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Che326 11 12A
Che326 11 12A
• CHEMICAL
• REACTION
• ENGINEERING I
• FIRST OF THREE COURSES
1
Chemical Reaction Engineering
field that studies
1. the MECHANISMS and RATES of chemical
reactions and
2. the DESIGN of the reactors in which they take
place
RATES: HOW FAST REACTION OCCURS
MECHANISMS: proposed series of steps by which
reaction is assumed to occur at molecular level
DESIGN :TYPE , SIZE and REACTION CONDITIONS IN
THE REACTOR
2
Chemical Reaction Engineering
•at the heart of virtually every chemical
process.
•Reactor may be small but crucial to the
economics of the process
•It separates the chemical engineer from
other engineers.
•Process Industries Draw Heavily on
Chemical Reaction Engineering
3
Chemical Reactor and TYPICAL CHEMICAL PROCESS
Physical treatment step chemical treatment step Physical treatment step
PRODUCTS
RAW
MAT
RECYLE
1. DECOMPOSITION
2. COMBINATION
3. ISOMERIZATION
7
Definition of Rate of Reaction
• The reaction rate is the rate at which a species loses its
chemical identity per unit volume.
• The rate of reaction (mol/dm3/s) of a species i can be
expressed as either
*the rate of consumption or Disappearance of i : -ri
or as
*the rate of formation or production (Generation) of i :
ri
negative sign indicates the amount or concentration of
the reactant i decreases because it is used up during the
reaction
** for non homogeneous reactions other definitions
prevail
8
Reaction Rate for a solid catalyzed
heterogeneous reactions
• For a catalytic reaction, we refer to -rA',
which is the rate of disappearance of
species A on a per mass of catalyst basis.
(mol/gcat/s)
9
Rate of Reaction
is a function of the following parameters:
1. Concentration of reacting species
2. Temperature of reacting species
3. Pressure( gas phase reactants/ products)
4. the type of catalyst (if any)
Rate of Reaction is independent of the type of
reaction system (batch, plug flow reactor, etc.)
rB = 0.2 mole/dm3/s
• HETEROGENEOUS reactions
I. Gas-solid
II. Gas-liquid
III. Gas-solid-liquid
IV. liquid-liquid
Another classification
• CATALYTIC REACTIONS AND
• NON-CATALYTIC REACTIONS
12
KINETICS of HOMOGENEOUS reactions
• THE RATE LAW:
• in general, different reactants react and
products are formed at different rates,
• hence the rate of reaction/formation is
always stated with respect to a specific
reactant or the rate of formation of a specific
product.
• The rate of reaction thus refers to the rate at
which the reactant is consumed
13
THE RATE OF REACTION
For many reaction systems, the rate of disappearance
of A is/can be mathematically decomposed into two
terms:
-rA = k(T)x f(Ci)) where
•f (Ci ) is a function of the concentration of the reactants
• This relationship between the concentration of
the reacting species and the rate of reaction is termed
the rate law.
•k is the specific rate constant of the reaction.
• It is most sensitive to the temperature of the reaction.
•The most commonly used and experimentally tested
relation between the specific rate constant and
14
temperature is the Arrhenius equation:
The Rate Law.
For many reaction systems, the rate of disappearance
of A is/can be mathematically decomposed into two
terms:
-rA = k(T)x f(Ci))
where
•f (Ci ) is a function of the concentration of the
reactants
•This relationship between the concentration of
the reacting species and the rate of reaction is termed
the rate law.
15
k is the specific rate constant of the reaction
•k is the specific rate constant of the reaction.
k k1 k2 k3 k4
slope=-Ea/R
Ln k
Higher Ea
Lower Ea
1/T
19
Least square method of obtaining Ea and k0
• Linearizing Arrhenius equation:
• yields a straight line equation :
• where - - -1
• Multiplying eqn.1 by x
• - - -2
• Summing all the n data points as given in the eqn.1
• - - -4
20
Summing all the n data points as given in
the equations 1 and 2:
Expt. # x = 1/T y = k x2 xy
1 x1 y1 (x1)2 x1 y1
2 x2 y2 (x2)2 x2 y2
--- --- --- --- ---
n xn yn (xn)2 xn yn
Σ Σ xi Σ yi Σ (xi)2 Σ xi yi
21
Least square method
• Eqn4/n: - - -5
• Eqn.6/ : - - -7
• Eqn.6- Eqn.7:
• Hence:
• 22
Activation energy: implications
• The smaller the activation energy of a reaction, the
lower is the sensitivity of the reaction to
temperature change
• The higher the activation energy of a reaction, the
greater is the sensitivity of the reaction to
temperature change
• The higher the Ea , the slower the rate will be.
