Reaction Engg. & Thermodynamics Lab: Department of Chemical Engineering

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CH394 Reaction Engg.

&
Thermodynamics
Lab
CH394

DEPARTMENT OF CHEMICAL ENGINEERING


ALIGARH MUSLIM UNIVERSITY, ALIGARH
DEPARTMENT OF CHEMICAL ENGINEERING

Course Number and Title CH 394 Reaction Engg. & Thermodynamics Lab
Credits 02
Course Category Departmental Core (DC)
Pre-requisite(s) CH 224,CH 314
Contact Hours (L-T-P) 0-1-2
Type of Course Laboratory Course
Course Assessment Report Preparation and Submission 40 Marks
Viva-voce 20 Marks
Sessional 60 Marks
End Semester Examination:
Viva-voce and/or Practical 40 Marks
Grand Total 100 Marks

COURSE OBJECTIVES :
1. Understand the significance of reaction rate constant & the role of catalyst in chemical reactions.
2. Know the objective of multiple reactor system.
3. Feel the importance of working in a group.
4. Write technical reports on their own.
5. Learn safe working procedures and a sense of responsibility and punctuality

Syllabus:
LIST OF EXPERIMENTS :
1. Kinetic study of a non-catalytic homogeneous liquid-phase second-order reaction in a batch
reactor: Determine the reaction rate constant for the saponification of ethyl acetate with sodium
hydroxide. [Equimolar]

2. Kinetic study of a non-catalytic homogeneous liquid-phase second-order reaction in a batch


reactor: Determine the reaction rate constant for the saponification of ethyl acetate with sodium
hydroxide. [non-Equimolar]

3. Kinetic study of a non-catalytic homogeneous liquid-phase second-order reaction in a plug flow


reactor: Determine the reaction rate constant for the saponification of ethyl acetate with sodium
hydroxide.

4. Kinetic study of a non-catalytic homogeneous liquid-phase second-order reaction in a CSTR:


Determine the reaction rate constant for the saponification of ethyl acetate with sodium hydroxide.

5. Determine the partial molar volume of a binary liquid mixture (ethanol-water) at the ambient
conditions as a function of concentration.

6. Determine the Residence Time Distribution and plot the RTD curve for a Tubular vessel. Find the
MRT for a given flow rate. Use a 5N NaOH solution as tracer.
7. Determine the Residence Time Distribution and plot RTD curve in a single CSTR. Find the MRT
for a given flow rate. Use a 5N NaOH solution as tracer.

8. Determine the Residence Time Distribution and plot the RTD curve for a system of series of 3
CSTRs. Find the MRT for a given flow rate. Use a 5N NaOH solution as tracer.

9. Kinetic Study of a non-catalytic solid-fluid reaction.

REFERENCE BOOKS:
1. Levenspiel, Octave, Chemical Reaction Engineering, 3rd Edition (2005), John Wiley & Sons,
Singapore.

2. Fogler, Scott H., Elements of Chemical Reaction Engineering, 4th Edition (2008), Prentice-Hall
of India, New Delhi.
3. Smith, J.M., Chemical Engineering Kinetics, 5th Edition (2002), McGraw-Hill, New York.
FORMAT OF REPORT
CH 394: Reaction Engg. & Thermodynamics Lab
Page Size: Report should be written on 29.5 cm X 23-Size (Thesis size) bond paper (A4).
Cover Page: It should contain the following:
Title of Experiment : ………………………………………………………………….
Experiment No. : ………………………………………………………………….
Date of conducting : …….………………...………………………………………….
Date of submission : ………………………………………………………………….

Conducted By:

(1)-------------------------------------- (2) --------------------------------- (3) ----------------------------


(4)------------------------------------- (5) -------------------------------------------------------------------
Group No. -------------------------------------------- Batch No-------------------------------------------
Submitted by: -----------------------------------------------------------------------------------------------
Faculty No. ------------------------------------------ Enrolment No. ------------------------------------
Contents of Report
1. Objective: Mention the objectives of the experiment point-wise.
2. Theory: It should be brief and to the point. Detailed derivations etc.
Should be omitted. However, relevant references may be given.
3. Description of the A short but otherwise complete description of the set-up
Experimental Set-up: including all important dimensions should be mentioned
along with a neat sketch of the experimental set-up .The
sketch should be drawn with a pencil only.
4. Procedure: Describe experimental procedure points-wise.
5. Observation & Results Observations should be given in tabular form. Relevant results
should be presented in tabular/graphical forms. All the graphical
form. All the graphs should be drawn with pencil only.
6. Sample calculations Complete calculations of one run should be given. Each
partner should give sample calculations for separate runs.
7. Discussion of the Results In the light of relevant theory, observations and errors,
discuss critically the results obtained. If the result
show some trends, discuss that also.
8. Conclusions: Important conclusions drawn from the study should be
mentioned point –wise.
9. Errors: Errors in the experimentation should be identified and
their Sources discussed.
10. Suggestions: Suggestions regarding the overall improvement of the
experimental setup/measurements should be discussed briefly.
11. References: All the relevant reference from where theory, data, and
experimental procedure etc. is taken must be properly mentioned
at the end of the report.

INSTRUCTIONS:
1. Come to the laboratory class well prepared with the theory and observation
2. Make rough sketch of the experimental setup and note down on it all the need dimensions and
information.
3. All observations and sketches are to be made on bond sheets (A4) only by each student. Get
the signature of the Instructor on them at the end of the class and attach them with the final
report. Observations should be complete with all required data, and information.
(Atmospheric pressure, Dry & Wet bulb temperature to be noted)
4. Separate report is to be prepared by each student for each experiment. Each student should
make sample calculations for separate run.
5. Report of the performed experiment is to be positively submitted on the next schedule turn,
failing which the student will not permitted in the class.
6. All reports are to be compiled in one file at the end of the year, which will be required to be
submitted at the time of his viva-voce examination.
KINETIC STUDIES IN BATCH REACTOR-I
(EQUIMOLAR)

Ex. No: Date :


OBJECTIVE:
To verify the order of reaction for the reaction and hence to determine the rate constant for the
reaction between equimolar quantities of NaOH and ethyl acetate in a batch reactor.

