Transition elements

Defining Transition elements

Transition elements – elements in the atoms or ions of which
the d- or f-sublevels are PARTIALLY filled with electrons.
Zn, Cd, and Hg having an electronic configuration of ns2(n-1)d10
are d-elements but are not transient.

d-elements
G3 G12 Transition
elements
3d
Coin metals
4d
5d
Platinum Metals

Among the transition elements are coin metals (Cu, Ag, Au) and noble
(platinum) metals (Ru, Rh, Pd, Os, Ir, Pt).
 Some features of transition elements

While the non-transition elements in each period vary from

metals to nonmetals, all transition elements are metals and
as a result conduct current, heat and can form alloys well;

Most transition metal compounds are colored and

paramagnetic, while most compounds of intransitive
elements are colorless and diamagnetic;

All transition metals form complex (coordination)

compounds.
 Non-transition and transition metals

s-elements d-elements
All valence Part of the valence electrons
electrons are is delocalized, some form
delocalized covalent bonds with
neighboring atoms
Bond - pure
metallic Bonding - covalent-metallic

Soft enough,
characterized by Solid, characterized by high
low t°melts t° melts (except Hg, Zn, Cd)
 Melting point of d-cells

Cr Fe

Rат 0,164 0,134 0,130 0,125 0,128

0,146 0,127 0,126 0,124 0,139
 Filling the valence level in 3d elements

Red dots show stable OS

The number of unpaired electrons increases in the first half of the series 6
and decreases in the second half.
Variety of oxidation states

1) The number of possible OS

increases from Sc to Mn. All
possible OS are
implemented for Mn;
2) The amount of possible OS
decreases from Mn to Zn
due to the pairing of d-
electrons;
3) The stability of higher OS in
the Sc-Zn series decreases.
Mn(VII) and Fe(VI) are
strong oxidizing agents.

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 Trends in transitional series

Increasing the stability of the highest

oxidation state (weakening of the
oxidative capacity)

Increased "hardness" (oxophilicity) and "softness" (chalcophilia) of

metals (including group 12 metals)

Increasing the oxidation potential for this OS

Decrease in the stability of the highest oxidation state (enhancements

of oxidative capacity)

Some increase in electronegativity and ionization energies

Improving atmospheric stability

These are just general trends. There are exceptions! 8

Transition metal coordination
compounds

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 Werner's theory
• Compounds consisting of other, simpler
compounds are called complex compounds
• Central atom - surrounded by molecules or
ions (ligands)
• Coordination number - the number of
Alfred Werner ligands in the internal coordination sphere of
Nobel Prize 1913 the complex

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 Complex means a central atom or metal ion
surrounded by a set of ligands..

[Co(NH3)6]3+ - complex
[Co(NH3)6] Cl3 is a complex compound (salt).
[Fe(CO)5] – complex and complex compound 11
 Строение комплексного соединения
Внешняя
сфера Внутренняя сфера

K3 [Fe(CN)6] Координационное
число

Ион-комплексообразователь Лиганды
(центральный атом)

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Side subgroup III of
group five of the
periodic table

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 Content in the earth's crust and
minerals
• Sc – 50 place. Tortveitit((Sc,Y)2Si2O7) and erastit
(Sc[PO4]·2H2O).
• Y – 28 place. An analogue of lanthanum, it is almost
always found together with lanthanides in minerals.
• La – belongs to the most strife. contained in
monazite ((Ce,La,Nd,Th)PO4), bastnesite
((Ce,La,Y)CO3F), loparite ((Na,Ce,Ca,Sr,Th)
(Ti,Nb,Fe)O3) and apatite (Ca5[PO4]3(F,Cl,OH)).

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 Open items
• Sc – the element was predicted by Mendelev (as
eka-boron) and discovered in 1879 by the
Swedish chemist Nilsson. It is named after
Scandinavia.
• Y – in 1794, the Finn Gadolin isolated ytterbite
from the mineral. It is named after the Swedish
town of Itterby.
• La – in 1839 the Swede Mosander. The name
comes from Ancient Greek. "hiding“.
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 Simple substances
Тпл., оС Ткип., оС D, g/cm3

Sc 1541  2837 3,0

Y 1528 3320 4,5

La 920 3447 6,2

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 Modifying Properties
• Sc(OH)3 – La(OH)3 increase in basic properties.