• Endothermic reactions have higher Ea and hence are
slower than exothermic ones
• The effect of a rise in temperature is more on the
rate of an endothermic reaction than on an
exothermic one because of the value of the Ea
23
Rate law [f(Ci )] and Order Of Reaction
aA + bB + cC dD
• For many reactions the dependence of the concentration on rate of reaction is of
the form
• f(Ci )=CAα CBβ CCγ
• where
• α is the order of reaction with respect to the reactant A
•
• β is the order of reaction with respect to the reactant B
•
• γ is the order of reaction with respect to the reactant C
•
• n= α +β +γ
• n= the overall order of reaction=the sum of the orders of reaction with respect to
each of the reactants
• The order of reaction with respect to A reactant is the power to which the
concentration is raised in the rate law expression.
• In the above expression, A, B and C are reactants
• That is f(Ci ) is the product of the concentration of the reactants each raised to a
power which is the order of reaction 24
Other forms of the Rate Laws
25
ELEMENTARY AND NON-ELEMENTARY
REACTIONS
• rate law- inadequate theoretical knowledge
• **determined experimentally
• In some cases, the order of reaction with respect to a
reactant corresponds to the stoichiometric coefficient
of the reactant in the reaction equation.
• When this happens we say the reaction is elementary.
• If for the reaction with the stoichiometric equation:
A + 2B Products, the rate law is: -rA =k CA CB2
• we say the reaction is elementary.
• Otherwise the reaction is non-elementary 26
Reaction Mechanisms
• The mechanism of a reaction is the series of
elementary steps by which the reaction is assumed to
occur at the molecular level.
• It is proposed to give the detailed explanation at the
molecular level on how a reaction proceeds.
When searching for a mechanism:
30
Molecularity & ORDER
• The Molecularity of a reaction, or a step within a
reaction, describes what happens on the molecular
level
• The order of a reaction describes what happens on
the macroscopic scale.
• We determine the order of a reaction by watching
the products of a reaction appear or the reactants
disappear.
• The molecularity of the reaction is something we
deduce to explain these experimental results.
31
Collision Theory Model Of Chemical
Reactions:
• explains the observed rate laws for both one-step
and multi-step reactions.
• model assumes that the rate of any step in a
reaction depends on the frequency of collisions
between the particles involved in that step.
• This is the basis for understanding the implications
of the collision theory model for simple, one-step
reactions, such as the following.
• ClNO2(g) + NO(g) NO2(g) + ClNO(g)
32
collision theory model of chemical reactions2
• The kinetic molecular theory assumes that the
number of collisions per second in a gas
depends on the number of particles per liter.
• The rate at which NO2 and ClNO are formed in
this reaction should therefore be directly
proportional to the concentrations of both
ClNO2 and NO.
• Rate = k(ClNO2)(NO)
33
collision theory model of chemical
reactions3
• model suggests that the rate of any step in a reaction is
proportional to the concentrations of the reagents
consumed in that step.
• The rate law for a one-step reaction should therefore
agree with the stoichiometry of the reaction.
• The following reaction, for example, occurs in a single
step.
• CH3Br(aq) + OH-(aq) CH3OH(aq) + Br-(aq)
• Because the reaction occurs in a single step, which
involves collisions between the two reactants, the rate
of this reaction is proportional to the concentration of
both reactants.
• Rate = k(CH3Br)(OH-)
34
collision theory model: multistep
chemical reactions4
• Not all reactions occur in a single step.
• The following reaction occurs in three steps,
(CH3)3CBr(aq) + OH-(aq) (CH3)3COH(aq) + Br-(aq)
• some of the steps are fast
• Some of the steps are very slow
• Since the steps are in series, the overall rate is
determined by the rate of the slowest step
• This is the rate-limiting step
35
collision theory model: multistep
chemical reactions5
• step1
• (CH3)3CBr (CH3)3C+ + Br- :Slow step
• step2
• (CH3)3C+ + H2O (CH3)3COH2+ :Fast step
• step3
• (CH3)3COH2+ + OH- (CH3)3COH + H3O :Fast step
• The overall rate of reaction is therefore more or less
equal to the rate of the first step.
