Lecture three

Rate Equation For Fluid-Solid Catalytic Reactions

By using Langmuir rate and isotherm expressions. The first-

order relationship between gas concentration Cg, adsorbed concentration
̅ , and total concentration on the surface 𝑪
𝑪 ̅ 𝒎 in the langmuir approach
permite great simplification in formulating rate equation.

9.1 Rate Of Adsorption, Desorption And Surface Reaction

1. Rate Of Adsorption:

𝒌𝒂
𝑨+𝒙→
←′ 𝑨. 𝒙 for one site on surface
𝒌𝒂

̅𝒗
Rate of adsorption 𝒓𝒂 = 𝒌𝒂 𝑪𝑨 𝑪 mol / s (g catalyst) (1)

̅𝑨
Rate of desorption 𝒓𝒅 = 𝒌′𝒂 𝑪 mol / s (g catalyst) (2)

The net rate of adsorption of a componant is given by the difference

between equations 1 and 2:

̅ 𝒗 − 𝒌′𝒂 𝑪
𝒓𝒂 = 𝒌𝒂 𝑪𝑨 𝑪 ̅𝑨

𝟏
̅𝒗 −
𝒓𝒂 = 𝒌𝒂 [𝑪𝑨 𝑪 ̅𝑨]
𝑪
𝑲𝑨

̅ 𝒗 : concentration of vacant sites per unit mass of catalyst.

𝑪

𝒌𝒂
𝑲𝑨 =
𝒌′𝒂

̅ 𝑨 : concentration of A in the gas phase at the catalyst surface.

𝑪

If ka ( the intrensic adsorption rate) is large with respect to other steps in

the overall conversion process, the concentration of A on the catalyst

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surface will be in equilibrium with the concentration of A in the gas
phase. The net rate of adsorption approaches zero, and the equilibrium
concentration of A is given by:

𝟏
̅𝒗 −
𝟎 = 𝒌𝒂 [𝑪𝑨 𝑪 ̅𝑨]
𝑪
𝑲𝑨

̅𝒗
̅ 𝑨 )𝒆𝒒. = 𝑲𝑨 𝑪𝑨 𝑪
(𝑪

2. Surface reaction for A⇌B

𝒌𝒔
𝑨. 𝒙 →
←′ 𝑩. 𝒙
𝒌𝒔

The net rate of this step would be:

̅ 𝑨 − 𝒌′𝒔 𝑪
𝒓𝒔 = 𝒌 𝒔 𝑪 ̅𝑩

𝟏
̅𝑨 −
𝒓𝒔 = 𝒌𝒔 [𝑪 ̅𝑩 ]
𝑪
𝑲𝒔

If ks is large with respect other steps that is surface reaction is very fast,
then :

𝟏
̅𝑨 −
𝟎 = 𝒌𝒔 [𝑪 ̅𝑩]
𝑪
𝑲𝒔

̅𝑩
𝑪
̅ 𝑨 )𝒆𝒒. =
(𝑪
𝑲𝒔

3. Desorption : the mechanism for the desorption of the product B may

be represented by:

𝒌′𝒅
𝑩. 𝒙 →
← 𝑩+𝒙
𝒌𝒅

The net rate of this step would be:

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 ̅ 𝑩 − 𝒌𝒅 𝑪𝑩 𝑪
𝒓𝒅 = 𝒌′𝒅 𝑪 ̅𝒗

𝟏
̅𝒗 −
𝒓𝒅 = −𝒌𝒅 [𝑪𝑩 𝑪 ̅𝑩 ]
𝑪
𝑲𝑩

𝒌𝒅
Where 𝑲𝑩 =
𝒌′𝒅

If kd is large, then the equilibrium concentration of B would be:

𝟏
̅𝒗 −
𝟎 = −𝒌𝒅 [𝑪𝑩 𝑪 ̅𝑩 ]
𝑪
𝑲𝑩

̅𝒗
̅ 𝑩 )𝒆𝒒. = 𝑲𝑩 𝑪𝑩 𝑪
(𝑪

9.2 Rate Equation In Terms Of Fluid-Phase Concentration At The

Catalyst Surface

At steasy state, the rates of adsorption ra, surface reaction rs , and

desorption rd are equal.

