Chemistry P Block Elements
Chemistry P Block Elements
Chemistry P Block Elements
Group 15 elements:
Symbol Atomic General
Electronic configuration introduction, electronic
number configuration, occurrence,
7 [He]2s22p3 oxidation states, trends in physical
N and chemical properties; nitrogen -
P 15 [Ne] 3s23p3 preparation, properties and uses;
As 33 [Ar]3d104s24p3 compounds of nitrogen:
Sb 51 [Kr]4d105s25p3
14 10 2 3 preparation and properties of
Bi 83 [Xe]4f 5d 6s 6p
ammonia and nitric acid, oxides of
nitrogen (structure only);
Phosphorous-allotropic forms; compounds .of phosphorous:
preparation and properties of Phosphine, halides (PCl 3, PCl5) and
oxoacids (elementary idea only)
Group 16 elements:
Symbol Atomic General introduction, electronic
Electronic configuration
number configuration, oxidation states,
8 [He]2s22p4 occurrence, trends in physical and
O chemical properties; Dioxygen:
S 16 [Ne] 3s23p4 preparation, properties and uses;
Se 34 [Ar]3d104s24p4 simple oxides; Ozone. Sulphur -
Te 52 [Kr]4d105s25p4
14 10 2 4 allotropic forms; compounds of
Po 84 [Xe]4f 5d 6s 6p
sulphur: preparation, properties
and uses of Sulphurdioxide;
sulphuric acid: industrial process of manufacture, properties and
uses, oxoacids of Sulphur (structures only).
Group 17 elements:
Symbol Atomic Electronic General introduction, electronic
number configuration configuration, oxidation states,
F 9 [He]2s22p5 occurrence, trends in physical and
chemical properties; compounds
Cl 17 [Ne] 3s23p5 of halogens: preparation,
Br 35 [Ar]3d104s24p5 properties and uses of chlorine
I 53 [Kr]4d105s25p5
and hydrochloric acid,
At 85 [Xe]4f 145d106s26p5
Interhalogen compounds,
oxoacids of halogens (structures
only).
Group 18 elements:
Symbol Atomic Electronic
number configuration
He 2 1s2 General introduction, electronic
Ne 10 [He]2s22p6 configuration. Occurrence, trends
Ar 18 [Ne] 3s23p6 in physical and chemical
Kr 36 [Ar]3d104s24p6 properties, uses.
Xe 54 [Kr]4d105s25p6
Rn 86 [Xe]4f 145d106s26p6
(iii) The ionization enthalpy of the group 15 elements is much greater than that of group 14
elements in the corresponding periods.
Ans: Because of the extra stable half-filled p orbital electronic configuration and smaller size.
(vi) The HNH angle value is higher than HPH, HAsH, and HSbH angles.
Ans: Due to increase in repulsion by the lone pair with increase in size of lone pair from N to Sb.
(xi) Oxides of nitrogen have open chain structures while those of phosphorus have closed
chain or cage structures.
Ans: Nitrogen has ability to form multiple bonds involving p-p overlap while Phosphorous
does not.
(xii) A nitrogen atom has five valence electrons but it does not form the compound NCl 5.
Ans: Because of absence of d-orbitals it can’t expand its covalency from 3 to 5.
(xiv) All the bonds in the molecules of PCl5 are not equal.
Ans: PCl5 has a trigonal bipyramidal shape in the gas space. A trigonal bipyramidal is an irregular
structure in which some bond angles are 90 degree and others of 120 degree resulting in unequal
P-Cl bond lengths
PCl5 + H2O POCl3 + 2HCl & PCl5 PCl3 + Cl2
According to VSEPR theory, axial bonds experience more repulsion and are thus longer
than equatorial bonds.
(xxx) H3PO2 and H3PO3 act as good reducing agents while H3PO4 does not.
Ans: In H3PO2, two H atoms are bonded directly to P atom & in H 3PO3 one H atom is bonded
directly to P atom which imparts reducing character to the acid, whereas in H3PO4 there is no H
atom bonded directly to P atom
(ii) Tendency to show –2 oxidation state diminishes from Sulphur to polonium in group 16.