THEORY:
The batch reactor is simple, needs little supporting equipment, and is therefore ideal for
small scale experimental studies on reaction kinetics. Industrially, it is used when relatively
small amounts of material are to be treated. In the batch reactor the reactants are initially charged
into a container, well mixed and left to react for a certain period. The resultant mixture is then
discharged. This is an unsteady-state operation where composition changes with time. However
at any instant the composition throughout the reactor is uniform.
The general mole balance equation for any reactor is given by,

𝑉
𝑑𝑁𝐴
= 𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑉 … … (1)
𝑑𝑡 0

Where
FAO= molar flow rate of component j in the stream entering the reactor.
FA = molar flow rate of component j in the stream leaving the reactor.
rA= molar rate of generation of component j by chemical reaction per unit Volume.
NA= Number of moles of component j inside the reactor.
A batch reactor has neither inflow nor outflow of reactants or products while reaction is
being carried out FAO=FA=0. The resulting general mole balance equation is,
𝑉
𝑑𝑁𝐴
= ∫ 𝑟𝐴 𝑉 … … (2)
𝑑𝑡 0

If the reaction mixture is perfectly mixed, so that there is no variation in the rate of reaction
throughout the reactor volume, we can take rA out of the integral and write the mole balance in
the form
𝑑𝑁𝐴
= 𝑟𝐴 𝑉 … … . (3)
𝑑𝑡
For a reacting mixture consisting of components A and B, the mole balance equation for
component A is,
𝑑𝑁𝐴
= 𝑟𝐴 𝑉 … … . (4)
𝑑𝑡

For equimolar quantities of component A and B, and if the reaction is second order with respect
to both components A and B, the reaction rate is given by,
−𝑟𝐴 = 𝐾𝐶𝐴2 … … … (5)
Combining the mole balance equation and the rate equation and integrating, we get
1 1 1
𝑡= [ − ] … . . (6)
𝐾 𝐶𝐴𝑂 𝐶𝐴

Expressing equation 6 in terms of initial concentration C AO and conversion XA, we get


𝑋𝐴
𝑡= ⁄𝐾𝐶 (1 − 𝑋 ) … … … (7)
𝐴𝑂 𝐴

REACTION:
The stoichiometric equation for the reaction between sodium hydroxide and ethyl acetate is
given by,
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH

PROCEDURE:
1. The solution of sodium hydroxide, hydrochloric acid, oxalic acid and ethyl acetate of
required strength are prepared.
2. Sodium hydroxide and hydrochloric acid solutions are standardized.
3. 1000 ml of sodium hydroxide is taken in the batch reactor. 1000 ml of ethyl acetate are
taken in a beaker.
4. Ethyl acetate solution is added to NaOH.
5. At the end of 1, 2, 5, 10, 15, 20, 30, 45 and 60 minutes, 20 ml of reaction mixture is
pipetted into the conical flask which contain 20 ml of HCl and hence the saponification
reaction is arrested.
6. The flasks are shaken and titrated against NaOH for the unconsumed HCl.
STANDARDISATION OF NaOH, NaOH vs. Oxalic acid (CH3COOCH2CH3)
S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2
3
Take NaOH in the burette.
Pipette out 10 ml (V1) Oxalic acid into 100 ml conical flask.
Volume of Oxalic acid V1 =
Normality of Oxalic acid N1 =
Volume of NaOH V2 =
Normality of NaOH N2 = (V1 ×N1)/V2 =

STANDARDISATION OF HCl, HCl vs. NaOH


S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2

Volume of NaOH V1 =
Normality of NaOH N1 =
Volume of HCl V2 =
Normality of HCl N2 = (V1× N1)/V2 =

TABULATION:
Vol. of HCl
Titre Vol. of HCl
Time used for
S. Value not used for CA XA XA / (1-XA)
‘t’ arresting ‘V6’
No. ‘V5’ arresting ‘V4’
V6 = Vo-V4
min ml ml ml mol/lit -- --

7
MODEL CALCULATION:
Normality of Sodium Hydroxide, N2 =
Normality of Hydrochloric Acid, N3=
Hydrochloric acid added to arrest the reaction, Vo =

Volume of Hydrochloric Acid not used for arresting , V4 = V5 x N2/ N3 =

where‘V5’ is the Titre value (i.e. volume of Sodium Hydroxide of Normality N2).

Volume of Hydrochloric acid consumed in arresting NaOH = V6 = Vo-V4 = =

Moles of HCl used consumed in arresting NaOH = Moles of Unreacted NaOH


= N3 x (Vo-V4) =N3 xV6 = =

Initial conc. of NaOH, CAo = Initial moles of NaOH


Vol. of Total Reaction Mixture

= N2 x Volume of NaOH (1000 ml)


Volume of Total Reaction Mixture (2000 ml)

Concentration of NaOH in the reaction mixture after time t,

CA = Moles of unreacted NaOH = N3 x V6


20 ml 20 ml

CA= =

CA
Conversion, XA = 1 - CA0 =

GRAPH:
XA/ (1-XA) vs t. The slope of the line is equal to KC AO from which the value of the
reaction rate constant (K) can be determined.
KCAo =
K=

RESULT:
The reaction between equimolar quantities of NaOH and ethyl acetate is carried out and
the results are given as follows.
1. The order of the reaction, n =
2. The rate constant (K) =
DISCUSSION OF RESULTS:
CONCLUSIONS:
SUGGESTIONS:
REFERENCES:
KINETIC STUDIES IN BATCH REACTOR-II
(NON-EQUIMOLAR)

Ex. No: Date :


OBJECTIVE:
To verify the order of reaction for the reaction and hence to determine the rate constant
for the reaction between non- equimolar quantities of NaOH and ethyl acetate in a batch reactor.

THEORY:
For a reacting mixture consisting of components A and B, the general mole balance
equation for component A in a batch reactor reduces to
dNA
= r A V … … . (1)
dt

If the reaction is first order with respect to both components A and B, the reaction rate is given
by,
−rA = KCA CB … … (2)
Combining the mole balance equation and the rate equation and integrating, we get,
1
t= [C − CAO ]ln[M − XA /M(1 − XA )] … . . (3)
K B0
C
Where M = CBO
AO

REACTION:
The stoichiometric equation for the reaction between sodium hydroxide and ethyl acetate is
given by,
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH

PROCEDURE:
1. The solution of sodium hydroxide, hydrochloric acid, oxalic acid and ethyl acetate of
required strength are prepared.
2. Sodium hydroxide and hydrochloric acid solutions are standardized.
3. 1000 ml of sodium hydroxide is taken in the batch reactor. 500 ml of ethyl acetate are
taken in a beaker.
4. Ethyl acetate solution is added to NaOH.
5. At the end of 1, 2, 5, 10, 15, 20, 30, 45 and 60 minutes, 20 ml of reaction mixture is
pipetted into the conical flask which contain 20 ml of HCl and hence the saponification
reaction is arrested.
6. The flasks are shaken and titrated against NaOH for the unconsumed HCl.

STANDARDISATION OF NaOH, NaOH vs. Oxalic acid (CH3COOCH2CH3)


S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2

Take NaOH in the burette.


