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Stoichiometry
and
Rate Laws
Outline
Stoichiometric Table
Batch systems:
Constant volume and
Constant pressure
Flow systems:
Liquid phase
Gas phase reactions that have a change in the total number of moles
Reactors with variable volumetric flowrates
Types of Reactions
Phase
Types of Reactions
Heterogeneous reaction
involves more than one phase, and the
reaction usually occurs at or very near the
interface between the phases
B
Irreversible reaction A
proceeds in only one direction and continues
until the reactants are exhausted
Equilibrium
Reversible reaction
proceeds in both forward and reverse
directions; continues until the equilibrium state
is reached
A
B
Rate Law
The Rate Law and the Reaction Rate Constant
General form of the rate law, which is an algebraic equation representing the
reaction rate as a function of the concentrations (activities) of various species:
rA k( T ) f ( C A ,C B ,...)
(1)
Exception
NaOH + HCl NaCl + H2O
Gas Phase:
Rate Law
Temperature Dependency from Arrhenius Law
k( T ) Ae E / RT
(2)
E1
ln k A ln A
R T
(3)
ln k, sec-1
ln k, sec-1
slope= -E/R
Low E
High E
1/T, K-1
1/T, K-1
Arrhenius Law
Rules of thumb:
ln k, sec-1
Low E
High E
1/T, K-1
Activation Energy, E
40 kJ/mol
160 kJ/mol
280 kJ/mol
400 kJ/mol
0 oC
11 oC
2.7 oC
1.5 oC
1.1 oC
400 oC
65 oC
16 oC
9.3 oC
6.5 oC
1000 oC
233 oC
58 oC
33 oC
23 oC
Arrhenius Law
Task
Consider the following elementary reactions :
Solution
1) Which reaction has the higher activation energy?
Arrhenius Law
Solution
4) Which reaction will dominate (i.e. take place the fastest) at high temperatures?
Arrhenius Law
Finding k(T) given k(T0)
k (T0 ) Ae E / RT0
k (T ) Ae E / RT
substitute A k T0 e E / RT0
k (T ) k (T0 )e
E
RT0
E
RT
E 1 1
k(T) k(T0 )exp
R T0 T
If we know:
The specific reaction rate k0(T0) at a temperature T0
The activation energy, E,
We can find the specific reaction rate constant k(T) at any other
temperature,
T, for that reaction
Arrhenius Law
Task
Determine the activation energy, E and frequency factor, A from the following data:
k (min-1)
0.001
0.050
T (oC)
0.0
100.0
Solution
E1
ln k A ln A
R T
k( T ) Ae E / RT
Elementary Reaction
Elementary and Non- elementary Reactions
Rate law can be derived from collision theory
rA k( T ) f ( C A ,C B ,...)
(1)
Elementary Reaction
4 collisions
A
Add another
molecule of A
6 collisions
B
A
Add another
molecule of B
B
9 collisions
Elementary Reaction
Elementary Reactions
If kinetic experiments results in a rate law, which corresponds to
the stoichiometric equation, we call such reactions elementary.
A +
Molecularity
Elementary step
Rate law
1. Unimolecular
A -> products
rate = k CA
2. Bimolecular
2A -> products
A + B -> products
rate = k C2A
rate = k CACB
3. Termolecular
3 A -> products
A + 2 B -> products
A + B + C -> products
rate = k C3A
rate = k CAC2B
rate = k CACBCC
Elementary Reaction
Elementary and Non-Elementary Reactions
Elementary Reaction
H2 + I2
2HI
rH 2 kCH 2 C I 2
Non-Elementary
Reaction
H2 + Br2
rHBr
2HBr
1/ 2
k1C H 2 C Br
2
k 2 C HBr / C Br2
Elementary Reaction
rA
General form of the rate law:
k AC A C B ...
