Tugas Teknik Reaksi Kimia Lanjut

Jawaban Exercise Chapter 6

OLEH: Ester Kristin Fatimatuz Zahroh Prima Anggraini

1.

The isothermal, first-order reaction of gaseous A occurs within the pores of a spherical catalyst pellet. The reactant concentration halfway between the external surface and the center of the pellet is equal to one-fourth the concentration at the external surface. (a) What is the relative concentration of A near the center of the pellet? (b) By what fraction should the pellet diameter be reduced to give an effectiveness factor of 0.7? Jawab: (a) Untuk reaksi orde pertama

Dimana Jika r = 0,5 Rp, = 0,5, CA = 0,25 CAS, =0,25

Sehingga menjadi:
* +

Dimana Menjadi:

= 4,131

Aturan LHopitals untuk mencari = 0,133

(b) Reaksi orde pertama pada spherical pellet: * Jika + = 2,77

= 0,7, menggunakan persamaan di atas maka

Karena

dan modulus Thiele berada pada dua kondisi berbeda maka

persamaan untuk pellet baru menjadi:

Laju Konstan dan efektifitas difusi tidak berubah:

= 4,131,

= 0,7, dan

= 2,77

2.

A second-order, irreversible reaction with rate constant k = 1.8 L mol-1 s-1 takes place in a catalyst particle that can be considered to be a one-dimensional slab of half width = 1 cm. The concentration of reactant in the gas phase is 0.1 mol L-1 and at the surface is 0.098 mol L-1. The gas-phase mass-transfer coefficient is 2 cm s-1. Determine the intraphase effectiveness factor. (Contributed by Prof. J. L. Hudson, Univ. of Virginia.) Jawab: Jika fluks permukaan sama dengan laju reaksi dengan asumsi steady state

Luas permukaan eksternal basis 1 ( )

Untuk menghitung faktor efektivitas intraphase, maka diperlukan laju reaksi maksimum. Laju reaksi maksimum atau

( Untuk basis volum 1 cm3

( Maka faktor efektivitas intraphase adalah:

3.

A second-order, irreversible reaction with rate constant k = 1.8 mol-1s-1 takes place in catalyst particle that can be considered to be one-dimensional slab of half width = 1 cm.

The concentration of reactant in the gas phase is 0.1 mol L-1 and at the surface is 0.098 mol L-1. The gas-phase mass-transfer coefficient is 2 cm s-1. Determine the intraphase effectiveness factor. (Contributed by Prof J. L. Hudson, Univ. Of Virginia).

Jawab: Untuk reaksi reversible, isotermal, dan orde pertama: ( Dimana C = CA + CB Asumsi CAS = 0,9 C ( ATAU ( Dimana ( ) ) dan
( )

=1

(
(

=1 )
) ( )

Oleh karena itu, Plot t terhadap

= untuk banyak nilai K dan dapat dilihat pada gambar dibawah ini.

4.

Consider the combustion of a coal particle occurring in a controlled burner. Assume the rate expression of the combustion reaction at the surface of the particle is given by: r = 106exp[-100/RgTs]Cs E in kJ mol-1 where the rate is in units of moles O2 reacted min-1 (m2 external surface)-1, Ts is the surace temperature of the coal particle in Kelvins and Cs is the surface concentration of O2. The estimated heat and mass-transfer coefficients from the gas phase to the particle are ht = 0.5 kJ minK-1m-2 dan kc = 0.5 m min-1, an the heat reaction is -150kJ (mol O2)-1. Consider the bulk temperature of the gas to be TB = 500oC and the bulk concentration of O2 will be 2 mol m-3. (a) What is the maximum temperature difference between the bulk gas and the particle? What is the observed reaction rate under that condition? (b) Determine the actual surface temperature and concentration, and therefore the actual reaction rate.

Jawab: (a) Perbedaan temperatur maksimum:

)(

= -300 K Ketika CAS = 0, ( )( )

(b) Untuk reaksi orde pertama pada pellet tak berpori:

Dimana ( )

Maka:
( ( )( ) )

)( = 1061 K = 0,0805mol m-3

)(

Laju aktual pada kondiai ini: = 0,960

5.

The irreversible, first order reaction of gaseous A to B occurs in spherical catalyst pellets with a radius of 2 mm. For this problem, the molecular diffusivity of A is 1.2 x 10-1 cm2 s-1 and the Knudsen diffusivity is 9 x 10-3 cm2 s-1. The intrinsic first order rate constant determined from detailed laboratory measurements was found to be 5.0 s-1. The

concentration of A in the surrounding gas is 0.01 mol L-1. Assume the porosity and the tortuosity of the pellets are 0.5 and 4, respectively. (a) Determine the Thiele modulus for the catalyst pellets. (b) Find a value for the internal effectiveness factor. (c) For an external mass-external coefficient of 32 s-1 (based on the external area of the pellets), determine the concentration of A at the surface of the catalyst pellets. (d) Find a value for the overall effectiveness factor.

Jawab: Rp = 2 mm = 0.2 cm DAB = 1.2 x 10-1 cm2 s-1 DKA = 9 x 10-3 cm2 s-1 K = 5.0 s-1 CAB = 0.01 mol L-1

Modulus Thiele untuk pellet katalis Faktor efektivitas internal * * + +

Jika diasumsikan steady state, laju transfer massa adalah sama dengan laju reaksi, maka

jika = 32 s-1, maka konsentrasi A di permukaan,

( )

mol/L

Faktor efektivitas keseluruhan (

6.

