 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 > bromide> iodide,2 T Periadie Classification of Elements and Perio ‘Less electropositive elements, suchas Table 1.3 Melting Points of Chlorides of Period o F , i Chi Be, Ga and Al form polymeric halides having Three Elements and Their Bonding Character partly ionic bonding with layer or chain [Name of Property ~ lattices, The lattice of SiCl, consists of discrete |.C°mPOUNdS I rctting point | Type of bonding molecules, which are highly polar. The bonds eC) in PCl,, and S,Cl, are less polar than those of | NaCl 308 Tonic SiCI, On moving across the periodic table from | MgCl, 75 Partly ionic left to right, the electronegativity difference | AICI, 192 Partly ionic decreases and the trend shifts towards covalent | sic, -68 Partly covalent halides. The gradual change in bond type and PCI, -93 Partly covalent melting points of the chlorides on moving | s,ci, -80 Partly covalent across period 3 of the periodic table is shown in Table. 1.3. As the intermolecular forces in covalent halide molecules are weak van der Waal's forces $0 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. Iodides, as being the largest and more polarizable ions, possess the strongest van der Waal's forces and therefore have higher melting and boiling points than those of other covalent halides, The variation in bonding character is also present in descending from top to bottom in the halogen group. In general, for a metal the order of decreasing ionic character of the halides is: fiuoride > chloride > bromide > iodide. For example, AIF, is purely ionic compound having melting point 1290°C and fairly a good conductor, whereas, All, is predominantly covalent with melting point 198°C and electrically a non-conductor. 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 ionic and PbCI, is fairly covalent. This can again be explained by the high polarizing power of Pb“ as compared to that of Pb™. b) Hydrides ‘The binary compounds of hydrogen with other elernents are called hydrides. According to the nature of bonding, hydrides may be broadly classified into three classes: ionic, covalent and intermediate, The elements of group IA and the heavier members of group IIA form ionic ‘hydrides, which contain H’ (Hydride) ion: These hydrides\are crystalline solid compounds, with high melting and boiling points and whichi condnct/electricity in molten state. The tendency towards covalent character increases on moving from left to right in the Periodic Table. Hydrides of beryllium and magnesium represent the class of intermediate hydrides. Their properties are in ‘between the ionic and covalent hydrides: They bave!polymeric’structures and covalent nature,—_—_—_—_—_—_ Chemistry XIU lis! Table 1.4. Hydrides of the Elements of IA to VIIA and IIB Subgroups. IA HA IB 1A IVA VA VIA VIA Lil Bel, cH, NH, HO HE NaH MgH, SiH, PH, HS HCI KH CaH, ZnH, GeH, AsH, H,Se HBr RbH StH, aH, SnH, SbH, H,Te HI CsH Bal, : PbH, BiH, IONIC INTERMEDIATE COVALENT The covalent hydrides are usually gases or volatile liquids. They are nén-conductors and dissolve in organic solvents. Their bond energies depend on the size and the clectronegativity 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 hydride and the least stable are those of thallium, lead and bismuth. These hydrides are formed by elements with electronegativity values greater than 1.8 (Pauling Scale). Since the electronegativity ofhydrogen. is, 2:15 most of these hydrides aN ola arses Melting and Boiling points of Hydrides covalent bonds in which hydrogen is Groups IV A and VLA carrying a slight positive charge. On moving from left to right across a period Hydrides Properties the electronegativity of the other |(Greup IVA) [Melting point (°C) [Bolling point C) element increases and the hydrogen- || CH a cw element bond becomes more polar. Due | * ae # 2 ae to eh pau as oe HON ey aH “32 and HF are capable offorminghydrogen |e. yay 7 bonds between their molecules. The [=m aa re boiling points of covalent hydrides ag 85.5 ~603 generally increase on descending « | yfse aK -42 group as shown in Table 1.5, except the | 4-7 = 49 =h hydrides like H,O, HF and NH, which, due to hydrogen bonding, have higher boiling points than mightbe expected. c) Oxides Oxygen forms compounds, called oxides, with almost every other element in the periodic table. Since, many of these havé quite unusual properties, there is an extensive and varied chemistry of the compounds of oxygen. Oxides can be classified in more than one ways: based upon the type of bonding they have as well as their acidic or basic character. We shall discuss here the classification based on their acidic or basic behaviour. In this chapter, you have already studied that metal oxides are basic in character as they yield bases in water andication of Elements and Periodicity non-metallic oxides are acidic because they form acids in water. Basic oxides and acidic oxides react With one another to give salts, for example: NaOw + SOs —> Na,SOm There isa third type of oxides, which show both acidic and basic properties, these oxides are called amphoteric oxides. The classification of elements which form oxides of acidic or basic and amphoteric properties is shown in Table 1.6. . Table 1.6: Classification of Oxides Based on their Acid and Base Character 1A IVA VA ~ BASIC AMPHOTERIC ACIDIC ‘The oxides of alkali and alkaline earth metals except beryllium are basic and contain O™ ions. The O* ion has high affinity for proton and cannot exist alone in an aqueous solution. Therefore, it immediately takes proton from water and forms OH" ion. Oxides of nonmetallic elements i.e. of C, N, P and S are acidic in nature. They generally dissolve in water to produce acidic solutions. Oxides of relatively less electropositive elements, such as BeO, Al,0,, Bi,O,and ZnO are amphoteric and behave as acids towards strong bases and as bases towards strong acids ZnO (s) + H,SO,() —> — ZnSO, +H,OW ZnO (s)+2NaOH aq) +H,O() —> —Na,[Zn(OH),]J aq) In a given period, the oxides change from strongly basic through weakly basic, amphoteric and weakly acidic to strongly acidic, e.g. Na,O, MgO, Al,,, P,O,., SO, Cl,O,.The basic character of main group metal oxides increases on descending a group of the periodic table, (€.g. BeO < MgO < CaO Cue) + 1,00 Sn0,() + Cu) —> Sn) + CO,@) Hydrogen also shows marked differences with carbon and rest of the group members. For example, carbon and silicon form long chain compounds, when their atoms combine with each other, while hydrogen does not form such compounds. Similarly, carbon can simultaneously form bonds with more than one elements, whereas hydrogen due to having only one electron can combine with only one elementata time. Some of the properties of hydrogen are similarto those of the elements of certain groups, as discussed above, but it is a fact that hydrogen is a unique element whose properties do not match exactly with any of the groups in the periodic table. However, due to partial resemblancein properties with alkali metals and monovalent nature, hydrogen is usually placed at the top of elements in group IA. KEY POINTS lL. Although a number of chemists attempted to classify the elements but Dmitri Mendeleev gave the most useful and comprehensive classification. 2. In Mendeleey's periodic table the elements were arranged according to the ascending order of their atomic masses. » ‘The modem periodic law states “if the elements are arranged in ascending order of their atomic numbers, their chemical properties repeatin a periodicmanner.”” In modem periodic table elements with similar properties are placed in eight verticalwr OO TT lo Clasfcaton of Elements and Periodicity 10. ll. 12. 1h 21. 22) ‘columns called groups. Each group is divided into two subgroups A and B. Normal or typical elements are placed in subgroup A and transition elements are placed in subgroup B. fi ‘The seven horizontal rows of the periodic table are called “periods”. Metals‘of subgroups IA and IIA are called Alkali metals and Alkaline earth metals, . respectively. Members of subgroup VIIA are called halogens. Due to their less reactivity the elements shown in subgroup VIII A are called noble gases. Elements of periodic table can also be classified into s-block, p-block, d-block and fblock elements depending upon the valence orbital which is in the process of completion. Elements of periodic table can also be divided into metals, non-metals and metalloids depending upon their properties, Atomic radii increase from top to bottom in a group and decrease along period. Positive ions are always smaller than their parent atoms while the negative ions are usually largerthan the atoms from which they are formed. Tonization energies increase along a period and decrease down the group. Electron affinities generally increase with increasing atomic number within a period and decrease from lighter to heavier elements in a given group. Metallic character of elements increases down the group and decreases along aperiod. ‘The oxidation state of a typical element is directly or indirectly related to the group number to which the element belongs in the