Tr ansition Element

The only app you need to prepare for

& Coor dination

JEE Main JEE Adv. BITSAT WBJEE MHT CET and more...

4.8 50,000+ 2,00,000+

Compound
Rating on Google Play Students using daily Questions available

With MARKS app you can do all these things for free

Solve Chapter-wise PYQ of JEE Main, JEE Advanced, NEET, BITSAT, WBJEE, MHT CET & more

Create Unlimited Custom Tests for any exam

Attempt Top Questions for JEE Main which can boost your rank

Track your exam preparation with Preparation Trackers

Complete daily goals, rank up on the leaderboard & compete with other aspirants

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available
 QUIZRR 3 4 QUIZRR
TRANSITION ELEMENTS & COORDINATION COMPO
POUUND These elements exhibit oxidation state of + 2 in their compounds. In + 2 oxidation state
d-orbitals are fully filled,
I nt r od uc t i on
Zn+2 ă 3d 10, Cd+2 ă 4d 10, Hg+2 ă 5d 10

De
Deffini
nittion and El
Eleect ron
oniic Conf
nfiigurat ion of At
Atom
om
omss Therefore, Zn, Cd and Hg do not exhibit general properties shown by transition elements
but form a group (12) by themselves with similar properties.
The elements lying between s and p-block elements of the periodic table are collectively known
(iv) Elements Sc, Y and La exhibit the common oxidation states + 3, in which (n ă 1)d orbitals
as tra nsitiona l elements (T.E.Ês) : These elements either in their atomic state or in any of their
are vacant (d0). Therefore, these elements also do not show general characteristic properties
common oxidation state have partly filled (n-1) orbitals of (n-1)th main shell. In these elements
of transition elements.
the differentiating electron enters (n-1)d orbitals of (n-1)th main shell and such these are called
d-block elements. (v) True transition elements, thus, are

The valence shell configurations of these elements can be represented by (n-1)d 1ă10
.ns 0, 1, 2
. The 3d (i) Ti V Cr Mn Fe Co Ni Cu
configurations clearly show that strictly, according to the definition of d-block elements, Cu, Ag 4d (ii) Zr Nb Mo Tc Ru Rh Pd Ag
and Au should be excluded from d-block elements, since these elements, both in their atomic state 5d (iii) Hf Ta W Re Os Ir Pt Au
[with configuration (n-1)d 10ns1] and in their + 1 oxidation state [with configuration (n-1)d 10], do
6d (iv) Rf Db Sg Bh Hs Mt
not have partly filled (n-1)d -orbitals. Similarly Zn, Cd and Hg which, both in their atomic state
It is because all the above elements have partially filled (n -1)d orbitals in their atoms or
[(n-1)d 10ns2] and in + 2 oxidation [(n-1)d10] do not contain partly filled (n-1)d orbitals, should
in one or more of the of the chemically important ions. Therefore, these are true transition
also be excluded from d-block elements. Similar is the case with Pd atom with configuration
elements in the strict sense.
4d 105s0. Yet, in order to maintain a rational classification of elements, these elements (viz Cu, Ag,
Zn, Cd, Hg and Pd) are also generally studied with d-block elements.
Ge ne
nerr al Pr ope rti es
All the d-block elements are classified into four series viz 3d, 4d, 5d and 6d series corresponding
to the filling of 3d, 4d, 5d and 6d orbitals of (n-1)th main shell. Each of 3d, 4d and 5d series (a) They all are metals.
has ten elements while 6d series has at present only one element viz AC89 whose valence shell (b) They are hard, strong, high melting, high boiling metals that conduct heat and electricity.
configuration is 6d1 7s2. (c) Many are electropositive to dissolve in mineral acids, a few are noble (Pt, Au etc.)
(d) They exhibit variable oxidation states.
Impo
porrtant P
Pooint
ntss T
Too b
bee rre
emembe red
(e) Form paramagnetic compounds.
(i) Electron configuration of Cr and Cu (f) Form variety of complex compounds.
Cr (24) [Ar] 183ds5s1 (g) Many of the compounds are coloured.
Cu (29) [Ar]183d 104s1 (h) Compounds undergo hydrolysis.
The 3d5s1 and 3d 104s1 configuration are preferred due to greater stability of half and fully (i) Many of the transition metals and their compounds act as catalyst.
filled orbitals (HUNDÊs Rule).
(j) Form very important alloys.
(ii) Electron configuration of second and third transition series elements is not similar to first
transition series. The full explanation is beyond the scope of IIT-JEE. It can only be said At
Atom
om
omiic an
andd Io
Ionnic radii
this point that small energy gap with increasing atomic number is one of the reasons.
The atomic and ionic radii decrease from Sc to Cu, but the variation is small. The outer most
(iii) Zinc, Cd and Hg have fully filled (n-1)d 10 orbitals in their configuration.
electron configuration is (n ă 1)dX ns2. The screening power of d-orbitals is small and electrons are
10 2
Zn 3d 4s being added in inner orbitals [(n ă 1)d orbitals. Therefore, change in radii, atomic and ionic both,
Cd 4d 105s 2 are small.
Hg 5d 106s 2

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 5 6 QUIZRR
Ionic radii Melting poi
oinnts of Tr ans
nsiit ion me
mettals

Ti2+ V+2 C+2 Mn +2 Fe2+ Co+2 Ni 2+ Cu+2 Zn +2 W

Ta Re
Nb
r (Å) 0.80 0.73 0.80 0.90 0.85 0.80 0.76 0.69 0.74 Os
Hf
Ru Ir
In a group, the atomic and the ionic radii increase with increase in atomic number (because Mo Te
Zr
new orbitals are added in the configuration). It is followed in the first and the second Rh Pt
V
transition series. But the radii of the third transition series elements are almost equal to the mp(Ĉ C)
second transition series elements. The reason for this equality, in radii is the lanthanide La Ti Fe Co Ni
Y Cr
contraction. Pd Au
Sc. Al Cu
Radii in Å Ag
Mn
Sc Ti V Cr Mn Fe Co Ni Cu Zn Zn
Cd
Hg
r (Å) 1.44 1.32 1.22 1.17 1.17 1.17 1.16 1.15 1.17 1.25
Transition metals
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
The above graph shows thată
r (Å) 1.62 1.45 1.34 1.29 ă 1.24 1.25 1.28 1.34 1.41
(i) 5d metals have highest mp.
La Hf Ta W Re Os Ir Pt Au Hg
(ii) mp increases with increase in the number of unpaired electron in d orbitals and then
r (Å) 1.69 1.44 1.34 1.30 1.28 1.26 1.26 1.29 1.34 1.44 decreases, when number of unpaired electrons in dăorbitals decreases.
(iii) Mn and Tc show anomalous values.
Bondi
dinng in Tr
Traansition me
mett als a
annd its ef
efffe ct on pr
proope
perrties (iv) W has highest mp.
All transition elements are metals. They are high melting, high boiling and have high heat of
I on
oniiza ti o n En
Enee rg y
atomization and high densities. All these properties show that the atoms in transition elements
are held together by strong metallic bonds. The strength of metallic bond very much depends In a period, the first ionization energy gradually increases from left to right. This is mainly due
upon number of valence electrons. Larger the number of valence electrons stronger the metallic to increase in nuclear charge. Generally, the ionization energies of transition elements are
intermediate between those of s and p-block elements. The first ionization potential of the 5d-
bond. In the transition elements a minimum of three electrons are present, (n ă 1)d1ns 2 . The
elements are higher than those of 3d and 4d-elements due to poor shielding of 4f-electrons.
presence of d-electrons contribute much towards metallic bonding (d ă d overlap) and the
From 3d  4d series, general trend is observed but not from 4d  5d series because of incorporation
strength increases with in the number of unpaired electrons in the orbitals. Also the difference
of the 14 lanthanides elements between La and Hf. Third period of transition elements have the
between the mp and the bp is large. This indicates that metallic bond is present in molten state
highest ionization energy. This reflects the fact that increase in radius due to addition of extra
also. shell is compensated by the decrease in radius due to lanthanide contraction.
Ti V Cr Mn Fe Co Ni Cu As the radius of 4d and 5d-elements more or less remains the same, due to which Zeff of elements
mp 1660 1710 1600 1260 1535 1490 1450 1083 of 5d series is higher, which results in high ionization energy of the 5d-elements of transition
series.
bp 3260 3450 2660 2150 3000 2900 2730 2600
Ox ida
datt ion stat es

All transition metals exhibit variable oxidation states. It arises due to removal of electrons from
inner d -orbital.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 7 8 QUIZRR
6 2
Fe(26) [Ar] 183d 4s Element and Electron Arrangement of Unpaired
Fe2+ [Ar] 183d 6 oxidation states configuration outermost electrons electrons
Fe3+ [Ar] 183d 5
Fe(26) [Ar] 183d6 4s2 4
Element and Electron Arrangement of Unpaired
oxidation states configuration outermost electrons electrons Fe2+ [Ar]183d 6 4

3d 4s
Ti(22) [Ar]183d2 4s2 2 Fe3+ [Ar]183d 5 5

3d Co(27) [Ar]183d7 4s2 3

Ti2+ [Ar]183d 2 2
Co +2 [Ar]183d 7 3
3d
Ti+3 [Ar]183d 1 1
Co +3 [Ar]183d 6 4

V(23) [Ar] 183d3 4s2 3 Ni(28) [Ar] 183d8 4s2 2

V +2 [Ar]183d 3 3 Ni2+ [Ar]183d 8 2

V +3 [Ar]183d 2 2
Ni+4 [Ar]183d 6 4
+5
V [Ar]18 _________ 0
Cu(29) [Ar]183d 10 4s1 1
Cr(24) [Ar] 183d5 4s1 6

Cu + [Ar] 183d 10 0
Cr+2 [Ar]183d 4 4

Cr+3 [Ar]183d 3 3 Cu+2 [Ar]183d 9 1

Cr+6 [Ar]18 _________ 0 Besides, the above given oxidation states, lower oxidation state (0 or + 1) are also exhibited by
5 2 transition metals. But these are stable only in complexes especially with ăacid ligands. Compounds
Mn(25) [Ar] 183d 4s 5
in different oxidation states differ in properties. Common observations are :

Mn +2 [Ar]183d 5 5 (i) Most common oxidation state is + 2 for first series. (It shows greater stability of 3d orbitals
over 4s)

Mn +4 [Ar]183d 3 1 (ii) The + 1 state is stable (dry state) only for Cu in simple compounds.
(iii) Bonds in + 2 or + 3 states are mostly ionic.
Mn +6 [Ar]183d 1 3 (iv) + 2 state forms basic oxide and hydroxides.
+7 (v) Higher oxidation states + 4, + 5, + 6, + 7 etc. form covalent compounds ( MnO4 has covalent
Mn [Ar]18 _________ 0
Mn ă O bond).

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 9 10 QUIZRR
(vi) Oxides (or hydroxides) in higher oxidation states are acidic Exa mpl
plee 1

VO Basic Compare the magnetic moments of Fe2+ and Fe3+.

V2O5 Acidic Solution :
CrO Basic Following the same procedure as above try to calculate the magnetic moments of the two given
CrO3 Acidic species

(vii) Higher oxidation state is more stable down a group n for Fe2+ = 4ø = n(n  2) B.M. = 4 6 = 24 B.M.

Fe + 2, + 3 Mn + 7, MnO4 S O agent
n for Fe3+= 5ø = n(n  2) B.M. = 5 7 = 35 B.M.
Ru + 4, + 6 Te
Fe 2+ 24
Os + 8 (OsO4) Re + 7, ReO 4 not an O agent 
Fe 3+ 35
(viii) Higher oxidation states are found in oxygen and fluorine compounds only
Ex
Exaa mpl
plee 2
Mn 2O7 , MnF7, CrO4 , MnO4 etc.
Find the oxidation state of Cr in the given complex K 2[Cr(NO)(NH 3)(CN)4], ø = 1.73 BM.
(ix) Oxides in intermediate oxidation states are amphoteric.
Solution :

TiO 2  ø = 1.73

VO2  Amphoteric
ø= n( n  2)  1.73
Mn 2O 3
n (n + 2) = 3
 n = 1
Magne tic pr
prop
op
opee rties
 Number of unpaired electron = 1
The substances can be either paramagnetic or diamagnetic. A paramagnetic substance is one  Cr is in + 1 oxidation state.
which is weakly attracted into a magnetic field and a diagmagnetic substance is one which is
repelled by a magnetic field. The paramagnetic behaviour arises due to the presence of one or Col ou
ourr of C om
ompple x Co
Commpounds
more singly occupied atomic orbitals, while diamagnetic behaviour is due to presence of unpaired
electrons in the atomic orbitals. Many ionic and covalent compounds of transition elements are coloured. In contrast compounds
of the să and păblock elements are almost always white. When light passes through a material,
It is represent as ø in Bohr magnetons, it is deprived of those wavelengths that are absorbed. If wavelength of the absorption occurs in
the visible region of the spectrum, the transmitted light is coloured with the complementary colour
  n n  2 BM, to the colour of the light absorbed. Absorption in the visible and UV regions of the spectrum is
caused by changes in electronic energy. Thus, the spectra are sometimes called electronic spectra.
where n = number of unpaired electrons.
Colour may arise from an entirely different cause in ions with incomplete d or f-subshells. This
Transition metals and most of their compounds contain unpaired electrons in their different source of colour is very important in most of the transition metal ions.
oxidation states. Therefore, they are paramagnetic.
In a free isolated gaseous ion, the five dăorbitals are degenerate that is they are identical in
energy. In actual practice, the ion will be surrounded by solvent molecules if it is in solution, by
other ligands if it is in a complex, or by other ions if it is in a crystal lattice. The surrounding

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 11 12 QUIZRR
groups affect the energy of some dăorbitals more than others. Thus, the dăorbitals are no longer Co3+ + 6NH 3  [Co(NH3) 6 ]3+
degenerate and at their simplest they form two groups of orbitals of different energy. Thus, in
Fe 2+ + 6CN ă  [Fe(CN)6]4ă
transition element ions with a partly filled dăsubshell it is possible to promote electrons from one
dălevel to another dălevel of higher energy. This corresponds to a fairly small energy difference The reason for transition elements are good in forming complexes are :
and so light it absorbed in the visible region. The colour of a transition metal complex is dependent (i) Small size and high effective nuclear charge
on how big the energy difference is between the two dălevels. This in turn depends on the nature (ii) Availability of low lying vacant dăorbitals which can accept lone pair of electrons donated
of the ligand and on the type of complex formed. Thus, the octahedral complex [Ni(NH3)6 ] 2+ is by a ligand.
blue, [Ni(H 2O) 6] 2+ is green and [Ni(NO 2)6] 4ă is brown-red. The colour changes with the ligand
used. The colour also depends on the number of ligands and the shape of the complex formed. Cat alytic Pr opert ies
The source of colour in the lanthanides and the actinides is very similar, arising from f  f Transition metals and their compounds are known to act as good catalyst due to the following
transitions. With the lanthanides, the 4făorbitals are deeply embedded inside the atom and are reasons :
well-shielded by the 5s and 5p-electrons. The făelectrons are practically unaffected by complex (i) Due to the variable oxidation states, they form unstable intermediate compounds and provide
formation. Hence, the colour remains almost constant for the particular ion regardless of the a new path with lower activation energy for the reaction (Intermediate compound formation
ligand. theory)
Some compounds of the transition metal are white, for example Cu2Cl2, ZnSO4 and TiO2. In this (ii) In some cases the finely divided metals or their compounds provide a large surface area for
compounds, it is not possible to promote electrons within the dălevel. Cu+ and Zn2+ has a d 10 adsorption and the adsorbed reactants react faster due to the closer contact (Adsorption
configuration and the dălevel is completely filled. Ti4+ has a d 0 configuration and dălevel is theory)
empty. In the series Sc(III), Ti(IV), V(V), Cr(VI) and Mn(VII), these ions may all be considered 1. TiCl 3 Used as Natta catalyst for coordination polymerization of ethene to polyethene
to have an empty dăsubshell; hence dăd spectra are impossible and they should be colourless. 2. V2 O 5 Converts SO 2 to SO 3 in the contact process for making H2SO 4
However, as the oxidation state increases, these states become increasingly covalent. Rather than
3. MnO2 Used as a catalyst to decompose KClO 3 to give O2
forming highly charged simple ions, they form oxoions like TiO2+, VO 2+, VO 43, CrO 42 and MnO4 . 4. Fe Used in HaberăBosch process for making NH3 (as promoter)
VO+2 is pale yellow, but CrO 24 is strongly yellow coloured and MnO4 has an intense purple 5. Pd Catalyst for hydrogenation
colour in solution, though the solid is almost black. The colour arises by charge transfer mechanism. 6. Pt/PtO Adam catalyst used for reduction of triple bond to double bond
In MnO4 , an electron is momentarily transferred from O to the metal, thus momentarily changing 7. CuCl2 Deacon process or making Cl 2 from HCl
O2ă to O ă and reducing the oxidation state of the metal from Mn(VII) to Mn(VI). Charge transfer 8. Ni As Raney nickel for hydrogenation reaction
requires the energy levels on the two different atoms to be fairly close. Charge transfer always
produces more intense colours than the colours generated due to dăd transitions. Charge transfer For
ormmation of Al
Alll oys
is also possible between metalăion and metalăion as seen in prussian blue, Fe4[Fe(CN 6)]3 .
As the transition elements have similar atomic sizes hence in the crystal lattice, one metal can be
The s and păblock elements do not have a partially filled dăsubshell, so there cannot be any dă
readily replaced by another metal giving solid solution and smooth alloys. The alloys so formed
d transitions. The energy required to promote an s or păelectron to a higher energy level is much
are hard and often have high melting point.
greater and corresponds to ultraviolet light being absorbed. Thus, compounds of s and păblock
elements are typically not coloured. I nt
nteer sti ti al Com po
poun
un
undd

Compl e x For mat io n Transition metals form a number of interstitial compounds. In which they take up atoms of small
size e.g. H, C, B and N in the vacant spaces in their lattices. The presence of these atoms results
The transition elements have a huge tendency to form coordination compounds with Lewis Base,
in decrease in malleability and ductility of the metals but increases their tensile strength.
i.e., with groups which are able to donate an electron pair. These groups are called ligands. A
ligand may be a neutral molecule such as NH3 or ion such as Clă or CN ă etc.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 13 14 QUIZRR
Zinc, Cadm
dmiium and Mercury Ferric Oxide ă Fe2 O3 (Reddish Brown)

(a) These are the elements of group 12 having electronic configuration (n ă 1) d10 ns2 and + Preparation :
2 oxidation state. In these elements the d-subshell is full, hence these are regarded as non- (i) In lab, it can be prepared by heating ferrous sulphate or ferric hydroxide.
transition elements which is evident from the following characteristics. 2FeSO4  Fe2O3 + SO2  + SO3 
(i) They do not show variable valency except mercury. 2Fe(OH)3  Fe2O 3 + 3H 2O
(ii) Many of their compounds are white (ii) It is also obtained as a by product in the manufacture of sulphuric acid from iron pyrites.
(iii) Their melting and boiling points are very low. 4FeS2 + 11O2  2Fe2 O3 + 8SO 2
(b) Unique structure of mercurous ion ă Unlike Zn and Cd, Hg exhibits + 1 well as + 2 oxidation Properties :
state. Thus mercurous ion exists are Hg 22+ and not as Hg +.
It is a reddish brown powder, insoluble in water but soluble in acid. Amphoteric in nature and
(c) Structure of mercurous ion ă It consists of two atoms linked by a covalent and (ă Hg ă reacts with acids and alkalies.
Hg ă)2+ and explains the diamagnetic character of mercurous ions if it was Hg + (presence
NaFeO2 + H 2O  Fe 2O3 + NaOH
of an unpaired electron in 6s orbital), mercurous salt should have been paramagnetic.
(d) Anomalous behaviour of mercury, Fe2 O3 + 6HCl  2FeCl3 + 3H 2O

(i) It is liquid at ordinary temperature while Zn and Cd are solids. Fe2 O3 + Na 2CO 3  2NaFeO2 + CO 2
(ii) It is less electropositive than hydrogen and therefore does not displace hydrogen from Sodium ferrate

acids while Zn and Cd does.

(iii) It does not form hydroxide or peroxide, while Zn and Cd do so Ferr ic C
Chhloride (R
(Ree d Bl
Blaack)

(iv) Mercuric oxide, on heating, gives metallic mercury and oxygen while oxides of Zn and Anhydrous ferric chloride, Fe 2Cl6 is obtained by heating iron filing in a stream of dry chlorine.
Cd are stable towards heat. The compound sublimes and collects in the form of deep red-black flaky crystals.
(v) HgCl2 is covalent while zinc and Cd chlorides are ionic. With NH 3, HgCl2 gives a white 2Fe + 3Cl2  Fe 2Cl6
ppt. of Hg(NH 2)Cl, while Zn and Cd salts from complex ions, [M(NH 3)4]2+. It dissociates on heating above 973 K first into FeCl3 and then into FeCl2 and Cl 2.

973K 
COMPOUNDS O
OFF IRON Fe2 Cl6  2FeCl3  2FeCl2  Cl 2 

Ferrous Sulphate or Green vitriol (FeSO 4.7H2 O) Its aq. solution is acidic in nature due to hydrolysis.
The name green vitriol is given because of its green colour.
FeCl3 + 3H2O  Fe(OH)3 + HCl
(i) On heating, green FeSO4.7H2 O gives a white anhydrous salt. On strong heating it forms
Fe2 O3, SO 2 and SO 3. It is soluble in water, alcohol and ether and forms hydrates. The most common hydrate of iron
FeCl3.6H2O is yellow in colour.
heating
FeSO4 .7H2 O  FeSO4  7H2 O
White Ferrous Ammonium Sulphate (MohrÊs Salt), FeSO4.(NH4) 2SO 4.6H2O
It is prepared by crystallising a solution containing equivalent amounts of iron (II) sulphate and
heating ammonium sulphate. It is a pale green crystaline compound which does not effloresce like ferrous
2FeSO4  Fe2 O3  SO2   SO3 
sulphate.
Brown

(ii) With nitric oxide, ferrous sulphate turns brown due to the formation of nitroso ferrous COMPOUNDS OF COPPER
sulphate FeSO4.NO.
Cupric chloride, CuCl2 .2H2 O (Green Crystal)

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 15 16 QUIZRR
Preparation : Cup
uprric O
Oxxide, CuO ((B
Black )
2Cu + 4HCl + O2  2 CuCl2 + 2H 2O It is called black oxide of copper.
Preparation :
CuO + 2HCl  CuCl 2 + H2O
(i) It is prepared by heating following copper compounds :
Properties : 1
Cu 2O + O  2CuO
(i) It is deliquescent compound and is readily soluble in water. The dilute solution is blue but 2 2
concentrated solution is, however, green. The blue colour is due to complex cation
2Cu + O2  2CuO
[Cu(H2O) 4] 2+
Cu(OH) 2  CuO + H2O
(ii) On heating forms Cu2 Cl2
2Cu(NO3) 2  2CuO + 4NO 2 + O2
2CuCl2  Cu2Cl 2 + Cl 2
(ii) On commercial scale, it is obtained by heating malachite, which is found in nature.
(iii) CuCl2 + Cu  Cu2 Cl2
CuCO 3.Cu(OH) 2  2CuO + CO2 + H 2O
2CuCl2 + 2H  Cu 2Cl2 + 2HCl
Properties :
2CuCl2 + SnCl 2  Cu2 Cl2 + SnCl4
It is black powder, insoluble in water but dissolves in acids. It is reduced to metallic copper by
Cop
oppe
pe
perr Su
Sullpha
hatte (Blue Vi
Vittriol), CuS
uSOO 4.5H 2O reducing agents like H, C and Co.
CuO + H2  Cu + H2 O
Preparation :
(i) It is prepared by dissolving copper (II) oxide or copper (II) carbonate in dil. sulphuric acid. Compoun
unds
ds of Silv e r
CuO + H 2SO 4  CuSO 4 + H2O
Silver Nitrate, AgNO 3 (Lunar Caustic)
CuCO3 + H 2SO4  CuSO4 + CO2 + H2O
Preparation :
On evaporation, solution is concentrated, blue crystals of CuSO 4.5H2O separate out on
cooling. Heat
3Ag + 4HNO3   3AgNO3  2H2 O + NO 
(ii) On a large scale, copper (II) sulphate is obtained by passing air through a hot mixture of (Dilute)

copper and dil. H2SO4 .

Properties :
2Cu + 4H+ + O2  2Cu 2+ + 2H2 O
(i) Heat
2AgNO3   2AgNO2 + O2

Properties :
red Heat
2AgNO3 +   2Ag + 2NO2 + O2
(i) On heating CuSO4.5H 2O loses water molecules as follows.
(ii) It reacts with iodine in two ways.
373 K 423 K
CuSO4 .5H2 O   CuSO4 .H2 O  CuSO4  CuO  SO3
Strong 100 C 150 C (a) When iodine is in excess
5AgNO 3 + 3I 2 + 3H2O  HIO 3 + 5AgI + 5HNO3
(ii) CuSO4 + 6NH4OH  [Cu(NH 3)4 ] (OH)2 + (NH4) 2SO4 + 4H 2O
(b) When AgNO3 is in excess
SchweitzerÊs reagent
6AgNO 3 + 3I 2 + 3H2O  AgIO 3 + 5AgI + 6HNO3
(iii) 2CuSO4 + 4KI  Cu2 I2  + I2  + 2K 2SO 4.
(iii) When treated with alkali, it gives precipitate of silver oxide, which dissolves in excess of
A mixture of copper sulphate and lime, under the name of Bordeaux mixture is used as a
NH4OH
fungicide in agriculture.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 17 18 QUIZRR
2AgNO3 + 2NaOH  Ag 2O  + 2NaNO 3 + H 2O Chl
hlooride s o f L e ad
brown ppt
Lead chloride, PbCl2
2AgNO3 + 2NH 4OH  Ag2 O  + 2NH4 NO3 + H2O
Preparation :
Ag2O + 4NH4OH  2[Ag(NH 3)2 ]OH + 3H 2 O
Prepared by slow direct combination or by the action of boiling concentrated HCl on lead (its oxide
(iv) 2AgNO3 + Na2 S2O3  Ag2S2 O3 + 2NaNO 3 or carbonate).

Ag2S 2O3 + 3Na2S2O3  2Na3[Ag(S2O3 )2 

Pb + Cl 2  PbCl2

Silve r B
Brromi
midde, Ag
AgBBr Pb + 2HCl  PbCl2 + H 2 
PbO + 2HCl  PbCl 2 + H2O
Preparation :
The usual method of preparation is to precipitate PbCl2 as a white crystalline precipitate by
By adding AgNO3 solution to soluble bromide solution.
adding a soluble chloride to a lead salt solution.
Properties :
Pb (NO3 )2 + 2NaCl  PbCl2 + 2NaNO 3
(i) It is insoluble in water and conc. acid but soluble in excess of strong solution of ammonia
Properties :
(e.g. AgCl is soluble in dilute solution of NH4 OH, AgI is insoluble in NH 4OH solution.
It is sparingly in cold water but more soluble in hot water. In concentrated solutions of Cl ă ions,
(ii) Silver halides, are also soluble in KCN and hypo solutions
it dissolves forming complex ions, [PbCl3 ]ă and [PbCl4] 2ă.
(iii) On heating, it melts to red liquid.
(iv) It is used as the light sensitive material in photographic films. It is the most sensitive silver Lead te trachl or
oriide
de,, Pb Cl 4
halide to photo-reduction.
Properties :

COMPOUNDS OF Z INC PbCl4 is a yellow only liquid. it is heavy and dissolves in organic solvents. It is a covalent and
unstable compound, readily decomposes on heating.
Zinc Oxide ă ZnO

Preparation : PbCl4  PbCl2 + Cl2 
It is prepared by burning zinc metal in air or by heating the zinc carbonate or zinc nitrate. It is easily hydrolysed by water and forms a double salt with NH 4Cl.
2Zn + O2  2ZnO PbCl4 + 2H2O  PbO2 + 4HCl
ZnCO3  ZnO + CO 2 Lead tetrabromide and tetraiodide are unknown, so the dihalides dominate the halogen chemistry
2Zn(NO3 )2  2ZnO + 4NO2 + O2 of lead.

Properties : OXI
XIDDES OF LEAD
Zinc oxide is a white power and becomes yellow on heating and the colour disappears on colling.
Lead monoxide, PbO
(i) It dissolves readily in mineral acids and forms the corresponding salts with alkalies, it forms
Preparation :
zincates [Zn(OH)4] 2ă

ZnO + 2HCl  ZnCl 2 + H 2O 2Pb(NO3 )2  2PbO + 4NO 2  + O2 
ZnO + 2NaOH + H 2O  Na 2[Zn(OH) 4]

PbCO3  PbO + CO2 
(ii) It reduced to metallic zinc when heated with carbon or hydrogen
ZnO + C  Zn + CO Dry air has no action on lead, but in moist air it tarnishes, forming a film of oxide first and finally
basic carbonate, which protects it from further action. On heating in air or oxygen, it forms
ZnO + H 2  Zn + H 2O
litharge, PbO. But prolonged heating gives red lead, Pb3O4 .

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 19 20 QUIZRR
2Pb + O2  2PbO Red le
leaad, Pb3 O4
6PbO + O 2  2Pb 3O4 Preparation :
Properties : Roasting of litharge in air at 450ĈC gives a bright red powder.
(i) At room temperature, it is a yellow amorphous powder that is insoluble in water but dissolves 6PbO + O2  2Pb3O4
in acids as well as alkalies.
It is also known as sindur.
PbO + 2HCl  PbCl 2 + H2O
Properties :
PbO + 2NaOH  Na2PbO 2 + H 2O
Thus, it behaves as an amphoteric oxide. The acetic properties being rather feeble. Sparingly soluble in water but dissolves in dilute nitric acid.

