The p-Block Elements

Group 15 Elements
Introduction :
This Group consists N, P, As, Sb, Bi and Moscovium(Mc). Group 15 elements are called as Pnitogens. General electronic
configuration of these elements is ns2 np3.

Table : Atomic and Physical properties of Group 15 Elements

Atomic and Physical properties more than that of group 14 elements in the respective
Atomic and Ionic Radii : periods.
 Atomic size and ionic size increases on moving down  IE1: N > P > As > Sb > Bi
the group.
 From As to Bi only a small increase in covalent radius Electronegativity :
is observed. This is due to the presence of completely  Electronegativity decreases down the group. However,
filled d or f orbitals in heavier members. amongst the heavier elements, the difference is not that
 Atomic radius: Bi > Sb > As > P > N much.
 E.N.: N > P > As > Sb = Bi
Ionisation Enthalpy:
 Ionisation enthalpy decreases down the group. Due to
Physical properties
the extra stable half-filled p-subshell and smaller size,
 All members of nitrogen family are polyatomic. N2 is a
the ionisation enthalpy of the group 15 elements is

1 C HEMISTRY
The p-Block Elements

diatomic gas rest others are solids. • Nitrogen is restricted to a maximum covalency of 4 since
 Due to decrease in ionisation enthalpy and increase in only four (one s and three p) orbitals are available for
atomic size, metallic character increases down the group. bonding.
 Nitrogen and Phosphorus are non-metal, Arsenic and • Other elements of this group except nitrogen have
Antimony metalloid, Bismuth and Moscovium(Mc) are vacant d-orbitals in the outermost shell which can be
metals. used for bonding (covalency) and hence, expand their
 The boiling point increase down the group but the covalence as in PF6–.
melting point increases upto As and then decreases Anomalous properties of nitrogen:
upto Bi. Due to its smaller size, higher E.N., higher I.E. and
 Except nitrogen, all the elements show allotropy. absence of d-orbitals Nitrogen differs from the rest of
the members.
Occurrence • N form p – p multiple bonds with itself and with other
Nitrogen : elements having small size and high E.N. (e.g., C, O).
• In Atmosphere N2 is present 78% by volume. Other elements of this group except nitrogen do not
• In the form of protein it is also present in plants and form p – p bonds, because due to large size they cannot
animals. have effective overlapping. Thus, nitrogen exists as a
• In Earth crust : Chile saltpeter (NaNO3) and Indian diatomic molecule with a triple bond (one  and two )
saltpeter (KNO3) are main source of nitrogen. between the two atoms. Consequently, its bond
Phosphorus : enthalpy is very high. On the other side P, As and Sb
• Phosphorus is present in Minerals of apatite family form single bonds as P–P, As–As and Sb–Sb while Bi
Ca9(PO4)6·CaX2 (X = F, Cl or OH) e.g., Fluorapatite forms metallic bonds in elemental state.
Ca9(PO4)6·CaF2 • Because of higher interelectronic repulsion of the lone
These are main components of phosphate rocks. pairs the single N–N bond is weaker than the single
• Phosphorus is also present in bones, living cell, plant P–P bond. As a result the catenation tendency is
matter. weaker in nitrogen.
• Arsenic, Antimony, Bismuth are present mainly in the • Nitrogen cannot form d – p bond as the heavier
form of sulphide minerals. elements can e.g. R3P = O or R3P = CH2 (R = alkyl group).
Phosphorus and arsenic can form d – d bond also
Chemical Properties with transition metals when their compounds like
P(C2H5)3 and As(C6H5)3 act as ligands.
Oxidation states and their stability
• – 3, + 3 and + 5 are common oxidation states of these Reactivity towards hydrogen:
elements.
• EH3 type hydrides are formed by all the elements of
• Bi hardly forms any compound in –3 oxidation state.
Group 15.
Stability of –3 oxidation state decreases down the group • From NH3 to BiH3 the thermal stability of hydrides
due to increase in size and metallic character.
decreases. Thus the reducing character of the hydrides
• Due to inert pair effect the stability of +5 oxidation
increases. NH3 is only a mild reducing agent while BiH3
state decreases and that of +3 state increases down is the strongest reducing agent amongst all the
the group.The only existing Bi (V) halide is BiF5.
hydrides.
• N shows +1, +2, +4 oxidation states also when it reacts
 Thermal stability, bond dissociation enthalpy, bond
with O2. angle and basic nature of these hydrides decreases on
• P also shows +1 and +4 oxidation states in some
moving down the group.
oxoacids.
 Reducing character, Acidic nature increases on moving
• For nitrogen, all oxidation states from +1 and +4 tend to down the group.
disproportionate into +5 and –3 in acidic solution.
 Boiling Point : PH3 < AsH3 < NH3 < SbH3 < BiH3
Ex. 3HNO2  HNO3 + H2O + 2NO
 Melting Point : PH3 < AsH3 < SbH3 < NH3
Similarly, in case of phosphorus nearly all intermediate
oxidation states disproportionate into +5 and –3 both
Reactivity towards oxygen:
in alkali and acid.
 E2O3 and E2O5 type of oxides are formed by all the
• +3 oxidation state in case of As, Sb and Bi become elements of nitrogen family. The E2O3 type oxides of N
increasingly stable with respect to disproportionation.
and P are purely acidic, that of As and Sb amphoteric
and those of Bi is basic.

