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CHE 312 Chemical

Ch i l Reactor
R t Engineering
E i i

CHAPTER THREE
RATE LAWS AND STOICHIOMETRY

By: Dr. Yaser Dahman

Outline

 Definitions and Relative rate of reactions

 Rate law and order of reaction

 Elementary and non‐elementary rate laws

 Equilibrium reaction constant (K) and reaction rate constant(kA)

 Stoichiometric tables (Batch and flow reactors, constant volume)

 Variable volume (batch and flow reactors)

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Definitions
 Homogeneous reactions: All the reactants in these reactions are in one
phase (gas, or liquid or solid)

For Examples:
N2 (g) + O2 (g)  2NO (g) (gas phase)
HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l) (liquid phase)

 Heterogeneous reactions: All the reactants in these reactions involve

more than one phase (including catalytic reactions).

For Example:

Definitions
• Reversible Reaction: Chemical reactions which proceed in both directions
forward and backward simultaneously are known as reversible reactions.
These reaction never go to completion but always continue in both
directions.
For Example:

• Irreversible Reaction: Chemical reactions which proceed to completion in

one direction only are known as irreversible reactions. In these reactions
products do not form reactants again
For example
CaCO3  CaO + CO2

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Molecularity of reaction
The number of reacting species, which are involved in simultaneous collision
to bring about a chemical reaction.

Unimolecular (single reactant)

A → B + C (Decomposition) A → A’ (Isomerization)

Bimolecular (2 reactants)
A + B → C + D (most common; Combination)

Termolecular (3 reactants)
A + B + C → products (less likely to exist)

Relative Rates of Reactions

Relative rates can be obtained from relative stoichiometry.

Considering,
aA + bB  cC + Dd

Relative reaction rates

(rates of reaction are in mol/dm3.s)

a
Rate of consumption of A and B : rA = rB
b

c
Rate of formation of C and D : rC = rD
d

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Unimolecular Reactions
Reaction rate law is a function of reaction rate constant kA and concentrations

A  Product

Reaction Rate Law is: ‐rA = kA (T) [fn(CA)]

 rA  kC A Power Law Model

Order of reaction
The order of reaction refers to the powers to which the concentration of A is
raised in the kinetic rate law (α)

Α = 1 (Linear and elementary 1sr order reaction in A and overall order)

A ≠ 1 (Nonlinear and nonelementary reaction)

Units of equation
‐ rA :Concentration per unit time per unit volume.
kA : varies with the order of reaction.

Units of Reaction Rate Constant

CA ‐rA Reaction Order Rate Law k

mol/m3 mol/m3 s 0th ‐rA = k mol/m3 s

1st ‐rA = kCA s‐1

2nd ‐rA = kCA2 m3/mol s

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Units of Reaction Rate Constant

A  Product

Reaction rate equation (rate law): ‐rA = kACAn

For n‐order reaction: k = (Concentration)1‐n

Time

Bimolecular Reactions
Reaction rate law is a function of reaction rate constant kA and concentrations

A + bB  cC + dD

Reaction Rate Law is: ‐rA = kA (T) [fn(CA,CB,…)]

 rA  kC A C B Power Law Model

Order of reaction
The order of reaction refers to the powers to which the concentrations are
raised in the kinetic rate law.

Units of equation
‐ rA :Concentration per unit time per unit volume.
kA : varies with the order of reaction.

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Example

If the rate law for the non‐elementary

non elementary reaction
A + bB  cC + dD
is found to be ‐rA = kCA2CB

Then the reaction is

2nd order in A
1st order in B
3rd order overall.

Elementary Rate Laws

Elementary reaction is a reaction which involves only a single transition state with no
intermediates.

Example: Bimolecular reaction

O + CH3OH  CH3O + OH

For elementary reactions the stoichiometric coefficients are identical to the power in the rate law.

‐ rO = k CO CCH3OH

Example: oxidation if nitric acid 2NO +1O2  2NO2

2 1
- rNO = kNOCNO CO2

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Non‐Elementary Rate Laws

Non‐Elementary reactions are complex reactions (chemical chain reaction).
They can occur in multiple elementary reaction steps.

For non‐elementary reactions the stoichiometric coefficients are not identical to the power in the rate law.

