3 d and f Block Elements

SUMMARY-
1. The d-block ofthe periodic table contains the elements of the groups 3-12 in which the d orbitals
are progressively filled in cach of the four long periods.
2. The fblock consists of elements in which 4f and 5f orbitals are progressively filled. They are
placed in a separate panel at the bottom of the periodic table.
3. There are mainly four series of the transition metals, 3d series (Sc to Zn), 4d series (Y to Cd),
5d series (La and Ht to Hg) and 6d series which has Ac and elements from Rt to Cn.
4. The two series of the inner transition metals; 4f (Ce to Lu) and 5f (Th to Lr) are known as
lanthanoids and actinoids respectively.
5. According to IUPAC, transition metals are defined as metals which have incomplete d subshell
either in neutral atom or in their ions. Zinc, cadmium and mercury of group 12 have fall d
configuration in their ground state as well as in their common oxidation states and hence, are not
regarded as transition metals.
6. The d-block occupies the large middle section of the periodic table flanked between s-and p-blocks
in the periodic table. The d-orbitals of the penultimate energy level of atoms receive electrons
giving rise to four rows of the transition metals, i.e., 3d, 4d, 5d and 6d.
7. In general the electronic configuration of outer orbitals of these elements is (n-1)d-0ns2. The

n-1) stands for the inner d orbitals which may have one to ten electrons and the outermost ns
orbital may have one or two electrons. General electronic configuration of f-block is (n-2)fl-l4

(n-1)d0ns
8. General Properties of the Transition Elements (d-Block):

) Physical Properties
metallic properties such as high tensile
(a) Nearly all the transition elements display typical electrical
thermal and conductivity and metallic
strength, ductility, malleability, high
and Mn, they have one or more typical metallic
lustre. With the exceptions of Zn, Cd, Hg
structures at normal temperatures.
the exception of Zn, Cd and Hg) are very hard and have
(b) The transition metals (with
low volatility.
Their melting and boiling points high. The high melting points of these metals are
are
(c) number of electrons from (n-1 )d in addition to
attributed to the involvement of greater
metallic bonding. In any row the meting points of
the ns electrons in the interatomic and Tc and
except for anomalous values of Mn
these metals rise to a maximum at d5
number increases.
regularly as the atomic
fall
the number of valence
of atomisation. In general, greater
(d) They have high enthalpies of atomisation is an
resultant bonding. Since the enthalpy
electrons, stronger is the of a metal, metals with
the standard electrode potential
important factor in determining tend to be noble in their
atomisation (i.e., very high boiling point)
very high enthalpy of
reactionsS.
G« a l s ISC Examination 37
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 Transition Metals Thev have relatively high density and
Sizes of
Variation in Atomie and lonie possess high melung
(i)
in given series show progressive decrease in r adius
d...
i The lanthanides exhibit a principal points.
(Eu) and +4 (Ce") oxidationoxidation
a
same charge
In general, ions of the the new clcctron enters a d orbital
cach ee
+2 state of 3. However, some ciements also exhuhst
numbc1. This is becausc states.
with increasing atomic
inereases by unity. It may
be rccalled that the shiclding effect ((v) Many of the lanthanide jons are coloured due
time the nuclear charge allraction between the nuclear to the electronic transition
thc nct elccirostatic 4/-levels. bctween dilierent
a d electron is
not that effective, hence
decreases. The same trend
and the ionic radius
and the outermost electron incrcases i) The majornty of the lanthanide Ons
charge exhibit
the variation within a series is
The lanthanide ions that do not paramagnetism
duc to the presence of unpared
observed in the atomic radii of a given serics. However, electrons.
is series are compared exhibit paramagnetism are those with ciher no
when atomie sizes of one
quite snmall. An interesting point cmerges is associatcd
4/-clectrons, e.g, La and Ce" or with
a completed
4/-level, Yb" and
with those of the corresponding elements in the other series. This phenomenon
(vii) The lanthanides readily tamish in air and burn
eg.
Lu
must be filled before the 5d
series of elements to give trioxides (except which toms
the orbitals which cacsium,
with the intervention of 4/ CeO,).
results in a regular decrease in atomic radii called
begin. The filling of 4/ before 5d orbilal (viii) The oxides and hydroxides of the lanthanides are basic in character
for the expectled increase in atomie
Lanthanoid contraction which cssentially compensates
of the lanthanoid contraction is that the (ix) The lanthanide compounds are generally predominantly ionic
size with increasing atomic number. The net result
Hf 159 pm) and have
second and the third d series exhibit similar radii (e.g., Zr 160 pm. 10. The gradual deerease in atonie size across the first transition clement serics is called lanthanoid
similar physical and chemical properties much more than that expected on the basis contraction.
very
of usual amily relationship.
11. Properties of actinides
than those of s-block clements but lower
(ii) lonisation energies of transition elements are higher i) CGeneral clectronic configuration is (Rn) 5/o o«ds 7s'.
series.
than p-block elemcnts. It generally increases fronm left to right in the
oxidation states.
(ii) The elements are all silvery white metals
(iv) Transition metals exhibit a varicty of (ii) The melting points of the actinides are moderately high.
due involvement of and (n-1)
The variable oxidation states of transition metals are to ns