J. M. Smith (J. M. Smith, Chemical Engineering Kinetics, 2nd ed., McGraw-Hill New York, 1970, p.395) presents the following observed data or Pt catalyzed oxidation of SO2 at 480oC obtained in a differential fixed-bed reactor at atmospheric pressure and bulk density of 0.8 g/cm3. Mass velocity (g h cm ) 251 171 119 72
-1 -2

Bulk Partial Pressure SO2 0.06 0.06 0.06 0.06 SO3 0.0067 0.0067 0.0067 0.0067 O2 0.2 0.2 0.2 0.2

Observed rate (mol SO2/h/gcat) 0.1346 0.1278 0.1215 0.0956

The catalyst pellets were 3.2 by 3.2 mm cylinders and the Pt was superficially deposited upon the external surface. Compute both external and temperature gradients and plot CSO2 and T versus the mass velocity. Can you draw any qualitative conclutions from this plot? If the reaction activation energy is 30 kcal/mol, what error in rate measurement attends neglect of an external T? What error prevails if, assuming linear kinetics in SO2, external concentration gradients are ignored? Hints:

Catalyst pellet is nonporous Reaction carried out with excess air air = 1.339 g/h/cm @ 480oC

DSO2-air = 2.44 ft2/h @ 480oC B = void fraction of bed = 0.4 Sc = 1.28 Prandtl number = = 0.686

Cp = 7.514 cal/mol/K a= = 18.75 mm-1

Hr = -30 kcal/mol Jawab: Flux melalui boundary layer:

Dimana A adalah SO2 Pada steady state, flux massa sama dengan laju diobservasi dari reaksi. Oleh karena itu:

Faktor Colburn J:

Dimana Sc = 1,28 Bilangan Reynold:

Diameter partikel, dp:

Dimana d merupakan diameter pellet silinder dan h merupakan panjang dari pellet silinder

Oleh karena itu, diameter efektif adalah: = 3,92 mm

Bilangan Reynold sebagai fungsi G:

( )

Kecepatan, u, seba.gai fungsi G

Koefisien transfer massa: ( ( ) )

(

= 2739 G1/2

) ( )

Plot gradien konsentrasi:

Menentukan T Dimana Hr = -30 kcal mol-1

Temperatur gradien: * +[ ]

Dimana merupakan densitas fluida, A adalah SO2, yfa adalah

(
) ( | | | | ( | | ) | |

Temperatur gradient sebagai fungsi dari G dapat dilihat pada gambar dibawah ini

Perhitungan eror pada temperatur gradien: k pada permukaan = ks = A exp k pada bulk = ks = A exp

Perbandingan konstanta laju: [ Maka: = 1,46 % eror = 32% ( )]

Kinetika orde pertama robs = k CA r pada permukaan = rs = ks CAS r pada bulk = rB = kB CAB Perbandingan rs dan rB: = (1,46) % eror = 16% = 1,19

7.

The importance of diffusion in catalyst pellets can often be determined by measuring the effect of pellet size on the observed reaction rate. In this exercise, consider an

irreversible reaction occuring in catalyst pellets where the surface concentration of reactant A is CAS = 0.15 M. Data: Diameter of sphere (cm) robs (mol/h/cm3) 0.2 0.25 0.06 0.80 0.02 1.8 0.006 2.5

(a) Calculate the intrinsic rate constant and the effective diffusivity (b) Estimate the effectiveness factor and the anticipated rate of reaction (robs) for a finite cylindrical catalyst pellet of dimension 0.6 cm x 0.6 cm (diameter = length). Jawab: (a) Thiele modulus untuk reaksi orde pertama, spherical pellet

robs = k CAS

Perbandingan yield 2 sphere besar: 3

Perbandingan 2 pellet terkecil = 0,3 = 1,39

Grafik observe rate vs radius partikel:

Efektivitas difusi dan konstanta laju intrinsik: k = 46 = 4,6 x 10-3

(b) Untuk silinder, karakteristik parameter panjang:

Dimana

merupakan setengah panjang silinder,

= 0,1 cm

Modulus Thiele pada paraneter panjang: Dan faktor efektivitas adalah:

Maka dari itu,

= 10 dan

= 0,1

robs = 0,00069 mol cm-3 s-1

8. Isobutylene (A) reacts with water on an acidic catalyst to form t-butanol (B). (CH3)2C=CH2 +H2O = (CH3)3COH When the water concentration greatly exceeds that of isobutylene and t-butanol, the reversible hydration reaction is effectively first order in both the forward and reversible directions. V. P. Gupta and W. J. M. Douglas [AICHE J., 13 (1967) 883] carried out the isobutylenehydration reaction with excess water in a stirred tank reactor utilizing a cationic exchange resin as the catalyst. Use the following data to determine the effectiveness factor for the ion exchange resin at 85oC and 3.9 percent conversion. Data: Equilibrium constant @ 85oC = 16.6 = [B]/[A] = 2.0 x 10-5 cm2 s-1 Radius of spherical catalyst particle = 0.213 mm

Density of catalyst = 1.0 g cm-3 Rate of reaction at 3.9 prent conversion = 1.11 x 10-5 mol s-1 gcat-1 CAS = 1.65 x 10-2 M (evaluated at 3.9 percent conversion) = 1.72 x 10-2 M (reactor inlet concentration) (Problem adapted from C. G. Hill, Jr., An Introduction to hemical Engineering Kinetics and Reactor Design, Wiley, NY, 1977). Jawab: ( )

Dimana k1 adalah konstanta laju untuk reaksi maju. robs = k1 CAS

= 1,63

Maka 0,511 = 1,312 s-1