periodictable. The electrical conductance of an element depends upon the number of free or moveable electrons. ‘There are three types of halides: ionic, polymeric and covalent. Halides of group IA are ionic innature, have three dimensional lattices with high melting and boiling points. There are three types of hydrides formed by the elements of periodic table: ionic, intermediate and covalent. Highly polarhydrides show hydrogen bonding in them. ‘Oxides may be divided on the basis of their acidic, basic or amphoteric character. Metallic oxides are basic in character, non-metallic oxides are acidic in character and ‘oxides of less electropositiye elements like Zn.and Pb are amphoteric. Hydrogen is unique element of the periodic table, Due to similarities in properties it can beplacedat the top of group IA orIVAor VIIA.Ql @ Gi) ii) (iv) ) (vi) (vii) (viii) (es) (x) Q2. @ Gi) Gi) Gy) ) Wi) (vii) (viii) ) & 3. @ i) EXERCISE Fillin the blanks. Mendeleev in his periodic table, arranged the elements according to their atomic Vertical columns in modem periodic table are called and horizontal rows are called Members of group VIIA are called and alkali metals is the family name of group members. Metals form oxides and non-metals form oxides. Hydrogen can be placed above the groups ofthe 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. Due to having partly filled d-orbitals metals usually show variable valency. Melting and boiling points ofhalogens, down the group. Indicate True or False. InMendeleev's periodic table elements Be, Mg, Zn and Cd are placed in the same group. ‘The second and third periods contain eighteen elements each. Alkaline earth metals are present in Group ITA. Metals are present in the top right comer of the periodic table. Metalloids are presentin the lower halfof GroupsIVA, VA and VIA Hydrogen forms uninegative ion like halogens. Oxidation state ofan elementis related to the number of period itbelongs. Diamond isa good conductor of electricity: Melting points of halogens decrease down the group. Zinc oxide is an example of amphoteric oxide. Multiple choice questions. Encircle the correct answer. Keeping in view the size of atoms, which order is the correct one? a) Mg>Sr b) Ba>Mg oc) Iw>Ce. @ Clr Mark the correct statement: a) _Na‘issmallerthanNaatom 6) Na’ islargerthanNaatom — ©) CVissmallerthanClatom d) Cr (jos) and Cl tun) ceeqal ars————— Periodic Classification of Elements and Periodicity Gi) (iv) @) Wi): (vii) iii) Gx) Mark the correct 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. d). _ All the noble gases are present in the same period Which statement i a) _Allthe metals are good conductor of electricity. b) _Alll the metals are good conductor of heat. c) All the metals form positive ions. 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 IIA, IVA and VIA elements d) Hydrogen resembles in properties with ITA, 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. d) _ 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. c) 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. c) Metallic character remains the same from left to right along a period. d) Metallic character remains the same down the group. Mark the correct statement: a) _ Melting points of halogen is decreased down the group. b) Melting points of halogens inierease down the group. o) Melting points of halogens remain the same throughout the group. d) Melting points of halogens first increase and then decrease down the group.Chemistry XI ae 19! @® Q4. Q5. Q6. A Qs. Q9. Q10, Qu Q2 Q13. Qi Mark the correct statement: a) Covalent character of metal halides increases from left to right in a period. b) _ Boiling points of Group IVA hydrides decrease down the group. ©) __ Ionic character of hydrides increases from left to right in a period. 4) The basicity of group IIA oxides decreases on descending the group. What are the improvements made in the Mendeleev's periodic table? How the classification of elements in different blocks helps in understanding their chemistry? How do youj fy the position ofhydrogen at the top of various groups? Why the ionic radii ofnegative ions are larger than the size oftheir parent atoms? Why ionization energy decreases down the group and inereases along a period? Why the second value of electron affinity ofan element is usually shown with a positive sign? Why metallic character increases from top to bottom ina group of metals? Explain the variation in melting points along the short periods. Why the oxidatio tate of noble ga susually zero? Why diamond is anon-conductor and graphiteis fairly a good conductor? Give briefreason forthe following. a) dand f-block elements are called transition elements. oe b) Lanthanide contraction controls the atomic sizes of elements of 6th and 7th periods. c) The melting and boiling points of the elements increase from left to the right upto the middle of s- and p-block elements and decrease onward. 4) Theoxidation states vary ina period butremain almostconstant in agroup. ) _ Thehydration energies of the ions are in the following order: Al*>Mg">Na” f) Tonic character of halides decreases from leftto the right ina period. 2) _Alkalimetals 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, Na,O is basic while P,O, is . acidic in character.ethe electronic configuration ofs-block elements in sequence. 2 The occurrence of group IA and ITA elements and the peculiar behaviours of lithium and beryllium. 3, The difference in the physical properties of group IA and IIA elements as well as the differences in the chemical behaviour of their compounds. 4. Thecommercial preparation ofsodium. 5. _ Howsodiumhydroxideis commercially prepared. 6. _Theroleof gypsum and lime in agriculture andindustry. 2.1 INTRODUCTION The s-block elements are the metals in Group IA and Group ITA of the periodic table. They are called the s-block elements because s-orbitals are being filled, in their outermost shells. The elements of group IA except hydrogen are called “Alkali metals” while those of ILA are named “Alkaline-earth metals”. ‘The name alkali came from Arabic, which means 'The Ashes'. The Arabs used this term for these metals because they found that the ashes ofplants were composed chiefly of sodium and potassium. Alkali metals include the elements, lithium, sodium, potassium, rubidium, cesium and francium. These are yery reactive metals, produce strong alkaline solutions with water. The alkaline-earth metals are beryllium, magnesium, calcium, strontium, barium and radium. They are called alkaline-earth because they produce alkalies in water and are widely distributed in earth's crust. ? ‘The alkali and alkaline earth metals include the most reactive electropositive elements anda study oftheir electronic configurations will help in understanding their properties. 2.1.1 Electronic Configurations ofs-Block Elements. Alkali Metal Alkali metals have only one electron in''s' orbital of their valence shell. All alkali metals Tose their one electron of the valence shell to form monopositive ions M” because their ionization energy values are very low. They form ionic compounds and show +1 oxidation state. EEChemistry X17 a The electronic configurations and some physical constants of alkali metals are given in Table2.1. P ‘Table 2.1 Electronic Configurations and Physical Constants of Alkali Metals Properties Li Na K Rb Cs | ‘Atomic number 3 il 19 37 55 Electronic configurations Is2s' | [NeJ3s' | [Ari4s! | [Kr]ss‘ | [Xe]6s! Ionization energy (ki/mol) 520 | 496 419 403 316 Electron affinity (ki/mol) 60 53 48 45 47 Electronegativity 10 09 08 08 07 Atomic radius 152 186 27 248 265 Tonic radius of |+ion(pm) 76 102 138 152 167 Melting points(°C) 181.0 98 6 39.0 | 285 Boiling poimts(°C) 1347 | 881 166 705 690 Density gin/em’ at (20°C) os3 | 097 | 0.86 1.53 19 Heat of hydration (kJ/mol) 505 475 384 345 310 Alkaline Earth Metals Alkaline earth metals have two electrons in 's' orbital of their valence shell. All alkaline carth metals lose their two electrons to form dipositive ions M™, because their ionization energy values are low. They form ionic compounds and show + 2 oxidation state. The electronic configurations and some physical constants of alkaline earth metals are given in Table 2.2. Table 2.2 Electronic Configurations and Physical Constants of Alkaline Earth Metals Properties Be” Mg Ca ‘Atomic number 4 12 20 Electronic configurations 1s2s [Ne]3s* | [Ar]4s* Tonization energy (ki/mol) 899 738 590 Electron affinity (ki/mol) 240) 230 156 Electronegativity 15 Gia) 1.0° ‘Atomic radius 112 Tonicradius of 2+ion (pm) RD Melting points (°C) ieee Boiling points (°C) 2500 Density, gm/cm’ at (20°C) Tasos Heat ofhydration (ki/mol) 2590Tal Block Element Ingoing downa group the number of shells increases by one at each step and equal tothe number oftthe period to which the element belongs. 