d-electrons in bonding. (iv) The ionic size of the actinides decreases gradually along the serics.
with mineral acids (V) The actinides have the ability to exhibit several oxidation states. IHowever, +4 oxidation släle
(v) Most of the transition metals are sulficicntly electropositive. They react
is preferrcd in actinides.
liberating FH, gas.
(vi) Some actinoid clements can exist in 6 oxidation state, c-g., uranun, neptunium and
(vi) Transition clements and many of their compounds are paramagnetic.
is plutonium.
(vii) Formation of coloured compounds (both in solid state as well as in aqucous solution)
anoiher very common characteristic of transition metals. This is due to absorption of some (vii) Many actinide elements are radioactive. beyond uranium are man-made
The clements
(vii) The actinides have a much greater tendency to form complexes than lanthanides.
radiation from visible light to cause d-d transition of electrons in transition metal atoms.
the transition elements have the form d and /-block clemcnis and their comp0unds. notable
ability many useful applications of the
to
(viin) In contrast to s and p-block elements, 12. There are

This is because these elements them being in varicties of steels, catalyst, complexes, organi¢ syntheses, ctc.
complexes. among
(a) have small highly charged ions, and
(b) contain vacant d-orbilals. QUESTION BANK
(ix) Many transition metals and their compounds act as catalysts in a variety of rcactions.
(x) Transition metals form a large number of interstitial compounds [1 Mark]
(xi) A large number of alloys are formed by transition metals. lt is due to their atoms mutualy
A. Multiple Choice Questions
substituting their positions casily in their metal erystal lattices. among the following
Tdentily the incorrect statement
properlics among
themselves
(xin) The oxides of transition metals in lower oxidation states arc generally basic in nature and and erratic chemical
(a) d-block elements show irregular
those in filled d-orbitals and no otherpartially filled orbitals.
higher oxidation states
amphoteric or acidic in nature.
are La and Lu have partially
(xii) The Fblock elements have been divided in two series depending r the (D lanthanoids is very similar.
upon the fact whetn (C) chemistry of
The various

last electron (differentiating electron) enters 4f-orbitals or 5/-orbitals and accordingly called shiclded.
(d) 4f and 5f orbitals are cqually This is
lanthanides or actinides respectively. states in general than the Janihanods.

2. actinoids exhibits more umber of oxidalion

(xiv) Actinides show several oxidation states but +3 oxidation highest
ne

state is most common.

oxidation state shown by actinides is +7. n because
a) The 5f orbitals are more buried than the 4/ orbilals. ot the wave function
9. their angular part
Properties of the lanthanides between 4/ and 5/ in
OThere is a similarity
(i) General electronice configuration is reactive than
the lanthanords.

[Xe] 4/- 56s. CThe actinoids are more

the nucleus
than the 4f
orbitals.

ii) The metals further from

and
are
silvery-white in colour.
They are malleable, ductile, have low
gtn The 5f orbitals extend
are good conductors of heat and
electricity.
tens Semester-
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 statements is incorrect?
elemcnts, which of
the following 11. What would be nmagnelic moment of
Gd" (Z
with the transition 64)?
3. In context clements (Sc to Mn), all the 4s (a) 7.9 BM
first five transition (b) 3.62 BM
oxidation states of the (c) 10.60 BM
(a) In the highest (d) 9.72 BM
and 3d electrons are
used for bonding. Iron exhibits 2 and t) OXTdalion state.
to involve all the 3d electrons n Which of the following
cxceeded, the tendency incorrect'? statements about iron is

