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Interpretation of Batch Reactor Data

The document discusses different methods for determining the rate law of chemical reactions from batch reactor experimental data, including integral, differential, initial rate, half life, and Ostwald's isolation methods. It then provides examples of how to apply these methods to determine the rate law for reactions occurring in both constant volume and variable volume batch reactors. Specific steps are outlined for using the integral and differential methods to analyze reaction rate data from constant volume and varying volume batch experiments.

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Hritik Lal
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465 views10 pages

Interpretation of Batch Reactor Data

The document discusses different methods for determining the rate law of chemical reactions from batch reactor experimental data, including integral, differential, initial rate, half life, and Ostwald's isolation methods. It then provides examples of how to apply these methods to determine the rate law for reactions occurring in both constant volume and variable volume batch reactors. Specific steps are outlined for using the integral and differential methods to analyze reaction rate data from constant volume and varying volume batch experiments.

Uploaded by

Hritik Lal
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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Interpretation of Batch Reactor Data

 Analyses of kinetic data


1. Integral method – Integrated rate equations for different order reactions
2. Differential method
3. Initial rate
4. Half life method
5. Ostwald’s isolation method

 Batch Reactor
• Constant volume
• Variable volume (constant pressure)
Rate equation using integral method
(constant volume)
• Given: Composition of the reactant at various times

• To find: A rate equation to represent the data

• Solution:

• Guess first order kinetics  ln (CA0/CA) vs t (should give a straight line)

• Guess second order kinetics  1/CA vs t (should give a straight line)

• Guess nth order kinetics Plot CA vs t  draw a smooth curve  use fraction life method
and plot log tf vs log CA0  slope gives the reaction order  for rate constant, take a point
on CA vs t curve and substitute in the original fractional life equation.
Rate equation using differential method
(constant volume)
• Given: Composition of the reactant at various times

• To find: A rate equation to represent the data

• Solution:

• Plot CA vs t  smooth curve to represent the data

• Find slopes at selected concentration values these slopes = rate of reaction at these compositions

• Rate expression to represent the data (rA vs CA)

• Take log on both sides and plot log (rA) vs log (CA)  straight line  slope gives the order of the
reaction and intercept gives the reaction rate.
Varying volume batch reactor
• Differential method
• Same as constant volume except replace dCA/dt with (CA0/VεA)*(dV/dt)
• Plot ln V vs t and take slopes.

• Integral method
• Zero order  plot ln (V/V0) vs t  straight line passing through origin  slope kεA/CA0
• First order  plot –ln(1-(ΔV/ εAV0)) vs t  straight line passing through origin  slope = k
• Second order  plot the entire algebraic expression vs t  straight line passing through origin
 slope = k
• nth order  not useful
Practice problems
•• In
  a gaseous reaction, the time for half change (t ½) for the various initial partial pressures (p)
of the reactant was given as follows:

pA0 (torr) 200 300 400


t½ (min) 150 99.8 75.3

Find the order of the reaction.

Hint: t ½ is proportional to
CA0 is proportional to pA0
Replace CA0 by pA0 and solve.

Answer: n=2
• The partial pressure of azomethane was observed as a function of time at 600K.
The results are tabulated below. Confirm that the decomposition is first order and
find the rate constant at this temperature.
CH3N2CH3  CH3CH3 +N2
Time (s) 0 1000 2000 3000 4000

Partial pressure, torr 820 572 399 278 194


(mmHg)

Hint: CONCENTRATION is proportional to PARTIAL PRESSURE


Replace CA in rate equation by PA and solve (for various time t, find k  if k = same for all t
confirmed that the reaction is first order).

OR

Plot ln (pA0/pA) vs t  if straight line passing through origin  first order


• In studying the kinetics of decomposition reaction, the concentration of the
reactants were determined analytically at different times. The following results were
obtained. Determine the order and rate constant for the reaction.

Time, min 0 10 20 40 100 125


Conc, 0.1 0.0714 0.0556 0.0385 0.02 0.0167
mol/L

Answer: -rA = 0.4 (L/mol)(min)-1 CA2

• A polymerization reaction occurs at constant temperature in a homogeneous phase.


30% of the monomer reacts in 40 minutes for the initial monomer concentrations of
0.3, 0.5 and 0.9 mol/L. Find the reaction rate.

Answer: 0.00892 (min)-1 CA


 • The kinetic data for the reaction of sulphuric acid with diethyl sulphate in ana aqueous solution at 22.9°C
are as follows. The reaction taking place is of the form A+B 2C. Find the rate equation for this reaction if
the initial concentrations of sulphuric acid and diethyl sulphate are each 5.5mol/L

Time, min 0 41 48 55 75 96
CC, mol/L 0 1.18 1.38 1.63 2.24 2.75

Time, min 127 146 180 267 368 ∞


CC, mol/L 3.31 3.76 4.11 4.86 5.32 5.80

• Hint:
• Integrated Rate eqn for second order reversible reaction
• CA = CC/2
• Tabulate t, CA, Xa, ln [z]
• Plot ln [z] vs t  slope will give k for forward reaction
• Find k for backward reaction

Answer: -rA = (6.63e-4)CaCb – (1.33e-4)Cc2


Hint:
• Relate pressure to concentration
and tabulate t and Ca
• Plot Ca vs t  slopes  -rA
• Plot ln(-rA) vs lnCA.
• Intercept k
• Slope  order

Answer
-rA = 5.75 (l/mol)(min)-1Ca2
• A zero order homogeneous gas phase reaction A rR takes place in a constant volume bomb, P = 1
atm when t=0 and P= 1.5atm when t=1min. If the same reaction with the same feed composition and
initial pressure takes place in a constant-pressure apparatus, find V at t=1min if V=1 at t=0.

• Hint:
• Integrated rate equation for zero order reaction  write concentration in terms of pressure
• Find k
• Find εA for variable volume
• Integrated rate equation for VVBR in terms of pressure  use CVBR k and find V

Answer :
V = 1.648L

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