Temperature-dependent
term
(4)
Concentration-dependent
terms
The order of a reaction refers to the power to which the concentrations are raise
The overall order of the reaction: n = + +
2 NO
+ O2
2 NO2
2N2O
2
rNO k NO C NO
CO 2
CO
+ Cl2
rCO kCCOC
H2 + Br2
rHBr
COCl2
3/ 2
Cl
k1C H 2 C
2HBr
1/ 2
Br2
k 2 C HBr / C Br2
rN 2O
i) CO2
1>>
ii) CO2
1<<
k CO2
+ O2
k N 2O C N 2O
1 k CO2
k CO2 rN O kN OCN O
2
2N2
kN2OCN2O
rN2O
k CO2
Rate Law
Examples of Forms of Rate Law and Units of Reaction Rate Constant
Zero-order:
rA k A
mol
mol
rA 3
k
A
3
dm
sec
dm sec
mol
dm 3 sec
First-order:
[k]=sec-1
Second-order:
dm 3
k
mol sec
Third-order:
dm 6
k 2
mol sec
rA k AC A
mol
1
mol mol
rA 3
C
3
A
A
3
sec
dm sec
dm dm sec
rA k AC A2
2
dm 3
mol
mol
2 mol
rA 3
A
A
dm sec
mol sec
dm dm sec
rA k AC A3
3
dm 6
mol
mol
3 mol
rA 3
A
A
2
9
dm sec
mol sec
dm dm sec
Rate Law
Task
1
What is the reaction rate law for the reaction: A B C
2
if the reaction is elementary?
Calculate the rates of A, B, and C in a CSTR where the concentrations
are
CA = 1.5 mol/dm3, CB = 9 mol/dm3 and kA = 2 (dm3/mol)(1/2)(1/s).
bB
k
k-1
cC
dD
At thermodynamic equilibrium:
c
d
CCe
C De
KC a b
C Ae C Be
KC is an equilibrium constant
Units
(5)
mol
3
dm
d c b a
k forward
k
KC
k reverse k -1
(6)
c
d
CCe
C De
KC a b
C Ae C Be
kA
k-A
A
Forward reaction A
B
Reaction rate with respect to species A
rA k AC A
rA k AC A
Reverse reaction B
k-A
disappearance of species A
(7)
formation of species A
(8)
rA k AC B
formation of species A
(9)
A, forward
A, reverse
k AC A k A C B
(10)
k AC A k AC B k A ( C A
KC
k forward
k
k reverse k -1
k A
CB )
kA
kA
k-A
At equilibrium:
KC
C Be
C Ae
rA 0 k A (C Ae
CBe
After rearranging:C Ae
KC
C
K C Be
C Ae
(11)
(12)
CBe
)
KC
Stoichiometry
Stoichiometry
Stoichiometry provides information on relative quantities of reactants
and products in chemical reactions.
rA f (C j )
C j h j (X )
rA g (X )
Batch
Differential
N A0
Algebraic
dX
rAV
dt
Integral
t N A0
X A (t )
dX
rAV
FA 0 X
(rA ) exit
C X
A0
( rA )exit
V
CSTR
PFR
FA0 dX
rA
dV
V FA0
C A0
X out
X in
X out
X in
PBR
FA0 dX
rA
dW
W FA0
dX
rA
dX
rA
X out
X in
dX
rA
Stoichiometry: Extent
Relative quantities (extent)
Reaction
Initial quantities
Quantities remaining at
t=t
Quantities reacted
[13]
The extent E of the reaction is the relative number of moles reacted/ generate
Rates
Rate of disappearance of A =
Rate of disappearance of B =
Rate of appearance of C
=
= =
[14]
t=0
NA0
NB0
NC0
ND0
NI0
= 0 0
moles of A
moles of A in
a system volume introduced into the
at conversion X system volume
moles B reacted
b
b
moles A reacted ( N A0 X )
a
a
moles of A
reacted when
conversion reached X
t N A0
X A (t )
Species
Initially
(mol)
Change
(mol)
NA0
( N A0 X )
NB0
NC0
ND0
NI0
Total
NT0
b c d
1 N A0 X
a a a
b
( N A0 X )
a
c
( N A0 X )
a
d
( N A0 X )
a
dX
rAV
Remaining
(mol)
N A N A0 N A0 X
b
N A0 X
a
c
N C N C 0 N A0 X
a
d
N D N D0 N A0 X
