This document provides a review of various methods for analyzing reaction rate data, including the method of half-lives, initial rates, and differential reactors. It discusses determining reaction order and rate constants, as well as considerations for maximizing selectivity and yield in parallel, series, and complex reaction schemes. Various reactor configurations are examined in the context of concentration requirements and selectivity, including CSTR, PFR/PBR, batch, and semi-batch reactors.
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- The document provides information on chemical vapor deposition (CVD) growth of silicon and germanium films, including elementary surface reactions and rate equations.
- It also discusses catalyst deactivation kinetics and models, types of catalyst deactivation including sintering, fouling, and poisoning. Equations are provided for modeling the decay in catalyst activity over time.
- The document reviews the design and modeling of a moving-bed reactor, where catalyst deactivation occurs and spent catalyst is continuously regenerated while maintaining steady-state operation. Rate equations are developed to model the reactor performance.
This document discusses key concepts related to reaction kinetics and reactor sizing including:
- Rate laws and how reaction rates depend on concentration and temperature
- Deriving equations to relate reaction rates to conversion for different reactor types
- Methods for numerically evaluating integrals to determine reactor volumes from rate equations
- Sizing continuous stirred-tank reactors, plug flow reactors, and packed bed reactors
- Considerations for reactors in series and reversible reactions
This document discusses reactor design for multiple reactions. It begins by describing types of reactors including batch, semi-batch, and continuous. Design parameters like volume, flow rate, concentrations, kinetics, temperature, and pressure are discussed for reactor selection. Equations for mixed flow and plug flow reactor design are presented. Plug flow reactors are generally smaller than continuous stirred tank reactors (CSTRs) for a given conversion. Methods for maximizing the desired product in parallel and series reactions include adjusting conditions like concentrations, temperatures, and choosing the proper reactor type. Multiple reactor systems with reactors in series or mixed flow reactors of different sizes can be used for high conversions that a single reactor cannot achieve.
L1 Introduction and molar balances.pptxssuserdea4ba
This document contains slides from a lecture on chemical reaction engineering (CRE). It introduces CRE as the synthesis of thermodynamics, kinetics, fluid mechanics, heat and mass transfer, and economics to design and understand chemical reactors. It discusses how to design reactors by considering the reaction stoichiometry, kinetics, type of reactor, and size of reactor. Basic concepts covered include the different types of reactors (CSTR, batch, PFR) and using material balances to model reactors.
The document discusses mass transfer limitations in catalytic pellet reactions. It begins by establishing that the molar rate of mass transfer from the bulk fluid to the external catalyst surface must equal the actual reaction rate. Derivations are shown for mole balances at the pellet surface and expressions for the overall reaction rate that account for both internal and external diffusion limitations. Rate equations are provided depending on whether the reaction is limited by external diffusion, internal diffusion, or the surface reaction itself. The ways reaction rates vary with parameters like superficial velocity, particle size, and temperature indicate which type of limitation is occurring. Examples are given to determine whether a reaction shown in a rate vs condition graph is limited by external diffusion based on how the rate changes with flow
Control loop configuration of interacting unitsSomen Jana
What is an Interacting Unit?
Several units interact with each other through material or energy flows.
How to determine the feasible loop configuration in interacting units?
Steps:
Divide the process into separate blocks.
Determine the degree of freedom and no of controlled and manipulated variables for each block.
Determine the feasible loop configurations for each and every block.
Recombine the blocks with their loop configurations.
Eliminate the conflicts among the control system of the various blocks.
Control loop configuration of interacting unitsSomen Jana
What is an Interacting Unit?
Several units interact with each other through material or energy flows.
How to determine the feasible loop configuration in interacting units?
Steps:
Divide the process into separate blocks.
Determine the degree of freedom and no of controlled and manipulated variables for each block.
Determine the feasible loop configurations for each and every block.
Recombine the blocks with their loop configurations.
Eliminate the conflicts among the control system of the various blocks.
L7b Pressure drop, CSTR start up and semibatch reactors examples.pptxPatelkevinJayeshkuma
- The document describes the start-up of a continuous stirred tank reactor (CSTR) operating under isothermal conditions for a first-order irreversible reaction.
- Mathematical models are developed to determine the concentration of the reactant A (CA) as a function of time during the transient period before reaching steady-state.
- It is shown that CA will reach 99% of its steady-state value when t = 4.6τ, where τ is the characteristic time for the reactor.
- Methods for analyzing semi-batch reactors are also presented, including mole balances to determine how CA and CB change over time for a reversible reaction.
L18b Deducing mechanisms example problems.pptxSatyamJaiswal90
- The document provides information on chemical vapor deposition (CVD) growth of silicon and germanium films, including elementary surface reactions and rate equations.
- It also discusses catalyst deactivation kinetics and models, types of catalyst deactivation including sintering, fouling, and poisoning. Equations are provided for modeling the decay in catalyst activity over time.
- The document reviews the design and modeling of a moving-bed reactor, where catalyst deactivation occurs and spent catalyst is continuously regenerated while maintaining steady-state operation. Rate equations are developed to model the reactor performance.
This document discusses key concepts related to reaction kinetics and reactor sizing including:
- Rate laws and how reaction rates depend on concentration and temperature
- Deriving equations to relate reaction rates to conversion for different reactor types
- Methods for numerically evaluating integrals to determine reactor volumes from rate equations
- Sizing continuous stirred-tank reactors, plug flow reactors, and packed bed reactors
- Considerations for reactors in series and reversible reactions
This document discusses reactor design for multiple reactions. It begins by describing types of reactors including batch, semi-batch, and continuous. Design parameters like volume, flow rate, concentrations, kinetics, temperature, and pressure are discussed for reactor selection. Equations for mixed flow and plug flow reactor design are presented. Plug flow reactors are generally smaller than continuous stirred tank reactors (CSTRs) for a given conversion. Methods for maximizing the desired product in parallel and series reactions include adjusting conditions like concentrations, temperatures, and choosing the proper reactor type. Multiple reactor systems with reactors in series or mixed flow reactors of different sizes can be used for high conversions that a single reactor cannot achieve.
L1 Introduction and molar balances.pptxssuserdea4ba
This document contains slides from a lecture on chemical reaction engineering (CRE). It introduces CRE as the synthesis of thermodynamics, kinetics, fluid mechanics, heat and mass transfer, and economics to design and understand chemical reactors. It discusses how to design reactors by considering the reaction stoichiometry, kinetics, type of reactor, and size of reactor. Basic concepts covered include the different types of reactors (CSTR, batch, PFR) and using material balances to model reactors.
The document discusses mass transfer limitations in catalytic pellet reactions. It begins by establishing that the molar rate of mass transfer from the bulk fluid to the external catalyst surface must equal the actual reaction rate. Derivations are shown for mole balances at the pellet surface and expressions for the overall reaction rate that account for both internal and external diffusion limitations. Rate equations are provided depending on whether the reaction is limited by external diffusion, internal diffusion, or the surface reaction itself. The ways reaction rates vary with parameters like superficial velocity, particle size, and temperature indicate which type of limitation is occurring. Examples are given to determine whether a reaction shown in a rate vs condition graph is limited by external diffusion based on how the rate changes with flow
Control loop configuration of interacting unitsSomen Jana
What is an Interacting Unit?
Several units interact with each other through material or energy flows.
How to determine the feasible loop configuration in interacting units?
Steps:
Divide the process into separate blocks.
Determine the degree of freedom and no of controlled and manipulated variables for each block.
Determine the feasible loop configurations for each and every block.
Recombine the blocks with their loop configurations.
Eliminate the conflicts among the control system of the various blocks.
Control loop configuration of interacting unitsSomen Jana
What is an Interacting Unit?
Several units interact with each other through material or energy flows.
How to determine the feasible loop configuration in interacting units?
Steps:
Divide the process into separate blocks.
Determine the degree of freedom and no of controlled and manipulated variables for each block.
Determine the feasible loop configurations for each and every block.
Recombine the blocks with their loop configurations.
Eliminate the conflicts among the control system of the various blocks.
L7b Pressure drop, CSTR start up and semibatch reactors examples.pptxPatelkevinJayeshkuma
- The document describes the start-up of a continuous stirred tank reactor (CSTR) operating under isothermal conditions for a first-order irreversible reaction.
- Mathematical models are developed to determine the concentration of the reactant A (CA) as a function of time during the transient period before reaching steady-state.
- It is shown that CA will reach 99% of its steady-state value when t = 4.6τ, where τ is the characteristic time for the reactor.
- Methods for analyzing semi-batch reactors are also presented, including mole balances to determine how CA and CB change over time for a reversible reaction.
1. Study of speed with which a chemical reaction occurs and the factors affecting that speed
2. Provides information about the feasibility of a chemical reaction
3. Provides information about the time it takes for a chemical reaction to occur
4. Provides information about the series of elementary steps which lead to the formation of product
The document discusses chemical kinetics and provides information about:
- The factors that affect the speed of a chemical reaction, including concentration, temperature, and catalysts.
- How to determine the rate law, rate constant, order, and mechanism of reactions from experimental data.
- The relationship between concentration and time for reactions of different orders (zero, first, and second order).
- How to calculate half-life, effect of temperature on reaction rate using the Arrhenius equation, and the role of homogeneous and heterogeneous catalysts.
Chemical kinetics is the study of the speed of chemical reactions and factors that affect the reaction rate. It provides information about reaction feasibility, timescales, and reaction mechanisms. The rate of a reaction can be examined by measuring changes in reactant or product concentrations over time. Reaction rates are determined experimentally and may follow zero-order, first-order, pseudo-first order, or second-order rate laws depending on the rate-determining step. Factors like temperature, concentration, physical state, and catalysts influence reaction rates.
This document describes using ASPEN Plus dynamic simulation software to model and control a continuous stirred tank reactor (CSTR) process. It introduces key dynamic simulation concepts and outlines the steps to:
1) Build a process flowsheet model in steady-state, including reactions, streams and equipment.
2) Convert the model to dynamic mode and input dynamic parameters.
3) Add a level controller to the CSTR and tune it using open-loop testing and the Ziegler-Nichols method.
4) Simulate the dynamic behavior of the controlled process to evaluate controller performance.
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This document discusses reactor design for multiple reactions. It describes types of reactors including batch, semi-batch, plug flow, and continuous stirred-tank reactors (CSTRs). It also covers parameters for reactor design like volume, flow rate, concentrations, kinetics, temperature, and pressure. The document discusses plug flow versus CSTR design and designing for parallel, series, and complex reaction networks. It provides methods for maximizing desired products in multiple reaction systems, including adjusting conditions, choosing proper contacting patterns and reactors, and optimizing space-time or residence time. The document also presents equations for modeling multiple reactions occurring in a CSTR.
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1) The conversion process typically involves physical preparation of raw materials, a chemical reaction step, separation of unconverted materials, and separation of unwanted and wanted products.
2) Chemical reaction engineering is concerned with designing chemical reactors and analyzing their performance. This involves determining factors like reactor size, flow configuration, and product distribution.
3) Key concepts in designing chemical reactors include steady-state vs. unsteady-state conditions, ideal vs. non-ideal mixing, conversion, selectivity, yield, and throughput. Material and energy balances are also important.
4) Common reactor types
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Cab 3024 reactor synthesis problem exerciseayimsevenfold
1. The document discusses several reaction systems and questions regarding the optimal reactor type and conditions to maximize the formation of desired products and selectivity.
2. It provides examples of parallel and consecutive reactions, and asks to determine the best reactor and operating conditions based on kinetic rate information to maximize certain products over byproducts.
3. Factors like reaction order, temperature, concentration and reversibility of reactions are considered in selecting the most suitable reactor type and settings.
The document outlines how to use the Polymath software to solve various chemical reaction engineering problems involving reactors like CSTR, batch, and PFR. It provides examples of solving single and multiple reactions in these reactors, and discusses how Polymath can be used to determine profiles like conversion, yield, temperature, and flow rates. The document also covers how to account for pressure drop and heat effects when modeling reactions in PFRs.
The document discusses several types of chemical reactors, including recycle reactors, autocatalytic reactors, and considerations for optimizing reactor performance and operating conditions. It addresses recycle stream ratios, performance equations, temperature progression, and non-ideal flow concepts such as residence time distribution, states of aggregation, and mixing effects.
The document describes a laboratory experiment to determine the reaction order and rate constant of the reaction between sodium hydroxide (NaOH) and ethyl acetate (CH3COOC2H5). The group prepared 0.1 M solutions of each reactant and mixed them in a batch reactor at room temperature while measuring conductivity over time. Calculations using the conductivity readings showed the reaction was second order. The rate constant was determined to be 1.291651 × 10-3 at 21°C based on the nonlinear ln(CA/CAo) vs time graph.
Non-imaging nuclear medicine devices include gas-filled detectors, dose calibrators, scintillation detectors, gamma well counters, and thyroid probes. Dose calibrators use ionization chambers to measure radioactivity proportional to emission rates. Gamma well counters and thyroid probes use scintillation detectors with high detection efficiency and collimation respectively to measure samples and thyroid uptake. Liquid scintillation counters dissolve samples in scintillating fluid to detect low energy emissions with 100% efficiency.
This document discusses the properties and design considerations of continuously stirred tank reactors (CSTRs), also known as back-mixed reactors. It outlines key characteristics of CSTRs such as perfect mixing, uniform conditions throughout the reactor, and identical properties at the inlet and outlet. Advantages include low cost and easy temperature control. Disadvantages are lower reaction rates due to diluted reactant concentrations compared to the inlet. Mass and energy balances are derived and used to determine the reactor volume required for a given conversion based on kinetic data and operating conditions. Examples are provided to demonstrate solving for reactor size and temperature based on specified conversions.
Unit Operations and water and wastewater treatment2 ideal reactor modeling.pdfamyw1990
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This document is a chapter summary for a chemistry textbook on reaction rates. It defines reaction rates and discusses how rates depend on concentration, temperature, and catalysts. It also covers experimental determination of rates, rate laws, reaction mechanisms, and the effects of temperature. Key equations discussed include the rate law, integrated rate laws for first and second order reactions, the Arrhenius equation relating reaction rate and temperature, and transition state theory to explain the activated complex.
This lab report summarizes an experiment examining the impact of ethyl acetate flow rate on conversion in a plug flow reactor at 21°C. Students measured conductivity at four increasing flow rates and calculated conversion using conductivity readings. Results showed conversion decreased as flow rate increased, because higher flow rates gave reactants less time to fully react before exiting the reactor. The experiment helped students learn how conversion in a plug flow reactor is affected by changing an inlet flow rate.
The document discusses reactor modeling and simulation in HYSYS. It provides information on defining different reactor types in HYSYS including conversion reactors, CSTRs, PFRs, Gibbs reactors, and equilibrium reactors. For each reactor type, it lists the requirements in terms of reaction stoichiometry, kinetics models, and other parameters that must be specified to define the reactor in HYSYS.
1. Study of speed with which a chemical reaction occurs and the factors affecting that speed
2. Provides information about the feasibility of a chemical reaction
3. Provides information about the time it takes for a chemical reaction to occur
4. Provides information about the series of elementary steps which lead to the formation of product
The document discusses chemical kinetics and provides information about:
- The factors that affect the speed of a chemical reaction, including concentration, temperature, and catalysts.
- How to determine the rate law, rate constant, order, and mechanism of reactions from experimental data.
- The relationship between concentration and time for reactions of different orders (zero, first, and second order).
- How to calculate half-life, effect of temperature on reaction rate using the Arrhenius equation, and the role of homogeneous and heterogeneous catalysts.
Chemical kinetics is the study of the speed of chemical reactions and factors that affect the reaction rate. It provides information about reaction feasibility, timescales, and reaction mechanisms. The rate of a reaction can be examined by measuring changes in reactant or product concentrations over time. Reaction rates are determined experimentally and may follow zero-order, first-order, pseudo-first order, or second-order rate laws depending on the rate-determining step. Factors like temperature, concentration, physical state, and catalysts influence reaction rates.
This document describes using ASPEN Plus dynamic simulation software to model and control a continuous stirred tank reactor (CSTR) process. It introduces key dynamic simulation concepts and outlines the steps to:
1) Build a process flowsheet model in steady-state, including reactions, streams and equipment.
2) Convert the model to dynamic mode and input dynamic parameters.
3) Add a level controller to the CSTR and tune it using open-loop testing and the Ziegler-Nichols method.
4) Simulate the dynamic behavior of the controlled process to evaluate controller performance.
Energy Conversion Technology 2 - Binary power plant presentationRiccardo Pagotto
The document discusses the optimal design of binary cycle power plants for medium-temperature geothermal fields. It provides background on geothermal energy and geological settings. It then describes how binary cycle power plants work, including the heat recovery cycle, recovery heat exchanger, and cooling system. Temperature ranges for the geothermal fluid, reject fluid, and condenser are provided. The document also analyzes merit parameters like efficiency to optimize plant design, and evaluates performance using different working fluids over a range of temperature conditions. The conclusion covers advantages like sustainability and low emissions, but also disadvantages like dependence on geological factors and initial costs.
This document discusses reactor design for multiple reactions. It describes types of reactors including batch, semi-batch, plug flow, and continuous stirred-tank reactors (CSTRs). It also covers parameters for reactor design like volume, flow rate, concentrations, kinetics, temperature, and pressure. The document discusses plug flow versus CSTR design and designing for parallel, series, and complex reaction networks. It provides methods for maximizing desired products in multiple reaction systems, including adjusting conditions, choosing proper contacting patterns and reactors, and optimizing space-time or residence time. The document also presents equations for modeling multiple reactions occurring in a CSTR.
The document discusses the conversion process of raw materials to products through chemical reactions. It covers key concepts in chemical reaction engineering including:
1) The conversion process typically involves physical preparation of raw materials, a chemical reaction step, separation of unconverted materials, and separation of unwanted and wanted products.
2) Chemical reaction engineering is concerned with designing chemical reactors and analyzing their performance. This involves determining factors like reactor size, flow configuration, and product distribution.
3) Key concepts in designing chemical reactors include steady-state vs. unsteady-state conditions, ideal vs. non-ideal mixing, conversion, selectivity, yield, and throughput. Material and energy balances are also important.
4) Common reactor types
The document discusses kinetics of stability and accelerated stability testing. It provides details on zero order, first order and second order reactions. It explains the determination of rate constants, half life and time for 90% degradation using kinetic equations. The document also discusses Arrhenius equation for predicting shelf life from accelerated stability studies conducted at elevated temperatures. It summarizes the guidelines for stability testing of active pharmaceutical ingredients and finished pharmaceutical products as per ICH.
ReactIR as a Diagnostic Tool for Developing Robust, Scalable Synthetic Processesplaced1
The document discusses using ReactIR technology to provide insights into chemical reactions and processes. It presents three case studies where ReactIR was used: (1) monitoring an unstable acid chloride intermediate in a Vilsmeier reaction, (2) studying mixed anhydride formation with unstable intermediates, and (3) gaining understanding of a chiral resolution process. ReactIR allowed observing reaction components in real-time, identifying side reactions, and gaining mechanistic insights in all three cases.
Cab 3024 reactor synthesis problem exerciseayimsevenfold
1. The document discusses several reaction systems and questions regarding the optimal reactor type and conditions to maximize the formation of desired products and selectivity.
2. It provides examples of parallel and consecutive reactions, and asks to determine the best reactor and operating conditions based on kinetic rate information to maximize certain products over byproducts.
3. Factors like reaction order, temperature, concentration and reversibility of reactions are considered in selecting the most suitable reactor type and settings.
The document outlines how to use the Polymath software to solve various chemical reaction engineering problems involving reactors like CSTR, batch, and PFR. It provides examples of solving single and multiple reactions in these reactors, and discusses how Polymath can be used to determine profiles like conversion, yield, temperature, and flow rates. The document also covers how to account for pressure drop and heat effects when modeling reactions in PFRs.
The document discusses several types of chemical reactors, including recycle reactors, autocatalytic reactors, and considerations for optimizing reactor performance and operating conditions. It addresses recycle stream ratios, performance equations, temperature progression, and non-ideal flow concepts such as residence time distribution, states of aggregation, and mixing effects.
The document describes a laboratory experiment to determine the reaction order and rate constant of the reaction between sodium hydroxide (NaOH) and ethyl acetate (CH3COOC2H5). The group prepared 0.1 M solutions of each reactant and mixed them in a batch reactor at room temperature while measuring conductivity over time. Calculations using the conductivity readings showed the reaction was second order. The rate constant was determined to be 1.291651 × 10-3 at 21°C based on the nonlinear ln(CA/CAo) vs time graph.
Non-imaging nuclear medicine devices include gas-filled detectors, dose calibrators, scintillation detectors, gamma well counters, and thyroid probes. Dose calibrators use ionization chambers to measure radioactivity proportional to emission rates. Gamma well counters and thyroid probes use scintillation detectors with high detection efficiency and collimation respectively to measure samples and thyroid uptake. Liquid scintillation counters dissolve samples in scintillating fluid to detect low energy emissions with 100% efficiency.
This document discusses the properties and design considerations of continuously stirred tank reactors (CSTRs), also known as back-mixed reactors. It outlines key characteristics of CSTRs such as perfect mixing, uniform conditions throughout the reactor, and identical properties at the inlet and outlet. Advantages include low cost and easy temperature control. Disadvantages are lower reaction rates due to diluted reactant concentrations compared to the inlet. Mass and energy balances are derived and used to determine the reactor volume required for a given conversion based on kinetic data and operating conditions. Examples are provided to demonstrate solving for reactor size and temperature based on specified conversions.
Unit Operations and water and wastewater treatment2 ideal reactor modeling.pdfamyw1990
This document discusses mass balances and ideal reactor models for water and wastewater treatment processes. It covers batch reactors, continuously stirred tank reactors (CSTR), and plug flow reactors (PFR). Batch reactors have no inflow or outflow, while CSTRs and PFRs have continuous inflow and outflow. CSTRs provide complete mixing, while PFRs provide no mixing between fluid elements. The document derives the governing equations for each reactor type and compares their performance by example, showing PFRs can achieve higher conversions than CSTRs for a given residence time.
This document is a chapter summary for a chemistry textbook on reaction rates. It defines reaction rates and discusses how rates depend on concentration, temperature, and catalysts. It also covers experimental determination of rates, rate laws, reaction mechanisms, and the effects of temperature. Key equations discussed include the rate law, integrated rate laws for first and second order reactions, the Arrhenius equation relating reaction rate and temperature, and transition state theory to explain the activated complex.
This lab report summarizes an experiment examining the impact of ethyl acetate flow rate on conversion in a plug flow reactor at 21°C. Students measured conductivity at four increasing flow rates and calculated conversion using conductivity readings. Results showed conversion decreased as flow rate increased, because higher flow rates gave reactants less time to fully react before exiting the reactor. The experiment helped students learn how conversion in a plug flow reactor is affected by changing an inlet flow rate.
The document discusses reactor modeling and simulation in HYSYS. It provides information on defining different reactor types in HYSYS including conversion reactors, CSTRs, PFRs, Gibbs reactors, and equilibrium reactors. For each reactor type, it lists the requirements in terms of reaction stoichiometry, kinetics models, and other parameters that must be specified to define the reactor in HYSYS.
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L9b Selectivity example problems.pptx
1. L9b-1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Review: Analysis of Rate Data
• Constant-volume batch reactor for homogeneous reactions: make
concentration vs time measurements during unsteady-state operation
• Differential reactor for solid-fluid reactions: monitor product concentration
for different feed conditions during steady state operation
Goal: determine reaction order, a, and specific reaction rate constant, k
• Data collection is done in the lab so we can simplify BMB, stoichiometry,
and fluid dynamic considerations
• Want ideal conditions → well-mixed (data is easiest to interpret)
Method of Excess
Differential method
Integral method
Half-lives method
Initial rate method
Differential reactor
More complex kinetics
2. L9b-2
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
A
A
dC
kC
dt
a
A products
1 1
A A0
1 1 1
t
k 1 C C
a a
a
A A0 1 2
1
C C at t = t
2
1
1 2 1
A0
2 1 1
t
k 1 C
a
a
a
1
1 2 A0
2 1
ln t ln 1 lnC
k 1
a
a
a
ln (t1/2)
ln CA0
Slope = 1- a
A A
r kC a
Plot ln(t1/2) vs ln CA0. Get a straight
line with a slope of 1-α
Review: Method of Half-lives
Half-life of a reaction (t1/2): time it takes
for the concentration of the reactant to
drop to half of its initial value
3. L9b-3
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Review: Method of Initial Rates
• When the reaction is reversible, the method of initial
rates can be used to determine the reaction order and
the specific rate constant
• Very little product is initially present, so rate of reverse
reaction is negligible
– A series of experiments is carried out at different initial
concentrations
– Initial rate of reaction is determined for each run
– Initial rate can be found by differentiating the data and
extrapolating to zero time
– By various plotting or numerical analysis techniques relating -rA0
to CA0, we can obtain the appropriate rate law:
A0 A0
r kC a
4. L9b-4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Conversion of reactants
& change in reactant
concentration in the bed
is extremely small
Review: Differential Catalyst Bed
FA0
Cp
CA0
FAe
Fp
W
L
r’A: rate of reaction per unit mass of catalyst
flow in - flow out + rate of gen = rate of accum.
A0 Ae A
F F r W 0
A0 Ae 0 A0 Ae
A
F F C C
r
W W
When constant flow rate, 0 = :
0 p
0 A0 Ae
A
C
C C
r
W W
Product
concentration
The reaction rate is determined by measuring
product concentration, Cp
5. L9b-5
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Review: Multiple Rxns & Selectivity
A B C
k1 k2
A
C
B
k2
k1
2) Series rxns
3) Complex rxns
1) Parallel / competing rxns
Desired product
A+B C+D A+C E
k1 k2
D
D U
U
F molar flow rate of desired product
S
F molar flow rate of undesir
Exit
E ed pr
x oduct
it
D
D U
U
N moles of desired product
S
N moles of undes
Fi
ir
nal
Fi ed pr u
nal od ct
instantaneous rate selectivity, SD/U
D
D U
U
r
rate of formation of D
S
rate of formation of U r
overall rate selectivity,
D U
S
D
D
A
r
rate of formation of D
Y
rate of consumption of A r
instantaneous yield, YD
(at any point or time in reactor)
overall yield,
D
Y
D
D
A0 A
F
Y
F F
flow
D
D
A0 A
N
Y
N N
batch
at
exit
at
tfinal
Maximize selectivity / yield to maximize production of desired product
6. L9b-6
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Review: Maximizing SD/U for
Parallel Rxns
E E
D U
D RT 1 2 1 2
D U A B
U
A
S e C C
A
a a
What reactor conditions and
configuration maximize selectivity?
a) If ED > EU
Specific rate of desired reaction kD increases:
Use higher temperature
b) If ED < EU
less rapidly with increasing T
Use lower temperature(not so low
that the reaction rate is tiny)
more rapidly with increasing T
To favor production of the desired product
1 2 1 2
a) 0
a a a a
Now evaluate concentration:
→ Use large CA
1 2 1 2
b) 0
a a a a
→ Use small CA
1 2 1 2
c) 0
→ Use large CB
1 2 1 2
d) 0
→ Use small CB
7. L9b-7
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Concentration Requirements &
Reactor Selection
CA00
CB00
CA0
CB0
How do concentration requirements play
into reactor selection?
CSTR:
concentration is
always at its
lowest value
(that at outlet)
PFR
PFR (or PBR): concentration is
high at the inlet & progressively
drops to the outlet concentration
CA(t)
CB(t)
D
kD
A+B
U
kU
Batch:
concentration is
high at t=0 &
progressively drops
with increasing time
Semi-batch: concentration
of one reactant (A as
shown) is high at t=0 &
progressively drops with
increasing time, whereas
concentration of B can be
kept low at all times
CB0
CA
8. L9b-8
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
D
kD
A+B
U
kU
1 2
High CB
favors
desired
product
formation
1 2
High CB
favors
undesired
product
formation
(keep CB
low)
a1 a2
High CA favors desired
product formation
a1 a2
High CA favors undesired
product formation
(keep CA low)
PFR/PBR
Batch reactor
When CA & CB are low (end time
or position), all rxns will be slow
High P for gas-phase rxn, do not
add inert gas (dilutes reactants)
PFR/PBR w/ side streams feeding
low CB CB
←High CA
Semi-batch
reactor, slowly
feed B to large amount of A
CB
CB CB
CSTRs in
series
B consumed before leaving CSTRn
CA00
CB00
CA0
CB0
CSTR
PFR/PBR
PFR/PBR
w/ high
recycle
• Dilute feed with inerts that are
easily separated from product
• Low P if gas phase
PFR/PBR
Side streams feed low CA
←High CB
CA
Semi-batch
reactor slowly feed
A to large amt of B
CA
CA CA
CSTRs in
series
9. L9b-9
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Different Types of Selectivity
instantaneous rate selectivity, SD/U
D
D U
U
r
rate of formation of D
S
rate of formation of U r
D
D U
U
F molar flow rate of desired product
S
F molar flow rate of undesir
Exit
E ed pr
x oduct
it
overall rate selectivity, D U
S
D
D U
U
N moles of desired product
S
N moles of undes
Fi
ir
nal
Fi ed pr u
nal od ct
D
D
A
r
rate of formation of D
Y
rate of consumption of A r
instantaneous yield, YD
(at any point or time in reactor)
overall yield, D
Y
D
D
A0 A
F
Y
F F
flow
D
D
A0 A
N
Y
N N
batch
Evaluated
at outlet
Evaluated
at tfinal
10. L9b-10
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Series (Consecutive) Reactions
(desired) (undesired)
A D U
k1 k2
Time is the key factor here!!!
Spacetime t for a flow reactor Real time t for a batch reactor
To maximize the production of D, use:
Batch
or PFR/PBR or
n
CSTRs in series
and carefully select the time (batch) or spacetime (flow)
11. L9b-11
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Concentrations in Series Reactions
A B C
k1 k2
-rA = k1CA
rB,net = k1CA – k2CB
k1
A A
1 A
A
0
0
A 1
A
dF dC
dV dV
C C e
k C k C
t
How does CA depend on t?
How does CB depend on t?
1 A
B
2 B
k C
dF
C
d
k
V
k1
A0
1
B
2 B
0 C e
k
dC
d
k C
V
t
k
B 1
1 A0 2 B
dC
k C e k C
d
t
t
Substitute
k
B 1
2 B 1 A0
dC
k C k C e
d
t
t
Use integrating
factor (reviewed
on Compass)
k2
B k k
2 1
1 A0
d C e
k C e
d
t
t
t
k k
1 2
B 1 A0
2 1
e e
C k C
k k
t t
0
V
t
C A0 A B
C C C C
12. L9b-12
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The reactor V (for a given 0) and t that maximizes CB occurs when dCB/dt=0
k k
1 A0
B 1 2
1 2
2 1
k C
dC
k e k e 0
d k k
t t
t
1
opt
1 2 2
k
1
ln
k k k
t
0
V
t
so opt 0 opt
V t
A
B
C
k1
A A0
C C e t
k k
1 2
B 1 A0
2 1
e e
C k C
k k
t t
C A0 A B
C C C C
topt
Reactions in Series: Cj & Yield
13. L9b-13
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
E E
D U1
D U D U
D T 1 1
A C
U1
A
e C C
A
a a
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
2000
T 0.5
D A C
r C
00e C
8
300
T
U A C
1
10
r C C
e
D
D U1
U1
r
S
r
Need to maximize SD/U1
2000 300
0.5 1 1 1
T
D U A C
1
800
S e C C
10
Plug in
numbers:
1700
0.5
T
D U A
1
S 80e C
A+C D desired
kD
A+C U1 undesired
kU1
To maximize the production of the desired product, the temperature should be
a) As high as possible (without decomposing the reactant or product)
b) Neither very high or very low
c) As low as possible (but not so low the rate = 0)
d) Doesn’t matter, T doesn’t affect the selectivity
e) Not enough info to answer the question
E
RT
k T Ae
E/R
ED > EU, so use higher T
14. L9b-14
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
E E
D U1
D U D U
D T 1 1
A C
U1
A
e C C
A
a a
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
2000
T 0.5
D A C
r C
00e C
8
300
T
U A C
1
10
r C C
e
D
D U1
U1
r
S
r
Need to maximize SD/U1
2000 300
0.5 1 1 1
T
D U A C
1
800
S e C C
10
Plug in
numbers:
1700
0.5
T
D U A
1
S 80e C
A+C D desired
kD
A+C U1 undesired
kU1
To maximize the production of the desired product, CA should be
a) As high as possible
b) Neither very high or very low
c) As low as possible
d) Doesn’t matter, CA doesn’t affect the selectivity
e) Not enough info to answer the question
E
RT
k T Ae
αD < αU1, so high CA favors undesired
product formation (keep CA low)
15. L9b-15
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
E E
D U1
D U D U
D T 1 1
A C
U1
A
e C C
A
a a
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
2000
0.5
T
D A C
r 800e C C
300
T
U A C
1
r 10e C C
D
D U1
U1
r
S
r
Need to maximize SD/U1
2000 300
0.5 1 1 1
T
D U A C
1
800
S e C C
10
Plug in
numbers:
1700
0.5
T
D U A
1
S 80e C
• Since ED>EU1, kD increases faster than kU1 as the temperature increases
• aD<aU1, keep CA low to maximize CD with respect to CU1
• rD and rU1 are 1st order in CC, so changing CC does not influence selectivity
A+C D desired
kD
A+C U1 undesired
kU1
• Operate at a high temperature to maximize CD with respect to CU1
• HOWEVER, high CC will increase the reaction rate and offset the slow
reaction rate that is caused by low CA (that’s a good thing)
What reactor should we use?
16. L9b-16
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
2000
0.5
T
D A C
r 800e C C
300
T
U A C
1
r 10e C C
Need to maximize SD/U1
1700
0.5
T
D U A
1
S 80e C
• aD<aU1, keep CA low to maximize CD with respect to CU1
• rD and rU1 are 1st order in CC, so changing CC does not influence selectivity
A+C D desired
kD
A+C U1 undesired
kU1
• ED>EU1, operate at a high temperature to maximize CD with respect to CU1
• HOWEVER, high CC will increase the reaction rate and offset the slow
reaction rate that is caused by low CA (that’s a good thing)
What reactor should we use?
←High CC
Semi-batch reactor
slowly feed A to large
amount of C
CA
PFR/PBR w/ side streams feeding low CA
A
C PFR
17. L9b-17
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
How does the selection of reactor/reactors scheme and conditions
change if D can react with C and form another undesired product?
2000
0.5
T
D A C
r 800e C C
300
T
U A C
1
r 10e C C
Need to maximize SD/U1 and SD/U2
1700
0.5
T
D U A
1
S 80e C
A+C D desired
kD
A+C U1 undesired
kU1
D+C U2 undesired
kU2
8000
6 T
U C D
2
r 10 e C C
D
D U2
U2
r
S
r
2000
0.5
T
A C
8000
6 T
C D
800e C C
10 e C C
6000
4 0.5 1
T
D U A D
2
S 8 10 e C C
• aD<aU1, keep CA low
• ED>EU1, operate at a high T
• High CC increases rxn rate &
offsets slow rxn from low CA
• Since ED<EU21, kD increases slower than kU2 as T increases ⇨ operate at low
T to maximize CD
• aD>aU2, keep CA high to maximize CD
• rD, rU1 & rU2 are all 1st order in CC, so changing CC does not influence
selectivity, but high CC will offset the rate decrease due to low CA
• Low CD reduces the production of U2
Conflicts with maximizing SD/U1!
Conflicts with maximizing SD/U1!
Conflicts with producing the product D!!!
18. L9b-18
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
A
C PFR, high T
Maximize SD/U1 & SD/U2
1700
0.5
T
D U A
1
S 80e C
A+C D desired
kD
A+C U1 undesired
kU1
D+C U2 undesired
kU2
6000
4 0.5 1
T
D U A D
2
S 8 10 e C C
• aD<aU1, keep CA low
• ED>EU1, operate at a high T
• Want to maximize CD
• ED<EU2, operate at low T
• aD>aU2, keep CA high
• Low CD reduces production of U2
• High CC increases rxn rate & offsets slow rate caused by low CA
Consider relative magnitude of SD/U1 and DD/U2 as a function of position in PFR
PFR w/ side streams feeding low CA
High T, CC is initially high, CA is low
→ high SD/U1
Initially CD=0 → rU2=0. Both gradually
increase down reactor
Initially high SD/U2 (because CD is low),
but SD/U2 gradually decreases down
reactor
• At some distance down the reactor,
significant amounts of D have formed
• SD/U2 becomes significant with respect
to SD/U1
• At this point, want low T, high CA &
low CC
PFR 2, low T
19. L9b-19
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
If a CSTR were used with CA = 1 mol/L and CD= 1 mol/L, at what
temperature should the reactor be operated?
