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3.1 Basic Definitions

Types of reaction： (1) Homogeneous reaction (one phase)
(2) Heterogeneous reaction ( >one phase)
Reaction usually occurs at the interface
between the phase.
(1) Reversible reaction
(2) Irreversible reaction
The molecularity of a reaction is the number of atoms, irons, or
molecules involved (colliding) in a reaction step.
=> Unimolecular =>reaction involving one atoms.
Bimolecular => reaction involving two atoms.
Termolecular=> reaction involving three atoms.

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Unimolecular reaction：
Radioactive decay

The rate of disappearance of U is given by the rate law.

Bimolecular reaction：

The probability of a termolecular reaction occurring is almost

nonexistent, and in most instances the reaction pathway follows a
series of bimolecular reactions.

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3.1.1 Relative Rates of Reaction
不同物種之相對反應速率可由計量係數之比例獲得。

當每一莫耳A消耗，可產生c/a莫耳的C
Rae of formation of C=c/a (Rate of disappearance of A)

同理,
在reaction 2-1中：

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For example：

If

=>

=>
=>

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3.2 The Reaction Order and the Rate Law
Rate Law：

Rate law or kinetic expression

The rate law gives the relationship between reactor rate
and concentration.
Ex：

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3.2.1
Power Law Models and Elementary Rate Law
由實驗觀察 =
=> Power Law Model 表示式最常用

Overall order of the reaction：

For example：
The units of the specific reaction rate constant are

(單位隨反應次數改變)

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For example：

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Elementary reaction：

That evolves a single step. Such as the bimolecular reaction

between oxygen and methanol.

此反應方程式係數與速率式中之次方相同
=>此反應和速率式為 Elementary (由Collision theroy)

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事實上，很多反應其計量係數和速率式次數相同
=>但非Elementary
=>由於其反應路徑包含了活性之中間產物和串聯反應
=>此些反應可稱為”follows an elementary rate law”
For example：

The rate constant, k, is defined with respect to NO

For example：

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結論：
(1) 雖然有許多反應由多個步驟和反應路徑所組成；但是速率式中之
次數卻與其計量係數相同。
=>follow an elementary rate law
(2) 速率式是由實驗得到，非由計量係數判定
(3) 速率式與反應器種類無關
(4)

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3.2.2 Nonelementary Rate Laws
大部份之homogenous and heterogeneous reactions 不是elementary
rate law.
Homogenous reactions：
•總反應次數或是各別成份之次數，並非一定都是整數
For example：
•有一些反應的速率式非常複雜，無分單獨，分為受溫度或僅受濃度影響。
For example：

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•k及k’受溫度影響很大
當這樣的速率式出現時，只能在特殊的情況下反應
For example：
(1) CO2 <<1, O2濃度很低
-rN2O=KN2OCN2O
=>對N2O與整個反應而言，為一階反應
(2) CO2 >>1, O2濃度很高
=>對O2而言是-1階
=>對N2O而言是+1階
=>此常出現於固體觸媒催化的液相或是氣相反應
=>以上之反應階數(特殊情況下)Apparent reaction orders
For example： Free-radical mechanism

=>液相反應亦會出現
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Heterogeneous reactions：
For many gas-solid catalyzed reaction 速率式習慣以分壓代替濃度表示
For example：
Follow Langmuir-Hinshelwood kinetic
kB, kT：adsorption constant (K．Pa-1 or atm-1)

(1) For ideal gas law：

(2)
-rA’：the rate of reaction per unit weight catalyst
-rA ：the rate of reaction per unit volume
ρb：bulk density of the catalyst particles in the fluid media.

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3.2.3 Reversible Reactions
可逆反應的速率式在平衡時，必需與熱力學上的關係式一致。
For example：

Kc=(mol/dm3)d+c-b-a
For example：
How to write rate laws for reversible reactions consider this gas-
phase reaction to be elementary and reversible.

Forward specific reaction rate constant, kB

Reverse specific reaction rate constant, k-B

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Step:
(1) Benzene(B) is being depleted by the forward reaction

The rate of disappearance of benzene is

=>
(2) For the reverse reaction between diphenyl(D) and hydrogen(H2)

The rate of formation of benzene is

The net rate of formation of benzene is the sum of the rates of formation
from the forward reaction(3-11) and the reverse reaction(3-12).

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The rate law for the rate of disappearance of benzene, -rB

=>

If exothermic reaction：T increase => KC decrease

If endothermic reaction：T decrease => KC increase

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The rate of formation of diphenyl, rD

Using the relationship given by 3-1 for the general reaction

=>

比較eq.3-15 and 3-16

=>
濃度平衡常數：

At equilibrium, -rB≡0
=>
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From Appendix C, eq.C-9
If the total number of moles is no change and the heat capacity
term, ∆CP=0, the temperature dependence of the concentration
equilibrium constant is

If we know the equilibrium constant at one temperature T and the

heat of reaction, ∆HoRX. We can calculate the equilibrium constant
at any other temperature T.
Case I Case II
For endothermic reaction For exothermic reaction

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3.3 The Reaction Rate Constant
k=f(T), 與物質濃度無關
k=> specific reaction rate of the rate constant
(1) For a gas-phase reaction
k=f(P)
(2) For a liquid system
k=f(ionic strength, choice of solvent)

Arrhenius equation：

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The reasons are in order to react：
(1) 碰撞之分子需要能量打斷鍵結，藉以形成新鍵結
(2) 反應分子間之立體障礙或是電子反力需克服，分子間才能靠近
The activation energy can be thought of as barrier to energy transfer
(from the kinetic energy to the potential energy) between reacting
molecules the must be overcome.
For example：

Energy barrier：
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For example：

T increase
Kinetic energy increase
Molecular collision increase
Increase the stretching and bending of the bond
Reach an activated state
Bond breaking and reaction

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(1) The molecules in the shaded area have sufficient kinetic
energy to cause the bond to break and reaction to occur.
(2) T increase
=>more molecules have sufficient energy to react as noted by
an increase in the shaded area, and the rate of reaction, -rA,
increase.

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Calculation of the activation energy：
T1, k1
T2, k2 =>實驗求得
…

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活化能越高 => 反應速率對溫度越敏感
Form Arrhenius equation
T=T0 =>
T=T =>

The ratio =>

If we know the specific reaction rate k0(T0) at T0 and

activation energy, E, we can find k(T) at T=T

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3.4 Present States of Our Approach to
Reactor Sizing and Design

If the rate of disappearance of A=>

=> The rate law

Table 3-5 Design equation

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Summary