C HEMISTRY 2
 The p-Block Elements

Reactivity towards halogens:

EXAMPLE-2
 EX3 and EX5 type halides are formed by these elements. The correct order of the reducing strength of the given
 Except those of nitrogen All the trihalides of these compound is
elements are stable. In case of nitrogen, only NF3 is (1) PH3 < NH3 < AsH3 < SbH3 < BiH3
(2) NH3 < AsH3 < PH3 < SbH3 < BiH3
known to be stable.
(3) NH3 < PH3 < AsH3 < SbH3 < BiH3
 Trihalides except BiF3 are predominantly covalent in
(4) BiH3 < SbH3 < AsH3 < PH3 < NH3
nature. Ans. (3)
 Due to absence of vacant d-subshell Nitrogen does Sol : NH3 < PH3 < AsH3 < SbH3 < BiH3 (reducing strength)
not form pentahalide. As we move down the group reducing strength of
hydrides increases because bond dissociation
Reactivity towards Metals : energy decreases and bond becomes weak.
 With metals, group 15 elements form binary compounds
showing -3 oxidation state e.g., GROUP 16 ELEMENTS : The Oxygen family
Ca3N2, Ca3P2, Na3As, Zn3Sb2, Mg3Bi2 Introduction:
EXAMPLE-1  Group 16 elements are O, S, Se, Te, Po and Livermorium
(Lv).
Melting point of hydrides of nitrogen family follows
 Oxygen and S are non-metal, Se and Te metalloids,
the order
whereas Po is a radioacitve metal.
(1) NH3 < PH3 < AsH3 < SbH3
(2) PH3 < NH3 < AsH3 < SbH3  They are also known as chalcogens (the ore forming
(3) PH3 < AsH3 < NH3 < SbH3 elements) because a large number of metal ores are
(4) PH3 < AsH3 < SbH3 < NH3 oxides or sulphides.
Ans. (4)  General electronic configuration of these elements is
Sol: Due to hydrogen bonding melting point of NH 3 is ns2np4. Six electrons are present in valence shell of
maximum among Nitrogen family hydrides. these elements.
Table : Some Physical Properties of Group 16 Elements

Property O S Se Te Po
Atomic number 8 16 34 52 84
Atomic mass/g mol1 16.00 32.06 78.96 127.60 210.00
Electronic configuration  He 2s2 2p4  Ne 3s 2 3p4 [Ar]3d10 4s 2 4p 4  Kr  4d10 5s2 5p4  Xe 4f 14 5d10 6s2 6p4
a
Covalent radius/(pm) 66 104 117 137 146
Ionic radius, E 2 /pm 140 184 198 221 230b
Electron gain enthalpy, / 141 200 195 190 174
 eg H kJ mol1
lonisation enthalpy   i H1  1314 1000 941 869 813
1
/kJmol
Electronegativity 3.50 2.58 2.55 2.01 1.76
 298 K  
d
Density/g cm 3 1.32c
2.06 4.19e 6.25
Melting point / K 55 393f 490 725 520
Boiling point / K 90 718 958 1260 1235
Oxidation states 2, 1,1, 2 2, 2, 4, 6 2, 2, 4, 6 2, 2, 4, 6 2, 4

Atomic and Physical properties:

