12/6/2018

Term ProjecT
KineTic DaTa analysis

Subject: Chemical Reaction Engineering

Submitted to: SIR SAQIB JAVED

Submitted By:

NAME: Reg. No.

ANWAR HUSSAIN 2016-CH-242
ATEEQ UR REMAN 2016-CH-244
BASIT ALI 2016-CH-224
MUJTABA IMTIAZ 2016-CH-262
NOMAN ASLAM 2016-CH-220
Department of Chemicals, polymers, composite & Materials Engineering. UET Lahore (K.S.K)
Campus.
 Table of Contents

 Saponification
 Kinetics data analysis
 Experiment
 Liquid phase batch Reactor
 Procedure & Precautions
 Observation
 Calculation
 Results
 Discussion
 References
 Saponification
Theory:
Saponification is basically the hydrolysis of a carboxylic acid ester with aqueous solution
of a base. The applications of saponification reaction are numerous i.e.

 textile: to remove calcium salts,

 paint and dye: for darkening colors,
 leather industry: for removing acids, etc.

Soap is a chemical compound that has become a sort of daily necessity to us due to its high
efficiency in the processes of cleaning and washing.

How the soap molecule is so good in hygiene? A soap molecule has a very special property
that is one end of its molecule is hydrophilic (water soluble) and the other end is hydrophobic (oil
soluble). The hydrophilic end consists of some strong alkali and the hydrophobic end is made up
of long chain of carboxylic acid. During the process of washing, the hydrophilic end of the soap
molecule dissolves in water and the hydrophobic end dissolves in oil. The form a specific spherical
shape shown below:

The spherical shapes are called micelles. Since the amount of water present is so much more than
the oil droplets, the oil gets pulled apart and trapped inside the sphere of soap molecules. Next, the
water can wash the spheres off effortlessly as colloids. This is a classic example of a surfactant.

Saponification is basically a soap manufacturing process in which we react an aqueous

alkali with a fatty acid resulting in the production of a carboxylate salt and an alcohol. Through
various research and development, the saponification reaction is being continuously improved.
The best reaction now developed is currently of dichloromethane/methanol as a solvent with low
NaOH concentration. The general reaction equation is:

NaOH+ CH 3COOR → CH3COO-Na+ + ROH

 In this experiment, we make ethyl acetate react with sodium hydroxide as a special case
of saponification reaction. The products formed are sodium acetate and ethanol.

NaOH+ CH3COOC2H5 → CH3COO- Na+ + C2H5OH

Mechanism:
The mechanism for saponification is:

1)

2)

3)

In literature, it is considered as a second order reaction.

The final product (soap molecule) is a white hygroscopic (water absorbing) crystalline
powder. Besides cleaning, it also has various other applications which include:

 in cement manufacturing,
 in buffer solutions or
 as additive in food products.

It also has various medical uses like:

 an electrolyte replenisher,
 for correcting sodium level in hyponatremic patients or
 for urine alkalization.
Important Properties:
 The molecular weight of sodium acetate is 82.03 g/mole.
 It has a melting point of 58 degrees C and a boiling point of 120 degrees C.
 Sodium acetate has a solubility of 500 g/L at 20 degrees C.
 Its crystals have a pH of 7.5 to 9.0.

Other chemically similar compounds are sodium acetate anhydrous, sodium ethanoate, sodium
ethanoate anhydrous, acetic acid sodium salt, ethanoic acid, sodium salt and natrium acetic.

Hazards:
 Sodium acetate also has a very low toxicity. It can be seen by the fact that when it was
orally ingested to the mice, it required an amount of 3530mg of sodium acetate per kg of
rat body for it to be fatal. In humans, inhalation of sodium acetate can make throat sore.
Direct eye contact can cause irritation. However, overall, its toxicity is quite low.

 Ethyl acetate can be considered mildly toxic. It is a colorless liquid with a sweet, nail
polish like odor. Despite its use in many common household products, ethyl acetate has
the potential to be seriously hazardous if handled incorrectly. It is also highly flammable
and explosive and can cause serious burns when mishandled. It can also cause damage to
internal organs in case of prolonged intake. Exposure to high concentrations can cause
serious problems like congestion of liver, kidney, anemia, leukocytosis, swelling and
breathing problems. When tested on rats, exposure to a high dose of 3600 mg/kg/day of
ethyl acetate led to problems like decreased body weight and food consumption.

 Sodium hydroxide is a white, noncombustible, odorless, hygroscopic and corrosive solid.