(ii) It is easily reduced to the metallic state by hydrogen, carbon or carbon monoxide. Pb3 O4 + 4HNO3  2Pb(NO3 )2 + PbO2  + 2H2O

(iii) In the red form of PbO, the Pb(II) ions are four co-ordinate but the O 2ă
ions around the The above reaction indicates that red lead may be considered as plumbous ortho plumbate,
Pb(II) lie in a square. 2PbO.PbO 2.

POTASSI
SSI UM DICHROM AT
ATEE (K2 Cr2 O 7 )
L e a d d i o x i d e , P b O2
When chromite [Fe(CrO2) 2] is fused with Na2CO 3 in air (or NaNO3) sodium chromate Na2 CrO 4
Preparation :
is formed.
Action of cold concentrated nitric acid on red lead gives lead nitrate in solution while lead dioxide
is thrown as a chocolate powder. 
2 Fe (CrO 2)2 + 4 Na2CO 3 + O2  4Na 2CrO4 + 4CO2 + Fe2O3
Pb3 O4 + 4HNO3  PbO2  + 2Pb(NO3 )2 + 2H2O
The fused mass is extracted with water and filtered. The filterate is concentrated and acidified
Properties :
with H2SO 4. It produces Na2Cr2O7.
(i) It is a chocolate coloured powder insoluble in water and dilute acids.
2Na2 CrO4 + H 2SO 4  Na 2Cr 2O7 + Na2 SO4 + H 2O
(ii) It liberates oxygen on gentle heating.
The sodium is concentrated and then saturated with KCl orange crystal of K2Cr 2O 7 separates out.
2PbO 2  2PbO + O2 
Na2 Cr2O 7 + 2 KCl  K 2Cr2 O7 + 2NaCl
(iii) At 440ĈC, it is converted into red lead, Pb3 O4.
Sodium dichromate is hygroscopic but not the K2Cr 2O7. Therefore, K 2Cr2O 7 is preferred over
440C Na 2Cr 2O 7.
3PbO2   Pb 3O 4  O 2 

(iv) PbO2 is an amphoteric oxide. Properties :

PbO 2 + 4HCl  PbCl 2  + Cl 2  + 2H2 O (i) It is orange crystalline solid. Soluble in water, colour is due to charge transfer.

2PbO 2 + 2H2SO4  2PbSO4  + 2H2 O + O2 

(v) It is a good oxidizing agent. It oxidizes manganous salts to pink permanganic acid when
boiled in nitric acid solution.
2MnSO4 + 5PbO 2 + 6HNO 3  2HMnO4 + 2PbSO4 + 3Pb(NO 3)2 + 2H2O
(ii) With alkali (i.e. pH > 7) it turns yellow due to the formation of chromate.
(vi) In alkaline medium, chromium hydroxide is oxdized to yellow chromate by PbO2.
K2Cr 2 O7 + 2KOH  2K2CrO 4 + H2O
2Cr(OH) 3 + 10KOH + 3PbO2  2K2CrO 4 + 3K 2PbO2 + 8H2 O
(iii) When K2 Cr2O 7 is heated it gives O2
The maroon form of lead(IV) oxide, PbO2, crystallizes in the rutile structure. This oxide is
a component of the cathode of a lead-acid battery.  4K CrO + 2Cr O + 3O
4K2Cr 2O 7  2 4 2 3 2

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 21 22 QUIZRR
But (NH4) 2Cr2O 7 on heating gives N2
CrO5 + amyl alcohol  deep blue
 CrO5 is not stable in aq. medium and decomposes to Cr+3 and O 2.
(NH 4 )2 CrO 7  Cr2O3  4H2O + N 2
(Orange) (Green) 4CrO5 + 12H+  4Cr +3 + 7O 2 + 6H2 O
(iv) Solid K2Cr 2O 7 with conc. H 2SO4 forms a red solution. The red is dichromic acid. (vii) K2Cr 2 O7 as quantitative reagent
K2Cr 2O7 + H2 SO4  H2 Cr2 O7 + K 2SO4 The acidic solution of K 2Cr2 O is an oxidizing agent. The solution is a primary standard as :
When the solution is concentrated bright orange (or red) crystals of CrO 3 are formed. (a) K2Cr 2O7 prepared very pure

Crytallisation (b) Solution of K2Cr 2O stable

Red solution 
 CrO3
(c) The solution is much less readily reduced by organic substances
That is K2Cr2O7 is dehydrated by conc. H2 SO4 to bright orange solid CrO3. The (K2Cr 2O 7
(d) Not affected by light.
+ conc. H2SO4 ) mixture is used for cleaning glassware as it is highly oxidizing.
(v) K2Cr 2 O7 as oxidizing agent
Str uc
uctt ur
uree of Cr2 O72
K2Cr 2 O7 is a good oxidizing agent in acid medium and reacts as
The structure involves two tetrahedra joined through Oăatom. Cr is sp3 in Cr2O72 . The structure
Cr2 O72 +
 6e  14H  3+
2Cr(aq)  7H2 O EĈ = 1.36 V
is
(green)
Cr ă O (bridging) = 1.78 Å
It oxidizes :
Cr Cr Cr ă O (terminal) = 1.61 Å
Fe2+  Fe 3+ O
(H2 S) Să2  S Cr Cr = 131Ĉ
(bridging)
Iă  I2
The Cr ă O bonds have multiple bond nature due to (d ă p) interaction.
SO2  SO 42

Reactions : POTASS
SSIIUM PER
ERMMANGNA
NATTE (KMnO 4)

2 + 3+ When MnO2 (Pyrolusite) is fused with KOH and KNO3 (O.A.) K2MnO4 (green) is formed. It
Cr2 O7  6 e  14H  2Cr  7H2 O
(K 2MnO 4) is oxidized by Cl 2 to KMnO 4.
Fe2+  Fe3+  e]  6
(i) fuse
MnO2 + 2KOH + KNO 3 
(ii) water
 K MnO + KNO + H O
Cr2 O72  6Fe2+  14H+  2Cr+3  6Fe2+  7H2 O 2 4 2 2

Thus SO2 and H 2S turn orange solution of K 2Cr2 O7 (acidic) to green due to the reduction 2K2MnO4 + Cl 2  2KMnO4 + 2KCl
Oxidation of K2MnO 4 may be caused electrolytically (better).
+3
of Cr2O7 2 ion to Cr(aq) .
Anode reaction 2MnO 42  2MnO4  2e
ă
(vi) K2Cr 2 O7 as qualitative reagent
To test H 2O2 : K 2Cr2 O7 (or K 2CrO4 ) in acid solution + amyl alcohol, when treated with H2O 2, Cathode reaction 2H 2O + 2eă  2HO ă + H2
CrO5 is formed. It dissolves in amyl alcohol making deep blue solution.
Oxidized solution on concentration gives violet (deep purple) crystals of KMnO4 (The crystals
CrO42  2H+  2H2 O2  CrO5  3H2 O however, appear almost black).

CrO72  2H+  4H2 O2  2CrO5  5H2 O

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 23 24 QUIZRR
Properties : and itself is reduced to Mn+2 . Therefore, pink solution of KMnO4 is decolourised in all of the
(i) Violet solid colour is due to charge transfer. above reactions. In the case of Să2, white S precipitates.

MnO 4 + 5e + 8H +  Mn+2 + 4H2O] ï 2

O
C 2O 42  2CO 2  2e ] ï 5
O · Mn · O
2 MnO4  16H +  2C2 O42  2Mn +2  10CO2  8H2 O
O
Other reactions can be written in the same way.
(ii) KMnO4 is soluble in water and the solution is red violet.
FeSO 4 solution (light green) decolourises MnO4 solution in acid medium. But if excess
(iii) KMnO4 is widely used as a laboratory oxidizing agent. It is oxidant in neutral, acid and
basic solutions. The reaction are : MnO4 is added a black ppt. is formed. It is due to oxidation of Mn+2 to MnO2 .
(a) In acid medium :
acid
MnO 4  5Fe2+ + 8H+  Mn+2  5Fe3+ + 4H 2O
MnO4  5e + 8H +  Mn +2  4H2 O, EĈ = 1.54 V (pink) (colourless)
(pink) (colourless)
Mn +2 + 2H2 O  MnO 2 + 2e + 4H+ ] ï 3
(b) Neutral or dil. alkali :
MnO 4  3e + 4H +  MnO 2  2H 2O ] ï 2
MnO4  3e + 2H2 O  MnO2  4HO 
(black solid) 3 Mn +2  2 MnO 4  2H 2O  5MnO 2  4H+

(c) conc. alkali : In alkaline solution (Iă) is oxidized by MnO4 to iodate (IO 3 )

MnO4  e  MnO42

Iă + 6HO ă  IO 3 + 6e + 3H2O

Hydrochloric acid (HCl) is not used to create acid medium as MnO4 oxidizes Clă to Cl 2
MnO 4  3e + 2H 2O  MnO 2  4HO  ] ï 2
(Clă ă Cl 2, EĈ = 1.34 V).
I   2 MnO4  H2 O  IO3  2MnO2  2OH 
+ +2 5
MnO 4 + 5Cl + 8H  Mn + / 2Cl 2
ă

(iv) KMnO4 as volumetric reagent

In acid medium MnO4 oxidizes, Standard acidic solution of KMnO 4 is oxidizing agent and is used as a volumetric reagent.
S ă2  S But it is a secondary standard (not a primary standard like K2Cr2O 7), because KMnO 4
converts to MnO2 in water and oxidizes H2 O to O2 . The reaction is, however, very slow.
Fe 2+  Fe3+
Iă  I 2 MnO 4 + 3e + 4H +  MnO2 + 2H2O] ï 2

NO 2  NO 3 H 2 O  2H+  2e + 1 / 2 O2 ]  3

SO 2  SO 42
2 MnO4  2H +  2MnO2  H2 O + 3
/2 O2
H 2O2  O2
It is for the above reason; KMnO 4 solution in volumetric analysis is standardized before
C2O4 2  CO 2 every use.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 25 26 QUIZRR
Titration with KMnO4 solution does not require indicator. It acts as a self-indicator because (ii) Actinides
even a drop of dil. KMnO4 imparts pale pink colour to the solution. Th (Z = 90) to Lr (Z = 103) ă (7th period)

It is used for the estimation of iron, H2O 2, NO2 , MnO2 (in pyrolusite) etc. General configuration [Rn] 5f1ă14 6d 0ă1 7s 2

Ge ne
nerra l Ch ara cter ist ics
Exa mpl
plee 3
Lanthanides exhibits (III) oxidation state (some elements show (II) and (IV) also).
50 mL aqueous solution of FeSO4 required 12 mL of 0.02 M KMnO4 in acid medium for
complete oxidation. Calculate the molarity of ferrous sulphate solution. Many of the compounds are coloured. In the Lanthanide elements, there is a regular decrease in
the radius as the period is traversed. This is known as „Lanthanide contraction‰.
Solution :
The reason for this contraction is that as we proceed from one element to the next element in the
Balanced redox reaction for oxidation of ferrous ion to ferric ion is
Lanthanide series, the nuclear charge, i.e., atomic number increases by one unit and one electron
2+ + 2+ 3+ is added to the 4f- energy shell. On account of the very diffused shapes of f-orbitals, the 4f
MnO4 + 5Fe + 8H  Mn + 5Fe + 4H2O
electrons shield each other quite poorly from the nuclear charge. Thus, the effect of nuclear
1 mole of KMnO4 = 5 mole of FeSO 4
charge increase is more than the changed shielding effect. This brings valence shell nearer to the
MV nucleus and hence the size of atom or ions goes on decreasing as we move in the series.
Number of moles of KMnO4 used =
1000
CO-ORD
RDIINATION C
COOMPOUND
0.02 ï 12
=  2.4  10 4 Some Basic terms
1000
To be read from NCERT book
 Number of moles of FeSO4 in 50 mL solution = 5 ï 2.4 ï 10 ă4
= 12.0 ï 10ă4 Class ifi cat ion of Li gan ds

There are two ways ligands can be classified :

n
Thus, molarity of FeSO4 =  1000
V (I) Classification based on donor and acceptor properties of the ligands.
(i) Ligands having one or more lone pair(s) of electrons are further classified as
12  104 (a) Ligands containing vacant -type orbitals can receive back donated -electrons
=  1000  0.024
50 from the metal ion in low oxidation state. Such ligands have filled donor orbitals
in addition to unsaturated organic molecules. Such ligands have filled donor orbitals
f-Bl
Bloock Elements in addition to vacant -acceptor orbitals. Thus, in the complexes formed by such
  
These are also referred as Âinner transition elementsÊ. These are two series of elements, formed by ligands, both metal and the ligand act as donor and acceptors  M   L .
  
filling of 4f and 5f-subshells. The elements in which 4f-subshell is filled are called lanthanides
(b) Ligands, which have no vacant orbitals to get back donated electrons from the
and the elements in which 5f-subshell is filled are called actinides.
metal. e.g. H2O, NH3 , Fă etc.
Ele ct ro nic C on
onffi g ur
uraat io n (ii) Ligands having no lone pair of electrons but -bonding electrons. e.g. C2 H4, C 6H 6
C 5H9ă etc.
(i) Lanthanides
(II) Classification based on te number of donor atoms present in the figuers :
Ce (Z = 58) to Lu (Z = 71) ă (6th period)
Such ligands are of following types :
General configuration : [Xe] 4f1ă14 5d 0ă1 6s2

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 27 28 QUIZRR
(i) Monodentate or unidentate ligands (vi) Chelating ligands : When a bidentate or a polydentate ligand is attached through
The ligands that can co-ordinate to the central metal ion at one site only are called two or more donor atoms to the same metal ion forming a ring structure, the ligand
monodentate ligands. Such ligands may be neutral molecules, negatively or positively is called chelating ligand.
charged ions. For example, The chelating ligands form more stable complexes than ordinary unidentate ligands.
+
F , Cl , CN , OCN , H2O, NH 3, NO2, NO , NH 2NH+3 etc.
ă ă ă ă
IUPAC NO MEN
ENCC LAT UR
UREE OF CO
COMM PLEX ES
A monodentate ligand having more than one lone pair of electrons may simultaneously The following rules are used for naming all types of complexes :
co-ordinate with two or more atoms and thus acts as a bridge between the metal ions.
(1) In case of ionic complexes, the cationic part is named first followed by the anionic part,
In such a case, it is called a bridging ligand and the complex thus formed is known
irrespective of the fact, whether cation or anion or both are complex.
as bridged complex. For example, OHă , Fă, NH2 , CO, O 2ă, SO24 etc. (2) In naming of complex ion, the ligands are namd first in the alphabetical order followed by
(ii) Bidentate ligand : Ligands, which have two donor atoms and have the ability to co- name of the metal ion.
ordinate with the central atom/ion at two different sites are called bidentate ligands. (3) When there are several ligands of the same type then prefix di, tri, tetra, penta are provided
For example, to the ligands. If in ligandÊs name any of this prefix is already present, then to avoid
confusion bis, tris etc. are provided rather than di, tri etc. and ligandÊs name is placed in
 
H2 N · (CH2 )2 · NH2 (ethylenediamine) paranthesis.
(4) Name of all negative ligands ends with ÂOÊ while the name of all positively charged ligands
(iii) Tridentate ligands : The ligands having three coordination sites are called tridentate
ends with Â-iumÊ. Neutral ligands have no special ending.
ligands. For example,
Name of negative ligands
  
e.g. H2 N · CH 2 · CH 2 · NH · CH2 · NH 2 Ligand Name Ligand Name

Diethylenetriamine F Fluoro NH2 Amido

ă

(iv) Polydentate ligands : The ligands having four or more co-ordination sites are called
polydentate ligands. For example, Cl ă Chloro NO2 nitro

H H Br ă Bromo NO3 nitrato

N · CH 2 · CH 2 · N
N · (CH2)2 · N
CH2 CH2 Iă Iodo S 2O23 thiosulphato
(CH2 )2 (CH2)2 H2 C O=CăO O·C=O CH2
O2ă Oxo SO 24 Sulphato
N N CăOă ăO ·C
H H O O O22 Peroxo CO 23 Carbonato
H H
Triethylenetetramine Ethylenediamine OH ă Hydroxo SCNă Thiocynato
(trine) tetraacetate ion (EDTA)
CNă Cyano SO 23 Sulphito
(v) Ambidentate ligands : They have two or more donor atoms but, while forming NC ă
Isocyanido CH3COO ă
Acetato
complexes only one donor atom is attached to the metal ion. The examples of such
N3ă Nitrido Hă Hydrido
ligands are CN ă, NO 2 NCSă, NCOă etc.
N 3 azido S2ă Sulphide

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 29 30 QUIZRR
Note : Negative organic ligand having ăyl suffix is NOT replaced by ă O.
OH
Eg. CH 3 · methyl (b) (H2O)4 Fe Fe (H2O)4 (SO4)2
OH
CH 3 · CH2 ethyl
Tetraaquoiron (III) ă di ă ø ă hydroxo ă tetraaquoiron (III) sulphate
· cyclopentadienyl (8) For deciding the alphabetical order of ligands, the first letter of the ligandÊs name is to be
considered and prefixes di, tri, tetra, bis etc. are not considered.
Name of positive ligands
NO ă · nitrosonium Some Ex
Exaamples :
NO +2 · nitronium
[Pt(NH3) 6]Cl4 Hexaammineplatinum (IV) Chloride
NH2NH+3 · hydrazinium
[Co(NH3 ) 4(H2O))Cl]Cl Tetraamineaquochlorocobalt (II) chloride
(5) Usually common names are provided to the neutral ligands except :
H 2O ă Aqua / Auqo [Cr(H 2O)4Cl 2] + Tetraaquodichlorochromium (III) ion

NH 3 ă ammine [Co(NH3 ) 5(NCS)]Cl2 Penta amineisothiocyanatocobalt (III) chloride

CO ă carbonyl [Ni (CN) 4] 2ă Tetracyanonickelate (II) ion
NO ă Nitrosyl Na 3[CO(NO2)6 ] Sodium hexanitro cobaltate (III)
(6) Oxidation state of Central metal as is represented by roman numerals including zero
K3[Fe(CN)5NO] Potassium pentacyanonitrosyl ferrate (II)
immediately after metalÊs name in small bracket (paranthesis).
Fe(CO)5 Pentacarbonyliron (0)
In case of naming of complex anion, central metal atom has suffix ă ate along with its
English/Latin name. But in case of complex cation or complex neutral molecule, central Ni(DMG)2 Bis (dimethylglyoximato) nickel (II)
metal atom has no specific suffix.
Usually latin names are used for those metals of which chemical symbol is derived from their Ex
Exaa mpl
plee 1
latin name except Give the systematic names for the following coordination compounds :
English name Latin name 1. [Cr(NH3 )3 (H2 O) 3]Cl 3
Hg Mercury Hydragesium Answer :
Sb Antimony Stibine triamminetriaquachromium(III) chloride
W Tungston Wulfrum Solution :
(7) In case of polynuclear or bridging complex compound (having 2 or more bridging compounds) The complex ion is inside the parentheses, which is a cation.
a prefix ø ă before the name of each different bridging group is added. Two or more bridging
The amine ligands are named before the aqua ligands according to alphabetical order.
groups of the same type are indicated by di-ø ă, tri ă ø ă etc. When a bridging ligand is
Since there are three chlorides binding with the complex ion, the charge on the complex ion must
attached to more than two metal atoms or ions, this is indicated by a subscript to ø.
be + 3 (since the compound is electrically neutral).
NH 2 From the charge on the complex ion and the charge on the ligands, we can calculate the oxidation
(a) (en)2 Co Co (en)2 (SO4)2 number of the metal. In this example, all the the ligands are neutral molecules. Therefore, the
OH
oxidation number of chromium must be same as the charge of the complex ion, + 3.
Bis(ethylenediamine) Cobalt (III)ă øăamido ă ø ă hydroxo ă bis(ethylene diamine)cobalt
(III)sulphate

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 31 32 QUIZRR
2. [Pt(NH 3) 5 Cl]Br3 7. Pt(NH3) 2Cl4
Answer : pentaamminechloroplatinum (IV) bromide Answer : diamminetetrachloroplatinum (IV)
Solution : Solution :
The complex ion is a cation, the counter anion is the 3 bromides. This is a neutral molecule because the charge on Pt+4 equals the negative charges on the four
The charge of the complex ion must be + 3 since it bonds with 3 bromides. chloro ligands.

The NH3 are neutral molecules while the chloride carries ă 1 charge. If the compound is [Pt(NH3)2Cl2]Cl 2, eventhough the number of ions and atoms in the molecule
are identical to the example, it should be named : diamminedichloroplatinum (II) chloride, a big
Therefore, the oxidation number of platinum must be + 4.
difference.
3. [Pt(H2NCH 2CH2 NH2 )2Cl 2]Cl 2
8. Fe(CO) 6
Answer : dichlorobis (ethylenediamine) platinum (IV) chloride
Answer : pentacarbonyliron (0)
Solution : ethylenediamine is a bidentate ligand, the bis-prefix is used instead of di-.
Solution :
4. [Co(H2NCH2CH 2NH2 ) 3]2 (SO4) 3 Since it is a neutral complex, it is named in the same way as a complex cation. The common name

Answer : tris(ethylenediamine)cobalt (III) sulfate of this compound, iron carbonyl, is used more often.

Solution :
9. (NH4 )2 [Ni(C2O4 )2(H 2O)2 ]
The sulfate is the counter anion in this molecule. Since it takes 3 sulfates to bond with two
Answer : ammoniumdiaquabis (oxalato) nickelate(II)
complex cations, the charge oneach complex cation must be + 3.
Solution :
Since ethylenediamine is a neutral molecule, the oxidation number of cobalt in the complex ion
The oxalate ion is a bidentate ligand.
must be + 3.
Again, remember that you never have to indicate the number of cations and anions in the name
10. [Ag(NH3 )2][Ag(CN) 2]
of an ionic compound.
Answer : diamminesilver(I) dicyanoargentate(I)

5. K4[Fe(CN) 6]
WER NER’S T HEO
HEORRY
Answer : potassium hexacyanoferrate(II)
When aqueous ammonia is added to a solution of cobalt dichloride, CoCl2, a blue precipitate forms
Solution :
of the corresponding hydroxide, Co(OH)2, which dissolves on the addtion of an excess of ammonia
potassium is the cation and the complex ion is the anion.
to give a solution that immediately begins to absorb oxygen and turn brown. From the oxidized
Since there are 4 K+ binding with a complex ion, the charge on the complex ion must be ă 4. solution, the following compounds can be isolated :
Since each ligand carries ă 1 charge, the oxidation number of Fe must be + 2. Composition Colour
The common name of this compound is potassium ferrocyanide. (I) CoCl3.6NH3 Orange-yellow
(II) CoCl3.5NH3 .H2O Pink
6. Na2 [NiCl4]
(III) CoCl3.5NH3 Purple
Answer : sodium tetrachloronickelate(II)
A great many other compounds of this type can be prepared, (i) by starting with other cobalt salts,
Solution :
and (ii) by carrying out further reactions with the compounds first obtained. Among these other
The complex ion is the anion so we have to add the suffix ăate in the name of the metal. compounds are two other chlorides :
(IV) CoCl3.4NH3 Violet
(V) CoCl3.4NH3 Green

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 33 34 QUIZRR
At first sight, the properties of compounds (I) - (V) are very puzzling : certain metallic elements. The number of species considered to be added to the simple
(i) All of them fail to give a brown precipitate of Co(OH)3 when treated with sodium hydroxide compounds give rise to the concept of secondary valence.
solution - a property expected of compounds containing the Co3+ ion. Only on boiling does Example : In [Pt(NH 3 )6 ]Cl4 secondary valency of Pt is 6
a precipitate form. (2) Primary valencies are satisfied by negative ions, secondary valencies may be satisfied by
(ii) All of them fail to give ammonium chloride when treated with concentrated hydrochloric acid negative ions or neutral molecules.
- a reaction that would be expected of a compound containing ammonia. Only on boiling (3) Ligands satisfying secondary valencies are directed towards fixed positions in space giving
with sodium hydroxide is ammonia evolved. a definite geometry to the complex, but the primary valencies are non-directional. Six valencies
(iii) While all of them give a precipitate of silver chloride when treated with silver nitrate in are directed towards a regular octahedron while four are directed towards either a tetrahedral
aqueous solution, the amount that is precipitated in the cold is in some cases less than manner or square planar.
expected, as shown in the table below. In these cases the full amount is only obtained by On the basis of postulates (1) and (2) & (3), Werner formulated compounds (I)ă(IV) as shown
leaving the solution to stand for a long time or by boiling it. diagrammatically below. Ordinary valency bonds are designated by black lines (ăăăăăă) and
(iv) The five compounds give different numbers of ions in solution, as judged from (a) the bonds between neighbouring atoms by dotted lines (...........). The cobalt atoms have their ordinary
electrical conductivities of their solution in comparison with those of other electrolytes, (b) valency of three (as in CoF3) and are given a coordination number of six. The other atoms are
the extent to which they depress the freezing point of water. The number of ions judged to given coordination numbers to match (e.g. four for the nitrogen atom in NH3, leaving one for the
be present are shown in the table below. cobalt).
Moles of AgCl Number of ions present Cl Cl
NH3 NH3
precipitated per mole in solutions per CoCl3 H3N NH3 H3N NH3
(I) CoCl 3.6NH3 3 4 Co Cl Co Cl
H3N NH3 H3N NH3
(II) CoCl3.5NH3.H2 O 3 4 NH3 OH 2
(III) CoCl3.5NH3 2 3 Cl Cl
CoCl3 .6NH3 CoCl3.5NH3.H 2O
(IV) CoCl 3.4NH3 1 2

These properties, and those of many other compounds of a similar kind, were brilliantly rationalized
Cl
by Alfred Werner in 1893. He proposed what is now referred to as his „coordination theory‰, for NH3 Cl
which he was awarded a Nobel prize in 1913. Its principal postulates are as follows : H3N NH3 H3N NH3
Co Co Cl
The first theory was called the WernerÊs theory of co-ordination compounds.
H3N NH3 H3N NH3
(1) Metals possess two types of valencies : Cl Cl
Cl
(a) Primary valency or ionizable valency : It is also referred to oxidation state.
CoCl3 .5NH3 CoCl3.4NH3
Primary valences were obvious from the stoichiometries of simple compounds such as
NiCl 2, Fe2(SO 4)3 and PtCl 2.
Now if in these formulations the black lines are taken to be ionic bonds, and the dotted and double
(b) Secondary valency : The valency which a metal atom or cation exercises towards lines are taken to be bonds of a non-ionic character, the properties of compounds (I)ă(IV) given
neutral molecules or negative groups (ligands) in the formation of complex ions. The above are fully explained. Thus (I) and (II) would be expected to give three Cl ă ions in solution,
secondary valency is also called the coordination number. New materials were frequently (III) only two, and (IV) only one. This leads to the customary formulations :
observed when other, independently stable substances, e.g. H2 O, NH 3 and KCl, were
(I) [Co(NH3)6]Cl 3 containing the [Co(NH3)6] 3+ ion;
added to these simple compounds giving, for example, NiCl 2. 4H2O, Co 2(SO4)3.12NH 3
(II) [Co(NH3)5H 2O]Cl 3 containing the [Co(NH5) 6H2 O]3+ ion;
or PtCl 2.2KCl. Such species were called complex compounds, in recognition of the
stoichiometric complications they represented, and were considered characteristic of (III) [CoCl(NH3) 5]Cl 2 containing the [CoCl(NH 3)5 ]2+ ion;
(IV) [CoCl2 (NH3)4]Cl containing the [CoCl 2(NH 3 )4] + ion.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 35 36 QUIZRR
Exa mpl
plee 2 VALENCE BOND THEORY
A, B & C are three complexes of chromium (III) with the empirical formula H12 O6 Cl3Cr. All To be read from NCERT book
the three complexes have water and chloride ion as ligands. Complex A does not react with
concentrated H2SO4 where as complexes B and C lose 6.75% & 13.5% of their original mass
respectively on treatment with concentrated H2 SO4. Identify A, B & C.
Ex
Exaa mpl
plee 4

Solution : The magnetic moment of [MnBr 4] 2ă is 5.9 B.M. What is the geometry of this complex ion?
A = (Cr(H 2O) 6]Cl 3 Solution :
[Cr(H2O 6]Cl3 + H2SO 4  No reaction because in it all H 2O molecules are present in coordinate Since the coordination number of Mn2+ ion in this complex ion is 4, it may be either tetrahedral
sphere. (sp 3 hybridisation) or square planar (dsp2 hybridisation) as shown below at (b) and (c). But the
B = [Cr(H 2O) 5Cl]Cl 2 . H2O fact that the magnetic moment of the complex ion is 5.9 BM. Shows that it should be tetrahedral
in shape rather than square-planar.
[Cr(H 2O)5Cl]Cl2 . H2O + H 2SO 4  One mole of H2O is removed because its is present outside
the coordination sphere) (a) Mn2+ ion 3d 4s 4p
Molecular wt of complex = 266.5 (3d5 )

% loss = 18
  100 = 6.75%
266.5 (b) [MnBr4] 2ă 3d 4s 4p
3 ïï ïï ïï ï
C = [Cr(H2O) 4 Cl2]Cl.2H2 O (sp hybridisationă
[Cr(H 2O)4Cl 2]Cl.2H2 O + H2SO 4  Two mole of H 2O are removed tetrahedral shape) (n = 5,  = 5.9 B.M) ă ă ă ă
Br Br Br Br
(Because these are present outside the coordination sphere
sp3 hybridisation-
tetrahedral shape
2  18
 % loss =  100  13.50%
266.5
3d 4s 4p
(c) [MnBr4] 2ă
Ex
Exaa mpl
plee 3 ïï ïï ïï ï ï
2
(dsp hybridisationă
A metal complex having composition Cr(NH 3)4 Cl2Br has been isolated in two forms A and square planar shape) Br ă Br ă Bră Bră
B. The form A reacts with AgNO3 to give a white precipitate readily soluble in dilute
aqueous ammonia, whereas B gives a pale yellow precipitate soluble in concentrated dsp2 hybridisation-
square planar shape
ammonia. Write the formula of A and B and state the hybridisation of chromium in each
case. Also calculate their magnetic moments (spin - only value).
Exa mple
Exa ple 5
Solution :
Formula of A is [Cr(NH3) 4ClBr]Cl + AgNO 3  AgCl  (white) How would you account for the following ?