Examples:
2Sc(OH)3 + 3H2SO4 = Sc2(SO4)3 + 3H2O;
Sc(OH)3 + NaOHконц. = Na3[Sc(OH)6]

2La(OH)3 + 3H2SO4 = La2(SO4)3 + 3H2O

La(OH)3 + NaOH р-р = no reaction
 Retrieval and properties
1) 2MCl3 + 3Ca = 3CaCl2 + 2М - calciumthermy
2) 2) М2O3 + 6HF = 2МF3 + 3H2O (heating)
3) Melt electrolysis MF3 or MCl3
It is impossible in an aqueous solution, because
WATER is restored!
4) Silvery-white metals, refractory, reactive:
easily soluble in dilute acids:HNO3, H2SO4, HCl,
CH3COOH

2М + 6HCl = 2МCl3 + 3H2

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 Chemical properties
The main properties are pronounced.
Exception – Scandium(in hot, terminal alkali):
2Sc + 6NaOH + 3H2O = 2Na3[Sc(OH)6] + 3H2

When heated, they interact O2 (Burn), H2, N2, Cl2, C, S,

P

2Y + 3Cl2 = 2YCl3 ( 200ºС,)

2La + N2 = 2LaN (ЭN + 3Н2О = Э(ОН)3 +NН3)

La + 2С= LaС2 (1000 ºС) 19

(ЭС2 + Н2О = Э(ОН)3 +С2Н2 + H2)
 Basic connections
• M2O3 oxides– refractory, poorly soluble in water,
soluble in acids
But: La2O3 + 3H2O = 2La(OH)3 (Rapidly)
Absorb СО2 и Н2О out of thin air→ La2(СO3)3, La(OH)3

• Hydroxides M(OH)3 – poorly soluble bases of medium

strength
• Soluble salts– halides, nitrates, acetates, perchlorates
• Poorly soluble salts– carbonates, phosphates, oxalates,
and Fluoride (small cation and small anion)

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 Application
LaNi5 – hydrogen storage in batteries;
Y – in nuclear reactors;
LnBa2Cu3O7-x – comparators;

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Side subgroup IV of
group IV of the
periodic table

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 Elements of Group 4

El. Conf. r,M0 r,M4+ d Oxidation state

(Å) (Å)

Ti 3d24s2 1,45 0,60 1,32 +4, +3, (+2), 0

Zr 4d25s2 1,60 0,72 1,22 +4, (+3), 0

Hf 5d26s2 1,59 0,71 1,23 +4, (+3), 0

The properties of Zr and Hf are very similar.

Higher oxidation states are characteristic. Reduced forms are
more characteristic of Ti
 Content in the earth's crust and
minerals
• Ti – 9th place, rutile (TiO2), ilmenite
(FeTiO3), perovskite (CaTiO3)
• Zr – 21 places, scattered and rare,
baddeleyite (ZrO2), zircon (ZrSiO4)
• Hf – 52nd place, no own minerals, 2% in Zr
minerals

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 Open items
• Ti – in 1791 Eng. Gregor, in 1795 German
Claproth. In Greek mythology, the Titans are
the children of the Earth goddess Gaia and the
sky god Zeus.
• Zr – in 1789 the German Claprot made of half-
precious stone zircon, golden (Persian).
• Нf – in 1922 in Copenhagen Kostern and Hevesi,
Latin "Hafnia" - the name of the capital of
Denmark.
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 Simple substances
Тпл., оС Ткип., оС D, g/cm3
Ti 1800 3330 4,5
Zr 1857 4340 6,5
Hf 2227 4620 13,1
Getting complicated,
MO2 + 2C + 2Cl2 = MCl4 + 2CO
MCl4 + 2Mg = M + 2MgCl2 (900oC, Ar)
the problem of separation of Zr and Hf
Alloys, coatings, structural materials
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 Properties of simple substances
M + O2 (or 2S) = MO2 (or MS2) (when heating powders)
Ti + 2Г = TiГ4
(Г = F(150oC), Cl(300oC), Br(360oC), I(550oC))
2Ti + 6HCl = 2TiCl3 + 3H2 (when heated)
M + 6HF = H2[MF6] + 2H2 (complexation)
M + 5H2SO4. = H2[M(SO4)2] + 2SO2 + 4H2O
Ti + 4HNO3конц. + (n–2)H2O = TiO2.nH2O↓() + 4NO2
-titanium acids, insoluble in acids and alkalis
Ti + 2NaOHконц. + H2O = Na2TiO3 + 2H2
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 Properties of simple substances (Zr and
Hf)
(chelation)

M + 6HF = H2[MF6] + 3H2

M + 4CH3COOH + 6F- = [MF6]2- + 4CH3COO- + 2H2

M + 5H2SO4 конц. = H2[M(SO4)3] + 2SO2 + 4H2O

3M + 4HNO3 + 18HF = 3H2[MF6] + 4NO + 8H2O

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 Oxides M4+
MO2 – colorless, refractory, insoluble in
water, chemical. Inert
TiO2 – titanium white
ZrO2 - diamond simulator (cubic
zirconia)
TiO2 - rutile (reddish),

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 "Acids" and "salts" M4+
CaO + TiO2 = CaTiO3 (perovskite)
TiO2 + K2CO3 = K2TiO3 + CO2
Titanates, zirconates, hafnates:
MI2ЭО3, MI4ЭO4
Titanates are fully hydrolyzed:
K2TiO3 + (n+1)H2O = TiO2.nH2O↓() + 2KOH
   (when standing, when T)
 -the form is soluble in acids and alkalis

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 Комплексы
Фторидные комплексы: [MF6]2-
[MF7]3-, [MF8]4- для Zr и Hf

[M(acac)4] – летучие соединения (MO CVD)

[Hf(ox)4]4-
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