a
N B N B0
NI NI0
d c b
NT NT 0 1 N A0 X
a a a
+ 1 0
[15]
+ 1
= 0 + 0
0
0
= 0 + 0
where
= /
= +
[16]
CB
N B 0 ( b / a )N A0 X B N A0 ( b / a )N A0 X
V
V
CB
N A0 B (b / a) X
V
[18]
()
= 0
0
Initially
(mol)
A
NA0
N B 0 B N A0
NC 0 C N A0
N D 0 D N A0
N I 0 I N A0
Total NT0
Change
(mol)
( N A0 X )
Remaining
(mol/dm3)
(mol)
N A N A0 N A0 X
CA
N A 0 (1 X)
V
b
N
X C N A0 B (b / a) X
( N A0 X ) B
A0
B
a B
a
V
c
c
N A0 C (c / a) X
( N A0 X ) N C N A0 C X
C
a
a C
V
d
d
( N A0 X ) N D N A0 D X C N A0 D (d / a) X
a
a D
V
NI0
NI NI0
CI
V
N T N T 0 N A0 X
+ H2O
CO2 + H2
V nR
T
P
()
= 0
0
Initially
(mol)
Change
(mol)
Remaining
(mol)
(mol/dm3)
NA0
( N A0 X )
N A N A0 N A0 X
C A C A0 (1 X )
NB0
NC0
ND0
NI0
N B N A0 B X
a
N C N A0 C X
a
N D N A0 D X
a
NI NI0
CB C A0 B (b / a) X
b
( N A0 X )
a
c
( N A0 X )
a
d
( N A0 X )
a
Total
NT0
N T N T 0 N A0 X
CC C A0 C (c / a) X
CD CA0 D (d / a ) X
CI CI 0
A +
Rate law
rA kCACB
C A C A0 (1 X )
CB CA0 B (b / a) X
rA kCA0 (1 X ).CA0 B (b / a) X
rA kC2 A0 (1 X )B (b / a) X
Design Equation
F X
V A0
(rA ) exit
V FA0
X out
X in
dX
rA
rA f (X )
Task
A component of soap (sodium stearate) is produced by saponification of glyceryl
stearate with aqueous caustic soda according the following equation:
3 NaOH + (C17H35COO)3C3H5
3 C17H35COONa + C3H5(OH)3
Production is carried out in a batch reactor. The initial mixture consists solely of sodium
hydroxide at a concentration of 10 mol/dm3 and glyceryl stearate at a concentration
of 2 mol/dm3. What is the concentration of glycerine when the conversion of sodium
hydroxide is (a) 20% and (b) 90%?
A +
Leaving
FA
FB
FC
FD
FI
Flow systems
Batch System
N A N A0 N A0 X N A0 (1 X )
Nj0
Nj
Fj0
Fj
Fj
q
moles / time
moles
[19]
+ +
CA
FA FA0
(1 X )
q
q
CB
FB FB 0 (b / a ) FA0 X
q
q
[20]
CC
FC FC 0 (c / a ) FA0 X
q
q
CD
FD FD 0 (d / a ) FA0 X
q
q
The parameter :
Fi 0 Ci 0v Ci 0
y
i0
FA0 C A0v C A0 y A0
Initially
(mol / time)
Change
(mol / time)
( FA0 X )
FA0
FB 0 B FA0 b ( F X )
A0
a
c
( FA 0 X )
FC 0 C FA0
a
d
( FA 0 X )
FD0 D FA0
a
C
D
I
FI 0 I FA0
Total
FT0
Remaining
(mol / time)
FA FA0 (1 X )
b
FB FA0 B X
a
FC FA0 C X
a
FD FA0 D X
a
FI FA0 I
d c b
FT FT 0 1 FA0 X
a a a
FT FT 0 FA0 X
For liquid-phase reactions, the volumetric flow rate does not practically
change in the course of reaction: v = v0 = Const
FA0
(1 X ) C A0 (1 X )
q0
FA FA0 (1 X )
CA
FB FA0 B X
a
C B C A0 B X
a
FC FA0 C X
a
C C C A0 C X
a
FD FA0 D X
a
C D C A0 D X
a
Stoichiometric Table
+ +
For most batch and liquid-phase reactions and some gas-phase reactions
the volumetric flow rate or reaction volume does not change, however:
volume (or volumetric flow rate) will change in the following situations:
d c b
1 0
a a a
N2
3H2
2NH3
Stoichiometric Table
Volume Change with Reaction
The first four columns of the stoichiometric tables are always valid
Assumptions concerning a volume change were made when expressing
