F-BLOCK ELEMENTS

Presented By :
RAMESH.R
PGT CHEMISTRY
KENDRIYA VIDAYALAYA THIRUVANAMALAI
 Contents
 Lanthanide Complexes
 Introduction  Separation Of Lanthanides
 Ion Exchange
 Lanthanides  Solvent Extraction
 Some Contrasts Between Lanthanides And
 Electronic Configurations Pre-
 transition & Transition Metals
Oxidation States
 Chemical Reactivity
 Lanthanide Contraction
 Variation Of Properties
 Actinides
 Metallic Radii
 Density
 Electronegativity
 Ionization Enthalpy
 Magnetic Behavior
 Color Properties
  Electronic Configurations
 Oxidation States
 Actinide Contraction
 Variation In Properties
 Complex Formation Tendency
 Chemical Properties
 Similarities And Differences Between Lanthanides And Actinides
 Magnetic & Spectral Properties

Reference Books
 Inorganic Chemistry For B.Sc. Of all Indian Universities By R.L.Madan and G.D.Tuli.
 Inorganic Chemistry by Catherine E.Housecraft and Alan G.Sharpe.
 Inorganic Chemistry Principles of Structure and Reactivity By James E.Huheey,Ellen A.Keiter,Richard
L.Keiter.
 Concise of Inorganic Chemistry By J.D.Lee
INTRODUCTIO
N
 • The elements in which the additional electrons enters (n-2)f orbitals are called inner
transition elements. The valence shell electronic configuration of these elements can
be represented as (n – 2)f0-14(n – 1)d0-1ns2.
• 4f inner transition metals are known as lanthanides because they come
immediately after lanthanum and 5f inner transition metals are known as actinoids
because they come immediately after actinium.
 Electronic
Configuration
Element name Symbol Z Ln Radius
Ln3+
Ln3/
pm

Lanthanum La 57 [Xe]6s25d1 [Xe]4f0 116

Cerium Ce 58 [Xe]4f16s25d1 [Xe]4f1 114
Praesodymium Pr 59 [Xe]4f36s2 [Xe]4f2 113
Neodymium Nd 60 [Xe]4f46s2 [Xe]4f3 111
Promethium Pm 61 [Xe]4f56s2 [Xe]4f4 109
Samarium Sm 62 [Xe]4f66s2 [Xe]4f5 108
Europium Eu 63 [Xe]4f76s2 [Xe]4f6 107
Gadolinium Eu 64 [Xe]4f76s25d1 [Xe]4f7 105
Terbium Tb 65 [Xe] 4f96s2 [Xe]4f8 104
Dysprosium Dy 66 [Xe] 4f106s2 [Xe]4f9 103
Holmium Ho 67 [Xe] 4f116s2 [Xe]4f10 102
Erbium Er 68 [Xe] 4f126s2 [Xe]4f11 100
Thulium Tm 69 [Xe] 4f136s2 [Xe]4f12 99
Ytterbium Yb 70 [Xe] 4f146s2 [Xe]4f13 99
Lutetium Lu 71 [Xe] 4f146s25d1 [Xe]4f14 98
Oxidation state
 Lanthanide H ydrides
Preparation: Heat at 300-350°C, Ln + H 2 LnH2

Properties of LnH2
• black, reactive, highly conducting, fluorite structure

• Most thermodynamically stable of all binary metal hydrides

• Formulated as Ln3+(H-)2(e-) with e- delocalized in a metallic conduction

band

• Further H can often be accommodated in interstitial sites,

frequently non-Stoichiometric.

• e.g. LuH x where x = 1.83-2.23 & 2.78-3.00

• H igh pressure on (H2 + LnH 3)

• Reduced conductivity: salt-like Ln3+(H-)3 except for Eu and Yb

(the most
stable LnII)
 LaC2 reacts with water to form ethyne, C2H2 and a mixture of
complex hydrocarbons.

 LaC2 is a metallic conductor, in contrast to CaC2 which is an insulator.

 The crystal structure of LaC2 shows that it contains C2 units with a C-
C bond length of
130.3 pm, which is longer than the C-C bond length in calcium
carbide,119.2 pm,
which is close to that of ethyne.

 The structure of LaC2 can be described as La3+C2-2(e-) where the electron enters
the conduction band and antibonding orbitals on the C2 anion, increasing the
bond length.
LANTHANIDE CONTRACTION:
As the atomic number increases each
element ,succeeding
contains one more electron in the 4f orbital and one
proton in the nucleus. The 4f electrons are ineffective in
screening the outer electrons from the nucleus causing imperfect
shielding . As a result there is a gradual increase in the nucleus
attraction for the outer electrons consequently gradual
decrease in size occur. This is called Lanthanide contraction.
Consequences
 Variation of
properties
Metallic radii
• Decreases with increase in atomic
numbers (174-208 pm).
• Comparable with those of S-
block elements.