Formula of B is [Cr(NH3) 4Cl 2]Br + AgNO3  AgBr  (yellow) (a) [Fe(CN)6] 3ă is weakly paramagnetic while [Fe(CN6] 4ă is diamagnetic.
3
Cr is in + 3 oxidation state i.e. 3d system
(b) Ni(CO)4 possesses tetrahedral geometry while [Ni(CN)4] 2ă is square planar.
Therefore the hybridisation of Cr is sp3d 2 and spin only magnetic moment.
(c) [Ni(CN)4]2ă is diamagnetic while [NiCl4 ]2ă is paramagnetic.
øS = n( n  2)BM

øS = 3(3  2)BM = 3.87 BM

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 37 38 QUIZRR
Solution :
Strong field ligands like CN ă, CO, en, NO2 have very strong electron donating tendency,
(a) [Fe(CN)6 ]3ă involves d 2sp3 hybridization.
hence electrons of central metal ion pair up against HundÊs rule and low spin complexes are
3d 4s 4p formed.
Fe3+ (d 5 )
[Fe(CN)6 ]3ă Impo
porrtant po
poiints on Ba
Bacck b on
ondding
ïï ïï ïï ïï ï ï
Back bonding is more dominant than  bonding in carbonyl complexes.
2 3
d sp hybridization Ć If back bonding increases, electrons in  orbitals of CO increases, thus its bond order decreases,
One dăorbital is singly occupied, hence it is weakly paramagnetic in nature. consequently bond length increases and vice versa.
[Fe(CN)6 ]4ă involves also d 2sp3 hybridization but it has Fe 2+ ion as central ion. Ć Shape of anti bonding orbital of CO is

3d 4s 4p
Fe2+ (d 6 )
[Fe(CN)6 ]4ă ïï ïï ïï ïï ï ï C O

d 2sp 3 hybridization
All orbitals are doubly occupied, hence it is diamagnetic in nature. Therefore back bonding takes place with dry orbital metal which is identical in shape.

3
(b) In the formation of Ni(CO)4, nickel undergoes sp hybridization, hence it is tetrahedral in Ex
Exaa mpl
plee 6
shape.
In the following compounds, which has greater bond length of CO ?
3d 4s 4p
[V(CO)6 ]ă & [Mn(CO)6 ]+
Ni 3d8 4s2
Solution :
Ni(CO)4 ïï ïï ï ï
V = [Ar] [4s2] [3d3]
3
sp hybridization
Mn = [Ar] [4s2] [3d5]
(c) In [Ni(CN)4] 2ă ion, Ni2+ undergoes dsp 2 hybridization, hence it is square planar in shape.
3d 4s 4p Vă =
Ni2+
[Ni(CN)4 ]2ă Mn + =
ïï ïï ïï ï
V can easily donate the electron to CO through backbonding as compared to Mn has it has half
dsp2 hybridization of orbital.
In [Ni(CN) 4]2ă, all orbitals are doubly occupied, hence it is diamagnetic; while in [Ni(Cl4 ]2ă, So backbonding is greater with vandium thus, CO has greater bond length in [V(CO)6] ă.
two orbitals are singly occupied, hence it is paramagnetic in nature.
4p Ex
Exaa mpl
plee 7
3d 4s
[NiCl4]2ă ïï ïï ïï ï How will you distinguish between the following isomer pairs
(a) (i) [CoBr(NH 3)5]SO4 and
3
sp hybridization (ii) [Co(SO 4) (NH3)5 ]Br
TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 39 40 QUIZRR
(b) (i) [Cr(H2O) 6]Cl 3 and (viii) Dichlorotetraamminecobalt (III) ion
(ii) [CrCl(H2 O)5]Cl 2 H 2O (ix) Potassium pentacyanonitrosylcobaltate (III)
(c) (i) Cis [PtCl2 (NH3 )2] and (x) Sodium ethylnediaminetetraacetato chromate (II)
(ii) trans [PtCl2 (NH3)2] Solution :
(d) The two enantiomers of [CoCl2 (en)2] + (i) [Fe(H2 O) 6]SO4
Solution : (ii) K[Ni(CN)4 ]
(a) Isomer (i) gives white ppt of BaSO4 with BaCl 2 whereas isomer (ii) does not form a precipitate (iii) K3[Al(C 2 O4)3]
with BaCl2 . (iv) [PtCl(NO2)(NH 3)2 ]
(b) The water molecule in isomer (ii) is lost easily on heating leading to weight loss whereas the (v) K4[Fe(CN) 6]
water molecule in isomer (i) are not easily, being coordinated to the central atom.
(vi) [PtCl(NH3 )2 ] +
(c) Cis isomer (i) has dipole moment, the trans isomer (ii) does not.
(vii) [CoCl 2(en) 2]+
(d) One isomer is dextrorotatory whereas the other is laevorotatory.
(viii) [CoCl 2(NH 3) 4 ]+
(ix) K2[Co(CN)5NO]
Exa mpl
plee 8
(x) Na2 [Cr(CH 3COO) 4(en)]
Draw structure of
(i) 2 - C 2H4)]ă
ZeiseÊs salt anion [PtCl3( Exa mpl
plee 10
(ii) [Al(CH3) 3] 2.
A solution containing 0.319 g of complex CrCl3.6H 2O was passed through cation exchanger
Solution : and the solution given out was neutralised by 28.5 ml of 0.125 M NaOH. What is the correct
H
H H H H formula of complex ?
C C
Cl Me Me Solution :
C Al Al The Cl atoms outside the co-ordination sphere will be ionised to produce the acid, HCl.
Pt H H Me Me Thus, milliequivalent of Clă ions outside = milliequivalent of HCl formed
C
Cl Cl = milliequivalent of NaOH used
H H H
= 28.5 ï 0.125
= 3.56
Ex
Exaa mpl
plee 9
0.319
Write down the formulae of the following coordination compounds. mole or 1.197 millimole of complex produce 3.56 milliequivalent or millimoles of Cl ă. Thus,
266.5
(i) Hexaaqua Iron (II) sulphate
1 mole of complex will give 3 mole of Clă, i.e. all the three Cl atoms are outside the co-ordination
(ii) Potassium tetracyanonickelate (III) sphere. Thus, the complex is [Cr(H2O)6 Cl3 .
(iii) Potassium trioxalatoaluminate (III)
(iv) Chloronitrodiammineplatinum (II) Ex
Exaa mpl
ple
e 11
(A), (B) and (C) are three complexes of chromium (III) with the empirical formula H12O6Cl 13Cr.
(v) Potassium hexacyanoferrate (II)
All the three complexes have water and chloride ions as ligands. Complex (A) does not
(vi) Chlorodiammineplatinum (II) ion
react with concentrated H2SO 4, whereas complexes (B) and (C) lose 6.75% and 13.5% of their
(vii) Dichlorobis (enthylenediamine) cobalt (III) ion original weight, respectively, on treatment with concentrated H 2SO4 . Identify the octahedral
complexes (A), (B) and (C).
TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 41 42 QUIZRR
Solution : CRYSTAL F
FIIEL
ELDD THEORY
(A) : [Cr(H2 O) 6]Cl3 (Violet) To be done from NCERT
(B) : [Cr(H2 O) 5Cl]Cl 2.H2O (Green) Molecular weight = 266.5 ISOMERISM :
(C) : [Cr(H2 O) 4Cl2]Cl.2H 2O (Dark green) Two or more substances having the same molecular formula but different structural or spatial
Compound (A) contains six water molecules as co-ordinated water and thus, does not lost H2O on arrangements are called isomers. They are of two types :
treatment with H2 SO4 . Compound (B) contains five water molecules as co-ordinated water and isomerism
one molecule as lattice water which is lost to H2 SO4 showing a loss of 18 g out of 266.5 g, i.e.,
6.75% loss. Similarly, compound (C) contains four co-ordinated water-molecules and two molecules
structural isomerism stereoisomerism
of lattice water, which are taken out by H 2SO 4 to show a loss of 13.5%.
(i) ionization isomerism (i) Geometrical
Exa mpl
plee 12
(ii) Coordination isomerism or cis-trans isomerism
(a) Write down the IUPAC nomenclature of the given complex along with its hybridisation (iii) Linkage isomerism (ii) optical isomerism
and structure (iv) Hydrate isomerism
K2 [Cr(NO)(NH3 )(CN)4]; ø = 1.73 B.M. (v) Ligand isomerism
(b) Draw the structures of [Co(NH3)6 ]3+ , [Ni(CN)4 ] 2ă and [Ni(CO)4]. Write the hybridisation
of atomic orbitals of the transition metal in each case. St
Strr uc
uctt ur
uraal isomerism :
Solution : This type of isomerism due to the difference in structures of coordination compounds.
(a) Potassium amminetetracyanonitrosoniumchromate (I) (i) Ionization isomerism : Complexes that have the same empirical formula and are produced
Cr is in + 1 oxidation state and possess d2sp3 hybridisation with one unpaired electron. by the interchange of the position of the ligands inside the complex zone and outside the
complex zone are called ionisation isomers. They give different ions on ionization. For example
 n (n  2)  1(1  2)  3  1.73 BM.


[Co(NH 3)4Cl2]NO 2  [Co(NH ) Cl ] + + NO ă
3 4 2 2
(b) [Co(NH3 )6] 3+ : Co3+ is d2 sp3 hybridised to show octahedral shape.
[Co(NH 3)4Cl(NO2 )] 

 [Co(NH ) Cl(NO )]+ + Cl ă
NH3 3 4 2

H 3N NH 3 (ii) Coordination isomerism :

3+ Ionic coordination compounds that contain complex cations and anions can exist as isomers
Co
H 3N if the ligands associated with the two metal atoms are exchanged. For example :
NH 3
H 3N (1) [Pt(NH 3) 4 ] [PtCl6 ] and [PtCl2 (NH3) 4] [PtCl4]
[Ni(CN)4 ]2ă : Ni2+ is dsp 2 hybridised to show square planar shapae. (2) [Co(NH3)6] [Cr(CN)6] and [Cr(NH3) 6] [Co(CN)6 ]
ă ă
NC CN (iii) Linkage isomerism : Isomerism which results when a given ligand is joined to the central
Ni2+ atom through different atoms of the ligand. For example
ă
NC CN
ă [Co(NH 3 )5(NO2)]Cl2
3
[Ni(CO)4] : Ni is sp hybridised to show tetrahedral shape. CO and [Co(NH 3 )5(ONO)]Cl2
Here, the ligand NO2ă may attach with the central ion either through O-atom or through
N-atom.
Ni
OC CO (iv) Hydrate isomerism : This type of isomerism arises due to the different position of water
CO molecules inside and outside the coordination sphere. For example
TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 43 44 QUIZRR
[Cr(H2O) 6]Cl 3 and [Cr(H 2 O)5Cl]Cl2.H2 O (b) Octahedral
Violet colour Blue green colour L1 L1, L2 L6, L 3
(v) Ligand isomerism : Some ligands themselves are capable of existing as isomers, for example L5 L4
diaminopropane can exist both as i.e. L1 , L6 L1, L3 L6, L 2

C H2  C H CH3 M L2 , L4 L1, L4 L6, L 5

| CH2  CH2  C H2
| | | L3 , L5 L1, L5 L6, L 4
NH2 NH2 and NH2 NH2 L2 L3
1,2 diaminopropane 1, 3-diaminopropane opposite adjacent (Cis)
L6 (trans)
when these ligands are associated to form complexes, these complexes are isomers of each
other. (1) CNă4 Sq planar complexes
e.g. [Co (1, 2-diaminopropane)2Cl2 ] + and
The following types of four coordinated sq. planar complexes show cis-trans isomerism.
[Co (1, 3-diaminopropane) 2Cl2] +
(i) MA2B2
[Pt(NH 3)2Cl2] diammine dichloro Pt (II)
Stereo isomerism
Stereo isomerism in coordination compounds arises due to different spatial arrangement of ligands H3 N Cl Cl H3N
around the central metal ion.
Pt Pt
Geometr i cal iso me
merri sm
H3 N Cl H 3N Cl
In complexes ligands may occupy different sites. When the ligands in question occupy adjacent Cis trans
positions it is called ÂCisÊ (Cis, Latin, meaning „On this side‰) and when they occupy opposite sites, (Clă and NH3 ligands are adjacent) (Cl ă and NH3 ligands are opposite)
it is called ÂtransÊ (trans, Latin meaning „across‰). Therefore, geometrical isomerism is also called Cis and trans isomers may be distinguished by dipole moment measurement
ÂCis ă Trans Âisomerism. This type of isomerism is not possible for complexes of CN 2 or 3 or for
CN 4, tetrahedral complexes. (ii) MABX2
L
[Pt(NH 3)PyCl2] (Py = pyridine C5 H5N)
L H 3N Cl H3N Cl
M
L·M·L L Pt Pt
M L
Py Cl Cl Py
L L L
CN2 CN3 CN4 Cis trans

(Linear) (r PL) (Td) (iii) [MABCD]

In this complexes all ligand positions are adjacent not opposite. However, cis-trans isomerism is [PtNH3(NH 2OH)Py NO2 ]+ Ammine hydroxylamine pyridine nitro Pt (II)
common in square planar and octahedral complexes. In such complexes three of the ligands (B, C or D) may be trans to A.
(a) Square planar H3 N NO2 O2 N NH3 NO2 NH2OH
L1 L4 L1, L2
Pt Pt Pt
L1, L3 L2, L3
M
L2, L4 L3, L4 Py NH2 OH Py NH2 OH Py NH3
L2 L3 L1, L4 Such complexes are best denoted as [M < AB > CD], the ligands in the angular brackets are
opposite (trans) adjacent (Cis) trans to each other.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 45 46 QUIZRR
(v) Geometrical isomerism is also found in square planar complexes containing unsymmetrical (ii) [Co(en)2Cl2]+
bidentate ligands e.g. [M (AB)2], gly = NH 2 ă CH 2 ă COO ă
Cl Cl
N Cl N N

Co Co

N N N N
N Cl

Cis trans

A few complexes of the type [MA 3X3 ] are also known e.g. [Rh(Py) 3Cl3]

Cl Cl
Py Cl Py Cl

Rh Rh
(2) CN ă 6 (Octahedral complexes)
Geometrical isomerism in octahedral complexes is also very common. The familiar examples Py Cl Py Py
include compounds of the type :
Py Cl
(i) [MA4X 2]
Facial (fac) Meridional (mer)
(ii) [MA4XY]
(iii) [M(AA)2X 2] Largest numbers of geometrical isomers are found for complex of the type [MABCDEF] where
each ligand is different e.g. [Pt (Py) (NH3 ) (NO2 ) ClBrI].
(iv) [M(AA)2XY]
Unsymmetrical bidentate ligands also produce cis-trans isomers, e.g. [Cr(gly) 3].
(v) [MA2X 2Y 2]
Where M = Co (III), Cr (III), Rh (III), Pt (IV) etc. gly gly
O O
A ă A = Symmetrical bidentate ligands
N N N N
X & Y = ă ive ligands.
For example Cr gly Cr gly
+
(i) [Cr(NH3 )4Cl2] O O O O
+ + gly gly
Cl Cl N O
cis trans
H3N Cl H3 N NH3

Cr Cr Pr epar ati on
onss of comple x c ompoun
unds
ds

H3N NH 3 H3 N NH3 Complex compounds are generally prepared by the following methods :
(i) Substitution reaction in aq. solutions
NH3 Cl
This method involves a reaction between a metal salt in aq solution and a coordinating
Cis trans agent, e.g. aq. solution of CuSO4 and excess NH 3 forms a Cu2+ ammine.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 47 48 QUIZRR
[Cu(H 2O) 6]SO 4 + 4NH 3  [Cu(NH 3) 4]SO4 + 6H2O If EAN of an element in a complex is equal to atomic number of a noble gas. The complex is
(Blue) (Deep Blue) considered to be more stable.
(ii) Substitution reactions in the absence of solvent
Exa mpl
plee 13
Direct reaction between anhydrous metal salt and liquid NH3 produces metal ammines, e.g.
NiCl 2 + 6NH 3(l)  [Ni(NH3 ) 6]Cl 2 Draw the structures of [Co(NH3) 6]3+, [Ni(CN)4] 2ă and [Ni(CO)4 ]. Write the hybridisation of
Yellow Violet atomic orbitals of the transition metal in each case.

(iii) Redox reactions Solution :

Co(II) salt forms a Co(III) complex Hybridization of Co+3 is d2sp3 , shape is octahedral.

4[Co(H2O) 6]Cl2 + 4NH 4Cl + 20NH3 + O2  4[Co(NH3 )6]Cl 3 + 26H2 O

NH 3
NH3 NH3
Sta b ility of complex c om
ompo
po
poun
un
undd in sol
oluut ion
Co
Complex formation can be seen as a Lewis acid ă base reaction. The Mn+ is Lewis acid and the
ligands are Lewis bases. If the interaction between Mn+ and the ligands is strong, the complex NH3 NH3
is thermodynamically stable. The reaction between Mn+ and the ligands can be written as NH3
Mn+ + xLmă  [MLX) p+, where (n+) + (m ă) = (p+)
Hybridization of Ni+2 is dsp 2 so shape is square planar.
The equilibrium constant k is stability constant and it is defined as
NC CN
[ML X ] p 
k
[M n ][Lm  ] X Ni

The numerical value of k gives an indication of thermodynamic stability. Some stability constants NC CN
are given below : 3
Hybridisation of Ni is sp so shape is tetrahedral.
K
CO
Ag+ + 2NH 3  [Ag(NH3 )2 ] + 1.6 ï 107
Ni
Co3+ + 6NH 3  [Co(NH3) 6]3+ 5.3 ï 1033
CO CO CO
Cu2+ + 4CNă  [Cu(CN4) 2ă] + 2.0 ï 1027
Cu2+ + 4NH 3  [Cu(NH3) 4]2+ 4.5 ï 1011
Col
oloour of T ransi
sittion meta l compou
ound
nd
ndss
2+
The value of k for Cu complexes with NH 3 and CNă show that cyanocomplex is more stable than
A chemical substance looks coloured if it absorbs a portion of visible light ( ă 3800 ă 7800 Å) and
NH3 complex.
transmits the rest. For example, if a compound absorbs the yellow-red (6000 ă 7500 A) it appears
green (i.e. transmitted light) i.e. the colour is complementary colour. Absorption of radiation excite
Ef
Efff ective at
atoomic num
numbber (EAN
AN)) rrul
ul
ulee
electron to higher energy state. Therefore, when a substance looks coloured, it means that absorption
Sidwick proposed effective atomic number (EAN) to explain the stability of metal in a complex. of visible light and transition of electron must have taken place. Most of the transition metal
EAN is defined as the total number of electrons on the metal atom or ion after the complex compounds are coloured. It arises due to the following reasons :
formation which should be equal to that of the next higher noble gas. (i) d-d transition
If Z is the atomic number, (O.N). is the oxidation number and (C.N.) is the co-ordination number
(ii) Charge transfer
of the central metal atom or ion in the complex then
EAN = Z ă (O.N.) + 2 ï (C.N.)
TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 49 50 QUIZRR
The d–d t ransit ion Col
oloo ur of aqua com
ompple xes

The five dăorbitals of a free ion are degenerate i.e. have equal energy. But in the presence of Aquo ion dăelectrons Colour
ligands (H 2O, NH3, CN ă, Fă etc.) the dăorbitals split. It depends on structure of the complex (Oh, 3+
[Sc(H 2O) 6] O Colourless
Td, Sq, Pl etc.).
[Ti(H2O) 6] 3+ d1 Violet
2
dx2ăy2 dz [V(H 2O) 6 ] 3+ d2 Blue
dxy dyz dxz eg [V(H 2O) 6 ] 2+ d3 Violet
t2
[Cr(H2 O) 6] 2+ d4 sky-blue
10DqÊ t 10Dq (or 0 )
Free ion [Fe(H2 O) 6] 3+ d5 Colourless
d -- orbitals
e [Fe(H2 O) 6] 2+ d6 Pale-green
dx2 ăy2 dz 2 t 2g
dxy dyz dxz [Co(H 2O) 6] 2+
d 7
Pink
ML4 (Td) ML6 (Oh) [Ni(H2 O) 6]2+ d8 Green
[Cu(H2O) 6] 2+ d9 Blue
Let us consider Ti(H2O) 63+. It is an Oh complex. The dăorbitals split as, [Zn(H 2O) 6 ] 2+ d10 Colourless

Colours due to dăd transition are faint. Metal ions which have d0, d5 and d10 configurations are
2 2 2
dxăy dz colourless, if at all coloured not due to dăd transition.
eg

Col
oloour and charge tr ans
nsffer
3+ 1
Ti (3d ) Many transition metal ions or compounds such as MnO4 ă, CrO4 ă2, Cu 2 O, CdS etc are coloured.
t 2g They have their dăorbitals either vacant or fully filled.
dxy dyz dxz
Ion or Oxidation state of
dăelectrons Colour
and single electron occupies t2g level. When light falls on the complex t2g electron is excited to e g Compound transition metal
level. MnO4ă Mn +7 3d 0 Purple
(t1 2g e0g  t 02g e1g i.e. CrO4 ă2
Cr +6
3d 0
Yellow
Cu2O Cd+ 3d 10 Red
eg eg
hv CdS Cd+2 4d 10 Yellow
t2 g t2g
Colour in such compounds is explained by charge transfer mechanism. In MnO 4ă , Mn+7 is oxidizing
agent and Oă2 is reducing agent. As oxidizing agent picks up electrons and reducing agent gives
This excitation takes place when the compound absorbs radiation corresponding to   5000 Å,
(grenish-yellow light). Therefore, transmitted wavelength corresponds violet light and the complex up electrons, electrons moves from Oă2 to Mn +7 .

looks violet. As electron transition takes place from one group of d orbitals to the other, it is called
Oă2
dăd transition. The dăd transition is shown by transition metal ions of electron configurations, d1,
d2, d 3 , d4, d 6, d 7, d8 , and d9. Oă2 Mn+7 Oă2
e

Oă2

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 51 52 QUIZRR
Due to such movement of electrons the ion is coloured. Cl H
:O H
The colour of brown ring compound [Fe(H2 O)5NO]2+, and Fe 3+[Fe2+(CN) 6] are also due to charge VCl 4 + H 2O V VOCl2 + 2HCl
transfer. Cl (green)
Cl
Cl (change transfer)

e e

2+ 3+ 2+
O R G AN
ANOOMETALLI C COMP OUNDS
[Fe (H2 O)5 NO] Fe [Fe (CN) 6]
(deep brown) (deep blue) These compounds constitute a broad class of substances in which carbon atom is directly bonded
to a metal. Thus organic compounds in which metal atom is directly linked to carbon atom are
Colours due to charge transfer are intense (deep). known as organometallic compounds.
For example, NaC  CNa is an organometallic compound as sodium is directly linked to carbon
Hy drol ys
ysiis of T ransiti on m etal com
omppou
ounnds whereas C2H5ONa, Ti(OC2H5) 4 are not organometallic compounds since the metal atom is linked
Splitting of water molecules by ions is known as hydrolysis. Cation hydrolysis takes place when to carbon through oxygen. Some representative organometallic compounds are
charge density on the cation is high. C2H5MgBră Ethyl magnesium bromide

Charge (C 2H5) 2 Zn ă Diethyl zinc

Charge density =
Ionic radius (CH 3) 2Cd ă Dimethyl cadmium

Transition metal ions on the average are small in size and the common oxidation states are + 2, C6H5Li ă Phenyl lithium

+ 3 etc. Therefore, their charge density is high and they under go hydrolysis. (C 2H5) 4 Pb ă Tetraethyl lead

H Alkyl or aryl magnesium halides (RMgX or ArMgX) are also called as Grignard reagents.
n+ nă1 +
M :O [M(OH)] +H
H C l a s s if
ifii c a t i on o f O r g a no
nomm e t a l l i c C o m po
pouunds
Thus, soluble salts of transition metals from slightly acidic solution.
(i) Ionic compounds of electropositive metals :
FeCl3 + Water  Solution, slightly acidic. These compounds are mostly formed between the electropositive metals and the carbon compounds
Water
FeCl3  3+ which are mostly acidic in nature. Thus organometallic compounds of alkali metals and alkaline
 Fe + 3Cl
ă

earth metals consist of ions or ion pairs.

H
Fe
3+
:O Fe(OH) 2+ + H + Ră Na+ RăMg2+ Xă
H
Alkyl sodium Alkyl magnesium
H halide
3+
Cr :O Cr(OH) 2+ + H + Ră C  Că Na + Ră Zn2+ Ră
H
Sodium alkynide dialkyl zinc
H These compounds are normally soluble in hydrocarbon solvent. They are very reactive towards air
Cu2+ :O Cu(OH)
2+ +
+H
H and water. The stability of these compounds depends upon the structure of the carbon containing
part of the compound.
Due to such hydrolytic reaction, cations, such as Mn+7 , Cr+6, etc. are not stable in water

Mn+7 + 4H 2O  MnO 4ă + 8H+ (ii) ăbonded complexes :

Cr+6 + 4H2O  CrO 4ă2 + 8H+ In a ăbonded complex, a metal and a carbon atom of the ligand are joined together with a sigma
bond. This means that the ligand contributes 1 electron and is therefore called one electron donor.
Covalent transition metal compounds, such as TiCl4, VCl 4 etc are hydrolysed due to ability of Tetramethyl tin, (CH3)4 Sn and trimethyl aluminium, (CH3)3Al are ăbonded oroganometallic
transition metal ion to expand coordination number by the use of empty dăorbitals.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 53 54 QUIZRR
compounds. (CH3)3Al exists as dimer and has structure analogous to diborane. Two methyl groups CO CO CO
CO CO CO
act as bridges between two aluminium atoms.

CH 3 M CO Fe Ni
H3 C CH3
Al Al CO CO
CO CO
H3 C CH 3 CH3 CO CO
[M (CO) 6] CO CO
Trimethyl aluminium
(M = Cr, Mo, W) [Fe (CO)5 ] [Ni(CO)4 ]
(iii)  ăcomplexes :
In metal carbonyl the oxidation state of the metal is zero. These metal carbonyls may be monomeric
These are organometallic compounds which involve the use of ăbonds present in organic
bridged or polynuclear.
compounds. For example, ZeiseÊs salt, ferrocene and dibenzene chromium are organometallic
compounds of this type. In all these compounds the ăelectrons of the organic compound interact
Bo nd
ndii n g i n O r g a n o me
mett a l l i c C o m p o un
unds
ds
with the metal ion and thus occupy one of the coordination sites. For example in ferrocene and
dibenzene chromium, the iron and chromium atoms are sandwiched between two aromatic rings. (a) Bonding in metal carbonyls :

C The metal-carbon bond in metal carbonyls has  as well as  character.

(i) ăoverlap
Cl C +
K
Pt H H In a sigma bonded complex, the lone pair of electrons is present on the bonding orbital
Cl Cl of carbon monoxide. This bonding orbital containing lone pair interacts with the empty
Zeise's salt K [Pt Cl3 (n2 ă C2H 4)] dăorbital of the metal to form a metal-carbon bond as shown below :

2+
Fe
Cr
(ii) ăoverlap :
In addition to this, the antibonding orbitals of CO can also overlap with the filled dă
5
orbitals of the metal resulting in back bonding as explained earlier. Thus metal carbonyls
Ferrocene Fe (  ă C 5H 5) 2
become much more stable compounds due to multiple bonding in them.
[bis cyclopentadienyl iron] dibenzene chromium Cr (6 ă C6H 6)2

The number of carbon atoms involved in the formation of ăcomplexes with metals is indicated
by the power of  x (eta). For example, ferrocene is represented as Fe[5(C6H6) 7] indicating that
5ăcarbon atoms or cyclo pentadienyl anion are involved in ăcomplexation with the metal. Similarly
one can write dibenzene chromium as [Cr(6ăC6H6)2] indicating that all the six carbons of benzene
are involved in ăcomplexation with chromium.

(iv) Metal Carbonyls : It is important to note here that -bond is in the nodal plane of the -electrons
These are the complexes where carbon of carbon monoxide donates a pair of electrons to the whereas -overlap is perpendicular to the nodal plane.
metal. Nickel carbonyl and iron carbonyl are the common examples.

TRANSITION ELEMENTS & COORDINATION COMPOUND TRANSITION ELEMENTS & COORDINATION COMPOUND
 QUIZRR 55

(b) Bonding of alkenes to a transition metal

The bonding of alkenes to a transition metal to form complexes has two components. First,
the ăelectron density of the alkene overlaps with a -type vacant orbital on the metal atom.
Second is the back bonding formed by the flow of electron density from a filled dăorbital on
the metal into the vacant xăantibonding molecular orbital on the carbon atom as shown.

C C
M + + +
+ C
C
 ă overlap

C + C ă
M M
ă +
C C

The only app you need to prepare for

JEE Main JEE Adv. BITSAT WBJEE MHT CET and more...

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available

With MARKS app you can do all these things for free

Solve Chapter-wise PYQ of JEE Main, JEE Advanced, NEET, BITSAT, WBJEE, MHT CET & more

Create Unlimited Custom Tests for any exam

Attempt Top Questions for JEE Main which can boost your rank

Track your exam preparation with Preparation Trackers

Complete daily goals, rank up on the leaderboard & compete with other aspirants

TRANSITION ELEMENTS & COORDINATION COMPOUND

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available
 The only app you need to prepare for

JEE Main JEE Adv. BITSAT

4.8
WBJEE

Rating on Google Play

50,000+
MHT CET

Students using daily

and more...