Pipette out 10 ml (V1) Oxalic acid into 100 ml conical flask.
Volume of Oxalic acid V1 =
Normality of Oxalic acid N1 =
Volume of NaOH V2 =
Normality of NaOH N2 = (V1 ×N1)/V2 =

STANDARDISATION OF HCl, HCl vs. NaOH


S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2

Volume of NaOH V1 =
Normality of NaOH N1 =
Volume of HCl V2 =
Normality of HCl N2 = (V1× N1)/V2 =

TABULATION:
Titre Vol. of HCl Vol. of HCl
Time ln (M-XA)
Value not used for used for CA XA
S. ‘t’ M(1-XA)
No. ‘V5’ arresting ‘V4’ arresting ‘V6’

min ml ml ml mol/lit -- --
1
2
3
MODEL CALCULATION:
Normality of Sodium Hydroxide = N2 =
Normality of Hydrochloric Acid = N3 =
Normality of Ethyl Acetate (for which the EA solution is prepared) = N4 =
Hydrochloric Acid added to arrest the reaction= Vo =
Volume of Hydrochloric Acid not used for arresting = V4 = V5 x N2 =
N3
where‘V5’ is the Titre value (i.e. volume of Sodium Hydroxide of Normality N2).
Volume of Hydrochloric acid consumed in arresting NaOH = V6 = Vo-V4 = =

Moles of HCl used consumed in arresting NaOH = Moles of Unreacted NaOH


= N3 x (Vo-V4) =N3 xV6 ==
Initial conc. of NaOH, CAo = Initial moles of NaOH
Volume of Total Reaction Mixture
= N2 x Volume of NaOH in the reaction mixture(1000 ml)
Volume of Total Reaction Mixture (1500 ml)
Concentration of NaOH in the reaction mixture after time‘t’ ,
CA = Moles of unreacted NaOH
Volume Reaction mixture
CA = N3 x V6 / 20 ml =

Initial concentration of Ethyl Acetate, CBo =Initial moles of Ethyl Acetate


Volume of Total Reaction Mixture
= N4 x Volume of Ethyl Acetate(500 ml)
Vol. of Total Reaction Mixture(1500 ml)
=
M = CBo / CAo =
CA
Conversion, XA = 1 - CA0 =

GRAPH:
Make a plot of ln [M-XA/M (1-XA)] Vs t. From the graph, slope = K(CBo-CAo). The value of the
Reaction rate constant (K) was calculated from the value of slope.
From the graph,
K=

RESULT:
The reaction between equimolar quantities of NaOH and ethyl acetate is carried out and
the results are given as follows.
1. The order of the reaction =
2. The rate constant (K) =

DISCUSSION OF RESULTS:
CONCLUSIONS:
SUGGESTIONS:
REFERENCES:
TITLE: KINETIC STUDIES IN A PLUG FLOW REACTOR

Ex. No: Date :


OBJECTIVE :
To determine the rate constant for the saponification of ethyl acetate with sodium hydroxide in a
plug flow reactor at ambient temperature.

THEORY:
In addition to the batch and back mix reactors another type of reactor commonly used in
the industry is tubular reactor. It consists of a cylindrical pipe and is normally operated at steady
state. If the flow is highly turbulent and the flow field can be modeled by that of a plug flow i.e.,
there is no radial variation in concentration, then the reactor is referred to as a plug flow reactor.

In plug flow reactor ,the concentration of reactant decreases progressively through the system and
in mixed flow the concentration drops immediately to a low value .Because of this fact , a plug
flow reactor is more efficient than the mixed flow reactors for reaction whose rates increases with
reactant conditions.

The reactants are continuously consumed as they down the length of the reactor i.e., the
concentration varies continuously in the axial direction through the reactor. Consequently, the
reaction rate, which is a function of concentration, will also vary axially.
The general mole balance equation for any reactor is given by,

𝑉
𝑑𝑁𝐴
= 𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑉 … … (1)
𝑑𝑡 0

Where,
FAO= molar flow rate of component j in the stream entering the reactor.
FA = molar flow rate of component j in the stream leaving the reactor.
rA= molar rate of generation of component j by chemical reaction per unit Volume.
NA= Number of moles of component j inside the reactor.
To develop the plug flow reactor design equation we shall divide conceptually the reactor
into a number of sub volumes so that within each sub volume V, the reaction rate may be
considered spatially uniform. Consider a sub volume located at a distance y from the entrance of
the reactor and also consider the reactant mixture consists of component A and B only. Let F A(y)
represent the molar flow rate of species A into the sub volume ∆V at y and F A (y+∆y) the molar
rate of flow of species A out of the volume at the location (y+∆y).

For a tubular operated at steady state,


𝑑𝑁𝐴
= 0 … … (2)
𝑑𝑡
In spatially uniform volume,
𝑉
𝑟𝐴 𝑉 = ∫ 𝑟𝐴 𝑉 … … … . (3)
0

Hence, equ (1) becomes


𝐹𝐴 (𝑦 + ∆𝑦) − 𝐹𝐴 (𝑦) + 𝑟𝐴 ∆𝑉 = 0 … … … … (4)

In this expression r A is an indirect function of y i.e., r A is a function of reactant


concentration, which is a function of the position y down the reactor. The volume V is the product
of the cross sectional area A, and the reactor length ∆y i.e.,
∆𝑉 = 𝐴∆𝑦 … … … … … … (5)

Substitute in equ (4) for ∆V, divide by ∆y and then take the limits as y approaches to zero, to
obtain
𝑑𝐹𝐴⁄
𝑑𝑉 = 𝑟𝐴 … … … … … . (6)
Since, the volumetric flow rate, VO is constant
𝑑𝐹𝐴⁄ 𝑑𝐶𝐴⁄
𝑑𝑉 = 𝑑 (𝑉0 𝐶𝐴 )⁄𝑑𝑉 = 𝑉0 𝑑𝑉 = 𝑟𝐴 … … … (7)
For non- equimolar quantities of components A and B, the reaction rate is given by
-rA = kCACB
The rate expression in terms of conversion of A and rate constant “K” is given by
1
𝑌 = 𝐾𝜏 = 𝐶 𝑙𝑛{(𝑀 − 𝑋𝐴 )/(𝑀(1 − 𝑋𝐴 ))}
𝐴0(𝑀−1)
The conversion of component A is (CAO-CA)/CAO

REACTION:
The stoichiometric equation for the reaction between sodium hydroxide and ethyl acetate is
given by,
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH

DESCRIPTION OF EXPERIMENTAL SET UP :


The set up consists of two feed tanks through which two reactants are fed to the reactor .Rotameters
are provided to measure the individual flow of chemicals.The flow rate can be adjusted by
operating the needle valve provided on respective Rotameter .The compressed air is used for
circulation of feed. Pressure guage,pressure regulator,&safety valve are fitted in the air compressed
line .The concentration of feed and the product coming out from the reactor are analyzed by
chemical titrations and check the effect and performance of the reactor .