concentration in terms of conversion
[21]
Z = a compressibility factor
NT = an overall number of moles in a gas mixture
[22]
P0V0 Z 0 N T 0 RT0
P0V0 Z 0 NT 0 T0
V V0
P0 Z
N
T
T
P Z 0 N T 0 T0
[23]
Stoichiometric Table
Volume Change with Reaction in a Batch System
V V0
P0 Z
N
T
T
P Z 0 N T 0 T0
N T N T 0 N A0 X
[24]
N
NT
1 A0 X 1 y A0 X
NT 0
NT 0
N
d c b N
1 A0 A0 y A0
NT 0
a a a NT 0
Equation [25] now becomes:
Equation [23]:
NT
1 y A0 X 1 X
NT 0
V V0
[27]
P0 Z T
(1 X )
P Z 0 T0
[28]
Stoichiometric Table
Volume Change with Reaction in a Batch System
V V0
P0 Z T
(1 X )
P Z 0 T0
P0
T
(1 X )
P
T0
V V0
and equation [29] can be used to calculate the pressure change as a
function of T and X
[29]
FT
Pq
P
q qZRT ZRT
[30]
FT P0 T
FT 0 P T0
FT FT 0 FA0 X
[33]
F
FT
1 A0 X 1 y A0 X 1 X [34]
FT 0
FT 0
[31]
[32]
P0 T
P T0
[35]
q q0 (1 X )
P0 T
P T0
Fj
q
F j FA0 j S j X
Thus:
Cj
Cj
FA0 ( j S j X )
q0 (1 X )
P T0
P0 T
C A0 ( j S j X ) P T0
(1 X )
P0 T
[36]
Cj
C A0 ( j s j X ) P T0
(1 X )
P0 T
Change
(mol/time)
Remaining
(mol/time)
A
B
C
D
I
FA0
(mol/volume. time)
1 X P T0
C A C A0
(
1
X
)
P0 T
(b / a) X P T0
C B C A0 B
(1 X ) P0 T
( FA0 X )
FA FA0 (1 X )
FB 0 B FA0
b
( FA0 X )
a
FC 0 C FA0
c
( FA 0 X )
a
FB FA0 B X
a
FC FA0 C X
a
(c / a ) X
CC C A0 C
(1 X )
P T0
P0 T
FD0 D FA0
d
( FA 0 X )
a
FD FA0 D X C D C A0 D (d / a) X
(1 X )
a
P T0
P0 T
FI 0 I FA0
FI FA0 I
CI
C A0 I P T0
(1 X ) P0 T
2 SO2 + O2 2 SO3
Calculate concentrations of all species at the following conversion of SO2: 0; 0.25;
0.5; 0.75; 1, if the total pressure is 1485 kPa and the temperature is constant at
227oC. Note that air composition is 21% O2 and 79% N2.
Solution
1
2
3A + 2B 3 C +5 D
is carried out in a flow reactor operated isothermally at 427C and 28.7 atmospheres.
Pressure drop can be neglected. Express the rate law and the concentration of each
species as a function of conversion and as a function of the total molar flow rates. The
entering volumetric flow rate is 10 dm3/s and the specific reaction rate,k is 200
dm12/mol4s. The feed is equal molar in A and B.
Solution
1
3A + 2B
3 C +5 D
is carried out in a flow reactor operated isothermally at 427C and 28.7 atmospheres.
Pressure drop can be neglected. Express the rate law and the concentration of each
species as a function of conversion and as a function of the total molar flow rates. The
entering volumetric flow rate is 10 dm3/s and the specific reaction rate is 200 dm12/mol4s.
The feed is equal molar in A and B.
1
3A + 2B
3 C +5 D
is carried out in a flow reactor operated isothermally at 427C and 28.7 atmospheres.
Pressure drop can be neglected. Express the rate law and the concentration of each
species as a function of conversion and as a function of the total molar flow rates. The
entering volumetric flow rate is 10 dm3/s and the specific reaction rate is 200 dm12/mol4s.
The feed is equal molar in A and B.
Summary