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Friday, December 20, 2019

Silicon Carbide(SiC): Carborundum:

Silicon carbide (SiC) is a compound of silicon and carbon. It is extremely rare on Earth in mineral form (moissanite) and it has semiconductor properties. It has a bluish-black appearance. It has a large number of crystalline forms.
Preparation: When Silica treated with carbon at around 2000 to 2500 give carbide
Properties:(1) SiC also known as carborundum which is very hard .(2) Silicon carbide is inert and not attack by even HF.
(3) Silicon carbide when treated with NaOH give silicates and carbonate .


(4) Silicon carbide is covalent carbide.
(5) Silicon carbide has a high sublimation temperature and is a good heat conductor. It's expansion with increase in temperature is low. Also, it has high electric field breakdown strength.
(6) Silicon carbide exhibits the phenomenon of polymorphism, and hence has a large number of crystalline forms. Alpha silicon carbide is the most common polymorph and has a hexagonal crystal structure, while Beta Silicon Carbide has zinc blende structure.

Silicon Oxide : Silica (SiO2):



Silicon is unable to form pp - pp bond with oxygen atom due to its relatively large size. Thus it satisfies its all four valency with four oxygen atoms and constitutes three - dimensional network. In this structure each oxygen atom is shared by two silicon atoms. Three crystalline modification of SiO2 are quartz, cristobalite and tridymite of which quartz and cristobalite are important.
Quartz (rock crystal) is the purest form of silica. It is used in preparation of costly glasses and lenses. It is also used as piezoelectric material (crystal oscillators and transducers).
Several amorphous forms of silica such as silica gel and fumed silica are known. Silica gel in made by acidification of sodium silicate and when dehydrates, is extensively used as a drying agent in chromatographic and catalyst support.

STRUCTURE OF SILICA:

PREPARATION OF SILICA:
Artificially silica can be obtained by following methods
PROPERTIES OF SILICA:
Pure silica is colourless but sand is brownish or yellowish due to presence of impurities of iron oxide.
Question: Why SiO2 is solid while CO2 is a gas?
Answer: This is because SiO2 exists in silicate form where Si forms tetrahedron SiO42- ions which are regularly attached with each other and form a giant network structure hence remains solid.

Wednesday, December 18, 2019

What is Steric Inhibition in Resonance of SIR effect ?

SIR stand for Steric Inhibition in Resonance, means as per name steric means size, inhibition means some kind of hindrance, little hurdle, and resonance means delocalisation of conjugate points.
We know that planarity is the main condition for resonance that means resonance can occur only when all the atom involved in resonance lie in the same plane or nearly in the same plane. Any change in structure which destroys planarity of molecule will restrict or inhibit resonance, this phenomenon is known as steric inhibition of resonance.

SIR effect finds immense use in explaining Stability of carbocation, acidity and basicity of organic compounds:

For example(1): Ortho substituted Benzoic acid is more acidic then meta or para substituted benzoic acid irrespective of nature of group (electron donating group or electron withdrawing group) 
When a group present in the ortho position with respect to carboxylic group creates steric strain resulting in rotation of the carboxylic group and shifting it out of plane of the benzene ring as a result the carboxylic group can no longer participate in ring resonance and thereby the acidity increases as delocalization of negative charge equally on the both oxygen atom of  conjugate base ( carboxylate ion) of the benzoic acid , hence carboxylate ion more stablised. This is  also called Ortho effect.
Note:  However for groups like -NH2 or -OH does not experience SIR effect due to small size and –CN is linear group so SIR effect not applicable.
For example (2):  N,N,2,6-Tetramethyl aniline is more basic than  N,N-Dimethyl aniline. In cas of N,N-Dimethyl aniline its dialkyl derivatives the NMe2 group is coplanar with benzene ring.  So p-electron (lone pair) on N atom and pi orbitals are remain in the same plane. For this the p-electron on N-atom can delocalized via pi orbital in the benzene ring and its result the electron availability in para position is high and less available at nitrogen atom and hence less basic.

On the other hand , in case of N,N,2,6 tetramethyl aniline having two bulky methyl group in ortho position of the benzene ring , the NMe2 group can not remain in the same plane. That is why the p-electron on N-atom cannot delocalized through pi orbital in para position. (due to steric inhibition of resonance)  It is localized at nitrogen atom Thus 2,6-Dimethyl aniline  derivative is more basic.