When the solid comes in contact with water, it can cause combustion through intense
heat. The sodium hydroxide is not really toxic but the danger comes from its
corrosiveness. It can cause severe damage to skin and eye since it can react with protein.
Children are more vulnerable to its corrosion as compared to adults. Continuous intake
can cause vomiting and blood may come in severe cases. According to a study, death can
result at 2nd or 3rd day of exposure due to shock, asphyxia from glottis edema or
pneumonia. Due to sever tissue and cell destruction, cancer may develop as a side effect.

Kinetic Data Analysis:

The official definition is that the kinetic data is a specific data structure used to track a
continuously moving attribute of a geometric system. In chemical engineering, we refer the data
regarding the reaction rates, effect of various variables, rearrangement of atoms, formation of
intermediates, etc. Of a chemical reaction as, kinetic data. We manipulate this data through a
special set of techniques called kinetic data analysis to get useful information like order of reaction
and rate equation.

Two types of techniques used in this type of analysis are:

1) Differential Method:

The data required for this process is concentration of reactant A w.r.t time. For constant volume
batch reactor with nth order reaction we can write:

= −𝐾𝐶 Or 𝑙𝑛 − = 𝑙𝑛 𝑘 + 𝑛 𝑙𝑛 𝐶
Thus if we can plot ln(-dCA/dt) vs. lnCA from the data, we will get a straight line whose slope gives
the order of the reaction and whose intercept gives the logarithm of the rate constant.

Next for finding dCA/dt, we can use several methods like numerical differentiation, graphical
method, and polynomial fit method.

2) Integral Method:

The integral method follows the following steps:

1) An order of the given reaction is assumed.

2) The general batch reactor equation is integrated according to the assumed order.
3) The quantities are rearranged in such a manner so as to give a real equation.
4) The graph is plotted.
5) If the line is straight than the order, we assumed initially is correct otherwise we have to
redo all steps by assuming a new order. The slope and intercept of this graph shall give us
our required values i.e. rate constant ‘k’.

Example:

 For first order reactions (V = constant):

dCA/dt = kCA By integrating ln (CA)/ (CA0)-= kt

so, ln (CA) has to be plotted vs. time

 for second order reactions,

(1/CA)-(1/CA0)=k*t
so, 1/CA has to be plotted vs. time, to get k

 For the nth order reaction (n ¹ 1): CA1-n-CA01-n=k(n-1) t so plot CA1-n vs. t to get Rate
laws of even more complex nature can be used in this method. Judging whether the
data actually fall on the prescribed can be difficult sometimes, especially if the
available data points are not very numerous.
 EXPERIMENT
Objective:
Conduct a saponification reaction by reacting ethyl acetate and sodium hydroxide and perform
kinetic data analysis on the experimental data.

Apparatus:
 Liquid-phase batch reactor.
 Chemical containers
 Stirring motor
 Weight balance
 1 x 100ml flask
 2 x 1000ml flasks
 Dropper
 Burette
 Pipette

Chemicals Required:
 Ethyl Acetate
 Caustic Soda (Sodium Hydroxide)
 Hydrochloric acid
 Phenolphthalein

Chemical Reaction:
NaOH+ CH3COOC2H5 → CH3COO- Na+ + C2H5OH.

Liquid Phase Batch Reactor:

All reactants & Products are in liquid phase.

The equipment consists of the following Parts:

Reactor:

It is a batch reactor equipped with a slow speed agitator and provided with steam jacket. Reactor
is properly insulated with glass wool. The capacity of reactor is 36 liters and its material of construction is
mild steel. Provision is made for the addition of reactants, namely, butanol, acetic acid and sulfuric acid. A
thermocouple is installed in a reactor to measure temperature of the reactor.
Feed Tank

There are two overhead feed tanks for Caustic soda (material of constructions: aluminum) ethyl
acetate (material of construction: aluminum). All tanks are provided with gauge glasses.

Steam Boiler

A miniature steam boiler is provided to supply low pressure saturated steam to the reactor
such that the contents of the reactor could be maintained at a temperature of 100oC throughout the residence
time of reactants.

Product Receiver
The product receiver is of sufficient capacity and made of mild steel.