• The first step is therefore called the rate-limiting step
in this reaction because it literally limits the rate at
which the products of the reaction can be formed.
36
collision theory model: multistep
reactions6
• Because only one reagent is involved in the rate-
limiting step, the overall rate of reaction is
proportional to the concentration of only this
reagent: Rate = k((CH3)3CBr)
• The rate law for this reaction therefore differs from
what we would predict from the stoichiometry of
the reaction.
• Although the reaction consumes both (CH3)3CBr
and OH-, the rate of the reaction is only
proportional to the concentration of (CH3)3CBr.
37
H2(g) + Cl2(g) ---> 2 HCl(g) is made up
of 4 elementary steps.
Cl2 2Cl.
Cl. + H2 HCl + H.
Cl. + Cl. Cl 2
38
Reaction Mechanism A
• eg. 2 NO(g) + 2 H2(g) ----> N2(g) + 2 H2O(g)
This appears to be a 4 particle reaction as written.
Impossible!! Hence cant be a single step reaction
• Actual reaction mechanism is :
• step #1: 2 NO + H2 ----> N2 + H2O2
• slow since it involves a rare three particle collision.
• This is the slowest and therefore is the step that
determines the rate of all the other steps.
• step #2: H2 + H2O2 ------> 2 H2O fast reaction
• Overall rate is therefore given by 39
Reaction Mechanism B
• -r NO =k CNO2 CH2
• Termolecular reaction steps require three
molecules coming together at the same
time
• They are rare because three-body
collisions in the gas phase are rare
• 4 particle reactions are therefore
virtually Impossible!!
40
general rules to explain rate laws
1. The rate of any step in a reaction is directly
proportional to the concentrations of the
reagents consumed in that step.
2. The overall rate law for a reaction is
determined by the sequence of elementary
steps, or the mechanism, by which the
reactants are converted into the products of
the reaction.
3. The overall rate law for a reaction is
dominated by the rate law for the slowest
41
step in the reaction.
Activation Energy and the Activated Complex
• Activation Energy is the energy that must be
reached by 2 colliding molecules before a reaction
can take place
• From Collision Theory the rate of a reaction
depends on two factors.
1) The number of collision per unit time between
the reacting species.
2) The fraction of these collisions that are successful
in producing a mew molecule.
For a reaction to occur, molecules must collide not
only with sufficient energy
42
Activation Energy and the Activated Complex2
• The reactants can get to the point of highest
potential energy (the "activated complex" or
"transition state" -) only if they initially have
sufficient kinetic energy to turn into the
potential energy of the activated complex.
• activated complex is that arrangement of
reactants which can proceed to products
without further input of energy.
• The activated complex can not be isolated;
43
Activation Energy and the Activated Complex2
44
Relationship Between the Activation Energies of
Opposing Reactions
• Slow reactions have high activation energies.
• Fast reactions have relatively low activation
energies.
• An endothermic reaction always has a greater
activation energy and a slower rate than the
opposing exothermic reaction.
• An increase in the temperature affects the
rate of the endothermic reaction more than
that of the exothermic reaction.
45
Obtaining the rate law: by
1. Monitoring the levels of reactants or
products as the reaction progresses-i.e.
as a function of time of reaction
2. Testing for the rate law which is
consistent with the measured kinetic
data
3. Equipment used are batch or flow
reactors
46
Chemical kinetics or reaction kinetics
• the study of rates of chemical processes.
• includes
• investigations of how different experimental
conditions can influence the speed of a chemical
reaction and yield information about the
reaction's mechanism and transition states,
• as well as the construction of mathematical
models that can describe the characteristics of a
chemical reaction
47
Obtaining the kinetic data:
batch reactor types
Vessel containing reaction contents as reaction progresses
Flow reactors 48
Typical Features Of A Batch Reactor
• Probes for monitoring –temperature, Pressure, pH,
other concentration parameters
• Connection to a condenser
• Connection to atmosphere if relief valve ruptures
• Jacketed for heating/ cooling reactor contents
• *coils for cooling/heating reactor contents
• Perforated coils for sparging
• *Sampling points
• Sight glass to observe reactor contents
• Charging points
• Discharge points
49
Kinetic Data
• Direct measurement of concentration
• Direct measurement of pressure-for gas phase
reactions
• Measurement of parameters which are related to
concentration of species
• -pH of solutions
• - conductance of solutions
• -absorbance of solutions
• -colours of solutions
• -etc
50
Kinetic Data: Chemical Methods
• These are mainly titration methods and they can be
highly accurate.