2.1.2 Occurrence of Alkali Metals ‘Table 2.3 Common Minerals of The Most Important Alkali Metals Dueto high reactivity, the alkali metals foccurinmature in the combined state. None of. |~2Zco-aeral_CRemicalormu’s _} thealkali metalsis found free innature, Sodium |L!thium i and potassium are abundant alkali metals and [SPedumene LiAMSiO)), each constitutes about 2.4 percent of earth's |Sedum crust. Most of the earth's crust is composed of |RockSalt(Halite) NaCl insoluble alumino-silicates ofalkali metals. eae saltpeter pa: ie Lithium deposits, usually in the form |N#"°" ia,CO, HH of complex minerals, are widely scattered over |""°"* Na,CO,.2NaHCO,.2H,0 the earth, An important commercial source of |2°™_ Na,B,0,-10H,0 lithium is the mineral spodumene, LiAMSiO,),. [Potassium Small amounts of rubidium and Saar pee GH,O a a ee /Alunite(Alum Stone) K,SO,.Al(SO,),.4Al(OH), been prepared artificially in the laboratory and is very unstable, thus a very little is known aboutthis metal. Table 2.4 Common Minerals of the Alkaline-Earth Metals 2.1.3 OccurrencéofAlkaline Earth Metals -U=™=2tMiner#| Chemica! Formula jeryllium Being very reactive, alkaline earth metals (Beryl Be,Al,(Si0,), also do not occur in free state. The compounds of |Chrysoberyl ALBeO, these metals occur widely in nature. Magnesium Magnesium and calciumare very abundant |Magnesite Mgco, in earth's crust. The outer portion of the earth was _|Dolomite MgCO,.CaCO,, originally in the form of silicates and alumino- |Camallite KCLMgCl,,6H,0) silicates of alkaline earth metals. Magnesium and |EPsomsalt MgSO,7H,0 calcium, with sodium and potassium are present in [S04 ton® (talc) H.Mg\(Si0,), ieee seme’ Asbestos CaMg(SiO,), . 5 : Calcium Magnesium halides are found in sea |eaicite(Limestons) CaCO, Water. Magnesium is an essential constituent of | Gypsum CaS0,210 SoD ; Fluorite CaF, Calcium phosphate, Ca,(PO,), andcalcium |Phosphorite Ca,(PO,), fluoride, CaF, are also found as minerals. Calcium Strontium is an essential constituent of many living |Strontionite $1C0, ‘organisms. It occurs as skeletal material in bones, Barium teeth, sea-shells and egg shells. Barite BaS0, aChemistry X17 a Radiumis arare element. It is of great interest because of its radioactive nature, 2.1.4 Peculiar Behaviour of Lithium In many of its properties, lithium is quite different from the other alkali metals. This behavior is not unusual, because the first member of cach main group of the periodic table shows marked deviation from the regular trends of the group asa whole, ‘The deviation shown by lithium can be explained on the basis ofits small radiusand high charge density. The nuclear charge of Li’ ion is screened only by a shell of two electrons. The so called 'anomalous' properties of lithium are due to the fact that lithium is unexpectedly far less electropositive than sodium. Some of the more important differences of lithium from other alkali metals are listed below: 1. Lithium is much harder and lighter than the other alkali metals. 2. The lithium salts of anions with high charge density are generally less soluble in water than those of the other alkali metals, e.g. LiOH, LiF, Li,PO,,Li,CO,. 3. Lithium forms stable complex compounds, although complex formation generally is not aproperty of alkali metals. One of the stable complexes formed by lithium is [Li(NH,),J" 4 Lithium reacts very slowly with water, while other alkali metals react violently. 5. Lithium salts of large polarizable anions are less stable than those of other alkali metals, Unlike other alkali metals lithium does not form bicarbonate, tri-iodide or hydrogen sulphide at room temperature, 6. When burnt in air lithium forms only normal oxide, whereas the others form peroxides or superoxides. 7. Lithium hydride is more stable than the hydrides of other alkali metals. Lithium compounds are more covalent, that is why its halides are more soluble in ‘organic solvents and the alkyls and aryls of lithium are more stable than those of other alkali metals. 9. _Lithiumis the leastreactive metal of all the alkali metals. 10. When acetylene is passed over strongly heated lithium, it does not produce lithium acetylide, but other alkali metals form the corresponding metallic acetylides. 2Nat+ C,H, —> NaC=CNa + H, Sodium acetylide ll, Lithium has low electropositive character, thus its carbonaté and nitrate are not'so stable and therefore decompose giving lithium oxide. Carbonates of other alkali metals do not decompose. Decomposition of lithium nitrate gives different products than the nitrates of other alkali metals, Li,CO,(s) — = Li,0@)+CO,@) ALINO\s) —> 2Li,0(9)+4NO,(2)+0, (2) 2NaNOys) —> 2NaNO,@)+0,@)s-Block Elements ‘12, Lithium hydroxide when strongly heated, forms lithium oxide but the other alkali metal hydroxides do not show this behaviour. , 2LiOHe -B#45—Li,O@)+ HOW 13. _Lithiumreacts with nitrogen to formnitride, while the other members of the group do not give this reaction. 6LI@+Ni@ — > 2Li.Nw 14. Lithium chloride has an exothermic heat of solution, whereas chlorides of sodium and potassium have endothermic heats of solution. 15. Lithium carbide is the only alkali metal carbide formed readily by the direct reaction. 21.5 PeculiarBehaviour of Beryllium Beryllium is the lightest member of the series and differs from the other group IIA elements in many ways. This is due to its small atomic size and comparatively high electronegativity value. The main points of difference are: 1. _ Beryllium metal is almost as hard as iron and hard enough to scratch glass. The other alkaline earth metals are much softer than beryllium but still harder than the alkali metals. 2. The melting and boiling points of beryllium are higher than other alkaline earth metals. (Table 2.2). 3. __Asreducing agents, the group IIA metals are all powerful enough to reduce water, at least in principle, However, with water, beryllium forms insoluble oxide coating that protects it from further attack. 4. _ Beryllium in particular is quite resistant towards complete oxidation, even by acids, because ofits BeO coating. 5. _ Beryllium is the only member of its group which reacts with alkalies to give hydrogen. The other members do not react with alkalies. Bejs)+2NaOH(aq) 4 —> ‘Na,BeO,(s) + H,(s) Sodium beryllate 2.2 GENERALBEHAVIOUR OFALKALI METALS ‘The reducing property of ari clement depends on'the magnitude ofits ionization energy. Reducing agent is a substance which can lose electrons. Since alkali metals have got low ionization energies, so they are strong reducing agents. They are highly electropositive. They Teactreadily with halogens giving alkali metal halides. 2.2.1 Trendsin Chemical Properties of Alkali Metals ne Low ionization energies make the alkali metals, the mostreactive family of metals. 2 Very high second ionization energies indicate that oxidation number higher than +1, areThe cations of alkali metals have low charge and large radii than the radius of any cation from the same period, so the lattice energies of their salts are relatively low. Consequently, most of the simple salts of the alkali metals are water soluble. Most of the salts are dissociated completely in aqueous solution and the hydroxides are among the strongest bases available. They react with oxygen and the surface is tamished due to the oxides formed. Only lithium bums in airto form the normal oxide, Li,O (white solid). 4LigtO@ —> 2Li,0® = Lithium oxide The exposed metals are oxidized almost immediately by oxygen in air, and in the presence of moisture. The oxides formed react with CO, in the atmosphere to form: carbonates. Li,0@)+CO,(@) = —> Li,CO,(s) Lithiumoxide Lithium earbonate Sodium will undergo a similar reaction, but only if the supply of oxygenis limited. Inthe presence of excess of oxygen, sodium forms the pale yellow peroxide. 2Na(s)+O,(e) — Na,0,(s) Sodium peroxide Potassium, rubidium and caesium react with oxygen to form superoxides (orange yellow). Caesium explodes spontaneously when itis in contact with air or oxygen. K@+O,@) —: KO,(s) Potassium superoxide Very rapid reactions occur when alkali metals react with water. A small piece of sodium (potassium or lithium) floated on water reacts vigorously to liberate hydrogen and produce metal hydroxide. The reaction is highly exothermic. The energy produced by the reaction may even ignite the hydrogen. PANE (+ 2H Ow — > 2NaOH@q+H, ie) The reaction becomes increasingly vigorous from lithium to caesium, Potassium, rubidium and caesium are so highly reactive that they react with ice even at-100°C. Alkali metals form ionic hydrides with hydrogen. 2M) +H, () ——4 2M*H™%) Rubidium ‘and caesium react violently with hydrogen at room temperature. The other three metals require elevated temperature in order to form the hydride. Lithium and sodium hydrides are useful sources ofhydrogen when treated with water. LiH@+H,O@ —> LiOH (q+ H,(@) Due to the presence of hydride ion (H), the ionic hydrides are used as powerfulreducing agents,Block Elements 7, _Lithiumis the only Group IA metal that combines with nitrogen and carbon to form nitride and carbide, respectively. GLIQ+N@) —> 2Li.No Lithium nitride ALi@+Cw —> LIC Lithium carbide Alkali metals react easily with halogens to give halides. Lithium and sodium, for example, react slowly with chlorine at room temperature. Molten sodium burns with a brilliant yellow flame ina chlorine atmosphere to form sodium chloride. 