2,00,000+
Questions available
SOLUTIONS
With MARKS app you can do all these things for free

Solve Chapter-wise PYQ of JEE Main, JEE Advanced, NEET, BITSAT, WBJEE, MHT CET & more

Create Unlimited Custom Tests for any exam

Attempt Top Questions for JEE Main which can boost your rank

Track your exam preparation with Preparation Trackers

Complete daily goals, rank up on the leaderboard & compete with other aspirants

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available
 QUIZRR 3 4 QUIZRR
S OLU
OLUTIO
TIO
TIONNS mass of solute component
Parts per million (ppm) =  106
total mass of solution
Introduction
mass of solute component
A „solution‰ is defined as a homogeneous mixture of two or more substances (called as compo- Parts per billion (ppb) =  109
total mass of solution
nents), the relative proportion or composition of which may vary between certain limits.

T y pe
pess of S o lu
lutt io
ionns V AP
APOO U R P R E S SUR
SUR E

Following types of solutions are generally considered When a liquid is placed in a closed container, it evaporates and
converts to vapour. After some time, the liquid and the vapour
(a) gas in gas (b) liquid in liquid
reaches equilibrium, i.e., the rate of evaporation becomes equal to
(c) gas in liquid (d) solid in liquid
the rate of condensation. At this point of time the pressure exerted
The component of a particular type of solution which is present in the greater quantity is called by the vapours of the liquid on the surface of the liquid and on the
solvent while the other component(s) is called the solute. However, in the case of a solution walls of the container is called the vapour pressure of the liquid.
formed from a solid and a liquid, the liquid is always referred to as the solvent even though there
Does the vapour pressure of a liquid depend on the volume of the
may be the cases when the solid is present in the larger quantity.
vessel, shape of the vessel or the amount of liquid taken in the
A solution is unsaturated if it can still dissolve more solute at the same temperature; when it container ?
can dissolve no more of the solute at the same temperature it is said to be saturated.
These questions can be answered by invoking the concept of equilibrium constant. For the equi-
It is possible to obtain supersaturated solution, i.e., solutions which contain more dissolved librium, liquid 
 
 vapour, the Kp for the equilibrium would be = Pvap, since this is the
solute than they should at a particular temperature, by cooling a hot concentrated solution of a pressure exerted by the vapours at equilibrium (by definition). We know Kp depends only on
solid in a liquid in the absence of traces of solids (even dust). In order to ensure that a particular temperature and the nature of substance. This means that vapour pressure of a liquid will also
solution is saturated but not supersaturated there must be a small amount of excess solute be constant at a given temperature and will depend on temperature and the nature of liquid.
present.
Therefore, it should be noted that whatever be the volume or shape of the vessel, or the amount
Ć Supersaturated solutions are not in equilibrium with the solid substance. Thus, if a small of liquid in it (assuming it to be more than the minimum amount required), the vapour pressure
crystal of solute (say sodium thiosulphate) is added to its supersaturated solution, the excess of a liquid is constant at a given temperature and changes only with the change of temperature
immediately crystallises out, which is usually quite fast. of the liquid.
Moreover, on addition of any substance to the liquid, as long as the substance does not dissolve
Kind of solution Example
in the liquid and completely covers the surface, the vapour pressure of a liquid remains constant.
1. Gas in gas Air (O2, N 2, Ar and other gases)
2. Gas in liquid Carbonated water Ad
Addi
di
diti
ti
tion
on of a N on-
on-Vo
Vo
Vola
la
lati
ti
till e So
Solu
lu
lute
te t o a V ol
olat
at
atii le S ol
olve
ve
vent
nt
3. Gas in solid H2 in platinum metal (adsorption) When a non-volatile solute is added to a liquid (solvent), it is found that the vapour pressure of
4. Liquid in liquid Mixture of hydrocarbons (gasoline) the solution is less than the vapor pressure of the pure liquid. This is because of the following
5. Liquid in solid Dental amalgam (Hg in Ag) two reasons

6. Solid in liquid Sea water (NaCl and other salts in water) 1. Attraction between the solute and solvent molecules

7. Solid in solid Metal alloys such as 14ăcarat gold (Au and Ag) 2. Reduction in the number of solvent molecules per unit area of the surface.
Let us understand these two reasons.
Note : Closely related to weight percent and particularly useful for dilute solutions are the
Soluteăsolvent attraction : When the solute is non-volatile, it is always invariably a solid. The
concentration units parts per million (ppm) and parts per billion (ppb).
reason a solid would dissolve in a liquid is the attraction that the solvent has for the molecules/

SOL UTIONS SOL UTIONS

 QUIZRR 5 6 QUIZRR
ions of the solute. Therefore, there is a strong solute-solvent attraction present in the solution. For a solution of different compositions made from A and B, the plot of PA , PB against A and
Moreover, this attraction would be dependent on the nature of solute, as different solutes will B is shown as follows :
have different extent of attraction with the same solvent. To do away with the dependency on
the nature of solute, we would like this attraction to have negligible impact on the vapour I n th
thee g
grr ap
aphh
pressure of a solution.
Two dotted lines 1 and 2 show variations in partial pressure
P PBO
Reduction in the number of solvent molecules : When a non-volatile solute is dissolved in 3
with increasing mole fraction and the solid line 3 gives the
a liquid, it distributes itself homogenously throughout the solution. Therefore, it occupies the total vapour pressure P exerted by the solution as a whole PAO 2
surface of the liquid also. This reduces the number of solvent molecules present per unit area on at any composition.
1
the surface. This further diminishes the number of vapour molecules that are in equilibrium with PB
Note : The solutions which obey RaoultÊs Law at all compo-
the molecules of the liquid present per unit area on the surface. Thus, the vapour pressure gets PA
sitions of solute in solvent are called as Ideal Solutions.
reduced.
The plot of partial pressure Vs mole fraction of such solution
The first cause would be dependent on the nature of solute and the second cause is independent is typical and in general like the graph shown here.
of the nature of solute. To eliminate the first cause, we propose that those solutions in which the mole fraction (X)
When solute is non-volatile : In such a solutions, the XB = 0 XA = 0
solvent content is very high and the solute content is very low (highly dilute solutions) are the
surface molecules of only solvent will escape and contribute
ones in which the nature of solute plays an insignificant role towards lowering the vapour
to the vapour phase i.e., there is no contribution from solute in the vapour phase. The vapour
pressure of a solution. This is because the solute amount being very small, the change in the
pressure of such a solution is equal to the partial vapour pressure of solvent molecules (= PA).
vapour pressure on changing the nature of the solute would also be small. Such infinitely dilute
solutions are called ideal solutions. In these solutions, the lowering of vapour pressure depends P = PA = PĈA A (from RaoultÊs law)
only on the amount of solute and not on its nature. For binary solution : A + B = 1  A= 1 ă B

R AO
AOUU LT
LT’’ S LA
LAWW PA0  PA
  B
P 0A
The partial vapour pressure of a component in such type of solution is given by RaoultÊs Law.
It states that the partial vapour pressure of each component in the solution is directly proportional
to its mole fraction. PA0  PA
The expression is called as Rela tive Lowering of Vapour Pressure for a solution.
Let A and B be the mole fractions of solvent (A) and solute (B) molecules in the solution and P0A
PA and PB be the partial pressures of A and B respectively. Then according to RaoultÊs Law :
Another form of RaoultÊs Law can now be stated as :
PA  A and
Relative Lowering of vapour pressure for a solution containing non-volatile solute is equal to the
PB  B
mole fraction of the solute.
From the results of various experiments, it has been observed that :
PA = PĈA A and Ideal Solution
PB = PĈ B B Ć An ideal solution consisting of two components A and B is one in which the intermolecular
PĈ A and PĈ B are vapour pressures of pure A and B. attraction A ... A, B ... B and A ... B are equal. For such cases,

Now the total vapour pressure (P) of the solution is given by DaltonÊs Law of partial pressures Hm = 0, Vm = 0 (m stands for mixture)
as follows:
In such cases there is no deviation from RaoultÊs law
P = PA + PB
Ć If attraction A ... B are greater than average of A ... A and B ... B attraction then vapour
 P = PĈA A + PĈ B B pressure of the mixture is less than the expected value. In such cases, V m = ă ve,

SOL UTIONS SOL UTIONS

 QUIZRR 7 8 QUIZRR
Hm = ăve,and there is ă ve deviation from RaoultÊs law. Boiling point in such cases is larger Deviation from RaoultÊs Law
than expected. Positive Negative Zero
Ć If A ... B attractions are smaller than the average of A ... A and B ... B attractions deviation deviation deviation
then vapour pressure of the mixture is larger than the expected value. For such cases, H = + ve)
(  H = ă ve)
( H = 0)
(
Vm = + ve, Hm = + ve, and there is + ve deviation from RaoultÊs law. (i) ethanol + cyclohexane (i) acetone + chloroform (i) benzene + toluene

Boiling point in such cases is smaller than expected. (ii) acetone + carbon (ii) benzene + chloroform (ii) n-hexane + n-heptane
disulphide
(iii) acetone + benzene (iii) nitric acid + chloroform (iii) ethyl bromide + ethyl iodide
PoA
(iv) ethanol + acetone (iv) acetone + aniline (iv) chlorobenzene + bromo
V.P.
benzene
l
P oB Pt ota (v) ethanol + water (v) water + nitric acid
(vi) carbon tetrachloride + (vi) diethyl ether + chloroform
PA chloroform

PB Ptotal P oA
0 XA 1 V.P.
1 XB 0
P oB PA
 
 Vapour pressure diagram for real solutions of two liquids A and B that exhibit a negative 
 
 deviation from RaoultÊs law. The vapour pressure of both A and B are less than predicted  PB
 
 by RaoultÊs law. The dashed lines represent the plots for ideal solutions. 
PB
A mixture of chloroform and acetone forms a solution with negative deviation from RaoultÊs XA
0 1
law. Chloroform (CHCl3) molecule is hydrogen-bonded to acetone (CH3COCH3) as shown : 1 XB 0

CH3 Cl  Vapour pressure diagram for real solutions of two liquids A and B that exhibit a positive deviation 
 
C O H ·C Cl  from RaoultÊs law. The vapour pressure of both A and B are greater than predicted by RaoultÊs 
 
CH3 Cl  law. 
The dashed lines represented the plots for ideal solutions.
This results in decrease of escaping tendency of molecules for each component and thus Ć In case of + ve and ă ve deviations the boiling point composition curves have minima or
vapour pressure decreasesăa case of negative deviation. maxima. The separation of such solutions into their component canÊt be obtained by simple
or fractional distillation and these are called azeotrope mixture. An azeotropic mixture
Mixture of ethanol and acetone forms a solution with positive deviation. Ethanol molecules
boils at a constant temperature and distills over without undergoing any change in its
are H-bonded. If acetone is added, these molecules get in between ethanol molecules and
composition.
thus H-bonding breaks. This changes the intermolecular pattern and escaping tendency of
ethanol and acetone molecules increases and thus vapour pressure increasesăa case of There are two types of azeotropes called as minimum boiling azeotrope and maximum
positive deviation. boiling azeotrope, respectively. Solutions of ethanol and water show such a large deviation
from RaoultÊs law that there is a maximum in the vapour pressure curve and hence a
minimum in the boiling point curve.
SOL UTIONS SOL UTIONS
 QUIZRR 9 10 QUIZRR
Ex a m pl
plee 1
hence, P Total = PA XA + PB (1 ă XA)
How many grams of sucrose must be added to 360 g of water to lower the vapour pressure
also X´ A = mole fraction of A in the vapour = 0.35
by 1.19 mm Hg at a temperature at which vapour pressure of pure water is 25 mm Hg ?
Solution : PA XA
X´A =  0.35
Given P = 1.19 mm Hg PA X A  PB

1  X A 
Psolvent = 25 mm Hg
By RaoultÊs law 575 X A
= 575 X  390 1  X
A  A
P
= Xsolute this gives X A = 0.27
Psolvent
hence, total pressure
1.19 P total = 575 ï 0.27 + 390 ï 0.73
 Xsolute =  0.0476
25 = 440 Torr
 Xsolvent = 1 ă 0.0476 = 0.9524 Composition of liquid mixture,
 A = 27 mol %, B = 73 mol %
n solvent
= 0.9524 Total pressure = 440 Torr
ntotal

Ex
Exaa m pl
plee 3
360
nsolvent =  20
18 At a certain temperature, the vapour pressure of pure ether is 646 mm and that of pure
acetone is 283 mm. Calculate the mole fraction of each component in the vapour state if
nsolvent 20 the mole fraction of ether in the solution is 0.50.
 ntotal = =  21
0.9524 0.9524 Solution :

 nsolute = 21 ă 20 = 1 = 1 ï 342 g In the given solution, both ether and acetone are volatile, so from RaoultÊs Law, we can have
= 342 g vapour pressure of solution (P).
Let A : ether and B : acetone
Ex
Exaa m pl
plee 2
P = P A + PB = PA0 A + PB0 B
The vapour pressure of pure liquid A at 300 K is 575 Torr and that of pure liquid B is 390
Torr. These two compounds form ideal liquid and gaseous mixtures. Consider the equilib-  P = 646 ï 0.5 + 283 ï 0.5 = 464.5 mm
rium composition of a mixture in which the mole fraction of A in the vapour is 0.35. Now mole fraction in vapour state is given as follows :
Calculate the total pressure of the vapour and the composition of the liquid mixture.
PA P0  646  0.5
Solution : A (vapour) = = A A = = 0.695
P P 464.5
A and B are volatile liquids, given

PA = 575 Torr, PB = 390 Torr PB P0 283  0.5

B (vapour) = = B B = = 0.305
P P 464.5
let mole fraction of A in solution = XA

SOL UTIONS SOL UTIONS

 QUIZRR 11 12 QUIZRR
Colligative Properties Calculation of molecular mass from relative lowering of vapor pressure
Certain properties of solutions depend only on the number of particles of the solute (molecular or A known mass WB of the non-volatile solute is dissolved in a known mass (WA) of the volatile
ions) present in definite volume of the solution and do not depend on the nature of solute. Such solvent to prepare a dilute solution and relative lowering of vapor pressure is determined ex-
properties are called colligative properties. perimentally. Knowing the molecular mass (MA) of the solvent, molecular mass (M B) of the solute
can be determined as follows :
A few colligative properties are :
(i) Relative lowering of vapour pressure WA WB
nA = M , nB = M
A B
(ii) Elevation of boiling point
(iii) Depression in freezing point nB WB / MB
XB = n  n = W / M  W / M
(iv) Osmotic pressure A B A A B B

Relative lowering of vapor pressure is given by

(i) Relative lowering of vapour pressure :
The relative lowering of vapour pressure is a colligative property as it depends only on the P P0A  PA WB / M B
  XB 
concentration of the solute and it is independent of its nature. PA0 PA0 WA / MA  WB / MB
Consider a binary solution consisting of non volatile solute in a volatile solvent. The vapour
For dilute solutions WB /M B << WA /MA and hence in the above expression W B/MB may be
pressure of the solution (P) is equal to vapor pressure of solvent (PA) in the solution, which in
neglected in the denominator as compared with WA /M A.
turn is directly proportional to its mole fraction in solution.
P = PA P0A  PA WB / M B WB MB
 
PA0 WA / MA MB WA
= PA0 A ... (i)

where  A = mole fraction of solvent WBM A  PA0 

MB   0 
If mole fraction of solute is B then WA P P 
 A A
A +  B = 1 or A = 1 ă B ... (ii)
In this expression all the parameters are known except MB and hence M B can be calculated.
From eq. (i) and (ii) PA = PA0 (1 ă B) = P0A ă PA0 B
Ex
Exaa m pl
plee 4
PA0 ă PA = PA0 B
Dry air was passed through a container having a solution of a non-volatile solute in water.
The solute weighed 26.66 g and the solvent weighed 200 g. The air then went into a solvent
P0A  PA container and then finally through a tube containing fused calcium chloride. The loss in
 B
PA0 weight of water container is 0.087 g and gain in weight of CaCl2 tube is 2.036 g. Calculate
the molecular weight of the non-volatile solute present in the solution.
Solution : We can use the relation
P0A  PA
 B
PA0 P0  Ps n loss in weight of solvent
 = loss in weight of solution
Ps N
is called the relative lowering of vapor pressure and is equal to the mole fraction of the solute.
26.66
0.087 M 26.66  18 26.66  18  1.949
P nB n =  ; M  53.75
Now,  B   B {for dilute solutions : nA + n B  nA} 2.036  0.087 200 200  M 200  0.087
PA0 nA  nB nA
18

SOL UTIONS SOL UTIONS

 QUIZRR 13 14 QUIZRR
EL EV
EVAT
AT
ATII ON O
OFF B
BOI
OI
OILL IN
INGG PO
POII NT Boiling Point Elevation Constant (Kb ) : It is the elevation in point achieved when a solution
of a non-volatile solute of concentration 1 molal is boiled. Its boiling units are K kg molă1. Kb is
The boiling point of a liquid may be defined as the temperature at which the vapor pressure of
related to molar enthalpy of vaporization as
the liquid becomes equal to the atmospheric pressure.

Y M RTb2
Kb 
Hvap  1000
Atmospheric Pressure
B D where M = molar mass of solvent,
P
t R = Universal gas constant,
en
sol v Tb = boiling point of pure solvent and
P´ re
Pu n H vap = enthalpy of vaporization of solvent.
ti o
lu
Vapor Pressure

A So
Ex
Exaa m pl
plee 5
C
A solution containing 0.512 g of naphthalene (molar mass 128.2 g molă1 ) in 50 g CCl 4 yields
 Tb a boiling point elevation of 0.402 K, while a solution of 0.6216 g of an unknown solute in
the same mass of the solvent gives a boiling point elevation of 0.647 K. Find the molar mass
X
Temprature T0 T1 of the unknown solute.
Solution :
The vapor pressure curves for the pure solvent and solution consisting of a non-volatile solute is Tb, ă Tb,CCl = Tb, = K b mnaphthalene
naphthalene 4 naphthalene
represented diagrammatically. AB is the vapor pressure curve for pure solvent and CD is vapor
Tb, unknown solute
ă T b,CCl = Tb, unknown solute
= Kb m unknown solute
pressure curve for the solution. T0 represents the boiling point of pure solvent and T1 represents 4
the boiling point of solution. In the presence of a non-volatile solute the solution has to be heated  Tb, unknown solute
ă Tb, naphthalene
= Tb, unknown solute
ă T b, naphthalene
to a slightly higher temperature so that the vapor of the solution becomes equal to atmospheric = Kb ï (munknown solute
ă mnaphthalene )
pressure and solution begins to boil. The differences in the boiling points are represented as Tb ,
which is the elevation in boiling point. Tb, naphthalene 0.402K
Kb  
mnaphthalene  
T b = K b m  
 0.512 g   1000 kg1
Kb : molal boiling point elevation constant or ebullioscopic constant of solvent  128.2 g mol1 
m : molality of the solution  50 g 
 

n  0.402  50  128.2
Hence, Tb  K b  B  1000  Kb   5.03 K kg mol1
 gA  0.512  1000

1000 K b g B  0.6216 g  1000 g kg  1 0.512 g  1000 kg 1 

 Tb  0.647 K  0.402 K  5.03 K kg mol 1   
gA M B  Mg mol 1  50g 128.2g mol 1  50 g
 

Solving for M we get,

M = 96.68 g molă1.

SOL UTIONS SOL UTIONS

 QUIZRR 15 16 QUIZRR
DE PR
PREE SS
SSII ON I N F R EE
EEZI
ZI
ZINN G P O IN
INTT The phenomenon of osmosis may be illustrated in a simple man-
ner by tying an animal membrane, e.g., bladder, over the end of
Freezing point of a substance is defined as the temperature at which the vapor pressure of the
an inverted thistle tube, which is then partly filled with a concen-
solid form is in equilibrium with liquid form of the substance. In other words, solid and liquid
trated solution of sucrose (cane sugar) and dipped into a beaker
forms of the substance has same vapor pressure. Since the vapour pressure of a solution is less Hydrostatic
of water, as shown in the given figure. The level of the liquid will
than that of pure solvent, the freezing point of the solution will be lower than that of pure Pressure
rise in the tube until the hydrostatic pressure so produced is
solvent.
sufficient to stop the flow of water. It is seen, therefore, that as
Let Tf be the depression in freezing point, then a result of osmosis, a pressure is developed which opposes the Sucrose
solution
Tf = T f ă T0 tendency for the solvent to pass through the semipermeable
Membrane
membrane into the solution. This pressure is called the osmotic
Tf : freezing point of solution
pressure of the solution. It is defined as „the excess pressure
T0 : freezing point of pure solvent that must be applied to a solution to prevent the passage
Water
Tf = K f m into of solvent when the liquids are separated by a per-
fectly semipermeable membrane‰.
K f : molal boiling point elevation constant or cryoscopic constant of solvent.
There has been some tendency to think pressure as a pressure produced by the solution, but this
m : molality of solution point of view is misleading. The osmotic pressure is brought into existence only when the solution
is separated from the solvent by a semipermeable membrane. The resulting osmosis or tendency
1000 K f gB
T f  for osmosis to occur then produces an excess pressure in the solution. When this excess pressure
gA M B
attains the value of the osmosis pressure, the tendency for solvent to enter the solution is exactly
Final point Depression Constant (Kf) : It is the depression in freezing point achieved when counterbalanced by the reverse tendency and a condition of equilibrium results.
a solution of a non-volatile solute of concentration 1 molal is frozen. Its units are K kg molă1 . For the accurate measurement of osmotic pressure, it is necessary to have a membrane that is
Kf is related to the molar enthalpy of fusion as perfectly semipermeable. Artificial membranes made of copper ferrocyanide, Cu 2Fe(CN)6 , is the
best material for osmosis.
M RT12 The osmotic pressure of a dilute solution of a non-volatile solute is given by V = nRT
Kf 
Hfusion  1000
n
 RT
where M = molar mass of solvent, V

R = universal gas constant,

w RT
Tf = freezing point of pure solvent and 
M V
Hfusion = enthalpy of fusion of solid solvent
w 
where  is the osmotic pressure in atmospheres, n = number of moles of solute   in V litres
M
4. O S MO
MOTI
TI
TICC P RE
RESS SU
SURE
RE of solution at temperature T (Kelvin), R = 0.0821 Lit atm K ă1 mol ă1. C is the molarity of the
Osmosis is defined as the spontaneous flow of solvent into solution or from a more dilute to a more solution. Measurement of osmotic pressure provides a method of determining molecular weights
concentrated solution, when the two solutions are separated by a suitable membrane. The mem- of proteins, polymer and other macromolecules.
brane allows the free passage of the solvent but not of the dissolved substances. Membranes If two solutions are of equal concentrations at the same temperature, they have the same osmotic
possessing this property are said to be semipermeable. pressure and they are said to be isotonic. If two solutions have unequal osmotic pressures, the
more concentrated solution is said to be hypertonic and the more dilute solution is described as
hypo tonic. To study the contents of red blood cells, which are protected by a semipermeable

SOL UTIONS SOL UTIONS

 QUIZRR 17 18 QUIZRR
membrane, a technique called haemolysis is used. The red blood cells are placed in a hypo tonic
weight of solute
solution, when water moves into the cells. The cells swell and eventually burst releasing the  % By weight =  100
weight of solution
haemoglobin and other molecules.
When a bacterial cell is placed in a hypertonic solution (high concentration), the intracellular  Wt. of water = 85 g; wt. of urea = 5 g; wt. of glucose = 10 g
water tends to move out of the cell by osmosis. This causes the cell to shrink. T = TUrea + TGlucose

Ex a m pl
plee 6 1000  1.86  5 1000  1.86  10
T = 
60  85 180  85
Find the molecular weight of the polymer having the concentration of 9.6 g/l and exerting
an osmotic pressure of 2.56 torr at a temperature of 298 K. = 1.824 + 1.216 = 3.04
Solution :  Freezing point = 0 ă 3.04 = ă 3.04ĈC
      = CRT
Ex
Exaa m pl
plee 9
2.56 9.6  0.0821  298
 1.4 g of acetone dissolved in 100 g of benzene gave a solution which freezes at 277.12 K.
760 M
Pure benzene freezes at 278.4 K. 2.8 g of a solid (A) dissolved in 100 g of benzene gave a
or M = 69727.5 g/mol. solution which froze at 277.76 K. Calculate the molecular weight of (A).
Solution :
Ex
Exaa m pl
plee 7
For acetone + Benzene mixture :
A very small amount of a non-volatile solute (that does not dissociate) is dissolved in 56.8
cm3 of benzene (density 0.889 g cmă3). At room temperature, vapour pressure of this solu- K´f  1000  w
tion is 98.88 mm Hg while that of benzene is 100 mm Hg. Find the molality of this solution. T =
mW
If the freezing temperature of this solution is 0.73 degree lower than that of benzene, what
is the value of molal freezing point depression constant of benzene ?
1000  Kf  1.4
Solution : (278.40 ă 277.12) =
100  58

P  Ps w M 100  98.88 w  78  1000

        1000  Kf  1.4
Ps m W 98.88 m  W ï 1000
or 1.28 = ...(1)
100  m

 w  1000  1.12  1000 For solute (A) + Benzene mixture (Let m be the mol. weight of A)
or molality    0.1452
 m  W  78  98.88
1000  K f  2.8
Also T = K´f ï molality (278.40 ă 277.76) =
100  m
0.73 = K´f ï 0.1452  K´ f = 5.028 K molality ă1
1000  K f  2.8
Ex
Exaa m pl
plee 8 or 0.64 = ...(2)
100  m
An aqueous solution containing 5% by weight of urea and 10% by weight of glucose. What
By Eqs. (1) and (2), m = 232
will be its freezing point ? K´f for H2 O is 1.86Ĉ molă1 kg.
Solution :  Solution has 5% by weight urea and 10% by weight glucose

SOL UTIONS SOL UTIONS

 QUIZRR 19 20 QUIZRR
Ex a m pl
plee 10 By Eqs. (1) and (2),

If boiling point of an aqueous solution is 100.1ĈC. What is its freezing point ? Given latent
heat of fusion and vaporization of water are 80 cal gă1 and 540 cal gă1 respectively.  Tf  A mB 3  mA 1 
    
Solution :  Tf  B =
mA 1  mB 3 

For a given aqueous solution

For solution S1 : Let 2V mL solution of A is mixed with 3V mL solution of B.
Tb = K´b ï molality
5  2V 10V
Weight of A in 2V mL or 2V g = g = g
100 100
Tf = K´f ï molality
5  3V 15V
Weight of B in 3V mL or 3V g = g = g
 Tb K ´b RTb2 1000lf 100 100
 = = 
 Tf ´
Kf 1000l v RTf2
Total weight of solution = 5V

 Tb Tb2  lf  0.1V 0.15V 

K f  1000   
 Tf =  mA m B  1000K f 0.1m B  0.15m A 
Tf2  lv  Tf S1 
 10V 

4.9  mA  mB
5V 
 Tb = 100 + 273 = 373 K  100 

Tf = 0 + 273 = 273 K
For solution S 2 : Similarly, have
lf = 80 cal g ă1
lv = 540 cal gă1 1000  K f 0.15m B  0.10mA   0.9898
( T f)S =
2 4.85  mA  mB
Ex
Exaa m pl
plee 11

Two solutions of non-volatile solutes A and B having molar mass ratio of A and B (M A/MB)
as 1/3 are prepared by dissolving 5% (wt./vol.) of each in water. Calculate the ratio of
 Tf  S1 (0.1 mB  0.15 mA )  0.9898
freezing point depression. If the two solutions are mixed to prepare a new solution (S1) by
Thus,
 Tf S2 =
(0.10 mA  0.15mB )
mixing in the ratio 2 : 3 by volume and another new solution (S 2) is obtained by mixing in
  S1
Tf
(0.1 3 mA  0.15 mA )  0.9898
the ratio 3 : 2, find out
 Tf  S2 . Assume density of solution A and B equal to one. =
(0.10m A  0.15  3m A )
Solution :
For 5% solution of A : 0.45  0.9898
=  0.81
0.55
K f  5  1000
( T f )A = ... (1)
m A  95
VA
VAN’
N’
N’TT H O FF F AC
ACTO
TO
TORR (i )
For 5% solution of B :
Since colligative properties depend on the number of particles of the solute, in some cases where
K f  5  1000
( T f )B = ...(2) the solute associates or dissociates in solution, abnormal results for colligative properties are
m B  95
obtained.