• They are generally reserved for simple reactions in
solution where either only the reactant or the
product concentrations are being monitored.
• Here sampling errors and speed of analysis are
crucial.
• Chemical methods have been largely superseded by
modern black box techniques, though, in certain
types of solution reaction, they can still be very
useful.
51
Physical Methods:1
• These use a physical property dependent on
concentration and must be calibrated
• much more convenient than chemical
methods.
• In situ measurement can often be made in,
and analysis is often very rapid.
• Automatic recording gives a continuous trace.
• It is vital to make measurements faster than
reaction is occurring.
52
Physical methods:2
pH and EMF methods
1. using a glass electrode sensitive to H3O+
• Reactions which occur with change in H3O+ or a change in [OH-] to be
followed with ease.
• A pH meter measures pH directly, and
• a millivoltmeter measures EMFs directly, and these are related to
H3O+
E.g.In CH3COOCH3(aq) +OH-(aq) CH3COO(aq) +CH3OH(aq)
• OH-(aq) is removed, [H3O+] will increase and the pH will decrease
with time, with a corresponding change in EMF and
In CH3COOCH2CH3(aq) + H3O+ aq) CH3COOH(aq) +CH3CH2OH(aq)
• In the acid hydrolyses of esters H3O+(aq) is removed, and
• the pH increases with time, with a corresponding change in EMF.
53
Kinetic Data: Pressure Changes In Gas Phase
Reactions For Constant-Volume Batch Reactors
• for gas phase reactions which occur with
an overall change in the number of
molecules and
• consequently show a change in total
pressure with time.
• Ideal gas law pV = nRT and
• P α n :if V and T are constant
54
Kinetic Data: Volume Changes In Gas Phase
Reactions For Constant-Pressure Batch
Reactors
• for reactions which occur with an overall
change in the number of molecules in the
gas phase and
• consequently show a change in volume
with time.
• PV = nRT
• P α n :if V and T are constant
55
Kinetic Data: Conductance
Methods
• useful when studying reactions involving ions.
1. (CH3)3CCl(aq) +H2O(l) (CH3)3COH(aq) + H+(aq)
+Cl-(aq)
• Ions are produced, and the conductance rises with
time.
60
The Extent of Reaction (or sometimes
the degree of advancement).
• The extent of, ξ , is defined as
• ξ = (Ni – Ni0)/ υi
• where
• Ni0 = number of moles of i into reactor (t=0)
Ni = number of moles of i out of reactor (t = t)
• υi =stoichiometric coefficient of i
• Ni = Ni0 + υi ξ
• ξ (mol/s) is same for all species, must be positive
• a dummy variable that reflects how far each
reaction proceeds.
61
*
• υi is positive for a product
• υi is negative for a reactant
• . If there is more than one reaction going on,
there will be an extent term for each reaction.
So for i components and j reactions:
62
Relating the concentrations of species in
the reaction mixture: Stoichiometric Table
• Lets consider components of a reaction system,
including inerts-I-that have been charged to the
reactor.
• All quantities are written in terms of one(A) of the
components of the reaction system.
• Amounts and concentrations of species change as
the reaction progresses
• balance of the reacting system is carried out when
the fractional conversion of the chosen reactant, A,
is XA
63
Stoichiometric Table
• Useful in relating the relationship between
the *Concentrations of various species in the
reaction mixture with time
• *enables easy representation of the rate law
in terms of a single variable
• *enables easy calculation of the partial
pressures of various species for gas phase
reactions
• *enables easy calculation of the mole
fractions of various species in the reaction
64
Stoichiometric Table at XA for constant volume batch
reactor
Compon Initial Change due Moles Concentration
ent charge [2] to reaction, remaining, Ni [4] Ci [5]
[1] [3]
A NA0= NA0θA -NA0XA NA0θA -NA0XA NA0 (θA -XA)/ V
= NA0 (θA -XA) = CA0 (θA -XA)
Total
N0=NA0(θA + θB + θC + θD + N=N0 + NA0 XA [(d/a)+ (c/a)-(b/a)-1] 65
Stoichiometric Table3
• Column 1 lists the various components of the reaction
system- reactants, products and inerts (I)
• Column 2 lists the amount of the various components
initially charged to the reactor, all amounts expressed
in terms of NA0 and θi0.
