Lanthanides
Lanthanides consist of elements that follow lanthanum and involve the filling of 4f subshell
Atomic number Name Symbol Ln Ln3+
57 Lanthanum La [Xe]4f0 5d1 6s [xe]
58 Cerium Ce [Xe] 4f2 5d0 6s2 [xe] 4f1
59 Praseodymium Pr [Xe] 4f3 5d0 6s2 [xe] 4f2
60 Neodymium Nd [Xe] 4f4 5d0 6s2 [xe] 4f3
61 Promethium Pm [Xe] 4f5 5d0 6s2 [xe] 4f4
62 Samarium Sm [Xe] 4f6 5d0 6s2 [xe] 4f5
63 Europium Eu [Xe] 4f7 5d0 6s2 [xe] 4f6
64 Gadolinium Gd [Xe] 4f7 5d1 6s2 [xe] 4f7
65 Terbium Tb [Xe] 4f9 5d0 6s2 [xe] 4f8
66 Dysprosium Dy [Xe] 4f10 5d0 6s2 [xe] 4f9
67 Holmium Ho [Xe] 4f11 5d0 6s2 [xe] 4f10
68 Erbium Er [Xe] 4f12 5d0 6s2 [xe] 4f11
69 Thulium Tm [Xe] 4f13 5d0 6s2 [xe] 4f12
70 Ytterbium Yb [Xe] 4f14 5d0 6s2 [xe] 4f13
71 Luthethium Lu [Xe] 4f14 5d1 6s2 [xe] 4f14
A comparison of the electronic configurations of the lanthanide elements illustrates the preferred
stabilities of half-filled and fully filled subshells. Thus the gadolinium atom has a 5d electron
above a half-filled 4f subshell, and similarly both ytterbium and lutetium exhibit 4f14 subshell
configurations. Lutetium and gadolinium form only tripositive ions, since this state gives them
stable electronic configurations. Europium and ytterbium and gadolinium would be expected to
form stable dipositive ions in addition to their tripositive ions, as is actually observed. Cerium
and terbium attain the f0 and f7 configurations, respectively, in their +4 oxidation states.
When the electronic configuration Is 4f0-145d16s2 the oxidation number is 3 which is okay but how
when electronic configurationis 4f0-145d06s2 the oxidation number could be 3? Shouldn't that be
2?
When these elements form ions, the electrons of outer shell should be lost preferentially; the 4fn
electrons should be inert due to the presence of outer 5d and 6s orbitals/electrons. But we should
also realize that all lanthanides are of big atomic radii, so they could have high coordination
numbers to stabilize themselves whether in solid or aqueous state. The high coordination number
requires the central ion to have a higher positive charge to counterbalance the negative filed
generated by the ligands. So after losing the outermost shell electrons, i.e., 6s2 and 5d (if it has
electrons), some lanthanides tend to lose one more electron (from the 4f orbital) to attain
stability.
When the +3 oxidation state is reached, the atom bears such a high amount of positive charge
that it becomes very difficult to remove electrons further.
The +4 oxidation state usually reverts to the +3 state, and thus acts as a strong oxidizing agent. In
the same vein, the +2 oxidation state usually reverts to the +3 state, and thus acts as a strong
reducing agent.
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Electronic Configuration
[Xe] 4fn+1 5d° 6s2 or [Xe] 4fn 5d1 6s2
The general valence shell electronic configuration of lanthanides is 4f1−146s2.
Electronic configurations of lanthanum and lanthanides are listed in the table
Atomic Number Name Symbol Electronic configurations Radii/pm
Ln Ln2+ Ln3+ Ln4+ Ln Ln3+
57 Lanthanum La 5d16s2 5d1 4f0 - 187 106
58 Cerium Ce 4f15d16s2 4f2 4f1 4f0 183 103
59 Praseodymium Pr 4f36s2 4f3 4f2 4f1 182 101
60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99
61 Promethium Pm 4f56s2 4f5 4f4 - 181 98
62 Samarium Sm 4f66s2 4f6 4f5 - 180 96
63 Europium Eu 4f76s2 4f7 4f6 - 199 95
64 Gadolinium Gd 4f75d16s2 4f35d1 4f7 - 180 94
65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92
66 Dysprosium Dy 4f106s2 4f10 4f9 4f8 177 91
67 Holmium Ho 4f116s2 4f11 4f10 - 176 89
68 Erbium Er 4f126s2 4f12 4f11 - 175 88
69 Thulium Tm 4f136s2 4f13 4f12 - 174 87
70 Ytterbium Yb 4f146s2 4f14 4f13 - 173 86
71 Lutetium Lu 4f145d16s2 4f145d1 4f14 - - -
Atomic and Ionic Sizes of Lanthanides
Atomic and ionic radii of lanthanides decrease with an increase in atomic number. This
gradual decrease is known as lanthanides contraction.
