MUHAMMAD NAWAZ SHREEF

UNIVERSITY OF
ENGINEERING AND
TECHNOLOGY, MULTAn.
Chemical Department

CHEMICAL REACTION
ENGINEERING LAB PROJECT
PROPOSAL.
presented to:
Mam mina Arshad
presented by:
GROUP # 02

ZIA UR REHMAN 2019-CH-05

Ahmad Habib 2019-CH-09 (Leader)
Muhammad Mujahid 2019-CH-15
Allyan Javaed 2019-CH-22
Ali Awais 2019-CH-30
OBJECTIVE:
To find the order and the reaction rate constant (k) of
the neutralization reaction of sodium hydroxide and
benzoic acid in a stirred batch reactor and also find the
activation energy (E) for the neutralization reaction
through Arrhenius equation.
Table of content:
Neutralization reaction
Methodology
Activation energy
Arrhenius equation
Batch reactor
Conductivity
Conclusion
References
Theory
NEUTRALIZATION REACTION
• A neutralization reaction can be defined as a chemical reaction in which an acid and
base quantitatively react together to form a salt and water as products. In a
neutralization reaction, there is a combination of H+ ions and OH- ions which form
water. A neutralization reaction is generally an acid- base neutralization reaction.
REACTION OF NAOH AND BENZOIC ACID
 This is a neutralization reaction between a weak acid and a strong
base, which will result in a salt and water for products, just as with
strong acid/strong base neutralization reaction. In this reaction
benzoic acid is primary standard and NaOH is secondary standard.

C7 H6 O2 H2O + C7H5O2Na
Apparatus required:

Beakers 500ml
Glass rod
Batch reactor
Weighing balance
Magnetic stirrer and hot
plate (for stirring)
Service unit
Batch reactor
Conductivity meter
Thermometer
Benzoic acid
solution

Hot plate
for stirring

Conductivity rod Weighing balance

 Conductivity Flow rate of pump G1 and G2
Stirring speed
temperature

Drums for feed D1

& D2

Water tank

Thermostat
Chemicals required:

Distilled water
NaOH
Benzoic acid

Sodium hydroxide Benzoic acid

Chemical reaction:
C6H5COOH + NaOH C6H5COONa + H2O
Procedure:
 Make 0.5L batches of 0.03M NaOH and 0.02M benzoic acid.
 Adjust the set point temperature to 25oC.
 Set the speed of the stirrer at 60%.
 Feed the reactor with NaOH and benzoic acid carefully.
 Start noting the conductivity reading after equal interval of time i.e. 30
second.
 Note the final conductivity reading when the reaction becomes steady
state.
 Calculate the concentration CA (a1), conversion of NaOH (XA) and
conversion of the product (XC).
 Draw a graph between CA and time t if it gives straight line with negative
slope it is zero order reaction.
 Draw a graph between -lnCA/CAo and time t if it gives straight line then
it is 1st order reaction.
 Draw a graph between 1/CA and time t if it gives a straight line then it
is 2nd order reaction.
 If it is not any of these orders then use nth order equation to find the
order of reaction.
 Find the rate constant (k) of the reaction from the slope by using
formula (2nd order):
m=k

Repeat the same procedure at 40oC, 55oC at same speed.

Then calculate the activation energy of the reaction at these given
temperatures by using Arrhenius equation.

Zero order
1st order
 2nd order

1
Slope = k

.
t
C NaOH

time
Precautions:
 Take readings carefully from the stopwatch.
 Check electrical configuration carefully.
 Take the readings carefully from the conductivity meter.
 Always wear lab coats.
Observations & calculations:
Benzoic acid solution:
mass
molarity 
M .W  vol.
mass
0.02 
122.12( g / mol )  0.25L
1.22 g
mass 
0.5 L
Sodium hydroxide solution:
mass
molarity 
M .W  vol.
mass
0.03 
39.997( g / mol )  0.25 L
0.6 g
mass 
0.5 L
 Co-relations
At
t=∞ Case-2
Case-1 If
if
CCin7 H6O2 < CinNaOH CCin7 H6O2  CNaOH
in