• The definition of θi0, listed at the bottom of Table 2.1
makes this simplification possible. This column is
calculated from the composition of the initial charge to
the reactor.
• Θi = Ni0/ NA0 ;ΘA = NA0/ NA0 =1 ; ΘB = NB0/ NA0
•
• ΘC = NC0/ NA0 ;ΘD = ND0/ NA0 ; ΘI = NI0/ NA0
66
•Column 3 lists the changes in the amounts of each
component due to chemical reaction when the
fractional conversion of A is XA.
• These changes are negative for a reactant because it
is consumed during the reaction.
• For a product the changes are positive.
• The quantities are based on the stoichiometric
equation. From the stoichiometry,
•[Amount of B reacted]/[amount of A reacted] =b/a
If the change in A (amount of A reacted) is NA0XA,
Then
[The amount of B reacted] =(b/a) x [amount of A
reacted] =(b/a) NA0XA.
67
• Column 4 is simply the summation of columns 2
and 3. Hence the amount of B remaining at
fractional conversion of A of XA
=amount present initially + change in B
= NA0θB-NA0XA(b/a)= NA0 [θB-XA(b/a)]
76
Integral Method: 1st order wrt a single reactant,
A, constant-volume batch reactor
First order reaction: A B
77
The first order rate law
• is a very important rate law:
• radioactive decay and many chemical
reactions follow this rate law
• some of the language of kinetics comes from
this law.
•
• This form is called an "exponential decay."
• This form appears in many places in nature.
• it gives rise to a concept called "half-life."
78
Integral Method: 2nd order wrt a single
reactant, A, constant-volume batch reactor
• 2A products
79
80
nth order reaction: nA products
• If the order for type of reaction is not known, one
can assume directly an nth order reaction
• instead of testing for orders of 0, 1 and 2
successively.
• For an nth order reaction (constant density reaction
mixture) : -rA=-dCA/dt =k CAn
82
Differential Method Of Analysis
dC i
k f (C i )
dt
• makes use of the differential form of the rate law:
• Concentration vs. time data is differentiated
numerically or graphically in order to obtain values
of [-dCA/dt ].
• method is most easily applicable when the rate is
dependent on the concentration of only one
component.
• If the rate depends on more than one component,
the method is easily adapted by combining it with
the method of excess. 83
Differential method: rate depends on the
concentration of a single reactant
• rate law is of the form:-rA = [-dCA/dt]= kCAα
• ln(-dCA/dt)= lnk + α ln CA
ln (-dCA/dt)
slope= α
intercept= lnk
ln CA
85
Obtaining (-dCA/dt):
Any mathematically convenient and accurate
method of obtaining the slope
• measuring the slope of the tangent to the CA vs t.
plot at various points as shown in
• fit a polynomial of sufficient accuracy to the CA vs. t
plot :
• CA(t)=a0 + a1t + a2t2 + a3t3+ a4t4
• Microsoft Excel can be easily used for this.
• Differentiating equation with respect to t yields
• dCA(t)/dt= a1 + 2a2t + 3a3t2+ 4a4t3
86
slope of the tangent to the CA vs t. plot
87
slope of the tangent to the CA vs t. plot
at different points
88
Differential method of analysis
• By choosing the appropriate times and
reading from the CA vs t plot or calculating CA
from eq., one can obtain the (-dCA/dt) vs t
• other methods of obtaining dC(t)/dt
include:
– plotting ∆CA/∆t versus t and using the
method of equal area to obtain dCA/dt
–Use of the differentiation formula such as
the 3-point formula for data of equal time
intervals t 89
Differential method: rate depends on the
concentration of more than one reactant
•Applied by combining with the method of excess.
