ACYCLIC HYDROCARBONS THE SOLID STATE

(Open chain structures containing C and H only)

CONCEPT Although hydrocarbons are primarily consumed in fuels, non- Class Class The solid state chemistry covers the latest advances in advanced CONCEPT
MAP MAP
fuel applications of hydrocarbons are of great importance to inorganic materials with applications ranging from energy
society and the economy. Certain hydrocarbons can be found in XI XII storage systems, electronic materials and sensors to the more
lubricating oils, greases, solvents, fuels, wax, asphalts, cosmetics traditional, but increasingly hi-tech materials and industries
and plastics. that include glass, cement and refractories.

Saturated Unsaturated
SOLIDS
Classification based Classification based on
C—C single bonds present C—C multiple bonds present on Crystal Lattice Magnetic Properties

Crystalline Solids Amorphous Solids · Diamagnetic Substances : Substances which are

Alkanes Alkenes ( C C ) Alkynes ( C C ) weakly repelled by external magnetic field, e.g., N2,
General formula, CnH2n + 2 General formula, CnH2n General formula, CnH2n – 2 · True solids. · Isotropic. NaCl, Zn, TiO2, etc.
· Anisotropic. · Pseudo solids or supercooled · Paramagnetic Substances : Substances which are
liquids. weakly attracted by external magnetic field, e.g., O2,
Preparation Preparation Preparation · Have definite pattern of
· Do not have a definite pattern of Cu2+, Fe3+, Cr3+, etc.
· From alkyl halides : · Hydrogenation of alkynes : · From calcium carbide : arrangements of atoms, ions arrangement. · Ferromagnetic Substances : Substances which show
Dry ether or molecules. · Short range order.
2R—Br + 2Na R—R + 2NaBr (a) R—C C—R¢ + H2 CaC2 + 2H2O Ca(OH)2 + C2H2 permanent magnetism even in the absence of
(Wurtz reaction) Pd/C R R¢ · Dehalogenation : · Exhibit plane, axis and centre · Do not show any symmetry. external magnetic field, e.g., Ni, Fe, Co, etc.
R—X can be converted to alkane C C
(Lindlar’s catalyst) KOH
H H CH2—CH2 CH2 CHBr of symmetry. · Antiferromagnetic Substances : Substances which
(cis-alkene) Primitive Unit Cells
using Zn + CH3COOH, have zero net dipole moment even though they have
(b) R—C C—R¢ + H2 NaNH2 · Long range order. · Constituent particles are present
Zn + dil. HCl, Zn–Cu + C2H5OH, Br Br
Na/liq. NH3 R H CH CH · Are categorised according to only at the corners of the unit large number of unpaired electrons, e.g., MnO.
LiAlH4, Zn + NaOH, NaBH4 and C C
or LiAlH4 H R¢ cell. · Ferrimagnetic Substances : These are the substances
Ph3SnH reducing agents. intermolecular forces into :
(trans-alkene) Properties · Consist of 7 types of arrangements which possess very small net magnetic moment even
· From carboxylic acids : · Dehydrohalogenation : Molecular, ionic, metallic and
· Acidic nature : with cubic as most symmetric and though they have large number of unpaired electrons,
Red P/HI liq. NH3 covalent solids.
RCOOH RCH3 + H2O + I2 H H + 1 triclinic as least symmetric. e.g., Fe3O4.
D b CH CH + Na CH CNa + H2
2RCOONa + NaOH Na2CO3 + RH alc. KOH H H 2
H—C—C—H
a
C C · Addition reactions :
Electrolysis D H H
2RCOOK + 2H2O CH CH Pt/Pd/Ni CH3—CH3 Z×M
H X (b-elimination) Crystal Lattice and Unit Cells Cubic System d= g cm–3
R—R + 2CO2 + H2 + 2KOH H2 a3 × NA
· Dehalogenation : Br