SOL UTIONS SOL UTIONS

 QUIZRR 21 22 QUIZRR
Dissociation : Let us consider the case of acetic acid dissolved in water. Let the number of mole
of acetic acid dissolved be ÂnÊ.  
n 1  
Experimental colligative property  2 

   1   i , VanÊt Hoff factor
 CH COOă + H+
CH3COOH  Theoretical colligative property n 2
3

Initial no. of mole n 0 0 Therefore, for dissociation i > 1 and for association i < 1. When a solute neither dissociates nor
After dissociation n(1 ă ) n n associates, the VanÊt Hoff factor is equal to 1.
Total mole of solute = n(1 + )
Ex
Exaa m pl
plee 12
Theroctical colligative property (for example Tb) based on the number of mole of CH 3COOH
added) Acetic acid associates in benzene to form a dimer. 1.65 gm of acetic acid when dissolved in
100 gm of benzene raised the B.P. by 0.36ĈC. Calculate the VanÊt Hoff factor and degree of
n
Tb = Kb m = Kb ï  1000 , where W is the mass of solvent in gm. association of acetic acid. (k b for benzene = 2.57 ĈC/m )
W
Solution :
Experimental colligative property would be given by Calculation of VanÊt Hoff factor :
First calculate molecular mass from elevation in boiling point
n(1  )
T´ b = K b m´ = Kb ï  1000
W 1000 kb gB
MB =
g A  Tb
Experiment colligative property n  1   
  1     i, VanÊt Hoff factor
Theoretical colligative property n 1000  2.57  1.65
=  117.8
100  0.36
Association : Let us consider the case of acetic acid dissolved in benzene. Let the number of mole
of acetic acid dissolved be ÂnÊ it forms dimer in benzene. Normal molecular mass
 i =
observed molecular mass
2CH3COOH 

 (CH 3COOH)2

60
=  0.509
Initial no. of mole n 0 117.8
After dissociation n(1 ă ) n/2 Calculation of degree of dissociation
Total mole of solute = n(1 ă /2) Let x = degree of dissociation
2CH3COOH  (CH 3COOH)2
Theoretical colligative property (for example Tb) (based on the no. of mole of CH 3COOH added)
1 0
n 1 ă x x/2
Tb = K b m = K b ï  1000 , where W is the mass of solvent in gm.
W Total mass = 1 ă x/2

Experimental colligative property would be given by x

1
total mass 2
i 
  initial mass 1
n 1  
T´ b = K b m´ = Kb ï  2
 1000
W x
1
 0.509 = 2  x = 0.982
1

SOL UTIONS SOL UTIONS

 QUIZRR 23 24 QUIZRR
Ex a m pl
plee 13
Normal molar mass 60 g mol 1
When dissolved in benzene, a compound C38H 30 partially dissociates by the following equa- VanÊt Hoff factor = Observed molar mass 
118g mol1
tion : C38H30  2 C19 H 15. 25.6 gm of C 38 H30 is dissolved in 400 gm of benzene, the freezing
point is lowered by 0.680ĈC. What % age of C38H 30 molecules have dissociated ? (k f = 4.9)   1    1 
= 0.508  1    1  n    1    1  2    1   / 2
Solution :      
Calculate observed molecular mass (due to dissociation) as done in above example and then by /2 = 1 ă 0.508 = 0.492
calculating i, find x.
  = ï 0.492 = 0.984
OR Use the following approach.
Thus acetic acid is 98.3% associated in benzene.
Tb = i kb m
Now, if we include VanÊt Hoff factor in the formular for colligative properties we obtain the
normal results.
 Tb  gA 0.68  400
i 
kb ( gB / MB )  1000 25.6
4.9   1000 P1o  P1 n
486 1. Relative lowering of vapour pressure,  iX 2  i
P1o n N
 i = 1.0538
2. Osmotic pressure,  = iCRT
C38H 30  2 C19 H15
3. Elevation in boiling point, Tb = i. 1000 ï K b ï molality
1 ă x 2x 4. Depression in freezing point, Tf = i 1000 ï Kf ï molality
Total mass = 1 ă x + 2x = 1 + x Note : The value of i is taken as one when solute is non electrolyte.
total moles
i
initial moles Ex
Exaa m pl
plee 15
A 0.5 percent aqueous solution of Potassium Chloride was found to freeze at 0.24ĈC. Cal-
1 x culate the VanÊt Hoff factor and degree of dissociation of the solute at this concentration
 1.0538 
1
(Kf for water is 1.86).
 x = 0.0538 Solution :
 % age of dissociation = 5.38%
i  1000 K f w
T f =
W. M
Ex
Exaa m pl
plee 14

Acetic acid (CH3COOH) associates in benzene to form double molecules. 1.65 g of acetic acid i  1000  0.5  1.86
0.24 =
when dissolved in 100 g of benzene raised the boiling point by 0.36ĈC. Calculate the VanÊt 100  74.5
Hoff factor and the degree of association of acetic acid in benzene (Molal elevation con-
stant of benzene is 2.57). 0.24 100 74.5
i =  1.923
1000  0.5  1.86
Solution :
Normal molar mass of acetic acid = 60 i = 1 + (n ă 1)
1.923 = 1 + (2 ă 1)
Observed molar mass of acetic acid
1.923 = 1 + 
wsolute 2.57  1.65  1000  = 1.923 ă 1 = 0.923
M  Kb  1000   118
Wsolvent  in gms  T 100  0.36 or  = 0.923 or 92.3%

SOL UTIONS SOL UTIONS

 QUIZRR 25 26 QUIZRR
S OL
OLVE
VE
VEDD E XA
XAMM PL
PLES
ES As both solutions are isotonic,
 KCl = glucose
Ex
Exaa m pl
plee 1

If the apparent degree of ionization of KCl (KCl = 74.5 gm molă1 ) in water at 290 K is 0.86. w1 40
1.86   RT =  RT
74.5 180
Calculate the mass of KCl which must be made up to 1 dm3 of aqueous solution so as to
produce the same osmotic pressure as the 4.0% solution of glucose at that temperature.
40 74.5
Solution :  W1 = 
180 1.86
Due to ionization of KCl
= 8.9 gm
KCl  K+ + Clă
Ex
Exaa m pl
plee 2
Initial moles 1 0 0
1 kg of an aqueous solution of Sucrose is cooled and maintained at ă 4ĈC. How much ice
Moles after dissociation 1 ă   
will be separated out if the initial molality of the solution is 0.75 ?

i
1    Solution :
 1  
1 Sucrose is a non-electrolyte, hence i = 1
Molecular weight of sucrose (C12H 2O11) = m = 342 gm mol ă1
From question, degree of ionization =  = 0.86
Molality of the solution = 0.75 m
 i = 1 + 0.86 = 1.86
= 0.75 mol kgă1 solvent
For Osmotic pressure of glucose,
= 0.75 ï 342 gm Sucrose per kg solvent
For 4% glucose solution, Weight of glucose = 40 gm,
= 256.5 gm Sucrose per kg solvent
Volume of solution = V = 1 L = 1 dm3
Hence, weight of 1 molal solution = 1000 + 256.5 = 1256.5 gm
Molecular weight of glucose C6H 12O6 = m = 180
256.5
Sucrose present in 1 kg solution =  1000 = 204.14 gm
1 1256.5
 glucose = n   RT, where glucose = osmotic pressure of glucose
V
Weight of solvent (H 2O) present in 1 kg solution = 1000 ă 204.14 = 795.86 gm
Since depression in freezing point
w 1 40 1
=  R T =   RT
m V 180 1 w 1000
Tf = K f ï i ï ï
m W
Similarly, KCl = i  n  1 RT = 1.86  n  1  RT Where W = weight of solvent
V V
w = weight of the solute
w 1
= 1.86  1   RT 204.14 1000
m1 V or, 4 = 1.86 ï 1 ï 
342 W

 W = 277.55 gm
= 1.86  w 1  1  RT
74.5 1 i.e., weight of solvent required to maintain this solution at ă 4ĈC is W = 277.55
Hence rest weight of H 2O will convert into ice.
Hence amount of ice formed = 795.86 ă 277.55 = 518.31 gm

SOL UTIONS SOL UTIONS

 QUIZRR 27 28 QUIZRR
Ex a m pl
plee 3
1000  K b  w
Also, Tb =
The osmotic pressure of an aqueous solution of sucrose is 2.47 atm at 303 K and the molar Wm
volume of the water present is 18.10 cm3. Calculate the elevation in boiling point of the
solution. Given  H vap = 540 cal/g. Assume volume of solvent equal to volume of solution. 1000  0.513  24
=  0.354
Solution : 600 58
 = CST
 B. pt. of solution = 99.725 + 0.354
2.47 = C ï 0.0821 ï 303
= 100.079ĈC
 C = 9.93 ï 10ă2 M
Thus, 1 litre solution of sucrose contains 9.93 ï 10ă2 mole of sucrose or 9.93 ï 10ă2 ï 342 g of Ex
Exaa m pl
plee 5
sucrose.
A 0.025 M solution of a monobasic acid has a freezing point of ă 0.06ĈC. Find the value of
 Volume of solution = Volume of solvent = 1000 mL
Ka of this acid. Kf of water = 1.86 K/m. Assume that molarity is equal to molality.
1000 Solution :
 Mole of water =
18.10 Calculate VanÊt Hoff factor using the relation :
T f = i Kf m Taking m  M
1000
 Weight of water =  18 = 994.475 g
18.10
 Tf 0.06
 i    1.29
2
Kf m 1.86  0.025
9.93  10
Thus, molality of solution =  9.985  10 2 M
994.475  10 3 VanÊt Hoff factor is given as :
HA  H+ + Aă
RTb2
T b = Kb ï molality =  molality 1 ă   
1000l
total moles 1
i 
2  373  373
 9.985  10  initial moles 1
2
= 1000  540
 i = 1 +  = 1.29          = 0.29
= 5.145 ï 10ă2 +
HA  H + A

Ex
Exaa m pl
plee 4 c ă c c c

The molecular weight of an organic compound is 58 g/mol. 24 g of this dissolved in 600 g 2

C 2 0.025   0.29
 2.96  10 
of water, calculate its boiling point when vapour pressure of water becomes 760 mm at 3
 Ka  
1 1  0.29
99.725ĈC. Kb of H2 O is 0.513 K kg molă1 .
Solution :
Ex
Exaa m pl
plee 6
B. pt. of H 2O = 99.725ĈC
Given worganic = 24 g, wH = 600 g, 1.0 gm of monobasic acid when dissolved in 100 gm of pure waters lowers the freezing point
compound 2O
by 0.168ĈC. 0.2 gm of the same acid when dissolved and titrated required 15.1 ml of N/10
morganic compound
= 58
base. Determine the degree of dissociation of the acid. Kf of water is 1.86 K/m.

SOL UTIONS SOL UTIONS

 QUIZRR 29 30 QUIZRR
Solution : Freezing point of the solution = 0 ă 19.91ĈC = ă 19.91ĈC
Calculate the molecular mass (observed from colligative property) using the relation : Weight of solution = weight of solute + weight of solvent = 23.94 + 69.888 = 93.828 gm

Kf  gB  1000 1.86  1 1000 wt. of the solution


93.828
 97.99 ml
M0    110.6 Volume of the solution =
 Tf  g A 0.168  100 density of the solution 0.95751

Now calculate the actual molecular mass from neutralisation experiment w1 1000 23.94 1000
Molarity of solution =    mol lită1 = 7.63 M
m1 V(in ml) 32 97.99
0.2
 1000  0.1  15.1 (meq of acid = meq of base)
M /1
Ex
Exaa m pl
plee 8
 M = 132.45
The freezing point of an aqueous solution of KCN containing 0.1892 mol kgă1 of solvent was
M 132.45 found to be ă 0.704ĈC. On adding 0.095 mol of Hg (CN)2, the freezing point of the solution
i  actual   1.19
M0 110.6 was found to be ă 0.530ĈC. If the complex ă formation takes place according to the following
equation.
HA  H+ + Aă
Hg(CN) 2 + nKCN  23
1 ă     Kn [Hg(CN) n+2] (K f = 10 )



 i = 1 +  = 1.19 What is the formula of the complex ? Kf (H2 O) is 1.86 kg molă1 K.

  = 0.19 Solution :
Tf (KCN solution) = 0.704ĈC
Ex
Exaa m pl
plee 7
Molality of KCN solution = 0.1892
30 ml of CH 3OH (d = 0.7980 gm cm ă3 ) and 70 ml of H2 O (d = 9984 gm cmă3) are mixed at 25ĈC i = (1 + x)
to form a solution of density 0.9575 gm cm ă3. Calculate the freezing point of the solution
Tf = Kf ï m ï i
Kf (H2O) is 1.86 Kg mol ă1 K. Also calculate its molarity.
Solution : T f 0.704
i   1  x    2.0
Weight of CH3 OH (w1) = 30 cm3 ï 0.7980 gm cm ă3 = 23.94 gm Kf m 1.86  0.1892

Weight of solvent (H 2O) (w2) = 70 cm 3 ï 0.9984 gm cmă3 = 69.888 gm

This gives x = 1, indicating 100% ionization of KCN
w1 1000
 Tf of the complex = 0.530
 Molality of solution =
m1 w2
Molality of Hg (CN)2 = 0.095 mol kgă1
Where m1 = molecular weight of CH 3OH = 32
Kn[Hg(CN) n+2] 

 nK+ + [Hg(CN)n+2] ă
23.94 1000
m =   10.7046 m 1 0 0
32 69.88
1 ă  n 
As we know that
here i = (1 ă ) + n +  = 1 + n
Depression in freezing point, Tf = Kf ï i ï molality,
For CH3 OH, i = 1   = 1

Tf = 1.86 ï 10.7046ĈC = 19.91ĈC  i = 1+ n

SOL UTIONS SOL UTIONS

 QUIZRR 31 32 QUIZRR
Tf = Kf ï i ï molality 278.4 ă 277.4 = 5 ï i ï 0.262
0.503 = 1.86 ï 1 ï 0.095 or 1 = 5 ï i ï 0.262

0.503 1
i 3 i  0.262
1.86  0.095 5

= 0.763
1 + n = 3
1 ă /2 = 0.763
or n = 2
  = 0.47
Hence, the complex is K2[Hg(CN) 4]
Hence the molality of A after dimer is formed = (1 ă ) ï initial molality

Ex
Exaa m pl
plee 9 = (1 ă 0.48) ï initial molality
= 0.52 ï 0.262
The freezing point of a solution of acetic acid (mole fraction is 0.02) in benzene 277.4 K.
Acetic acid exists partly as a dimer 2A  A 2. Calculate equilibrium constant for 
Molality of A2 after dimer is formed =  molality
dimerisation. Freezing point of benzene is 278.4 k and (Kf for benzene is 5). 2
Solution :
0.48
Let acetic acid = A =  0.262
2
Benzene = B
= 0.24 ï 0.26
Assume,  part of A forms dimer
= 0.06288
2A 

 A2 The equation constant

1 0
 A2   0.06288
1 ă  /2 Keq =
 A2 (0.13624)2

1      / 2 = 3.39 kg molă1
 i =
1
Ex
Exaa m pl
plee 10
= 1 ă /2
Mol. fraction of A = xA = 0.02 Find Ka , the ionization constant of tartaric acid if a 0.100 molal aqueous solution of tar-
taric acid freezes at ă 0.205ĈC. Assume that only the first ionization is of importance and
Mol. fraction of B = xB = 0.98
that 0.1 m = 0.1 M. Kf = 1.86 kg molă1 K.
x A 1000 Solution :
Molarity of A in B = m  X
B B
Assuming that the tartaric acid be a monobasic as AH. It ionizes as

0.02 1000
 AH 

 A + H+
=
78 0.98
Initially conc. C 0
= 0.262 mol kgă1 of Benzene
Conc. after dissociation C(1 ă ) C C
Since Tf = Kf ï i ï molality

SOL UTIONS SOL UTIONS

 QUIZRR 33

C(1  )  C   C 
Here, i = , where  = degree of dissociation
C

C(1  )
=  1 
C

Molal concentration = 0.1

Tf = Kf ï Cm ï 1
  = 0.1

 A    H  2
    C   C   C
Ka =
 AH C 1    1  

 0.12  0.1
 1.11  10 
3
Ka = The only app you need to prepare for
1  0.1

 Ka = 1.11 ï 10ă3.
JEE Main JEE Adv. BITSAT WBJEE MHT CET and more...

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available

With MARKS app you can do all these things for free

Solve Chapter-wise PYQ of JEE Main, JEE Advanced, NEET, BITSAT, WBJEE, MHT CET & more

Create Unlimited Custom Tests for any exam

Attempt Top Questions for JEE Main which can boost your rank

Track your exam preparation with Preparation Trackers

Complete daily goals, rank up on the leaderboard & compete with other aspirants

SOL UTIONS

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available
 P-BLOCK
The only app you need to prepare for

JEE Main JEE Adv. BITSAT WBJEE MHT CET and more...

4.8
Rating on Google Play
50,000+
Students using daily
2,00,000+
Questions available

ELEMENT
With MARKS app you can do all these things for free

Solve Chapter-wise PYQ of JEE Main, JEE Advanced, NEET, BITSAT, WBJEE, MHT CET & more

Create Unlimited Custom Tests for any exam

Attempt Top Questions for JEE Main which can boost your rank

Track your exam preparation with Preparation Trackers

Complete daily goals, rank up on the leaderboard & compete with other aspirants

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available
 QUIZRR 3 4 QUIZRR
P-BLOCK ELEMENTS (a) Small size

Int rodu
ducctio n : (b) Absence of vacant d-orbital
(c) High IP
The right side of the periodic table having group number 13, 14, 15, 16, 17 and 18 are known
as p-block elements. These elements have 3, 4, 5, 6, 7 and 8 electrons in their outer most shell,
Some Important Characteristics of PăBlock In Tabular Form
respectively. The last electron of these groupsÊ elements occupies the position in p-sub shell that
is why they are called as p-block elements. Their general configuration is ns2np1-6. Sr. No. Property Along period Along group
(left to right) (top to bottom)
So
Somme Impo
porr tant P
Prrop
opee rtie s of P-
P-BBlock

1. Electron affinity : 1. Atomic radii Decreases Increases

Electron affinity increase from left to right along the period amongst the p-block elements and it 2. Ionization potential Increases Decreases
decreases from top to bottom. But group 15 is having exceptionally low values of electron affinity 3. Electron affinity Increases Decreases
and is due to extra stability because of the presence of exactly half filled orbital in their valence 4. Electro negativity Increases Decreases
shell. Similarly, elements of group 18 (noble gases) have zero affinities due to presence of complete
5. Metallic character Decreases Increases
octet which provides them stability.
6. Oxidizing property Increases Decreases
2. Metallic Character 7. Reducing property Decreases Increases

The metallic character is governed by

(i) Size of atoms and GROUP 13 EL
ELEEM ENTS
(ii) Ionization energy.
Elements : B, Al, Ga, In, TI.
The elements having bigger size and low ionization energy has a greater metallic character. After
Group 13 elements are boron (B), aluminium (Al), Gallium (Ga), Indium (In) and thallium (TI).
combining both above mentioned factors we observe that the elements with above two properties
Boron is the only non-metal in this group others are metal. Non-metallic character of boron is due
are located in left corner of p-block and strong non-metallic elements are located at right corner
to its small size and high ionization energy. The general valence shell electronic configuration of
and a diagonal strip of elements thus two, having in between properties are called as metalloids.
these elements is ns2np1.

3. Oxidation state
Gener al Tr
Tree nd
ndss in Physic al Pr
Prop
op
opeert ies
The p-block elements shows variety of oxidation states both positive and negative. Some of the
p-block elements show different oxidation state due to inert ă pair effect, where the lower oxidation Sr.No. Property Boron Aluminium Gallium Indium Thallium
state is more predominant. 1. Configuration 2
[He]2s 2p 1 2
[Ne]3s 3p 1 2
[Ar]4s 4p 1 2
[Kr]5s 5p 2
[Xe]6s26p1
2. Common + 3 + 3 + 3 + 3 + 3, + 1
4. Diagonal relationship
oxidation state
On moving diagonally across the periodic table the element show certain simplarities.
3. Atomic radius 83 143 135 167 170
Li Be B C
(pm)
4. First ionization 801 578 579 558 589
energy (KJ/mol)
Na Mg Al St
5. Electro negativity 2.0 1.5 1.6 1.7 1.8
Note : Elements of 2nd period differ from their own group elements in some of the properties. This
is due to the following reasons :

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 5 6 QUIZRR
1. Density In + 3 oxidation state Al has very high charge to radius ratio (~ 6.0). So, it is also covalent in
Generally increases down the group but aluminium has an exceptionally low density. its anhydrous compounds. However, in aq. solution tricovalent Al (e.g. AlCl3 ) becomes ionic due
to high hydration energy of Al+3 (4665 KJ molă1) [Al(OH 2) 6] 3+.3Clă. The soluble compounds are
2. Melting point and Boiling point quite acidic due to hydrolysis (high charge to radius ratio of Al +3).
B to Ga decrease then Ga to TI increase Ga has lowest M.P. (29.8ĈC) and therefore liquid at room
[Al(OH 2) 6] +3 + H 2O  H3O + + [Al(H 2O) 5OH]+2
temperature.

TI is ionic in + 1 oxidation state, TICl ionic. The TI+ ion resembles K + and Rb+. It is because radii
3. Atomic radii and ionic radii
of the ions are comparable (K+ ~ 1.38 Å, TI ~ 1.5 Å, Rb ~ 1.52 Å). Therefore, TIOH is a strong
On moving from B to TI the size increases due to addition of new energy shells at each step down base like group ă 1 hydroxides. Tricovalent compounds, MX3 , are electron deficient as octet
the group but Ga is smaller than Al. around the central atom is not complete.

F Cl
4. Ionization energy
Generally IE decreases down the group but Ga has higher IE than Al exceptionally due to smaller Al
B
in size as compared to Al.
F F Cl Cl

5. Metallic character (Six electrons around B or Al)

Electropositive character increases down the group hence metalic character also increase down the
Such compounds remove their electron deficiency by :
group but aluminium is having high metallic character than Gallium due to low IE than Ga.
(i) Back ă bonding
6. Inter Pair Effect In BX3, B is sp2 and has a vacant p-orbital perpendicular at the triangular plane. X-atom
has filled p-orbital. The overlap resulting into ăbonding.
When we go down the group in p block element, stable positive valency decreases by a factor of
2. This effect is known as inert pair effect. It arises mainly due to poor shielding effect 3d and F
4d series element. This result into increase in effective nuclear charge and greater hold on valence F
S electrons by nucleus. These s electrons canÊt be pulled easily out which decreases the valency B Resonance
by a factor of 2. B
F F
e.g. In 14th group while carbon & silicon show + 4 valency, while Pb is mostly stable in +2 state. F F

7. Oxidation states and nature of bond (ii) Coordination with Lewis bases
The group ă 13 elements show variable oxidation states of + 3 and + 1. For lighter members + B has vacant orbital which accepts electron pair from F ă.
3 state is more stable than + 1. Thus for Tl, + 1 state is more stable than + 3. It is due to inert F
pair effect. The 6s2 pair does not prefer to form bonds and is called inert pair. The basic reason
ă ă
for such an effect is bond energy. The MăCl bond energy in MCl3 compounds are as follows : B +F BF4
MCl3 MăCl, energy (KJ molă1) F F

Ga 242 Al(OH) 3 + HOă  Al(OH) 4
In 206
(iii) Polymerisation
TI 153
AlCl3 removes electron deficiency by dimerisation.
The ionisation energies of B is very high. It is, therefore, covalent in its compounds, always
tricovalent (2s22p1 electrons).
2AlCl  Al2Cl6
P-BLOCK ELEMENTS P-BLOCK ELEMENTS
 QUIZRR 7 8 QUIZRR
Dimer is made easily because Cl has lp and Al has vacant orbital. Ć Boron reacts directly with elements forming borides which are hard and refractory.

3Mg + 2B  Mg 3B2

Cl Cl Cl
Al Al
Cl Cl Borides are decomposed by acids forming boranes
Cl
Mg 3B 2 + 6HCl  3MgCl2 + B2H6
AlCl 3 is not stabilized by back bonding. It is due to the following facts :
diborane
(i) p-orbital of Al is large, so păp overlap is not effective.
Ć Aluminium is far more reactive than boron but in air and water it is stable. It is due to the
(ii) 8 electron core in Al causes larger repulsion (8e ă 8e) destabilizing back bonding effective.
formation of aluminium oxide, Al2O3 layer, that makes it passive for further attack. HNO3
BX3 can not stabilize by dimerisation. B is small in size. The dimer will have small ring. also makes Al passive by oxide layer formation.
Ć Reaction of Al with O2 is exothermic and is called thermite reaction.
X X X
B B
X X 3
X 2Al(s) + O (g)  Al 2O 3(s), H = ă 1670 kJ
2 2
So, it is not stable.
The thermite reaction involves so much energy that it can be dangerous. The Al becomes
white hot and often causes fires. For this precise reason, mixture of Al and an oxide such
REAC TIO NS OF EL
ELEEMEN TS
as Fe2O3 or SiO2 (a source of oxygen) were used to make incendiary bombs during World
Pure crystalline boron is very unreactive. However, it is attacked at high temperatures by strong War II.
oxidising agents such as a mixture of hot concentrated H2SO4 and HNO3 or Na 2O2.
BX3
2B(s) + 6HNO3 (aq)  2H3BO3 (aq) + 6NO2 (g)
H3BO3 + NO2
MxB y
In contrast, finely divided amorphous boron (containing about 2ă5% impurities) is more reactive. X2
M
Reactions are summarised in Table below HNO3 al
et
Reactions of Group 13 (IIIA) Elements m

Reaction Comment N2 O2
BN BORON B 2O 3
Ć 4M + 3O2  2M2 O3 Reaction at high temperature; with Al exotohermic, a
protective oxide layer is formed and TI also forms TI2O. NaOH
NH3 base
Ć 2M + N2  2MN Only Al and (B) form nitrides BN, a slippery white solid
S
with layer structure similar to graphite.
BN + H 2 Na 3BO 3 + H 2
Ć 2M + 3X2  2MX 3 All form MX3, Tl also form TlX. Iodide of Tl3+ (TlI 3) is not
formed; but TlI reacts with I2 forming TlI 3 (Tl +, I3ă) B2S3

Ć 2M + 2NaOH + 2H2O  B, Al and Ga only form NaMO2 Bo

Borr on : Ex
Extt ract ion
2NaMO 2 + 3H2 acid 
Ć Na2 B4O7.10H2O   H3BO3  H 2O + B 2O3
Ć 2M + 6NH3  2M(NH2 )3+ 3H2 All form amides except B which forms BN. orthoboric acid

2B + 2NH 3  2BN + 3H2 B2O3 + 6Na 


 2B + 3Na 2O

Ć 2M + 6H+  2M3+ 3H2 Metals liberate H 2, but HNO3 makes Al passive. B2O3 + 3Mg 

 2B + 3MgO

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 9 10 QUIZRR

red hot Ć Solution of Borax is alkaline in nature. This is due to hydrolysis

Ć 2BCl3 + 3H2 
filament
 2B + 6HCl

Ć Pyrolysis of BI 3 Na2 B4 O7  7H2 O 

 2NaOH + 4H3 BO3


Strong Weak
alkali acid
red hot
2BI 3 
filament
 2B + 3I2
2. Boric acids and oxides
Ć thermal decomposition of B2 H6
(i) H3BO3 or B(OH) 3 orthoboric acid
B2H6 

 2B + 3H2 (ii) HBO2 metaboric acid
(iii) H2B4O7 pyroboric acid
Com po
poun
un
unds
ds of Bo ro n
100Ĉ C 140Ĉ C
1. Borax (Na2B4 O7 .10H2 O) H3BO3 HBO2 H2B4O7
Ć The actual formula is Na2 [B 4O5(OH)4].8H2O
OH red hot

O Bă O B 2O 3
Na2 HO · B O B · OH 3. Boron Trioxide, B2O 3
ă
O B O Ć 2H3BO3  B 2 O3 + 3H2 O

OH It is a white hygroscopic solid. It absorbs moisture and converted into boric acid.
Ć Action of heat
B2O3 + H2O  2HBO 2
Heat 740C
Na2 B4 O7 .10H2 O   Na2 B4 O7 
 2NaBO2  B2 O3
 10H 2O
sodium Boric HBO2 + H 2O  H3BO 3
metaborate
anhydrid

Glassy mass Ć 2B2 O3 + P 4O10  4BPO4

Ć Various reactions of borax Ć It is reduced by magnesium

Na2 CO3 + H3 BO3 Heated

B2O3 + 3Mg   2B + 3MgO

4. Boron halide
NaOH Na2B4O 7

NaBO2 NaBO2 + B2O 3 CaF2 + H2 SO4 + H3 BO3 (or B2 O3 )
4 C i th

Sodium H2O
NH e d w
l

metaborate
HCl 
at

H3BO3 + NaOH
He

CuO 
H2 O ă
Heated BF3 H3 BO3 + BF4
BN strongly NaCl + H 3BO3
(also called 100Ĉ C Cu(BO2)2
inorgonic graphite) (Blue) 180Ĉ C NaH
B2O3
HBO 2 Boric anhydride
B2H6

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 11 12 QUIZRR
5. Boron Hydrides Ć Boric acid (H3BO 3) and silicic acids (H4 SiO 4) are weak crystalline.

excess NH 3 Ć They do not dissolve in cold dilute acids but do so in alkaliesăboron only in fused alkalies
B 2H 6.2NH 3 and silicon in both fused and aqueous alkalies.
low temp.
2B + 2NaOH + 2H2O  2NaBO2 + 3H2
excess NH 3
B2H6 + NH3 (BN) x
high temp. boron nitride Si + 2NaOH + H2O  Na2SiO 3 + 2H 2

ratio : 2NH3 : 1B2 H6 Com pou nds of Al umi n ium

B 3N 3H 6
high temp. borazine
1. Aluminium oxide or Alumina, Al 2O3

Ć B2H6 . 2NH3 is ionic and forms borazine on heating. Borazine is called inorganic benzene. 2Al(OH)3  Al2O 3 + 3H 2O

H Al 2(SO4) 3  Al 2O3 + 3SO 3

H N H (NH 4)2SO 4 . Al 2(SO4 )3 . 24H2O  Al 2O 3 + 2NH 3 + 4SO3 + 25H2O

B B
2. Aluminium Chloride
N N AlCl 3 exists as a dimer, thus attaining an octet of elections.
B
H H Cl Cl Cl

H Al Al

Cl Cl Cl
Similarity between Boron and Silicon (Diagonal Relationship)
Ć Both form volatile hydrides (called boranes and silanes) which spontaneously catch fire on However, when the halides dissolve in H 2O, the high enthalpy of hydration is sufficient to break
exposure to air and are easily hydrolysed. the covalent dimer into [M(H2O)6 ]3+ and 3Xă ions.
Ć Halides of both (except BF 3) are easily hydrolysed :
AlCl3 + 3H2O  Al(OH) 3 + 3HCl
BCl 3 + 3H2O  H 3BO3 + 3HCl
3. Alums

SiCl 4 + 4H2O  H 4SiO 4 + 4HCl Alums have general formula

M2 SO 4 . M´ 2(SO 4) 3 . 24H2 O
Ć Boron forms binary compounds with several metalsăthese are called borides. Silicon form
where M stands for monovalent basic radicals such as Na+ , K+, Rb+, Cs +, Ag+ etc. and M´ for
silicides. Borides and silicides are hydrolysed by H 2O forming boranes and silanes :
trivalent basic radicals such as Al3+, Cr3+ , Fe3+ , Mn 3+, Co 3+
Mg3 B2 + 6H 2O  3Mg(OH)2 + B2H 6 Some examples of alums are :

Al4Si3 + 12H2O  4Al(OH)3 + 3SiH4 Potash Alum K2SO4 . Al2 (SO4)3 .24H2O
Ferric alum (NH4) 2SO 4.Fe2(SO 4) 3
Ć B2O3 and SiO2 are acidic in nature and are important constituents of glass. Borate and
silicates have tetrahedral BO4 and SiO4 structural units, respectively. Alums are crystalline compounds. In alums each metal ion is surrounded by six water molecules
Ć Both are semi-conductors. and the crystals of alums consists of [M(H2 O) 6]+, [M´(H 2O)6 ]3+ and SO 24 ions.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 13 14 QUIZRR
G R O UP
UP––14 Oxi dation stat e s and Bond
ndiing

Elements of this group are p-block element. Carbon and Si are non-metals (Si slightly metallic), Groupă14 elements show variable oxidation states of + 2 and + 4. The stability of + 2 state is very
Ge is metalloid, Sn and Pb are metals. stable for Pb. It is due to inert pair effect.
Carbon has three isotopes, they are : C +4 +2
Isotope No. of neutron Abundance Nature Si
12
C 6 98.9% Ge
Stable isotopes
13
C 7 1.1% Sn
Pb
Radioactive Stability decreases Stability increases
14
C 8 Trace
tó = 5770 yrs
Carbon and Si have high ionisation energy. Therefore, they are covalent in their compounds.
Tin and Pb form ionic compounds having appreciable covalent nature. It is because Sn and Pb
Physical properties of groupă14 elements
are not very large and have 18e core.
Property C Si Ge Sn Pb Carbon and Si differ widely in their bonding pattern. It is because of the following reasons :

Atomic no. 6 14 32 50 82 Property C Si

Electronic ă 2s2 2p2 ă 3s23p 2 3d 104s 24p 2 4d105s25p2 4f 145d106s2 6p 2 2 2
Valence orbitals and 2s 2p 3s23p2 (3d0)
structure electrons
Atomic radius
Number of bonds or
(A) [covalent radius] 0.77 1.17 1.22 1.40 1.44 coordination number 4 only More than 4 (5 or 6)
Ionic radius (A) 0.15 0.41 0.53 0.71 0.84
-bonding Very effective No (p-p)  bonding but
Metallic radius (Å) -- -- 1.37 1.62 1.75
(păp)  bonding (p ă d)  bonding. Using
Ionisation vacant 3d orbitals
energy (ev) [I] 11.3 8.2 7.8 7.3 7.4
CăC bond energy 356 KJ molă1 226 KJ mol ă1
[II] 24.4 16.3 15.9 14.6 15.0
Low, however,
Electronegativity 2.5 1.9 1.8 1.7 1.7
heterocatenation is
mp (ĈC) > 3550 1410 937 232 327 Catenation property Very high pronounced due to strong
bp (ĈC) 4827 2355 2830 2260 1744 Si ă O bond (368 KJ molă1)

{The values are not to be remembered, these are given to show the variations}
The features of certain Si compounds having Si ă O and Si ă N bonds are explained by (d ă p)
Note : bonding. For example,
(i) The radii of Si and Ge are very similar due to d-block contraction. Also Sn and Pb have
(CH3) 3N triangular Pyramidal
almost similar radii due to lanthanide contraction.
(SiH3)3N triangular Planar
(ii) Ionisation energy vary as C > Si ~ Ge > Sn < Pb. Silicon and Ge have comparable IE due
to similarity in their radii. (SiH3)2 O < (Si ă O ă Si)  144Ĉ

The radius of Sn is smaller than Pb but Pb has higher IE than Sn. It is due to higher Z* for Pb Trisilylamine, (SiH3) 3N, is trogonal planar due to (d ă p)  bonding involving filled N 2pz orbital
as F ă orbital is least shielding. and vacant Si 3dxy orbitals.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 15 16 QUIZRR
Tin is found as  ă Sn, and  ă Sn.