If the reactant B is in large excess then and the
concentration of A is monitored as a function of time
dC A
- kC A C B kC A C B0 kC A
dt
•By now reacting under conditions of excess
reactant A, the concentration versus time data of
component B is obtained.
dC A
-
kC A CB kC A0 CB k CB
dt 90
Method of half-life:
Half-life period or the half-life
• of a decaying material is the time it takes for the
amount of decaying material to be reduced to half.
• The half-life is characteristic of the decaying
(originally radioactive) materials.
• The half life of a limiting reactant (t1/2), is the time
required for the concentration of the reactant to be
reduced to half of its original value.
• The time it takes for the concentration to half its
value.
• The dependence of the half-life on concentration
reflects the way in which the rate of reaction
depends on concentration. 91
Method of HALF-LIFE: ZERO ORDER
93
half-life for a FIRST ORDER reaction:
ln (CA0/ CA ) =kt
• At half-life, t= t1/2, CA=0.5CA0
95
Any Fractional Life-time For A First Order
Reaction
• The relaxation time is the time when the
concentration becomes 1/e of the original.
• At relaxation time, and CA=(1/e)CA0,
• Ln[CA0 /(CA0 /e)]=ln(e)=1=kτ
• hence
• Since (1/e)CA0,= 0.3679 CA0
• At the relaxation time the reaction has gone
to XA =[CA0 - 0.3679 CA0 )/CA0]=0.632
=63.2 per cent completion 96
relaxation time for a first order reaction
• *
97
half-life for a second order reaction
1 1
kt
CA C A0
99
half-life for nth order reaction:
In general the half life of a reaction
• depends on the concentration of the reactant
• and the order of the reaction.
1 n 1 n
C (0.5 1)
A0
t1/ 2
(n 1)k
101
log –log plot of t1/2 versus CA0
(0.51n 1)
int ercept
(n 1)k ln(CA0)
102
different slope signs depending on the
order of reaction
• *
Orders of reaction =1
ln CA0
103
Method of excess or Method of isolation
• technique used to simplify the analysis of complex
rate expressions
• The method consists of effecting runs with all but
one component in such sufficient excess that its or
their concentration(s) remain(s) essentially constant
during the run.
• By monitoring the concentration of this ‘isolated’
reactant as a function of time, the order with
respect to the isolated’ reactant can be determined
by any of the techniques discussed
104
Method of excess or Method of isolation
• the rate law for the reaction: A +B products
• – rA= -dCA/dt =k CAα CBβ
• If B is the reactant in excess,
• A is the ‘isolated’ reactant
• CA changes while CB remains virtually constant
during the reaction.
• Hence
• – rA= -dCA/dt =(k CBβ )CAα=(k CB0β )CAα = k' Caα
105
• *
ln(-rA)
ln(CA0)
106
Method of excess.3
• k' is a pseudo-α-order rate constant.
• The reaction is a pseudo- α -order reaction,
because it behaves as if it were α -order
although it is not really α-order.
• It is α-order with respect to only A.
• k' is not a true constant
• its value varies with the initial concentration
of B, CB0.
107
*
• By performing a series of experiments in
which CB0 varies but is always much larger
than CA0, one obtains k' as a function of CB0
ln(k')
ln(CB0)
109
METHOD OF INITIAL RATES
• method uses the initial rate of reaction to
simplify the analysis of obtaining the rate law
of complex rate expressions.
• This involves effecting the same reaction at
preferably the same temperature but using
different initial concentrations of reactants.
• There is more certainty about the
measurement of the initial concentrations and
any interference about the effect of side
reactions are also avoided in this method.
110
METHOD OF INITIAL RATES:
Primary Problem Of Method
• difficulty in accurately determining the initial rate.
• Difficult to determine the initial rate, because as
soon as the reaction begins, the rate slows down
(unless the order is zero)
• Measuring the rate as close to the start of the
experiment, measuring the rate and extrapolation
to obtain the rate at t=0 invariably entails some
errors.
