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Anda di halaman 1dari 50

Stoichiometry

and

Rate Laws

Outline

Arrhenius Law

Elementary reaction

Order of Reaction

Rate Law for reversible reactions

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

Homogeneous reaction

involves substances of only one phase

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)

~ independent of the species concentrations

The specific reaction rate

constant, kA, is always referred to

a particular species

Exception

NaOH + HCl NaCl + H2O

Liquid Phase: k=f(temperature, total pressure, ionic strength, choice of solvent )

Gas Phase:

Rate Law

Temperature Dependency from Arrhenius Law

k( T ) Ae E / RT

(2)

E = activation energy (J/mol or cal/mol),

R = gas constant (8.314 J/mol.K=1.987 cal/mol.K)

T = absolute temperature (K)

result in their chemical interaction

Minimum energy that molecules must have to react

E1

ln k A ln A

R T

(3)

E , k~ less sensitive to the

temperature

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

increase in temperature

of activation energy and temperature

Low E

High E

1/T, K-1

Average

Temperature

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

Any given reaction is more temperature-sensitive at lower temperatures than

at higher temperatures

Arrhenius Law

Task

Consider the following elementary reactions :

Solution

1) Which reaction has the higher activation energy?

3) Which reaction is virtually temperature insensitive?

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)

Reactant particles must collide with each other.

Reaction is a result of the collision of a single molecule A with a single

molecule B

reactant bonds can change into product bonds.

Only those collisions with enough energy to exceed E can lead to

reaction.

Rate of reaction is proportional to the number of such collisions.

reactant.

Elementary Reaction

A

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 +

equation

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

(atoms) involved (colliding) in the reaction.

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

Rate law reflects a limiting step or combination of limiting steps

The rate limiting step is the slowest step in the sequence of steps

leading to product formation

The overall rate of reaction depends on this slowest step

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

respect to nitrous oxide

Apparent reaction order:

-1 with respect to O2

1 with respect to N2O

Overall zero order

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).

One more limit condition for reversible reactions: Equilibrium State

The state in which the concentrations of the reactants and products

have no net change over time

The rate of reaction is identical for all species and equal zero -rA 0

aA

bB

k

k-1

cC

dD

k-1 = Reverse reaction rate constant

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

ratio between rates of forward and

reverse reactions

k forward

k

KC

k reverse k -1

(6)

thermodynamic

equilibrium relationship

c

d

CCe

C De

KC a b

C Ae C Be

reaction must be consistent

with

with specified rate law of

forward and reverse

reactions

A

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)

The overall rate of formation of

species A r r

r

A

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

C

rA k A (C A B )

KC

Check of the consistency with thermodynamic equilibrium:

A

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

Task

Here kfA and krA are the forward and reverse specific reaction rates both

defined with respect to A.

Stoichiometry

Stoichiometry

Stoichiometry provides information on relative quantities of reactants

and products in chemical reactions.

and excess in our previous lecture.

reactors. Rate of reaction is a function of thermodynamic quantities

such as temperature and also concentration of the species.

Conversion of the limiting reactant is a function of the concentration

and therefore rate of reaction is a function of the conversion: ri=f(Xi).

To evaluate the integrals associated with the design equations of

the form

the functional form of ri(X) has to be found.

Stoichiometry provides a solution for this challenge.

rate law

rA f (C j )

C j h j (X )

rA g (X )

Mole Balance for Different Reactors

Reactor Type

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

0

0

[13]

The extent E of the reaction is the relative number of moles reacted/ generate

Relative reaction rates

Reaction

Rates

Rate of disappearance of A =

Rate of disappearance of B =

Rate of appearance of C

=

= =

[14]

Constructing stoichiometric table

t=0

NA0

NB0

NC0

ND0

NI0

t=t

NA

NB

NC

ND

NI

the conversion of the limiting reactant A

reached X. Composition of the product:

NA, NB, NC, ND and NI moles of substances

A, B, C, D and I, respectively

From the definition of conversion

= 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

A +

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

Total number of moles changed

The total number of moles of all active species (reactants and products) at

conversion X of species A:

= 0 +

+ 1 0

[15]

reacted

=

+ 1

= 0 + 0

0

0

= 0 + 0

where

= /

stoichiometric table using:

=

= +

[16]

Expressing all in terms of NA0

In order to define all concentrations on a basis per mole of A we

introduce the parameter :

N

C

y

i i 0 i 0 i 0

[17]

N A0 C A0 y A0

The final equation for concentration of species B:

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]

A +

()

= 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

Sealed vessel (gas phase reaction)

~Example:

Laboratory bomb calorimeter

(to measure the heat of combustion

of a particular reaction)

(ideal gas law applies)

~ Example: coal gasification

PV nRT

CO

+ H2O

CO2 + H2

V nR

T

P

(except polymerizations)

~ Solvent dominates

~ Changes in the density of the solute do not affect

the overall density of the solution significantly

A +

()

= 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%?