Because of the lanthanides contraction, the radii of the elements of the 3 rd transition series are
very similar to those of the corresponding elements of the 2nd transition series elements.
Oxidation States of Lanthanides
Lanthanides exhibit the oxidation state of +3. Some of them also exhibit the oxidation state of +2
and +4.
a noble gas configuration e.g. Ce4+ (f0)
a half filled f shell e.g. Eu2+ (f7)
a completely filled f shell e.g. Yb2+ (f14)
Lanthanide contraction
It is observed that in lanthanide series, there is a progressive decrease in the atomic and ionic
radii with increasing atomic number. This regular decrease with increase in atomic number is
called lanthanide contraction. This is due to the weak shielding of f orbitals. These f orbitals are
unable to counter balance the effect of increasing nuclear charge because of which the size keeps
on decreasing with increase in atomic umber.
Causes of Lanthanide Contraction:
As we move along the period from left to right in
lanthanide series, the atomic number increases i.e.
number of protons keeps on [Link] every
proton added in the nucleus the extra electron
goes to the same 4f orbital.
The 4f orbital shows poor shielding effect because
of which there is a gradual increase in the
effective nuclear charge experienced by the outer electrons. Thus, the attraction of the nucleus
for the electrons in the outermost shell increases in atomic number.
Consequence of Lanthanide Contraction
Separation of Lanthanides: Without lanthanide contraction all the lanthanides would have
same size because of which if would have been very difficult to separate them but due to
lanthanide contraction their properties slightly vary. The variation in the properties is utilized
for separating them.
Basic Strength of Hydroxide: Because of the lanthanide contraction, size of M 3+ ions
decreases and there is increase in covalent character in M–OH and hence basic character
decreases.
Similarity of 2nd and 3rd transition series i.e. 3d and 4 d series: The atomic sizes of
second row transition elements and third row transition elements are almost similar. This is
also an effect of lanthanide contraction. As we move down the from form 4d to 5d series, the
size must increase but it remains almost same due to the fact that the 4f electrons present in
the 5d elements show poor shielding effect.
The 4f-electrons constitute inner shells and are rather ineffective in screening the nuclear charge. Thus,
there is a gradual increase in the effective nuclear charge experienced by the outer electrons. So the
attraction of the nucleus for the electrons in the outermost shell increases as the atomic number increases
and the electron cloud shrinks
Lanthanides and Actinides Vary in Electron Filling Order
The lanthanides and the actinides make up the f block of the Periodic Table. The lanthanides are
the elements produced as the 4f sublevel is filled with electrons and the actinides are formed
while filling the 5f sublevel. Generally speaking, the lanthanides have electron configurations
that follow the Aufbau rule. There are some variations, however, in a few of the lanthanide
elements. We will expand a tiny portion of the Periodic Table below to show what happens to
some of the electron configurations in the lanthanide and actinide series.
58 59 60
61 62 63 64 65 66 67
68 69 70
71
Lanthanid Ce Pr Nd
Pm Sm Eu Gd Tb Dy Ho
Er Tm Yb
Lu
es 14 14 14
14 15 15 15 15 16 16
16 16 17
175
0 1
5 0 24 7 9 3 5
7 9 3
95 10 10 10
90 91 92 93 94 96 97 98 99
A 0 1 2 103
Th Pa U Np Pu Cm Bk Cf Es
Actinides m Fm Md No Lr
23 23 23 23 24 24 24 25 25
24 25 25 25 260
2 1 8 7 4 7 7 1 2
3 7 8 9
Look, for example, at the electron configuration for cerium, the first element of the lanthanide
series. Cerium, Ce, is element number 58.
58Ce: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f1 5s2 5p6 5d1 6s2 or Ce: [Xe] 4f1 5d1 6s2
58
Now look at the electronic configuration for praseodymium, an element used in the making of
aircraft engines but also in lighting for making movies. Praseodymium, Pr, is element number 59
and has the following electron configuration.