(b) Once the d configurationis

(a) Famous compounds are more
bonding decreases.
state is also shown by these easily hydrolysed then the
addition to the normal
oxidation states, the zero oxidation
(b) Ferrous oxide is more basic in nature than corresponding ferric compounds.
(c) In the ferric oxide.
clements in complexes.
and form cationic (c) Ferrous compounds are
relatively ionic than the
more
oxidation states, the transition
metal show basic character corresponding ferric compounds
(d) In the highest (d) Ferrous compounds are less volatile than the
complexes. corresponding ferric compounds.
its +3 oxidation state, which of 13. The colour of light absorbed by an
aqueous solution of CuSO, is
of lanthanoids (Ln) by is dominated
4. Knowing that the chemistry (a) Orange-red (b) Blue green
incorrect? (c) Yellow
the following statements is (d) Violet
are gcnerally
colourless. 14. Which of the lollowing arrangements does not
(a) Ln (11l) compounds represent the correet order of the property stated
basic in character. against it?
(b) Ln (I) hydroxides are mainly in its compounds is predominantly
size of the Ln (1) ions the bonding (a) V2' <
Cr" <

Mn*" <

Fe: Paramagnetic behaviour

(c) Because of the large
ionic in character. (b) Ni2 < Co < Fe" <Mn': lonic size
with increasing atomic number.
The ionic sizes of Ln(lIl) decrease
in general (c) Co" < Fe'" < Cr" < Sc*": Stability in aqucous solution
d)
successive elements Cr,Mn,Fe (d) Se < Ti < Cr < M n : Number of oxidation states

5. The corect order of EeM Valucs with negative sign for the four
and Co is 15. Four succesSive members of the lirst row transition clements are listed below with atomic
Mu> Cr> Fe > Co
Mn> Fe Co (b) numbers. Which
(a) Cr> >

Fe Mn > Cr> Co
one
ofthem is expected to have the highest F"value?
(c) Cr> Fe > Mn > Co (d) > (a) Cr (Z = 24) (b) Mn (Z - 25) (c) Fe (Z = 26) (d) Co (Z = 27)

following statements is not correct?

6. The content of the lanthanoids, which of the 16. The colour of KMnO, is due to
of lanthanoids is not easy.
(a) Because of similar propertics the separation (a) L M charge transfer transition (b) a - o transitio
formation of compounds in +4 state for all the
(b) Availability of 4/ electrons results in the (c) M> L charge transfer transition (d) d - d transition
members of the series.
17. Disproportion can be shown by
increasing atomic number in
(c) There is a gradual decrease in the radii of the members with
series.
(a) MnO; in acidic medium (b) Cu' in aqucous medium
th
(c) Ci, in alkaline medium (d) All of these
(d) All the members exhibit +3 oxidation state.
18. With increase atomie number the ionic radii
7. Which is not a correct slatement on of actinides:
Ce 58, Lu 71, La 57, Yb 70) (a) Contract slightly (b) Increase gradually
(At Nos, = = =

(a) Ce has o configuration (b) Lu" has f configuration (c) Show no change (d) Change irregularly
(c) Colour of Yb3" ion is pink (d) La is diamagnetic 19. In aqueous solution Eu" acts asS

8. Which of the following forms stable +4 oxidation state? (a) an oxidising agent (b) reducing agent
(a) La (Z = 57) (C) can act as redox agent (d) none of these
(b) Cu (Z= 63) (c) Gd (Z = 64)
(d) Ce (Z
=
58)
The of transition elements are found to be the combination with A and
9. The d-electron
configuration Mn*", of Cr", vhich 0 highest oxidation states
one of the
and Co* Fe2 are d', d', d" and d' respectively B, which are :
following will exhibit the lowest paramagnetic behaviour? (c) 0, CI (d) F, CI
[At Nos. Cr 24, Mn 25, Fe 26, Co
= = = (a) F, O (b) 0, N
27] =

a)[CHH),P (b) [Co(H,O)P ()[Mn(H,O),P* (d) [Fe(H,O)F ANSWERS

10. Which
of the following paramagnetic ions would exhibits 8. (d) (d)
order 5BM? (At. no. Mn =

25)
magnetic moment (spl (d) 2. (d) 3. (d) 4. (a) 5. (b) 6. (b) 7. (c)
Mn 15. (d) 16. (a) 17. (d) 18. (a)
25, 10. (c) 14. (a)
Cr 24, V =
23, Ti =
22 11. (a) 12. (a) 13. (a)
(a) V? 19. (b) 20. (a)
(6) Ti2
(c) Mn2 (d) C Examinatton
40 Goyal's ISC Class-12 Jor Semester-2

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 [1 Mark) D. Assertion-Reason
B. Fill in the Blanks
by
1 Mark]
oxidation states 1S shown the following questons.
maximum number of ln t staretnent ot
the aassertion followed
1. In the first transition series, by a statement of reason is given
surtace area and Choose the correct answer out of the following choices:
good catalyst as they provide
2. Transition metals act
as