Element Allotrope Structure

Si · N Si N
Graphite Layer structure
C Diamond Cubic structure
Fullerence Carbon cluster
The large angles at O of disilyl ethers (R3Si) 2O, is due both to electronic and steric factors.
Si -- Diamond structure
Ca t e n a t io n
Ge -- Diamond structure
The property of self-linking is known as catenation. It depends mainly on bond energy. The  ă Sn Diamond structure
CăC bond energy is very high. Therefore, C has maximum catenation property. The bond energy
Sn  ă Sn Cubic structure
decreases down the group and so also the catenation property, i.e.
 ă Sn Simple cubic structure
C >> Si > Ge  Sn >> Pb
Pb -- ccp
Bond Bond Energy (KJ molă1)

C ă C 356 (a) G r a ph it e

Si ă Si 210 ă 250 It is soft dull looking greasy substance and is electrical conductor. Graphite has two-dimensional
Ge ă Ge 190 ă 210 layer structure.

Sn ă Sn 105 ă 145 Layers are made up of sp2 hybridized C atoms. Each C is joined with three other C atoms through
 ă bonds forming hexagonal rings. Each C is left with its fourth valence electron in a p-orbital.
Sulphur also shows catenation because S ă S bond energy is relatively high. Boron, Si, P shows They overlap and form  bonds. These  bonds are delocalized. Therefore, all C ă C bond distances
heterocatenation as B ă O, Si ă O and P ă O bond energies are high. in graphite are equal (1.415 Å). Sheet to sheet distance in graphite is 3.35Å. It is known as C
ă dimension. Layers are joined by weak Van der waals force.
Bond Bond Energy (KJ molă1) The weak force between layers allows one layer to slide over the other. It imparts softness to
S ă S 226 graphite. It is, therefore, used in pencils for writing. Due to delocalized  electrons graphite is a
conductor (though along the sheet not perpendicular to it). Hence, it is used as electrode.
B ă O 560 ă 790
Si ă O 368
C
P ă O ~ 340
C C

Al
Allo
lo
lottr op
opyy an d st ruc ture
C C C
All the elements are solid. Carbon and Sn only show allotropy. C C C C

Carbon has three crystalline allotropes :

C C C C
(a) Graphite
C C C
(b) Diamond and
(c) Fullerene. C C C

C C

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 17 18 QUIZRR
(b) D i a m on d St ruc
ucttur
uree of C 60

It is colourless transparent hardest substance known and is insulator. Cut diamond is sparkling
solid (due to refraction). Diamond has cubic unit cell. Each C is sp3 hybridised and is joined with
four other C atoms through  ă bonds.

C
C Silicon exists only in diamond structure. A graphite like structure for Si is not possible because
C
it has no propensity to form (p ă p) bond.
C
Tin exists in three forms,  ă Sn,  ă Sn and  ă Sn.

 · Sn  · Sn  · Sn
As C ă C bond energy (356 KJ mol ă1) is very high and diamond has a giant structure, it is very (Grey) (White) (Brittle)
(Non ă metallic (Metallic distorted (Rhombic)
hard. This structure is responsible for its insulator property. diamond structure) close packed)

Density of diamond (3.51 g/cc) is greater than graphite (2.22g/cc). This shows that to convert
Se
Semi
mi
micc on
ondu
du
ducct or pr
prop
op
opeer ty of Si and Ge
graphite into diamond, pressure must be applied. There is the equilibrium.
Silicon and to a less extent Ge are important semiconductor materials. Pure Si and Ge are non-
15000 atm
Graphite  conductor of electricity. However, when they are droped with group ă 13 or group ă 15 elements,

300 k
 diamond

they become semiconductor.

Graphite can be transformed into diamond at a reasonable rate at high pressure and ~ 300 K in (i) Ge dopped with In
the presence of a transition metal (Fe, Cr, Pt) catalyst. Ge ă 4s2 4sp2
In ă 5s2 5p1
(c
(c)) F ul l e r e ne s
When Ge is dopped with In, there is one electron less at In site. There develops a positive
Fullerenes are carbon clusters having cage like structures. hole in the lattice which makes Ge conducting. Such a semiconductor is called p ă type
(positive ă type) semiconductor.
Fullerenes C 60 and C70 can be separated by chromatogrphic method over alumina. Many other
fullerenes also exist such as C32 , C50, C76, C84 etc. (ii) Ge dopped with As
Ge ă 4s2 4p2
The fullerenes C60 is well known. It has a soccer ball structure which contains 12 five ă membered
and 20 six membered rings. The rings are unsaturated. The C60 fullerene is called Buckminster As ă 4s 24p3

fullerene in honour of American architect Robert Buckminster Fuller. When As is dopped in Ge, there is one electron excess at As site. Due to this excess electron
Ge conducts electricity. Such a semiconductor is called n ă type (negative type).

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 19 20 QUIZRR
Ć The normal valency of the elements is four, but apart from carbon, the elements can make
Ge Ge Ge Ge more than four bonds. This is because they make use of a set of d-orbitals in bonding. Thus
availability of d-orbitals (empty but electrons of ns2 and np2 can be excited into this) is
Ge Ge In Ge
responsible for the ability of the elements, except carbon, to make complex ions such as
Ge Ge Ge Ge SiF 62ă.
+In
Ge Ge Ge Ge Energy
Ge Ge Ge Ge
3d
Ge Ge Ge Ge
very large
Ge Ge Ge Ge energy gap,
can not 3d
Ge Ge Ge Ge
Ge Ge Ge Ge use 3d orbitals
+As relatively small
2p in bonding energy gap, can
Ge Ge As Ge
use 3d orbitals
in bonding
Ge Ge Ge Ge 3p
Carbon
Ge Ge Ge Ge
silicon
M ul
ultt i pl e Bo
Bonnd ing
Fig. Energy difference between 2p and 3d energy levels in
In Group 14, carbon is the only element capable of forming comparatively stable multiple bonds
carbon and between 3p and 3d energy levels in silicon.
with another C atom and also with N, O etc. Examples are alkenes (> C = C <), alkynes (ă C 
C ă), imines (> C = N ă), nitriles (ă C  N ă), ketones (> C = O), etc. None of the other elements Ć The main chemical differences between silicon and carbon are :
of the group forms stable compounds containing multiple bonds. Recently, some ă Si does not form stable double bonds
success has been achieved in synthesising compounds with > Si = Si < and Si = C ă Si does not form very stable Si ă Si bonds.
< double bonds, but their details are beyond the scope of this course. Stoichiometric
ă Si has vacant 3d-orbitals in its valence shell into which it can accept electrons from
analogues like SiO2, SnO2 and (Me 2SiO)n are known which are giant macromolecules
donor atoms.
containing MăOăM linkages.
The tendency of formation of multiple bonds easily, in case of carbon, is because of Ć Some carbon compound are less reactive than the corresponding compounds of the other
the high bond energy and a small atomic radius of carbon is compared to other members of the group. CCl4 has no interaction with H 2O (hydrolysis) whereas SiCl4 does by
elements of the group. So its p-orbitals can approach the p-orbitals of the other C, use of empty 3d-orbitals.
O or N atom for an effective overlap essential for -bond formation. p-orbitals Ć All the elements give hydrides. Carbon, of course gives an immense number, but silicon and
Ć Silicon also uses d-orbitals in multiple bonding, In case of N(CH3) 3 , geometry is germanium also show a wide variety.
pyramidal, but in case of N(SiH3 ) 3 it is planar. It is due to the fact that in the
CH 4 methane (alkane)
 ăd
latter, the lone pair of N-atom is transferred to empty d-orbitals of silicon (p 
SnH 4 Stannane
overlapping) :
SiH 4 silane
PbH4 plumbane
N N GeH 4 germane

CH3 CH3 SiH3 SiH3 Carbon hydrides will not ignite in air unless a flame is put to them. Apart from silane, SiH4 ,
CH3 SiH3 the silicon hydrides are less well behaved. Si3H8 is spontaneously flammable in air :
pyramidal planar
(no  bonding) (păd bonding) Si 3H 8(l) + 5O2(g)  3SiO 2 (s) + 4H2O(l)

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 21 22 QUIZRR
Alkanes as well as silane are not hydrolysed however, traces of alkali converts silane into (ii) Covalent carbides,
hydrated silica SiO 2 . nH 2 O. (iii) Interstitial carbides.
Ć As we descend the group, acidic nature of the oxides decreases and basic nature of the oxides
(i) Ionic carbides
increases.
Three types of ionic carbides are found :
Oxides Nature Oxides Nature
(a) Methanides,
CO, CO2 acidic SnO, SnO 2 amphoteric (b) Acetylides,
SiO2 acidic PbO, PbO2 basic (c) Propynide.
GeO, GeO2 amphoteric Pb3O 4 amphoteric Ionic carbides are decomposed by water (or dil. Acid) at room temperature. The liberated anions
are also immediately hydrolysed. It affords a method of classification.
Si, Ge, Sn and Pb form oxides MO2 . SiO2 is infinite three-dimensional network solid of
silicon and oxygen atoms connected by single covalent bonds. GeO 2, SnO2 and PbO2 are all (a) Methanides : (Că4 unit)
solids and exist in several modifications. Those carbides which are hydrolysed to give CH4 are called methanide. They are supposed
to contain Că4 unit.
Exa mple 1
Be2 C + 4H2O  2Be(OH) 2 + CH4
Why is graphite a better electrical conductor than diamond and why does the conductivity
of graphite depend on direction ? Al4C3 + 12H 2O  4Al (OH)3 + 3CH 4
Solution :
Graphite has a two-dimensional sheet like structure in which each carbon atom uses sp2 hybrid (b) Acetylides : (C2 ă2 unit)
orbitals to form trigonal planar  bonds to three neighbouring carbon atoms. In addition, each Those which are hydrolysed to C2H 2 are called acetylides. They are common and formed by
carbon atom uses its remaining p-orbital, perpendicular to the plane of the sheet, to form a  bond. Group ă 1, Group ă 2, Mg, Ca, Sr, Ba, Zn, Cd, Cu, Ag, Al and La metals.
Because each carbon atom must share its  bond with its three neighbours, the  electrons are Gr ă 1
delocalised and are free to move in the plane of the sheet. As a result, the electrical conductivity M2 C 2
Cu, Ag
of graphite in a direction parallel to to the sheet is about 1020 times greater than the conductivity
Gr ă 2
of diamond. The conductivity of graphite perpendicular to the sheets of carbon atoms is lower MC2
because electrons must hop from one sheet to the next. The substance or crystal that show Zn, Cd
different properties in different directions is called anisotropic. Al, La M2 (C2)3

Ex
Exaa mple 2 CaC2 + 2H 2O  Ca(OH)2 + C2H2

Why elemental silicon does not form graphite like structure as carbon does ? Explain.
Al 2(C2) 3 + 6H2O  2Al(OH) 3 + 3C 2 H2
Solution :
4ă
(c) Propynide : (C3 unit)
This is due to the reluctance of silicon to form p-p multiple bonds because of large size of silicon
atom. Hence Si exists only in diamond form. Such carbides hydrolyse to propyne

Mg2C 3 + H 2 O  2Mg(OH)2 + CH 3 ă C  CH

Comp ou
ounnds of C arb on a nd Si
Silli c on

1. Carbides : Binary compounds of carbon are called carbides, SiC, CaC2, Al4C 3 etc. Three types are (ii) Covalent carbides
found : Elements which compares with C in size and electronegativity form such carbides, Be, B, Si etc.
(i) Ionic or salt like carbides, Boron and Si carbides are more important.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 23 24 QUIZRR

SiO 2 + 2C  Si + 2CO

  CO is very toxic and rapidly forms a bright red complex with haemoglobin of blood.
Thus preventing haemoglobin to carry oxygen to cells, using oxygen deficiency to
High temp
Si + C   SiC unconsciousness and then death.

Silicon carbide (SiC) is called carborundum. It is very inert and extremely hard. (b) Carbon dioxide (CO2)

High temp  CO2 is acidic oxide

B 2O3 + C   B 4C
 CO2 is biologically important
B4C is a also very hard, infusible and inert. It is used to make bulletproof clothing.
(i) Maintains pH of blood, due to the equilibrium
These covalent carbides (or  ă Al2 O3) are comparable in hardness to diamond (MohÊs scale).
CO2 + H2O  HCO3 + H+
Hardness  Diamond > B 4C > SiC >  ă Al2O 3
(ii) Main components of photo synthesis
(iii) Interstitial carbides
Chlorophyll
Transition metals form such carbides, in which C atoms occupy octahedral voids. Such materials 6CO2  6H2 O   C6 H12 O6  6O2
Sun light
are very hard, electrically conducting and have very high mp. For example : TiC, ZrC, MoC, WC  Glucose
etc.
(iii) The reverse process of the above takes place in the process of respiration.

2. O x i de s C6H12O 6 + 6O2  6CO2 + 6H 2O + Energy

Electrons of this form oxides of the type MO and MO2. Carbon forms suboxides also, e.g., C3O2 .  CO2 is used in the synthesis of urea
NH2
Oxides C Si Ge Sn Pb 
CO2 + 2NH3 H2NCO2NH4 O C + H2 O
CO Ammonium
NH2
GeO SnO PbO Carbamate
Urea
MO (neutral) X  
ampoteric
 CO2 is gas at NTP and has the structure O == C == O. The (p ă p) bonding is very
GeO 2 SnO 2 PbO 2 effective. Therefore, even in solid state discrete CO2 molecules exist. The intermolecular
MO 2 CO SiO 2  
ampoteric forces are weak Van der WaalsÊ force.
 acidic   Solid CO2 is called Âdry iceÊ or ÂcardiceÊ.

Silicon dioxide, SiO2 , unlike CO2 is a solid. The (p ă p)  bonding is not effective in SiO2 like CO2 .
(a) Carbon monoxide (CO)
It is due to larger size of Si and more core electrons (8e) in Si. Therefore, to stabilize; SiO 2 contains
It forms many important gaseous mixtures of industrial use
a continuous lattice of Si and oxygen atoms joined by covalent bonds. Each Si is sp3 and is joined
(i) Water gas or synthesis gas CO + H2 with 4 O + atoms and each O ă atom with two Si ă atoms. A macromolecule is formed, hence SiO2
(ii) Producer gas CO + N2 is a solid.
(iii) Coal gas CO + H2 + CH4 + C O 2 O O

 CO is a neutral oxide. O Si O Si O
 Carbon monoxide has a triple bonded C atom, one s and two p bonds (best explained
O O
by MO model).
 CO, however, is a strong ligand towards transition metals and form variety of complexes O Si O Si O
known as carbonyls, Ni (CO)4, Fe(CO)5 etc. They are stable due to synergic bonding.
O O

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 25 26 QUIZRR
Ha lide
dess M X2 a
and
nd M X 4 Exa mple 4

Group ă 14 elements form tetrahalides of the type MX4 (X = F, Cl, Br, I) except PbI4. SiCl2 is solid while SiCl4 is liquid at room temperature. Why ?
PbI4 does not exist due to strong oxidizing power of Pb+4 and reducing nature of I ă ion. The Pb+4 Solution :
is strong oxidizing agent due to greater stability of Pb+2 (inert pair effect). SiCl 2 is more ionic than SiCl 4 by FajanÊs rule. Therefore it has greater m.p. so it is solid at room
Thus, MX4, [M = C, Si, Ge, Sn, X = F, Cl, Br, I] temperature while SiCl4 is liquid.
Germanium, Sn and Pb also for MX2. The stability of MX 2 is maximum for Pb+2 .
Hy
Hydr
dr
drii des :
SnF2 is sparingly soluble in water and is used in fluoride containing tooth pastes.
The MX4 halides are all colourless except GeI 4 and SnI4 which are bright orange solids. Colour All element of this group form hydrides.
in these halides is due to charge transfer. Carbon forms a large number of chain and ring compounds due to high catenation property. They
are :
+4 ă +4 ă
Sn I Ge I Alkanes CnH 2n+2
e e Alkenes CnH 2n
Alkynes CnH 2nă2
All tetrachlorides except CCl4 are hydrolysed by water. Cyclo alkanes and cycloalkynes
Carbon tetrachloride is not hydrolysed because : Aromatic hydrocarbons (C6H6 )
(a) carbon in CCl 4 is coordinatively saturated Silicon (others also) form saturated hydrides only which are called silanes, SinH2n+2 (Si ~ 8).

(b) C ă Cl bond is less polar SiCl 4 + LiAlH4  SiH4 + AlCl 3 + LiCl
X C = 2.5, XCl = 3.0,  = 0.5
Si
Silli co ns :
Silicon tetra chloride (SiCl4 ) is extensively hydrolysed. It is because :
They are organosilicon polymers having empirical formula approximately R2SiO. Polymers are
(a) Si ă Cl bond is more polar very stable due to strong Si ă O and Si ă C bonds. Silicones can be prepared as oils, resins, plastics
X Si = 1.8, XCl = 3.0,  = 1.2 etc. They are :
(b) Si in SiCl4 can increase its coordination number by using 3d orbitals  Inert

The tetra halides of Si, Ge, Sn and Pb can increase their coordination numbers by using d orbitals  Water repellent
and can form haloanions.  Heat resistant
 Electrical insulator
SiF 4 + 2Fă  SiF62
All these properties make silicones very useful.
SnCl 4 + 2Cl ă  SnCl6 Hydrolysis of alkyl chlorosilanes produces products having Si ă OH bonds. They do not dehydrate
like gem diols (of C).
The hexacoordinated halo anions are octahedral having sp 3d2 hybridised central atom (Si).
R Cl R OH R
Si + H2 O Si Si O
Ex
Exaa mple 3 R Cl (ă2HCl) R OH R
CCl4 can not be hydrolysed but SiCl4 can be. Why ? Si l ic a t e s
Solution : Silicates are solids having Si ă O bonds. Most of the rocks and even soil contain silicates. Alkali
Vacant d orbital is not present in carbon so it can not extend its configuration like Si. Therefore metal silicates are water soluble. They are made on a large scale as
it can not be hydrolysed.
~ 1500C
Na2 CO3 + SiO2   Na4SiO 4, (Na2SiO 3) n etc. + CO 2

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 27 28 QUIZRR
They are used in detergents. The concentrated aq. solution of Na 4SiO 4 is solid like and as known Na2CO 3 + SiO2   Na2SiO3 + CO2

as water glass. Variety of silicates are found but in all the basic unit is the SiO4 tetrahedron.

ă
CaCO3 + SiO2  CaSiO 3 + CO 2
O
By varying the proportions of the three basic ingredients, and by adding other substances, we can
Si or
alter the properties of the glass as given :
ă
Oă O
Oă Ć Calcium-alkali silicate glass ă normal domestic glass for windows
Sodium silicate ă soda glass used in cheap laboratory glassware
Each O ă atom carries one unit negative charge. In polymeric silicates SiO4 units share
O ă atoms(s). It provides a way of classification. Ć Fining agents such as NaNO3 or As2O 3 are added to remove bubbles.
Ć Decolorising agents may be added to eliminate impurities and to obtain colourless glass.
Or thos ilic ate s (M ono
nonn uc
uclle a r sili c at
atee s) CaF2 is sometimes added to make opal glass.

These are silicates having discrete SiO 44 ions. Metal ions are surrounded by Oăatoms. Glass is attacked by HF and this property is used to make marking on the glass (etching)

Na2SiO3 + 6HF  Na2SiF 6 + 3H 2O

(in glass)

CaSiO3 + 6HF  CaSiF6 + 3H2 O

HF, however does not attack wax. The portion of the glass on which etching is to be done is
Si 2O7–6 ) :
Pyrosili cates ((Si covered with wax layer. Markings are carved on the wax layer with a pin and HF is poured on
the carved parts and left for sometime. After washing with water, wax is removed and permanent
When two SiO4 units share only one O ă atom pyrosilicates, Si2O76 , are formed. These are also marking is obtained.
discrete units.
Exa mple 5
Oă O Oă
Si Si The standard free energies of formation of B2O3 and MgO are ă 1194 kJ molă1 and ă 569 kJ
O ă Oă molă1 respectively. Should it be possible to prepare boron by reacting B 2O3 with magnesium ?
O
ă
Oă Solution :

Glas s B2O3 + Mg  2B + 3MgO

Solids are most stable in crystalline form. However, if a solid is formed rapidly (for example, when G Ĉ = Gproduct ă GĈ reactant
a liquid is cooled quickly), its atoms or molecules do not have time to align themselves and may
= 3GĈf (MgO) ă GĈf (B2 O3)
become locked in positions other than those of a regular crystal.
= 3(ă 569) ă (ă 1194)
If we mix sodium carbonate and calcium carbonate with sand and fuse the mixture at about
1500ĈC, we get a liquid mixture of sodium and calcium silicates. When this mixture is cooled, it = ă 513 kJ molă1 [GĈf (element) = 0]
becomes viscous and eventually ceases to flow; it becomes solid ăcalled glass. Glass is thus super- The negative sign of GĈ shows that the reaction should be spontaneous. (However, the reaction
cooled liquid (solid solution). Amorphous solids, such as glass, lack regular three dimensional is initially endothermic when two reactants are heated.)
arrangement of atoms. Glass thus refers to an optically transparent fusion product of inorganic
materials that has cooled to a rigid state without crystallising.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 29 30 QUIZRR
Exa mple 6 Exa mple 9

(i) What type of bonding holds the layer in graphite ? What would you expect to happen when :
(ii) Why will graphite conduct electricity well in a direction parallel to the planes of (a) Tin is heated with a concentrated aqueous solution of sodium hydroxide
hexagons, but not at all well in a direction perpendicular to the planes ? (b) Sulphur dioxide is passed over lead dioxide
(iii) What is the name we give to crystal or substances, that show different properties in (c) Carbon disulphide is shaken with aqueous sodium sulphide
different directions ?
(d) Dichlorosilane is hydrolysed by water
Solution :
(e) 4 mol of ClCH2 SiCl3 react with 3 mol of LiAlH4 in diethyl ether solution ?
(i) Van der Waals bonding
Solution :
(ii) The delocalised orbitals in graphite lie parallel to the planes and electrons can move along
the planes making use of these orbitals; conduction is good parallel to the planes. There is (a) Sn + 2OHă + 4H2 O  [Sn(OH)6 ]2ă + 2H2
no overlap of orbitals perpendicular to the planes, so conduction is poor in this direction.
(b) PbO2 + SO 2  PbSO4
(iii) They are anisotropic.

(c) CS2 + Na2 S  Na2 CS3

Ex
Exaa mple 7
sodium thiocarbonate
If you had a mixture of CO and CO 2, how would you find out relative proportions of the H OH
two gases in the mixture ? (d) SiH2Cl2 + 2H2O  Si +2HCI
Solution : H OH
Method I : Mixture of CO2 is run into Ca(OH) 2 solution. CO2 is absorbed by Ca(OH)2 and thus
H
residual volume will be that of CO.
Si=O + H2 O
Ca(OH)2 + CO2  CaCO 3 + H 2O H

Method II : Mixture of CO and CO2 is passed over heated charcoal :

(e) 4ClCH2SiCl3 + 3LiAlH4  4ClCH2SiH 3 + 3LiCl + 3AlCl3
CO2 + C  2CO
Ex
Exaa mple 1 0
Increase in volume will be due to CO2. By measuring total volume after passing over heated
charcoal, composition of mixture of CO and CO2 can be determined. Suggest syntheses (starting from deuterium oxide as the only source of deuterium) for:
(a) B2D6 (b) B(OD)3 (c) B 3N3 D6 (d) B (CH 2CH 2 D)3.
Ex
Exaa mple 8 Solution :
CO and CNă ions are highly poisonous. A sign that some one has been poisoned by either (a) P2O5 + 3D2 O  2D3PO4
of these two chemicals is that the personÊs blood changes colour. They both have the effect
of preventing oxygen being taken up by the blood stream. What might happen to Mg3B 2 + 2D 3 PO4  Mg3 (PO4) 2 + B 2D6
haemoglobin to stop oxygen being taken up ?
(b) B2O3 + 3D2O  2B(OD) 3
Solution :
CO and CNă ions are able to bond more strongly to the iron atom in haemoglobin than can (c) Mg3N2 + D2 O  ND3 + Mg(OD)2
oxygen. If you were to breathe in CO for any length of time, your haemoglobin would become
2ND3 + B2D 6  [D 2B(ND 3)2)][BD4 ] 

 B 3N3 D6
saturated with CO molecules rather than oxygen. As a result, all the body processes that rely on
a supply of oxygen gradually cease. Death is the result. (d) 6CH2 = CH2 + B2 D6  2B(CH2CH2D)3

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 31 32 QUIZRR
Exa mple 1 1 Al3+ > Ga3+ > In 3+ > TI3+
(most stable)
Explain the following :
Al+ < Ga+ < In + < TI+
(a) Boron does not usually form a cation :
(most stable)
B has
(IE)1 = 801 kJ mol ă1, (IE)2 = 2427 kJ molă1, (d) CO2 is a gas but SiO 2 is a solid :
(IE)3 = 3659 kJ mol ă1  Carbon and silicon (Group 14, IVA) have four valence electrons. We might expect carbon
 Thus, the total energy required to give B 3+ ions is far more than that which would be and silicon to form oxides with similar properties. In CO2 the ability of C and O atoms to
compensated by lattice energies of ionic compounds or hydration of such ions in solution. form  bonds through the side-wise overlap of their 2p orbitals is strong. The result is strong
Thus formation of cation (like B3+ ) is not possible. CătoăO double bonds and a very stable triatomic molecule.
O=C=O
(b) The polarity of BăX bonds is in the order : BăF > BăCl > BăBr but Lewis acidicity shows
Silicon, being in third period, would have to use 3 p orbitals to form double bonds with
the sequence : BF3 < BCl 3 < BBr3.
oxygen. The side-wise overlap of these orbitals with the 2p orbitals of oxygen is too limited
 With increase in polarity of BăX bond, acidity also increases and should be thus in the for  bond formation. From an energy stand point, a stronger bonding arrangement results
order : if the Si atoms from four single bonds with O atoms (bond energy : 464 kJ/mol) rather than
BF3 > BCl3 > BBr3 two double bonds (bond energy : 640 kJ/mol) since each O atom must be simultaneously
But Lewis acidity is in reverse order : bonded to two Si atoms, the result in a network of ăSiăOăSiăbonds and thus a hard (giant)
solid :
BF3 < BCl3 < BBr3
There is lateral overlap of the vacant 2p orbital of B with one completely filled orbital of F leading O O
to p-p bonds between B and F. This BăF bond thus acquires double bond character. This also
O
leads to compensate electron deficiency of boron and thus Lewis acid character of BF 3 is reduced. O S O S O
This p-p bonding decreases going from BF 3 to BBr3 and thus Lewis acidic nature increases in
Si
the order : O O
O O
O
BF3 < BCI3 < BBr3 O S O S O
excite
B
2p1 2p2 O O
ground state
2s1 2s1 (e) SiCl4 is hydrolysed but CCl4 is inert to hydrolysis :
excited state
 SiCl4 and CCl 4 are covalent compounds. Carbon has maximum covalency of four while
silicon has six. Thus CCl4 is inert towards water and is not hydrolysed but SiCl4 can
F F coordinate with 2 mol of H2 O molecules and is thus readily hydrolysed :
B F B F
SiCl4 + 2H2O  Si(OH)4 + 2HCl
F F
Cl Cl
H Cl Cl H
(c) Al and Ga are trivalent in their compounds but in case of Tl, monovalent compounds H2 O + Si + OH2 O Si O
are the most stable. Why ?
H Cl Cl H
 It is due to Âinert pairÊ effect due to which stability of + 3 state decreases and that of + 1 Cl Cl
state increases while going down the group (in this case Group 13) Silicon with covalency six

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 33 34 QUIZRR
Exa mple 1 3
ă2HCl
(SiH 3)3 N is a weaker base than (CH3) 3N. Explain.
Cl
H Cl Cl H Solution :
2H 2O
O Si O OH S OH In (SiH3) 3N, the lone pair of electrons on nitrogen is involved in păd back bonding, while such
bonding is not possible (CH 3)3 N as d-orbitals are not present in carbon. Hence, the lone pair of
H Cl Cl H
Cl electrons on nitrogen in (CH3) 3N is available for donation to Lewis acids, exactly acting as
Silicon with covalency six stronger base.