3 C HEMISTRY
The p-Block Elements

Atomic and Ionic Radii : property is prominently displayed by sulphur (S8). The
 The size of oxygen atom is exceptionally small. Due to S—S bond is important in biological system and is
increase in the number of shells , atomic and ionic radii found in some proteins and enzymes such as cysteine.
increases from top to bottom in the group.
 Atomic radius: Te > Se > S > O Occurence :
 Oxygen is the most abundant of all the elements on
Ionisation Enthalpy : earth. It forms about 46.6% by mass of earth’s crust.
 The element of this group have lower ionisation enthalpy Dry air contains 20.946% oxygen by volume.
values compared to those of group 15 in the same
periods. This is due to the extra stable half-filled  Sulphur is present in earth crust only 0.03-0.1%
electronic configurations in group 15 elements. Ionisation • Combined sulphur exists mainly as sulphates like :
enthalpy decreases down the group. gypsum (CaSO4.2H2O), epsom salt (MgSO4.7H2O),
 IE1: O > S > Se > Te baryte (BaSO4).
• Sulphides such as : galena (PbS), zinc blende (ZnS),
Electron Gain Enthalpy : copper pyrites (CuFeS2).
 Oxygen atom, has less negative electron gain enthalpy • Traces of sulphur occur as H2S in volcanoes.
than sulphur. From sulphur onwards the value again • Organic materials such as eggs, proteins, garlic, onion,
becomes less negative upto polonium. mustard, hair and wool contain sulphur.
 Electron affinity: S > Se > Te > Po > O  Selenium and tellurium are Found as metal selenides
and tellurides in sulphide ores.
Electronegativity :  Polonium :
 Next to fluorine, oxygen has the highest Occurs as decay product of thorium and uranium
electronegativity value amongst all the elements. Down minerals.
the group, electronegativity decreases with an increase
in atomic number. Chemical Properties
 E.N.: O > S > Se > Te Oxidation states and their stability
 Except oxygen other elements of the group exhibit +2,
EXAMPLE-3 +4, +6 oxidation states but +4 and +6 are more common.
 The stability of -2 oxidation state decreases down the
The number of unpaired electrons in the p-subshell of group.
oxygen atom is  Sulphur, selenium and tellurium usually show +4
(1) 1 (2) 2 (3) 3 (4) 4 oxidation in their compounds with oxygen and +6
Sol. (2) oxidation state with fluorine.
Oxygen electronic configuration is 1s2, 2s2 2p4  The stability of +6 oxidation state decreases down the
1s 2s 2p group and stability of +4 oxidation state increases (inert
     pair effect).
 Bonding in +4 and +6 oxidation states are primarily
covalent.
EXAMPLE-4
Identify the element having highest density from Anomalous behaviour of oxygen in Group 16:
following.  This is due to its small size and high electronegativity.
(A) O (B) S (C) Se (D) Te  Strong hydrogen bonding is present in H2O, which is
Ans. (D) absent in H2S.
Sol: Density increases down the group in oxygen family  Due to absence of d orbital in oxygen, it’s maximum
covalency is four and but rarely exceeds to two.
Physical Properties :  Other elements can show covalency more than four.
 The melting and boiling points increases with an
increase in atomic number down the group. Reactivity with hydrogen:
 There is larger difference between the melting and  H2E type hydrides are formed by all these elements.
boiling points of oxygen and sulphur because oxygen Their acidic character increases from H2O to H2Te.
exist as diatomic molecules (O2) whereas sulphur exists  Because bond enthalpy decreaes down the group.The
thermal stability of hydrides also decreases from H2O
as polyatomic molecule (S8).
to H2Po.
 All the hydrides except water possess reducing
Catenation Tendency:
property and this character increases from H2S to H2Te.
 Catenation tendency decreases down the group. This

C HEMISTRY 4
 The p-Block Elements

Reactivity with oxygen: used in photocopying machines and also a decolouriser

 Chalcogens form oxides of the EO2 and EO3 types where of glass.
E = S, Se, Te or Po.
 Ozone and SO2 are gases while SeO2 is solid.
 Reducing property of dioxide decreases from SO2 to
EXAMPLE-5
TeO2 ; SO2 is reducing while TeO2 is an oxidising agent. Which of the following compounds does not exist?
 S, Se and Te also form EO3 type oxides. All the oxides (1) SF6 (2) S2Cl2 (3) SCl2 (4) Se2Br2
are acidic in nature. Ans. (3)
Sol:
Reactivity toward the halogens:
 Chalcogens form halides of the type EX2, EX4 and EX6.
The stabilities of the halides follows the order F– > Cl– EXAMPLE-6
> Br– > I–. Which hydride does not shows reducing porperty
 Amongst hexahalides, hexafluorides are the only stable (1) H2Te (2) H2Se (3) H2S (4) H2O
halides. All hexafluorides are gaseous in nature. Ans. (4)
 Only SF6 exist among the hexahalide of sulfur.
 Amongst tetrafluorides SF4 is a gas, SeF4 liquid and Group 17 Elements :
TeF4 a solid Introduction:
 All elements except selenium form dichlorides and  Group 17 consists F, Cl, Br, I, At and Tennessine (Ts).
dibromides. The well known monohalides are dimeric F2 and Cl2 are gases, bromine is a liquid while iodine is
in nature, Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and a solid.
Se 2 Br 2 . These dimeric halides undergo  They are known as the halogens (Greek halo means
disproportionation as given salt and genes born i.e., salt producers).
2Se2Cl2  SeCl4 + 3Se.  General electronic configuration of these elements is
 Selenium has property of photo conductivity and is ns2 np5.