For the Homogeneous Reactions : CO + Cl2  COCl2

3/2
- rCO = k CCO CCl2

Decomposition of nitrous oxide : 2NO2  2NO + O2

k CNO
2
-rNO =
2 1 + k’CO2

Non‐Elementary Complex Reaction

k CN2O
-rN =
2O 1 + k’CO2

For the above equation the following holds true

 Both k and k’ are temperature dependent

 An overall reaction order cannot be estimated (as powers of

concentration are both in the numerator and denominator)

 However can obtain a reaction order at limiting conditions,

For example,

If k’C O2 << 1 (negligible), the reaction would be apparent (or psuedo) first‐
order with respect to NO2.

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Reversible and Equilibrium conditions

 Reactions proceed in both directions until it reaches equilibrium

 Net rate of formation of any species is equal to its rate of formation in the forward
reaction plus its rate of formation in the reverse reaction

 For reversible reactions, the net rate of reaction is the sum of the rates of both
forward and reverse reactions

ratenet = rateforward + ratereverse

 At equilibrium, the rate of reaction is identically zero for all species

ratenet = 0 ( ‐rA = 0)

 At equilibrium, the concentrations are related by the thermodynamic relationship

for the equilibrium constant, KC

IMPORTANT: Reaction orders cannot be deduced from Reaction Stoichiometry!!!

(Except for elementary reactions)

Equilibrium Reaction constant (K)

Prove that for the following elementary equilibrium reaction
kB
2B D + H2
k‐B
CD CH2
(equilibrium constant) KC =
CB2
kB and k‐B : Forward and reverse specific reaction rate constants
Forward reaction (disappearance of B’s) –rB,forward = kBCB2

Reverse reaction (formation of B’s) rB,reverse = k‐BCDCH2

Overall rate equation :rB ≡ rB,net ≡ rB,forward + rB,reverse

rB = ‐kBCB2 + k‐BCDCH2

 ‐rB = kBCB2 ‐ k‐BCDCH2

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Equilibrium Reaction constant (K)

k-B
 -rB = kB CB2 - CDCH2
kB

kB
Let Kc = (Equilibrium constant)
k-B

CDCH2
 -rB = kB CB2 -
Kc

rB rD rH2
We Know that = =
-2 1 1
rB r
 rD = and rH2 = B
-2 -2

Equilibrium Reaction constant (K)

At equilibrium,
rB ≡ rB,net = 0

CDCH2
 -rB,net = kB CB2 - =0
Kc

CD CH2
Kc =
C B2

Concentration equilibrium constant (Kc) decreases with increasing

temperature for exothermic reactions and increases with increasing
temperature for endothermic reaction.

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Temperature Effect on K
The Van't Hoff relation describes the effect of temperature on the equilibrium
constant K. Thus,

If ∆HT0 is essentially independent of T, this can be integrated to give:

Reaction rate constant (kA)

 Independent of the concentrations of species involved in the reaction
 Also called ‘specific reaction rate’ or the ‘rate constant’.
 Strongly dependent on temperature for both gas and liquid reactions
 For gas phase reactions, it is a function of total pressure
 In liquid phase reaction, it is a function of ionic strength and type of solvent

kA can be correlated by Arrhenius equation

k  Ae  E / RT
Where,
A : pre‐exponential factor or frequency factor
E : activation energy (j/mol)
R : gas constant, 8.314 J/mol.K
T : absolute temperature

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Activation Energy Term

It is the barrier to energy transfer from kinetic energy to
potential energy between reacting molecules that must be
overcome for
f reaction
ti tot occur.
Simply, the minimum amount of energy that must be possessed
by reacting molecules before the reaction will occur

For the reaction

Reaction Rate Constant

k is the specific reaction rate (constant) and is given by the Arrhenius Equation:

k
 E / RT T ∞ kA
k  Ae k0
T0

Equation of straight line y = mx + C

T

E1
ln k  ln A    (
(0,ln A))
R T  ln k
Slope : -E/R
Slope = ‐E/R Intercept : ln A

 E  1 1 
k T2   k T1  exp    
1/T
 R  T1 T2 

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Example
Determination of Activation Energy

T (K) k (s‐1)
Calculate the activation energy for
the decomposition of benzene 313 0.00043
diazonium chloride to chlorobenzene
and nitrogen.
319 0.00103

