CL 335: Chemical Engineering Lab III

RE 305: Interfacial (Liquid-Liquid)Nitration

Date of Experiment: 13th January, 2012 Date of Submission: 20th January ,2012

Group A5-(A):
09D02002 09D02013 09D02015 Nitin Mehra
Prateek Maheshwari Ashish Mendhekar

Aim: To study the nitration of nitrobenzene (NB) in a stirred cell reactor at a liquid-liquid interface by obtaining the rate of reaction.

Motivation: Numerous industrial processes involve two reacting phases and are processed in continuous flow reactors. Aromatic nitration is one of the most widely used reactions in organic process industry. Aromatic Compounds find wide use in the manufacture of dyes and explosives. Moreover Liquid liquid interfacial reaction which we study in this experiment is an important aspect of study for two immiscible liquids which is a wide area for research. The schematic representation of the overall reaction involved in the experiment is Apparatus Diagram

Apparatus: Reaction kettle, impeller, thistle funnel, syringe, standard flask, NaOH solution, Spectrophotometer.

Chemicals: Nitrobenzene, Nitrating mixture(HNO3+H2SO4+H2O), Acetone, Distilled water

Theory & Formulae:

The reaction involves electrophilic substitution of nitrobenzene in the presence of nitrating mixture. The nitrating mixture contains H2SO4(80% by wt.), HNO3(1 %by wt.), H2 O(19% by wt.) Mechanism:

The reaction exhibits second order kinetics and the rate expression can be given by:Rate = k2[RNO2 ][NO2 +] = k2[RNO2 ][HNO3] Also k2 = K*k2

Where k2 and k2 are constants and K is the extent of dissociation of HNO3 to yield [NO2+]. Industrial nitration involves two phase systems, aqueous containing ions and organic phase containing polar aromatic molecules. Due to concentration of charged species at the interface, reaction occurs at bulk aqueous phase and at the interface. R = Ri + Rb Ri Reaction at Interface and Rb is reaction at bulk Therefore rate depends on y Volume of aqueous phase and respective concentration Rb= k2[RNO2 ][HNO3 ]V y Interfacial area and species concentration at the interface.

Ri= k2[RNO2 ][NO2 +]A The effect of degree of agitation on the overall rate can be studied to check which of the two mechanisms is dominant. The reaction in the experiment is conducted on the flat/dispersed phase. Procedure: 1. Charge 50 ml of nitrating mixture in the stirred cell reactor. 2. With the help of thistle funnel slowly add 50 ml of nitrobenzene to the nitrating mixture so that it gets spread evenly on its surface. 3. Withdraw 0.5-1 ml sample from the organic phase, this reading corresponds to zero reaction time. Keep the impeller 50% above interface. 4. Start the motor and set the impeller speed between 45- 50 rpm (considered to be an optimum speed in our case). 5. Take 0.5 ml 1 ml samples from Organic phase at intervals of 15 minutes till 75 minutes 6. Samples are quenched with distilled water to separate organic phase (insoluble), which is analyzed using Janovsky test for presence of m-Nitrobenzene content. Data Analysis: The organic phase sample (.1 g) is taken in a volumetric flask (25 ml) and diluted with acetone. 10 ml of this sample in a beaker to which is added 0.6 ml of NaOH solution (.25 % by wt.).Violet colour starts developing. The sample is analysed after 10 min. on a UV spectrometer. Note the absorbance at 573 nm wavelength. Janovsky test: This test is used for analyzing m-DNB content in the mixture. In this test the meta-Dinitrobenzene is oxidized with excess base to a strongly coloredenolate with subsequent reduction of the dinitro compound to the aromatic nitro amine thus forming the basis to analyze it. Formulae used: 1. Concentration of m-DNB per weight of sample       

2.

% conversion based on HNO3 taken             

3. Calibration Curve used :

y=0.123x

Observation table:
Conc. Of DNB per litre of Acetone solution (mg/l) Wt. of sample per ml Acetone (gm/ml) Conc. Of DNB per wt of sample Percentage conversion based on HNO3

Time (min)

Wt of sample taken for analysis (gm)

Absorbance

0 15 30 45 60 75

Sample calculation for 1st reading: Equations of the calibrating curve: y=0.123x where y=absorbance of the sample x=concentration of m-DNB in acetone(mg/l) So, x= /.123= mg/l

4. Concentration of m-DNB per weight of sample        /25)= gm of m-DNB/gm of sample =( *10-6 )/( 5. % conversion based on HNO3 taken

   

  

 

moles of DNB formed = moles Total weight of organic phase= Wt. of sample = gm gm

Moles of HNO3 in nitrating mixture= % conversion = %

Graph of % conversion v/s time. Plot of % conversion with time with intercept not equal to zero:

Slope=0.020min-1

Plot of % conversion with time with intercept =0

Result:
The rate of reaction as calculated (i) (ii) From the slope of the plot between % conversion v/s time by setting intercept as zero comes out to be min-1. From the slope of the plot between % conversion v/s time by fitting the graph on data points comes out to be min-1.

Error Analysis:
Error in concentration Error in absorbance y is least count error of the spectrophotometer i.e. 0.001 y = 0.123*x y/y = x/x x = (y/y)*x = = (.001/0.087)*0.707
= 0.008

Error in calculation of slope is ( *100 = %

Sources of Error: 1. Ideally at t = 0 , when the reaction just starts , concentration of DNB = 0 ,but it is evident by data collected that our first reading was taken little after start of reaction 2. Due to improper quenching the NaOH added reacts to neutralize rather than complexing. 3. Human error while measuring and transferring volumes of fluids and chemicals used. 4. Care has to be taken to prevent formation of stable drops of organic phase during the pouring operation.

Precautions: 1. Stirrer should be placed at interface and its speed should be kept low. 2. Sample should be quenched with distilled water properly to separate the polar components. 3. The interface should not be disturbed while pouring the organic phase. 4. While collecting samples for weighing make sure no nitrating mixture is allowed