To express the rate solely in terms of fluid concentrations, the adsorbed

̅𝑨 , 𝑪
concentrations 𝑪 ̅𝑩 , 𝐚𝐧𝐝 ̅𝑪𝒗 must be elimenated from equations
above.

The resultant rate equation involves all the rate constants k i and the
equilibrium constants Ki . There are too many constants to obtain from
experimental rate data.

To solve this problem, we suppose that one step in the overall reaction
controls the rate. Then the other two steps occure at near- equilibrium
conditions.

Example 1:

Find the rate equation of the following catalytic reaction A ⇌ B

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Solution

adsorption 𝑨 + 𝒙 ⇌ 𝑨. 𝒙

surface reaction 𝑨. 𝒙 ⇌ 𝑩. 𝒙

desorption 𝑩. 𝒙 ⇌ 𝑩 + 𝒙

over all reaction A⇌B

1. Surface reaction controlling:

From previous discussion, the surface reaction rate equation is:

𝟏
̅𝑨 −
𝒓𝒔 = 𝒌𝒔 [𝑪 ̅𝑩 ]
𝑪 (1)
𝑲𝒔

̅ 𝑨 𝐚𝐧𝐝 𝑪
𝑪 ̅𝑩 will be those correspobding to equilibrium for adsorption
and desorption steps:

(𝑪 ̅𝒗
̅ 𝑨 )𝒆𝒒. = 𝑲𝑨 𝑪𝑨 𝑪 (2)

(𝑪 ̅𝒗
̅ 𝑩 )𝒆𝒒. = 𝑲𝑩 𝑪𝑩 𝑪 (3)

Substituting equ. 2 and 3 into equ.1 gives:

̅𝒗 − 𝑲𝑩 𝑪𝑩 𝑪
𝒓 = 𝒌𝒔 [𝑲𝑨 𝑪𝑨 𝑪 ̅𝒗 ] (4)
𝑲𝒔

̅𝒗 can be expressed in terms of total

The concentration of vacant site 𝑪
̅𝒎:
concentration of sites 𝑪

̅𝒎 = 𝑪
𝑪 ̅𝒗 + 𝑪
̅𝑨 + 𝑪
̅𝑩 (5)

Substituting equ. 2,3 into equ. 5 gives:

̅𝒎 = 𝑪
𝑪 ̅ 𝒗 + 𝑲𝑨 𝑪𝑨 𝑪
̅𝒗 + 𝑲𝑩 𝑪𝑩 𝑪
̅𝒗

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Then :

̅𝒎
𝑪
̅𝒗 =
𝑪 (6)
𝟏+𝑲𝑨 𝑪𝑨 +𝑲𝑩 𝑪𝑩

Now combining equations 4,6 to give a relatively simple expression for

the rate in terms of fluid-phase concentration:

𝑲𝑨 𝑲𝒔 𝑪𝑨 −𝑲𝑩 𝑪𝑩
̅𝒎
𝒓 = 𝒌𝒔 𝑪 (7)
𝑲𝒔 +𝑲𝒔 𝑲𝑨 𝑪𝑨 +𝑲𝒔 𝑲𝑩 𝑪𝑩

Equation 7 can be further simplified using equilibrium constant for

overall reaction K;

𝑪
𝑲 = ( 𝑩)
𝑪 𝑨 𝒆𝒒.

And this can be related to adsorption and desorption constant by:

̅𝑩 𝑲𝑩 ⁄𝑪
𝑪 ̅𝒗 ̅
𝑪 𝑲𝑨
𝑲= ̅𝑨 ⁄𝑲𝑨 𝑪
̅𝒗 = ( ̅𝑩 ) (8)
𝑪 𝑪𝑨 𝒆𝒒. 𝑲𝑩

̅𝑩
𝑪
And since 𝑲𝒔 = ( ̅ ) then
𝑪𝑨 𝒆𝒒.