(Kolbe’s electrolysis method) CH3—C CH CCl2 Centred Unit Cells
Methanol 4
· From carbonyl compounds : X—CH2—CH2—X + Zn CH3—CBr2—CHBr2 Constituent particles are present at the corners and at : Type Simple cubic bcc fcc
D
NH2NH2 (vic. dihalides) H2O · the centre of the unit cell (bcc) 1 1 1 1
RCOCH3 C H ONa R—CH2CH3 CH2 CH2 + ZnX2 CH3—C CH CH3—C CH2 Z 8×8=1 8 × 8+ 1 × 1 = 2 8 × 8+ 6 × 2 = 4
2 5 · the centre of each face of the unit cell (fcc)
(Wolff-Kishner reduction) · Dehydration of alcohols : OH C. No. 6 8 12
Conc. H2SO4 Isomerisation · the centre of any two opposite faces (End-centred)
Zn/Hg CH3—C—CH3
RCOCH3 conc. HCl RCH2CH3 + H2O CH3CH2—OH D
d a d a d 3a
Relation of r= 2= 2 r= 2=2 2 r= 2= 4
(Clemmensen reduction) CH2 CH2 O Types of Defects Non-stoichiometric Defect since d = a a 3a
r, d & a since d = 2 since d = 2
Properties Properties Commercial Uses Arises due to the
Stoichiometric Defect Packing
· Substitution reaction : · Addition of halogen : · Alkanes : Ethane is used for making (Intrinsic or presence of constituent 52.4% 68% 74%
Efficiency
CH3CH2CH2Cl CCl4 CH2—Br hexach loro et hane w hich is an Thermodynamic Defect) particles in non-
CH3CH2CH3 Cl2 CH2 CH2 + Br2
stoichiometric ratio.
(Brown CH2—Br artificial camphor. Higher alkanes in Does not disturb the Voids
CH3—CH—CH3 colour) (Colourless) the form of gasoline, kerosene oil, stoichiometry of solid. Type Size No. of Voids
Cl · Addition of halogen acid :
Order of reactivity : diesel, lubricating oils and paraffin Octahedral 0.414 R N
Markownikoff ’s
CH3—CH CH2 + HBr wax are widely used. Tetrahedral 0.225 R 2N
Alkanes : 3° > 2° > 1° > CH4 rule Frenkel Defect Schottky Defect
Halogens : F2 > Cl2 > Br2 > I2 Br · Alkenes : Ethene is used as a general
anaesthetic. It is a starting material for Ü It is due to missing of ions Ü It is due to equal no. of Metal Excess Defect : Arises due to anionic vacancies, leaving a
· Oxidation : CH3—CH—CH3
(usually cations) from the cations and anions missing hole which is occupied by an electron thus, maintaining electrical
HBr addition in presence of peroxide a large number of compounds such as
(a) Combustion or complete oxidation : lattice sites and these from lattice sites.
follows anti-Markownikoff ’s rule, glycol, ethyl halides, ethyl alcohol, balance. The anionic sites, occupied by unpaired electrons, are
CnH2n+2 + 3n + 1 O2 known as Kharasch effect or peroxide occupy interstitial sites. Ü It results in decrease in called F-centres and these impart colour to crystals.
2 ethylene oxide, etc.
effect. Ü It has no effect on the density of crystal.
nCO2 + (n + 1)H2O + heat · Alkynes : Acetylene is used as a Metal Deficiency Defect : Arises when metal shows variable
density of crystal. Ü This is found in the highly
· Oxidation : general anaesthetic under the name
(b) Catalytic oxidation : alk. KMnO4 Ü This is found in crystal ionic compounds having valency i.e., in transition metals. The defect occurs due to missing of
Cu-tube CH2 CH2 + H2O + O2 naracylene. Acetylene is used as an a cation from its lattice site and the presence of the cation having
2CH4 + O2 2CH3OH 298-303 K with low coordination no. cation and anion of same
100 atm / 473K illuminant.
9 : 1 HO—CH2—CH2—OH e.g., AgI, ZnS, etc. size, e.g., NaCl, CsCl, etc. higher charge in the adjacent lattice site.