• Fairly large size.

• Eu and Yb show very surprisingly irregular

sizes because of repulsion between
greater number of f- electrons.
 Density
• Low densities (6.77 – 9.74 g/CC).
• Don’t show definite trends with rise in
atomic number.
• Eu and Yb have low values of density than
expected. Ionization
Enthalpies
• Fairly low I. E
• First ionization enthalpy is around 600
kJ mol-1, the second about 1200 kJ
mol-1 comparable with those of
calcium.
Electronegativity values
• Due to low I. E, lanthanides have high
• Range 1.0 – 1.15 (Allred and Rochow scale). electropositive character

• Comparable with E.N. values of S-block

elements.
• So, Ln compounds are expected to form
ionic compounds.
MAGNETIC PROPERTIES
• For Sm3+at room temperature, the first excited state and for Eu3+, the first excited state and even the
second and third excited states are populated.
• In each of these ions, the J value is higher than that of the ground state and μ is expected to be greater
J

than that
of only the ground state.
 La3+ is diamagnetic (due to f0).

 M ax value at N d.

 Sudden drop to 1.47 for Sm.

 Increases again reaching max

value for Dy and Ho.

 Touching zero at Lu (f14

electron).
• The absorption spectra of the compounds of trivalent
Ln ions show sharp line like bands (fainter color
comparative to TMs) in the U.V., visible or near infrared
regions.

• The bands are so sharp that they are very useful for
characterizing the lanthanides and for their quantitative
estimations.
Lanthanides have poor tendency to form
complexes
• Although the lanthanide ions have high charge (+3), yet the size of their ions is very large (charge/size =
small).

• So, they have poor tendency to form complexes.

• They form complexes mainly with chelating agents (beta-diketone, EDTA, 2,2’-bipyridyl, and beta-
hydroxy
quinoline.

• Complex formation tendency and stability increases with increasing atomic number.

• This fact is utilized in the separation of lanthanides.

 Chemistry of all lanthanides is almost identical
• They all have similar outer electronic configuration and display mainly +3 oxidation state in their
compounds.

• Their similarity is much closer than that of ordinary transition elements because lanthanides differ mainly in
the number of 4f electrons.
• 4f electrons are buried deep in the atoms.

• Due to L. C. there is very small difference in the size of all the 15 trivalent lanthanide
ions

Important uses of Lanthanides

• Ce glass cuts off heat and UV light and so used in glare- reducing spectacles.

• Ce-Mg alloys are used in flashlight powders.

• Nd oxide dissolved in selenium oxychloride is one of the most powerful liquid
lasers known so far.

• Ce salts are used in analysis, dyeing, lead accumulators, medicines and as

catalyst.

• Ln elements and their compounds are being used in nuclear control, shielding
and fluxing devices.
SEPARATION OF LANTHANIDES:
Except promethium, they occur together in earth’s crust in
various forms and very difficult to separate from each other because all the
lanthanides have the same size and charge (of +3 unit).

The chemical properties of these elements which depend on the

size and charge are, therefore, almost identical. Hence, their isolation from
one another is quite difficult. However, the following methods have been
used to separate them from one another.
 Separation of Ln: Ion exchange method

 This is the most rapid and most effective method for the isolation of individual lanthanide elements
from the mixture. An aqueous solution of the mixture of lanthanide ions (Ln3+aq) is introduced into
a column containing a synthetic cation exchange resin such as DOWAX-50 .The resin is the
sulphonated polystyrene containing-SO3H as the functional group. As the solution of mixture moves
through the column, Ln3+aq ions replace H+ ions of the resin and get themselves fixed on it:

Ln3+aq + 3H (resin) → Ln(resin)3 + 3H +aq

sulphonated polystyrene
 The bonding of the lanthanide ion to the resin depends on its size, i. e, the smaller the size of
the lanthanide ion, the more firmly it is bound to the resin and vice versa. Since lanthanide ions
are hydrated, therefore size of the hydrated ions should be considered for binding purpose.
Hydration of the ions depends upon size i. e, smaller the size of the ion greater will be the
hydration. Therefore in case of lanthanide ions, the smallest lanthanide ion, namely will be the
most heavily hydrated. Thus it will have the maximum size and therefore the least firmly bound
to the resin while reverse will be the case with La+3 which will be the most firmly bound to the
resin

 A solution containing several lanthanide ions is dropped slowly down a column of

synthetic ion exchange resin so that the lanthanide ions are bound less firmly to the resin in the
order La+3 to Lu+3. They are then eluted from the column by using a solution containing citric
acid and ammonium citrate. For the ammonium ions elute the metal ions from the resin as:
3N H 4 + + Ln (resin) → 3N H 4 resin + Ln+3
The metal ions then form a complex with the citrate
ions.