Atomic and physical properties

Element F Cl Br I At
Atomic Number 9 17 35 53 85
Atomic Mass 19 35.45 79.90 126.90 210
2 5 2 5 10 2 5 10 2 5 14 10 2 5
Electronic configuration [He] 2s 2p [Ne] 3s 3p [Ar] 3d 4s 4p [Kr] 4d 5s 5p [Xe] 4f 5d 6s 6p
Covalent Radius / pm 64 99 114 133
–
Ionic Radius X / pm 133 184 196 220
–1
Ionization enthalpy / (kJ mol ) 1680 1256 1142 1008
–1
Electron gain enthalpy /(kJ mol ) – 333 – 349 – 325 – 296
Distance X -X/pm 143 199 228 266
–1
Enthalpy of dissociation (X2 )/kJ mol 158.8 242.6 192.8 151.1
Electronegativity 4 3.2 3.0 2.7 2.2
Melting point / K 54.4 172 265.8 386.6
Boiling point / K 84.9 239.0 332.5 458.2

Atomic and physical properties:

Atomic and Ionic Radii
 These elements have smallest size in their respective periods due to maximum effective nuclear charge .
 Atomic and ionic radii increases from fluorine to iodine due to increasing number of shells.
 Atomic radius: I > Br > Cl > F

Ionisation Enthalpy
 They have less tendency to lose electron. Thus they have very high ionisation enthalpy. Due to increase in atomic size,
ionisation enthalpy decreases down the group.
 I.E1: F > Cl > Br > I

5 C HEMISTRY
The p-Block Elements

 Sea water contains Cl–, Br– and I– of Na, K, Mg, Ca,

Electron Gain Enthalpy but mainly NaCl (2.5% by mass). Deposits of dried
 In the corresponding period halogen have maximum up seas contain NaCl and carnallite ( KCl
electron affinity. Because atoms of these elements have MgCl2·6H2O).
only one electron less than stable noble gas
configuration.
 Electron gain enthalpy becomes less negative down EXAMPLE-7
the group. Sea weed are important source of -
 Due to small size of fluorine atom, the negative electron [CPMT 82, 86]
gain enthalpy of fluorine is less than that of chlorine. (A) Iron (B) Chlorine
As there are strong interelectronic repulsions in the (C) Iodine (D) Bromine
relatively small 2p orbitals of fluorine and thus, the
Ans. (C)
extra incoming electron experience much repulsion.
 Electron affinity: Cl > F > Br > I Sol: In sea weed iodine is mainly present.

Electronegativity Chemical Properties:

 The electronegativity decreases down the group. Oxidation states and trends in chemical
Fluorine is the most electronegative element in the reactivity
 These elements show –1 oxidation state. But
periodic table. Their electronegativity is very high.
chlorine, bromine and iodine exhibit + 1, + 3, + 5 and
 E.N.: F > Cl > Br > I + 7 oxidation states also.
 The fluorine atom has no d orbitals in its valence
shell and therefore cannot expand its octet. Being
Physical Properties: the most electronegative, it exhibits only – 1
 Their melting and boiling points steadily increase oxidation state.
with atomic number.  The higher oxidation states of chlorine, bromine
and iodine are shown in combination with the small
and highly electronegative fluorine and oxygen
 All halogens are coloured. F2 has yellow, Cl2 atoms e.g., in interhalogens, oxides and oxoacids.
greenish yellow, Br2 red and I2 is violet colour.  The ready acceptance of an electron is the reason
Becuase absorption of radiations in visible region for the strong oxidising nature of halogens. F2 is the
results in the excitation of outer electrons to higher strongest oxidising halogen and it oxidises other
energy level. halide ions in solution or even in the solid phase.
 The decreasing oxidising ability of the halogens in
 F2 and Cl2 react with water. Br2 and I2 are only aqueous solution down the group is evident from
sparingly soluble in water, but are soluble in their standard electrode potentials.
organic solvents such as CHCl3, CCl4, CS2 and  F2 + 2X–  2F– + X2 (X = Cl, Br or I)
hydrocarbons to give coloured solutions. Cl2 + 2X–  2Cl– + X2 (X = Br or I)
 The X-X bond disassociation enthalpies have Br2 + 2I–  2Br– + I2
trend : Cl – Cl > Br – Br > F – F > I – I. The reason for  All the halogens are highly reactive. They react with
the smaller enthalpy of dissociation of F2 is the metals and non-metals to form halides. The reactivity
of the halogens decreases down the group.
relatively larger electrons-electrons repulsion
 Fluorine oxidises water to oxygen whereas chlorine
among the lone pairs in F2 molecule where they are and bromine react with water to form corresponding
much closer to each other than in case of Cl2. hydrohalic and hypohalous acids. The reactions
of iodine with water is non- spontaneous . I– can be
oxidised by oxygen in acidic medium; just the
Occurrence :
reverse of the reaction observed with fluorine.
Fluorine: Exist as insoluble fluorides. 2F2 (g) + 2H2O  4H+ (aq) + 4F– (aq) + O2 (g)
 Fluorspar - CaF2, Cryolite - Na3AlF6, X2 (g) + H2O  HX(aq) + HOX(aq)
Fluoroapatite - 3Ca3(PO4)2CaF2. (where X = Cl or Br)
4I– (aq) + 4H+ (aq) + O2 (g)  2I2 (s) + 2H2O
 Small quantities are also present in soil, river water
plants, bones and teeth of animals.

