Gaseous State Diazonium Salt

CONCEPT A gas occupies a volume about 1600 times greater

General formula : ArN2+X – CONCEPT
X may be Cl –, Br –, HSO–4 , BF 4–, etc.
–
than that of an equal weight of liquid. If gas is
compressed to 1/1600th of its volume above Azo dyes can be prepared using diazonium salts, these contain a highly delocalised
critical temperature (which is different for each system of electrons which delocalise in both benzene rings and the two nitrogen atoms
gas) no phase change occurs and the resulting bridging the rings. This extended delocalisation give colours to these azo compounds.
CLASS XI substance is a gas that is just as dense as a liquid. Modifying the group present in molecule can give rise to different colours. CLASS XII
Gas Laws Graham's Law of Diffusion Preparation Chemical Properties
Boyle’s law : It states that at a constant temperature (T), r1 v1 / t1 d2 M2 The reaction of converting aromatic primary amine to Reactions Involving Displacement of Diazo Group
P  (1/V) or PV = constant  P1V1 = P2V2 
r2 v 2 / t 2

d1

M1 diazonium salt is called diazotisation.
 Charles’ law : It states that at constant pressure (P), + – OH
NH2 N2Cl
V  T or (V/T) = constant  V1/T1 = V2/T2
H3PO2 + H2O Warm
Avogadro law : It states that at constant temperature (T) Dalton's Law of Partial Pressure 273 K
+ NaNO2 + 2HCl + NaCl + 2H2O H2O
and pressure (P), V  n or (V/n) = constant
 Gay Lussac’s law : It states that at constant volume (V), It states that “at a given temperature, the total pressure (Ptotal) Aniline Benzene I NO2
diazonium chloride
P  T or (P/T) = constant. exerted by two or more non-reacting gases occupying a
KI HONO
definite volume is equal to the sum of partial pressures of the N2 + KCl + + HCl + N2
Heat Cu2O
Boyle's Law component gases”. Physical Properties
Ptotal = p1 + p2 + p3 + .... (where p1, p2, p3 are partial pressures
of component gases) Br
Colourless crystalline solids. – Cl
N+2 Cl
 Readily soluble in water, less soluble in alcohol. Cu/HBr

Gatterman Reaction
N2 + Cu2Cl2
 These are unstable and explode in dry state.  + N2
Kinetic Molecular Theory of Gases Their aqueous solutions are neutral to litmus.
HCl, 

Sandmeyer’s Reaction
All gases are made up of a very large number of minute Cl
Charles' Law
particles like atoms or molecules. Applications Cu/HCl
Br
N2 +
 The molecules are in continuous random motion in all  Cu2Br2
+ N2
directions. To produce water-fast dyed fabrics by immersing the fabric HBr, 
Molecular collisions are perfectly elastic. in an aqueous solution of the diazonium compound,
T T (°C) –273.15 T (°C)  The intermolecular forces of attraction are negligible. followed by immersion in a solution of the coupler. F
The average kinetic energy of a gas molecule is directly  Synthesis of organic compounds. HBF4 CN
Ideal Gas Equation proportional to the absolute temperature. Diazonium salts are light sensitive and break down near  CuCN
 Kinetic gas equation : PV = 1/3 mnu2 UV or violet light. This property has led to their use in KCN/ + N2
Balz-Schiemann Reaction
PV = nRT [R = gas constant] document reproduction.
0.0821 L atm K–1 mol–1 R 0.083 L bar K–1 mol–1 Molecular Speed
8.314 J K–1 mol–1 (gas constant)
1.99 cal K–1 mol–1 –
N2+Cl Reactions Involving Retention of Diazo group
Root mean square velocity : Average velocity :
CH3
Deviation from Ideal Gas Behaviour (Real Gas) 3RT 8 RT + N N N The azo products obtained have an extended conjugate
urms  uav 
M M CH3 system having both aromatic rings joined through
Real gas follows gas laws only at high temperature and low Most probable speed : N p-dimethylaminoazobenzene —N N— bond.
H3 C CH3 (Butter yellow)
pressure.  These compounds are often coloured and are used as a dye.
2 RT
 an2  ump  ump : uav : urms = 1 : 1.128 : 1.224
 It follows van der Waals’ equation;  P   (V  nb)  nRT M –
 V2  N+2 Cl
–
OH N+2 Cl NaOH
Compressibility Factor + OH N N OH
OH N
dil. N
Maxwell–Boltzmann Distribution Curve + p-Hydroxyazobenzene
NaOH (Orange dye)

1-Phenylazo-4-naphthol –
N2+Cl NH2
-Naphthol

where, Z is compressibility
H+, 
factor which measures the deviation + N N NH2
from ideal behaviour. Rearranges
p-Aminoazobenzene
Relation between critical constants and van der Waals’ (Yellow dye)
a 8a
constants : Vc  3b , Pc  , Tc  N N
2 27 Rb
27b
 As the value of a increases, the critical temperature (Tc) N+2Cl– OH
dil.
OH
NaO3S
–
N+2 Cl + N(CH3)2
+
also increases. Higher the critical temperature of the gas, NaOH
more easily it liquefies. 1-Phenylazo-2-naphthol NaO3S N N N(CH3)2
-Naphthol
The ease of liquefaction order : Cl2 > CO2 > CH4 > H2 > He (Orange dye) Methyl orange