CHAPTER 4 1 [ 2. . C / ( q ) ] +1 =k .

q 1 /2 katalis, reaksinya akan berlangsung jauh lebih

Laju reaksi cepat diawal, lambat di belakang.
Meknisme baru dugaan doang, setelah itu dicocokin
dengan data percobaan. 3 tipe reaktor skala lab:
batch(reaksi lambat), continue/CSTR(reaksi
kompleks, data batch menyulitkan), PFR(reaktor
khusus).
Metode diferensial (batch: V=konstan)
berguna untuk reaksi yang kompleks, hanya
digunakan atau cocok digunakan untuk menentukan
orde reaksi. Pada metode differential digunakan
teknik coba2 (hanya estimasi) untuk turunan
pertamanya. Persamaan differential cocok untuk
orde yang rendah, orde 1 dan orde 2. Turunan
pertama yang diestimasi pada metode ini
menyebabkan nilai konsatanta lajureaksi cukup
besar. Tidak akurat perubahan konstanta laju reaksi
sebesar exponential. Jadi kurang efektif untuk
menentukan nilai k (konstanta laju reaksi). Selain itu
turunan pertama yang diestimasi memeperbesar
faktor kesalahan nilai k.
Ad C n
(r A ) = dt =k . C A
Linearisasi:
ln (r A ) =ln k + n. ln C A
t 1 /2 = C C =C A 0
1/2 A C A 0 cepat. Katalis mempercepat reaksi maju dan
Waktu paruh : k . C A0 ln 2 .t pd wktu akhir rx mndur dengan besar yang sama.
[ 2. . C /( +q ) ] +1
C
1/ 2 Important catalyst properties:
1. Harus aktif : klo rx cpat, wktu lbih singkat
*Knduktivitas : swt konstanta yg nunjukin
d C
A kmampuan swt lar utk mhantar listrik.
produksinya bsa lbih bnyk, kal pke reaktor
kontinu reaktornya tdk bsar krn wktu tinggal di
(r A ) = dt =k . C A . C B y = m *Pseudorate : laju rx semu (mis: aslinya rx orde 2, reaktor singkat.
x tp dr hsil exp solah2 orde rxnya 1). Dlm phtungan,2. Selektivitas tinggi : mngarahkan rx ke produk yg
dmn hnya C 1 rxtan yg diperhi-tungkn sdgkn rxtan lain diinginkan (biasanya rx-nya paralel, ada
Cari CB dalam bentuk CA : aA + bB k
dianggap konstan. limbah), menekan produk samping
P 2 3. Umur katalis : klo pabrik bulk chem, rx-ny kontinu,
CC =C A 0C A=C A 0 . x A ; K = wktu operasiny pnjang &non-stop shg saat
C B 0 C B b k
CHAPTER 5
[ ]
b 2 operasi, katalis hrs tetap aktif spy biaya
= C B = C B 0 ( C A 0C A ) Katalis tidak dibutuhkan karena reaksi 1 arah operasiny ga bsr. Tiap kali pbrik start-up akn
C A 0 C A a a 2
dan blgsng cpat. Kunci reaksi berjalan baik: mhabiskan bnyk biaya, energi &bahan, jd
q= 4 ; =C A 0 . C B 0 1.ikatan dengan reaktan cukup kuat(antara rekatan
dengan katalis). Kalo tidak kuat, katalis tidak
sbaiknya tdk sering di start up.
4. Biaya katalis harus hemat : jangan sampai biaya
1 C C berfungsi dengan baik. untuk katalis lebih besar daripada income
. ln B ln B 0 =k . t 1 2.ikatan dengan produk kal terlampau kuat di Types of catalysis :
C B C A CA C A0 =[ C A 0+ CB 0 ] ; =1 permukaan katalis karena katalis dibutuhkan tidak
Homogeneous catatalysis : reactants & catalyst
K terlalu banyak-banyak, dan katalis akan digunakan
sama fasa (liquid/gas)
untuk reaktan lain.
Produk katalitik cracking adalah karbon dan Heterogeneous catalysis : reactant & catalyst bda
Rx orde n: : Reaktor kontinu utk rx yg cpat & kompleks. menutupi katalis. Ngilangin karbonnya pake udara fasa (kat : solid/liq, rxtan : liq/gas)
d C A n
Reator batch utk rx yg rlatif lmbat & sdrhna. panas dan jadi CO2 dan CO dianasin dgn suhu Biocatalyst : enzim mrpkn katalis alami yg kom-
(r A ) = dt =k . C A 1. MTD DIFERENSIAL bgus utk ngitung orde
rx, klo dipake bwt ngitung k krg akurat.
tinggi, biar CO jadi CO2. ponen utmanya brp protein, harus
Katalis bisa diaktifkan dengan pengotor- memperhatikan suhu dan temperatur. Enzim
Caranya: pengotor yang ikut bahan baku. Belerang adalah mrpkan katalis plg efisien:highly active (10 8-
CA
- Linearisasi (-rA) ln(-rA) = ln k + ........ musuh katalis. Sulfur ditentukan dan by pass. 1011- fold rate increase) & extremely selective.
- Bqn grafik CA thd t, regresi polinom (pngkatnya
dC A Semua yag ada oksigen(CO2, amonia, dll) Properties
Homoge Heteroge

y = a + b.x dt
=k .C An disesuaikan, smpe dpt R21).
- Pers garis yg didpt (CA=...tn+...tn-1+...) diturunin
merupakan musuh katalis.
Pringkat bhn kimia yg plg bnyk diproduksi:
Activity
Selektifitas
n
Varying
tinggi
n
Varying
rendah
CA 0
Initial rate method (konversi <10%): dCA 1. Ethene/etilen: lwt hydrocarbon cracking, katalis
heterogen.
Reaction
Mild Drastis
n
(r ) =k . C
A 0 A0 skali shg dpt
dt (=-rA). 2. As. sulfat: lwt oksidasi SO2, ktalis heterogen.
conditions