2Na()+Clig» — 2NaCls) Potassium, cubidium and caesium react vigorously with all the halogens, forming metal halides. All alkali metals form their sulphides when treated with molten sulphur. The general Teaction | 2Mi+Sis) ~=—> M,S) (M=Li,Na,K,etc.) 2.2.2 Trendsin Chemical Properties of Alkaline Earth Metals 1, ‘The alkaline earth metals burn in oxygen to form oxides or in the case of barium, the peroxide. Beryllium is the least reactive metal in the group. It is resistant to complete oxidation and stable in air at ordinary temperature but oxidizes rapidly at about 800°C. ‘Therefore beryllium is not tarnished by atmospheric attack but the other metal soon loses the silvery appearance. 2Be (+O, > 2Be0) When exposed to air magnesium quickly becomes coated with the layer of MgO. This layer protects the surface from further corrosion at ordinary temperature. 2Mg(3)+O,(s) —> 2Mg01s) When magnesium is burnt in air a small amount of nitride is also formed along with magnesium oxide: When barium is heated in air or oxygen at 500 - 600°C, its peroxide is formed. Ba(s)+0,() =“, Ba0,(5) Barium peroxide 2. Hydrides are produced by treating the! molten alkaline carth metals with hydrogen, ‘usually under high pressures. “Magnesium reacts with hydrogen at high pressure andl in the presence of a catalyst (Mgl,) forming magnesium hydride. Mgis FH, (9 TSS Mel, (3) Similarly = Cais) +H, (e) —+> Cali (9 3: __ All Group II-A elements react with itrogen| on heating giving nitrides. For example,Chemistry XII ™ Tint ‘magnesium reacts with nitrogen to give magnesium nitride. 3Mgm+Ni@ —> MgNio Noaned ide The nitrides hydrolyse vigorously when treated with water, giving ammonia and the respective hydroxides. Mg,N;0s) + 6H,019 —> 2NH,(e+3Mg(OHD, is) 4, With sulphur, magnesium gives magnesium sulphide, MgS. The other Group I-A metals also react similarly. Mg(s) +S —> MgSe) Magnesium sulphide 5. AllgroupII-Aclements react directly with halogens giving halides ofthe type MX, ¢.g. Caw) +Cly —> CaClisy 6. Magnesium is more reactive than beryllium, even though it isnot attacked by cold water. Magnesium reacts slowly with boiling water and quite rapidly with steam to liberate hydrogen. Mgt HOw “> MgO) +Hyey Steaw Beryllium does not react with water even at red hot temperature but remaining alkaline earth metals produce hydroxides with water. M(i+2H,0() “* M(OH),(6)+Hyi 2.2.3 General Trends in Properties of Compounds of Alkali and Alkaline Earth metals ) Oxides Alkali metal oxides dissolve in water to give strong alkaline solutions. Forexample: Li.) +H,0¢) —> -2LiOH tq) 2Na,0,(s)+ 21,019 —>* 4NaOH a +O,ig) ‘The reaction of an alkali metal oxide with water is an acid-base reaction and not an oxidation reduction reaction since no element undergoes a change in its oxidation number. The reaction simply involves the decomposition of water molecule by an oxideion. OF (aq) + H,0(% —> 20H tay _ The basic character of alkali metal oxides increases down the group. Potassium superoxide (KO,) has a very interesting use in breathing equipments for mountaineers and in space craft. Ithas the ability to absorb carbon dioxide while giving out oxygenatthe same time. 4KO,(s)+2CO.2) —> 2K,CO,(s)+30, (8) The solubility of alkaline-earth metal oxides in water increases down the group. BeO and MgO are insoluble but CaO, SrO and BaO are soluble and react with water to form ‘the corresponding hydroxides. The basic character of the oxides of alkaline earth metals increases: down the group. The — seeLithium oxide (Basic) Sodium oxide Basic) Potassium oxide (Basic) Beryllium oxide (Basic) Calcium oxide (Basic) BeO is amphoteric in nature since itreacts with both acids and bases. BeO(s) + H,SO,(aq) —> BeSOaq +H, BO) +2NaQH (aq) —> —Na,BeO,(s)+H,010 Sodium berylate ii) Hydroxides The alkali metal hydroxides are all crystalline solids, very soluble in water except LiOH, which is slightly soluble. They are generally hygrsocopic and are very strong bases, execpt LiOH. The solubility of alkaline earth metal hydroxides in water increases down the group. Be(OH), is quite insoluble, Mg(OH), is sparingly soluble while Ba(OH), is more soluble. This increase in solubility is due to low lattice energy of hydroxides which is, in turn, due to higher ionic size. Alkali metal hydroxides are stable to heat except LiOH, while alkaline earth metal hydroxides like Mg(OH), and Ca(OH), decompose on heating. 20H = =, Li,0~@+H,OW Mg(OH),@) 5 — MgO «)+H,0(0 A saturated solution of Ca(OH), in water is called lime water and is used as a test for CO,, A suspension of Mg(OH), in water is called milk of magnesia and it is used for treatment of acidity in stomach. iii) Carbonates The carbonates ofalkali metals are all soluble in water and are stable towards heat except 1i,CO, which is not only insoluble but also decomposes on heating to lithium oxide. The” decomposition is made easy because the electrostatic attraction in converting from carbonate to ‘oxide is considerable, In case of large cation like K* inK,CO,, the gain in electrostatic attraction isrelafively much less and the decomposition is difficult. ‘Sodium carbonate is very important industrial chemical. At temperature below 35.2°C, 1Na,CO, crystallizes out from water as Na,CO,,10H,O, which is called washing soda. Above this temperature it crystallizes as Na,CO,.H,0. On standing in air, Na,CO,.10H,O slowly loses water na Converted to a white powder Na,CO,.H,O. The solution of Na,CO, in water is basic due toGag a a Na,CO;(@) +20) —> — 2NaOH (oq)-HH,CO, aa) Unlike the alkali metal carbonates, the alkaline earth metal carbonates are only very slightly soluble in water, with the solublity decreasing down the group. They also decompose on heating and the ease of decomposition decreases down the group. CaCO). —> Ca0G)+CO;(e) The ease of decomposition can be related to the size of the metal ion, the smaller the ion, the moreis the lattice energy of the resulting oxide and hence higher the stability of the product. iv) Nitrates ; Nitrates of both alkali and alkaline earth metals are soluble in water. Nitrates of Li, Mg, Ca and Ba decompose on heating to give O,, NO, and the metallic oxide whereas nitrates of Na and K decompose to give different products. ALINO,) —> — 2Li,0()+4NO,@)+O,t) 2Mg(NO}),¢) —> 2MgO)+4NO,(e)+Ozte) 2Ca(NO,),() —> — 2CaO()+4NO, (9 +O, 2NaNO,(s) = —> — 2NaNO, (0) +O, (2) vy) Sulphates 9 All the alkali metals give sulphates and they are all soluble in water. The solubilities of sulphates of alkaline earth metals, gradually decrease down the group. BeSO, and MgSO, are fairly soluble in water. CaSO, is slightly soluble, while SrSO, and BaSO, are almost insoluble. Calcium sulphate occurs in nature as gypsum CaSO,.2H,O. When it is heated above 100°C, it loses three quarters of its water of crystallization, giving a white powder called’ Plaster of Paris. 2€aSO,.2H,O(s) —> (CaSO,),.H,0¢)+3H,0H Gypsum Plasterof Paris : 2.3. COMMERCIALPREPARATION OF SODIUM BY DOWN’S CELL Most of sodium metal is produced by the electrolysis of fused: sod chloride. Snes melting point of sodium chloride is 801°C, some calcium chloride is added to lowerits melting point and to permit the furnace to operate at about 600°C. In the electrolytic cell, the large block of graphite at the centre is the anode, above which there is a dome for the collection of chlorine. The | cathode is a circular bar of copper or iron which surrounds the anode but is separated from it by an iron screen, which terminated in a gauze. The arrangement permits the electric current to pass¥ s-Block Elements freely but prevents sodium and chlorine from mixing after they have been set free at the electrodes, Fig. 2.1. ‘Sodium metal rises in a special compartment from which itis taken out at intervals. The cell produces dry chlorine and 99.9 percent pure sodium. The process is carried out at 600°C and ithas the following advantages. (2) Themetallic fogisnot produced. (b) Liquid sodium can easily be collected at 600°C. (©) _ Material of the cell isnotattacked by the products formed during the electrolysis. During the process the following reactions take place: NaCl) = —> Nalin Ch (0, Atcathode wee — Nain Atanode Chin _— V2Cl, (e+ Le 2.4 COMMERCIAL PREPARATION OF SODIUM HYDROXIDE BY THE DIAPHRAGM CELL Sodium hydroxide is manufactured on a large scale by the electrolysis of aqueous solution of common saltin a diaphragm cell Fig. 2.2 (a). The cell is é made of steel tank. An oblong perforated steel vessel “(nec s lined inside with asbestos diaphragm serves as a cathode. It is provided with a constant level device to keep the vessel filled to the specified level with brine. A graphite anode is held within the U shaped diaphragm and itprojectsintothesalt solution. Thesteam is blown _cathoue during the process which keeps the electrolyte warm and helps tokeep the perforations clear. Saar The chlorine released at the anode, rises into ~ the dome at the top while hydrogen released at the cathode, escapes through a pipe. The sodium Fig.2.2(a) Nelson Cell for the hydroxide solution slowly percholates into a catch Production of NaOH basin, Bodhracorss, Wal n biese solution hydroxide solution ‘The Fig, 2.2 (b) shows a simplified version of the cell in order to understand