C HEMISTRY 6
 The p-Block Elements

Anomalous behaviour of fluorine reacts with Mg to give Mg3N2.

 Fluorine shows this behaviour due to its small size,
highest electronegativity, low F- F bond dissociation
EXAMPLE-8
enthalpy, and non availability of d orbitals in valence Which reaction is possible -
shell. (A) I2 + 2NaBr – Br2 + 2NaI
 Most of the reactions of fluorine are exothermic (due
to the small and strong bond formed by it with other (B) I2 + 2NaCl – Cl2 + 2Nal
elements).
 HF is liquid (b.p. 293 K) due to strong hydrogen (C) Br2 + 2NaCl – Cl2 + 2NaBr
bonding. Other hydrogen halides are gases.
(D) Cl2 + 2NaBr – Br2 + 2NaCl
 It forms only one oxoacid while other halogens form a
Ans. (D)
number of oxoacids.
Sol: Cl2 is better oxidising agent than Br2 and I2, it can oxidise
Reactivity towards hydrogen: Br– and I– into corresponding Halogen.
 Affinity for hydrogen decreases from fluorine to iodine
with increasing atomic number. They all form hydrogen
EXAMPLE-9
halides with hydrogen . They dissolve in water to form
hydrohalic acids. Which one of the following elements can have both
 The stability of these halides decreases down the group positive and negative oxidation state?
due to decrease in bond (H–X) dissociation enthalpy [AFMC 94]
in the order : (A) F (B) I
H – F > H – Cl > H –Br > H – I . (C)Li (D) He
 The acidic strength of these hydrides increases in the Ans. (B)
order : HF < HCl < HBr < HI. Sol: F have only –ve oxidation state
Reactivity towards oxygen : Li have only +ve oxidation state
 Most of the oxides of halogen are unstable. OF2 and
I have –ve as well as +ve oxidation state
O2F2 are two oxides of fluorine. These oxide are
essentially oxygen fluorides because of the higher
electronegativity of flurorine than oxygen . Only OF2 is EXAMPLE-10
the thermally stable at 298 K. Which is the most volatile compound
 OF2 and O2F2 are strong fluorinating agents. O2F2 [IC070223]
oxidises plutonium to PuF6 and the reaction is used (1) HF (2) HCl
in removing plutonium as PuF6 from spent nuclear (3) HBr (4) HI
fuel. Q. dkSulk lokZf/kd ok"i'khy ;kSfxd gS \ [IC070223]
 Cl2, Br2 and I2 form oxides in which the oxidation (1) HF (2) HCl
states of these halogen vary from + 1 to + 7. A
(3) HBr (4) HI
combination of kinetic and thermodynamic factors
Q. MkkiÚke ðÄkhu çkk»Ãkþe÷ MktÞkusLk fÞwt Au ?
lead to the generally decreasing order of stability
(1) HF (2) HCl (3) HBr (4) HI
of oxides formed by halogens, I > Cl > Br. The higher
Ans. (2)
oxides of halogens tend to be more stable than the
Sol. Hydride – HF HCl HBr HI
lower ones.
 Cl2O, ClO2, Cl2O6 and Cl2O7 are highly reactive B.pt (in K) – 293 189 206 238
oxidising agents and tend to explode. ClO2 is used Becouse of having low b.p. HCl is more volatile.
as a bleaching agent for paper pulp and textiles and
in water treatment. EXAMPLE-11
 Br2O, BrO2, BrO3 are the least stable halogen oxides Elements of which one of the following groups will
and exist only at low temperature. They are very
form anions most readily ?
powerful oxidising agents.
 I2O4, I2O5, I2O7 are insoluble solids and decompose (1) Oxygen group
on heating. I2O5 is very good oxidising agent and is (2) Nitrogen group
used in the estimation of carbon monoxide.
(3*) Halogens
Reactivity towards metals : (4) Alkaline earth metals
 Halogen form metal halides with metals. For e.g., Br2
Ans. (3)

