42 Interfacial (Liquid-Liquid) Nitration

Aim
To study the kinetics of nitration of nitrobenzene (NB) in a stirred cell reactor at a liquid-liquid
interface.

Reaction

Figure 42.1: Nitrobenzene to Di-nitrobenzene

Reactants
1. Nitrobenzene (A.R.), ρ = 1.2 g/ml.
2. Nitrating mixture, ρ = 1.735 g/ml.

Equipment
Reaction Kettle, Impeller, Geared motor, Thistle funnel, Syringe, Standard ask, NaOH solution,
Spectrophotometer.

Theory
The reaction involves electrophilic substitution of substrate i.e. nitrobenzene in presence of the
nitrating mixture.
(+) (−)
HN O3 + 2H2 SO4 
 N O2 + H3 O(+) + 2H2 SO4
i.e. H SO (−)
HO − N O2 −−2−−→
4
HSO4 + HO(+) H
H SO (−) (−)
N O2 −−2−−→
4
H3 O(+) + HSO4 + N O2
The controlling step is the attack of N O2(+) on nitrobenzene.
Rate = k2 [RN O2 ][N O2 ]+ = k2 [RN O2 ][HN O3 ]


(42.1)
where k2 = Kk2 , and K is the extent of dissociation of HNO3 to yield NO(+)


2 ion. The reaction
exhibits second order kinetics.
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Industrial nitration involves two phase system; aqueous phase containing ions such as H
(+) , HSO(−) ,
4
(+) (−)
NO2 and NO3 and organic phase containing polar aromatic molecules. The charged species
present in the bulk aqueous phase will tend to concentrate at the interface depending on the surface
charge. Therefore, the reaction can occur in the interfacial mono-layer in addition to the reaction
in the bulk. Thus, the overall rate of reaction may be written as:

R = Ri + R b (42.2)

where R = total rate of reaction, mol/h, and Ri and Rb = rate of reaction at interface and bulk
respectively, mol/h. Ri and Rb can be expressed as:



Ri = k2 [RN O2 ]∗ [N O2 ]∗ A Rb = k2 [RN O2 ][HN O3 ]V (42.3)

∗ ∗
where, [RNO2 ] , [NO2 ] = concentration of nitrobenzene and nitronium ion per unit area of mono-
2

2
layer, mol/m , and k2 = interfacial reaction rate constant, m /mol h, and A = interfacial area,
2
m .

The rate of bulk reaction depends upon volume of the aqueous phase while it is independent of the
interfacial area. Exactly opposite behaviour is exhibited by the interfacial reaction. The eect of
the degree of agitation on the overall rate can therefore be studied in order to check whether one
or the other mechanisms are dominant.

Procedure
1. Charge 100 ml of nitrating mixture to the Stirred Cell reactor.

2. Set the impeller at the interface.

3. With the help of thistle funnel, slowly add nitrobenzene (100 ml) so that it is evenly spread
on the surface of the nitrating mixture.

4. Withdraw sample (1 ml) from the organic phase. This sample corresponds to zero reaction
time.

5. Start the motor and set the impeller speed. The reaction is conducted at at inter-
face/dispersed system.

6. The reaction is monitored for the presence of m-dinitrobenzene (m-DNB) by withdrawing

samples (0.5-1.0 ml) from the organic phase at an interval of every 15 min for 1.5 hrs. The
sample is quenched with distilled water and the organic phase after separation is analyzed for
m-DNB content by Janovsky test.

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Analysis
The organic phase sample ( 0.1 g) is taken in a volumetric ask (25 ml) and diluted with acetone.
10 ml of this sample is taken in a beaker to which is added 0.6 ml of NaOH solution (0.25% by wt.).
Violet colour starts developing. The sample is analyzed after 10 min on a UV-spectrometer. Note
the absorbance at 573 nm wavelength (λ).

Calculations
Equation of the calibrating curve
y = 0.123x + 0.01719
where, x = concentration of m-DNB in acetone (mg/l)
1. Concentration of m-DNB per weight of sample =
x × 10−6
weight of sample per ml of acetone
2. % conversion based on HNO3 taken
moles of DNB formed × total weight of organic phase
100 ×
wt. of sample
moles of HNO3 in nitrating mixture
Determine % conversion for each sample. Draw a graph of % conversion vs time. Slope obtained
from the plot corresponds to the rate of reaction.

Observations and Results

Time (min) Wt. of sample taken Absorbance Concentration of DNB
for analysis per weight of sample

Conclusions and Comments

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