PROCEDURE:
1. Initially the tanks are filled with 0.1N NaOH and Ethyl acetate solution.
2. The titration for standardizing of NaOH with oxalic acid and standardizing HCl with NaOH
using phenolphthalein indicator is done.
3. The flow rate for NaOH and ethyl acetate in the ratio of 1:1 is adjusted with rotameter.
4. After attained steady state, 10 ml of reaction mixture from the exit of the PFR is pipetted
into the conical flask, which contain 20 ml of std N/10 HCl, and hence the saponification
reaction is arrested. The sample (30 ml ) is titrated against NaOH to obtain the conversion.
5. The volume of NaOH consumed is taken and tabulated for various flow rates.
6. The procedure is repeated for various flow rates.
7. For calculating the conversion at equilibrium condtion, collect the sample 10 ml ,in an
empty conical flask and allow the reaction to proceed for completion for two hours .After
two hours titrate the solution with N/10 HCL using phenolphthalein as indicator. Note the
volume of N/10 HCL used .
8. Repeat all the steps for different flow rates of feed.
STANDARDISATION OF NaOH, NaOH vs. Oxalic acid (CH3COOCH2CH3)
S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2
3
Take NaOH in the burette.
Pipette out 10 ml (V1) Oxalic acid into 100 ml conical flask.
Volume of Oxalic acid V1 =
Normality of Oxalic acid N1 =
Volume of NaOH V2 =
Normality of NaOH N2 = (V1 ×N1)/V2 =

STANDARDISATION OF HCl, HCl vs. NaOH


S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2

Volume of NaOH V2 =
Normality of NaOH N2 =
Volume of HCl V3 =
Normality of HCl N3 = (V2× N2)/V3 =

TABULATION:
Flow Flow Vol. of
rate of rate of Titre HCl
CA k
Sl. NaOH EA M Value not used 
mol/lit XA Y (l/mol.min)
No. (lpm) (lpm) ‘V5’ for min
(experimental)
(vAo) (vBo) ml arresting
‘V6’ml
1
2
3

OBSERVATIONS AND CALCULATION:


Normality of oxalic acid N1 =
Normality of NaOH N2 =
Normality of HCl N3 =
Normality of Ethyl Acetate (for which the EA solution is prepared) = N4 =
Volume of the reactor (VR) =
(Use the length and diameter of the PFR)
 = Volume of the reactor (V)/ Total volumetric flow rate (vo)
CAo = Initial conc. of NaOH = FAo / vo = Moles/time of NaOH
Total volumetric flow rate
= N2 x volumetric flow rate of NaOH (vAo)
Y Total volumetric flow rate (vo)
=
CA = concentration of unreacted NaOH at any point along the reactor
= Moles of unreacted NaOH = N2 x Volume of unreacted NaOH
Volume of reaction mixture Volume of reaction mixture
=
Moles of unreacted NaOH = Moles of HCl used for arresting the reaction
Volume of HCl added initially = V4 =.
Volume of HCl not used for arresting = V6 = V5 x N2
N3
Where ‘V5’ is the Titre value.
Therefore volume of HCl used for arresting = V4 – V6
Moles of HCl used for arresting = N3 x (V4 – V6) = Moles of unreacted NaOH

Then, calculate CA = Moles of NaOH unreacted


Volume of Reaction mixture (20 ml)

Initial concentration of Ethyl Acetate, CBo = N4 x volumetric flow rate of NaOH (vBo)
Total volumetric flow rate (vo)
=
M = CBo / CAo =
Conversion, XA = CAo - CA
CAo
1
𝑌 = 𝐾 = 𝐶 (𝑀−1) 𝑙𝑛{(𝑀 − 𝑋𝐴 )/(𝑀(1 − 𝑋𝐴 ))}
𝐴0

K=Y/ =
=V/Vo =
GRAPH:
Y vs. τ slope gives the value of k

RESULT:
The rate constant for the saponification of ethyl acetate with sodium hydroxide in a plug
flow reactor at ambient temperature (K) is
Kgraph =
Kexperimental =

DISSCUSSION OF RESULTS:
CONCLUSIONS:
ERRORS:
PRECAUTIONS AND SOURCES OF ERRORS :
SUGGESTIONS (If any ):
REFRENCES:
TITLE : KINETIC STUDIES IN A MIXED FLOW REACTOR

Ex. No: Date :


OBJECTIVE : To study of a non- catalytic homogeneous second order liquid phase reaction in
a C.S.T.R under ambient conditions.

THEORY:
The mixed flow reactor, also known as continuous stirred tank reactor (CSTR), is a
reactor in which the contents are well mixed and uniform throughout. Thus the exit stream from
this reactor has the same composition as the fluid within the reactor.
The general mole balance equation for any reactor is given by,
𝑉
𝑑𝑁𝐴
= 𝐹𝐴0 − 𝐹𝐴 + ∫ 𝑟𝐴 𝑉 … … (1)
𝑑𝑡 0

where
FAO= molar flow rate of component j in the stream entering the reactor.
FA = molar flow rate of component j in the stream leaving the reactor.
rA= molar rate of generation of component j by chemical reaction per unit Volume.
NA= Number of moles of component j inside the reactor.

When eqn (1) applied to a CSTR operated at steady- state conditions i.e., conditions within the
reactor do not change with time,
𝑑𝑁𝐴
= 0 … … (2)
𝑑𝑡
If the reaction mixture is perfectly mixed, so that there is no variation in rate of reaction
throughout the reactor volume, the generation term in mole balance equation becomes,
𝑉
𝑟𝐴 𝑉 = ∫ 𝑟𝐴 𝑉 … … … . (3)
0

Where V is the total volume of the reactor


Substituting equ.(2) and equ. (3) inequ (1), the general mole balance equation takes the familiar
form known as the design equation for CSTR
𝐹𝐴𝑜 − 𝐹𝐴
𝑉= … … … (4 )
−𝑟𝐴
For a reacting system consisting of reactants A and B only equ (4) based on component A
becomes
𝐹𝐴𝑜 − 𝐹𝐴
𝑉= … … … (5 )
−𝑟𝐴
For non- equimolar quantities of components A and B, the reaction rate is given by
-rA = kCACB
The rate expression in terms of conversion of A and rate constant “k” is given by
𝑋𝐴
𝐾 =
𝜏 𝐶𝐴0 (1−𝑋𝐴 )(𝑀−𝑋𝐴 )

The conversion of component A is 𝑋𝐴 = (CAO-CA)/CAO

EXPERIMENTAL SET UP :
The set up consist of two feed tanks through which two reactants are feed to the reactor. Rota
meters are provided to measure the individual flow of chemicals. The compressed air is used for
circulation of feed. The CSTR is fitted with stirrer for proper mixing from the top outlet of it
samples are collected for analysis. Pressure regulator & safety valve are fitted in the compressed
air line .Products coming out from the reactor are analyzed by chemical reactions.

REACTION:
The Stoichiometric equation for the reaction between sodium hydroxide and ethyl acetate is
given by,
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH

PROCEDURE:
1. 20L of N/10 NaOH solution is to be prepared by dissolving 80 gm of NaOH in 20 L of
water .
2. 20L of N/10 ethyl acetate solution is to be prepared by dissolving 176 ml of ethyl acetate
in 20 L of water .
3. Tanks are filled with these solutions respectively.
4. Equimolar feed rates of both the solution are to be passed in to the reactor and mixer of
the CSTR is started simultaneously. Constant stirring throughout the reactor is to be
ensured.
5. After attained steady state, 10 ml of reaction mixture from the exit of the MFR is pipetted
into the conical flask, which contain 20 ml HCl, and hence the saponification reaction is
arrested.
6. The sample is titrated against NaOH to obtain the conversion using phenolphthalein as
indicator (add NaOH from burrette).
7. The volume of NaOH consumed is taken and tabulated for various flow rates.
8. The procedure is repeated for various flow rates.