Oxidation states. (a) ASsertion and reaSOn both are corect

statements and reason is correct
hAssertion and reason both arc coTect
explanation for assertion
atomic radii due to statements but reason is not
Silver and gold atoms have nearly the same correct explanation for assertion
3. (c) Assertion is coTeCt statcment but reason is

arc metals.
wrong statement
4. Zn, Cd and (d) Assertion is wrong statcment but reason is correct statement.
not considered as transition element as it has completely filled d'
. are . Assertion (A) The most common oxuiation
atomic state as well as common oxidation state state exhibited by actinides is +2
conhguration in its Reason (R) All actimdes possess
twO electrons in 7s subshell.
configuration whercas Ti(IV) has configuration.
6. Ti(i) has 2. Assertion (A)
is
:
Zn 1on is diamagnetie
7. The gcneral outer shell clectronic configuration of transition clements Reason (R) The clectrons are lost from 4s orbital to form Zn'" ion
standard reduction potential in the first transition serics is
8. The only metal which has a posilive 3. Assertion (A) Zn, Cd and Hg cannot be regarded as transition elements.
:

Reason (R) These clements do not belong to the d-block

periodie of the table
ANSWERS 4. Assertion (A) : The basic strength of oxides and hydroxides of lanthanoids decrease with increase

4. Hg. non-transition In atomic number.

2. large, variable 3. lanthanoid contraction
1. Manganese Reason (R) :The size
7. (n-1)d10 ns2 8. Copper of cation of lanthanoids incrcases wih increase in atomic
number.
5. Zn, Hg & Cd
6. d d
5. Assertion (A) : The pair of elements r-1f. Wb-Ta, Mo-w.Pd-P1, A-Au posses almost the
same values of atomic radii.
[1 Mark]
C. Match the Following Reason (R) :The occurrence of lanthande contraction cancels the expccted increase in the
. Column I (catalyst) Column 1l (process) atomic radii values from Hf to Hg.

(a) Ni in the presence of H, (i) Contact process 6. Assertion (A) : Lanthanoids show less oxidation states than aclinoids.

(i) Vegetable oil to ghee Reason (R) : 4 fsubshell is dep-seated than Sf

(b) Cu,Cl,
(ii) Sandmeyer reaction 7. Assertion (A) AgBr is yellow coloured.
(c) V,0
(d) Finely divided iron (iv) Haber's process Reason (R) :AgBr is unstable in presence of sunlight,
8. Asertion (A) : LufOH), is more basie than CeOi).
2. Column I (Aqueous solution of salt) Column l (colour)
Reason ( R ) : Lu has smaller size than Le"
(a) FeSO,,7H,0 i) Green
(b) NiCI.4H,O (ii) Light Pink ANSWERSs
7. (b) 8. (d)
(e) MaCl,4H,O (ii) Pink 1.(d) (b) 3. (c) . (c) 5. (a) 6. (a)

(d) CoCL.6H,0 (1V) Pale green

[2 Marks]
3. Column 1
Column
SShort Answer Type Questions
reas0n
(a) Oxidation state of Mn in MnO, is
+2
U s e the data to answer the following and also Justily givn
Mn Co
(b) Most stable oxidation of Mn is Cr
(i) +3 . 0.28
(c) Most stable oxidation state of Mn in 0.91 I8
oxides is (i) + +1.97
E 1.57 +),77
(d) Characteristics oxidation state of
lanthanoids is (iv) +7 medium, Cr or
Fe and why
R IS a stronger reducing agent in aqucous
oxidation and why?
ANSWERSs W h i c h is the most stable ion in 2
I. (a) (i)
(b) (i) (c) () indicates, strong Oxidising agent
(d) (iv) 2. (a) (iv) (d) (in) (1) gher value of elcctrode potentialis easily oxidiscd
3. (a) (ii)
(b) (i) (b)(i) (c) (i) to
Cr".
(c) (i) (d) (iv) out of Cr? or Fe. Cr
oyol's 1SC Cnce,
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42
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ester-2 Bruminl
E Questton
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 iil Which ion 1s the
strongest oxidising
[Ar]3d 4s agent?
(1i) Cr (ii) Which is colourless?
Cr Ar]3 : Mn has 3d' configuration.
iv) Which ion has the higher number of
unpaired electrons'?
[Ar 3d' 4s Ans. (i) Cr" because half filled t, level.
Mns which is most stable.