59Pr: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 4d10 4f3 5s2 5p6 6s2 or Pr: [Xe] 4f3 5d0 6s2
59
Notice the d electron is no longer a part of the electron configuration. There are three lanthanide
metals that have properties similar to the d block. These are cerium, Ce, lutetium, Lu, and
gadolinium, Gd. All of these metals contain a d electron in their electron configuration. The
rest, like praseodymium, simply fill the 4f sublevel as the atomic number increases.
Unlike the lanthanide family members, most of the actinide series are radioactive. Most of the
elements in the actinide series have the same properties as the d block. Members of the actinide
series can lose multiple numbers of electrons to form a variety of different ions. The noble gas
electron configuration for the elements of the actinide series are shown below:
Noble Gas Electron Configuration for the Actinide Series
Element Electron Configuration
Thorium (Th) [Rn] 6d2 7s2
Protactinium (Pa) [Rn] 5f2 6d1 7s2
Uranium (U) [Rn] 5f3 6d1 7s2
Neptunium (Np) [Rn] 5f 46d1 7s2
Plutonium (Pu) [Rn] 5f6 7s2
Americium (Am) [Rn] 5f7 7s2
Curium (Cm) [Rn] 5f7 6d1 7s2
Berkelium (Bk) [Rn] 5f9 7s2
Californium (Cf) [Rn] 5f10 7s2
Einsteinium (Es) [Rn] 5f11 7s2
Fermium (Fm) [Rn] 5f12 7s2
Mendelevium (Md) [Rn] 5f13 7s2
Nobelium (No) [Rn] 5f14 7s2
Lawrencium (Lr) [Rn] 5f146d1 7s2
Lesson Summary
The lanthanide and actinide series make up the inner transition metals.
The lanthanide series fill up the 4f sublevel and the actinide series fill up the 5f sublevel.
The first, middle, and last member of the lanthanide series have properties of the f block
and the d block.
Many of the actinide series have properties of both the d block and the f block elements.
Similarities Between Lanthanides and Actinides
1. Both lanthanides and actinides involve the filling of f-orbitals.
2. Both exhibit a common oxidation state of +3.
3. Both are electropositive and very reactive.
4. Both exhibit magnetic and spectral properties.
5. Lanthanides exhibit lanthanide contraction and actinides exhibit actinide
contraction.
Difference Between Lanthanides and Actinides
Lanthanides Actinides
They have the ability to show a maximum Actinides show variable oxidation states of + 3, + 4,
oxidation state of + 4 + 5, + 6 and + 7.
They have smaller tendency to form They have a good tendency to form complexes with
complexes. ligands such as thio-ethers.
All lanthanides are non-radioactive except
They are radioactive in nature.
promethium.
They do not form oxo-ions Actinides form oxo-ions such as UO+, NpO2+.
They are non radioactive in nature. Actinides are radioactive.
Uses of Lanthanides
1. They don’t find any use in their pure state. They are used in the production of alloys of
steel to improve the strength and workability of steel. A well known alloy is mischmetal
which is used in making magnesium based alloy (Mg mixed with 3% of mischmetal).
This is a pyrophoric alloy which is used in making bullets, shells and lighter flints.
2. Their oxides are used in the glass industry for polishing glass and making colored glass
for goggles and television screens.
3. Mixed oxides of lanthanides are used in petroleum cracking.
4. Due to their paramagnetic and ferromagnetic nature, they are used in magnetic and
electronic devices.
5. Ceric sulphate is a well known oxidizing agent which is used in volumetric analysis.
Uses of Actinides
The most useful actinides are thorium, uranium and plutonium.
1. Thorium is used in the atomic reactors and in the treatment of cancer. Their salts are used
in making incandescent gas mantles.
2. Uranium is used as nuclear fuel. Their salts are used in the glass industry for imparting
green color, ceramic industry, textile industry and in medicines too.
3. Plutonium is also used as nuclear fuel and for making atomic bombs.
QUESTIONS
1. Lanthanides occur in only one oxidation state. What is the oxidation state? Explain the
reason for this
2. What do you understand by the term “lanthanide contraction”? What are its causes and
consequences?
3. Highlight the similarities and differences between lanthanides and actinides
4. What are the simiularities between lanthanides and actinides?
5. Highlight three uses each of lanthanides and actinides
