NCERT Nitrogen Chemistry PDF

Unit The p -Block 7 d Objectives Element...

Unit The p -Block 7 d Objectives Element Elementss he After studying this Unit, you will be able to appreciate general trends in the chemistry of elements of groups pu T 15,16,17 and 18; is Diversity in chemistry is the hallmark of p–block elements manifested learn the preparation, properties in their ability to react with the elements of s–, d– and f–blocks as and uses of dinitrogen and well as with their own. re R phosphorus and some of their bl important compounds; describe the preparation, In Class XI, you have learnt that the p-block elements are placed in groups 13 to 18 of the periodic table. E properties and uses of dioxygen 2 1–6 and ozone and chemistry of some Their valence shell electronic configuration is ns np simple oxides; 2 (except He which has 1s configuration). The properties know allotropic forms of sulphur, be C of p-block elements like that of others are greatly chemistry of its important influenced by atomic sizes, ionisation enthalpy, electron compounds and the structures of gain enthalpy and electronegativity. The absence of d- its oxoacids; orbitals in second period and presence of d or d and f o N describe the preparation, orbitals in heavier elements (starting from third period properties and uses of chlorine and hydrochloric acid; onwards) have significant effects on the properties of elements. In addition, the presence of all the three types know the chemistry of of elements; metals, metalloids and non-metals bring tt © interhalogens and structures of oxoacids of halogens; diversification in chemistry of these elements. enumerate the uses of noble Having learnt the chemistry of elements of Groups gases; 13 and 14 of the p-block of periodic table in Class XI, appreciate the importance of you will learn the chemistry of the elements of these elements and their subsequent groups in this Unit. compounds in our day to day life. 7.1 Group 15 Group 15 includes nitrogen, phosphorus, arsenic, antimony and Elements bismuth. As we go down the group, there is a shift from non-metallic to metallic through metalloidic character. Nitrogen and phosphorus are non-metals, arsenic and antimony metalloids and bismuth is a typical metal. no 7.1.1 Occurrence Molecular nitrogen comprises 78% by volume of the atmosphere. In the earth’s crust, it occurs as sodium nitrate, NaNO3 (called Chile saltpetre) and potassium nitrate (Indian saltpetre). It is found in the form of proteins in plants and animals. Phosphorus occurs in minerals  of the apatite family, Ca9(PO4)6. CaX2 (X = F, Cl or OH) (e.g., fluorapatite Ca9 (PO4)6. CaF2) which are the main components of phosphate rocks. Phosphorus is an essential constituent of animal and plant matter. It is present in bones as well as in living cells. Phosphoproteins are present in milk and eggs. Arsenic, antimony and bismuth are found mainly as sulphide minerals. The important atomic and physical properties of this group elements along with their electronic configurations are given in Table 7.1. Table 7.1: Atomic and Physical Properties of Group 15 Elements d Property N P As Sb Bi he Atomic number 7 15 33 51 83 –1 Atomic mass/g mol 14.01 30.97 74.92 121.75 208.98 2 3 2 3 10 2 3 10 2 3 14 10 2 3 Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p pu T Ionisation enthalpy I 1402 1012 947 834 703 is –1 (∆iH/(kJ mol ) II 2856 1903 1798 1595 1610 re R III 4577 2910 2736 2443 2466 bl Electronegativity 3.0 2.1 2.0 1.9 1.9 a Covalent radius/pm 70 110 121 141 148 E b b b c c Ionic radius/pm 171 212 222 76 103 d e Melting point/K 63* 317 1089 904 544 be C d f Boiling point/K 77.2* 554 888 1860 1837 –3 g h Density/[g cm (298 K)] 0.879 1.823 5.778 6.697 9.808 o N Grey α-form at 38.6 atm; Sublimation temperature; a III b 3– c 3+ d e f E single bond (E = element); E ; E ; White phosphorus; At 63 K; Grey α-form; * Molecular N2. g h Trends of some of the atomic, physical and chemical properties of the group are discussed below. tt © 2 3 7.1.2 Electronic The valence shell electronic configuration of these elements is ns np. Configuration The s orbital in these elements is completely filled and p orbitals are half-filled, making their electronic configuration extra stable. 7.1.3 Atomic and Covalent and ionic (in a particular state) radii increase in size Ionic Radii down the group. There is a considerable increase in covalent radius from N to P. However, from As to Bi only a small increase in covalent radius is observed. This is due to the presence of completely filled d and/or f orbitals in heavier members. 7.1.4 Ionisation Ionisation enthalpy decreases down the group due to gradual increase Enthalpy in atomic size. Because of the extra stable half-filled p orbitals electronic no configuration and smaller size, the ionisation enthalpy of the group 15 elements is much greater than that of group 14 elements in the corresponding periods. The order of successive ionisation enthalpies, as expected is ∆iH1 < ∆iH2 < ∆iH3 (Table 7.1). Chemistry 166 7.1.5 The electronegativity value, in general, decreases down the group with Electronegativity increasing atomic size. However, amongst the heavier elements, the difference is not that much pronounced. 