the purpose of diaphragm. When the electrolysis takes place, chlorine is given off at'the anode according to the following % ‘Anode Diaphragm Cathode 2Ch Gy —> Chis 2e compartment om Seep atitticeen is discharged by the reduction of water. Fig.2.2(b)‘Chemistry XT = ae 2HOW + 20 —> 20H Gg Hye (Cathode) ‘The overall result of the above reactions is that the brine loses its chloride ions and the solution turns increasingly alkaline in cathode compartment. We can face two major problems during the working of the cell. 1. Chlorine produced can react with hydroxide ions in cold giving hypochlorite ions. Cl (g)+ 20H (aq) = —> OCT fqn + CF (aqy + H,0 19, 2. _- Hydroxide ions may be attracted towards anode, where they can be discharged releasing oxygen gas. This oxygen gas may contaminate the chlorine and renders itimpure. The first problem is solved by using asbestos diaphragm. This keeps the two solutions separate while allowing sodium ions to move towards the cathode. This movement of ions keeps the current flowing through the external circuit. The second problem is solved keeping the level of brine in anode compartment slightly higher, this keeps the direction of flow of liquid toward the cathode and thus preventing the possibility of hydroxides ions to reach the anode. The solution that flows out of the cathode compatment contains 11% NaOH and 16% NaCl. Evaporation of this solution crystallizes the less soluble NaCl which is filtered off, the liquid left contains about 50% NaOH and only 1% NaCl as an impurity. For commercial purposes this small impurity is not important. 2.5 ROLEOFGYPSUM INAGRICULTUREAND INDUSTRY (a) Roleof Gypsumin Agriculture Gypsum, a hydrated calcium sulphate, is a mineral that occurs in large deposits throughout the world. Gypsum is applied tothe soil as a source of calcium and sulphur. The calcium supplied by gypsum in fertilizers is of importance in crop production in areas where soils are subject to extensive leaching. Sulphur has been recognised as an essential constituent of plants. For centuries, sulphur compounds had been applied to soils because of their observed beneficial effect on plant growth. Aside from serving asa constituent of protein and various other compounds in plants, sulphurhas an influence on chlorophyll development in plant leaves. Although not a constituent of chlorophyll, plants deficient in sulphur exhibit a pale green colour. ‘The root system of several plants have been observed to be greatly enlarged by the application of sulphur. It has been reported that good crops are produced by the application of sulphurcontaining materials such as gypsum. , (b) Role of Gypsum in Industries When gypsum is heated under carefully controlled conditions, it loses three quarters of water of crystallization. The resulting product is called Plaster of Paris. Gypsum must not be heated too strongly as the anhydrous salt is then formed which absorbs water slowly. Such plaster———_—— ee iscalled'Deadbumt’, Plaster of Paris when mixed with half of its weight of water forms a plastic type viscous mass and then sets to a hard porous mass. This process is completed within 10 to 15 minutes. During the process expansion about 1% in volumealso occurs, which fills the moulds completely and thus a sharp impression is achieved. Plaster of Paris is used for making plaster walls, casts of statuary, coins, etc. Tt is used in surgery, Plaster of Paris bandages are used for holding in place fractured bones after they have been set. Special plasters contain plaster of Paris and other ingredients which vary with the demands of the use to which they are to be put. ‘Two varieties ofplasters are made. (1) Cement Plaster. It is plaster of Paris to which usually glue or other oils have been added as retarders to prolong the time ofsetting. (2) Hard Finish Plasters ‘These are made by the calcination of the anhydrous sulphate with alum or borax. These plasters are set very slowly but give ahard finish: ‘When mixed with wood pulp and allowed to set in the form of boards, it forms a material, much usedin the construction of buildings as wall boards and partitions. Gypsum is also used asa fillerin paper industries. Portland cement is made by strongly heating a finely powdered mixture of clay and limestone. The final product, known as clinker, is cooled and then ground into a very fine powder. During the grinding about 2% of gypsum is added which prevents the cement from hardening too rapidly. The addition of gypsum increases the setting time of cement. 2.6 ROLEOFLIMEINAGRICULTURE AND INDUSTRY Lime, (CaO) is a soft, white compound which is obtained by the thermal decomposition of CaCO,. (a) Role of Lime in Agriculture ‘Large quantities of calcium oxide are used in agriculture for neutralizing acidic soils. It has been found that application of lime to acidic soils increases the amount of readily soluble phosphorus. ‘Calcium oxide is also used in large amounts for making lime-sulphur sprays which have . astrong fungicidal action. The hydroxide of calcium is obtained when the oxide of the calcium is allowed to react with water. The process is called slaking of lime and itis anexothermic reaction. CaO(s)\+H,O1) —+ Ca(OH), (5) Slaked lime: Functions ofCaleium in Plant-Growth ‘The presence of calcium is essential for the normal development of plants. The quantitySY of calcium required by different plants varies considerably. An adequate supply of calcium appears to stimulate the development of root hairs and, in fact, the entire root system, Calcium is also necessary for normal leave development and tends to accumulate in leaves as well as in bark. An adequate supply of calcium is also essential for the optimum activity of microorganisms that produce nitrates. The effect of calcium on the supply of available phosphorus in the soil is of special significance. Soils containing sufficient calcium are slightly alkaline in nature, When a deficiency of calcium exists various substances such as aluminium and manganese may accumulate in plants in harmful concentrations. (b) Role of Lime in Industries 1 Large quantities of lime are used in the extraction and refining of metals. 2, Limes also used in paper, cement and leather industries” 3 The ability of lime to react with sand at high temperature forming calcium silicate (CaSiO,) serves as an important basis for glass manufacture. 4. Lime is used in ceramic industry for producing different types of sanitary materials. 5. Ordinary mortar, also called lime mortar, is prepared by mixing freshly prepared slaked lime (one volume) with sand (three or four volumes) and water to form a thick paste. This material when placed between the stones and bricks hardens or sets, thus binding the blocks firmly together. The equations for the chemical reactions which take place when. mortar hardens are: CaO) +H,0 0 —> Ca(OH), Ca(OH), @)+CO,~@) —> CaCO, @)+H,0~ Ca(OH), (s)+Si0,() —> CaSiO,(s)+H,0@ 6. __Limeisalso used in refining of sugar and other food products. 7. Lime is used in the manufacturing of bleaching powder, which is used for the bleaching ofthe fabric and paper pulp. 8. Asuspension of the calcium hydroxide is called milk of lime and is used as a whitewash. 9. When limeis heated with coke at about 2800°C in an electric furnace, calcium carbide is produced, which on hydrolysis yields acetylene (C,H). ’ CaO) +3C~) —> CaC,(s)+ CO) Calcium carbide 10. Lime is often employed as a dehydrating agent, for example, in the preparation of — absolute alcohol and the drying of ammonia gas. A mixture of sodium hydroxide and a calcium hydroxide (soda lime) is often employed to remoye both water and carbon’ dioxide from certain gases.a _ Block is KEY POINTS 1. _Theelements of group IA except hydrogen are called ‘alkali metals’ while those of group TAarenamedas alkaline earth metals. ot Alkali metals have only one electron in s-orbital of their valence shell, They lose one electron ofthe valence shell forming monovalent positive ions. 3. Alkaline earth metals have two electrons in s-orbital of their valence shell. They lose twoelectrons forming dipositive ions M™. 4. Spodumené, Chile saltpetre, trona, borax, carnallite, sylvite, alunite, halite, natron, are thecommon minerals of alkali metals. 5. Beryl, magnesite, dolomite, epsom salt, asbestos, calcite, gypsum, strontionite and barite are the important minerals of alkaline earth metals. 6. Lithium behaves different from the other alkali metals. 7. __ Lithium forms only normal oxide, whereas the others form higher oxides like peroxides and superoxides, : 8. Beryllium is the only member of group II, which reacts with alkalies, to give hydr The other members do not react with alkalies. 9. Nitrates of lithium, magnesium and barium on heating give oxy#en; nitrogen peroxide and the corresponding metallic oxides, 10. When gypsum is heated above 100°C, it loses three quarters of its water of crystallization, giving white powder of CaSO,.1/2H,0 which is called Plaster of Paris i. Sodium is prepared by the electrolysis of molten sodium chloride in Down's cell. 12. _Calciumisnecessary for development of leaves and it tends to accumulate in leaves and bark. An adequate quantity of calcium is essential for the optimum activity of Microorganisms that produce nitrates. 