Ans: The outer electronic configuration of group 16 elements is ns 2 np4. These elements therefore
have the tendency to gain two electrons to complete octet. Since electro-negativity and I.E.
decrease on going down the group, tendency to show –2 oxidation state diminishes.
(iii) Oxygen generally exhibit oxidation state of –2 only whereas other members of the
family exhibit +2, +4, +6 oxidation states also.
Ans: Oxygen is an electronegative element thus exhibit oxidation state of –2. .Other members of
the family have d orbitals and therefore, can expand their octets and show + 2, + 4, + 6 oxidation
states also.
(iv) There is large difference between the melting point of Oxygen & Sulphur.
Ans: The large difference between the melting and boiling points of oxygen and sulphur may be
explained on the basis of their atomicity; oxygen exists as diatomic molecule (O 2) whereas
sulphur exists as polyatomic molecule (S8).
(ii)Halogens have max. negative electron gain enthalpy in the respective periods of the
periodic table.
Ans: Halogens have the smallest size in their respective periods and therefore high effective
nuclear charge. As a consequence, they readily accept one electron to acquire noble gas electronic
configuration.
(vii) Fluorine exhibit oxidation state of –1 only whereas other halogens exhibit +1, +3, +5, +7
oxidation states also.
Ans: Fluorine is the most electronegative element and cannot exhibit any positive oxidation state.
Other halogens have d orbitals and therefore, can expand their octets and show + 1, + 3, + 5 and +
7 oxidation states also with more electro-negative elements.
(xvi) HF is least volatile whereas HCl is most volatile among all halogen acids.
Ans: HF is associated with intermolecular hydrogen bonding, so it is least volatile whereas HCl
is gas and has least surface area, therefore minimum Vander waals forces of attraction and
minimum boiling point.
(xviii) The boiling point of hydrogen halides varies in the order: HF > HI>HBr>HCl.
Ans: The boiling point of HF is highest due to intermolecular hydrogen bonding then
HI>HBr>HCl. (Decreasing Vander waals forces)
(xix) Interhalogen compounds are more reactive than related elemental halogens.
Ans: In general, inter halogen compounds are more reactive than halogens due to weaker X–X 1
bonding than X–X bond. Thus, ICl is more reactive than I2.
(xxiii) OF2 should be called oxygen fluoride and not fluorine oxide.
Ans: OF2 should be called oxygen fluoride and not fluorine oxide. Since oxygen is less
electronegative than fluorine, OF2 should be called oxygen diflouride.
(xxvi)When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric
chloride.
Ans: Its reaction with iron produces H2.
Fe + 2HCl FeCl2 +H2 .Liberation of hydrogen prevents the formation of ferric chloride.
(viii) Of the noble gases only Xenon is known to form real chemical compounds.
The ionization energy of xenon is relatively low and therefore, it is possible to excite the paired
electrons from np orbitals to nd sub-shell.
(ix) Noble gases form compounds with fluorine and oxygen only.
Because fluorine and oxygen are strong oxidizing agents (most electronegative elements)
(x) Helium is used for inflating aeroplane tyres & filling balloons for meteorogical
observations.
Helium is a non-inflammable and light gas
(xiii) Xenon readily forms compounds but Krypton does not form compounds easily.
Xenon has lower ionization energy than Krypton, therefore, Xe forms compounds.
(i) A translucent white waxy solid (A) on heating in an inert atmosphere is converted to its
allotropic form (B). Allotrope (A) on reaction with very dilute aqueous KOH liberates a
highly poisonous gas (C) having rotten fish smell. With excess of chlorine forms (D) which
hydrolyses to compound (E). Identify compounds (A) to (E).
Ans: :P4 (White or Yellow Phosphorus) P4 ( Red Phosphorus)
(A) (B)
P4 + KOH PH3 + KH2PO4 P4 + 10Cl2 4 PCl5
(C) Phosphine (D)Phosphrous penta-
chloride
PCl5 + H2O POCl3 + HCl
(E) Phosphorus oxy chloride
(ii) Discuss the general characteristics of group 15 elements with reference to their
electronic configuration, oxidation state, atomic size, and ionization enthalpy and electro
negativity.
Ans: Electronic configuration : ns2np3
Oxidation state, atomic : -3, +3 and +5.
