Silver

Facts About Silver

Silver is the shiny white, lustrous transition metal of Group 11 or IB in the periodic table with atomic number 47 and the symbol Ag. It has been used since the ancient age for making jewelry and coinage due to its decorative beauty and unreactive properties. The name silver comes from Assyrian serpu or Gothic silbur meaning white and from the Latin name, Argentum means shiny white (Greek latter Argos).

Silver forms an FCC crystal lattice with characteristic silvery-white colour.

Where is Silver Found?

The relative occurrence of metal in the earth’s crust is 0.08 ppm while that of gold is 0.004 ppm.

It is widely distributed in nature as sulfide ore like a silver glance or argentite (Ag₂S). Horn silver (AgCl) is also found in some minerals in Chile and New South Wales formed by the action of salt water. It is now largely discovered as a byproduct of the extraction of copper and lead.

Silver is found in various countries such as the United States, Canada, Peru, Mexico, Bolivia, and New South Wales. In India, it is obtained from Kolar gold mines produced from the smelting of Zawar lead ores.

Properties of Silver

Chemically, silver metal is a quite unreactive chemical element with a good conductor of electricity.

In learning chemistry, it dissolved in water to the extent of 0.07 mg liter⁻¹ in the presence of dissolved oxygen. It is attacked by atmospheric sulfur compounds, mainly hydrogen sulfide (H₂S).

Silver
Symbol	Ag
Discovery	Approx 3000BC
Name derived from	Assyrian serpu or Gothic silbur meaning white and from the Latin name, Argentum means shiny white (Greek latter Argos)
Common isotope	47Ag107
Oxidation states	2, 1
CAS number	7440-22-4
Periodic properties
Atomic number	47
Atomic weight	107.868
Electron per cell	2, 8, 18, 18, 1
Electronic Configuration	[Kr] 4d10 5S1
Group	11
Period	5
Block	d-block
Physical properties
State at 20 °C	Solid
Melting point	961.8 °C or ​1763.2 °F
Boiling point	2162 °C or ​3924 °F
Density	10.49 g/cm3
Electrical resistivity	15.87 nΩ m
Molar heat capacity	25.350 J mol−1 K−1
Crystal structure	Face-centred cubic (fcc)
Atomic properties
Atomic radius (non-bonded)	2.11 Å
Covalent radius	1.36 Å
Electronegativity	1.93 (Pauling scale)
Electron affinity	125.62 kJ mol−1
Ionization energy (kJ mol−1)	1st	2nd	3rd
	730.99	2072.26	3360.58

Electron Configuration

The 47 electrons of the silver atom are distributed in different energy levels to show the following electronic configuration given below the picture,

Silver in the Periodic Table

It is placed in group 11 in the periodic table with d-block elements.

The atomic states of copper, silver, and gold or noble metal contain ns¹ (n−1)d¹⁰ outer electron configuration or filled d-subshell. They are considered transition metals because, in +2 or +3 oxidation number or state, they possess incompletely filled d-orbital.

Production of Silver

• Mostly silver was obtained as a byproduct for the production of copper, lead, and zinc by collecting anode slime or mud.
• The anode slime or mud is heated with dilute sulfuric acid in a stream of air to dissolve some metals.
• The remaining anode slug was heated with lime and silica to remove most of the base metal as a slug.
• Finally, Ag-containing materials are dissolved in dilute nitric acid.
• Electrolysis of AgNO₃ solution gives a pure form of silver metal at the cathode.

Extraction of Silver from Ore

• It is extracted from its important ores by leaching the finely powdered ore with dilute (0.4 percent) sodium cyanide solution.
• The sludge is ignited well with air. The Na₂S is oxidized by aeration, otherwise, it would tend to reverse the reaction.
• The sludge is removed by filtration and the filtrate silver is precipitated by zinc or aluminum.
• The precipitate is washed and melted with a flux of nitrate to remove the excess zinc.

Chemical Compounds

The physical and chemical properties of silver are similar to the two vertical neighbors copper and gold on the periodic table. The higher effective nuclear charge or ionic potential and large shielding electron suggest that the covalent bonding of Ag and Au compounds are stable in +1 and +2 states.

The +1 state is the most common oxidation state of silver which offers oxides, sulfides, halides, and a number of oxoacids salts.