13. __ Limeisusedin paper and glass industries. Itis also used forrefining sugar and other food products, EXERCISE QI. Fillintheblanks: @ Alkali metals are. reactive than alkaline earth metals. Alkali metals decompose water vigorously producing nev (iii) _ When heated in a current of dry hydrogen, alkaline carth metals form white crystals of _and hydrogen. the type MH,. (iv) The beryllium oxide, like the oxide ofaluminium isamphoteric, while the hydroxides of the othermembers of the group II-A are if (v) ‘The elements of the group I-A are termed as alkali metals, because their are alkaline. (vi) Spodumeneis an ore of_ metal. (vii) _ Alkali metal nitrates on heating give the corresponding and oxygen.‘Chemistry XIT Te. 35 T (viii) » (ix) @) @ @ Gi) Gi) (iv) (vy) (vi) (vii) (viii) (x) @& Q3. @ Gi) (ii) (iv) (vy) i) (vii) (viii) Na,CO,,H,O is the chemical formula ofa mineral of sodium which is knowns. Metallic bicarbonates are decomposed on heating into their carbonates, alongwith and. . Metal nitrates other than the alkali metals on heating decompose into the corresponding. metal along with the evolution of nitrogen peroxide and oxygen. Indicate True or False. A Group I-A elements are called alkali metals because their chlorides are alkaline in nature Alkali metals are very good conductors of electricity, The hydroxides of alkali metals and alkaline earth metals are soluble in water. Plaster of Paris is a hemihydrate. Alkali metals have low melting and boiling pat ‘as compared to those of alkaline earth metals. Lithium carbonate is decomposed to its oxide, ou the carbonates of the other alkali metals are stable towards heat, Allalkali metal sulphates are insoluble in water. Lithium combines with nitrogen to form lithium nitride but other alkali metals do not react with nitrogen. Tronaisa mineral of lithium. Alkaline earth metals are stronger reducing agents than alkali metals, Multiple choice questions. Encircle the correct answer, Which one of the following does not belong to alkaline earth metals? (@) Be (b) Ra © Ba @ = Rn The oxide of beryllium is: ; (@) acidic (b) basic (c) amphoteric ~~ (d)_-~—«soneof these Which ion will have the maximum value ofheat ofhydration? (a) Na’ (bt) Cs* (ce) | Ba* (d) Mg” Which one of the followings not an alkali metal? (@) _ francium (6) caesium (c) rubidium(d) radium | Which of the following sulphates is not soluble in water? (a) sodium sulphate (b) potassium sulphate ‘ (c) _zincsulphate (4) bariumsuphate i The element caesium bears resemblance with: > (=) Ca (e) cr (c) __bothofthese metals (@ —_ noneofthese metals Chile saltpetre has the chemical formula:" (a) NaNO, @®) -KNO, (©) Na,B,0, @_—_Na,CO,H,0 ‘The mineral (CaSO,.2H,O) has the general name:(x) @&) Q4. Qs. Q6. Qi. Qs. Qo. Qil. @ @) °) @) ©) @ Qi0. a ‘s-Block Elements (@) gypsum (&) dolomite (©) caleite (4) —_epsomsalt Down's cellis used to prepare: (8) sodiumcarbonate (b) —_sodiumbicarbonate (© sodiummetal (®) _ sodiumhydroxide Which element is deposited at the cathode during the electrolysis of brine in diaphragm cell? (@) iH, ) Na Oo ad @ 2 @ Give ‘the names, electronic configurations and occurrence of s-block elements, (b) Discuss the peculiar behaviour of lithium with respect to the other members of alkali metals. i Discuss the trends in chemical. properties of compounds like oxides, hydroxides, carbonates, nitrates and sulphates of A and IIA group elements. Compare the chemical behaviour of lithium with magnesium. (@) _ Mention the properties of beryllium in which it does not resemble with its own - family. (6) _ Whyisthe aqueous solution of Na,CO, alkaline in nature? (2) Describe with diagram the manufacture of sodium by Down's cell. (6) _Pointoutthe threeadvantages of this process. (@) Compare the physical and chemical properties of alkali metals with those of alkaline earth metals. What happens when: Lithium carbonate is heated. Lithium hydroxide is heated to red hot. Berylliumis treated with sodium hydroxide. (iv) Lithiumhydrideis treated with water. Give formulas of the following minerals. (@ Dolomite (b) Asbestos (c) Halite (@) Natron © Beryl (®) Sylvite (g) Phosphorite ® Chilesaltpetre Answer the following questions briefly. Why are alkali and alkaline earth metals among the reactive elements of the periodic table? Why does lime water tum milky with CO, but becomes clear with excess CO,? How is gypsum converted into plaster of Paris? Why is 2% gypsum added in the cement? Why is lime added to anacidic soil? Howare lime and sand usedto make glass? Howis limemortar prepared?CHAPTER 3 GROUP IIIA AND GROUP IVA. ELEMENTS In this chapter you will learn ‘The names, electronic configurations and occurrence of IIIA and IVA group elements. ‘The peculiar properties of boron and carbon in their respective groups. The preparation and properties of borax and orthoboric acid. Thereactions of aluminium. Structures and properties of oxides of carbon and silicon, silicates, silicones and theiruses. aera en The uses of silicon and germanium in semi-conductor industries and lead in paints. 3.1 GROUPITIAELEMENTS The Group IIIA of the Periodic Table comprises the elements boron, aluminium, gallium, indium and thallium. Electronic configurations and some. physical properties of group IIIA elements are shown in Table3.1. The small size and high nuclear charge make boron non-metallic while all the other elements of this group are metals. The abrupt increase in metallic character from B to Al is associated with the increased size of aluminium atom. The increase in the atomic size is not regular in this group. This is duc to the presence of d electrons in heavier members which have poor shielding effect thans and pelectrons; Table 3.1 Electronic Configurations and Physical Properties of Group IIA Elements Properties B Atomicnumber 5 Electronic configuration‘Group IIA and Group IVA Elements 1457 1.85 2,70 3.1.1 Occurrence (Boron and Aluminium) Boron is not an abundant element. Itoccurs in traces in most soils and has been found to be essential in very small amounts forthe proper growth of many plants, Boron is always found in nature combined with oxygen, usually as oxyborate ions. Boron occurs principally Table 3.2 Common Minerals of Boron Nameof Minerals of Boron | Chemical Formula Borax orTincal ‘Na,B,0,10H,O Colemanite Ca,B,0,,.5H,0 Orthoboric Acid H,BO, as salts of various polyboric acids. Table 3.3 Common Minerals of Alu Aluminium is the third se Ghemical Form la most abundant element in the earth's crust (after oxygen and silicon). It occurs primarily as ‘| KAISiO, orK,0.A1,0,.6Si0, KH,AL(SiO,), H,AI{SiO)), H,0 or Al,0,2Si0,2H,0 alumino-silicate minerals found in the rocks of the outer portion of the ALO, earth. AIF,SiO, The other elements of (GL.072H.0 orAUOH),) group IIA gallium, indium and thallium are relatively rare and are obtained as by-products during the |p; processing of other metals. 3.1.2 Peculiar Behaviour of Boron Boron is the first member of the Group IIIA, it shows many dissimilarities with the members of its own group. The difference in the properties of boron and those of the other members of the series is mainly due to the large difference in their sizes and ionization energies. is Boronis the only element in GroupIIIA which is non-metallic in behaviour. 2 Itis the only element with less than four electrons in the outermost shell which is not aGhiemistry XU, 39, metal, 3. | Boron always uses all the three of its valence electrons for bonding purposes and its common oxidation states are+ 3 and —3. 4 One of the outstanding features of the chemistry of boron is its ability to form molecular addition compounds. 5.‘ Boron does not form ionic compounds with sulphate, nitrate or other anions because boron does not from a stable cation. 3.2, COMPOUNDS OF BORON 3.2.1 Borax (Sodium Tetraborate Na,B,O,.10H,O) Borax is the sodium salt of tetraboric acid. It is the most important of all borates. Occurrence: Borax occurs as a natural deposit called tincal in the dried uplakes of Tibet and California. Manufacture: 1. Formally borax was manufactured by treating a hot solution of boric acid with the proper amount of soda ash. 4H,BO, (aq +Na,CO,() —> Na,B,O,)+6H,0+C0,( Borered beet Borax 2. Nowadays borax is almost exclusively obtained from calcium borate. Finely powdered colemanite is boiled with Na,CO, solution, when CaCO, precipitates out and.a mixture of borax and sodium metaborate is formed. Ca,B,O,,(s)+ — 2Na,CO,(aq) —» 2CaCO,(s)+Na,B,O,(s)+2NaBO, (s) Colemanite The clear solution from the top is taken off and is then allowed to crystallize, when crystals of borax separate out. To get more borax, CO, is blown through the mother liquor, the sodium metaborate is decomposed into borax, which separates out in the form of fine crystals. _ 4NaBO,() + CO,(e) —> Na,CO,(s) + Na,B,0,(s) Sodiummetaborate Borax 3. Borax may also be obtained from tincal (Na,B,0;,10H,0) by’treating tincal with water and subsequently evaporating the clearsolution, when crystals of borax separate out. Properties: ‘ 1. Boraxisa white, crystalline solid. Itis sparingly sSlublein cold water butis more soluble: in hot water: 100 grams of water dissolve 3 grams of decahydrate at’ 10°C and 99.3 grams at 100°C. Ifa saturated solution be allowed to crystallize above 62°C, octahedral crystals of the pentahydrate, Na,B,O,.5H,O separate out, if the temperature is below” 62°C, the decahydrate is formed. Its aqueous solution is alkaline in nature due to hydrolysis, ecg untettem ea hiya ailNa,B,0,() +7H,0(0 —> 2NaOH ia) + 4H,BO, (6) ‘Strong alkali Weak acid The hydrolysis is prevented in the presence of glycerine. 