𝑲𝒔 𝑲𝑨
𝑲= (9)
𝑲𝑩

Then, rate equation can be written as:

𝟏
𝑪𝑨 −(𝑲)𝑪𝑩
̅𝒎
𝒓 = 𝒌𝒔 𝑲𝑨 𝑪 (10)
𝟏+𝑲𝑨 𝑪𝑨 +𝑲𝑩 𝑪𝑩

(A) If a reaction for which the adsorption is weak for all componants, the
denomator of eq. 10 approaches unity and the rate expression reduces to
the homogeneous form;

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 ̅𝒎 (𝑪𝑨 − 𝟏 𝑪𝑩 ) or
𝒓 = 𝒌𝒔 𝑲𝑨 𝑪
𝑲

𝟏
𝒓 = 𝒌 (𝑪𝑨 − 𝑪𝑩 ) (11)
𝑲

(B) If the product of a reaction is strongly adsorbed and the reactant

adsorption is weak, the term KdCB is much larger than all others in the
denomater, and if the reaction is also irreversible, then:

𝑪𝑨
̅𝒎
𝒓 = 𝒌𝒔 𝑲𝑨 𝑪 (12)
𝑲𝑩 𝑪𝑩

(c) If we suppose that B is only weakly adsorbed, while A is very

strongly adsorbed. Then, the rate expression, in analogy with eq. 12,
would become zero order in A; that is:

𝑪𝑨
̅𝒎
𝒓 = 𝒌𝒔 𝑲𝑨 𝑪 =𝒌 (13)
𝑲𝑨 𝑪𝑨

2. Adsorption Controlling

Let us now suppose that the adsorption of A is the slow step. Then the
surface reaction, and the desorption of B will occur at equilibrium (fast
step).

The rate can be formulated from adsorption equation:

𝟏
̅𝒗 −
𝒓 = 𝒌𝒂 [𝑪𝑨 𝑪 ̅𝑨 ]
𝑪 (14)
𝑲𝑨

̅𝑩
𝑪
̅ 𝑨 )𝒆𝒒. =
(𝑪 from rate of surface reaction
𝑲𝒔

(𝑪 ̅𝒗
̅ 𝑩 )𝒆𝒒. = 𝑲𝑩 𝑪𝑩 𝑪 from rate of desorption

̅𝒗
𝑲𝑩 𝑪𝑩 𝑪
̅𝑨 =
Then : 𝑪 (15)
𝑲𝒔

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 𝑲𝒔 𝑲𝑨
But 𝑲 =
𝑲𝑩

̅
̅ 𝑨 = 𝑲𝑨𝑪𝑩 𝑪𝒗
Then 𝑪 (16)
𝑲

Subtituting equ.16 into equ.14 gives:

𝟏
̅ 𝒗 [𝑪𝑨 − 𝑪𝑩 ]
𝒓 = 𝒌𝒂 𝑪 (17)
𝑲

̅𝒗 with its equivalent then:

If we change 𝑪

̅𝒎 (𝑪𝑨 − 𝟏 𝑪𝑩 )
𝒌𝒂 𝑪
𝑲
𝒓= 𝑲𝑨 (18)
𝟏+( 𝑲 +𝑲𝑩 )𝑪𝑩

3. Desorption Controlling

If the rate of desorption of product B controls the whole reaction, then:

𝟏
̅𝒗 −
𝒓 = −𝒌𝒅 [𝑪𝑩 𝑪 ̅𝑩]
𝑪 (19)
𝑲𝑩

(𝑪 ̅𝒗
̅ 𝑨 )𝒆𝒒. = 𝑲𝑨 𝑪𝑨 𝑪 from adsorption at equilibrium

̅𝑩
𝑪
̅ 𝑨 )𝒆𝒒. =
(𝑪 from rate of surface reaction at equilibrium
𝑲𝒔

̅𝒎 = 𝑪
Also 𝑪 ̅𝒗 + 𝑪
̅𝑨 + 𝑪
̅𝑩

̅𝒎 = 𝑪
𝑪 ̅ 𝒗 + 𝑲𝑨 𝑪𝑨 𝑪
̅𝒗 + 𝑲𝒔 𝑲𝑨 𝑪𝑨 𝑪
̅𝒗

𝒄̅𝒎
̅𝒗 =
𝑪
𝟏+𝑲𝑨 𝑪𝑨 +𝑲𝒔 𝑲𝑨 𝑪𝑨

Then :
𝟏
𝑪𝑨 −(𝑲)𝑪𝑩
𝒓 = 𝒌𝒅 𝒄̅𝒎 𝑲 (20)
𝟏+𝑲𝑨 𝑪𝑨 +𝑲𝑲𝑩 𝑪𝑨

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