7 C HEMISTRY
The p-Block Elements

Sol: Halogens have maximum electron affinity among with carbon

Ans. (1)
the elements of respective period, as they need Sol: F2 is best oxidising agent among the all halogens.
only one electron to form anion, thus they will
form anion easily Group 18 Elements :
Introduction:
 In this group He, Ne,Ar, Kr , Xe, Rn and oganesson(Og)
EXAMPLE-12 are present.All these elements are gases and chemically
The shape of inter halogen compounds XX’3 and unreactive.
XX’5 respectively are  They form very few compounds . Because of this they are
[IC071202] termed noble gases.
(1) Bent T-shaped and see-saw
Occurrence:
(2) Bent T-shaped and square pyramidal
 All the noble gases except radon occur in the
(3) Tetrahedral and see-saw
atmosphere.
(4) Trigonal planar and octahedral
 The main commercial source of helium is natural gas.
Ans. (2)
 Helium and sometimes neon are found in minerals of
Sol. The shape of inter halogen compounds XX’3 and XX’5
radioactive origin e.g., pitchblende, monazite, cleveite.
is Bent - T - shaped and square pyramidal respectively.
 Most abundant inert gas in air is Ar. Order of abundance
in the air is Ar > Ne > Kr > He > Xe.
 Xenon and radon are the rarest elements of the group.
EXAMPLE-13 Radon is obtained as a decay product of 226Ra.
Select the correct statement (s) from the following - 226
88 Ra  222
86 Rn + 42 He
(1) Fluorine displaces other halogens from the
corresponding halides
(2) Fluorine reacts slowly with halogens Table :Atomic and physical properties
(3) Fluorine does not decompose water
(4) Except fluorine, other halogens directly combine

Element He Ne Ar Kr Xe Rn
Atomic Number 2 10 18 36 54 86
–1 4 20.18 39.95 83.80 131.30 222.00
Atomic Mass/g mol
Electronic configuration 1s 2 [He] 2s 2 2p6 [Ne] 3s 2 3p6 [Ar] 3d104s 2 4p6 [Kr] 4d105s 2 5p6 [Xe]4f145d10 6s 26p6
Atomic Radius (pm) 120 160 190 200 220 –
Ionization enthalpy / (kJ mol –1 2372 2080 1520 1351 1170 1037
Density (at STP)/g cm –3 1.8 × 10–4 9.0 × 10–4 1.8 × 10–3 3.7 × 10–3 5.9 × 10–3 9.7 × 10–3
Melting point / K – 24.6 83.8 115.9 161.3 202
Boiling point / K 4.2 27.1 87.2 119.7 165.0 211

Atomic and physical properties:

Electronic Configuration:
 These elements have general electronic configuration ns2np6 except helium which has 1s2 . Many of the properties of noble
gases including their inactive nature are ascribed to their closed shell structures.

Ionisation Enthalpy
 Due to stable electronic configuration, these gases exhibit very high ionisation enthalpy. It decreases down the group
with increase in atomic size.
 I.E1: He > Ne > Ar >Kr > Xe

C HEMISTRY 8
 The p-Block Elements

 Xenon form few compounds mainly with most

Atomic Radii:
electronegative elements like fluorine and oxygen.
 Atomic radius decreases down the the group as number
of shells increases.
 The compounds of krypton are fewer. Only the
 He < Ne < Ar < Kr < Xe < Rn (atomic radius)
difluoride (KrF2) has been studied in detail.
Electron Gain Enthalpy  Compounds of radon have not been isolated but only
 They have no tendency to accept the electron and identified (e.g., RnF2) by radiotracer technique.
therefore, have larger positive values of electron gain  No true compounds of Ar, Ne or He are yet known .
enthalpy because of stable electronic configurations.
 E.A: He < Rn < Xe < Ar = Kr < Ne
EXAMPLE-16
Fluorine forms chemical compounds with
Physical properties
 They are mono-atomic gases. [IC070292]
 They are colourless, and tasteless.They are sparingly (1) He (2) Ne
soluble in water. (3)Ar (4) Xe
 They have very low melting and boiling points due to Ans. (4)
weak interatomic interaction in these elements. Sol: Xenon having large size and high reactivity among the
 Helium has the lowest boiling point (4.2K) of any known inert gases form compound with fluorine.
substance.
 He has unusual property of diffusing through most
commonly used laboratory materials such as rubber,
EXAMPLE-17
glass or plastics.
Which of the noble gases is most reactive :-
EXAMPLE-14 (1) He (2) Ne (3) Kr (4) Xe
The boiling point and melting point of inert gases are -
Ans. (4)
(1) Higher than halogens
(2) High Sol: Xenon is most reactive inert gas due to large size and low
(3) Very high ionisation energy among the inert gases.
(4) Very low
Ans. (4)
Sol: Very Weak Vander Waals forces leads to low boiling
and melting point of inert gases.