Size : Increases down the group.
Ionization enthalpy : Decreases down the group.
Electro negativity : Decreases down the group.
(iii)Nitrogen is anomalous in many properties. Why? Give two examples to show that
Nitrogen is anomalous in many properties.
Ans: Nitrogen differs from the rest of the members of this group due to its smaller size, high
electro-negativity, high ionisation enthalpy and non-availability of d orbitals. Nitrogen has unique
ability to form p π-p π multiple bonds with itself and with other elements having small size and
high electro-negativity. Nitrogen exists as a diatomic molecule with a triple bond (one s and two
p) between the two atoms. Consequently, its bond enthalpy is very high.
(xiii) Draw the structure of N2O, NO, N2O3, NO2 , N2O4, & N2O5.
Ans:
NO thus formed is recycled and the aqueous HNO3 can be concentrated by distillation upto ~
68% by mass. Further concentration to 98% can be achieved by dehydration with concentrated
H2SO4.
(xvii) Write the balanced equations involved in the laboratory preparation of nitric acid.
Illustrate how copper metal can give different products on reaction with HNO 3.
Ans: NaNO3 +H2SO4 NaHSO4 + HNO3.
3Cu + 8 HNO3(dilute) 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(conc.) Cu(NO3)2 + 2NO2 + 2H2O
(xxii)Write main differences between the properties of white phosphorus and red
phosphorus.
Ans: White phosphorus is a translucent white waxy solid. It is poisonous, insoluble in water but
soluble in carbon disulphide and glows in dark (chemiluminescence). It dissolves in boiling
NaOH solution in an inert atmosphere giving PH3.
P4 +3NaOH+3H2O PH3 + 3NaH2PO4 (sodium hypophosphite)
White phosphorus is less stable and therefore, more reactive than the other solid phases under
normal conditions because of angular strain in the P4 molecule where the angles are only 60°. It
readily catches fire in air to give dense white fumes of P 4O10.
P4 +5O2 P4O10
It consists of discrete tetrahedral P4 molecule.
Red phosphorus is obtained by heating white phosphorus at 573K in an inert atmosphere for
several days. When red phosphorus is heated under high pressure, a series of phases of black
phosphorus are formed.
Red phosphorus possesses iron grey lustre. It is odourless, nonpoisonous and insoluble in water
as well as in carbon disulphide. Chemically, red phosphorus is much less reactive than white
phosphorus. It does not glow in the dark.
(xxiii) Write the balanced equations involved in the preparation of PH3 (Phosphine).
Ans: P4 +3NaOH+ 3H2O PH3 +NaH2PO4
(xxiv)In what way can it be proved that PH3 is basic in nature?
Ans: PH3 reacts with acids like HI to form PH4I which shows that it is basic in nature.
PH3 + HI PH4I Due to lone pair on phosphorus atom, PH 3 is acting as a Lewis base in the
above reaction.
(xxv) What happens when white phosphorus is heated with concentrated NaOH solution in
an inert atmosphere of CO2?
Ans: P4 +3NaOH+ 3H2O PH3 +NaH2PO4
(xxvi) Write the balanced equations involved in the preparation of PCl3 & PCl5.
Ans: P4 + 6Cl2 4 PCl3
P4 + 10Cl2 4 PCl5
(xxvii) Draw the structure of PCl5 in the gaseous state and in the
solid state
Ans:
(xxix)Are all the five bonds in PCl5 equivalent? Justify your answer.
Ans: PCl5 has a trigonal bipyramidal structure and the three equatorial P-Cl bonds are equivalent,
while the two axial bonds are different and longer than equatorial bonds.
(xxx) Write the name and draw the shape of oxacids of phosphorous.
Ans:
(xxxvi) How do you account for the reducing behaviour of H 3PO2 on the basis of its
structure?
Ans: In H3PO2, two H atoms are bonded directly to P atom which imparts reducing character to
the acid.
1. Write the name and draw the shape of following of following: H 2SO4, H2SO3,H2S2O8 and
H2S2O7.
Ans:
2. Draw the structure of Sulphur in S8 (rhombic form) and S6 form.
Ans: S8 ring in both the forms is puckered and has a crown shape and in cyclo-S 6, the ring
adopts the chair form.
