Experimental Rate Determination Methods

Explain in detail the stepwise procedure of experimental methods for determining rates i)
differential flow reactor ii) Integral reactor

To determine reaction rates experimentally, chemical engineers use reactors like differential flow
reactors and integral flow reactors. Each reactor type offers a distinct method of data collection and
analysis. Here's a detailed stepwise procedure for each:

i) Differential Flow Reactor (DFR)

Also known as a plug flow reactor (PFR) operated at very small conversions (ideally <5%). The purpose
is to directly measure the reaction rate as a function of concentration.

Objective:

To determine the rate of reaction as a function of reactant concentration, under near-initial conditions.

Stepwise Procedure:

1. Set Up Reactor System:

Use a tubular flow reactor with small volume.

Ensure accurate flow control of reactants using flowmeters.

Maintain constant temperature and pressure using thermostatic baths and pressure
regulators.

2. Prepare Reactant Feed:

Prepare a known concentration of reactants.
Use inert gases if necessary to dilute the reactants (to reduce conversion).

3. Establish Steady-State Flow:

Begin pumping the reactants through the reactor.

Allow the system to reach steady state, where the outlet concentration becomes constant
with time.
4. Measure Outlet Concentration:

Use analytical tools (e.g., gas chromatography, UV-Vis spectroscopy) to measure exit
concentrations of reactants and/or products.
5. Ensure Small Conversion:

Keep conversion below ~5% so that concentration inside reactor ≈ inlet concentration.
This makes the rate = −rA calculated directly using:
​

F F
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 FA0 − FA
−rA =
​ ​

​ ​

V
Where:
FA0 = molar flow rate of A in,
​

FA = molar flow rate of A out,

​

V = volume of reactor.
6. Repeat for Different Feed Concentrations:

Change inlet concentrations.

Repeat steps 3–5 to get rate data at different concentrations.

7. Plot Rate vs. Concentration:

Plot −rA versus CA to determine rate law (e.g., first-order, second-order, etc.).
​ ​

ii) Integral Flow Reactor (IFR)

Also a plug flow reactor, but here significant conversion is allowed. Used when measuring rate over a
range of concentrations inside the reactor.

Objective:

To determine reaction rate by integrating the design equation over the reactor volume.

Stepwise Procedure:

1. Set Up Reactor:

Use a longer tubular plug flow reactor.

Include heating/cooling jackets to maintain isothermal conditions.

2. Prepare Feed Mixture:

Use known concentrations of reactants.

Maintain constant flow rate and pressure.

3. Reach Steady State:

Start the flow.

Wait until steady-state outlet concentration is achieved.

4. Measure Inlet and Outlet Concentrations:

Use analytical instruments to get CA0 and CA .

​ ​

5. Calculate Conversion:

CA0 − CA
X=
​ ​

CA0 ​

6. Apply Plug Flow Reactor Design Equation:

X
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 X
dX
V = FA0 ∫
−rA
​ ​ ​

0 ​

Rearranged as:

⋅( )
FA0 dX
−rA =
​

​ ​ ​

V dV

However, since we measure only inlet and outlet concentrations, assume average behavior over
the reactor and apply:

FA0 (X)
−rA =
​

​ ​

V
7. Repeat with Different Initial Concentrations:

Change CA0 or flow rate.

​

Repeat steps 3–6.

8. Fit Rate Law:

Analyze how −rA depends on CA or X to determine rate law and reaction order.
​

Summary Comparison

Feature Differential Flow Reactor Integral Flow Reactor

Conversion Very low (<5%) Can be significant
Rate Measured directly Obtained from integrated form

Accuracy High for initial rate Good over conversion range

Use Determining rate law form Confirming kinetics over conversion

Would you like an example calculation for either method?

Explain in detail the stepwise procedure of experimental methods for determining rates i)
Mixed flow reactor ii) Batch reactor reactor.