Ex
Exaa mple 1 4
OH
 2HCl
|
 HO  Si  OH (i) A white precipitate (B) is formed when a mineral (A) is boiled with Na2CO3 solution.
| (ii) The precipitate is filtered and the filtrate contains two compounds (C) and (D). The
OH
compound (C) is removed by crystallisation and when CO2 is passed through the
(f) (SiH3) 3N is planar while (CH3) 3 N is pyramidal : mother liquor left, (D) changes to (C).
(iii) The compound (C) on strong heating gives two compounds (D) and (E).
 In case of (CH3) 3N, lone pair on N and three covalent bonds with CH3 groups results in sp 3
(iv) (E) on heating with cobalt oxide produces blue coloured substance (F). Identify (A) to
hybridisation but lone pair-bond pair repulsion causes distortion hence gives pyramidal
(F) and give chemical reactions for the reactions at step (i) to (iv).
structure :
Solution :
(i) The mineral (A) is colemanite, Ca2B6O11 . 5H2O

boiled
Ca2B6 O11 + 2Na2CO3(aq)   2CaCO3 + Na 2B4 O7 + 2NaBO2
N
(B) Insoluble (C) (D)
CH3 CH3
CH3 Soluble

(ii) (C), the borax is crystallized. The mother liquor consisting sodium metaborate is treated with
But in case of (SiH3)3N, lone pair on the nitrogen is transferred to the empty d-orbitals of CO2.
silicon (p  ă d overlap) thereby causing planarity of unit. 4NaBO 2 + CO2  Na2B 4O7 + Na 2CO3

heated
(iii) Na2B4O 7.10H 2O 
Exa mple 1 2  Na2B 4O7 + 10H2 O
Anhydrous
AlF3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes
soluble. On addition of BF3, AlF3 is precipitated. Write the balanced chemical equations. strongly
Na2B4O 7 
heated
 2NaBO 2 + B2O3
Solution :
heat
3KF + AlF3  K 3AlF6 (iv) CaO + B 2O3   CO(BO2) 2
cobalt meta borate
K3AlF6 + 3BF3  AlF3 + 3KBF4 (blue coloured)

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 35 36 QUIZRR
Exa mple 1 5 Since, it is not easy from energy consideration to gain three electrons to achieve stable noble gas
PbCl4 is less stable than SiCl4. Why ? configuration, the formation of the tri-negative ion (M3ă) is rare. But, nitrogen being the smallest
and the most electronegative of all the members of the group, forms trivalent anion with reactive
Solution :
metals which have low ionisation energies. Thus, nitrogen forms ionic nitrides such as Li 3N,
Pb is more stable in + 2 stable due to inert pair effect while Sn is more stable in + 4 state as
Be3N 2, Mg3 N 2, Ca 3N 2. As the electronegativity of the other elements of the group, i.e., P, As, Sb
compared to Pb+4.
and Bi, is low, most of their compounds are covalent in nature.
GROUP 1 5 ELEM EN
ENTTS Nitrogen is not able to extend its coordination number beyond four, the other elements have

Elements : N, P, As, Sb, Bi coordination numbers of five as well as six. The extension of coordination number is due to the

Nitrogen and phosphorus are non-metals. The metallic character increases down the group due availability of d-orbitals in P, As, Sb and Bi, using which these elements can attain sp3d and sp3d 2
to lower I.E. and larger size. Hence, bismuth shows metallic character. The group state electronic hybridisation, e.g. in PCl5 and PCl6ă, respectively. Thus, nitrogen does not function as a Lewis
configuration is ns2np3 . acid whereas phosporus, arsenic antimony and bismuth do so. The hybrides of this group and
their alkyl derivatives act as Lewis bases, forming a number of addition complexes, e.g., NH 3 .
Tre nd
ndss i n Ch
Cheemic al R eact iv
iviity BF3 , CaCl2 . 4NH2, etc.

Most common oxidation states shown by group 15 elements are ă 3, + 3 and + 5. The stability Ć Stability of + 3 state increases and that of + 5 state decreases going down the group due
of highest oxidation state (+ 5) decreases down the group. to „inert pair effect‰, thus
The covalent character goes on decreasing as we move down the group in the sequence, P > As Bi3+ > Sb3+ > As 3+
> Sb > Bi. This is due to increasing size of atom which refers to FajanÊs rules. Bi5+ < Sb5+ < As 5+
3+ 5+
Sb and Bi are the heavier elements of the group and form M cations due to decrease in Bi salts are very rare and are good oxidising agents :
ionization enthalpy.
Bi5+ + 2eă  Bi 3+
In contrast to nitrogen, the phosphorus atom forms p=p bonding and forms both cyclic and open
chain compounds. Hence, it shows catenation. As3+ salts are good reducing agents :
As we move down the group there is a decrease is covalent character. As3+  As 5+ + 2e ă
N > P > As > Sb > Bi
Ć They form trihalide and penthalide (except N, which does not form NCl5 etc.) As we go down
Nitrogen is chemically less reactive, due to high stability of its molecule. N2 in which two nitrogen
the group, covalent nature decrease and ionic nature increases; thus NCl3 and PCl3 are
atoms are combined through a triple covalent bond (N  N) of which one is sigma () and two
covalent while BiCl 3 is ionic. This is also in accordance with FajanÊs rule : Smaller the size
are pie () bonds, thus posses high bond strength (941.4 KJ molă1)
of cation, larger the size of anion, greater the charge then greater the polarising power and
Nitrogen has one special feature that it can form p-p multiple bonds with itself, carbon and hence greater the covlalent nature. Halides are hydrolysed in water forming oxyacids or
oxygen due to its small size. In phosphorus rather p-p, d-p is found as in POX3. oxychlorides :

Gener al Tre nd
ndss in P hysica l Prop ert ies PCl3 + 3H 2 O  H 3PO 3 + 3HCl

Sr.No. Property Nitrogen Phosphorus Arsenic Antimony Bismuth SbCl3 + H2O  SbOCl  + 2HCl
1. Configuration [He]2s 2p 3 [Ne]3s23p3 [Ar]4s2 4p3 [Kr]5s2 5p3 [Xe]6s 2 6p3 (orange ppt)

2. Common oxidation state ă 3, + 3, + 5 ă 3, + 5, + 5 + 3, + 5 + 3, + 5 + 3 BiCl3 + H2O  BiOCl + 2HCl

3. Atomic radius (pm) 70 110 120 140 150 (white ppt)

4. First ionization 1403 1012 947 834 703

5. Electronegativity 3.0 2.1 2.0 1.9 1.9

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 37 38 QUIZRR
Comp ou
ounnds of N itr og en (ii) Di or trivalent metal nitrate decomposes on heating to NO2

Oxides of N Pb (NO 3)2 


 PbO + 2NO 2 + óO2
(i) Dinitrogen oxide (or nitrous oxide) N2O
Structure : NO2 is an odd electron (17 electrons) molecule and is paramagnetic. It has the

NH 4 NO3  N2O + 2H 2O structure

Structure : It is isoelectronic to CO2 and has linear structure. But unlike CO2 it has dipole
moment (0.16 D). It shows resonance

ă + + ă
N == N == O N N·O The unpaired electron ensures ready dimerisation to a diamagnetic colourless species N2O 4
(dinitrogen tetraoxide).
(2) Nitric oxide (NO)
2NO2  N 2O4
 Copper reacts with dil HNO3 (8M) to form NO. It is reduction of NO3
N2O 4 is planar
8HNO3 + 3Cu  3Cu(NO 3)2 + 4H2O + 2NO

 Commercially, NO is obtained by catalytic oxidation of NH3 (ostwald process for HNO 3)

Pt catalyst
4NH3  5O2   4NO + 6H2 O



Nitric oxide is a good ligand and form variety of complexes with transition metals which are
known as nitrosyls, Na2[Fe(CN) 5NO]
(5) Nitrogen pentaoxide N2O5
(3) Dinitrogen trioxide N2O3 It is obtained by dehydration of HNO3 by P2O5
It can be obtained by mixing NO and NO2 in equimolar quantities at low temperature.
2HNO3 + P2O5 

 2HPO3 + N 2O5
Low
NO + NO2   N2 O3
Temp.
(blue liq.)
Structure : N2O5 is solid and in this state it is NO2+ . NO3 i.e. nitronium nitrate. In gaseous state
( 30F)
it has the structure
In gaseous state it has the structure
O O

N O N

O O

AMMONIA ă NH 3
The N ă N distance is very large, 1.864Å It can be prepared in many ways :

(4) Nitrogen dioxide NO 2 (N 2O4 ) (i) Any ammonium salt on heating with alkali forms ammonia.

(i) Cu + conc. HNO3 

 NH 4 Cl + NaOH 

 NH3 + NaCl + H2O
 NO 2

Cu + 4HNO 3 
 2NH 4 OOCCH3 + Ca(OH) 2  NH 3 + Ca(CH3COO)2 + 2H 2O
 Cu(NO3 )2 + 2H 2O + 2NO2

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 39 40 QUIZRR
(ii) Ionic nitrides are hydrolysed by water to produce NH3 . HNO2

r e ag e
en g
Mg 3N 2 + 3H 2O  2NH 3 + 3MgO

ag izin

du nt
t

ci
id

ng
ox
(iii) NH+4 salts which contain non-oxidizing anions, on heating given NH 3. Iă MnOă4 /H+
I2 Mn2+
S Fe2+
NH 4Cl 

 NH3 + H2Cl H2
H2O2 Cr2O 72ă/H
+
SO2
3+
Non-oxidizing anions are Clă, SO24 , CO23 , CH3 COO , PO43 etc. S Fe
2ă 3+
SO4 H2O Cr
However NH +4 salts which contain oxidizing anions forms N2 or N 2O on heating.

Structure : H
NH 4 NO3(l)  N2 O + 2H 2O
O N
NH4 NO2  N 2 + 2H2 O O

(NH4 ) 2 Cr2 O7  N2 + Cr2O3 + 4H2O

NO2 has planar triangular structure

(iv) NH3 is manufactured by :

High pressure N
~ 450 C ă
(a) HaberÊs process N2  3H2 
  2NH3 (g) + Q

 O O
Fe (Fe2 O3 ) catalyst
MO Promoter 
Nitric acid (HNO3 )

(b) Cyanamide process HNO3 can act as an oxidizing agent.

CaC2  N2 
Electric
 CaCN2  C SO42ă S
furnace
(~ 1100 C) (Nitrolum) SO2
H 2S
Fe2+
Fe3+
S
HNO3 H2SO4

CaCN2 + 3H2O   CaCO 3   2NH 3 C I2
P

H2CO3 HIO3
Nitrous acid (HNO 2)
H2CO3

Ć It disproportionates to HNO3 (oxidation) and NO (reduction)

Aqua r egia
3HNO2 2NO + HNO 3 + H2O
+3 +2 +5 A mixture of conc. HCl and HNO 3 in the ratio 3 : 1 is called aquaregia. This is a powerful
reduction oxidizing agent and dissolves metals like Au and Pt. The two acids on mixing react as

oxidation 3HCl + HNO 3  NOCl + 2Cl + H 2O

The presence of NOCl and Cl makes aquaregia a powerful oxidizing agent.

Au + 3Cl  AuCl3

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 41 42 QUIZRR
NH3 is highly soluble in water by PH3 is insoluble in water. NH3 dissolves due to H-bonding.
AuCl3 + Cl AuCl 4 (or HAuCl 4, chloroauric acid)
ă

H
Pt + 4Clă  PtCl4 H O H
H
PtCl4 + 2Cl ă  PtCl 26 (or H 2PtCl6, Chloroplatinic acid) O H N H O H
Note : Au is not oxidized by HNO3 alone but by aquaregia. H
H H O H
R e d Phos ph or u s

Red phosporus is prepared by heating white phosphorus in the absence of air at 250ĈC for a few PH3 cannot form H-bond, so it is insoluble in water.
hours with a trace of iodine as catalyst in a closed iron vessel fitted with a safety valve. At the
Ox ide s of Ph
Phos
os
osph
ph
phor
or
orus
us
end of conversion, the product is ground under water and treated with hot caustic soda solution
to eliminate any unchanged white phosphorus. It is finally washed with hot water and dried by P ă oxides P4O6 and P4O 10
heating with steam.
Stream of air
Another allotrope of phosphorus is black phosphorus and is obtained by heating white phosphorus
 P4 X  P4O6

600 C

at 470 K under high pressure. A series of phases of black phosphorus are formed and one of these
Excess of air
phases consists of an extended layer structure in which each phosphorus is bonded to three P4   P4 O10

neighbours by single covalent bonds. Thermodynamically, black phosphorus is the most stable
These oxides are solids.
form.
White phosphorus, the form produced in the industrial synthesis, is a toxic, waxy, white solid that They differ from N oxides in stoichiometry and structure. It is due to inbality of P to form
contains discrete tetrahedral P4 molecules. Red phosphorus, by contrast, is essentially nontoxic (p ă p) bonds.
and has a polymeric structure : P 4O6 and P4O10 both have cage structure. The structures are based upon P4 tetrahedra.

P P P P
P4O6
P P·P P·P P·
P ·P In this oxide P ă atoms form a regular tetrahedron and O ă atoms are present at six edges of the
P P P P tetrahedron and bridge P ă atoms.
White phosphorus Red phosphorus
P
As expected for a molecular solid that contains small, non-polar molecules, white phosphorus has O O
a low melting point, (44ĈC) and is soluble in non-polar solvent such as CS2 . It is highly reactive, O
bursting into flames when exposed to air, and is thus stored under water.
P
O P
Phos ph
phii ne (P H3 )

(i) When a mixture of white P (P4 ) and NaOH soln. is heated, PH3 is formed. O P O

P4 + 2NaOH + 3H 2O 

 3NaH 2PO2 + PH3 P4O10
In this reaction some P2H 4 is also formed as side product. It is inflammable in air. In this oxide P4 tetrahedron has six edgeăbridging Oăatoms and four terminal Oăatoms. The
(ii) Ionic phosphides react with water to form PH3. terminal P ă O bonds have (d ă p) bonding. Therefore, there are two types of P ă O distances
in P 4O 10 large bridging P ă O and small terminal P ă O distances.
Ca3 P2 + 6H2O  3Ca(OH)2 + 2PH3

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 43 44 QUIZRR
O
Ć SO 3 + PCl 3  POCl 3 + SO2

P Ć PCl 3 + H2O  H 3 PO3 + 3H 2O

O O
O O Ć PCl 3 + HI  PI3 + 3HCl
O P O P O
P
Ć 3ROH + PCl  3RCl + H3PO3
P
O O
Ć ROH + PCl 5  RCl + POCl3 + HCl
O (d ă p) bonding in P 4O10

Exa mple 1 6
Oxy ac
aciids of P
Pb(NO3 )2
The common oxy acids of P are :

Oxidation
State of P Name Formula Proticity Structure F2 H2 O
+ 1 Hydrophosphorous F A B C + HNO3

acid (phosphinic acid) H3PO 2 1 Td HCI

CO 
+ 3 Phosphorous acid H3PO 3 2 Td.
G+H
D+E A+D+H2O
Td. Polymeric
+ 5 Metaphosphoric acid (HPO3)n 1 and contain PO4 Solution :
Td units A = NO2, N 2O4, C = HNO2, D = NO, E = CO2, F = NO2F, G = NOCl, H = Cl 2.
Td
+ 5 Orthophosphoric acid H3PO 4 3 Highly hydrogen Group 16 (VIA–The Cha
halc
lc
lcog
og
ogee ns
ns))
bonded Ć The first four elements are called chalcogens meaning ore forming (oxides, sulphides, selenides,
Td. (two tellurides).

+ 5 Pyrophosphoric acid H4P2O 7 4 tetrahedra Ć Similar to the groups discussed earlier, the metallic character in Group 16 increases with increasing
joined through O atomic number. Oxygen and sulphur are entirely non-metallic in their chemical behaviour. Selenium

ă atom) and tellurium though essentially non-metallic, assume increasing metallic character and are
termed as metalloids. Polonium is most metallic in the group.
220 C
H3 PO4  320C Density, melting and boiling points covalent and ionic radii, show a regular increase from oxygen
 H4P 2O7   (HPO3)
to polonium. The large difference in melting and boiling points between oxygen and sulphur can
be explained on the basis of their structure. Oxygen exists mostly as a diatomic molecule held
P ho sp ho r u s H al i d e s
together by weak van der Waals forces while others exist as polyatomic molecules, e.g., S8, Se8 ,
P4 + 6X2  4PX3 (in limited supply of X 2) etc., where the atoms are bonded by covalent bonds associated with high dissociation energy.
Their existence as diatomic and polyatomic molecules can be explained as follows. The bond
P4 + 10X2  4PX 5 (in excess amount of X 2) energy of the oxygen-oxygen double bond. O=O, is 498 kJ molă1. This makes the O=O bond
more than three times as strong as the OăO bond (bond energy for OăO is 142 kJ molă1). By
comparison the S=S bond is less than twice as strong as the SăS single bond (bond energy for

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 45 46 QUIZRR
ă1 ă1
S=S, 431 kJ mol ; SăS, 265 kJ mol ). This results in catenated ăOăOăOă chains begining Ć Unlike oxygen, the maximum coordination number of sulphur and other elements can
unstable relative to O=O, but catenated ăSăSăSă chains being stable relative to the molecule S=S. exceed four and valency is not limited to two because of available d-orbitals for bonding.
Stability of + 6 state decreases and that of + 4 state increases going down the group due
The elements of Group 16 are characterised by high ionisation energies. Their electronegativities
to inert-pair effect. It is :
decrease with increasing atomic number. Thus, in view of the fall in electronegativity, metallic
character within the group increases with increasing atomic size. Se4+ < Te4+ < Po 4+
Se6+ > Te6+ > Po 6+
Oxygen, the second most electronegative element, fluorine being the first, has a strong tendency
Ć The tendency to form multiple bonds to C, N and O decreases as we descend the group from
to accept two electrons and give O2ă ion. Thus, almost all metal oxides are ionic and contain O2ă
Se to Te. Thus S=C=S is moderately stable; Se=C=Se decomposes readily whereas Te=C=Te
ions. Usually oxygen exhibits an oxidation state ă 2 in its other compounds also. It exhibits
does not exist.
positive oxidation states only in a few compounds formed with fluorine, i.e., OF2 and O2F2. The
tendency for the formation of divalent anions decreases from sulphur downwards because of the Ć Thermal stability of the hyrdies decreases as we go down the group :
increasing size and decreasing electronegativity of the elements. Sulphur, selenium an tellurium H2 O > H2S > H 2Se > H 2Te > H2 Po
show a tendency for covalent with formal oxidation states + 2, + 4 and + 6 in compounds in which Ć They form halides of different oxidation number + 1, + 2, + 4 and + 6.
they are combined with more electronegative elements such as oxygen and halogens. In the Halides X Oxidation number
higher oxidation states of + 4 and + 6 of these elements electrons are unpaired and promoted to
S2X 2 F, Cl, Br, 1 + 1
vacant d orbitals.
SX 2 F, Cl + 2
Ć Selenium has unique property of photoconductivity and is used in photocopying (xerox)
machines and also a decoloriser of glass. Te and Po are highly toxic. Po is higher due to its SX 4 F + 4
intense radioactivity. Se and Te are found as selemides and tellurides in sulphide ores SX 6 F + 6
(Cu2Se, Cu 2Te). The colour of the red glass in the traffic signals is due to CdSe. Se2X2 Cl, Br + 1
Ć With valence electronic configuration ns2 np 4 the group 16 (VI A) elements are just two SeX2, TeX 2 Cl, Br + 2
electrons short of an octet configuration, and ă 2 oxidation state is therefore, a common one. SeX4, TeX 4 F, Cl, Br + 4
The stability of 2 state decreases with increasing metallic character as indicated by EĈ
TeX4 I + 4
(redox) values. This oxygen is powerful oxidising agent and H2Se and H2 Te are reducing
SeX6, TeX 6 F + 6
agent (EĈ values of Se and Te are negative). Because S, Se, and Te are much less
electronegative than oxygen, they are commonly found in positive oxidation states as + 4 in The stability of the halides decreases in the order F > Cl > Br > I. + 6 oxidation is observed
SF4, SO2 and H2 SO3 , and + 6 in SF6, SO3 , H2 SO 4 . in fluroide, while iodide of Te(TeI 4) is formed.

Ć H2Se and H2 Te are unpleasant gaseous hydrides like H 2S but less stable than H2 S, order SF6 is thermodynamically inert, non-toxic gas. Inertness of SF 6 is due to the presence of
being H2O > H 2S > H 2Se H2 Te > H2Po. sterically protected sulplhur atom. SF6 is used as a gaseous insulator in high voltage generators.
SF4 and SeF4 are good fluorinating agents and ăCOOH group can be converted into CF 3
Ć Oxoacids of S, Se and Te exist and H2SO 4 and H2 SeO4 and considered as strong acids.
and > C=O and ăP=O into CF 2 and ăPF 2 groups.
Ć The tendency for catenation decreases markedly as we go down the group. This property is
Ć Oxides of sulphur are more stable than the corresponding oxides of other elements.
prominently displayed by sulphur (S8). The SăS bond is important in biological system and
is found in compounds such as cysteine, some proteins and enzymes. Stable polyoxides and
Ozone ( O3 )
polysulphides are known. Examples are :
Ć In the laboratory, O3 can be made by passing oxygen through a strong electric field. An
HăOăOăH, HăSăSăH, HăSăSăSăH,
equilibrium is set up :
HăSăSăSăS ăH.
3O2(s)  2O3 (g)
Ć The metallic character increases as we descend the group. S is non-metal and insulator. Se
and Te are metalloids and are semiconductors. Po is a metal. Ć Some 30 km above the earthÊs surface oxygen molecules can be split apart by UV light from
the sun. Some of the atoms join with other oxygen molecules to make ozone :

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 47 48 QUIZRR

O2(g) + O(g)  O3(g) Potassium ozonide KO3 is an orange coloured solid and contains the paramagnetic O 3 ion.

Ć O3 is an unstable, dark blue diamagnetic gas, b.p. ă 112ĈC. The colour is due to intense Ć The amount of O3 in a gas mixture can be determined by passing the gas into a KI solution
absorption of red light. (at a constant pH 9.2 using borate buffer). The iodine that is liberated is titrated with
sodium thiosulphate solution.
NO + O3  NO2 + O 2
O 3 + 2Iă + H2O  I 2 + 2OH ă + O2
O3 + h  O2 + O 2
I 2 + 2S 2O3   2I ă + S4 O62

NO2 + O  NO + O2 Ć O3 also adds to unsaturated organic compounds at room temperature forming ozonides
which can be cleaved to aldehydes and ketones in solution :
Net reaction : 2O3 + h  3O2 O
ă based on reactive chlorine species from CFC
CH2 CH2
H2O/Zn
Cl + O3  ClO + O2 CH2 CH 2 + O3 2HCHO
O O
O 3 + hv  O + O2 Ć O3 is used as a disinfectant; it is used to purify drinking water since, it can destroy bacteria
and viruses. It is better than Cl 2 since, it (O3) avoids the unpleasant smell and taste of Cl 2
ClO + O  Cl + O2 and any excess O3 soon decomposes to O2.

Net reaction : 2O3 + hv  3O2 H2 O/ Zn  2CH CHO

CH · CH = CH · CH3  O3  3
Ć O3 is thermodynamically unstable, and decomposes to O2 :
KCl O3
2O 3  3O2 G = ă 163 kJ molă1
 MnO2
Ć O3 is an extremely powerful oxidising agent :
electrolysis
Air O2 H 2O
O3 + 2H+ + 2e ă  O 2 + H2 O

O3 + H2O + 2e ă  O 2 + 2OH ă strong

electric field
CH2=CH 2 Iă
3PbS + 4O3  3PbSO4 HCHO O3 I2
H2 O/Zn (H Cl+S
n Cl )
4ă NO 2
6NO2 + O3  3N2O5 ) ]
C N 6ă d es t oz on e la SnCl4
[Fe ( PbS roy in yer
OH S H 2O O2 +NO2
[Fe(CN)6 ]3ă
g rea
cti on

H2
S + H2O + O 3  H2 SO 4 NO 2 s

KO
S

H
2KOH + 5O3  2KO3 + 5O2 + H2 O PbSO 4 H 2SO4 N2O5 H2SO4 KO3

O3 + 2KI + H2O  I2 + 2KOH + O2 The molecules O3 is bent with an OOO angle 116.8Ĉ and equal OăO distance of 128 pm and
may be described 90Ĉ canonical forms.
3SnCl2 + 6HCl + O3  3SnCl4 + 3H 2O
O O+ O+
2[Fe(CN)6 ]4ă + H2O + O3  2[Fe(CN)6] 3ă + O 2 + 2OHă O 116.8Ĉ O O O O O
218pm

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 49 50 QUIZRR
Al lo tr opy a nd Po lymor phi sm o f S ul
ulph
ph
phur
ur Co mpo und of Su l ph
phuur

Many different molecular species are possible for the elemental sulphur, and this accounts for the Oxide :
existence of the large number of physical forms in which the element may appear. Allotropy is Sulphur forms several oxides of which sulphur dioxide (SO2 ) and sulphur trioxide (SO 3) are
more complex for the element sulphur than for any other element of group 16 (VI). Sulplhur may important.

exist as :
Su l p hu r di
diooxide
Ć rhombic sulphur (S ) which has sixteen S8 rings in a unit cell Preparation :

Ć monoclinic sulphur (S) which has six S 8 rings in its unit cell. 4FeS2 + 11O2  2Fe2 O3 + 8SO 2

Ć liquid sulphur (S ) comprised of S8 molecules. This is yellow, transparent, mobile liquid. Propert ies :
At 160ĈC, a remarkable transformation occurs. The S8 rings open up and join together into 1. As reducing agent
long spiral-chain molecules, resulting in : (i) Action on halogens :

Ć liquid sulphur (Sø) which is dark in colour and very thick and viscous. The chain SO 2 + Cl 2 + 2H2 O  H 2SO4 + 2HCl
length and viscosity of the liquid reach a maximum at about 180Ĉ C. At higher (ii) Action on FeCl 3
temperatures the chains break up and viscosity decreases again. At 445ĈC, this liquid boils,
2FeCl3 + SO 2 + 2H2O  H 2SO 4 + 2FeCl2 + 2HCl
producing :
2. Reaction with acidified KMnO4
Ć sulphur vapours, which consists of molecules ranging from S2 to S10, but predominantly
2KMnO4 + 5SO2 + 2H2O  K2SO4 + 2MnSO 4 + 2H 2 SO4
S8. At higher temperatures, S2 predominates. S2 is paramagnetic.
3. Reaction with acidified K2 Cr2O7
Ć Plastic sulphur forms if liquid sulphur (ø) is poured into cold water. It consists of chain-
like molecules and has rubber-like properties when first formed. On standing, it becomes K2Cr 2O7 + 3SO2 + H2 SO4  K2SO 4 + Cr2(SO4) 3 + H2O

brittle and finally converts to rhombic sulphur. Above transformations can be written 4. Oxidising property
as :
(i) 2H 2S + SO2  2H 2O + S 
95.5 C
  160 C 445 C
S    S   S   S 8 g 
(ii) SO 2 + 2Mg  2MgO + S 

2000 C 1000 C
S  S 2  S 4  S 6 Su l ph
phuur t r i ox i de

Preparation :
Ć If rhombic sulphur is heated rapidly, it fails to convert into monoclinic sulphur and melts
By dehydration of H2SO 4
at 113ĈC.
P2O5
Ć In cyclo-S6, the the ring adopts the chair form chain polymers, catena-S n are also H 2SO 4   SO 3  H 2O
heat

known.
Reaction : H2SO 4 + SO3  H 2S2O7

H2SO 4 saturated with SO3 is called oleum.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 51 52 QUIZRR
Oxyacids of sulphur : O O O
Based on the structural similarities, oxoacids or (oxyacids) of sulphur may be classified as :
HO O S OH HO S O O S OH
1. Sulphoxylic acid, H 2SO 2
2. Sulphurous acid series O O O
(a) Sulphurous acid, H2 SO3 Peroxomonosulphuric acid Peroxodisulphuric acid

(b) Thiosulphurous acid, H 2S2O2 (Structure of oxoacids of sulphur)

(c) Dithionus acid, H2 S2 O 4
(d) Di or pyrosulphurous acid H2S2 O5 Su l ph
phur
ur
urii c Ac
Acii d ( H 2SO4)
3. Sulphuric acid series
Ć As an oxidizing agent
(a) Sulphuric acid, H2 SO 4
(b) Thiosulphuric acid, H2 S2O 3 2HBr + H2SO 4  Br2 + SO2 + 2H2O

(c) Di or pyrosulphuric acid, H2S2O 7

K4[Fe(CN)6] + 6H 2SO4 + 6H2O  2K2SO4 + FeSO4 + 3(NH 4) 2SO 4 + 6CO
4. Peroxo-acid series
Peroxomonosulphuric acid (also called CaroÊs acid, H2SO5 ) 8HI + H2SO 4  H2S + 4I2 + 4H 2O
Perdisulphuric acid (also called MarshallÊs acid, H2S2 O8)
Ć As a dehydrating agent
O HO O
Conc. H2SO4
CH3CH 2OH 
S  CH 2 = CH2 + H2O
HO HO
HO S
S O S S S OH HO S O
Ć HO ă SO2 ă OH + 2PCl 5  SO2Cl2 + 2POCl3 + 2HCl
HO HO Sulphuryl Chloride
O O
Sulphurous acid Thiosulphurous acid Dithionous acid Pyrosulphurous acid O O

HO O
O S O S OH S
HO HO
S O O
ă

S S OH O
ă
O O
O OH O OH
S-atom is sp3 hybridised. SO24  ion is tetrahedral.
Sulphuric acid Thiosulphuric acid O S O
Ex
Exaa mp
mpll e 1 7
OH
Pyrosulphuric acid H2SO4 cannot be used to obtain HBr from KBr. Why ?