Figure 1: Liquid phase Batch Reactor

Design equation of Batch Reactor
General mole balance equation
Rate of input - Rate of output- Rate of disappearance = Rate of accumulation
𝒗 𝒅𝑵𝒋
Nj0 – Nj +∫𝒐 𝒓𝒋𝒅𝑽= ………………………
𝒅𝒕

A batch reactor has neither inflow nor outflow of reactants or products while the reaction is being carried
out. So Nj0 – Nj =0.
𝒗 𝒅𝑵𝒋
∫𝒐 𝒓𝒋𝒅𝑽= 𝒅𝒕
……………………………….

If the reaction mixture is perfectly mixed so that there is no variation in the rate of
reaction throughout the reactor volume, rj can be taken out of the integral and the
mole balance can also be written as
𝒅𝑵𝒋
= rjV……………………………………
𝒅𝒕

Procedure:
 Clean all apparatus thoroughly with water and make sure it is dry before use.
 Take 66.07g of ethyl acetate by using weight balance.
 Make a solution of 66.07g of ethyl acetate with 7.5 liter of water and pour it into the
chemical container ‘A’ fitted above the reactor.
 Take 60 g of sodium hydroxide by weight balance.
 Make a solution of 60g of sodium hydroxide with 15 liter of water and pour it into the
chemical container ‘B’ fitted above the reactor.
 Prepare a hydrochloric acid solution of 0.05 M molarity.
 When everything is ready, open the valves of both containers and let the chemical
solution flow to the reactor.
 When all the chemicals are in the reactor, close the valves, make sure the top cover of the
reactor is secured and start the stirrer motor.
 Use the stopwatch to take the samples out of the reactor for chemical analysis at time
intervals.
 Take a measured amount of the sample in the measuring flask and hydrochloric acid
solution in the pipette.
 Pour a few phenolphthalein drops in the sample in the flask.
 Titrate i.e. pour a measured amount of acid into the flask drop by drop into the flask with
shaking until the pink color of phenolphthalein disappears.
 Create a table of all observed acid and base amounts taken at regular intervals.
 Perform kinetic data analysis and calculate the order of reaction ‘n’ and rate constant ‘k’.
Precautions and Preventions:
 Always wear lab coat, gas mask, eye protection goggles, rubber gloves and closed shoes
in the laboratory premises.
 Do not touch any chemicals or apparatus unrelated to the concerned chemical equipment.
 Always perform experiments in the teacher or lab attendant’s supervision.
 Do not eat or drink in the laboratory.
 Be serious when performing experiments.

Observation and Calculation

Temperature = 25oC

Pressure = 1 atm

Initial No. of moles of NaOH =NAo= 1.5 mole

Initial No. of moles of CH3COOC2H5 =NBo= 0.75 mole

Initial Molarity of NaOH = 0.1 M

Initial Molarity of CH3COOC2H5 = 0.1 M

Molarity of Titrant acid (HCl) = 0.05M

Volume of NaOH solution = 15 litre

Volume of CH3COOC2H5 solution = 7.5 litre

Total Volume of mixture = 22.5 litre

Observation:
Time Volume of Volume of HCl Used
No of Obs. (min) NaOH sample (ml) (ml)

1 0 10 13.2

2 3 15 16.2

3 8 14 11.7
4 11 25 19

5 16 15 9.6

6 21 10 5.52

7 24 20 10.4
Calculation:
 Concentration of unreacted NaOH:
Formula
Molarity of NaOH(M1) = Concentration of unreacted NaOH (mol/litre) = CA

𝑀2 𝑉2
𝑀1 =
V1

M1 = Molarity of unreacted NaOH V 1 = Volume of NaOH sample

M2 = Molarity of HCl V 2 = Volume of HCl used

Concentration of
Time Volume of NaOH Volume of HCl unreacted NaOH (CA),
No of Obs. (min) sample (ml) Used (ml) (mol/lit)
1 0 10 13.2 0.0666
2 3 15 16.2 0.054
3 8 14 11.7 0.042
4 11 25 19 0.038
5 16 15 9.6 0.032
6 21 10 5.52 0.0276
7 24 20 10.4 0.026

Graph:

Time Vs Unreacted Concentration NaOH

0.07

0.06

0.05
CA (mol/lit)

0.04

0.03

0.02

0.01
0 5 10 15 20 25
Time (min)

Figure 2
  No of moles of unreacted NaOH
Formula:

No of moles of unreacted NaOH = NA = CA× V

CA = Concentration of unreacted NaOH

V = volume of mixture in the reactor

Concentration of No. of moles of

No of Obs. Time NaOH (mol/lit) unreacted NaOH
(min) CA (NA)

