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Therefore, step ii, involving the formation of nitronium ion (NO+2) should
be faster than reaction No. iii. On the basis of this mechanism, the rate
expression conforms to the observed behavior.
2. Condition - B
b. The other path is assumed as which does not involve the organic
compound.
The extent of any of two steps would have direct impact on the order of
reaction.
Nitration in Organic Solvent
With amount of HNO3 in large excess and in the
presence of Organic solvent such as (non-aqueous) acetic
acid, the kinetics of the nitration process depend directly
on the Concentration of the organic compound. Thus when
nitrobenzene ( NO 2) is nitrated in the presence
of organic solvent. The system is 1st order w.r.t. organic
compound.
It has been observed that the rate of reaction rises sharply with
increasing sulfuric acid concentration and reaches a maximum at
about 90% H2SO4 and then falls off at higher acid concentration.
ArN
O - - HOSO3H
1) Inhibiting effect
2) catalytic effect
INHIBITING EFFECT
CATALYTIC EFFECT:
2) The reaction mediums have concentration of nitryl ion very low thus
allowing the nitrodyl ion to compete favorably for substrate.
OXYNITRATION
1) Nitro methane
2) Nitro ethane
3) 2 nitro propane
4) 2 nitric butane
5) 1 nitro isobutene
6) 1- nitro 3 methyl butane
7) 2- nitor-3-methylbutane
2) The addition of oxygen increases the yield based on nitric acid but also
increases the oxidation of butane. The effects are shown in fig. oxygen
also increase the yield of nitro methane and nitro ethane and
decreases the yield of nitro butane.
3) Nitrogen dioxide also reacts with paraffins to yield nitroparaffins. At 325
C, a contact time of 1.9 min, and propane: NO 2 = 4.2, the percent
conversion of NO2 is 16.6 and the yields based on the moles of
hydrocarbons is 51 percent. The addition of oxygen lowers the
optimum temperature and improves conversion and yields. At 285 C,
contact time 3 min, and O2 : NO2 = 0.75, the conversion is 29 percent
and the yield is 71 percent.
NO2 NO2
(A) (B)
R N R RCO N R
NH
H2C CH2
H 2N C
NHNO2
N
NO2
NO2
RDX Tetryl Nitroguaidine
Methods of Preparation
Primary nit amines can not be prepared by the direct, nitration of primary
amines. Because of their sensitivity towards acid, they probably do not
survive in the strongly acidic environment of the nitration. They are gently
made by alkaline hydrolysis of nit amides.
HNO2 OH
The nitramides are readily prepared by nitration of the amide with 100%
nitric acid or with nitric acid, acetic anhydride, acetic acid mixture.
Primary nitramines can also be prepared from the appropriate urethane.
CICOOEt HNO 3 NH 3
RCNO HNO3
O2N N N NO2
N
NO2
N NO2
Hexamine RDX I
PROCESS EQUIPMENT FOR TECHNICAL
NITRATIONS
Labor Usage: For high rates of production when large batches are
used the labor efficiency of a batch process may be just as good as that
for a continuous process. This appears to be true for the large scale
industrial production of nitroglycerine and nitortoluene, for example:-
Hot sulfuric acid at 90 C is run from the heat insulated storage tank (B)
into one of a battery of nitrators (A1 to A4). Under vigorous agitation,
sufficient 63 percent nitric acid is added to the nitrator to produce a
mixed acid containing 4 percent HNO3. Sufficient benzene is then
delivered from its storage scale tank to react with al the nitric acid in the
nitrator. Upon completion of the reaction, which takes about 10 minutes,
the agitation is stopped and the charge permitted to settle. While the
separation of the nitrobenzene and spent acid proceeds, another
nitration is started, thus providing a continuity of operations.
PREPARATION OF A-NITRO NAPHTHALENE
NO2
+ HNO2 + H 2O
H2SO4 . 59.55%
HNO3 ... 15.85%
H2O .. 24.60%
HNO3 ratio .. 1.01
D.V.S. .. 2.04
During the addition of the acid, the temperature is kept at 35-50 C; but
after the whole of the acid has been run in, the temperature is raise
slowly to 65-70 C and maintained at that period for 1 hr. The agitation
is then stopped and the nitro naphthalene which floats on the surface is
decanted with part of the spent acid and delivered to a separator, a
heel of acid being left for the next nitration. After settling for 3 hr, the
spent acid is removed and the crude nitro naphthalene is delivered to
the washing and granulation kettle. Here it is made free for acid by
repeated washings with boiling water and alkali. Any free naphthalene
that may be present is removed by steam during the washing process.
The crystallizing point must be between 52 and 52.5 C.
The purification of the crude product is accomplished also by re-
crystallizing it from 10 percent of its weight of ligroin or solvent naphtha.
The success of the purification depends upon certain details of
manipulation, which include (1) use of a minimum of solvent and (2)
constant agitation while re-crystallization take place in order to assure
the formation of small crystals. The nitro naphthalene is dissolved in 10
percent of its weight of solvent naphtha and heated above the melting
point of the crude, i.e., above 50 C, until a homogeneous mixture is
formed. The resulting solution is cooled to 25 C with constant agitation,
and the thick slurry that is formed is centrifuged. The -nitro
naphthalene obtained in this manner has a solidifying point above 54.4
C. This is not yet pure, as the chemically pure material comes as
glistening yellow crystals which melt at 61 C.
PREPARATION OF NITROPARAFFINS
The conditions of nitration can be varied widely, but these have been
worked out to the optimum values of temperature, pressure, reaction
time, ration of reactants, and the like. The proportion of the four nitro
paraffins from propane is said by Bachman and Pollack to be about as
follows:-
Nitro methane 25%
Nitro ethane 10%
1-Nitro propane . 25%
2-Nitro propane . 40%
Nitrations in the vapor phase such as these are always accompanied by
competing oxidative and decomposition reactions which may produce
such organic materials as aldehydes, ketones, alcohols, carboxylic
acids, olefins, nitrolefins, and polymers. Such simple compounds as
CO2 and CO, NO, and H2O are also end products of the nitration
reaction. The nitrator is operated to minimize production of nitrogen, and
little excess nitric acid appears in the effluent stream.