• This involves effecting the same reaction at
preferably the same temperature but using
different initial concentrations of reactants. 111
METHOD OF INITIAL RATES:
• The rate law for reversible reaction
:A+B=C+D has the general form
• – rA= -dCA/dt =k CAα CBβ-k’CCa CDb
• At t=0, and with no products in the initial
charge, CC0=0; CD0=0;
• -rA=-rA0
• – rA0= -dCA0/dt =k CA0α CB0β
112
series of runs with the same CB0 but
different CA0, and measuring the rate [-rA0
• ln(– rA0)=ln(k. CB0β)+ α lnCA0
ln(– rA0)
slope=α
ln(k. CB0β)
ln(–CA0)
113
Runs with same CA0 but different CB0 and
measuring -rA0
• ln(– rA0)=ln(k. CA0 α)+ β lnCB0
ln(– rA0)
slope= β
ln(k. CA0α)
114
Least–square method
• The least–square method can be used to
obtain the best values of the parameters of
the rate law-the orders of reaction and the
rate constant.
• For a rate law of the form:
• Where y= ; x= ln CA ; ;
• Since the sums are easily set up, the two equations
have only two unknowns-m and c
117
best values for α and k by the least square methods
Run Xi Yi xiyi x i2
CAi (-rAj) =lnCA =ln(-rA)
1
Σ Σ Σ Σ
118
lnC ln(-r ) lnC *ln(-r ) (lnC )2
Least square method
•The two simultaneous equations are solved
for the unknowns.
•These are the best values of the parameters
obtainable from the experimental data
119
Least square method: complex rate
forms
• Linearizing
• yi = c + ax1i + ax2i
• Two independent variables:
• x1=lnCA and x2=lnCB
• The summation of the results of all the n
runs
•
120
Least square method: complex rate forms 2
• The summation of the runs :
n
122
Solving for the parameters
• We now have three equations in three unknowns,
namely the desired parameters
• This method becomes particularly useful when
simplifying methods such as the method of excess
cannot be used.
• It is obvious that the method can be applied when
more than three parameters from the rate law are
to be determined
123
VARIABLE VOLUME BATCH REACTORS
• dXA/dt= [1/εAV0]dV/dt
128
VARIABLE VOLUME BATCH REACTOR: -rA
• -rA=(-1/V)(dNA/dt)
• = (-1/ V0 (1 + εAXA)(dNA0 (1 –XA)/dt)
• = (-1/ V0 (1 + εAXA)(-NA0dXA)/dt)
• =[CA0/ (1 + εAXA)] [dXA/dt]
• -rA = =
129
Variable volume, constant pressure, isothermal batch reactor:
Zero order reaction
εA > 0
ln(V/V0)
εA < 0
130
VARIABLE VOLUME BATCH REACTOR: -rA
• For first order: -rA = [CA0/εA][d(lnV)/dt]=kCA
• Substituting for CA
• [CA0/εA][d(lnV)/dt]=k CA0(1 -XA)/(1 + εAXA)
• Simplifying
• [dV/V)/dt]=k εA(1 -XA)V0/V
• dV =kεA[(1 -(V- V0 )/εAV0)]V0 dt
• dV= k[εAV0-(V-V0)]=k[(1+εA)V0–V]dt Integrating
• -ln[(1+εA)V0–V]/[(1+εA)V0–V0]=kt
• -ln[V0+V0εA–V]/[εAV0]=-ln[V0εA–ΔV]/[εAV0]=kt
131
Variable volume, constant pressure, isothermal batch reactor:
first order reaction
-ln[1–ΔV/εAV0]
132
Q & A
• Nitric acid is made commercially from nitric oxide. Nitric oxide is
produced by the gas-phase oxidation of ammonia.
• 4NH3 + 5O2 4NO + 6H2O
• The feed consists of 15 mol% ammonia in air at 8.2 atm and 227°C.
• What is the total entering concentration?
• What is the entering concentration of ammonia?
• Set up a stoichiometric table with ammonia as your basis of
calculation.
– Express Ci for all species as functions of conversion for a constant-volume batch
reactor. Express PT as a function of X.
– Express Pi and Ci for all species as functions of conversion for a flow reactor.
• Write the combined mole balance and rate law solely in terms of the
molar flow rates and rate law parameters for C1 and C2 above.