Ln+3 + citrate ions → Ln citrate

complex

Since Lu+3 is the least firmly bound to resin therefore on

elution, Lu citrate complex is obtained first from the bottom of
the column while La citrate complex emerges last of all from
the bottom of the column. Complexing agents such as EDTA,
amino carboxylic acids and hydroxy carboxylic acids have also
been found to be convenient elutants.
Solvent extraction method: Separation of Lanthanides
Decreases in ionic
radius will
increases
complexation.
• First 4 member occur in
nature.
• Others are made artificially.
• All are toxic to humans.
As there is not much difference between 5f and 6d, it becomes difficult to know whether the
electron has entered 5f or 6d. This makes predicting electronic configuration difficult.

• The ground state electronic configuration of actinium, [Rn]6d17s2 is identical to that of lanthanum
and certainly the two elements possess alike chemical properties.
• The difference in energy between 5f and 6d orbitals in the starting of the actinide series is less
than that between the 4f and 5d orbitals for the lanthanides.
• Thus, both 5f and 6d orbitals are comprised in accommodating successive electrons.
• Therefore the filling of 5f orbitals in actinides is not quite so regular as the filling of 4f orbitals in
case
of the lanthanides.
• By the time plutonium and following members of the series are reached, the 5f orbitals seem
evidently to be of lower energy than the 6d orbitals, and therefore the electrons preferably fill the
former.

Actinides show higher oxidation states than Lanthanides

O xidation • Up to Uranium, stable oxidation states of
state
the elements is the one involving all the
electrons
valency
Neptunium forms the +7 state using all
the
valency electrons but this is oxidizing and the
most stable state is +5.

• Plutonium also shows states up to +7 and

Americium up
To +6 but the most stable state drops to Pu (+4) and
Am (+3).

• Berkelium in +4 state is strongly oxidizing but is more

stable than curium and americium in +4 state due to f7
configuration.

• Similarly, nobelium is markedly stable in +2 state due to

its f14 configuration.
 ACTINIDE CONTRACTION

• The contraction is caused due to imperfect shielding of one 5f electron by another in the same shell.

• As we move along the actinide series, the nuclear charge and the number of 5f electrons increase one unit by
each
step.

• Due to imperfect shielding (shape of f orbitals are very much diffused) the effective nuclear charge increases
which causes contraction in the size of electron cloud.

• In actinides contraction there are bigger jumps in contraction between the consecutive elements as compared
to lanthanides.

• Lesser shielding of 5f electrons compared to 4f electrons.

Variation in properties
• M. P. and B. P. – There is no regular trend in these
values.
• Density increases from left to right.

• M agnetic properties: Smaller than the predicted values due to quenching of

orbital
theoretically contraction.

• Reducing power (Eo values): All of them have relatively high Eo values (about 2 volts).

• Reactivity: Very reactive metals. The reactions of metals with oxygen, halogens and acids resemble
those
with lanthanides.

• Colored ions: Color depends upon the number of 5f electrons. Color is exhibited due to f-f transition.
Actinides have greater tendency to form complexes than
lanthanides

• Small and highly charged M4+ ions exhibit greater tendency towards
complex formation, e.g. Pu4+ forms very strong anion complexes.

• Most actinide halides form adducts with alkali metal halides. ThCl4
forms the complexes MThCl5, M2ThCl6, M3ThCl7.

• With pyridine, ThCl4 as well as ThBr4 form monopyridine complexes.

• Also form complexes with acetylacetone, oxine (8-

hydroxyquinoline), EDTA, such as tetrakiss-
(acetylacetonato)thorium, Th(acac)4 etc.
• UO 2 forms rather unstable complex with EDTA as compared to
lanthanides.
 Chemical properties

 All the actinides are not stable with respect to the radioactive disintegration, although the half-lives of the
richest isotopes of thorium and uraniumare so long that for numerous purposes their radioactivity can be
neglected.
 Like lanthanides, actinidesare as well electropositive and reactive metals.
 They react by water, oxygen, hydrogen, halogens and acids. Their hydrides are non-stoichiometric having ideal
formulae M H 2 and MH3.
 The metals as well react with most of the non-metals particularly whenever heated.
• The magnetic properties of actinide ions are more complex than those of
the lanthanide ions.
• 5f electrons are closer to the surface of the atom and is simply affected by
the
chemical environment; however not to the similar extent as do the d
electrons.
• The less sharply stated distinctions between the 5f and 6d electrons as
 SIMILARITIES

• Both the series show a +3 oxidation state.

• In both the series the f-orbitals are

filled gradually.
• Ionic radius of the elements in both
the series
decreases with the increase in atomic
number.

• The electronegativity of all the elements

in both the series is low and are said to

be highlyreactive.

• The nitrates, per chlorates and sulphates

of all the elements are soluble while the

hydroxides, fluorides and carbonates are