323 0.0018

328 0.00355

333 0.00717

Plot ln k vs 1/T

T, K k, s‐1 1/T ln k
313 0.00043 0.003195 ‐7.75173

319 0.00103 0.003135 ‐6.8782

323 0.0018 0.003096 ‐6.31997

328 0.00355 0.003049 ‐5.64081

333 0.00717 0.003003 ‐4.93785

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Solving for E and A

E1 0.003 0.0031 0.0032
ln k  ln A    -4
R T 
-55
Given that R = 8.314 J/mol.K y = -14612x + 38.925

ln k
-6

-7

-8
1/T

-E/R = -14612  E = 121,484.168 J/mol

ln A = 38.925  A = 8.034x1016 s-1

k = 8.034x1016 exp(‐121 484/RT) s‐1

Stoichiometric Tables

Tables that represent stoichiometric relationships between reacting molecules

for a single reaction

 We shall set up Stoichiometric Tables using A as our basis of calculation in

the following reaction: aA + bB  cC + dD

 We will use the stoichiometric tables to express the concentration as a

function of conversion and relations between A, B, C, D etc…

 We will combine Ci = f(X) with the appropriate rate law to obtain ‐rA = f(T, X)

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Batch systems

aA + bB  cC + dD

NA
NAo
NB
NBo
NC
NCo Reactor
ND
NDo
NI
NIo
X

Taking ‘A’ as the basis of calculations (limiting reactant), Dividing by ‘a’ throughout

A + (b/a)
(b/a)BB  (c/a)
(c/a)CC + (d/a)
(d/a)DD

Batch systems – Stoichiometric Tables

M l off A consumed
Moles d : NAOX

Moles of A remaining in the system : NAO – NAOX = NAO(1‐X)

Moles of B reacted = Stoichiometric ratio * moles of A reacted

b
= (NAOX)
a

Moles of B remaining in the system = NBO ‐ b (N X)

AO
a

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Batch systems – Stoichiometric Tables

c
Moles of C Produced = Stoichiometric ratio * moles of A reacted = (NAOX)
a

c (N X)
Moles of C in the system after production = NC0 + AO
a

d
Moles of D Produced = Stoichiometric ratio * moles of A reacted = (NAOX)
a

d (N X)
Moles of D in the system after production = ND0 + AO
a

Batch systems – Stoichiometric Tables

 Change in total number of moles for complete conversion

b c d
  1   
a a a
NT = NTo+δNAoX

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In Terms of Concentration

Batch System Stoichiometric Table

A + bB  cC + dD
Species Symbol Initial Change Remaining
A A NAo ‐NAoX NA=NAo((1‐X))
B B NBo= NAoΘB ‐(b/a)NAoX NB=NAo(ΘB‐bX/a)
C C NCo= NAoΘC (c/a)NAoX NC=NAo(ΘC+cX/a)
D D NDo= NAoΘD (d/a)NAoX ND=NAo(ΘD+dX/a)
Inert I NIo= NAoΘI 0 NIo= NAoΘI
Total T NTo δNAoX NTo+δNAoX

N io C y
i   io  io
N Ao C Ao y Ao N j

 N A0  j  j X 
If a=1
b c d
  1    δ = ‐1 –b + c + d
a a a

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Batch systems – Stoichiometric Tables

Constant Reactions Volume

o For liquids volume change with reactions is negligible when
no phase changes are taking place (density is constant)

o For gases, at constant temperature and pressure, the

volume will not change if the conditions of ideal gas are
applicable

o When a gas phase reaction occurs in a rigid (e.g. steel)

batch reactor:

Under constant volume assumptions :

Ni
= Ci Substituting in the previous equations
V

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Constant Volume Batch

If the reaction occurs in the liquid phase or if a gas phase reaction occurs in a rigid
(e.g. steel) batch reactor: Then V = V o

N A N Ao (1  X )
CA    C Ao (1  X )
V Vo
N B N Ao
CB    B  bX   C Ao  B  bX 
V Vo

If ‐rA = kACA2CB then  rA  k A C 3Ao (1  X ) 2 ( B  bX )

Thus we have –rA = f(T, X)

Flow System Stoichiometric Table

aA + bB  cC + dD

FAo FA

FBo FB

FCo FC
Reactor
FDo FD

FIo FI
X

A + (b/a)
(b/a)BB  (c/a)
(c/a)CC + (d/a)
(d/a)DD

Fio C v C y
i   io o  io  io
FAo C Ao v o C Ao y Ao

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Flow System Stoichiometric Table