2. When heated, borax loses water and swells up into a white porous mass due to the expulsion of water: on further heating it melts into a clear transparent glass, which dissolves many metallic oxides forming coloured beads. This reaction forms the basis of boraxbeadtest. Na,B,0,.10H,O@) —4> Na,B,0, (s) +2NaBO, (s) + B,O,(s) Giassymass 3. _Itsaqueous solution reacts with HCl or H,SO, to form boric acid: Na,B,O, (e—)+2HCl (aq) + 5H,O( = —> —2NaCl a) 4H,BO, «) Borax Boric acid ‘Na,B,0, (9)+H,SO, (eq) + 5H,019 — Na,SO, (aq)+ 4H,BO, (s) 4. When borax is heated with ammonium chloride, boron nitride is produced: Na,B,O,(s)+2NH,Cl(ag) —> 2NaCl(s)+2BN¢)+B,0,(9)+4H,0(0 5. Borax when dissolved in water ionizes as: NaB.0,) —> — 2Na‘ta)+B,0," Hydrolysis of B,,"ions occurs as follows: B,O,*@+7H,O® — 4H,BO, (s)+20H (aq) So, a strong alkali (NaOH) is formed which is highly ionized. On the other hand, boric acid (H,BO,) is ionized to a little extent; because it is a weak acid. Hence, solution of borax as a wholeis alkaline in nature. 6. Borax Bead Test Prepare a loop at the end of a platinum wire. Heat the wire and take a little powdered borax on the hot loop. Heat again, borax first swells up and then melts into colourless, glass like bead on the loop. Now put a few grains of the substance, under examination, on the beads and re-heat it first in the oxidizing flame and then in the reducing flame. Chemistry ofthe Borax-bead Test: Borax, when fused, is decomposed into sodium metaborate and boric anhydride, Na,B,0;() — +> 2NaBO,() +B,0,(s) ‘The metallic oxide formed from the substance, under examination, combines with B,O, giving the coloured metallic borates. With cupric oxide, the beads are coloured blue in the oxidizing flame because cupric borates are blue in colour, ‘CuO ,,, +B,0,~) —> Cu(BO)),«) Uses of Borax: 1. __Itisusedtoprepare borate glass, which is heat resistant, 2. Ttisused in softening of water,Itis employed in borax bead test, for the detection of metallic cations. Ttisused in metallurgical operations. Itis used as a flux in welding and in metallurgy. Itisused in leather industry for tanning and dyeing. 3 4. 5 6. _Itisemployed in making washing powders. 7 8 It is used in cosmetics, soaps, textiles, paints, medicine, match industry and as a preservative. 3.2.2 BoricAcids There are four important boric acids. Out of these orthoboric acid is the most important and the stable one. The remaining acids are stable in solid state and change into orthoboricacid in solution: () —_Orthoboric Acid, H,BO, (ii) Metaboric Acid, HBO, (iii) Tetraboric Acid, H,B,0, (iv) Pyroboric Acid, H,B,0, HBO,+H,O0 | —> HBO, Metabori acid Borie acid H,B,0,+5H,O —> — 4H,BO, Tetraboricacid Boric acid H,B,0,+3H,0 —> — 4H,BO, Pyroboric acid Boricacid Orthoborie Acid or Borie acid (H,BO,) It is a white crystalline chemical substance (triclinic) sparingly soluble in cold water (2.6% at 40°C) but dissolves readily in hot water (37% at 107°C). This temperature variation in solubility forms the basis for its separation and purification. Preparation of Boric acid on Commercial Scale ie From Colemanite On commercial scale, boric acid is prepared from a natural calcium borate called colemanite (Ca,B,O,,. 5H,O) by suspending it in boiling water while, sulphur dioxide is passed through it. Boric acid crystallizes out from the solution while, the other product CaSO, remains in thesolution, : * €2,B,0,,5H,0)+280,@+4H,0(9 —> * 2CaSO; 9+ 6H,B0;(0 , Colemanite a = 2. . From Borax Ahot concentrated solution of borax. erected ata eu ‘of conc. H,SO,. Oncooling, crystals of boric acid formed separate out. eI 2 _———— Group IIIA and Group IVA Elements Na,B,0,(s)+H,SO, (oq)+5H,O( = —> ——_Na,SO,) + 4H,BO, (5) Borax Boricacid ‘Properties of Boric Acid Boric acid is a white lustrous crystalline solid having a soft soapy touch, very slightly solubleincold water but fairly soluble in hot. 2. __Itisvolatileinsteam. 3. __Itreacts withethyl alcohol forming ethyl borate. H,BO,()+3C,HOH(9 —> (C,H,),BO,(9+3H,0 (0 4 When heated strongly, it swells to frothy mass losing water molecules. It is first converted into metaboric acid, then to tetraboric acid and finally to boric anhydride. HBO, —!%C, HBO,+H,O MetaboricAcid 4HB0, —*°>- 1,B,0,+H,0 Tetaborieac HBO, "> 28,0,+H,0 ‘ Boricanhydride 5 Itis avery weak acid and ionizes toa very limited extent mainly asa monobasic acid. H,BO,()+H,0() = —> [BCOH),J +H 6. _Itssolutionhasno effect onmethyl orange, although it turns blue litmus red. 7. _Itispartially neutralised by caustic soda to give borax. 4H,BO, (oa) +2NaOH (aa) —> NaB0,.,+7H,0(0 8. Whenboricacid is neutralized by soda ash (Na,CO,), borax is obtained. 4H,BO, (aq) +Na,CO, (aa) — > Na,B,0,6)+ 6H,0,,+CO,(), : Borax 9. __ Boric acid being a weak acid, cannot be titrated with alkalies in the usual manner. In the presence of glycerol, however, it can be titrated against a standard alkali using phenolphthaleinas an indicator. Uses of BoricAcid 1. __ Boric acid is used in medicines as an antiseptic, e.g, dusting powder, boric ointment and boric solution isusedas aneyewash. 2 Itis used in pottery as a glaze because borate glazes are more fusible than silicate glazes and possess. higher coefficient of expansion. 3. _Itisalsousedincandle industry forstiffening of wicks. 3.3. REACTIONS OFALUMINIUM 1. ReactionwithAir When a piece of aluminium sheet is exposed to moist air it acquires a thin, continuousCent a 43 coating of aluminium oxide, which prevents further attack on the metal by atmospheric oxygen and water under normal conditions. Because of this aluminium sheets are said to be corrosion free. However, if the aluminium powder is heated to 800°C and above, the metal will react with air to form aluminium oxide, Al,O,, and aluminium nitride, AIN. The reaction is accompanied by the evolution of heat and intense white light. This property of aluminium is made use of in flash light photography. 4AlG)+30,) —> 2A1,0,(5) 2Al@)+N,@) —> 2AIN@) Because of its ability to combine with both oxygen and nitrogen, the metal is often used to remove air bubbles from molten metals. Salt solutions corrode aluminium badly so aluminium and aluminium alloys are not suitable for marine use. 2. Reaction with Non-Metals Heated aluminium combines with the halogens, sulphur, nitrogen, phosphorus and carbon, accompanied by the evolution of heat. 2Al()+3Cl(s) —> 2AICl,(5) Aluminium on heating with hydrogen forms aluminium hydride. 2Al(s)+3H,(g) —> 2AIHy(9) 3. Reaction with Acids and Alkalies Aluminium is amphoteric. It dissolves in both acids and bases with the liberation of hydrogen gas. Aluminium reacts slowly with dilute acid and more rapidly with concentrated hydrochloric acid to displace hydrogen 2Al(s)+6HCI (aq) —> 2AICI, (aq) +3H, (2) Aluminium does not react with dilute sulphuric acid. However, it is oxidized by hot concentrated sulphuric acid to liberate sulphur dioxide gas. 2Al (0) +6H,SO, (cont) —> Al,(SO,), y+ 6H,0(0+3S0, (e) Aluminium does not react with nitric acid at any concentration, probably because of the formation of protective layer of aluminium oxide. The acid is said to render the aluminium: passive, Nitric acid is, therefore, frequently transported in aluminium containers. Aluminium dissolves in both sodium and potassium hydroxides to form’ a soluble: aluminate, with the evolution of hydrogen, 2Al()+2NaOH (aq)+6H,0(9 — > 2NaAK(OH),(aq)+3H,@), USES ils Aluminium is very light (nearly three times less dense than iron) but posseses high’ tensile strength. These properties account for its extensive use in the transport industries, inthe construction of aircrafts, shipsand cars.Group IilA and Group IVA Elements 2. Itis an excellent conductor of both electricity and heat. Thus, itis used as heat exchanger in chemical, oil and other industries. Heavy duty electrical cables are made of aluminium metal. Aluminium is an excellent reflector of radiant energy. For this reason, it is commonly used to insulate buildings. Aluminium foil is also used to jam radar. Ttis non-magnetic and is thus used in navigational equipment. Itisa good reducing agent and can thus be used for this purpose in the chemical and steel industries. It is non-toxic and can be used for making food and brewing equipments and in packaging. Aluminium readily forms alloys with other metals like copper, magnesium, nickel and zine. At homes, aluminium is found in the form of cooking utensils, window frames and kitchen foil. Aluminium is used for making petrol and milk storage tanks because it reflects heat and prevents them ofbeing overheated in the sun. GROUPIVA ELEMENTS Group IVA of the periodic table comprises elements, carbon, silicon, germanium, tin and ‘There is a marked change of properties from carbon to lead. This gradation is of such nature, however, that there are very few similarities between the extreme members. Thus carbon and lead differ very considerably; far more, for example, than do lithium and caesium in group TA. The electronic configurations of IVA group elements along with their physical properties are given in Table3.4. ‘Table 3.4 Electronic Configurations and Physical Properties of Group IVA Elements Properties g c Si Ge Sn Pb Atomicnumber 6 14 2 50, 2 Electronicconfiguration _| [He]2s'2p'| [Ne]3s'3p") [Ar]3d!