STANDARDISATION OF NaOH, NaOH vs. Oxalic acid (CH3COOCH2CH3)


S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2
3
Take NaOH in the burette.
Pipette out 10 ml (V1) Oxalic acid into 100 ml conical flask.
Volume of Oxalic acid V1 =
Normality of Oxalic acid N1 =
Volume of NaOH V2 =
Normality of NaOH N2 = (V1 ×N1)/V2 =

STANDARDISATION OF HCl, HCl vs. NaOH


S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2
3

Volume of NaOH V1 =
Normality of NaOH N1 =
Volume of HCl V2 =
Normality of HCl N2 = (V1× N1)/V2 =
TABULATION :

Flow Flow Total Flow Amount CA0 CB0 M CA CB XA Y  K


rate of rate of Rate VA of NaOH (min) (lit/
NaOH EA
Sl. (VAO+VBO) consumed mol.
(lpm) (lpm)
No VAo VBo min)
(ml)

3
OBSERVATION AND CALCULATIONS:
Diameter of the reactor, D =
Length of the reactor, L =
Total volume of the reactor, Vf = (π D2 L /4) =
Normality of NaOH, N1 =
Normality of HCl, N2 =
Volume of HCl used for arresting the reaction, VO =

MODEL CALCULATION:
Volume of reactor V =
Volumetric flow rate of the reactants, v =
Residence time, τ= V/v =
Volume of the contents in the conical flask V1 =
Volume of reaction mixture collected, V2 = V1-VO ml
=
𝑆𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑁𝑎𝑂𝐻 ×𝐹𝑙𝑜𝑤 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑁𝑎𝑂𝐻
Conc. Of NaOH in the feed stream, CAO = 𝑇𝑜𝑡𝑎𝑙 𝐹𝑙𝑜𝑤 𝑅𝑎𝑡𝑒

=
=
𝑆𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝐸𝐴 ×𝐹𝑙𝑜𝑤 𝑅𝑎𝑡𝑒 𝑜𝑓 𝐸𝐴
Conc. Of EA in the feed stream, CAO = 𝑇𝑜𝑡𝑎𝑙 𝐹𝑙𝑜𝑤 𝑅𝑎𝑡𝑒

=
=
(𝑁𝐻𝐶𝑙 ×𝑉𝐻𝐶𝑙 )− (𝑁𝑁𝑎𝑂𝐻 ×𝑉𝑁𝑎𝑂𝐻 )
Conc. Of NaOH in the reaction mixture collected, CA = 𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

=
=
Conc. Of EA in the reaction mixture collected, CB = CBO-CAO+CA
=
Conversion (Experimental) XA, Experimental = (CAO-CA)/CAO

=
𝑋𝐴
𝑌= = 𝜏𝐾
𝐶𝐴0 (1 − 𝑋𝐴 )(𝑀 − 𝑋𝐴 )
GRAPH:
𝑋𝐴
𝑌 (= ) vs τ (slope gives the value of K)
𝐶𝐴0 (1−𝑋𝐴 )(𝑀−𝑋𝐴 )

RESULT:
The rate constant for the saponification of ethyl acetate with sodium hydroxide in a plug
flow reactor at ambient temperature (K) is
Kgraph =
Kexperimental =

DISSCUSSION OF RESULTS:
CONCLUSIONS:
ERRORS:
PRECAUTIONS AND SOURCES OF ERRORS :
SUGGESTIONS (If any ):
REFRENCES:
TITLE : THERMODYNAMICS OF A LIQUID MIXTURE

Ex. No: Date :


OBJECTIVE:
To determine the partial molal volume of a component in a binary mixture at ambient
condition (given temperature and pressure).
.
CHEMICALS/ APPARATUS REQUIRED:
1. Two components(say, ethanol and distilled water)
2. Two specific gravity bottles(10/25 ml)
3. Graduated pipettes(10/25 ml)
4. Sufficient number of closed test tubes/ beakers(50/100 ml)
5. Digital balance.

THEORY:
Extensive properties of solutions (e.g. volume, energy, free energy etc.) are not truly additive when
pure components are mixed. Thus, when two liquids are mixed a decrease or an increase in the
volume may occur.The volume of a solution is dependent on its temperature (T), pressure (P) and the
amount of each component (n1, n2, ...) used to form the mixture; V (T , P, n1 , n2 ,...) . For a binary

system held at constant temperature and pressure, the differential volume change upon an
incremental addition or removal of either component is determined by:

 ∂V   ∂V 
=dV   dn1 +   dn2
 ∂n1 T , P ,n2  ∂n1 T , P ,n1
Where partial molal volume of ith component is given by:

 ∂V 
Vi =  
 ∂n1 T , P ,n j≠i
It must be emphasized, the partial molal volume of a substance in a solution is not equal to the Molal
Volume of the substance when pure. Moreover, it is the partial molal volume that is additive and not
the molal volume. This additivity rule is applicable to all other extensive properties of the mixtures..
For a two component system of A and B, mean molal volume is
 V0 
V = V0 V ( nA + nB )
 or=
 nA + nB 
 ∂V   ∂V 
VA = 0  =V + ( nA + nB )  
 ∂nA T , P ,nB  ∂nA T , P ,nB

 dV dxB   dV  (−nB )
=V + ( nA + nB )  .  =V + ( nA + nB )  
 dxB T , P ,nB ( nA + nB )
2
 dxB dnA T , P ,nB

 dV   dV 
= V − xB   or V= VA + xB  
 dxB T , P ,nB  dxB T , P ,nB
Thus, a plot of mean molal volume, V against the mole fraction xB is required to be drawn. The
intercept of the tangent of the obtained curve at some xB when extrapolated to xB=0 (or xA=1)
yields the molal volume of A, i.e. VA. Similarly, the intercept of the same tangent line when
extrapolated to xB=1 (xA=0) equals to molal volume of B, VB.

PROCEDURE:
1. Make sure that all the glassware and SG bottle are properly washed, clean and dry.
2. Record the Ambient Temperature and Pressure.
3. Determine the density of the pure solvents using SG bottle in duplicate.
4. Prepare 8-10 samples of binary mixture of the given solvents in the range of 10-90 % by
volume (Precision of the results will depend on how accurately these mixtures are
prepared).
5. Convert these volumes fractions (Step 4) into mole fractions with the known density(Step
3) and molecular weight of the components.
6. Determine the density of the mixtures prepared at Step4 using SG bottle in
duplicate/triplicate.
7. For accuracy and reproducibility of the results, Step 4-6 may be repeated.
8. From the data and calculations of Step 6, determine the molal volume of the mixture.
9. Draw a graph between molal volume and molal fraction of the mixture.
10. Calculate the partial molal volume of the component from the graph at different
composition.
11. Comment on your result (Thermodynamics) and prepare your report in the Standard
Format.
Observation Table
S.No Vol. of Vol. of Weight of Weight of Weight of
Etahnol Water mixture (1) mixture (2) mixture
(mean)
1 Pure
water
2 20 %
ethanol
40 %
3
ethanol
50 %
4
ethanol
60 %
5
ethanol
80 %
6
ethanol
Pure
7
ethanol