EXAMPLE-15
Noble gases are sparingly soluble in water, owing to
(1) Dipole-dipole interactions
(2) Dipole- induced dipole interactions
(3) Hydrogen bonding
(4) Induced dipole-instantaneous dipole interactions.
Sol. (2)
Water has permanent dipole and it induces a dipole in
the neighbouring atoms of noble gas. Because of this
weak interaction, the noble gases are sparingly soluble.

Chemical Properties :
 Completely filled valence shell, high ionisation energy
and more positive electron gain enthalpy is responsible
for their chemical inertness.
 In March 1962, Neil Bartlett, prepared a red compound
O2+ PtF6– and realised that the first ionisation enthalpy
of molecular oxygen (1175 kJ mol –1) was almost identical
with that xenon (1170 kJ mol –1). He made Xe+ PtF6 – by
mixing Pt F6 and Xenon.

9 C HEMISTRY
 NITROGEN FAMILY

Introduction Atomic properties: Physical Properties :

· Covalent radii : · N2 ® Gas with large bond
Pnictogens :
N < P < As < Sb < Bi enthalpy, rest elements are
N, P, As, Sb, Bi, Mc,
non-metal Metalloids metal
· Ionisation enthalpy : solid
General electronic N > P > As > Sb > Bi · B.pt ® Increases from top to
configuration : ns2np3. · Electronegativity : bottom
N > P > As > Sb = Bi · M.pt ® Increases upto
arsenic and then decreases
Occurrence upto bismuth.
Nitrogen : · Except nitrogen, all elements
· In Earth crust : Chile saltpeter (NaNO3) and Indian saltpeter show allotropy
(KNO3).
Phosphorus :
· Phosphorus is present in Minerals of apatite family
Ca9(PO4)6·CaX2 (X = F, Cl or OH)
e.g., Fluorapatite Ca9(PO4)6·CaF2.

Chemical Properties:
· Stability of +5 oxidation state decreases and stability of +3 oxidation state increases on moving down
the group due to inert pair effect.
· Common oxidation state : –3, +3 and +5
· All oxidation states +1 to +4 for nitrogen tend to disproportionate in acid solution
+3 +5 +2
3H N O 2 ® H N O3 + H2O + 2 N O
· Only BiF5 exist among Bi(V) halides.
· For phosphorus nearly all intermediate oxidation states disproportionate into +5 and –3 both in alkali
and acid solution.
· Maximum covalency of N and P are 4 and 6 respectively.
Hydrides:
MH3 type hydrides are formed by all the elements of this group.
(i) Melting point : NH3 > SbH3 > AsH3 > Ph3 (ii) Boiling point : BiH3 > SbH3 > NH3 > AsH3 > PH3
(iii) Bond dissociation enthalpy : NH3 > PH3 > AsH3 > SbH3
(iv) Basic nature : NH3 > PH3 > AsH3 > SbH3 > BiH3
Oxides:
Types of oxides : E2O3 and E2O5 N2O3, P2O3, As2O3, Sb2O3, Bi2O3
Acidic Amphoteric Basic
Halides:
Except nitrogen the rest of the elements form two type of halides : EX3 and EX5.
Among trihalides of nitrogen only NF3 is stable.
Anomalous Properties Of Nitrogen:
· Due to its small size, High electronegativity, High ionization enthalpy and Non-availability of d-orbitals
nitrogen shows anomalous properties.
th
· Only nitrogen form pp- pp multiple bonds in 15 group. P and As can form dp- dp bond.
· P-P single bond is stronger than N-N single bond.
 Occurence :
Introduction
Oxygen ® Most abundant
Chalcogens : element on earth.
O, S, Se, Te, Po, Lv, Group 16 Sulphur ® Gypsum
non-metal Metalloids metal Elements (CaSO4.2H2O), Epsom salt
(MgSO4.7H2O), Baryte (BaSO4).
General electronic configuration:
Galena (PbS), Zinc blende
ns2np4.
(ZnS), Copper pyrites (CuFeS2).