O O O O Solution :
H2SO4 oxidises HBr.
HO S S OH HO S (S)n S OH
Sodium thiosulphate (Na2S2O 3.5H2O) :
O O O O If one of the oxygen atoms in the sulplhate ion is replaced by sulphur, the resulting ion (S2O32ă) is
Dithionic acid Polythionic acid known as thiosulphate.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 53 54 QUIZRR
P r e p a r a t i on : Ex a mp
mpll e 1 8

(i) Sodium thiosulphate is prepared by boiling aq. solution of metal sulplhites with elemental Why sodium thiosulphate is used in photography ?
sulphur. Solution :
It can remove the undecomposed AgBr as soluble thiosulphate complex.
1 373K
Na 2 S O3  S8  Na 2S 2O3 2Na 2S 2O3 + AgBr  Na3 [Ag(S2 O 3) 2 ] + NaBr
8 H 2O

Hydrated sodium thioosulphate Na2S2 O3.5H 2O is known as HYPO.

H y dr
droog e n sul phide
(ii) SpringÊs reaction may be used for the preparation of sodium thiosulphate. It consists in
Preparation :
treating a mixture of sodium sulphide and sodium sulphite with calculate quantity of iodine.
Prepared by the action of dil. HCl or H2SO 4 on iron sulphide
Na 2 S + Na 2SO3  I2  Na 2 S2 O3  2NaI
FeS + 2HCl (dil)  FeCl2 + H 2S 

P r op
opee r t ie
iess : Properties :

(i) Reaction with dilute acids : It reacts with dilute acids to liberate sulphur dioxide gas along It is a colourless, poisonous gas having the smell of rotten eggs.
with precipitate of sulphur. 1. As reducing agent
(i) Action on halogens
Na2S2O 3 + 2HCl  2NaCl + H 2O + S + SO2
H2S + Cl 2  2HCl + S 
(ii) Reaction with BaCl2 : It gives white ppt. of barium thiosulphate.
(ii) Action on FeCl3
S2 O23  Ba2  BaS2 O3 
White
2FeCl3 + H2 S  2FeCl2 + 2HCl + S 

(iii) Reaction with silver nitrate solution : Gives white ppt. which quickly changes to yellow, 2. Reaction with acidified KMnO4
brown and finally black due to the formation of silver sulphide. 2KMnO4 + 3H2SO 4 + 5H2 S  K2SO 4 + 2MnSO4 + 8H2O + S 

3. Reaction with acidified K 2Cr2O7

S2 O32  2Ag  Ag2 S2 O3 
White ppt.
K2Cr2O7 + 4H2 SO4 + 3H 2S  K2SO 4 + Cr2(SO4) 3 + 7H2O + S 

Ag2S2O 3 + H2 O  Ag 2 S + H2SO 4

Ex
Exaa mp
mpll e 1 9
With conc. solution of sodium thiosulphate, silver nitrate gives no ppt.
The two atoms of sulphur in Na2 S2 O3 have
(iv) It reacts with silver salts to form sodium argento thiosulphate complex
(A) + 2 and + 4 oxidation state (B) ă 2 and + 6 oxidation state
AgBr + 2Na2 S2O3  Na3 [Ag(S 2O3) 2] + NaBr (C) + 4 and + 6 oxidation state (D) same oxidation states
Sodium argento
Solution : (B)
thiosulphate complex

(v) Thiosulphate  S 2O 32  ion is oxidized by iodine I2 to tetrathionate S4 O62

Ex
Exaa mp
mpll e 2 0
Bleaching action of SO 2 is due to

2Na2S2O3 + I2  Na 2S4 O6 + 2NaI (A) reduction (B) oxidation

(C) hydrolysis (D) its acidic nature
Solution : (A)

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 55 56 QUIZRR
Ex a mp
mpll e 2 1 Ex a mp
mpll e 2 5

When sulphur is boiled with Na2 SO3 solution, the compound formed is Which of the following reaction does produce SO2 ?
(A) sodium sulphide (B) sodium sulphate (A) Ag + H2SO 4 (conc.) 

 (B) CaSO4 + C 


(C) sodium persulphate (D) sodium thiosulphate
Solution : (D) (C) FeS2 + O 2 

 (D) Zn + H2SO 4 



Solution : (D)
Exa mp
Exa mpll e 2 2

The structure of dithionate ion is Ex

Exaa mp
mpll e 2 6

2ă 2ă In preparing a standard aqueous solution of MohrÊ salt, [FeSO4.(NH 4) 2SO4. 6H2O] a few millitres
O O O O
of H2 SO4 is added to the solution. The added H2SO4
(A) O S S O (B) O S S O (A) prevents reduction of the salt
O O O O O (B) prevents oxidation of the salt
(C) makes the solution homogeneous by converting insoluble Fe(OH) 2, which is formed by
2ă 2ă
O S hydrolysis, into soluble FeSO4
O (D) neutralizes the ammonia formed by hydrolysis
O S S
S Solution : (C)
(C) O O S O (D)
O O
O O
G r ou
oupp 1 7 ( H a lo
logg e ns
ns))
Solution : (B) Halogens (X2 )
Ć F2 is extremely reactive, and this causes great difficulties in the preparation and handling of the
Ex
Exaa mp
mpll e 2 3
element.
When SO2 gas is passed into an acidified solution of K2 Cr 2O7 , the oxidation state of ă Moissan (1886) prepared it from CaF2 :
chromium changes
CaF2 + H 2SO 4  CaSO4 + 2HF
(A) from + 12 to + 6 (B) from + 3 to + 6
(C) from + 6 to + 3 (D) from + 6 to + 4 KF + HF  KHF2

Solution : (C)
electrolysis
KHF2 
 H2  F2
at cathode at anode
Ex
Exaa mp
mpll e 2 4
ă Modern method uses graphite anode and steel cathode in a steam heated steel tank.
The stability of the hydrides of oxygen, sulphur, selenium and tellurium decreases in
ă If F2 were formed by the electrolysis of aqueous fluoride solution, it would immediately
the order
oxidise water to O 2
(A) H2 Te > H2Se > H2S > H 2O (B) H2 O > H2S > H 2Se > H2Te
F2 + 2H2 O  4HF + O 2
(C) H2 O > H 2S > H2Se > H2 Te (D) H2 O  H2S > H 2Te > H 2Se
Ć The commercial production of Cl2 is by electrolysis, either of concentrated aqueous NaCl or of
Solution : (B) molten salt such as NaCl(l) or MgCl 2(l) :

electrolysis
2NaCl + 2H2 O 
 2NaOH + H2  Cl2
 
at cathode at anode

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 57 58 QUIZRR
Ć Br 2 is obtained from sea water and brine lakes. Sea water contains about 65 ppm Br. Br2 is Ć Oxidising power is in order :
isolated in following which oxidises Bră to Br 2.
F2 > Cl2 > Br2 > I2 .
Cl 2 + 2Bră  Br2 + 2Cl ă
1
X 2 solid, liquid, gas   X   hydrated 
ă Br2 is quite volatile hence is removed by a stream of air. 2
ă Br2 is absorbed into aq Na 2CO3 solution when NaBr and NaBO 3 are formed :
F2 has the most negative GĈ value, hence is strongest oxidising agent and can oxidise Clă, Br ă
3Na 2CO 3 + 3Br2  5NaBr + NaBrO3 + 3CO 2 and Iă to respectively Cl2, Br2 and I 2. F 2 can also oxidise H2O to O2 .

or 3Br2 + 6OHă  5Br ă + BrO 3ă + 3H2O 1

F 2 + H2O  2HF + O2
2
Ć I2 is obtainable in small quantities from dried seaweed, since certain marine plants absorb and
concentrate Iă selectively in presence of Cl ă and Br ă. Low concentration of I ă are also found in Similarly Cl2 will oxidise Bră and Iă, and Br2 will oxidise Iă. In general any halogen (X 2) of lower
some natural brines (salt solutions) associated with oil fields.
atomic number will oxidise halide ions (Xă) of higher atomic number.
Chile saltpetre is mainly NaNO3 but it contains traces of sodium iodate NaIO 3 and sodium
The ionic character of the MăX bond decreases in the order MăF > M ă Cl > M ă Br > M ă I.
periodate NaIO 4.I2 is recovered by reducing IO3 to Iă by NaHSO3 and then oxidation of Iă to I2
by IO3 itself : Reaction Comment

+
Ć With H 2O
IO3 + 3HSO3  I + 3SO24  + 3H
ă

2F2 + 2H 2O  4H+ + 4Fă + O 2 Vigorous reaction with F2; atmospheric O2 can
5Iă + IO 3 + 6H+  3I2 + 3H2O oxidise Iă to I2 hence reverse reaction
Natural brine is treated with Cl2 water to oxidise Iă to I2 and the solution is passed through an 2X2 + 2H 2O  4H + + 4X ă + O2 Cl2 > Br2 > I 2 (F2 does not disproportionate).
ion-exchange resin which absorbs I 2 as I3 .I3 is removed from the resin by treatment with alkali. disproportionate +
X2 + H2O   X + HOX + H
ă

ă Reactivity of halogens is based on bond-energy (BE) value.

Ć With H 2
F2 > Cl2 > Br2 > I 2
H2 + X2  2HX All the halogoens with Br2 photochemical reaction,
Greater the BE, smaller the reactivity
with I2 very slow even at high temperature
MnO2
Ć With metals
conc. HCl
2M + nX2  2MNn Most metals form halides.
KMnO4 conc. HCl Cl 2 electrolysis NaCl (aqueous or molten) Ć With CO

Bră CO + X2  COX2 Only Cl2 , Br2 from carbonyl halide

ă
OH ă ă Ć With P
Br 2 Br + BrO3
2P + 3X2  2PX3 For F, Cl, Br, I

Iă 2P + 5X2  2PX5 For F, Cl, Br

Ć With S
I2
2S + X2  S 2X2 Cl, Br
lOă3
S + 2Cl2  SCl 4
Iă IO3ă
S + 3F2  SF6
in chile salt petre

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 59 60 QUIZRR
Ć With H 2S Ć There are never more than two different halogens in a molecule. The bonds are covalent because
of the small electronegativity difference. Ternary combinations occur in polyhalide ions (e.g.,
H2S + X 2  2HX + S All the halogens oxidise H 2S (S 2ă) to S
IBrClă)
Ć With SO 2
ă The electrical conductance of molten I2 is ascribed to self-ionisation
SO2 + X2  SO 2X 2 F and Cl
3I2  I+3  I3
Ć With NH3
ă The interhalogens are generally more reactive than the halogens (except F2 ). This is because
8NH3 + 3X2  N2 + 6NH4X F, Cl, Br the AăX bond in interhalogens is weaker than the XăX bond in the halogens.
Ć With halogens ă Hydrolysis of interhalogens gives halide and oxohalide Oxohalide is always formed from
larger halogens present.
X2 + X´2  2XX´ Interhalogen compounds
Ć With cold NaOH H O
2
BrF5  5F  BrO3
bromate ion
2NaOH + 2F2  2NaF + OF2 + H 2O
H2 O
2NaOH + X2  NaX + NaOX + H2O (X = Cl, Br) I 2 does not react under the same HCl Clă + IO ă3
Cl2 reacts with dry slaked lime forming condition iodate ion

bleaching powder H 2O
Clă + IOă
hypoiodite ion
Ca(OH)2 + Cl 2  CaCl(OCl) + H 2O
Ć With hot NaOH

6NaOH + 3X2  5NaX + NaXO3 + 3H 2 O (X = Cl, Br, I) An oma

oma l o u s B e h a v i o u r o f F l uor
uor i n e

Fluorine differs from other elements of the group because of its exceptionally small atomic and
Cl2 is used as a bleach or as a disinfectant (as in public water supplies). It reacts slowly with H 2O
ionic size and low fluorineăfluorine bond dissociation energy. The result of these differences is
to form HCl and HOCl. The hypochlorous acid then decomposes into HCl and O radicals, which
that fluorine is the most electronegative element in the periodic table and is a powerful oxidant.
kill bacteria.
Some differences between flourine and other halogens are :
Cl2 + H2 O  HCl + HOCl
Ć It is more reactive than other halogens because of low FăF bond energy, also due to its high
electronegativity the bond between fluorine and other elements is very strong so its compounds
HOCl  HCl + O
are more stable. Some of them are inert. e.g. SF6.
These oxygen radicals are very strong oxidising as well as effective bleaching and disinfecting
Ć Fluorine is almost invariably monocoordinate (coordination number = 1) and is never more
agent in aqueous solution of Cl2 or hypochlorite salts.
than mono covalent.
Ć The halogens react with each other to form interhalogen compounds of the type AX, AX3, AX5 and
Ć Fluorides are more ionic.
AX7 of which A is of higher atomic number as shown :
Ć Fluorine forms strong hydrogen bonds resulting in the properties of hydrogen fluoride being
AX AX3 AX5 AX7
anomalous.
CIF CIF3 CIF 5
Ć Fluorine is the strongest oxidising agent and oxidises the elements to their highest oxidation
BrF BrF3 BrF 5 state, for example in IF7, iodine has oxidation number seven.
IC l ICl 3 (I2Cl 6) IF 5 IF7 Ć The reactions of fluorine are also different from other halogens. Fluorine fumes in moist air
IBr and decomposes water to give oxygen, whereas other halogens are sparingly soluble in
BrCl water and react partly to give hydrohalic and hypohalous acids.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 61 62 QUIZRR

2F 2 + 2H2O  4HF + O2 Ć CaF2 has also SiO2 as impurity otherwise. HF formed would react with SiO 2 forming SiF4
and H2 SiF 6.
X2 + H 2O  HOX + HX
SiO 2 + 4HF  SiF 4 + 2H2O
Fluorine reacts with alkalies to yield the oxide, F2O :
SiF4 + 2HF  H2 [SiF6]
2F2 + 2NaOH  OF2 + 2NaF + H 2O

The other halogens react with alkalies to yield a solution of hypohalite ions, which may NaCl + H2 SO4 
150 C
 HCl + NaHSO4
Ć
disproportionate. The oxoacid of fluorine, HOF, prepared recently is very unstable. The oxides of conc. salt cake

fluorine are not acidic.

550 C 
NaHSO 4  NaCl   HCl + Na 2SO 4
Cl 2 + 2NaOH  NaClO + NaCl + H 2O
This method is called Âsalt-cakeÊ method involves formation of NaHSO4 (salt cake)

Ha l og
ogeen Acids Ć HF is only just liquid at room temperature and HCl, HBr and HI are gases. HF has
abnormally high boiling point due to intermolecular H-bonding which is not possible in other
Ć All the halogens acids (HF, HCl, HBr, HI) are known. In aqueous solution, they are typical halogen acids due to their smaller electronegativity values.
mineral acids whose acid strengths decrease in the direction of increasing bond energy, that
HCl < HBr < HI < HF
is
Some H-bonding also occurs in the gas, which consists of a mixture of cyclic (HF)6 polymers,
HI > HBr > HCl  HF dimeric (HF)2 and the monomeric HF.
  weak acid
strong acids ă

+
+ F  +
Ć HX can be prepared by direct combination of H2 and X2  H 
H
ă
134Ĉ  H
Fă F
H2 (g) + X 2(g)  2HX (g) 

ă reaction between H2 and F 2 is very fast,

Because of the tendency to form hydrogen bond, metal fluorides are solvated by HF giving
ă reaction between H2 and Cl2 is also rapid,
species of the type HF2 etc. KHF2 (KF. HF), KH2F3 (KF.2HF) and KH3 F4 (KF.3HF) are
ă but reaction between H2 and Br 2 or I2 is very slow.
known examples.
Gf of HF, HCl and HBr are large and negative suggesting that for them reaction Ć HF attacks glass, other halogen acids do not. Glass is silicates of sodium and calcium and
are converted into complex fluorides :
H2 + X2  2HX
Na2SiO 3 + 6HF  Na2SiF 6 + 3H 2O
goes to completion. For HI(g), G f is small and positive suggesting that HI should dissociate
CaSiO 3 + 6HF  CaSiF6 + 3H2O
2HI(g)  H 2 (g) + I2 (g)
Hence HF canÊt be stored in a glass vessel. Instead, it is stored in a wax-vessel which does
to some extent. However, because of the high activation energy the dissociation occurs only not react with HF. This unique property of HF of attacking glass is used for making
very slowly in the absence of a catalyst. As a result, HI(g) is quite stable at room temperature. permanent marking eg. glass-wares.
Thus, at room temperature decomposition of HI(g) is kinetically controlled (rather than Ć In the gaseous state, HX are essentially covalent. In aqueous solution, they ionise to form
thermodynamically controlled). H2O+ and Xă but not H + and Xă.
Ć CaF2 + H2 SO4 

 CaSO4 + 2HF H2O  HX  H 3O +  X 
base acid acid base

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 63 64 QUIZRR
HF has more ionic character (due to greater electronegativity difference) than HCl, HBr and Ba(ClO3) 2 can be prepared by passing Cl 2 in Ba(OH) 2 solution

HF  HCl
 <HBr
< HI
 6Ba(OH)2 + 6Cl2  Ba(ClO3 )2 + 5BaCl2 + 6H 2O
HI but acid strength varies as : weak
strong
They can also be produced by reactions of X2 with hot aq. base (NaOH)
Acid strength is dependent not on the electronegativity difference of H and X but on the
3X2 + 6HOă  XO 3 + 5Xă + 3H2 O
tendency of the hydrated molecule to form hydrogen ions :
KClO3 decomposes on heating, the product depends on temperature
HX (hydrated)  H+ (hydrated) + Xă (hydrated)
400 ă 500Ĉ C
Ć Dipole moment of HF is maximum and is in order (i) 2KClO 3 2KCl + 3O 2
[MnO 2]
HF > HCl > HBr > HI
1.19D 1.05D 0.80D 0.420D 150Ĉ C

P r e pa
parr a t io
ions
ns o f o x o a c id
idss Lower
(ii) 4KClO3 
Temp.
 3KClO4  KCl
Most of the oxo acids and acid anions of halogens are known only in solution. They can be

obtained by reaction of the free halogens with (i) water or (ii) aq. bases : Zn(ClO 3 ) 2  2ZnO + 2Cl 2  5O 2

X2 + H 2O  H + + Xă + HOX Chlorates are used in matches and fireworks. Sodium chlorate is used as a powerful weed killer.

X2  2NaOH  NaX + NaOX + H2 O Perbromic acid HOBrO 3

(cold dil.)

It is best prepared by oxidation of BrO 3 by F2 in 5M NaOH solution.

3X 2  6NaOH  5NaX + NaOXO 2  3H 2O
(conc. hot)
BrO 3  F2  2HO   BrO 4  2F   H 2O
(X = Cl, Br, I)
Solution of HBrO4 can be concentrated upto 55% (6 M), without decomposition. The hydrate
All the above reactions are rapid disproportionation of halogens.
HBrO4.2H2 O can be crystallized.
Note :
(i) Reaction of X2 and water can produce HOX only.
Periodic acid HO IO3
(ii) There is appreciable concentration of HOCl.
The common form in aq. solution of this acid is HIO4 and also H5 IO6. H5IO 6 is called paraperiodic
(iii) The HOI is negligible in a saturated solution of iodine.
acid (or orthoperiodic acid). It is a white crystal. It is decomposes on heating as

Ha
Hall i c a c i ds H O XO2 (X = Cl
Cl,, B r , I ) 100 C ~ 200 C
2H5IO6   2HIO4 
 I 2O5 + O2 + H2 O
 4H2 O
All the three halic acids are known. The acids HOClO2 and HOBrO 2 are known only in solution
and as salts. Only iodic acid (HOIO2) is stable out of aq. solution. It is a white solid. It can be The IO 4 ion is tetrahedral while (OH)5IO is octahedral. Periodates can be made by oxiding iodate
prepared by oxidizing I2 with conc. HNO3 or O3.
with Cl2 in alkaline solution.
I2 + 10HNO3  2HIO 3 + 10NO 2 + 4H 2O
IO3  Cl2  6HO  IO65  2Cl  3H2 O

HO
HOCC l O 2 a nd HO
HOBr
Br
BrOO2
C ă OH HIO4
·C=O
They can be made by treating barium halates with H2 SO4 + HIO 3
· C ă OH ·C=O
Ba(Cl O3 )2 + H 2SO4  2HClO3 + BaSO 4 

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 65 66 QUIZRR
St r u c t ur
uree o f ox
oxoo a n io
ions
ns P s e u d o h a l o g e n s a n d P s e u do
dohh al id es

Many substances have properties either like X2 or Xă (X = halogen). They are called pseudohalogens
Anions XOă XO2 XO 3 XO4
and pseudohalides. They contain two or more atoms in which one at least is N ă atom, such as
Total valence electrons 14 20 26 32 (CN)2, CNă , SCNă etc.
No. of bonds (= no. of bps) 1 2 3 4 Some pseudohalogens and pseudohalides
Electrons for bonds 8 16 24 32
Pseudohalogens Pseudohalides
Lone pairs (14 ă 8)/2 = 3 (20 ă 16)/2 = 2 (26 ă 24)/2 = 1 0
Cyanide ion CN ă
Total electrons pairs 1+ 3= 4 2+ 2= 4 3+ 1= 4 4ă 0 = 4
Structure Td Td Td Td Cyanamide ion CN 22

Shape Linear Angular  pyramidal Td Cyanogen gas (CN)2 Azid ion N3

XO ă
XO 2ă XO3ă XO4ă Thiocyanogen (SCN)2 Thiocyanate ion SCNă
O Cyanate ion OCNă
Fulminate ion ONCă

The cyanogen gas and CNă ion are best-known pseudohalogen and pseudohalide. They behave
X X X X
like X2 and Xă , e.g.,
O O O O
O O
(a) (CN)2 disproportionate in water like X 2
(CN)2 + H 2O  HCN + HOCN
O O O
(Linear) (Angular) (Pyramid) (Tetrahedral) Cl2 + H2 O  HCl + HOCl

St
Strr u c t ur
uree an
andd s h ap
apee (b) CNă behaves similar to Iă

Total 2Cu2+ 
(aq)  4CN(aq)  2CuCN +  CN 2
Molecules Bond Lone electron Structure Shape
pairs pairs pairs 2+
2Cu(aq)  4I  2CuI + I2
X´
Both the above reactions are reduction of Cu2+ to Cu+ by CNă and Iă ions.
X
XX´3 3 2 5 X´ T ă shaped (c) The solubility of metal halides and metal cyanides are very similar,
(tbp) X´
NaX and NaCN  Water-soluble
X´
X´ X´
AgX and AgCN  Water-insoluble

X (X = Cl, Br, I)
XX´5 5 1 6 Square
PbCl2 and Pb(CN) 2  Water insoluble
X´ X´ pyramid
(Oh) (d) Like halides pseudohalides (CNă , SCNă etc.) are good ligands CuCl24  , ZnCl24  , Cu(CN)24  .
X´ X´
{Please note, the word ligands will be dealt in chapter co-ordination complexes}
X´
XX´7 7 0 7 X Pentagonal (i) CN ă complexes with transition metals and Zn, Cd and Hg.
X´
bipyramid (ii) Most of the CNă complexes are ionic [Fe(CN)6] 4ă, [Ni(CN)4] 2ă, [Mn(CN)6 ]4ă etc.
X´
(pbp)
X´
(iii) CN ă can stabilize low oxidation states also, e.g [Ni(CN) 4] 4ă.

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 67 68 QUIZRR
Bl e a c h i n g P o w d e r Ć Helium has the lowest boiling point of any element, and its behaviour as a liquid is most
unusual. It will creep up the walls of the container in which it is placed and thus it exists
The exact chemical composition of bleaching powder is not yet known but it behaves as if it
in two phases in liquid helium, one of which has an extremely low viscosity.
contains calcium hypochlorite Ca(OCl)2 and basic calcium chloride, Cl2 .Ca(OH)2 .H2O

X e on f l u o r i d e s
Pr e pa r at io n
Xenon reacts directly with fluorine (only). The products depend on respective amounts of Xe and
It is prepared by passing chlorine over slaked lime
F2 and temperature also. The reactions are generally carried out in seal tubes.

Ca(OCl) 2  CaCl 2.Ca(OH) 2 . H 2O + H 2O

3Ca(OH)2 + 2Cl2    
2:1
Bleaching Powder XeF2
/P
1:5
P r op
opee r t ie
iess : Xe + F2 XeF4
/P
1. Reaction with dilute acids : With dilute acids, it gives chlorine which is known as 1 : 20 XeF6
available chlorine. /P

CaOCl2 + 2HCl  CaCl 2 + H2 O + Cl 2    heart

P  Pressure
CaOCl2 + H2 SO4  CaSO4 + H 2O + Cl2  These three fluorides are crystalline volatile substances which sublime at room temperature but
2. When treated with water it decomposes into calcium chloride and calcium hypochlorite. can be kept in nickel containers.
The fluorides are strong oxidising agents.
2CaOCl2 + H2O  CaCl2 + Ca(OCl) 2 + H2 O
XeF2 + 2HCl  Xe + Cl2 + 2HF
3. Bleaching powder reacts with CO2 (atmospheric) and gives chlorine which accounts for its
oxidising and bleaching actions.
XeF4 + 4KI  Xe + 2I2 + 4KF
CaOCl 2 + CO2  CaCO3 + Cl2 
XeF2 + Ce2(SO 4)3 + SO24   Xe + 2Ce (SO4) 2 + F 2
4. Action of heat : On heating bleaching powder gives a mixture of chlorate and chloride.
They are good fluorinating agents also.

6CaOCl2  Ca(ClO3 ) 2  5CaCl2
2SF4 + XeF4  2SF6 + Xe

G r ou
oupp 1 8 ((T
The N
Nooble G
Gaa s e s) Pt + XeF 4  Pt F4 + Xe
Ć Because of highest ionisation energy of group 18 elements in their respective periods, they
F
were given the name Ânoble gasesÊ and thus inert. However, at least in the case of xenon,
it is not so; it forms series of compounds. + XeF 2 + Xe + HF
Ć The noble gases are colourless, tasteless and odourless. In the liquid and solid states the only
forces of attraction among the atoms are very weak London or van der Waals forces.
Their reaction with water is different
Polarisability and interatomic interactions increase with increasing atomic number. The
attractive forces among the atoms are so small that they remain liquid at 1 atmospheric (a) XeF2 is water soluble and undergoes slow oxidative hydrolysis.
pressure even at a temperature of 0.001 K. 2XeF2 + 2H2O  2Xe + O2 + 4HF

P-BLOCK ELEMENTS P-BLOCK ELEMENTS

 QUIZRR 69

(b) XeF4 reacts with water violently to give XeO 3

3
3XeF4 + 6H2 O  2Xe + XeO 3 + O + 12HF
2 2

In this reaction XeF4 disproportionates and H2O is parthy oxidized.

(c) XeF6 also reacts violently to give XeO 3

XeF 6 + 6H2O  XeO 4 + 12HF

With small amount of water

XeF6 + H 2O  XeOF 4 + 2HF

Ex a mp l e

Xe cannot form XeF3 , XeF 5 type of compound.

Solution : The only app you need to prepare for
The electronic configuration of Xe is 5S2 5p 6. So, all the electrons are paired up and when it is
excited, then either 2 or 4 or 6 etc. electrons will be unpaired. There is no scope to get odd number
of unpaired electrons in its outer most shell. For this reason it cannot form XeF3 or XeF 5 type of
JEE Main JEE Adv. BITSAT WBJEE MHT CET and more...
compound.

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available

With MARKS app you can do all these things for free

Solve Chapter-wise PYQ of JEE Main, JEE Advanced, NEET, BITSAT, WBJEE, MHT CET & more

Create Unlimited Custom Tests for any exam

Attempt Top Questions for JEE Main which can boost your rank

Track your exam preparation with Preparation Trackers

Complete daily goals, rank up on the leaderboard & compete with other aspirants

P-BLOCK ELEMENTS

4.8 50,000+ 2,00,000+

Rating on Google Play Students using daily Questions available