Calculation Table:
S.No mi msi V0 nA nB xA xB

1 Pure
water
2 20 %
ethanol
40 %
3
ethanol
50 %
4
ethanol
60 %
5
ethanol
80 %
6
ethanol
Pure
7
ethanol
Model Calculation:
S.No Vm dVm/dxB dVm/dxA VA VB
(ml) (ml) (ml) (ml) (ml)

1 Pure water

2 20 %
ethanol
40 %
3
ethanol
50 %
4
ethanol
60 %
5
ethanol
80 %
6
ethanol
Pure
7
ethanol

RESULT:
1. The partial molal volume for pure water is:
2. The partial molal volume for pure ethanol is:
3. The partial molal volume for water and ethanol at mole fraction xB is:

DISSCUSSION OF RESULTS:
CONCLUSIONS:
ERRORS:
PRECAUTIONS AND SOURCES OF ERRORS :
SUGGESTIONS (If any ):
REFRENCES:
TITLE : RTD STUDIES IN PLUG FLOW REACTOR

Ex. No: Date :


OBJECTIVE:
(i) To Plot the E(t) curve and find the mean residence time for tubular vessel.
(ii) To characterize the vessel using different models for non ideal reactors.

THEORY:
In (ideal tubular reactor) Plug flow reactors, there is no mixing in the axial direction, the
residence time is the same for all elements of fluid. In non-ideal tubular reactors, due to stagnation,
channeling, recycling of fluid etc. the residence time will not be the same for all elements of fluid.
Therefore we have a residence time distribution (RTD). This is studied by introducing a tracer at
t=0 into the tubular reactor as a pulse input and then measuring the tracer concentration, C, in the
effluent stream as a function of time. The effluent concentration- time curve is referred to as the C
curve. From the area under the C curve E (t) is calculated and E curve is drawn.

PROCEDURE:
1. Tube dimensions (do ,L) to be noted .
2. 25 ml. of NaOH solution of strength 5 to 10 N is prepared .
3. 2 ltr.of 0.1 to 0.2 N HCL solution is to prepared.
4. Around 20 test tubes are taken ,which needs to be washed and cleaned with distill water .
5. KMnO4 solution is to be prepared for visual inspection of tracer
6. Water is allowed to flow into the tubular reactor at a constant flow rate ( ensuring the flow
is laminar)
7. Small amount of KMNO4 (in a small time interval) solution is to be injected and the time
of its appearance and disappearance to be noted.
8. NaOH (5ml) is added as a pulse input and simultaneously the stopwatch is started.
9. Samples are collected at the exit stream at regular time intervals, assuming the same
appearance and disappearance timings will be observed as in case of KMNO 4
10. The samples are titrated against HCl to determine the normality of NaOH present in the
exit stream using phenolphthalein as an indicator.
STANDARDISATION OF NaOH, NaOH vs. Oxalic acid (CH3COOCH2CH3)
S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2
3
Take NaOH in the burette.
Pipette out 10 ml (V1) Oxalic acid into 100 ml conical flask.
Volume of Oxalic acid V1 =
Normality of Oxalic acid N1 =
Volume of NaOH V2 =
Normality of NaOH N2 = (V1 ×N1)/V2 =

STANDARDISATION OF HCl, HCl vs. NaOH


S. No Burette reading (ml) Volume of NaOH Concordant value (ml)
(ml)
Initial Final
1
2

Volume of NaOH V1 =
Normality of NaOH N1 =
Volume of HCl V2 =
Normality of HCl N2 = (V1× N1)/V2 =

TABULATION:
S.No Time Vol. of HCl Normality of E(t) t x E (t) (t-tm)2 x E (t)
(t) consumed (ml) NaOH

7
Normality of NaOH : VNaOH× NNaOH = VHcl× NHcl
20×NNaOH=
NNaOH =

Normality of NaOH
E (t) =
Area under the N vs t curve (C Curve)

=
t

 tE (t )dt
0
Mean Residence Time = tm = t

 E (t )dt
0

 E (t )dt
0
=1

t
tm =  tE (t )dt
0

Area under the curve of t x E (t) Vs t gives, tm =



Variance,    t  t m 2 E t dt
2

Area under the curve of (t -tm)2 E (t) Vs t gives 2 =

NON- IDEAL REACTOR MODELS:


Description model: used for turbulent flows in pipes, laminar flow in long tubes, flow in packed
beds, long channels etc.
Analogous to Fick’s law of molecular diffusion the mixing by all means is given by the following
dispersion model:
𝜕𝐶 𝜕2𝐶
=D ; D is longitudinal or axial dispersion and quantifies the degree of back mixing in a
𝜕𝑡 𝜕 𝑥2

flow. A convenient form of the above equation is obtained by introducing the following
𝜕𝐶 𝐷 𝜕2𝐶 𝜕𝐶
dimensionless variables: z = (ut +x)/L;  = t/𝑡̅ = tu/L; = -
𝜕 𝑢𝐿 𝜕 𝑍 2 𝜕𝑍
𝐷
Where, = 𝑢𝐿 is vessel dispersion number. We have two sub-class for this model depending on the

magnitude of dispersion.
For small Dispersion (De/UL < 0.01)
1 (1−2 ) 𝐿
C (t) = exp (− 4𝐷/𝑢𝐿 ) ; t =𝑢 =𝑡𝐸
√4 𝐷/𝑢𝐿

and variance is given by:


𝜎2 𝐷
𝜎2 = 𝑡̅ 2 = 2𝑢𝐿.

There are many other ways to find the parameter D/uL. In this model the variance is directly
proportional to the vessel length and possesses additive property.

2 D
2
2
t m uL
D

uL
For large Dispersion (De/UL > 0.01)
In this case the C (t) or E (t) curves are not symmetrical and are dependent on the boundary
conditions. Only following two types of situations are mostly encountered.
For closed vessel:
Analytical expression for E (t) is not available.

2 D D
2
 
uL

𝐿
𝑡̅= 𝑢 =𝑡̅𝐸 , and 2  2  1  e D 
t m2 uL  uL   
 
D

uL
For open vessel:
This represents a commonly used experimental device e.g. a long section of pipe.
𝑢 (𝐿−𝑢𝑡)2
E (t) = exp( );
√4 𝐷𝑡 4𝐷𝑡

2
2
D D
𝐿
𝑡̅ =𝑢; 𝑡𝐸̅ = 𝑡̅ (1 + 2 𝑢𝐿), and
𝐷
 2  8 
tm2 uL  uL 
D

uL
Tanks in series Model:
It can also be used whenever the dispersion is not too large and can invariably replace the above
dispersion model.
1 𝑡 𝑁−1 𝑁𝑁 −𝑡𝑁⁄ 𝑉 𝜎2 1
E (t) = 𝑡̅ (𝑡̅ ) е 𝑡̅ ;𝑡̅ = =N𝑡𝑖̅ ; 𝜎2 = =
(𝑁−1)! 𝑣 𝑡̅ 2 𝑁

Number of tanks N is the characteristics parameter for tanks in series model. Here also the variance
is additive and is directly proportional to the number of tanks.