7.1.6 Physical All the elements of this group are polyatomic. Dinitrogen is a diatomic gas Properties while all others are solids. Metallic character increases down the group. Nitrogen and phosphorus are non-metals, arsenic and antimony metalloids and bismuth is a metal. This is due to decrease in ionisation enthalpy and increase in atomic size. The boiling points, in general, increase from top to bottom in the group but the melting point increases upto arsenic and then d decreases upto bismuth. Except nitrogen, all the elements show allotropy. 7.1.7 Chemical Oxidation states and trends in chemical reactivity he Properties The common oxidation states of these elements are –3, +3 and +5. The tendency to exhibit –3 oxidation state decreases down the group due to increase in size and metallic character. In fact last member of the group, bismuth hardly forms any compound in –3 oxidation state. The stability pu T of +5 oxidation state decreases down the group. The only well characterised is Bi (V) compound is BiF5. The stability of +5 oxidation state decreases and that of +3 state increases (due to inert pair effect) down the group. Nitrogen re R exhibits + 1, + 2, + 4 oxidation states also when it reacts with oxygen. bl Phosphorus also shows +1 and +4 oxidation states in some oxoacids. In the case of nitrogen, all oxidation states from +1 to +4 tend to E disproportionate in acid solution. For example, 3HNO2 → HNO3 + H2O + 2NO be C Similarly, in case of phosphorus nearly all intermediate oxidation states disproportionate into +5 and –3 both in alkali and acid. However +3 oxidation state in case of arsenic, antimony and bismuth becomes o N increasingly stable with respect to disproportionation. Nitrogen is restricted to a maximum covalency of 4 since only four (one s and three p) orbitals are available for bonding. The heavier elements have vacant d orbitals in the outermost shell which can be used for – bonding (covalency) and hence, expand their covalence as in PF6. tt © Anomalous properties of nitrogen Nitrogen differs from the rest of the members of this group due to its small size, high electronegativity, high ionisation enthalpy and non-availability of d orbitals. Nitrogen has unique ability to form pπ -p π multiple bonds with itself and with other elements having small size and high electronegativity (e.g., C, O). Heavier elements of this group do not form pπ -pπ bonds as their atomic orbitals are so large and diffuse that they cannot have effective overlapping. Thus, nitrogen exists as a diatomic molecule with a triple bond (one s and two p) between the two atoms. Consequently, its bond enthalpy –1 (941.4 kJ mol ) is very high. On the contrary, phosphorus, arsenic and antimony form single bonds as P–P, As–As and Sb–Sb while no bismuth forms metallic bonds in elemental state. However, the single N–N bond is weaker than the single P–P bond because of high interelectronic repulsion of the non-bonding electrons, owing to the small bond length. As a result the catenation tendency is weaker in 167 The p-Block Elements  nitrogen. Another factor which affects the chemistry of nitrogen is the absence of d orbitals in its valence shell. Besides restricting its covalency to four, nitrogen cannot form dπ –pπ bond as the heavier elements can e.g., R3P = O or R3P = CH2 (R = alkyl group). Phosphorus and arsenic can form dπ –dπ bond also with transition metals when their compounds like P(C2H5)3 and As(C6H5)3 act as ligands. (i) Reactivity towards hydrogen: All the elements of Group 15 form hydrides of the type EH3 where E = N, P, As, Sb or Bi. Some of the properties of these hydrides are shown in Table 7.2. The hydrides show regular gradation in their properties. d The stability of hydrides decreases from NH3 to BiH3 which can be observed from their bond dissociation enthalpy. he Consequently, the reducing character of the hydrides increases. Ammonia is only a mild reducing agent while BiH3 is the strongest reducing agent amongst all the hydrides. Basicity also decreases in the order NH3 > PH3 > AsH3 > SbH3 > BiH 3. pu T is Table 7.2: Properties of Hydrides of Group 15 Elements Property NH 3 PH 3 AsH 3 SbH 3 BiH3 re R bl Melting point/K 195.2 139.5 156.7 185 – Boiling point/K 238.5 185.5 210.6 254.6 290 E (E–H) Distance/pm 101.7 141.9 151.9 170.7 – be C HEH angle (°) 107.8 93.6 91.8 91.3 – ∆f HV/kJ mol–1 –46.1 13.4 66.4 145.1 278 o N ∆dissHV(E–H)/kJ mol–1 389 322 297 255 – (ii) Reactivity towards oxygen: All these elements form two types of oxides: E2O3 and E2O5. The oxide in the higher oxidation state tt © of the element is more acidic than that of lower oxidation state. Their acidic character decreases down the group. The oxides of the type E2O3 of nitrogen and phosphorus are purely acidic, that of arsenic and antimony amphoteric and those of bismuth predominantly basic. (iii) Reactivity towards halogens: These elements react to form two series of halides: EX 3 and EX 5. Nitrogen does not form pentahalide due to non-availability of the d orbitals in its valence shell. Pentahalides are more covalent than trihalides. All the trihalides of these elements except those of nitrogen are stable. In case of nitrogen, only NF3 is known to be stable. Trihalides except BiF3 are predominantly covalent in nature. no (iv) Reactivity towards metals: All these elements react with metals to form their binary compounds exhibiting –3 oxidation state, such as, Ca3N2 (calcium nitride) Ca3P 2 (calcium phosphide), Na 3As2 (sodium arsenide), Zn3Sb 2 (zinc antimonide) and Mg3Bi2 (magnesium bismuthide). Chemistry 168