A + (b/a)
(b/a)BB  (c/a)
(c/a)CC + (d/a)
(d/a)DD

Species Symbol Feed Change Effluent

A A FAo ‐FAoX FA= FAo(1‐X)
B B FBo= FAoΘB ‐(b/a)FAoX FB= FAo(ΘB‐ bX/a)
C C FCo= FAoΘC (c/a)FAoX FC= FAo(ΘC+cX/a)
D D FDo= FAoΘD (d/a)FAoX FD= FAo(ΘD+dX/a)

Inert I FIo= FAoΘI 0 FIo= FAoΘI

Total FTo δFAoX FT = FTo+δFAoX

Concentration ‐ Flow System:

b c d FA
  1    FT = FTo(1 + εX) CA 
a a a v

Flow Systems- Stoichiometric Tables

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Liquid Phase Flow System

Constant Volume: v = vo

FA FAo (1  X )
CA    C Ao (1  X )
v vo
F F
C B  B  Ao  B  bX   C Ao  B  bX 
v vo

If the rate of reaction were ‐rA = kCACB

 rA  k A C 2Ao (1  X)(B  bX)

This gives us ‐rA = f(T, X). Consequently, we can use the methods in Chapter 2 to size
reactors, either alone or in series.

Example 3-4

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Example 3-4

next table.

Example 3-4

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Batch Reactors with Variable Volume

 Variable volume is seldom encountered in batch reactors because
usually reactors are made of solid steel containers.

 Concentrations can be determined by expressing V (for a batch

system), or  (flowrate,for flow systems) as function of conversions

 Considering equation of state

PV = z NTRT ‐‐‐‐‐ (2)

(z is compressibility factor for non ideal gases)

At t = 0, POVO = zo NT0RTO ‐‐‐‐‐‐‐ (3)

Volume Change – Gas Phase

There are reactions where v or V may

change appreciably N2 + 3 H2  2NH3

Thus when calculating Ci(X) variable volume becomes important

PV = Z NT R T and
Eq. of State
PoVo = ZoNToRTo

 Po  T  Z  N
V  V      T

 P   T o
o
 Z o  N To

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NT = NTo+δNAoX

NAo = yAoNTo NT = NTo+δyAoNToX

ε = δ yAo NT = NTo (1 + εX
εX))

ε = change intotaltotalnumber
number of moles for complete conversion

of moles fed to the reactor

  ( 1    ) N A 0
b c d
a a a N T0

ε = δ yAo

Batch Reactors With Variable Volume

Dividing equation (I) by (II) we get

 P  T  Z  N
V  V o  o      T
-----(4)
(4)
 P  To  Z o  N To

We know that,
NT = NTO + NAOX -----(5)

NT = NTo (1 + εX)

b c d
ε = δ yAo and   1   
a a a

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Batch Reactors With Variable Volume

 Using eq (5) and (6), and substituting them in equation (4) for
NT , we get

Assuming that z will not change significantly in the gas

phase system (certain conditions of temperature and pressure )

Batch Reactors With Variable Volume

 This equation applies to a variable–volume batch reactor

 For rigid steel container, volume is constant ( = o)

 For constant volume systems, this equation can be used to

get relationship between pressure and temperature inside the
reactor

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Flow Reactors With Variable Volumetric Flowrate

The total concentration at any point in the reactor is

Taking
g the ratio of the above two equations
q we get
g

-------(7)

Flow reactors with variable volumetric

flowrate

(Refer to stoichiometry
y
table)
(7)

------(8)

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Flow Reactors With Variable Volumetric Flowrate

------(9)

Flow Reactors With Variable Volumetric Flowrate

(9)

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Flow Reactors With Variable Volumetric Flowrate

Gas Phase Flow System

T Po
v  v o (1  X) FT = FTo(1 + εX)
To P

FA FAo (1  X) To P (1  X) To P
CA    C Ao
v v o (1  X) T Po (1  X) T Po
FB FAo  B  bX  To P   bX  To P
CB    C Ao B
v v o (1  X) T Po (1  X) T Po

PAo y Bo C Bo FBo
C Ao  B   
RT y Ao C Ao FAo
If isothermal, isobaric & ‐rA = kACA2CB

C3Ao (1  X) 2  B  bX 
 rA  k A
(1  X) 3

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Reactions With Phase Change

In a gas‐phase reaction condensation may occur.

C2H6(g) + 2Br2(g)  C2H4Br2(g,l) + 2HBr(g)

C2H4Br2(g,l) may condense partially depending on thermodynamic considerations.