Convection Model:
When a tube is long enough and the fluid is not viscous, then the dispersion or tanks in series
model can be used to portray the vessel. While if the viscosity is large the parabolic velocity profile
in laminar flow will be the main cause for spread and in these extreme situation pure convection
model has to be applied. This is the deterministic model unlike the above two which are stochastic
models. The spread (=variance1/2) is directly proportional to the length of the vessel.
For the usual methods of introduction and measurement of tracer we have:
𝑡 ̅ 𝑡 ̅ 𝑉 𝐿
E (t) = 2𝑡 3 for t ≥ 2 ; 𝑡̅= 𝑣 =𝑢
𝑡̅
E (t) = 0 for t <2

To choose the appropriate model from the above three may refer to the chart 15.2 shown in O.
Levenspiel, first given by Ananthakrishnan et al. this chart is applied only for laminar flow.

GRAPHS:
1. Normality of NaOH vs. Time
2. E(t)Vs Time
3. t E(t) vs. Time
4. (t-tm)2 E(t) vs. Time

RESULTS:
1. The RTD studies in a plug flow reactor have been performed and the C and E curves are
drawn.
2. Dispersion Number of the vessel (=1/Pe=De/UL) is
3. Actual Mean residence time, tm =

DISSCUSSION OF RESULTS:
CONCLUSIONS:
ERRORS:
PRECAUTIONS AND SOURCES OF ERRORS :
SUGGESTIONS (If any ):
REFRENCES:
RTD STUDIES IN MIXED FLOW REACTOR

Ex. No: Date :


OBJECTIVE:
To study the flow behavior of a mixed flow reactor.

THEORY:
The feed introduced into a CSTR at any given time become completely mixed with the
materials already in the reactor. In other words, some of the atoms entering the CSTR leave from
it almost immediately, because material is being continuously withdrawn from the reactor, other
atoms will remain in the reactor because all the material is not removed from the reactor at one
time. Many of atoms, of course, leave the reactor after spending a period of time somewhere in
the vicinity of mean residence time. In any reactor, the distribution of residence times can
significantly affect its performance. The residence time distribution (RTD) of a reactor is
characteristics of the mixing that occurs in the reactor.

PROCEDURE:
1. Water is allowed to flow into the mixed flow reactor at a constant flow rate.
2. NaOH is added as a pulse input and simultaneously the stopwatch is started.
3. Samples are collected at the exit stream at regular time intervals
4. The samples are titrated against HCl to determine the normality of NaOH present in the
exit stream

STANDARDISATION OF NaOH, (NaOH vs. Oxalic acid)


S. No Volume of NaOH (ml) Burette reading (ml) Concordant value
(ml)
Initial Final
1
2

Volume of Oxalic acid V1 =


Normality of Oxalic acid N1 =
Volume of NaOH V2 =
Normality of NaOH N2 = (V1 ×N1)/V2=
STANDARDISATION OF HCl, (HCl vs. NaOH)
S. No Volume of NaOH Burette reading (ml) Concordant value
(ml) (ml)
Initial Final
1
2

Volume of NaOH V1 =
Normality of NaOH N1 =
Volume of HCl V2 =
Normality of HCl N2 = (V1× N1)/V2 =

TABULATION:
S.No Time (t) Vol. of HCl Normality of E (t) t E(t)
consumed (ml) NaOH ×10-3
×10-3
1

Normality of NaOH :VNaOH× NNaOH= VHcl× NHcl


20×NNaOH=
NNaOH=

Area under the curve of N vs. t curve(C Curve) =


Normality of NaOH
E (t) =
Area under the N vs t curve (C Curve)

E(t) =
t

 tE (t )dt
0
Mean Residence Time = tm = t

 E (t )dt
0

 E (t )dt
0
=1

t
tm =  tE (t )dt
0

Area under the curve of t x E (t) vs. t gives, tm =


 t / tm
Theoretically, for an ideal CSTR: tm E (t )  e
GRAPH:
1. Normality of NaOH vs. Time
2. E(t) vs. Time
3. t E(t) vs. Time
4. (t-tm)2 E(t) vs. Time

SAMPLE CALCULATIONS:

RESULT:
The RTD studies in a mixed flow reactor have been performed and the C and E curves are
drawn. From the curve the given reactor is a perfect MFR.
Mean Residence Time (t m) =

DISCUSSION OF RESULTS:
CONCLUSIONS:
SUGGESTIONS:
REFERENCES:
RTD STUDIES IN A SERIES OF CSTRs

Ex. No: Date :


OBJECTIVE:
1. To collect data and draw C and E curves by introducing a pulse input to a CSTR in series.
2. To determine mean residence time and calculate ‘N’ using Tank-in-series model

THEORY:
The feed introduced into a CSTR at any given time becomes completely mixed with
material already in the reactor. In other words, some of the atoms entering the CSTR leave it
almost immediately, because material being continuously withdrawn from the reactor, other
atoms remains in the reactor almost forever because all the material is never removed from the
reactor at one time. Many of the atoms, of course, leave the reactor after spending a period of
time somewhere in the vicinity of the mean residence time. In any reactor, the distribution of
residence times can significantly affect its performance.

PROCEDURE:
1. Water is allowed to flow into the mixed flow reactors which are connected in series at a
constant flow rate.
2. The flow rate of water is adjusted as desired and the stirrer is switched on.
3. 50 ml of NaOH is sucked into a hydro syringe and is fed into first MFR as a pulse input
and the stopwatch is immediately started.
4. 20 ml of samples are collected at the exit stream of each CSTR at regular time intervals.
5. This samples are titrated against HCl

STANDARDISATION OF NaOH (NaOH vs. Oxalic acid)


S. No Volume of NaOH (ml) Burettereading (ml) Concordant value
(ml)
Initial Final
1
2

Volume of Oxalic acid V1 =


Normality of Oxalic acid N1 =
Volume of NaOH V2 =
Normality of NaOH N2 = (V1 ×N1)/V2 =
STANDARDISATION OF HCl (HCl vs. NaOH)
S. No Volume of NaOH Burettereading (ml) Concordant value
(ml) (ml)
Initial Final
1
2

Volume of NaOH V1 =
Normality of NaOH N1 =
Volume of HCl V2 =
Normality of HClN2= (V1× N1)/V2 =

TABULATION:
S.No Time Vol. of HCl Normality of E (t) t x E (t) (t-tm)2E(t)
(t) consumed (ml) NaOH ×10-3
×10-3
1
2
3
4
5
6
7
8

Normality of NaOH :VNaOH× NNaOH= VHcl× NHcl


20×NNaOH=
NNaOH=

Normality of NaOH
E (t) =
Area under the N vs t curve (C Curve)