°4s'4p*| [Kr]4d"5s'5p'| [Xe]4f"'5d"6s'6p* Ionization energy (ki/mol) | 1086 786 761 708 715 Electron affinity(ki/mol) | —122.5 | =120 =116 121 =101 Electronagetivity 25 18 18 - 18 Bini: Atomicradius (pm) 1 1g 122 “140 146 Tonic radius of2+ion (pm) 60 na B 118 9 1420 945 232 327 3280 2850 2623 1750 234 | 532 7.26 11.34Chemistry XII a a es) Carbon and silicon are the only | | | | | . | oe non-metals in Group IVA. Carbon has ! the peculiar property of forming long carbon chains, silicon forms long chains | | | | | | of alternating silicon and oxygen atoms. (Carbon and Carbon Diikaged 1. Carbon and silicon both form oO acidic oxides, whereas the oxides of | | | germanium, tin and lead are amphoteric a innature. Ne \o% | Sea | aA ° 0 ° 2. Both carbon and silicon form covalent bonds. Their oxides are acidic and both form hydrides and chlorides. Silicon and Oxygen Linkages The elements of group IVA are characterized by a set of four valence electrons, which form two pairs. In the first three elements of IVA group, carbon, silicon and gertfianium, all the four outermost electrons arc used as valency electrons, while in tin and lead cither all four (stannic and plumbic compounds) or only one of the pairs of electrons (stannous and plumbous compound) is used for bonding. ‘The pair of valence electrons that do not readily take part in chemical combination is termed as inert pair. As in other groups, the inert pair effect is most marked in the element of highest atomic mass, namely lead. The increase in electropositive character from carbon through silicon, tin, and lead is pronounced. This trend is shown also by the increase in the metallic character of the elements with increased atomic mass. The Following are the Common Properties of Group IVA Elements: 1. Allthe elements of this group show a valency of four. 2. Allof them form hydrides, MH, 37 They form tetrachlorides, MCl,. 4. They also form the dioxides, MO,. 3.4.1 Occurrence of Carbon Carbon occurs naturally in two states. One is crystalline (graphite, diamond) form and the other is amourphous (coal, charcoal) form. 3.4.2 Occurrence of Silicon Silicon is very abundant, about 25% of }4 the mass of the Earth's crust being due to this element. J Silicon, unlike carbon, is not found in free state. Silicon is found asa majorconstituentGroup IITA and Group IVA Ele of rocks either in the form of silica or silicates. Most minerals other than sulphides, sulphates, phosphates and carbonates contain high proportion of silicon. As oxide, itis found as quartz inthe following forms: Rockcrystal, amethyst quartz, smoky quartz, rose quartz and milky quartz. Sandis largely silicon dioxide (silica), Opal isa hydrated variety of quartz. 3.4.3 Peculiar Behaviour of Carbon Carbon differs from the remaining members of Group IV-A in the following respects: 1. _ Carbon and silicon are nonmetals while the other members of the family are metalloids ormetals. 2. _Catenation or self linkage. Carbon has a tendency to form long chains of identical atoms. The type of linkage of identical atoms with each other is called catenation or self- linkage. The property of catenation decreases on moving down the group from carbon to. dead. The maximum tendency of catenation associate with carbon forms the basis of the carbon. compounds which constitute organic chemistry. 3.5 COMPOUNDS OF CARBONAND SILICON 3.5.1 Structure of Oxides of Carbon ‘Three oxides of carbon are known: @ Carbon monoxide, CO (i) Carbon dioxide, co, (iii) Carbonsuboxide, C,0, Outof these, the last oncis of little importance. Structure of Carbon Monoxide (CO) Carbon monoxide is diatomic molecule having triple bond between the two atoms. It is very slightly polar. The electronic structure of carbon monoxide can berepresentedas: :C? 10 Ttisusually writtenas: «C==O: It might appear from the above structure that the molecule should have a large dipole moment, butiin fact the moleculehasa small dipole moment (0.112D). ics Structure of the Carbon Dioxide Carbon dioxide exists in the gaseous state as linear molecules. The observed C—O bond distance is ps 115 pm and is in agreement with the structure shown. |_ Solid CO, has a face-centered cubic structure. Being linear itsdipolemomentis zero. 3.5.2 Oxides of Silicon Silicon Dioxide” ‘Silicon dioxide, SiO, called silica, is probably the most common and the most important i \ 4nig rr 7 compound of silicon. In silica every silicon atom is attached tetrahedrally to four oxygen atoms and each oxygen atom has two closessilicon neighbours. Vitreous silica possesses the following interesting and usefull properties. High transparency to light. Very refractory, does not soften below 1500 to 1600°C. Very low thermal expansion, Excellent insulator, Hard, brittle and elastic. Insoluble in water and inerts towards many reagents. Itis resistant towards all acids except HF. Guster the common crystalline form of silicon dioxide, is a hard, brittle, refractor, colourless solid which differs very markedly from carbon dioxide. Sayeeype Both carbon and silicon have four electrons in their valence shells and both also form four covalent bonds. So, why should there be a big difference between CO, and SiO,? ‘The answer lies in the fact that silicon atoms are much larger than carbon atoms and thus tend to surround themselves with more oxygen neighbours; silicon forms only single bonds with oxygen atoms whereas carbon may form double bonds. Carbon, in fact, forms double bonds with each of the two oxygen atoms to produce a small, symmetrical, linear molecule CO,,which is volatile and reasonably reactive. The silicon atom can be approached closely by four oxygen atoms and forms a single bond with each at tetrahedral angles. This structure can be continued in three dimensions to produce a continuous giant silicon oxygen network extending out to give the massive silicon dioxide crystal. In the interior of the silica network every silicon atom is bonded tetrahedrally with four oxygen atoms and every oxygen atom is bonded to two silicon atoms. The overall ratio of silicon to oxygen atoms is 1:2 / and the simplest formula for silica therefore is SiO,, The silicon oxygen bonds are strong and keep the atoms firmly in place. Note, however, that it is not the molecular formula for silica but the whole chunk of silica must be considered to be essentially one molecule. The atoms of silicon and oxygenat the surface of the chunk donot(Group IITA and Group IVA haveall their valence forces satisfied, as is shown by the high surface activity ofsilica. In each of the various crystalline forms of silica, there is a special pattem which i= repeated throughout the crystal in a regular definite crystal lattice. The regular tetrahedra— ‘arrangement of four oxygen atoms around each silicon persists in each crystalline form but the= Si-O-Si bond angles and the rotation about each Si-O bond are different in the different polymorphic species. ‘When crystalline silica is heated sufficiently it melts to give a viscous liquid having am random structure, presumably with the silicon atoms still on the average close to four oxygenm atoms and the oxygen atoms close to two silicon atoms, When this liquid silica is cooled it does= not crystallize readily, but usually it under supercools tremendously and eventually becomes- Tigid withouthaving undergone orientation into a regular crystal pattern. This rigid, highly under supercooled liquid is called vitreous silica or silica glass (frequently incorrectly referred to as fused quartz). 3.5.3 Silicates and their Uses ‘The compounds derived from silicic acids are termed as silicates. 1. _Sodiumsilicate, Na,SiO, This is a sodium salt of metasilicic acid H,SiO, It is known as water glass or soluble glass. Itis prepared by fusing sodium carbonate with pure sand. The process is carried out ina furnace called reverberatory furnace. Na,CO,@)+ SiO) —> NaSi0,~ + CO,« Romie Sodium silicate Sodium silicate is soluble in water and its solution is strongly alkaline due to the hydrolysis. chloride, ferrous sulphate, copper sulphate um silicate, they produce a very beautiful Uses of Sodium Silicate: 1. _Itisusedasafillerforsoap in soap industry. 2h Itis usedin textile as afire proof ‘agents, 3. _ It is used.as furniture polish. 4, Itisalsousedin calico printing. 2a Aluminium Silicate ‘Many importantssilicate rocks contain aluminium. The weathering of these rocks results in the disintegration of the complex silicates which they contain, The boiling and freezing of