CC7 H 5O2 Na = CinC7 H6O2  0.02mol / dm3 CC7 H5O2 Na  CNaOH

in
 0.024mol / dm3
Case-3
if

CCin7 H 6O2  CNaOH

in

 in
C NaOH  CNaOH  CCin7 H 6O2
= 0.004 mol/dm 3
if
T  298K
1.  C0 7 H5O2 Na  0
2.  0
NaOH  0.248 1  0.0184 T  298  C 0
NaOH

3.  C7 H5O2 Na  0.091 1  0.0284 T  298  CC7 H 5O2 Na

4.  NaOH  0.248 1  0.0184 T  298  CNaOH


 0   0NaOH   C0 7 H5O2 Na
    NaOH   C7 H5O2 Na
 • From the above relations the value of conductivity at different time and
temperature is:
for for
T = 25 C  298 K T = 40 C  313K
 0   0NaOH   C0 7 H5O2 Na  0   0NaOH   C0 7 H5O2 Na
 0  5.95mS  0mS  5.95mS  0  22.38mS  0mS  22.38mS
    NaOH   C7 H5O2 Na     0NaOH   C0 7 H5O2 Na
   0.992mS  1.82mS  2.812mS    1.27 mS  2.60mS  3.87mS
for
T = 55 C  328 K
 0   0NaOH   C0 7 H 5O2 Na
 0  38.81mS  0mS  38.81mS
    0NaOH   C0 7 H 5O2 Na
   1.54mS  3.37mS  4.91mS
 Sr. No. Time 1
At XA
t
CNaOH
(sec.)  t
NaOH
C t
NaOH XC  ln 0
CNaOH
t
C NaOH
T  25C  298K 01 0 5.05 0.0183 0.238 0.287 0.271 54.64
02 30 4.99 0.0179 0.254 0.306 0.293 55.87
03 60 4.95 0.0176 0.267 0.319 0.310 56.82
04 90 4.91 0.0174 0.275 0.331 0.322 57.47
05 120 4.87 0.0171 0.288 0.344 0.399 58.48
06 150 4.85 0.0170 0.292 0.351 0.345 58.82
07 180 4.82 0.0168 0.30 0.360 0.357 59.52
08 210 4.79 0.0166 0.308 0.370 0.369 60.24
09 240 4.79 0.0166 0.308 0.370 0.369 60.24
10 270 4.79 0.0166 0.308 0.370 0.369 60.24
 At
T  40C  313K

Sr# Time t
CNaOH 1
(sec.)  t
NaOH
C t
NaOH XA XC  ln 0
CNaOH
t
C NaOH
01 0 5.63 5.90*10-3 0.754 0.905 1.403 169.49
02 30 5.58 5.85*10-3 0.756 0.908 1.412 170.94
03 60 5.55 5.82*10-3 0.758 0.910 1.417 171.82
04 90 5.51 5.77*10-3 0.760 0.911 1.425 173.31
05 120 5.47 5.73*10-3 0.761 0.914 1.432 174.52
06 150 5.44 5.70*10-3 0.762 0.915 1.438 175.44
07 180 5.41 5.66*10-3 0.764 0.917 1.445 176.68
08 210 5.38 5.63*10-3 0.765 0.918 1.450 177.62
09 240 5.38 5.63*10-3 0.765 0.918 1.450 177.62
10 270 5.38 5.63*10-3 0.765 0.918 1.450 177.62
 At
T  55C  328 K
Sr. #. Time t
t
CNaOH 1
(Sec)  NaOH C t
XA XC  ln 0 t
C NaOH
NaOH CNaOH
01 0 6.27 4.80*10-3 0.8 0.960 1.609 208.33
02 30 6.22 4.77*10-3 0.801 0.961 1.616 209.64
03 60 6.17 4.74*10-3 0.802 0.963 1.622 210.97
04 90 6.13 4.72*10-3 0.803 0.964 1.626 211.86
05 120 6.09 4.70*10-3 0.804 0.965 1.631 212.77
06 150 6.04 4.67*10-3 0.805 0.967 1.637 214.13
07 180 6.01 4.65*10-3 0.806 0.968 1.641 215.05
08 210 5.97 4.62*10-3 0.808 0.969 1.648 216.45
09 240 5.97 4.62*10-3 0.808 0.969 1.648 216.45
10 270 5.97 4.62*10-3 0.808 0.969 1.648 216.45
XA
Graph between time and X A
It is the conversion of
0.9
sodium hydroxide into
sodium benzoate. 0.8