The salts are primarily ionic and quite soluble in water but Ag₂SO₄ and CH₃COOAg are sparingly soluble in water. The halide (except AgF) is formed by covalent chemical bonding.

Oxidation State

The +1 oxidation state of silver is the most common and stable. The first ionization energy is lowest for Ag. The sum of the first and second ionization is the lowest for Cu. The sum of first, second, and third ionization energy is the lowest for Au atoms.

The above fact reflects that Ag chemistry is predominant in the +1 oxidation state. However, copper and gold chemistry predominates in the +2 and +3 oxidation states.

The facts are also described by hydration energy.

• The hydration energy of the copper (II) ion is much higher than the copper (I) ion which overcomes the second ionization of Cu in an aqueous medium.
• Due to higher ionic radii of Ag, the hydration energy cannot stabilize Ag (II) ion over Ag (I).
• For gold atoms, atomization, ionization, and hydration energy favor the formation of Au (III) in an aqueous medium.

Silver Oxide

The dark brown silver oxide (formula Ag₂O) is obtained by adding alkali to an aqueous Ag⁺ ion. It is more soluble in alkali than pure water owing to the formation of Ag(OH)₂⁻.

Ag₂O dissolves in ammonia to produce [Ag(NH₃)₂]OH. When the solution is exposed to air, it deposits the black explosive silver nitride (Ag₃N). It is called fulminating silver.

Moist Ag₂O is used as a mild oxidizing agent for organic compounds.

A black oxide like AgO is formed by oxidation of Ag₂O with ozone molecule or by electrolysis 2M AgNO₃ solution.

Silver (II) Compounds

Ag (II) compounds are obtained by direct oxidation or disproportionate of the chemical element. They are extremely unfavorable due to the low heat of hydration of Ag⁺² ion.

AgF₂ is the only known silver halide obtained by the action of fluorine on AgF or Ag at 250 °C temperature. It is used as a fluorinating agent.

Silver (III) Compounds

Compounds of Ag (III) are very few, Ag₂O₃, Ag(OH)₄⁻, KAgF₄ or Cs₂KAgF₆ are the common examples of the +3 oxidation state of silver.

The formal oxidation number +1/2 is present in the yellow-green solid Ag₂F.

Uses of Silver

• Silver and its compounds are widely used in photography, in silver mirrors or plates, in silverware, jewelry, dentistry, and coins.
• It is also used in high-capacity electrical cells (Ag-Zn, Ag-Cd).
• Copper serves to increase the hardness of alloy to improve the wearing qualities.
• The photographic light sensitivity plate consists of an emulsion of fine-grain silver halides like bromide, chloride, or iodide (diameter < 1 μm) on a transparent medium like glass or celluloid.
• The halide, usually AgBr with some amount of AgCl and organic dyes but AgI is used in very fast films. Organic dyes act as a photosensitizer to help light absorption over the entire visible band.
• Silver plating in chemistry is done at the cathode of the electrolytic cell. A piece of pure Ag element acts as an anode with the electrolytic solution sodium dicyanoargentate, Na[Ag(CN)₂].

Detection of Silver Ion

Silver salts in an aqueous solution produce a curdy white precipitate of AgCl with chlorine ions. The precipitate is insoluble in nitric acid but readily dissolved in aqueous ammonia.

Ag⁺ also forms a red precipice (Ag₂CrO₄) with potassium dichromate solution which is insoluble in acetic acid.

All the silver compounds produce a lustrous white malleable bed on heating with sodium carbonate on charcoal. The bead may be dissolved in nitric acid and tested with hydrogen chloride (HCl).

Gravimetric Analysis

In learning chemistry or chemical science, silver may be estimated gravimetrically as chloride or by electrodeposition (coulometer), volumetrically.

• In Mohrs’s method, a known volume of standard sodium chloride solution triturated with AgNO₃ solution using potassium chromate as an indicator.
• In Volhard’s method, the silver nitrate (AgNO₃) is triturated by standard potassium or ammonium thiocyanate using ferric alum as an indicator.

The Ag⁺ ion forms a white precipitate of AgSCN but when the concentration falls below the solubility, the blood-red color of thiocyanate ions is produced as ferric ion.