10. Aluminium oxide (Al2O3) shows amphoteric character .Justify with chemical
reactions.
Ans: Al2O3 + 6HCl + 9H2O 2[Al(H2O)6]3+ + 6Cl-
Al2O3+ 6NaOH + 3H2O 2Na3[Al(OH)6]
15. Write differences between monoclinic Sulphur (α) and rhombic Sulphur (β).
Ans: Rhombic sulphur (α-sulphur) This allotrope is yellow in colour, m.p. 385.8 K and
specific gravity 2.06. Rhombic sulphur crystals are formed on evaporating the solution of roll
sulphur in CS2. It is insoluble in water but dissolves to some extent in benzene, alcohol and
ether. It is readily soluble in CS 2. α-sulphur is stable below 369 K and transforms into β-
sulphur above 369 K
Monoclinic sulphur (β-sulphur) Its m.p. is 393 K and specific gravity 1.98. It is soluble in
CS2. This form of sulphur is prepared by melting rhombic sulphur in a dish and cooling, till
crust is formed. Two holes are made in the crust and the remaining liquid poured out. On
removing the crust, colourless needle shaped crystals of β-sulphur are formed. It is stable
above 369 K
and transforms into α-sulphur below it.
16. Write the balanced equation involved in the laboratory preparation and industrial
preparation of Sulphur Dioxide.
Ans: Lab Prep.:- SO32-(aq) + 2H+ (aq) H2O(l) + SO2 (g)
Industrial Prep 4FeS (s) 11O2(g) 2Fe O (s) 8SO2 (g)
17. Draw the structure of Sulphur Dioxide. Comment on the nature of two S-O bonds
formed in SO2 molecule. Are the two S-O bonds in this molecule equal?
Ans:
21. Write the conditions to maximize the yield of H 2SO4 by contact process.
Ans: Low temperature and high pressure are the favourable conditions for maximum yield.
But the temperature should not be very low otherwise rate of reaction will become slow.
22. Mention the areas in which Sulphur Dioxide (SO 2) and sulphuric acid (H2SO4) plays
an important role.
Ans: Sulphur dioxide is used
(i) in refining petroleum and sugar
(ii) in bleaching wool and silk and
(iii) as an anti-chlor, disinfectant and preservative. Sulphuric acid, sodium hydrogen sulphite and
calcium hydrogen sulphite (industrial chemicals) are manufactured from sulphur dioxide.
Liquid SO2 is used as a solvent to dissolve a number of organic and inorganic chemicals
Sulphuric acid is a very important industrial chemical. A nation’s industrial strength can be
judged by the quantity of sulphuric acid it produces and consumes. It is needed for the
manufacture of hundreds of other compounds and also in many industrial processes. The bulk of
sulphuric acid produced is used in the manufacture of fertilizers (e.g., ammonium sulphate,
superphosphate). Other uses are in:
(a) petroleum refining (b) manufacture of pigments, paints and dyestuff
intermediates
(c) detergent industry
(d) metallurgical applications (e.g.,cleansing metals before enameling, electroplating and
galvanising
(e) storage batteries (f) in the manufacture of nitrocellulose products and
(g) as a laboratory reagent.
23. How is Sulphur Dioxide (SO2) an air pollutant?
Ans: It dissolves in rain water and produces acid rain.
28. When conc. H2SO4 was added into an unknown salt present in a test tube, a brown gas
(A) was evolved. This gas intensified when copper turnings were also added into this test-
tube. On cooling, the gas (A) changed into a colourless gas (B).(a) Identify the gases A and
B.(b) Write the equations for the reactions involved.
Ans: The salt is a Nitrate or Nitrite:
NO3- + Conc. H2SO4 SO4- + H2O + NO2
A- Brown gas
2NO2 N2O4
Brown gas Colourless
(i)Considering the parameters such as bond dissociation enthalpy, electron gain enthalpy
and hydration enthalpy, compare the oxidising power of F2 and Cl2.
Ans:F2 has more oxidising power than Cl 2. Because standard electrode potential value of F2 is
higher than Cl2 .Standard electrode potential value are dependent on the parameters bond
dissociation enthalpy, electron gain enthalpy and hydration enthalpy.
