Transition Element – Chemistry of Chromium
Transition Elements
Transition
elements (also known as transition metals) are elements that have partially
filled d-orbitals. IUPAC defines transition elements as an element having
a d subshell that is partially filled with electrons, or an element that has
the ability to form stable cations with an incompletely filled d-orbital.
In general, any
element which corresponds to the d-block of the modern periodic table (which
consists of groups 3-12) is considered to be a transition element. Even the f-block elements comprising the lanthanides and the
actinides can be considered as transition metals.
However, since the
f-block elements have incompletely filled f-orbitals, they are often referred
to as inner transition elements or inner transition metals.
General Characteristics of Transition Elements
The d-block
elements are known for their:
- Large charge: radius ratios
- High melting points and boiling points
- High densities and hardness.
- Formation of paramagnetic compounds
- Formation of colored ions/compounds
- Ability to form stable complexes
- These elements also exhibit a wide variety of oxidation states and tend to form compounds that act as catalysts in many chemical processes.
Chemistry of Chromium
Chromium is one of the important transition elements. Chromium is remarkable for its magnetic properties: it is the only elemental solid which shows antiferromagnetic ordering at room temperature (and below). Above 38 °C, it transforms into a paramagnetic state. Chromium is a member of the transition metals, in Group 6. Chromium has an electronic configuration of 4s13d5, owing to the lower energy of the high spin configuration.
Symbol Cr
Atomic
No 24
Atomic Mass 51.9961 amu
Electron Configuration [Ar]
3d5 4s1
Color Silver gray
Conductivity Good
conductor
Physical
State Solid
Melting
point 1907
oC
Boiling
point 2672
oC
Abundance 21st in Earth crust
Minerals of chromium Chromite (Fe.Cr2O3) Chrome Orchre (Cr2O3) Crocite (PbCrO4)
Oxidation
state +2, +3, +6
- +3 Oxidation state is most stable.
- In +2 oxidation state they act as a good reducing agent.
- In +6 oxidation state it acts as a strong oxidizing agent.
Acidic Character
The acidic character of chromium oxides is
increased by increasing oxidation state of chromium.
Oxides |
CrO |
Cr2O3 |
CrO3 |
Oxidation
state of Chromium |
+2 |
+3 |
+6 |
Nature |
Basic |
Amphoteric |
Acidic |
Chromic Compounds
The compounds in which the oxidation state
of Cr is +3 are called as chromic compounds.
Examples: Cr2O3, CrCl3
Chrome salt
Those compounds in which the oxidation
state of chromium is +2 is called as chrome salt.
Examples: CrCl2,
CrSO4·n H2O.
Uses of Chromium and its compounds
1) Chromite ore
The metallurgical grade is used primarily
to produce ferrochromium alloys, which are used in the production of stainless
and other special steels.
2) Metallic chromium and chromium alloys
- Chromium metal (pure) is used to prepare alloys with high purity
specifications. Chromium is thus an important and widely used alloying element
in ferrous and nonferrous alloys, including those based on nickel, iron-nickel,
cobalt, aluminium, titanium and copper.
3) Chromium [III] compounds
- Chromic acetate is used in printing and tanning, as a textile
mordant, a polymerization and oxidation catalyst, and an emulsion hardener.
- Chromic chloride is used for the production of commercial
solutions of the basic chlorides (Cr(OH)2Cl) by reaction with sodium
hydroxide.
- Chromic hydroxide has been used as a catalyst, a tanning agent, a
mordant.
- Chromic nitrate has been used as a catalyst and a corrosion
inhibitor.
- Chromic oxide (anhydrous and hydrated) is used as a pigment. A substantial
portion is also used in metallurgy in the manufacture of chromium metal and
aluminium-chromium master alloys and, to a lesser extent, as a catalyst, in
refractory brick, and as a chemical intermediate.
- Chromic phosphate is used in pigments, phosphate coatings and wash
primers, and as a catalyst.
4) Chromium[VI] compounds
- Chromium trioxide is used in chromium plating, particularly in the
production of automobiles. Uses in other metal-finishing operations include
aluminium anodizing, particularly on military aircraft; chemical conversion
coatings, which provide both decoration and corrosion protection; and the
production of phosphate films on galvanized iron or steel.
- Sodium chromate is used in inks, leather tanning, wood
preservation, corrosion inhibition, as a pigment in paint, water treatment,
drilling muds, textile dyeing, cutting oils, catalysts, and as a raw material
for the production of other chromium compounds.
- Sodium dichromate is the primary base material for the manufacture
of chromium chemicals, which are used in leather tanning, metal treatment,
drilling muds, textile dyes, catalysts, and wood and water treatment.
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