1 0 0.0666 1.5

2 3 0.054 1.2

3 8 0.042 0.9198

4 11 0.038 0.8208

5 16 0.032 0.688
0.0276 0.5823
6 21
7 24 0.026 0.54

Graph:

Time Vs Unreacted moles of NaOH

1.61

1.41

1.21

1.01
NA (mol)

0.81

0.61

0.41

0.21

0.01
0 5 10 15 20 25
Time (min)

Figure 3
  Order & Rate Constant of Reaction:
By integral method

Assuming Zero Order:

𝑑𝐶
− = 𝐾𝐶
𝑑𝑡
Integration yield

𝐶 − 𝐶 = 𝑘𝑡

Zero order
0.05
y = 0.0012x + 0.0184
0.045

0.04

0.035
CAo-CA(mol/lit)

0.03

0.025

0.02

0.015

0.01

0.005

0
0 5 10 15 20 25
Time(min)

Figure 4
Assuming First Order

𝑑𝐶
− = 𝐾𝐶
𝑑𝑡
By integrating

𝑪𝑨𝒐
𝒍𝒏 = 𝒌𝒕
𝑪𝑨
 First order
1.2

y = 0.0298x + 0.375
1

0.8
lnCAo/CA

0.6

0.4

0.2

0
0 5 10 15 20 25 30
Time(min)

Figure 5

Assuming 2nd Order

− 𝑑𝐶
= 𝑘𝐶
𝑑𝑡
Integrating between t =o1, CA= CAoCA
1 1
− = 𝑘𝑡
𝐶 𝐶

The slope of plot will be equal to k=specific rate constant

Intercept = 0
 Time CA CAo (1/CA) -(1/CAo)
(min) (mol/litre) (mol/litre) (mol/litre)

0 0.0666 0.0666 0

3 0.054 0.0666 3.503503504

8 0.042 0.0666 8.794508795

11 0.038 0.0666 11.30077446

16 0.032 0.0666 16.23498498

21 0.0276 0.0666 21.21686904

24 0.026 0.0666 23.44652345

Graph for 2nd order Reaction:

2nd Order
30

25
y = 0.9761x + 0.4974

20
(1/CA)-(1/CAo)

15

10

0
0 5 10 15 20 25 30
Time(min)
Order of reaction= 2

As plot of (1/CA) -(1/CAo) vs Time gives a straight line hence slope will be same at all point

According to straight line equation:

y=mx+c
Slope =m= 0.9761

By using equation

Specific rate constant = k = slope = 0.9761 min-1 litre-1mol-1

 Half-life of NaOH
Formula:

2 −1 1
𝑡 =
𝑘(𝛼 − 1) 𝐶𝐴
𝒕𝟏 = Half life of NaOH
𝟐
𝜶 = Order of reaction= 2
k = Specific rate equation= 0.9761 min-1mol-1
CAo= Initial Concentration of NaOH= 0.0666

By putting values

half-life of NaOH = 𝒕𝟏 = ( )
= 15.38 min
𝟐 . .

 Fractional Conversion of NaOH at the end of reaction:

Formula:

𝑁𝐴 − 𝑁𝐴0
𝜀𝐴 =
𝑁𝐴0

ƐA= Fractional Conversion of NaOH

NA = unreacted no. of moles of NaOH at end of reaction= 0.54 mol

NAo = initial no. of moles of NaOH = 1.5 mol

By putting values
0.54−1.5
𝜀𝐴 = = -0.64
1.5

(-) due to that no of moles NaOH decrease as the reaction proceed.

Results:
 By curve fitting Saponification reaction of ethyl acetate is bimolecular 2nd order reaction with a
specific rate constant k=0.9761mol-1min-1litre-1.
 The half-life of the NaOH is 15.38min.
 The fractional conversion of the NaOH is -0.64.

Comments and Discussion:

o If a reactant is taken in excess quantity rate of reaction become zero order with respect to that
reactant.
o Concentration of NaOH can be measured by ways like titration against HCl, Conductivity change
measurement. But concentration change of ethyl acetate cannot be measured easily.
o After 15.38 min no. of moles of the NaOH remained half of initial.
o Fractional is negative due to fact that no of moles of NaOH decreases as the Reaction Proceed.
o Temperature changes can affect the Specific rate constant. But order of reaction is independent of
temperature
o Specific rate constant may also be calculated by Arrhenius Equation
𝑬∕𝑹𝑻
𝒌 = 𝑨𝒆

References: