TEMPERATURE AND PRESSURE EFFECTS

•Thermodynamics of Chemical Reactions

•Non-isothermal Reactors
 TEMPERATURE AND PRESSURE EFFECTS

 In the search for favorable conditions for reaction we

have considered
 How reactor type and size influence the extent of conversion
and distribution of products.
 The reaction temperature and pressure also influence the
progress of reactions, and it is the role of these variables that we
now consider.
 TEMPERATURE AND PRESSURE EFFECTS
 First, we must find how equilibrium composition, rate of
reaction, and product distribution are affected by changes in
operating temperatures and pressures. This will allow us to
determine the optimum temperature progression.
 Second, chemical reactions are usually accompanied by heat
effects, and we must know how these will change the
temperature of the reacting mixture.
With this information we are able to propose a number of favorable reactor
and heat exchange systems those which closely approach the optimum
conditions.
Finally, economic considerations will select one of these favorable systems
as the best.
 SINGLE REACTIONS

 Single reactions, we are concerned with conversion level and

reactor stability. Questions of product distribution do not occur.
 Thermodynamics gives two important pieces of information;
heat liberated or absorbed for a given extent of reaction
maximum possible conversion.
 NON-ISOTHERMAL REACTORS
 Most chemical reactions are greatly affected by temperature.
 There are some reactions at isothermal condition, however, industrial
reactors often operate under non-isothermal condition. This is because
chemical reactions strongly depend on temperature, either absorbing (i.e.,
endothermic) or generating (i.e., exothermic) a large amount of heat.
 In non-isothermal conditions, the temperature varies from point to point, as
does the composition.
 In an ideal gas mixture, the concentration of a component depends on the
temperature (i.e. Ci= pi/RT), and the reaction rate is greatly affected by the
temperature through the rate coefficient (k = koe–E/RT).
 Either a heating/ cooling coil or an external heat exchanger can affect the
temperature.
 Some reaction rates double for a rise in temperature of 10–15oC, and
temperature affects the properties of the reaction mixture such as density,
specific heat, thermal conductivity and viscosity, enthalpy, as well as mixing
patterns and the energy for efficient mixing.
 CONTD. NON-ISOTHERMAL REACTORS

 Some reactors operate under adiabatic conditions, where there is

negligible heat input to the reactor.
 The design of non-isothermal reactors involves the simultaneous
solution of both mass and energy balances. In some reactors, such
as the packed bed or fluidized catalytic cracking unit (FCCU),
momentum balance is considered with both the mass and energy
balances.
 TEMPERATURE AND PRESSURE EFFECTS
 The heat liberated or absorbed during reaction at temperature T2
depends on
The nature of the reacting system
The amount of material reacting
The temperature and pressure of the reacting system

 It is calculated from the heat of reaction ΔHr, for the reaction in question.
When this is not known, it can in most cases be calculated from known
and tabulated thermochemical data on heats of formation ΔHf, or heats
of combustion ΔHc, of the reacting materials.
 These are tabulated at some standard temperature, T1, usually 25°C.
 GENERAL ENERGY BALANCE OF THE REACTIONS
 Isothermal conditions are most useful for the measurement of kinetic
data, real reactor operation is normally non isothermal.
 Within the limits of heat exchange, the reactor can operate
isothermally (maximum Heat exchange)or adiabatically (no heat
exchange)
For a closed reactor (e.g., a batch reactor), the potential and kinetic energy terms
In Equation are not relevant. Additionally, Ws ~0 for most cases (including the
Work input from the stirring impellers).
 TEMPERATURE AND PRESSURE EFFECTS

 By convention we define the heat of reaction at temperature

T as the heat transferred to the reacting system from the
surroundings when a moles of A disappear to produce r
moles of R and s moles of S with the system measured at the
same temperature and pressure before and after the change.
HEATS OF REACTION AND TEMPERATURE
 HEATS OF REACTION AND TEMPERATURE
At 25°C the reaction is strongly exothermic. But this reaction needs to be
run at at 1025OC. What is the ΔHr at that temperature, and is the reaction
still exothermic at that temperature?
 THERMODYNAMICS OF CHEMICAL REACTIONS
 The two main principles involved in establishing conditions for
performing a reaction are :
 Chemical kinetics
 Thermodynamics
Chemical kinetics is the study of rate and mechanism by which
one chemical species is converted to another. The rate is the
mass in moles of a product produced or reactant consumed per
unit time. The mechanism is the sequence of individual chemical
reaction whose overall result yields the observed reaction.
Thermodynamics is a fundamental of engineering having many
applications to chemical reactor design.
 Some chemical reactions are reversible and, no matter how fast a reaction
takes place, it cannot proceed beyond the point of chemical equilibrium in the
reaction mixture at the specified temperature and pressure.
 Thus, for any given conditions, the principle of chemical equilibrium
expressed as the equilibrium constant, K, determines how far the reaction can
proceed if adequate time is allowed for equilibrium to be attained.
 If the equilibrium constant K is very large, for all practical purposes the
reaction is irreversible. In the case where a reaction is irreversible, it is
unnecessary to calculate the equilibrium constant and check the position of
equilibrium when high conversions are needed.
 Both the principles of chemical reaction kinetics and thermodynamic
equilibrium are considered in choosing process conditions. Any complete rate
equation for a reversible reaction involves the equilibrium constant.
 The equilibrium constant of the reaction depends only on the temperature and
is used to determine the limit to which the reaction can proceed under the
conditions of temperatures, pressure, and reactant compositions that appear
most suitable
A 600 L tank reactor gives 75% conversion for a first order irreversible reaction. However, the
paddle turbine motor is underpowered and so the tank is not well stirred. In fact, a pulse-tracer
experiment to determine the residence time indicates that approximately 400 L of the tank may be
considered as a dead volume that does not interact appreciably with the input or output streams. If
you replace the stirrer with one sufficiently strong to obtain complete mixing throughout the
reactor volume, what conversion will be obtained?
 OPERATING TEMPERATURE, REACTION
TYPES, AND TEMPERATURE
The main factors affecting operating temperature are:
• Cost of maintaining the operating temperature (energy).
• Decomposition temperature of reactants and products.
• Possibility of operating at high pressures in the case of gas-phase
reactions.
• Effect of temperature and pressure on equilibrium in the case of
reversible reactions.
• Effect of temperature on the rate constants associated with each
elementary step in a multiple reaction.
• Properties of materials of construction.
 In irreversible reactions and in accordance with the
Arrhenius equation [k = ko exp (–E/RT)], it is possible to
operate at the highest possible temperature.
 In reversible reactions
The equilibrium constant K is related to the Gibbs standard
free energy change ∆GoT by
 Thermodynamics allows us to predict how chemical reactions
will change as a function of temperature and how changes in
the structure of molecules might affect the equilibrium
properties of a population of these molecules.
 ∆G— Change in free energy between reactants and products; this measures the
ability of the system to do work. Reactions with negative ∆G’s proceed spontaneously
and can be used to do work. Reactions with positive ∆G’s require an input of energy
for the reaction to proceed.
 ∆H— Change in enthalpy between reactants and products; this is the heat given off or
absorbed by a reaction at constant pressure. Reactions that absorb heat have positive
∆H’s and those that produce heat have negative ∆H’s.
 ∆S— Change in entropy between reactants and products; entropy is a statistical
measure of the number of states or accessible conformations. A positive ∆S is an
indication that the disorder or number of accessible of the system is increasing and
vice versa.
 ∆Cp— Change in heat capacity between reactants and products; when a solution of
molecules is heated, some of the thermal energy increases the kinetic energy of
molecules, increasing the temperature, whereas some of the energy results in faster
vibrations or rotation of the molecule. Heat capacity measures how much energy can
be stored by a molecule in these internal vibrations or rotations.
 CHEMICAL EQUILIBRIUM
 Consider a single homogeneous phase of one component of unchanging
composition. If it undergoes an isothermal reversible change and does work,
then from the first law of thermodynamics,

Now consider a homogeneous phase containing different substances or

components. Its phase contains

U = U(S, V, n1, . . . ni. . . nk)

 Variable composition

Constant composition
 CRITERIA FOR EQUILIBRIUM
 For a reversible change, dS = q/T. If we consider a closed system
undergoing a reversible change at dT = 0, dP = 0, then the only
form of work is pdV. From the first law,
 REACTION EQUILIBRIUM
Considering any generalized reversible chemical reaction, such that at
dT = 0 and dP = 0:

The chemical potential as a function of composition can be

expressed as
 GIBBS FREE ENERGY
 A criterion for equilibrium is that the total free energy
(Gibbs free energy, Gr) of the reaction is at a minimum
• If we add more reactant or
more product, the reaction
will proceed spontaneously
(without external help) as
long as the value for Gr
decreases.
• Thus, a reaction in the
direction of decreasing Gr is
spontaneous. A reaction in
the direction of increasing
Gr is not spontaneous, and
will not occur in a closed
system.
 where ai is the activity of i. Introducing into the change in the Gibbs statement,
and separating the standard state terms on the right side, gives
 IDEAL GAS MIXTURES
For an ideal gas mixture, ai = pi , which is expressed as

where p is the partial pressure. This is related to the total pressure as

the total pressure, PT, multiplied by the mole fraction of the component
in the mixture.
 REAL GASES—IDEAL GASEOUS SOLUTION
 In many cases, the assumption of ideal gases is not justified
and it will be essential to determine fugacity. An example of
such reactions is ammonia synthesis where the operating
pressure may be as high as 1,500 atm.

The fugacity in Equation is that of the component in the equilibrium mixture.

However, fugacity of only the pure component is usually known. It is also necessary
to know something about how the fugacity depends on the composition
 FUGACITY
 In chemical thermodynamics, the fugacity (fi) of a real gas is an
effective pressure which replaces the true mechanical pressure in
accurate chemical equilibrium calculations. It is equal to the
pressure of an ideal gas which has the same chemical potential as
the real gas.
 For example, nitrogen gas (N2) at 0°C and a pressure of 100 atm has
a fugacity of 97.03 atm. This means that the chemical potential of real
nitrogen at a pressure of 100 atm has the value which ideal nitrogen
would have at a pressure of 97.03 atm.
 In this case, it is possible to relate the fugacity, f, at equilibrium to the fugacity of the
pure component, f′, at the same pressure and temperature by
 The f′A, f′B, f′C, and f′D are determined for the pure gas at the pressure of the mixture and depend
on the pressure and the temperature.
 For an ideal gas reaction mixture, Kf= Kp

 The steps in the process are

where ∆Go is the difference between the free energies of the products and reactants when
each is in a given standard state
2. Determine the equilibrium constant Kf
3. Evaluate Ky
PRESSURE AND GAS PHASE REVERSIBLE REACTIONS
 Consider the reversible reaction of the form

 The activity ai of component is

The equilibrium constant K in terms of the fugacity is expressed as

Standard states at given temperature are commonly chosen as follows:
Gases-pure component at one atmosphere, at which pressure ideal gas
behavior is closely approximated.
Solid-pure solid component at unit pressure
Liquid-pure liquid at its vapor pressure
Solute in liquid- 1 molar solution; or at such dilute concentrations that the
activity is unity

For gas reactions standard states are usually chosen at a pressure of 1

atm. At this low pressure the deviation from ideality invariably is small;
hence fugacity and pressure are identical and fo = po = 1 atm
 From Equation, the larger the value for K, the higher the yield of the
product species at equilibrium. Also, if ∆Go is negative, the values of K
will be positive, and results in a large equilibrium conversion of
reactants into products.
Rules
 to determine whether a reaction is thermodynamically promising at a
given temperature:
 Van’t Hoff Equation
 The van't Hoff equation provides information about the temperature dependence of the
equilibrium constant.
 The van't Hoff equation may be derived from the Gibbs-Helmholtz equation, which gives
the temperature dependence of the Gibbs free energy.
 For the standard Gibbs free energy, the Gibbs-Helmholtz equation is
VAN’T HOFF EQUATION
 For endothermic reactions, ∆HR has a positive numerical
value if T2> T1 and k2> k1. The equilibrium constant K,
therefore, increases as the temperature increases. In this
case, the reactor is operated at the highest possible
temperature.
 For exothermic reactions, ∆HR has a negative numerical
value if T2> T1 and k2< k1. The equilibrium constant K
decreases as the temperature increases. Here, the
temperature is kept high so that the rate of reaction is
high, and then decreased as equilibrium is approached.
1. The thermodynamic equilibrium constant is unaffected by the
pressure of the system, by the presence or absence of inerts, or by
the kinetics of the reaction, but is affected by the temperature of the
system.
2. Though the thermodynamic equilibrium constant is unaffected by
pressure or inerts, the equilibrium concentration of materials and
equilibrium conversion of reactants can be influenced by these
variables.
3. K >> 1 indicates that practically complete conversion may be possible
and that the reaction can be considered to be irreversible. K << 1
indicates that reaction will not proceed to any appreciable extent.
4. For an increase in temperature, equilibrium conversion rises for
endothermic reactions and drops for exothermic reactions.
5. For an increase in pressure in gas reactions, conversion rises when
the number of moles decreases with reaction; conversion drops when the
number of moles increases with reaction.
6. A decrease in inerts for all reactions acts in the way that an increase in
pressure acts for gas reactions.
 General Graphical Design Procedure
Temperature, composition, and reaction rate are uniquely related for any single
homogeneous reaction, and this may be represented graphically in one of three ways
 General Graphical Design Procedure
The size of reactor required for a given duty and for a given
temperature progression is found as follows:
1. Draw the reaction path on the XA versus T plot. This is the operating
line for the operation.
2. Find the rates at various XA along this path.
3. Plot the l/(-rA) versus XA curve for this path.
4. Find the area under this curve. This gives V/FAo
Three major questions in reactor design are addressed.
What is the optimal temperature for a reaction?
How can this temperature be achieved or at least approximated in practice?
How can results from the laboratory or pilot plant be scaled up?
For non-isothermal reactors, where the temperature varies from point to point
within the reactor, the temperature dependence directly enters the design
calculations.
 Optimum Temperature Progression
The optimum temperature progression is that progression which minimizes V/FA0 for a
given conversion of reactant.
This optimum may be an isothermal or it may be a changing temperature: in time for a
batch reactor, along the length of a plug flow reactor, or from stage to stage for a series of
mixed flow reactors.
It is important to know this progression because it is the ideal which we try to approach
with a real system.
 It also allows us to estimate how far any real system departs from this ideal. The
optimum temperature progression in any type of reactor is as follows:
 At any composition, it will always be at the temperature where the rate is a maximum.
The locus of maximum rates is found by examining the r (T, C) curves.
 For irreversible reactions, the rate always increases with temperature at any
composition, so the highest rate occurs at the highest allowable temperature. This
temperature is set by the materials of construction or by the possible increasing
importance of side reactions.
For endothermic reactions a rise in temperature increases both the equilibrium
conversion and the rate of reaction. Thus, as with irreversible reactions, the highest
allowable temperature should be used.
For exothermic reversible reactions the situation is different, for here two opposing
factors are at work when the temperature is raised the rate of forward reaction speeds
up but the maximum attainable conversion decreases. Thus, in general, a reversible
exothermic reaction starts at a high temperature which decreases as conversion
rises.
 HEAT EFFECTS
 When the heat absorbed or released by reaction can markedly change
the temperature of the reacting fluid, this factor must be accounted for
in design.
 Heat and Mass Transfer
 If the reaction is exothermic and if heat transfer is unable to remove all
of the liberated heat, then the temperature of the reacting fluid will rise
as conversion rises. By similar arguments, for endothermic reactions
the fluid cools as conversion rises.
 ADIABATIC OPERATIONS
 Consider either a mixed flow reactor, a plug flow reactor, or a
section of plug flow reactor, in which the conversion is XA, as
shown in Figure.
 The latter form of the equation simply states that the heat released
by reaction just balances the heat necessary to raise the reactants
from TI to T2.

This figure illustrates the shape of the energy balance curve for both endothermic and
exothermic reactions for both mixed flow and plug flow reactors.
adiabatic operating lines for the reactor
The size of reactor needed for a given duty is found as follows,
For plug flow tabulate the rate for various XA along this adiabatic operating
line, prepare the l/(-rA) versus XA plot and integrate.
For mixed flow simply use the rate at the conditions within the reactor.
The best adiabatic operations of a single plug flow reactor are found by shifting
the operating line (changing the inlet temperature) to where the rates have the
highest mean value.
For endothermic operations this means starting at the highest allowable
temperature.
For exothermic reactions this means straddling the locus of maximum rates
 The best reactor type, that which minimizes V/FA0, is found directly
from this XA versus T graph.
 If the rate progressively decreases with conversion, then use plug
flow. This is the case for endothermic reactions .
 For exothermic reactions that have a large temperature rise during
reaction, the rate rises from a very low value to a maximum at
some intermediate XA, then falls. This behavior is characteristic of
autocatalytic reactions, thus recycle operations are best.
NON ADIABATIC REACTIONS
Construction of the rate-conversion-temperature chart from
kinetic data
starting with an R-free solution, kinetic experiments in a batch reactor give 58.1% conversion in 1
min at 65OC, 60% conversion in 10 min at 25OC. Assuming reversible first-order kinetics, find the
rate expression for this reaction and prepare the conversion-temperature chart with reaction rate as
parameter.
For a reversible first-order reaction, the performance equation for a batch
reactor is
 PERFORMANCE FOR THE OPTIMAL
TEMPERATURE PROGRESSION
 Using the optimal temperature progression in a plug flow
reactor for the reaction Let the maximum allowable operating
temperature be 95°C
 On the conversion-temperature graph draw the locus of maximum
rates.
 OPTIMUM MIXED FLOW REACTOR PERFORMANCE
(ADIABATIC)
A concentrated aqueous A-solution of the previous examples (C0 = 4 mol/liter, FA0 =
1000 mol/min) is to be 80% converted in a mixed flow reactor.
(a) What size of reactor is needed?
(b) What is the heat duty if feed enters at 25°C and product is to be withdrawn
at this temperature?
Following Fig. the mixed flow operating point
should be located where the locus of optima
intersects the 80% conversion line (point C
on Fig. )
Here the reaction rate has the value
 If a reactor is operated at non isothermal or adiabatic conditions then the
material balance equation must be written with the temperature, T, as a
variable. For example with the PFR, the material balance becomes:

Since the reaction rate expression now contains the independent variable T, the
material balance cannot be solved alone. The solution of the material balance
equation is only possible by the simultaneous solution of the energy balance.
 Show that the general energy balance, Equation, can simplify to an
appropriate form for either adiabatic or isothermal reactor operation

integrated as

If the reactor is operated at isothermal conditions, then no sensible heat effects

occur and
Equation becomes
 IDEAL BATCH REACTOR

(1 )How can one relate the temperature of the reacting system to the degree of
conversion that has been accomplished?
(2 )How does this temperature influence the subsequent performance of the system? In
responding to these questions the chemical engineer must use two basic tools
--------the material balance
--------the energy balance.

Heat input=change in sensible heat +energy consumed

by reaction
 IDEAL BATCH REACTOR
 In order to be able to evaluate the integrals in equations and one must know not only
the temperature dependence of the rate terms but also the relationship between the
fraction conversion and the temperature of the system
With fA= 0 and T 300 K at t=0
 The hydration of 1-hexene to 2-hexanol is accomplished in an adiabatic batch
reactor: The reactor is charged with 1000kg of a 10wt.%H2SO4 solution and
200kg of 1-hexane at 300K. Assuming that the heat capacities for the reactants
and products do not vary with temperature, the heat of reaction does not vary
with temperature, and the presence of H2SO4 is ignored in the calculation of
the heat capacity, determine the time required to achieve 50 percent
conversion and the reactor temperature at that point.
 NON-ISOTHERMAL PLUG FLOW REACTOR
 Consider a PFR operating at non- isothermal conditions.
 To describe the reactor performance, the material balance, must be
solved simultaneously with the energy balance, Equation.
 Assuming that the PFR is a tubular reactor of constant cross-sectional
area and that T and C do not vary over the radial direction of the tube,
the heat transfer rate Q can be written for a differential section of
reactor volume as
 NON-ISOTHERMAL PLUG FLOW REACTOR
 Show that the general energy balance Equation, can simplify to an
appropriate form for either adiabatic or isothermal reactor operation.

If TO is the temperature at the reactor entrance and the conversion is zero at this
point, then Equation can be written for any point in the PFR as:
Butadiene will react with ethylene in the gas Phase at temperatures above 500°C. If an equimolar
mixture of butadiene and ethylene at 450°C and 1atm is fed to a reactor, determine the space times
required to convert 10% of the butadiene to cyclohexene for isothermal and for adiabatic modes
of operation.
NON-ISOTHERMAL PLUG FLOW REACTOR
 NON-ISOTHERMAL PLUG FLOW REACTOR
 A PFR of dimensions L=2 m and d=0.2m is accomplishing a homogeneous
reaction. The inlet concentration of the limiting reactant is C0=0.3kmol/m3 and the
inlet temperature is 700K. Other data are:-
 ΔHr 104kJ/kmol,
 Cp= 1kJ/(kg-K),
 E=lOOkJ/mol,
 p 1.2kg/m3

 u=3m/s,

 k =5 s-I.
Calculate the dimensionless concentration (y =C/C0) and temperature (T/T0)
profiles for adiabatic (U =0) and non isothermal(U=70J/(m2-s-K)) operations.
THERMOCHEMISTRY FOR NONISOTHERMAL REACTOR DESIGN
FA0 FA XA = 0.7

Consider an exothermic, liquid-phase reaction operated adiabatically in a PFR (adiabatic

operation- temperature increases down length of PFR):
k
A B  E  1 1 
dXA rA    
E R T T
Mole balance: 
k  Ae RT k  k1 exp   1  
dV FA0
Arrhenius Equation
E 1 1 
dXA kCA0 (1 XA ) dXA     (1 X )
R T T A
Rate law: rA  kCA    k1 exp  1 
dV CA0u0 dV u0

Stoichiometry: FA  CA v0 Need relationships: X T V

u  u0 The energy balance provides this
CA  CA0 (1 XA ) relationship
 TERMS IN ENERGY BALANCE
dEˆ sys n n

 Q 
 W   FiEi in   FiEi out
dt i1 i1
Rate of accum of Rate of energy added energy leaving syst
Heat -
energy in = - work done + to syst by by mass flow out
in
system by syst mass flow in
n n
    FPV   FPV
W  P : pressure WS: shaft work
i i in i i out  Ws
i1 i1 Vi  specific volume
Flow work
Ei  Ui Internal energy is major contributor to energy term
dEˆ sys n n
  
 Q - Ws   Fi (Ui  PVi ) in -  Fi (Ui  PVi ) out
dt i1 i1
Hi  Ui  PVi
n n
Steady state:  W
0Q    F H   FH
s i0 i0 i i
i1 i1
Energy &
Accum of energy =0= Heat - shaft + work - Energy & work
in system in work removed by flow out
added by
flow in
 RELATE T TO CONVERSION
n n
Steady state:  W
0Q    F H   FH
s i0 i0 i i
i1 i1
F
Fi  Fi0   iFA0 X A  Fi  FA0  i   i X A  where i  i0
FA0
dEˆ sys n n
If XA0=0, then:  
 Q  Ws   Hi0 iFA0   HiFA0  i   i XA 
dt i1 i1
Multipl dEsys  n n
   H  F   H F   H F  X 
QW s i0 i A0 i A0 i i A0 i A
y out: dt i1 i1

Total energy dEˆ sys n n

 
balance (TEB)  dt  Q  Ws  FA0  Hi0  Hi  i    iHi FA0 X A
i1 i1 i
0 at steady state DHRX  T   heat of reaction
n n
 W
0Q   F  H  H     DH  T F X
s A0 i0 i i RX A0 A
i1 i1
Energy & Energy & work
Accum of = Heat - shaft + work added - removed by
energy in in work
by flow in flow out
system
 Q IN CSTR
CSTR with a heat exchanger, perfectly mixed inside and outside of reactor

FA0

Ta
T, X Ta

  UA(T  T)
Q a
T, X

The heat flow to the reactor is in terms of:

• Overall heat-transfer coefficient, U
• Heat-exchange area, A
•Difference between the ambient temperature in the heat jacket, Ta,
and rxn temperature, T
 TUBULAR REACTORS (PFR/PBR)
Integrate the heat flux equation along the length of the
reactor to obtain the total heat added to the reactor :

   A U(T  T)dA   V Ua(T  T)dV

Q a a
a: heat-exchange area per unit volume of reactor
A
a
V


dQ
 Ua(Ta - T)
dV Heat transfer to a perfectly mixed PFR in a jacket

For a jacketed PBR (perfectly mixed in jacket):

1 dQ dQ  Ua
  (T  T) Heat transfer to a PBR
b dV dW b a
 NONISOTHERMAL REACTOR DESIGN
Goal: Use TEB to design nonisothermal steady-state reactors

Steady–state total energy balance (TEB):

dEˆ sys n n
 W
0Q   F   H  H     DH  T F X
s A0 i0 i i RX A0 A
dt i1 i1
Needs to be “simplified” before we can apply it to reactor design
At a particular temperature:Hi  Hi (TR )  TT CpidT  no phase change 
R
T T
Hi  Hi0  Hi (TR )  TT CpidT   Hi (TR )  Ti0 CpidT   Ti0 CpidT
 R   R 
(Hi – Hi0) = - (Hi – Hi0) dEˆ sys n T
Substitute   
 Q  Ws  FA0   iCp,idT  DHRX  T  FA0 X A
dt i1Ti0

For a SS nonisotherm 0  Q n T
 W  F    C dT  DH  T  F X
s A0 i p,i RX A0 A
flow reactor: i1Ti0
Constant (average) n
 
0  Q  Ws  FA0  iCp,i  T  Ti0   DHRX (T)FA0 X A
heat capacities : i1
 RELATING DHRX(T) TO DH◦RX(TR) AND OVERALL
CHANGE IN HEAT CAPACITY
n T
 W
0Q   F    C dT  DH  T  F X
s A0 i p,i RX A0 A
i1Ti0
n n
 T  
DHRX  T   DHRX (TR )  TT DCP dT
DHRX  T     iHi (TR )  TR    iCpi dT R
i1 i1 
n
overall heat capacity: DCP    iCpi
i1 n
overall heat of reaction at reference temp: DHRX  TR     iHi  TR 
i1
n T
 W
0Q s A0 i p,i RX R
i1Ti0
TR 
  F    C dT  DH ( T )   T DC dT F X
P A0 A 
Only considering constant (average) heat capacities:
n
  F   C  T  T    DH (T )  DĈ  T  T   F X
 W
0Q s A0 i p,i i0  RX R P R  A0 A
i1
T = reaction temp Ti0 = initial (feed) temp TR= reference temp
 SOLVING TEB FOR CONVERSION
Always start with this TEB:
n
0Q   F   C  T  T    DH (T )  DC
 W ˆ  T  T  F X
s A0 i p,i i0  RX R P R  A0 A
i1

Rearrange to isolate terms with XA on one side of eq:

n
 FA0  iCp,i  T  Ti0   W     DH (T )  DC
 Q ˆ  T  T  F X
s  RX R P R  A0 A
i1

Solve for XA: n


 Q
FA0  iCp,i  T  Ti0   Ws
 i1  XA
  DHRX (TR )  DC
ˆ
P  T  TR  FA0


Plug in Q for the specific type of reactor, and solve this eq simultaneously
with design equation
 n
0Q W  F   C  T  T    DH (T )  DC
ˆ  T  T  F X
s A0 i p,i i0  RX R P R  A0 A
i1
Rearrange:
n
 FA0  iCp,i  T  Ti0   Q    DH (T )  DC
 W ˆ  T  T  F X
s  RX R P R  A0 A
i1

Which term in this equation is zero because we’re solving for an adiabatic
reaction?
a) dEsys/dt d) FA0
b) Q  e) None of the above
c) Ẇ
When the reaction is adiabatic (Q=0):
n
FA0  iCp,i  T  Ti0   Q    DH (T )  DC
 W ˆ  T  T  F X
s  RX R P R  A0 A
i1
n
   DH (T )  DC
 FA0  iCp,i  T  Ti0   0  W ˆ  T  T  F X
s  RX R P R  A0 A
i1
 SOLVING TEB FOR XA FOR AN ADIABATIC RXN
n
0Q W  F   C  T  T    DH (T )  DC
ˆ  T  T  F X
s A0 i p,i i0  RX R P R  A0 A
i1
Rearrange:
n
 FA0  iCp,i  T  Ti0   Q    DH (T )  DC
 W ˆ  T  T  F X
s  RX R P R  A0 A
i1
When shaft work can be neglected (Ẇ=0) and the reaction is adiabatic (Q=0):
n
 FA0  iCp,i  T  Ti0   0  0   DHRX (TR )  DC
ˆ  T  T  F X
P R  A0 A
i1

n
Solve for XA: FA0  iCp,i  T  Ti0 
 i1  XA
  DHRX (TR )  DC
ˆ
P  T  TR  FA0

n Solve this eq simultaneously
 iCp,i  T  Ti0  with design equation
 i1  XA Design eqs do not change,
  DHRX (TR )  DC
ˆP  T  TR  except k will be a function of T

T = reaction temp Ti0 = initial (feed) temperature TR= reference temp
 NON-ISOTHERMAL ADIABATIC OPERATION
Constant or mean heat capacities

 ( T  T )  F X  DH ( T )  ˆ
n
 
Q  Ws  FA 0  iC DCp( T  TR )  0
pi i0 A0  RX R 
i1

For a system with no shaft work (Ws (  0 ):

  0 ) & adiabatic operationQ

n
 (T  T )
 iCpi i0
Q  0
i1
X
 ˆ (T  T ) Xenergy balance W  0
  DHRX (TR )  DCp R 
s


CSTR, PFR, PBR, Batch

ˆ 
Usually, DCp( T  TR )  DHRX( TR ) Temperature
Adiabatic exothermic reactions
 FA0 X
Design equation (From mass balance) :V 
rA
Energy balance: Coupled
n
Q W F  C
s A0
   ˆ 
i pi (T  Ti0 )  FA0 X  DHRX (TR )  DCp (T  TR )  0
i1
With the exception of processes involving highly viscous materials,
the work done by the stirrer can be neglected (i.e. Ws  0 )
With heat exchanger:Q   UA(T  T)
a
n
 (T  T )  F X  DH (T )  DC
UA(Ta  T)  0  FA0  iC ˆ (T  T )  0
pi i0 A0  RX R p R 
i1
n
 (T  T )  F X  DH (T )  DC
 UA(Ta  T)  FA0  iC ˆ (T  T )
pi i0 A0  RX R p R 
i 1
UA(Ta  T) n   ˆ (T  T )
   iCpi (T  Ti0 )  X  DHRX (TR )  DCp R 
FA0 i1


UA(Ta  T) n
 ˆ ( T  T )    C
  X  DHRX (TR )  DCp R  i pi (T  Ti0 )
FA0  i1
Case 1: Given FA0, CA0, A, E, Cpi, H°I, and XA, calculate T & V

a) Solve TEB for T at the exit (Texit = Tinside reactor)

b) Calculate k = Ae-E/RT where T was calculated in step a
c) Plug the k calculated in step b into the design equation to calculate VCSTR

Case 2: Given FA0, CA0, A, E, Cpi, H°I, and V, calculate T & XA

a) Solve TEB for T as a function of XA
b) Solve CSTR design equation for XA as a function of T (plug in k = Ae-E/RT )
c) Plot XA,EB vs T & XA,MB vs T on the same graph. The intersection of these 2
lines is the conditions (T and XA) that satisfies the energy & mass
balance XA,EB = conversion determined from the TEB equation
XA,MB = conversion determined using the design equation
XA,exit
XA,MB Intersection is T and XA that
XA satisfies both equations
XA,EB

T Texit
FA0 FA

XA
T

distance
Negligible shaft work (Ẇ S=0) and adiabatic (Q=0)

a) Use TEB to construct a table of T as a function of XA

b) Use k = Ae-E/RT to obtain k as a function of XA
c) Use stoichiometry to obtain –rA as a function of XA
d) Calculate: XA
dX A
V  FA0 
XA0 rA  X A ,T 
A first order reaction A(l) → B(l) is to be carried out adiabatically in a CSTR. Given A,
E, T0, u0, CA0, and FA0, find the reactor volume that produces a conversion XA. The heat
capacities of A & B are approximately equal, & Ẇ S=0.
a) Solve TEB for T:
n
0  Q  Ws  FA0  iCp,i  T  Ti0    DHRX (TR )  DCP  T  TR   FA0 X A
 
 
n 0 0 i1
 FA0  iCp,i  T  Ti0     DHRX (TR )  DCP  T  TR   FA0 X A
i1
 
n
  iCp,i  T  Ti0     DHRX (TR )  DCP  T  TR   X A Multiply out
i1
 
n
  iCp,iT  iCp,iTi0   DHRX (TR )X A  DCP TX A  DCPTR X A Isolate T
i 1
n n
  iCp,iT  DCPTX A   DHRX (TR )X A  DCP TR X A   iCp,iTi0
i 1 i1
 n 
Factor out T  T   iCp,i  DCP X A   DHRX (TR )X A  DCPTR X A  Cp,A TA0
 i1 
Temp n Plug in values (∆Cp,
when 
 DH RX (TR )X A  DCP TR X A   iCp,iTi0 ∆H°RX(TR), Cp,i) given
specified T  i1
n
in problem statement
XA is  
  iCp,i  DCP X A  (look them up if
reached  i1  necessary) & solve
A first order reaction A(l) → B(l) is to be carried out adiabatically in a CSTR.
Given A, E, T0, u0, CA0, and FA0, find the reactor volume that produces a
conversion XA. The heat capacities of A & B are approximately equal, & ẆS=0.
a) Solve TEB for T of reaction when the specified XA is reached:
n
DHRX (TR )X A  DCPTR X A   iCp,iTi0
 T i1
n 
   C
i p,i  DC X
P A
 i1 
b) Calculate k = Ae-E/RT where T was calculated in step
(a)
Look up E in a thermo book
c) Plug the k calculated for the reaction’s temperature when the specified
XA is reached (in step b) into the design equation to calculate VCSTR

FA0 XA F X FA0 XA CA0u0 XA

V  V  A0 A  V  V
rA kCA kC A0 1  XA  kCA0 1  X A 

u0 X A
V
k 1  X A 
 Now, the first order reaction A(l) → B(l) is carried out adiabatically with
and inlet temp of 300 K, CPA = 50 cal/mol∙K, and the heat of reaction = -
20,000 cal/mol. Assume ẆS=0. The energy balance is:
n 0 0
 Q
FA0  iCp,i  T  Ti0   W 
s
XA  i1 DHRX  T   DHRX (TR )  DC
ˆ T  T 
P R
 ˆ  T  T  F
  DH RX (TR )  DC P R  A0

n
 T  T 
 iC n
pi 0  iCpi  1 CpA CP  T  T0 
 XEB  i1 i1 XEB  A
DHRX  T  DHRX  T 
From thermodynamics
XEB 50  T  300 
 XEB 
20000

From energy balance

T
The irreversible, elementary liquid-phase reaction 2A → B is carried out adiabatically in a flow reactor with
ẆS=0 and without a pressure drop. The feed contains equal molar amounts of A and an inert liquid (I). The feed
enters the reactor at 294 K with u0 = 5 dm3/s and CA0= 1 mol/dm3. What would be the temperature inside of a
steady-state CSTR that achieved XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/mol•K CpB= 30 cal/mol•K CpI = 15 cal/mol•K ∆HA°(TR) = -20 kcal/mol
∆ HB°(TR) = -50 kcal/mol ∆HI°(TR) = -15 kcal/mol
k = 0.02 dm3/mol•s at 350 K
n
 W
Start with SS EB & solve for T: 0  Q   F   C  T  T   DH (T)F X
s A0 i p,i i0 RX A0 A
i1
n
 0  0  0  FA0  iCp,i  T  Ti0   DHRX (T)FA0 X A
i1
n
 FA0  iCp,i  T  Ti0     DHRX  TR   DCP  T  TR   FA0 X A 
i1
 
n Multiply out brackets &
  iCp,i  T  Ti0     DHRX (TR )  DCP  T  TR   X A
i1
  bring terms containing T to
n 1 side n
  iCp,i T  DCP TX A  DHRX (TR )X A  DCP TR X A   iCp,iTi0
i1 i1
n
DHRX (TR )X A  DCP TR X A   iCp,iTi0
T i1
n
 iCp,i  DCP X A
i1
The irreversible, elementary liquid-phase reaction 2A → B is carried out adiabatically in a flow reactor with
ẆS=0 and without a pressure drop. The feed contains equal molar amounts of A and an inert liquid (I). The feed
enters the reactor at 294 K with u0 = 5 dm3/s and CA0= 1 mol/dm3. What would be the temperature inside of a
steady-state CSTR that achieved XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/mol•K CpB= 30 cal/mol•K CpI = 15 cal/mol•K ∆HA°(TR) = -20 kcal/mol
∆ HB°(TR) = -50 kcal/mol ∆HI°(TR) = -15 kcal/mol
k = 0.02 dm3/mol•s at 350 K
n
 DHRX (TR )X A  DCP TR X A   iCp,i Ti0
T i1
Start with SS EB & solve for T: n
 iCp,i  DCP X A
i1
b 1 cal  cal  DC  0
DCp  Cp  Cp  DCp   30   15 p
a B A 2  mol K  mol K
n  cal   cal  cal
 A  1 B  0 I  1  iCp,i = 1  15  + 1  15   30
i1  mol K   mol K  m ol K

1 cal   cal  cal

 DHRX TR   50,000
     20,000   DHRX TR  5000
 
2 mol   m ol  mol
The irreversible, elementary liquid-phase reaction 2A → B is carried out adiabatically in a flow reactor
with ẆS=0 and without a pressure drop. The feed contains equal molar amounts of A and an inert liquid (I).
The feed enters the reactor at 294 K with u0 = 5 dm3/s and CA0= 1 mol/dm3. What would be the temperature
inside of a steady-state CSTR that achieved XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/mol•K CpB= 30 cal/mol•K CpI = 15 cal/mol•K ∆HA°(TR) = -20 kcal/mol
∆ HB°(TR) = -50 kcal/mol ∆HI°(TR) = -15 kcal/mol
k = 0.02 dm3/mol•s at 350 K
n
 DHRX (TR )X A  DCP TR X A   iCp,i Ti0
Start with SS EB & solve for T: T i1
n
 iCp,i  DCP X A
i1
n cal cal
DCp  0  iCp,i  30 DHRX TR  5000
 
i1 mol K mol

 cal   cal  cal cal

  5000  X A  0   30  294K 5000 X A  8820
mol   mol K 
T  T mol mol
cal cal
30 0 30
mol K mol K

 TX 0.8  166.67K  0.8  294K  TXA 0.8  427.3K

A
The irreversible, elementary liquid-phase reaction 2A → B is carried out adiabatically in a flow reactor
with ẆS=0 and without a pressure drop. The feed contains equal molar amounts of A and an inert liquid
(I). The feed enters the reactor at 294 K with u0 = 5 dm3/s and CA0= 1 mol/dm3. What would be volume of
the steady-state CSTR that achieves XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/mol•K CpB= 30 cal/mol•K CpI = 15 cal/mol•K ∆HA°(TR) = -20
kcal/mol ∆ HB°(TR) = -50 kcal/mol ∆HI°(TR) = -15 kcal/mol
3
k = 0.02 dm /mol•s at 350 K

FA 0 XA
Solve the CSTR design eq for V at XA = 0.8 & T = 427.3K: VCSTR 
-rA
C A0 u0 X A
rA  kCA 2 Stoichiometry : CA  CA0 1  X A  Combine : VCSTR  2
k CA 02 1  X A 
dm3  10,000cal mol  1 1 
Need k at 427.3K: k  0.02 exp    
mol  s  1.987 cal mol  K  350K 427.3  
dm3 dm3
 k  0.02 exp  2.60124   k  0.2696
mol  s mol  s
dm3
5 0.8 
 VCSTR  s  VCSTR  370.9dm3
3
dm  mol  2
0.2696  1 3  1  0.8 
mol  s  dm 
The irreversible, elementary liquid-phase reaction 2A → B is carried out adiabatically in a flow reactor
with ẆS=0 and without a pressure drop. The feed contains equal molar amounts of A and an inert liquid (I).
The feed enters the reactor at 294 K with u0 = 5 dm3/s and CA0= 1 mol/dm3. Use the 2-point rule to
numerically calculate the PFR volume required to achieve XA=0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/mol•K CpB= 30 cal/mol•K CpI = 15 cal/mol•K ∆HA°(TR) = -20kcal/mol
∆ HB°(TR) = -50 kcal/mol ∆HI°(TR) = -15 kcal/mol
k = 0.02 dm3/mol•s at 350 K

• Use the energy balance to construct table of T as a function of XA

• For each XA , calculate k, -rA and FA0/-rA
• Use numeric evaluation to calculate VPFR
XA T(K) k(dm3/mol•s) -rA(mol/dm3•s) FA0/-rA(dm3)
0 294* 0.00129 0.00129
0.8 427.3* 0.2696* 0.010784
*Calculated in CSTR portion of this problem

dm3   1 1  dm3
k  0.02 exp 5032.7126K      k  0.00129
mol  s   350K 294   mol  s
2 dm3  mol2  2 mol
6 
2
rA  k CA0 1  X A   rA XA 0  0.00129 1 1  0   rA X 0  0.00129
mol  s  dm  A
dm3 s
dm3  mol2  2 mol
rA X 0.8  0.2696  1  1  0.8   r A XA 0.8  0.010784
A
mol  s  dm6  dm3 s
The irreversible, elementary liquid-phase reaction 2A → B is carried out adiabatically in a flow reactor
with ẆS=0 and without a pressure drop. The feed contains equal molar amounts of A and an inert liquid (I).
The feed enters the reactor at 294 K with u0 = 5 dm3/s and CA0= 1 mol/dm3. Use the 2-point rule to
numerically calculate the PFR volume required to achieve XA=0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/mol•K CpB= 30 cal/mol•K CpI = 15 cal/mol•K ∆HA°(TR) = -20
kcal/mol ∆ HB°(TR) = -50 kcal/mol ∆HI°(TR) = -15 kcal/mol
3
k = 0.02 dm /mol•s at 350 K
• Use the energy balance to construct table of T as a function of XA
• For each XA , calculate k, -rA and FA0/-rA
• Use numeric evaluation to calculate VPFR

XA T(K) k(dm3/mol•s) -rA(mol/dm3•s) FA0/-rA(dm3)

0 294 0.00129 0.00129 3876
0.8 427.3 0.2696 0.010784 463.6
3
 mol  dm mol
FA0  CA 0 u0  FA0  1 3  5 5
 dm  s s

mol mol
 FA0  5  FA0  5
 s  3876 dm3  s  463.6 dm3
  mol  
 rA  XA  0 0.00129  rA  X A  0.8 0.010784 mol
dm3 s dm3 s
The irreversible, elementary liquid-phase reaction 2A → B is carried out adiabatically in a flow reactor with
ẆS=0 and without a pressure drop. The feed contains equal molar amounts of A and an inert liquid (I). The
feed enters the reactor at 294 K with u0 = 5 dm3/s and CA0= 1 mol/dm3. Use the 2-point rule to numerically
calculate the PFR volume required to achieve XA=0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/mol•K CpB= 30 cal/mol•K CpI = 15 cal/mol•K ∆HA°(TR) = -20 kcal/mol
∆ HB°(TR) = -50 kcal/mol ∆HI°(TR) = -15 kcal/mol
k = 0.02 dm3/mol•s at 350 K

• Use the energy balance to construct table of T as a function of XA

• For each XA , calculate k, -rA and FA0/-rA
• Use numeric evaluation to calculate VPFR
XA T(K) k(dm3/mol•s) -rA(mol/dm3•s) FA0/-rA(dm3)
0 294 0.00129 0.00129 3876
0.8 427.3 0.2696 0.010784 463.6

X1
h
   
2-point rule:  f  x  dx   f X 0  f X1  where h  X1  X 0  h  0.8  0  h  0.8
2
X0
0. 8 
VPFR  3876dm3  463.6dm3 
2   

 VPFR  1736 dm3