E(t) =
t

 tE (t )dt
0
Mean Residence Time = tm = t

 E (t )dt
0

 E (t )dt
0
=1

t
tm =  tE (t )dt
0

Area under the curve oft x E (t)vst gives, tm =



Variance =  2   t  tm  E t dt
2

Area under the curve of(t -tm)2 E (t) vst gives 2 =


Number of Tanks, N= tm2/ 2 =
Theoretically, for ideal n CSTRs

n 1
 t  nn
tm E (t )    e  t n / tm
 tm  (n  1)!

tm2
tm  nti and   2

n
GRAPH:
1. t E(t) vs. Time
2. Normality of NaOH vs. Time
3. (t-tm)2 E(t) vs. Time

SAMPLE CALCULATIONS:

RESULT:
The Mean Residence time of fluid and the N using Tank-in-series model are calculated and the
results are given below,
1. Mean Residence time (t m) =
2. The value of N using Tank-in-series model =
DISCUSSION OF RESULTS:
CONCLUSIONS:
SUGGESTIONS:
REFERENCES:
KINETICS OF SOLID FLUID REACTION

Ex. No: Date :


OBJECTIVE:
a) Study the decomposition of calcium carbonate (CaCO3) in a muffle furnace.
b) Interpret the decomposition time data in terms of a suitable reaction model.
c) Predict the rate determining step from experimental data obtained.

APPARATUS USED: Weighing balance, weight box, Dessicator, Steel trays, Calcium
carbonate, Muffle furnace and tongs and gloves.

THEORY: Fluid solid reactions are numerous and of great industrial importance. Most common
examples are roasting of ores, burning of carbon/coke, decomposition of calcium carbonate etc.
For the design of reactors/kilns, it is necessary to know the kinetics of such solid-fluid reactions.
In this experiments, the rate limiting step in the decomposition of CaCO3 is to be known.
The decomposition of CaCO3 is an endothermic chemical reaction:
CaCO3 + ΔHR = CaO + CO2
(solid) (reaction enthalpy) (solid) (gaseous)

The forward reaction is favored by higher temperatures.


Decomposition of CaCO3, is reasonably represented by unreacted core model. Unreacted CaCO 3
model for spherical particles of changing size visualizes five steps occurring in succession during
reaction.
A (fluid) + b.B (solid) → Fluid and/or solid product.
Step 1: Diffusion of gaseous reactant ‘A’ through the fluid film surrounding the particle to the
surface of solid.
Step 2: Penetration and diffusion of ‘A’ through the blanket of ash to the surface of unreacted core.
Step 3: Reaction of gases with solids at this reaction surface.
Step 4: Diffusion of gaseous product through the ash film back to the external surface of the solid.
Step 5: Diffusion of gaseous product through the fluid film back into the main body of fluid [1].
Film Diffusion Resistance: This refers to the diffusion through the gas film surrounding the
reacting particle which could create a concentration gradient across the film. In most reactions the
resistance to diffusion through the ash layer is usually far greater than resistance to diffusion
through the gas film. The gas film resistance is therefore assumed to be negligible. It is generally
agreed that film diffusion effects are an insignificant factor in the decomposition of limestone.
Film diffusion is ignored.
Ash Diffusion Resistance: This is resistance to the flow of gas across the reacted product and
largely depends on the porosity of the product layer.
Chemical Reaction Control: This is when the actual reaction at the reacting surface is the rate
determining step.
It is not necessary that at a time all the steps may have a controlling influence on the reaction.
Depending on the type of reaction, some of them may control the overall rate of conversion.
Following are the conversion-time relations for various models for solids of identical size:
1. Diffusion through gas film controls: t/τ = xB (1)
2. Diffusion through ash film controls: t/ τ = 1 – 3(1 – xB)2/3 + 2(1 – xB) (2)
3. Chemical reaction controls: t/ τ = 1 – (1 – xB)1/3 (3)
Where
t = time in min.
xB = fractional conversion of solids.
τ = time (in min) for complete conversion of solid.

REACTION: Upon heating CaCO3 undergoes a reaction where bound CO2 is released from the
material and only CaO remains.
CaCO3 → CaO + CO2
Checking Purity of CaCO3 Sample
To check the purity of CaCO3 sample, calculate the formula weight by substituting the atomic
mass in the formula. CaCO3 → CaO + CO2
Ca = 40.08 (amu), C = 12.011 amu, O = 15.9994 amu
Ca + C + O (40.1) + (12.0) + [(16) x (3)]
CaCO3 → CaO + CO 100.1 [(40.1) + (16)] + [(12.0) + (16) x (2)]
(56.1) + (44) (100.1) (100.1) amu
If the measured values are almost exactly equal to the calculated values, then the sample is pure.
PROCEDURE:
1. Take about 100-150 grams of CaCO3 sample and crush it into pieces.
2. Pass the crushed CaCO3 sample through a sieve in order to obtain the desired particle size.
3. Divide the sample into five parts increasing order e.g 15 gm, 20 gm, 25 gm, 30 gm and 35
gm.
4. Take each part of the sample and using an impression/mould, form a spherical ball shape.
5. Measure the weight of each of the CaCO3 balls.
6. Maintain the temperature inside the furnace at about 1000oC.
7. Place the five CaCO3 samples in five steel trays.
8. The five trays are then placed in a common tray and kept in the furnace.
9. The time period for placement of all the samples in the furnace is recorded.
10. Each sample is removed from the furnace after every 30 minutes (half an hour).
11. The samples are then placed in a desiccator in order to avoid absorption of moisture during
cooling.
12. After cooling of each of the trays for approximately 30 minutes, they are weighed for
estimating the weight loss in each of the samples.
13. Conversion of solids by loss in weight of the samples is calculated in order to obtain
conversion versus time data (100% conversion corresponds to 44% loss in the weight of the
sample).
14. Best fit model will represent the decomposition of CaCO3 at the temperature of the study.

TABULATION:
Dry Bulb Temperature: oC
Wet Bulb Temperature: oC
Atmospheric Pressure:
Temperature of Muffle furnace: oC

S.No. Dimension Initial Weight of Final Weight of Difference in Time period


of Sample sample (gms) sample (gms) weight (gms) (min)
(cm)
1. 30
2. 60
3. 90
4. 120
5. 150
CALCULATIONS:
S.No. Loss in Moles XB (1-XB) (1-
weight of CO2 XB)1/3
= Mass formed t/ τ
of CO2
formed
Film Ash Chemical
diffusion layer reaction
control contol control
1.
2.
3.
4.
5.
6.

GRAPH:
Reading No.
Loss of mass = Mass of CO2 formed
= Initial weight – Final weight
Moles of CO2 formed = Mass/M.W of CO2
Conversion XB = Moles of CO2 formed/Initial moles of CaCO3
Initial moles of CaCO3 = Initial weight of sample/M.W of CaCO3

The standard deviation of a set of N data points is defined by the following relation;

As τ is constant in all three models, so we have compared the standard deviation of τ's calculated
from these models.
The values of t/τ for all the three models have been calculated and these have been used for
calculating τ for every experimental reading.
RESULT:
The rate limiting step as visible from the graph and standard deviation is found to be…

DISCUSSION OF RESULTS:
CONCLUSIONS:
SUGGESTIONS:
REFERENCES:

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