(v)Name two poisonous gases which can be prepared from chlorine gas.
Ans: Poisonous gases such as phosgene (COCl2), tear gas (CCl3NO2), mustard gas
(vi) Write the balanced equation involved in the laboratory preparation of chlorine gas.
(Hint: from MnO2 and KMnO4)
Ans: By heating manganese dioxide with concentrated hydrochloric acid.
MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O
However, a mixture of common salt and concentrated H2SO4 is used in place of HCl.
4NaCl + MnO2 + 4H2SO4 → MnCl2 + 4NaHSO4 + 2H2O + Cl2
(ii) By the action of HCl on potassium permanganate.
2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2
(vii) How is chlorine gas manufactured by Deacons process and Electrolytic process?
Ans: (i) Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in the
presence of CuCl2 (catalyst) at 723 K.
4HCl +O2 → 2Cl2 + 2H2O
(ii) Electrolytic process: Chlorine is obtained by the electrolysis of brine (concentrated NaCl
solution). Chlorine is liberated at anode. It is also obtained as a by–product in many chemical
industries.
(x) Give uses for each of the following ;(i) ClO2 (ii)I2O5 (iii)HCl (iv)Interhalogen compounds.
Ans:
(i) ClO2 is used as a bleaching agent for paper pulp and textiles and in water treatment.
(ii) I2O5 is a very good oxidising agent and is used in the estimation of carbon monoxide.
(iii) It is used
(a) in the manufacture of chlorine, NH4Cl and glucose (from corn starch),
(b) for extracting glue from bones and purifying bone black,
(c) in medicine and as a laboratory reagent.
(iv) These compounds can be used as non aqueous solvents. Interhalogen compounds are very
useful fluorinating agents. ClF3 and BrF3 are used for the production of UF6 in the enrichment of
235U.
U(s) + 3ClF3(l) UF6(g) + 3ClF(g)
(xvi)How can you prepare Cl2 from HCl and HCl from Cl2.Write reactions only?
electrolysis
Ans: 2HCl H2 + Cl2
Light
H2 + Cl2 2HCl
(xvii)Write the balanced chemical equation for the reaction of Cl 2 with hot and concentrated
NaOH. Is this reaction a disproportionation reaction? Justify.
Ans:3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2O, Yes, chlorine from zero oxidation state is
changed to –1 and +5 oxidation states.
(iii) Give the formula and describe the structure of a noble gases species which is
isostructural with
(i) BrO3- (ii) ICl4-(iii) IBr2-
Ans: (i) XeO3 (ii) XeF4 (iii) XeF2
(iv)Give two uses for each of the following: (i) Helium (ii) Neon (iii) Argon
Ans: Helium is used in filling balloons for meteorological observations.It is used as a diluent
for oxygen in modern diving apparatus because of its very low solubility in blood.
Neon is used in discharge tubes and fluorescent bulbs for advertisement display purposes. Neon
bulbs are used in botanical gardens and in green houses.
Argon is used mainly to provide an inert atmosphere in high temperature metallurgical processes
(arc welding of metals or alloys) and for filling electric bulbs. It is also used in the laboratory for
handling substances that are air-sensitive
(vii) What inspired N.Bartlett for carrying out reaction between Xe and PtF 6?
Ans In March 1962, Neil Bartlett, then at the University of British Columbia, observed
the reaction of a noble gas. First, he prepared a red compound which is formulated as O 2+PtF6-.
He, then realised that the first ionization enthalpy of molecular oxygen (1175 kJmol -1) was almost
identical with that of xenon (1170 kJ mol -1). He made efforts to prepare same type of compound
with Xe and was successful in preparing another red colour compound Xe +PtF6- by mixing PtF6
and xenon. After this discovery, a number of xenon compounds mainly with most electronegative
elements like fluorine and oxygen, have been synthesized.
(a)6XeF4 + 12H2O
(b) XeF6 +3H2O
(c) 2XeF2 + 2H2O
(d) XeF4+O2F2
(e) XeF2+ PF5
(f) XeF4 + SbF5
(g)XeF6 +MF