0.7
t
C 0.6
X A  1 NaOH
0
C NaOH
0.5
At T=298K
At T=313K

.
XA
0.4 At T=328K

0.3

0.2

0.1

0
0 50 100 150 200 250 300

time
XC Graph between time and XC
1.2
It is the conversion of the product i.e.
1
how much reactants are converted
into products. 0.8
X C 0.6
0.4
CC1
XC  0.2
CC
0
0 50 100 150 200 250 300
  0  1    0  1 
XC     CC1  CC      time
 0     0  
At T=298K At T=313K At T=328K
 t
C NaOH C t
Graph between time and NaOH
0.0185
 It is the concentration of
0.018
NaOH at different time
0.0175
which is being consumed. t
CNaOH 0.017

.
 The graph between 0.0165

concentration and time 0.016

gives negative slope but it 0.0155

0 50 100 150 200 250 300
doesn’t gives a straight time
line. So, the reaction is
not zero order.

  0  1  
  NaOH NaOH 
t 0 0
C NaOH  C  C  C NaOH
  0   
 t
C NaOH
 ln 0
C NaOH
t
CNaOH
 ln 0
Graph between time and CNaOH
0.45
0.4
The graph doesn’t gives a straight 0.35
line it shows that it is not a first order 0.3
reaction. t
CNaOH 0.25
 ln 0 0.2

.
CNaOH
0.15
0.1
0.05
0
0 50 100 150 200 250 300

time
 1
t
C NaOH
1
1.Graph between time and t
C NaOH
It is the graph at 298K, 313K, 61
328K. The graph between inverse f(x) = 0.0211272727272727 x + 55.3818181818182
60
of concentration and time gives a 59
straight line which shows that it is 58
a second order reaction. 57
Now, calculating the slope to find 1
t
56
C NaOH

.
the rate constant. 55
54
53
52
51
0 50 100 150 200 250 300
time
 At T=328K 2. At 313K
218
f(x) = 0.0321373737373737 x + 208.871454545455 180
216 178 f(x) = 0.0323151515151515 x + 170.143454545455
214 176
212 174
210 172

208 170
168
206
166
204
0 50 100 150 200 250 300 164
0 50 100 150 200 250 300
 1
• From the above graph i.e. graph between time and t , calculate
CNaOH
the slope which is equal to the rate constant “k”:
• At T = 298K
m=k 3
dm
k = 0.0211 mol.s
At T = 313K Temperature T k dm 3

dm
k = 0.0323 mol.s
3
(K) mol.s
298 0.0211
At T = 328K 3
dm 313 0.0323
k = 0.0321 mol.s
328 0.0321
Activation energy:
• The minimum amount of energy that is required to activate
atoms or molecules to a condition in which they can undergo
chemical transformation.

“The amount of energy required just to start a reaction is

called activation energy.”

• For example, activation energy is needed to start a car engine

or bike engine. Turning the key causes a spark that activates the
burning of gasoline in the engine.
Arrhenius Equation:
• The Arrhenius equation describes the relation between the rate of
reaction and temperature for many physical and chemical reactions. A
common form of the equation is:
• “A” is the frequency factor in this equation. A represents the frequency at
which atoms and molecules collide in a way that leads to a reaction. Its
value is negligible for such a small change in temperature like change of
10⁰C or 15⁰C.

EA

• e is the exponential factor in this equation.
RT

RT is the average kinetic energy, it will be apparent that the exponent is
just the ratio of the activation energy, Ea, to the average kinetic energy. The
larger this ratio, the smaller the rate, which is why it includes the negative
sign. This means that high temperatures and low activation energies
favor larger rate constants, and therefore these conditions will speed up a
reaction.
Plotting the Arrhenius equation in non-exponential form:

• The Arrhenius equation can be written in a non-exponential

form, which is often more convenient to use and to interpret
graphically. Taking the natural logarithms of both sides and
separating the exponential and pre-exponential terms:
EA
ln k  ln A 
RT
E 1
ln k     ln A
R T

y  mx  c
• Creating a plot of ln(k) versus 1/T will produce a straight line with
the slope –Ea /R.

• This affords a simple way of determining the activation energy

from values of k observed at different temperatures. We can
plot ln(k) versus 1/T, and simply determine the slope to solve
for Ea.