Here's a detailed explanation of the stepwise procedure of experimental methods for determining
reaction rates using:

1. Mixed Flow Reactor (MFR)

2. Batch Reactor

These are two commonly used reactor types in chemical kinetics experiments, each suited for different
conditions and objectives.

i) Mixed Flow Reactor (MFR)

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Also known as a Continuous Stirred Tank Reactor (CSTR), it is operated at steady state with perfect
mixing. The outlet composition is assumed to be the same as inside the reactor.

✅ Objective:
To determine the reaction rate from steady-state outlet concentrations under known flow and
concentration conditions.

Stepwise Procedure:

1. Set Up the Reactor System:

Use a stirred tank reactor with continuous flow inlet and outlet.
Ensure proper mixing using mechanical stirrers.

Maintain isothermal operation using a temperature-controlled bath or jacket.

2. Prepare and Feed Reactants:

Prepare known concentrations of reactants in feed tanks.

Use flowmeters to control and monitor the flow rate (Fₐ₀) of reactants.

3. Allow the System to Reach Steady State:

Let the reactor run until the outlet concentration becomes constant with time (typically
checked by periodic sampling).

4. Measure Outlet Concentration:

Use analytical methods like UV-Vis, gas chromatography, or titration to determine outlet
concentration CA . ​

5. Calculate Conversion (X):

CA0 − CA
X=
​ ​

CA0 ​

6. Apply Design Equation:

At steady state, for MFR:

FA0 (CA0 − CA )
−rA =
​ ​ ​

​ ​

V
or simply:

CA0 − CA
−rA =
​ ​

​ ​

τ
Where:
V = reactor volume
V
τ= v0 = space time (residence time)
​
​

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 7. Repeat with Different Inlet Concentrations:

Change the feed concentration or flow rate.

Repeat steps 3–6 to obtain rate data over a range of concentrations.

8. Plot and Determine Rate Law:

Plot −rA vs. CA to find the rate law and order of reaction.
​ ​

ii) Batch Reactor

A closed system where no material enters or leaves during the reaction. It's commonly used in labs for
kinetic studies.

✅ Objective:
To observe how concentration changes with time, allowing direct determination of rate expressions.

Stepwise Procedure:

1. Set Up the Batch Reactor:

Use a sealed reaction vessel (usually round-bottom flask or stirred tank).

Ensure adequate stirring for uniform concentration.
Place in a temperature-controlled environment (e.g., oil bath or thermostat).

2. Charge the Reactor:

Add known volumes and concentrations of reactants.

Seal the reactor and start timing immediately.

3. Sample the Reaction Mixture at Intervals:

At regular time intervals, withdraw small samples (using a syringe or valve).

Quench the reaction (e.g., by cooling or adding a neutralizing agent) if necessary.

4. Analyze Concentration:

Use appropriate analytical methods to determine the concentration of reactants or

products at each time point.

5. Plot Concentration vs. Time:

From the data, plot CA vs. t, or for conversions, plot X vs. t.

​

6. Determine Rate of Reaction:

Use differential method:

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 −rA = ( )
dCA​

​ ​

dt
Or use integrated rate laws for zero, first, or second-order to find which fits:

Zero-order: CA ​ = CA0 − kt ​

First-order: ln CA ​
= ln CA0 − kt ​

1
= C1A0 + kt
Second-order: C
A ​
​

​
​

7. Repeat for Other Conditions:

Vary initial concentrations or temperature and repeat to obtain more kinetic data.

8. Determine Rate Constant and Order:

From plots and rate expressions, determine:

Reaction order

Rate constant k

Activation energy (if done at multiple temperatures)

✅ Summary Comparison Table

Feature Mixed Flow Reactor (CSTR) Batch Reactor
Operation Continuous, steady state Closed, unsteady state

Mixing Perfect mixing Stirred, uniform concentration

Rate Determination From outlet concentration From concentration-time data

Application Industrial, continuous processes Laboratory, kinetic studies

Rate Law Derivation Plot −rA vs. CA ​ ​

Fit integrated/differential form

Would you like help with a sample calculation or plotting method for either reactor?

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