GERMANIUM(IV) CHLORIDE Property

Melting point:

-49.5 °C

Boiling point:

83 °C(lit.)

Density 

1.844 g/mL at 25 °C

vapor pressure 

76 mm Hg ( 20 °C)

refractive index 

1.4644

Flash point:

83.1°C

storage temp. 

Store below +30°C.

solubility 

Soluble in ether, benzene, chloroform, carbon tetrachloride. Insoluble in hydrochloric acid and sulphuric acid.

form 

Liquid

Specific Gravity

1.88

color 

Colorless

PH

<1 (H2O, 20℃)

Water Solubility 

DECOMPOSES

Sensitive 

Moisture Sensitive

Hydrolytic Sensitivity

8: reacts rapidly with moisture, water, protic solvents

Merck 

14,4410

Dielectric constant

2.4（25℃）

CAS DataBase Reference

10038-98-9(CAS DataBase Reference)

NIST Chemistry Reference

Germanium tetrachloride(10038-98-9)

EPA Substance Registry System

Germane, tetrachloro- (10038-98-9)

Safety

Hazard Codes 

C

Risk Statements 

14-34-67-40-37

Safety Statements 

26-27-36-45-8-36/37/39-25

RIDADR 

UN 3390 6.1/PG 1

WGK Germany 

3

RTECS 

LY5225000

F 

10-19

TSCA 

Yes

HS Code 

2827 39 85

HazardClass 

8

PackingGroup 

II

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Danger

Hazard statements

H290May be corrosive to metals

H314Causes severe skin burns and eye damage

H335May cause respiratory irritation

H410Very toxic to aquatic life with long lasting effects

Precautionary statements

P234Keep only in original container.

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P273Avoid release to the environment.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P303+P361+P353IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

GERMANIUM(IV) CHLORIDE Chemical Properties,Usage,Production

Physical Properties

Colorless liquid; density 1.879 g/cm3 at 20°C and 1.844 g/cm3 at 30°C; refractive index 1.464; solidifies at –49.5°C; decomposes in water; soluble in alcohol, ether, benzene, chloroform and carbon tetrachloride; insoluble in concentrated hydrochloric and sulfuric acids.

Preparation

Germanium(IV) chloride is prepared by reacting germanium metal with chlorine; or by treating germanium oxide, GeO2, with hydrochloric acid:
Ge + 2Cl2 → GeCl4
GeO2 + 4HCl → GeCl4 + 2H2O
Germanium(IV) chloride often is obtained as a byproduct of germanium metal production. The process involves heating germanium oxide, GeO2, with sodium chloride and coal. The vapors of germanium(IV) chloride and other volatile chlorides formed from the impurity metals are condensed. The product is isolated by fractional distillation. Further purification may be achieved by fractional distillation in 8N HCl and chlorine, or in the presence of other oxidizing agents in quartz stills.
Germanium(IV) chloride also is obtained by chlorination of germanium(II) chloride at ambient temperature. The reaction is rapid.
GeCl2 + Cl2 → GeCl4

Reactions

Germanium(IV) chloride reacts with water, hydrolyzing to germanium oxide and hydrochloric acid:
GeCl4 + 2H2O → GeO2 + 4HCl
The rate of hydrolysis is slower than the corresponding silicon analog, with hydrolysis occurring only partially. When heated with hydrogen at 1,000°C in a quartz reactor, it is converted into germanium(I) chloride, condensing onto the wall of the reactor:
2GeCl4 + 3H2→ 2GeCl + 6HCl
When vapors of GeCl4 are passed over germanium at elevated temperatures, the product is germanium(II) chloride, GeCl2:
GeCl4 + Ge→ 2GeCl2
Reaction with lithium aluminum hydride in ether forms monogermane, GeH4:
GeCl4 + LiAlH4 →GeH4 + LiCl + AlCl3
Reactions with antimony trifluoride, SbF3 in the presence of antimony pentachloride, SbCl5, form mixed halides of compositions: GeCl3F, GeCl3F2, GeCl2F2, and GeClF3.
Reactions with alcohols in the presence of an amine yield alkoxides:
GeCl4 + 4CH3OH + 4C2H5NH2 → Ge(OCH3)4 + 4C2H5N•HCl
Germanium forms six coordinate adducts, such as GeCl4(L)2 with many neutral ligands.

Chemical Properties

Colorless liquid. decomposes in water. Insoluble in concentrated hydrochloric acid; soluble in carbon disulfide, chloroform, benzene, alcohol, and ether.

Physical properties

Colorless liquid; density 1.879 g/cm³ at 20°C and 1.844 g/cm³ at 30°C; refractive index 1.464; boils at 86.5°C; solidifies at -49.5°C; decomposes in water; soluble in alcohol, ether, benzene, chloroform and carbon tetrachloride; insoluble in concentrated hydrochloric and sulfuric acids.

Uses

It is used as a catalyst in the conversion of carbohydrates into 5-hydroxymethylfurfural in ionic liquids, as a reducing agent in combination with triphenylphosphine (TPP) for the reduction of alpha-bromo carboxylic acid derivatives, and in the production of pure germanium. It also finds use as an intermediate for several optical processes. It is one of the most important dopants in silica glass for optical fibers. It is employed in the preparation of germanium dioxide which is used for wide camera lens, microscopy, IR-transparent glasses/windows/lenses, and for the core of fiber-optic lines.

Uses

Germanium(IV) chloride is used in the microwave preparation of Ge2Cl6, a colorless crystalline material which was included in a further study of low-valent germanium compounds.1
Germanium(IV) chloride is used in the preparation of many germanium compounds.

Hazard

Toxic material

Flammability and Explosibility

Non flammable

Safety Profile

Poison by intravenous route. Mddly toxic by inhalation. A skin, severe eye, and mucous membrane irritant. Will react violently with water or steam to produce toxic and corrosive fumes. When heated to decomposition it emits toxic fumes of Cl-. See also GERMANIUM COMPOUNDS.

Purification Methods

Traces of Cl2 and HCl can be removed from the liquid by blowing dry air through it for a few hours at room temperature or by shaking it with Hg or Hg2Cl2 and then fractionating it in a vacuum. It decomposes on heating at 950o. It has a sharp penetrating odour and fumes in moist air to give a chalky coat of GeO2. It is slowly hydrolysed by H2O to give GeO2, but distils from conc HCl. [Foster et al. Inorg Synth II 109 1946, Dennis & Hance J Am Chem Soc 44 304 1922, Schenk in Handbook of Preparative Inorganic Chemistry (Ed. Brauer) Academic Press Vol I p 715 1963.] LACHRYMATORY. Glass powder (100-300 mesh). Washed with 10% HNO3, water and dry in air.