Stoichiometric Table for Flow Systems

Entering

FA0

FB0

FC0

FD0

FI0

A +

Leaving

FA

FB

FC

FD

FI

Flow systems

Batch System

N A N A0 N A0 X N A0 (1 X )

Nj0

fluxes

Replaced by

Nj

Fj0

Fj

Cj

Fj

q

moles / time

moles

[19]

+ +

flow rate (FA, FB, FC, FD), the conversion X, and the volumetric flow

rate

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

Stoichiometric Table for Flow Systems

Species

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

Stoichiometric Table for Flow Systems (Liquid-Phase Reactions)

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:

number of moles

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

Equation of State is a fundamental equation for gas systems:

PV ZNT RT

time = 0

[21]

Z = a compressibility factor

NT = an overall number of moles in a gas mixture

[22]

P0V0 Z 0 N T 0 RT0

PV

Z NT T

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

conversion:

N T N T 0 N A0 X

[24]

N

NT

1 A0 X 1 y A0 X

NT 0

NT 0

species A in an initial

[25]

mixture

total number of moles fed to the reactor

[26]

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

the compressibility factor does not change significantly during the course of

the reaction: Z0Z

The volume of gas mixture for a variable volume batch reactor at any

time/conversion:

V V0

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]

Volume Change with Reaction in a Flow System

any point within the reactor:

CT

FT

Pq

P

q qZRT ZRT

reactor:

P0

CT 0

Z 0 RT0

[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]

(31) and (30) and assuming that

Z0Z:

q q0

function of conversion in a

continuous reactor:

[32]

of conversion can be obtained by

combining the equations (32) and

(34) :

q q0 (1 X )

P0 T

P T0

[35]

Concentrations as a Function of Conversion

q q0 (1 X )

P0 T

P T0

concentration of any species in a flow system can be defined as a function

of conversion:

Cj

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

Initially

(mol/time)

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

Task

A mixture of 28% SO2 and 72% air is charged to a flow reactor in which SO2 is

oxidized.

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

2 SO2 + O2 2 SO3

+

1

2

Task

The elementary gas phase reaction

k1

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

Task

The elementary gas phase reaction

k

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.

Task

The elementary gas phase reaction

k

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

- 15-Simulation of a Non-Isothermal Industrial Hydrotreating Reactor Using Simulink-libreDiunggah olehtalhawasim
- 03-ChemicalKineticsDiunggah olehPartha Bhattacharjee
- Modelamiento y simulación reactor NH3Diunggah olehJMZA
- Hedengren ThesisDiunggah olehHasan Ali Solak
- 307991349-Wastewater-Engineering-Treatment-5th-Edition-Solutions-Manual.pdfDiunggah olehAlinCalloway
- x Mat Che 3 l.o.che.CombiDiunggah olehShorya Kumar
- 400 Test ChemDiunggah olehshmlniz
- sdfgbnDiunggah oleh0721673895
- Şerbănescu2014 Article KineticAnalysisOfCellulosePyroDiunggah olehGodfrey Eric Muendo
- Expt. 3 Partial FRDiunggah olehJunko Tsukuda
- Gas Interchangeability 2011 v6 HighResDiunggah olehhack7024
- 0195096703 Chemical DynamicsDiunggah olehRodrigo Martinez
- Chapter 10 No 9Diunggah olehAin Fza
- A Theoretical Analysis for Oxidation of Titanium CarbideDiunggah olehAlfonso Bravo León
- eview Kinetics 2012Diunggah olehPreston Wong
- Apple JuiceDiunggah olehauliyahoke
- DislocationsDiunggah olehJadson Barbosa
- CHE502 W02C02Diunggah olehKema Technowaka
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