Atomic and Physical properties: Chemical properties:

· E.N. and I.E. decreases down the group The stability of +6 oxidation state decreases and
(E.A) S > Se > Te > Po > O stability of +4 oxidation state increases down the
· All elements show allotropy group due to inert pair effect.
· Maximum covalency of oxygen is 4 and · Melting point : H2O > H2Te > H2Se > H2S
general covalency is 2. · Boiling point : H2O > H2Te > H2Se > H2S
· M.Pt Te > Po > Se > S > O · Acidic nature : H2Te > H2Se > H2S > H2O
· B.Pt Te > Po > Se > S > O · S, Se, Te and Po form oxides of type EO2 and
· Oxygen (O2) is a gas whereas sulphur (S8) EO3, all are acidic in nature.
exist as solid. · These elements form halides of type EX6, EX4
and Ex2.
– – – –
· Stability order of halides : F > Cl > Br > I
· Among the hexahalides of sulphur only SF6 is
stable.
· All elements except oxygen form dichlorides
and dibromides
· Dimeric halides undergo disproportionation
2Se2Cl2 ® SeCl4 + 3Se
· SF4 is a gas, SeF4 a liquid and TeF4 a solid.

Anomalous behaviour of oxygen:

Due to small size, high electronegativity and
absence of d-orbitals oxygen shows anomalous
behaviour.
 HALOGEN
FAMILY
(GROUP 17)

Introduction : Occurrence :
Elements (F, Cl, Br, I, At) Fluorine : Fluorspar - CaF2, Cryolite - Na3AlF6,
General electronic Configuration: ns2np5 Fluoroapatite - 3Ca3(PO4)2·CaF2, Carnallite
(KCl·MgCl2·6H2O).

Chemical properties:
– –
· F2 + 2X ® 2F + X2 (X = Cl, Br or I)
– –
Atomic and physical properties: Cl2 + 2X ® 2Cl + X2 (X = Br or I)
– –
· Bond dissociation energy : Cl2 > Br2 > F2 > I2 Br2 + 2I ® 2Br + I2
· Electron affinity : Cl > F > Br > I · Oxidising power : F2 > Cl2 > Br2 > I2
· Electronegativity : F > Cl > Br > I · Reaction with H2O :
+ –
· Physical state : F2 , Cl2 , Br2, I2 2F2 (g) + 2H2O ® 4H (aq) + 4F (aq) + O2 (g)
(g) (g) (liq.) (solid) X2 (g) + H2O ® HX(aq) + HOX(aq)
· Colour : F2 , Cl2 , Br2 , I2 (where X = Cl or Br)
Yellow Greenish Re d Voilet 4I– (aq) + 4H+ (aq) + O2 (g) ® 2I2 (s) + 2H2O
yellow
· Acidic nature : HI > HBr > HCl > HF
· Br2 and I2 are soluble in organic solvent. · Boiling point : HF > HI > HBr > HCl
· Melting point : HI > HF > HBr > Hcl
· F form two oxides OF2 and O2F2. Compound
O2F2 oxidise Pu into PuF6.
· Stability order of oxides formed by halogen :
I > Cl > Br. The higher oxides of halogens are
more sable than the lower oxides.
· Oxides of halogen are good oxidising agent.
· I2O5 is used in the estimation of CO gas.

Anomalous behaviour of fluorine:

· Due to small size, highest electronegativity,
low F-F bond dissociation enthalpy and
absence of d-orbitals fluorine shows
anomalous behaviour.
 GROUP 18
ELEMENTS

Introduction Atomic and Physical properties:

· Noble gas : DHeg : Ne > Ar =Kr > Xe > Rn > He
He, Ne, Ar, Kr, Xe, Rn, Og · All are monoatomic, colourless,
· General electronic configuration : odourless and tasteless gases.
ns2np6 (except He). · Sparingly soluble in water.
· Very low melting and boiling points.
· Helium has the lowest boiling point
(4.2K) of any known substance.

Occurrence: Chemical Properties :

In the atmosphere all the noble · Their chemical inertness is caused
gases except radon occurs. Natural due to Completely filled valence shell,
gas is the main commercial source high ionisation energy and more
of helium. Xe and Rn are the rarest positive electron gain enthalpy.
elements of the group. Rn is obtained st
226 · 1 compound of noble gas element is
as a decay product of Ra.
formed by Neil Bartlett on the concept
Order of abundance in the air is
of similar I.E. of O2 and Xe
Ar > Ne > Kr > He > Xe.
Xe + PtF6 ® Xe+[PtF6]–
· Only the difluoride (KrF2) has been
studied in detail among the fewer
compounds of krypton.
· No true compounds of Ar, Ne or He
are yet known .