2000
0.5
T
D A C
r 800e C C
300
T
U A C
1
r 10e C C
Need to maximize SD/(U1+U2)
A+C D desired
kD
A+C U1 undesired
kU1
D+C U2 undesired
kU2
8000
6 T
U C D
2
r 10 e C C
D
D U U
1 2
U U
1 2
r
S
r r
2000
0.5
T
A C
300 8000
6
T T
A C C D
800e C C
10e C C 10 e C C
2000
0.5
T
D 300 8000
6
U U
1 2 T T
800
e 1
10
S
10 10
e 1 e 1
10 10
CA=1
CD=1
2000
T
D 300 8000
U U 5
1 2 T T
80e
S
e 10 e
Plot SD/(U1+U2) vs temperature to find the temperature that maximizes SD/(U1+U2)
20. L9b-20
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
0
0.5
1
1.5
2
2.5
3
3.5
4
0 200 400 600 800 1000
Temperature (K)
If a CSTR were used with CA = 1 mol/L and CD= 1 mol/L, at what
temperature should the reactor be operated?
2000
0.5
T
D A C
r 800e C C
300
T
U A C
1
r 10e C C
Need to maximize SD/(U1+U2)
A+C D desired
kD
A+C U1 undesired
kU1
D+C U2 undesired
kU2
8000
6 T
U C D
2
r 10 e C C
2000
T
D 300 8000
U U 5
1 2 T T
80e
S
e 10 e
S
D/(U1+U2)
600K
21. L9b-21
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
A B
kB
B B
mol
r k 2
L min
A C
kC
C C A
r k C
1
C
k 1 min
What is the expression for the yield of B for a CSTR?
B
B
A0 A
F
Y
F F
(overall yield)
B 0 B
B B
A0 0 A 0 A0 A
C C
Y Y
C C C C
We know CA0 and CA when XA=0.9. How do we get CB?
In - Out + Gen. = Accum.
B
B0 B B
dN
F F r V
dt
0 0
B
B r V
F 0 B 0
B
C
V
r
B
B
C
r
t
B
B
C
mol
r 2
L min t
Use the mole balance on A to find t (at 90% conversion)
In - Out + Gen. = Accum.
A
A
A0 A
d
V
F
N
r
F
dt 0
A0 A A
0 0 V
C C r
0
A0 A A A0 A A
C C r C C
V
r
t A0 A
A
C C
r
t
B
mol
2 C
L min
t
22. L9b-22
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
A B
kB
B B
mol
r k 2
L min
A C
kC
C C A
r k C
1
C
k 1 min
B
A
B
A0
C
Y
C
C
A0 A
A
C C
r
t
What is –rA?
CA0 = 4 mol/L, and at
XA=0.9, CA= 0.4 mol/L
A B C
r r r
A B C A
r k k C
A A
mol 1
r 2 C
L min min
A
A
A
A0 A0
A C
C C
mol 1
r
2 C
L min m
C
in
t t
Plug -rA back into
expression for t
mol 1 mol
2 0.4
L min mi
mol
4
L
mol
0.
L
n
4
L
t
1.5 min
t
Residence time for XA = 0.9
B
mol
2
L min
C
t
B
1.5min
mol
4
mol
2
L
L
mi
mo
L
n
4
Y
l
0.
B
Y 0.83
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
B
A
B
A
0
r
C
C
Y
t
23. L9b-23
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
A B
kB
B B
mol
r k 2
L min
A C
kC
C C A
r k C
1
C
k 1 min
What is the expression for the yield of B for a PFR?
B
B
A0 A
F
Y
F F
(overall yield) B 0 B
B B
A0 0 A 0 A0 A
C C
Y Y
C C C C
Use the mass balance to get CB
B
B
dF
r
dV
B 0
B
dC
r
dV
B
B
dC
r
dt
B
dC mol
2
d L min
t
CB
B
C 0
B0
mol
dC 2 d
L min
t
t
B B0
mol
C C 2 0
L min
t
Use the mole balance on A to find t (at 90% conversion)
A
A
dF
r
dV
A 0
A
dC
r
dV
A
A
dC
r
dt
A B C A
r k k C
A A
mol 1
r 2 C
L min min
A
A
dC mol 1
2 C
d L min min
t
CA
A
A
C 0
A0
dC 1
d
2mol L C min
t
t
A
A
dC mol 1
2 C
d L min
t
B
mol
mi
C 2
L n
t
0
24. L9b-24
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
A B
kB
B B
mol
r k 2
L min
A C
kC
C C A
r k C
1
C
k 1 min
B
B
A0 A
C
Y
C C
B
mol
in
C 2
L m
t
Use mole balance on A to find t (at XA = 0.9)
A B C A
r k k C
A A
mol 1
r 2 C
L min min
CA0 = 4 mol/L
CA = 0.4 mol/L
CA
A
C 0
A0 A
dC 1
d
mol min
2 C
L
t
t
A0
A
mol
2
1
L
ln 0
m
C
ol min
2
L
C
t
mol
2
1
L
ln
mo mol
0.
mol
l mi
L
n
2
L L
4
4
t
0.92 min t
B B
A0 A0
A
B
A
B
B
mol
C C
0.4
L
0
Y Y Y 0
.92m
m
i
ol
n
mol
C C
4
.5
L
2
r L min
C
1
t
Yield was better
in the CSTR, but
the residence
time was longer