• A reaction won’t occur unless atoms or molecules

of reactants come together. This happens only if the particles are
moving, and movement takes energy. Often, reactants have to
overcome forces that push them apart. This takes energy as well.
Still more energy is needed to start breaking bonds in reactants.
Graphical representation:
1
Graph betweenln Aand T

f(x) = − 717.06 x − 1

T (K) k dm3 1/T ln(k)

mol.s ln A
298 0.032 0.0034 -3.44

313 0.04 0.0032 -3.22

328 0.04 0.0031 -3.22 1

T
Activation energy:
E 1
ln k     ln A
R T
y  mx  c The minimum amount of energy
required to initiate the neutralization
From graph: reaction is 5.9616kJ/mol.
m= -717.06
So, E
m( slope) 
R
m  R  E
J
717.06  8.314  E
K .mol
J
E  5961.6
K .mol
kJ
E  5.9616
mol
Batch reactor:
• A batch reactor is the simplest type of reactor vessels use for
chemical or industrial processes.

“A typical batch reactor consists of a tank

where chemical reactions occur.”

• These tanks also have an agitator and an internal heating or

cooling system. Tank sizes range from one liter to 15,000 liters.
• The reactants are initially charged in a container ,are well mixed,
and are left to react for a certain period.
• The resultant mixture is then discharged.
Working principle:
• Batch reactors are used for most of the reactions carried out
in a laboratory. The reactants are placed in a test-tube, flask
or beaker. They are mixed together, often heated for the
reaction to take place and are then cooled. The products are
poured out and, if necessary, purified.
• A batch reactor has neither inflow nor outflow of reactants
or products while the reaction is being carried out
• This is an unsteady-state operation where composition
changes with time ; however , at any instant the
composition throughout the reactor is uniform
Advantages
• They are preferred for establishing or verifying kinetics because they
are:
• Simple in construction.
• Require little or no auxiliary equipment.
• Data can be collected easily if isothermal reactions are caried out
under constant volume condition.
• High conversions.
Disadvantages/Limitations
• Intensity of process is localized and not the global one
• Preferred for homogenous reactions only
• High labor costs per batch
• Difficulty of large-scale production
• Long idle time (Charging or Discharging times) leads to periods of no
production
• No instrumentation – poor product quality
Applications
• Typically for liquid phase reactions that require long reaction times
• Used only when small amount of product is required
• Favored when a process is in developmental stage or to produce
expensive products
• Used to make a variety of products at different times
Kinetics
Rate law for Zero Order Reaction
Assumptions:
• Isothermal
• Constant volume
• Irreversible reaction
Stoichiometry
A Product
Assumed rate law:
dC A
 rA   k
dt
• integrated rate law:
dC A  kdt
CA t
  dC
C A
A  k  dt
0

(C A  C A )  k (t )
C A  C A  kt
In terms of conversion:
C A X A  kt  C A  C A (1  X A )
So,
C A0
C A  C A  C A X A  kt for t
k
C A0
CA  0 for t
k
Conductivity:

“Conductivity is a measure of the ability of solution to pass an

electrical current.”

 Conductivity is highly dependent on temperature. When we

increase the temperature of a solution its conductivity also
increases.

 Its SI unit is Siemens per meter (S/m). But on service unit we noted
it in mS.
Neutralization and conductivity:

The conductivity of a neutralized acid-base mixture is dependent on the

salt produced:

If the salt produced is a soluble salt, then the neutralized acid-base
mixture is a good conductor of electricity. It is because soluble salts
produce lots of free moving ions in water.

If the salt produced is an insoluble salt, then the neutralized acid-base
mixture will be a conductor of electricity. It is because insoluble salts
produce very few free moving ions in water.
Conclusion

Rate constant:

We found the following rate constants at different temperatures:

Temperature T k dm3
(K) mol.s
298 0.0211

313 0.0323

328 0.0321
Activation energy:

The minimum amount of energy required to start

the neutralization reaction of benzoic acid and
sodium hydroxide is 5.9616 kJ/mol.
Reference
Chemical Reaction Engineering, 3rd Edition by Octave
Levenspiel.
https://www.chemistryscl.com/reactions/carboxylic-acid-NaOH-r
eaction/index.php
University of Engineering and Technology, Lahore lab manual,
Department of Chemical Engineering.