Mn [Ar]3d' G) Mn. as the change irom Mn" to Mn"

results in stable half-filled ( )
configuratiun
Arl3d 4s cii) Ti'. as T has empty d-orbitals therefore d-d transition
Fe cannot occur in
T
Fe Ar]3d" (iv) Mn (3 4*). t has 4 unpaired electrons
Co Ar]3d 4s 7. Account for the following
Co [Ar]3d E valucs tor transilion metals show
iTCgular variation.
contraction? Write its consequence? Ans. The irregular variation in E
2. What is lanthanoid increase in atomie number due to 1or transilion metals is due to irregular variationmuch
in 1onisalion
decrease in atomic radii with enthalpics (AH + AH) and also the sublimation enthalpies which are relatively less tor
Ans. Lanthanoid contraction is steady
effect of 4f orbital electrons. Mn (240 kJ mot ") and V (470 kJ mol )
poor shielding
almost same size as 4d series.
Consequence: Sd series have 8. Write one smilarity and one dillerence between the chemistry of lanthanoid and actinod
3. Give reasons for the following elements.
clectrons for
(i) Manganese has lower melting
even though it has a higher number otf unpaired Ans. Similarity between lanthanoids and actinoids
bonding. (i) Both lanthanoids and actinoids are electro-positive.
(ii) Cet is a strong oXidising agent. (ii) Both lanthanods and actinods manly show an oxidation state of +3 (any onc).
hough it has higher number of unpaired
(i) Manganese possesses lower melting point
even
Ans. Differences between lanthoids and actinoids
i.e., electrons are hcld tightly by
electrons because it has stable 3d 4s* configuration, (i) Lanthanoid contraction is smaller than the actinoid contraction.
metallic bond is much weaker than that of
nucleus so that the delocalisation in less and the (i1) Lanthanoids except promethuni are non-radioactive metals while actinoids are radioactive
proceeding element.
metals.
electron as +3 oxidation state
(ii) This is because Cel tends to change in Ce by gaining one
that it can oxidise water. 9. Explain the following observations.
is more stable. The E" value Ce"/Ce*" is 1.74 V wvhich suggests
() Zinc is not regarded as a transition clement.
4. Give reasons for the following:
(i) Transition elements and their compounds act as catalysts. (ii) Generally there is an increase in density of clements from titanium (Z 22) to copper
(ii) Actinoids show iregularities in their electronic configuration. (Z 29) in the first series of transition clements.
Ans. (i) Zinc has completely filled d-orbitals (34").
Ans. (i) The catalytic activity of transition metals is attributed to the following reasons
(a) Because of their variable oxidation states transition metals fornm unstable intermediale Hence, it is not regarded as a transilion elenment
compounds and provide a new path with lower activation energy for the reactio (ii) This is due to lanthanoid contraction (i.e. due to illing of 4f orbitals which have poor

(b) In some cases, the uransition metal provides a suitable large surface area with free shiclding eflect.)
valencies on which reactants are adsorbed. 10. Account for the following
(i) Because the energy differences between 5f, 6d and 7s subshells are very small. () CuCl, is more stable than Cu,C1,
5. Give reasons (11) Alomic radii of 4d and 5d series elements are nearly same.

i) Iron has higher enthalpy of atomisation then copper. solutions may be

Ans. ()CuCl, is more stable than Cu,C1,. The higher stability of Cu in aqucous
is in the second ionisation enthalpy
i) Se" colourless
Ans. () umber
aqueous solution whereas Ti
is coloured. attributed to its greater A, l° than that of Cu'. lt compensate
More of unpaired clectrons, higher is the enthalpy of atomisation. As
has four unpaired clectrons in 3d subshell whereas
Fe( 4) of Cu involved in the formation of Cu ions.

Cu(3d1° 4s') has only one elecron is * (11) This is due to filling of 4/ orbitals which have poor shiclding eflect (Lanthanoid
contraction
subshell. Therefore, metallic bonds in Fe are much
stronger than those in Cu and nene
has higher enthalpy of atomisation than I1.
copper. Give reason following
for the
than that lor (Cr"/Cr) couple.
(1i) Sc" (3a") has no d electron to absorb ()Evalue for (Mn'"/Mn') is highly positive
light for d-d transition and hence it is colour that of the lanthanoids
aqueous solution. Ti*" (3d') has one electron in d orbital which can absorb light on visible not so smooth as
) The ehemistry of actinoids clements is
region for d-d transition and hence it is coloured in is stable half
required change
filled d to

6. In the
aqueous solution. * )Much large third ionisation energy of Mn where
following ions Mn, V, Cr', Ti for this.
d is mainly responsible 7s subshells of actinoids
(Atomic no : Mn =
25, V =23, difference between 57, bd &
i) Which ion is most stable in
Cr 24, Ti =

22) his is duc to much smaller energy

of lanthanoids.
aqueous solution'? than 4/. Sd and 6s subshells
44 Evamination
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 Lanthanoid Contraction.
(iii) Why do actinoids show a
Wide
range of
the basis of oxidation states?
Justify Sdo 6
12. on
elements. Ans. i) 4/ ii) +3 and +4
6) Radii of 4d and Sd block
Trends in acidic character
of lanthanoids oxides. ..:sActinoids sh0W
(1) a wiude range ot
oxidation
(ii) orbitals in states due to
Due to lanthanoid contraction,
radii of 4d and Sd block elements
are nearly cqual. 7s actinoids comparable cnergies of 51. bd a d
Ans. ()) character of oxides for the
character decreases or acidic character increases as covalení 3. Account following
(ii) The basic
increases trom La to Lu. i
Manganese shows maNImum number
ot
OXidation states in 3d
ions expected to be coloured? ) E° value tor Mn Mn couple is much series.
13. (i) Which of the following are
iil
more
Ti is colourless whereas Va is coloured in positive
that for Cr/Cr
Ni", Ti', Cu', Sc", Zn aqucous solution.
Ans. (i) Mn,, has elcctronie configuration 3 4s
(11) How many unpaired electrons are present in cach of the following?
Fe, Co, Zn2" As all the seven electrons ot 3d and 4s subshell
its shows maximum number ol oxidation state
can
participate in bond formation, therclore,
Ans. (i) Ni", Ti." (ii) 5, 3, 0 (2 to +7) in 3d series
14. Write two uses of each Lanthanide and Actinides. ii) The positive E value tor Mn"/Mn couple is due to much higher third ionisation of Mn
where the change is d (extra siable)
Ans. Uses of lanthanides to
d'
(i) Addition of about 3% misch metal to magnesium increases its strength and is used in makmg (iii) Ti has no d clectrons, theretore il is colourless in
aqueous solution while V has one
unpaircd clectron in d orbitals, which can absorbs radiation in visible region for d-d transilion
jet engine parts.
(i) Steel mixed with La, Ce, Pr and Nd is used in the manufacture of tlame throwing tanks. and hence coloured n aqucous solution.
Uses of actinides 4. Answer the following
i) Uranium salis impart green colour to glass. () Write one ditference between transtion elements and p-block elements with reference to
(i) Thorium is uscd in the manufacture of fine rods for atomic reactors. variability of oxidation states.

15. Give reasons for the following (ii) Why do transition metal exhibit higher enthalpies of atomisation
i) Though copper, silver and gold have completely filled sets of d-orbitals yet they are (ii) Name an clement of lanthanoid series which is well known to show +4 oxidation state. is
considered as transition metals. it a strong oxidising agent or reducing agent'
(ii) Transition elements have many irregularities in their electronie configuration. Ans. (i) In transition elements, the oxidation states diller from cach other by unity, e g., Fe and Fe
Ans. () There metals in their common oxidation states have incompletely filled d-orbitals. etc., while in non-transition elements (p-block elemcnts), the oxidation states difler by two,
e.g., Cu has 3d' and Au has Sd configuration. c.g.. Pb and Pb", cte.
(i) In the transition elements, the (n-1)d subshell and ns subshell have very small difference (ii) Transition metal exhibit higher enthalpies of atomisation because they have strong netallie

energy. The incoming clectron may enter into ns or (n-1)d subshell. Hence, they show
in bonds as they have a large number of unpaired elcetrons
irregularities in their electronic configurations. (111) Cerium is well known to show +4 oxidation state. The E° value for CeCe is 1.74 V

which shows that it is a strong oxidisng agent.

F.Long Answer Type Questions (3 Marks) S. Give rcasons for the following
1. Give Reasons
for the following (i) Transition metals form complex compounds
() The only oxidation state shown by Scandium is +3. (1i) [Ti(H,0),1" is colourless. negative than expected.
(11) TE value for (Zn /Zn) and (Mn/Mn) are nmore
(ii) MnO is basic while Mn,0, is acidic. stales.
(ii) Actinoids show wide range of oxidation.
Ans. (i) The only oxidation shown Sc is +3 because in this +3 oxidation state scandium has
state by s. (1) The tendency to form complex compounds is duc to

stable d configuration. Small size and high charge on mctal i10n

clectrons donated by the ligand.
ii) In
[Ti(H,O), the oxidation state of Ti is +4 and it has empty d orbitals due to which no orbitals for accommodating
ne availability of d
than expecied is due to lact that
alter
radiation is absorbed for d-d ransition and hence it is colourless. Mn'/Mn are more negative
valucs Zn /Zn
for and and stable 3
m case of zinc
ii) The oxide in the lower oxidation state of a metal is basic from orbital, stable 3d" configuration
(as it has electrons to donate) while C h o v a l of electrons
is attaned.
in the higher oxidation state of the metal it is acidic. This is why MnO is basic whereas Contiguration in case of manganese of hd and 5/, 7
due to comparable energies
Mn,O, is acidic. cnoids show wide range of
oxidation states

2. Answer the
following orbitals in actinoids.
() What is the general electronic configuration of lanthanoids? v e reasons for the following
slates.
(ii) What are the common variable oxidation
oxidation metals show is
positive
states of Cerium (At no. 58)? ansition while that of
(Cu""Cu)
46 value for (Zn/Zn) is negative Evamination

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 whereas with oxygen
of Mn with
fiuorine is +4 +7 due to d-d transition. Under
(ii) Higher
oxidation state
in i ) This is the influence
show variable
oxidation states
because electrons and (n-1)
ns and t..
d transition metal complex split n of the
ligand attached, the
Ans. (i) Transition elements orbitals two sets of
orbitals
a

complexes they absorb a having slightly different energies. When

formation as they have nearly. white light falls on these
available for bond
are
extra stability Ot fully nled 3d orbitals of 72 the promotion ot electrons and particular colour from the white light
() Negative E° value
for Zn' Zn is due to
1onisation enthalpy to cons ) is due to this emitted radiations.
remaining colours are 10r
emitted. The colour of the complex
the of sublimation enthalpy and
On the other hand,
sum
balanced by hydration enthalpy of Cu2 Th
) for the
to Cu(aq) is so high
that it is not
10. State
reasons following:
value for Cu- Cu is positive. Unlike Cr, Mn", Fe" and the
subsequent other M2 ions of the 3d series of elements,
stab1lises manganese more than iuorine by forming multinle the 4d series and the da series metals
(ii) This is because oxygen bonds. generally do not form stable cationic species.
(i) C2 is reducing in nature while with the same d-orbital configuration (d4) Mn** is an
7. How w ould vou account the following:
(i) The oxidising power of oxonions are in the order V0 < Cr,0;< MnO; oxidising agent.
iii) In a transition series Or metal, the metal which
(ii) Cr is a stronger reducing agent than Fe*. (11) exhibit the greatest number of oxidation
occurs in the middle of the series.
(i) Cu ion is not known in aqueous solutions.
Ans. (i) The oxidising power of oxoanions are in the order VO; < Cr,0,5 < MnO,, this is due to Ans. i) Due to lanthanoid contraction the expected increase in size does not occur.
increase in the oxidation state of the metal ion. ii) Cr2 is reducing as its configuration changes from d to d, a more stable half filled 2
configuration while Mn°" is Oxidising as Mn** to Mn2* results a more stable half filled
(ii)
Cstableis half
a
strongerreducing agent than Fe
filled t, configuration.
as its configuratiom changes from to d', a more d configuration.
(ii) It is due to greater number of unpaired electrons in (n-1)d and ns orbitals at the middle of
(in) ion is
Cunegative known in aqueous solutions because Cu ions
not

AHof Cu than Cu, which compensates for the second

are more stalble due to more
ionisation enthalpy of
the series.
Cu 11. On the basis of Lanthanoid contraction, explain the following:
8. Explain the folowing observations (i) Nature of bonding in La,0, and Lu,O
i) There is close similarity in (i) Trends in the stability of oxosalts of lanthanoids from La to Lu.
a
physical
and chemical properties of the 4d and Sd series of the
transition elements, much more than expected on the basis of usual ii) Stability of the complexes of lanthanoids.
family relationship.
11) There is a gradual decrease in the atomic size of transition elements in the series with Ans. (i) La,0, is more ionic and Lu,O, is more covalent due to increase in covalent character from
Increasing atomic numbers. La to Lu.
(11) Lanthanum and Lutetium do not show
colouration in solutions. (At. No. La =57, Lu 11) (ii) Stability of oxosalts of lanthanoids from La to Lu decreases as the size decreases.
Ans. (i) There is a close of
similarity in physical and chemical properties of the 4d and 5d series of the ii) As the size of lanthanoids decreases, change/size ratio increases and hence the stability
transition elements much more than the complexes increases.
expected on the basis of usual family relationship. This
is because 5d and 4d series
elements have virtually the same atomic radii and ionic 12.
due to lanthanide contraction. Due to rad Answer the following questions
etc., the two elements of
equality in size of Zr and Hf, Nb and Ta, Mo and Ul () Which element of the first transition series has highest second ionisation enthalpy?
have the pair same properties. (11) Which element of the first transition series has highest third ionisation enthalpy?
(1i) There is gradual decrease in the atomic sizes of transition elements in a series
a
atomisation?
incTeasing atomic numbers due to poor wtn 11) Which element of the first transition series has lowest enthalpy of
attraction between the nucleus and the shielding
effect of d-electrons, the net electrostatic AIS. (1) Cu, As its configuration is 3d10 4s'. After loss of one electron from 4s it acquires stable 3d
outermost electrons
(1i) Lanthanum and Lutetium do not increases connguration.
electron is very difficult.
Hence, removal of 2nd
show colouration in solutions because both the elements
exhibit3 oxidation state in their 1) Zn. Thisis because Zn 3d10 4s3 and Zn2* is 3d which is stable electronic configuration
=

compound thus their cations do not posses any unpaired

electrons in them. hence removal of 3rd electron requires very high energy.
available
9. Give reasons subshell and no unpaired electron is
for the following: L n . This is because it has completely filled 3d
(i) Transition metals form ailoys. ii) Eu is a strong reducing agent. for metallic bonding
(ii) The transition metals generally from coloured 13.
Ans. (1) The transition metals have similar radii and
compounds. Answer the following: transition ser+es.
other characteristics. the third and fourth transition
elements of first
can Therefore, there metals
mutually substitute their position in their crystal lattices and form Name
of TP" on?
formed are hard and often have alloys. The alloys so (i) what is the theoretical magnetic moment
high melting point. Which of the two V(+5) or V(+4) is diamagnetic
(ii) The most common oxidation state of
+3 oxidation state
anthanoid is +3. Therefore, Eu2 tends to change to (ii) V(+5)
1.732 B.M.
by losing one electron. Hence, Eu2" is Ans. () Vanadium, Chromium (ii) V(1+2)
=

a
strong reducing agent.
48 49
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 Lanthanide and Actinides.
Actinide Contraction? Compare
14. What is regularly
decrease along tha
ions of actinides
Contraction: The size of the atorms or with increase in atomi
Ans. Actinide radii
decrease in the ionic
series as in the lanthanide
series. The steady contraction and is due to poor
is analogous to lanthanide
contraction. This
number is actinide
the 5f electrons.
shiclding of the nuclear charge by
Lanthanides and Actinides
Comparison of
Actinides
Lanthanides
addition to +3 oxidation state,
actinides also
1. Lanthanides show mainly +3 oxidation In +4, +5, +6|
oxidation states such as
state except in a few cases
where it is | show higher
and +7.
+2 and +4.
to form complexes.
2. The tendency to form complexes is less. They have a greater tendency
are more basic.
3. Lanthanide compounds are less basic. Actinide compounds
PuO.
form oxo ions such as UO;, NpO',
4. They do not form oxo ions They
actinides are radioactive.
5. Except promethium, these
are non-|All the
radioactive.

of lanthanide contraction.
15. Explain any three consequences
Lanthanide Contraction
Ans. Consequences of
transition series
) Resemblance of second and third
elements of second and third transition series
As result of lanthanide contraction the
a
elements of first and second transition series.
resemble each other much more than the

(i) Similarity among Lanthanides

Because of very small change in radii of lanthanides, their chemical properties are quite
similar. Thus, it is very difficult to separate the elements in pure state.

ii) Basicity difference

Due to lanthanide contraction, the size of lanthanide ions decrease regularly with increase in
atomic number. As a result of this their covalent character between lanthanide ion and O
ions increases from La to Lu*. Therefore, the basic strength of the hydroxide decreases
with increase in atomic number.

16. Account for the following:

(i) Transition metal ions have high enthalpy of hydration.
(ii) Chromium is a hard metal while mercury is a liquid.
typical
(ii) Most of the transition metals do not displace hydrogen from dilute acids.
Ans. (i) This is due to their small size and
large nuclear charge. This is so because when
more

W
along any transition series, the nuclear charge increases and size decreases.
(ii) Cr have five
unpaired d-electrons in the d-subshell (3d" 4s'). Hence, metallic bondsS re
ver

strong. In Hg, all the d orbitals in

are
completely filled (3d10 4s*). Hence, the metan
b o n d n y

is very weak.
iii) This is because most of the
transition metals have
negative oxidation potentials

O00