Assume the reaction is first order in both reactants
133
Total pressure in constant volume
batch reactors: gas phase reactions
component initial charge change due to moles remaining in terms of
Ni0 reaction at NA total moles
Ni
A NA0θA -( NA0-NA) NA0θA-( NA0-NA)
= NA0θ-(NT-N0) (a/Δn)
B NA0θB -( NA0-NA) (b/a) NA0θB -( NA0-NA)(b/a)
=NA0θB -(NT-N0)(b/Δn)
C NA0θC ( NA0-NA) (c/a) NA0θC +( NA0-NA) (c/a)
=NA0θC+(NT-N0)(c/Δn)
D NA0θD ( NA0-NA) (d/a) NA0θD +( NA0-NA) (d/a)
=NA0θD +(NT-N0)(d/Δn)
I NA0θI 0 NA0θI 134
• Total moles initially
• N0=NA0 (θA +θB + θC +θD +θI ) - - - 3.1
• Total moles remaining
• NT =NA0 (θA +θB + θC +θD +θI )-( NA0-NA)-( NA0-
NA)(b/a) +( NA0-NA)(c/a) +( NA0-NA)(d/a)
• Simplifying
• NT =N0+( NA0-NA)( d/a+ c/a- b/a-1)
• NT=N0+( NA0-NA)( d+ c- b-a)/a
• NT =N0+( NA0-NA)(Δn/a)
• ( NA0-NA)= (NT-N0)(a/Δn)
135
At constant temperature and volume
Pi=NiRT/V or Ni=Pi V/RT
component Ni
Pi=NiRT/V
A NA0 -(NT-N0)a/Δn PA= PA0 - (PT-P0)a/Δn
B NA0θB -( NT-N0)(b/Δn) PB= PA0θB - (PT-P0)b/Δn
C NA0θC +( NT-N0)(c/Δn) PC= PA0θC + (PT-P0)c/Δn
D NA0θD +( NT-N0)(d/Δn) PD= PA0θD + (PT-P0)d/Δn
137
A D
• A D. forward reaction
• The reactants, A , react to form the product D.
The reverse reaction is represented as
• A D. reverse reaction
• The products of the forward reaction D react
to form the reactants
• forward and reverse reactions take place
simultaneously
138
A D
• rate of the forward reaction depends on the
concentration of the reactant A
• rate of the reverse reaction depends on the
concentration of the reactant for the reverse
reaction-D.
• There is thus a net reaction in favour of the
faster of the reactions, depending on the
concentration of A and D
139
Dynamic Equilibrium: A D
• When the concentrations of the reactants and products
are such that the rate of the forward reaction is equal
to that of the reverse reaction then we have attained
the condition of dynamic equilibrium.
• When reactants and products are present in significant
quantities at equilibrium, the relationship is described
in terms of the equilibrium constant,
• the magnitude indicates of how far right the reaction
has gone.
• Irreversible reactions may thus be regarded as
reversible reactions whose equilibrium lie far to the
right-that is, the reaction mixture consists of either
reactants or products.
140
Equilibrium Constant
• The larger the value for the equilibrium constant
the more the reaction goes to completion.
• The value for K is large when products dominate the
mixture.
• The value for K is small when the reactants
dominate the mixture.
• Irreversible reactions can be thought to have an
infinite equilibrium constant so there are no
reactants left
141
the equilibrium constant
• Large K have values that are huge, 1 x 1034
• K = 1 neither reactants nor products are
favored
• Small K have values that are tiny, 4 x 10-41
142
First order reversible reactions:
mole/L
mole/L.min
i Ni0 Ni Ci
A NA0 -(NA0- NA) NA CA
D 0 (NA0- NA) NA0- NA CA0- CA
145
Separating variables leads to
Integrating leads to
146
At equilibrium, and .
• Simplifying
147
In terms of the fractional conversions
• *since CA=CA0(1-XA) and CAe=CA0(1-XAe). Hence
This simplifies to
=k1
• Hence a plot of vs. should give a straight
line through the origin with slope equal to k1 . 148
slope=k+k’
slope=k+k’
150
Consecutive/Series First Order irreversible
A k1 B k2 C
151
Assuming the reaction is elementary
as written –each step is first order-
• *
• Separating variables and integrating
• For component B, the net rate of reaction is
152
153
From the stoichiometry, it follows
• *
154
10
10 CA CA
9 CC
9
CC 8
8
7
7
6 k1=1.0/m 6
k1=1.0/min;
mole/L
mole/L
k2=10.0/min
in; 5
5 k2=2.0/min
4 4
3 3
2 CB 2 CB
1 1
0 0
-1 1 3 -1 1 3 5
t,min 155
t,min