Another example of phase change during reactions is A process used in the

manufacture of microelectronic
CVD = Chemical
Ch i l V Vapor D
Deposition.
ii materials.

Gas‐phase reactants or products are deposited as thin layers of solid : a phase

change similar to condensation

Production of Gallium Arsenide

Used in the production of computer chips.

GaCl2(g) + 1/2As2(g) + H2(g)  GaAs(g,s) + 2HCl(g)

Continuous Flow CVD reactors are being designed.

Consider an isothermal reaction

A(g) + bB  C(g) + D(g,l) Vapor pressure of D is Pv.

The gas‐
gas‐phase
Pv
concentration is
limited by y D ,e  After this point every mole
of product D condenses.
PT

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Stoichiometric table for A(g) + bB(g)  cC(g) + dD(g,l)

i Fio ΔFio Fi(g,l)

g,l) yi Fi(g) yi= FiL xi=
g, total Fi/FTg FiL/FTL
A FAo ‐FFAoX FAo(1‐X)
(1 X) yA FAo(1‐X)
(1 X) yA 0 xA

B FBo= ‐bFAoX FAo(ΘB‐bX) yB FAo(ΘB‐bX) yB 0 xB

FAoΘB
C FCo= cFAoX FAo(ΘC+cX) yC FAo(ΘC+cX) yC 0 xC
FAoΘC
D FDo= dFAoX FAo(ΘD+dX) yD>yDe ? yDeFTg yDe Fi(g,l)‐ xD
FAoΘD Fig
Tot FTo δFAoX FT = 1 FTg=ΣFi = 1 1
FTo(1+εX)

FAg  FBg  FCg

FTg 
(1  y De )

Example
Fill in the blank spaces for the reaction A + 2B + 3C 3D.

i Nio ΔNio Ni yi NGi gas yi NLi xi

total liquid

A 700 550

B 0.20 0.2

C 0.10 100 0.2

D 0.15 0.6

Total

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Solution

Mol Nio ΔNio Ni yi NGi gas yi NLi xi

total liliquid
id

A 700 ‐150 550 0.367 550 0.55 0 0

B 600 ‐300 300 0.2 200 0.20 100 0.2

C 650 ‐450 200 0.133 100 0.10 100 0.2

D 0 450 450 0.3 150 0.15 300 0.6

Total 1950 ‐450 1500 1 1000 1 500 1

Example 3‐5
A mixture of 28% SO2 and 72% air (air is 21% O2 and 79% N2) is charged to a flow
reactor in which SO2 is oxidized at total pressure of 1485 kPa (14.7 atm) and
constant
t t temperature
t t off 227 oC according
di tot the
th following
f ll i elementary
l t reaction:
ti

2 SO2 + O2 2SO3

 Set up a stoichiometric table using only the symbols (i.e., i, Fi)
 Derive the rate law of the reaction in terms of conversion (hint: use equation of state)
 Evaluate numerically the concentration of each species (including the inert) at a total
conversion of 75%.

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Example 3-5

Example 3-5

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Example 3-5

(8)

Example 3-5

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Example 3-5

Example 3-5

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Example 3-5

Reversible Reactions
Problem 3‐
3‐16(a)

F the
For h liquid
li id phase
h b
batch
h elementary
l reaction:
i

A+B ֐C
CA0=CB0= 2 mol/dm3
KC = 10 dm3/mol

a) Prepare stoichiometric table at equilibrium

b) Calculate concentrations of all species at equilibrium

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Reversible Reactions
Problem 3‐
3‐16(b)

Consider the following gas phase elementary reaction:

A ֐ 3C
Pure A enters at 400 k and 10 atm, where KC = 0.25 (dm3/mol)2

a)) C
Concentrations
t ti off allll species
i (batch
(b t h variable
i bl volume
l reactor).
t )
b) Constant volume batch reactor
c) Constant pressure batch reactor

Quiz 2

A mixture of 28% SO2 and 72% air (air is 21% O2 and 79% N2) is
charged to a flow reactor in which SO2 is oxidized at total
pressure of 1485 kPa (14.7 atm) and constant temperature of
227 oC according to the following elementary reaction:

2 SO2 + O2 → 2SO3

a) Set up a stoichiometric table using only the symbols (i.e.,

i, Fi)
b)) Derive the rate law of the reaction in terms of conversion
c) Evaluate numerically the concentration of each species
(including the inert) at a total conversion of 75%.

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