C A 1n=C A 01n +(n1) k .t 3. Propana: lwt hydrocarbon cracking, ktalis hterogen Variasi aplikasi terbatas
Tidak
terbatas
Importance of catalysis : increasing important in Sulit
linearisasialurin ke grafik ln(-rA)0 vs ln CA0 Permisahan
- Subs tiap t ke pers (-rA) dpt hrga (-rA) di-ln- synthesis, selectivity in production of fine katalis
(beda mudah
Metode integral y = c + m x fasa)
in. chemicals, clean processes, production of high-
Rx orde 1 : Untuk reaksi reversibel: - Alurin ke grafik ln (-rA) thp ln C regresi tech products/ materials, mild conditions (low Homogeneous catalysis:
Generally homogeneous catalysis refers to the
d C
A Orde 1
1 ( rx: A
B)
linear/multilinear, tgntng koef yg dibthkn.
2. MTD INTEGRASI bgus utk ngitung hrga k.
energy consumption).
Rekasi tanpa katalis butuh suhu tinggi use of organometalic complexes as the catalysts.
(r A ) = dt =k . C A Caranya: sehingga tumbukan yang terjadi makin banyak dan Contoh katalis homogen :
General aci& base catalysis (ester hydrolisis),
dC A - Uji orde rx. Orde utk rx homogen biasanya 0,1,2 cepat, reaksi yang berlangsung makin cepat
Lewis acids as catalysts (diels-alder rx), Organic
CA
=k 1 . C A k1 . C B (rx integer) sehingga butuh Ea yg lbih besar. Dgn katalis,

dC A C dt dC A energi untuk reksi

Ea
jadi lebih sedikit. catalysts (ion thiazolium di rx Cannizzaro),
Kmplks prophyrin(epoxidations, hydroxylation)
dt
=k .C A ln A =k .t
CA 0
- Pers
dt di-integral
K= A . e RT Proses enzimatik
CA 0 C A C A ,e .t
0 Coordination cmplex(polyester condensetion)
=ek R

- Alurin ke grafik regresi linear.

Catalytic antibodies

1 C A 0 C A ,e Hub. C dgn faktor konversi (X) :

Pada suhu konstan, reaksi dengan katalis Keuntungan : kinetikanya mudah dipahami, re-
membentuk senyawa kompleks sehingga butuh producibility, relatively mild reaction conditions,
Waktu paruh:
t 1 /2 = ln 2 C A 0C A energi lebih rendah untuk menghasilkan produk. high selectivity, easy modification of catalyst pro-
k dmn X A= C A =C A 0 ( 1X ) Kalo tidak pake katalis, reaksi dapat dipercepat perties, efficiency (all molecules are accessible),
A
C B 0 +C A 0 k ( K +1 ) CA 0 dengan meningkatkan suhu sehingga frekuensi mechanistic studies are relatively easy to perform
Rx orde 2: C A ,e = , k R= 1 tumbukan lebih banyak, reaksi lebih cepat (Ea (complex identification by IR,NMR,UV,etc)
diperkecil) Kerugian : water and oxygen sensitivity (jd saat rx
Ad C 2
K +1 K Hub.C dgn konduktivitas () : Syarat pake katalis : dilangsunkan tdk boleh kontak dengan udara),
(r A ) = dt =k . C A = ( C A 0C A ) wktu akhir 1. Reaktan & katalis harus cukup kuat ikatannya agar separation of catalyst and products often difficult

Orde 2 2 (rx: A+B 2.

tidak lepas sebelum bereaksi
Produk P harus bisa terlepas dari katalis kalo ga
Tahapan rx katalis homogen :
1. Asosiasi / disosiasi ligan (ligan dan pusat
CA katalisnya akan tracuni sehingga tidak dapat berikatan dengan ikatan koordinasi, ligan harus
rx: = & C =0 shg:
dC A 1 1 C+D) A dipake lagi. Makanya katalis yg diperlukan sedikit punya minimal 1 elektron bebas)
dt
=k .C A2
CA C A0
=k .dC
t A
=k 2 . C A .C B k 2 .C C . C D =
pd wktu akhir rx
3.
karena bisa trus dipae ulang
Katalis cuma ngubah kinetika reaksi tp
2. Rx insersi dan eliminasi
3. Serangan nukleofilik pada ligan koordinasi
CA 0
dt C A0 termodinamika reaksi tidak diubah (H rx,&Grx 4. Oksidasi dan reduksi pada pusat logam
menen-tukan konstanta kstimbangan rx, tidak 5. Adisi oksidatif / eliminasi reduktif
mengubah konversi kesetimbangan, cuma Heterogeneous catalysis:
mempercepat aja). Dengan menggunakan
 Many heterogeneous catalyst are multiphasic
(komponen >1). Some are uniform catalyst. Contoh

:
selektif
stabil (long lifetime) Order of
Pusat aktif:
Bersifat logam
* NH3 reactor : promoted Fe
* methanator : Ni-based [E]=[E]0-[SE] [E] = [E]0 - K[S]
prority
ZSMS (zeolit) acid catalystporous & active (dinonaktifkan 1 thaun 1x) Dalam bentuk atom, terdispersi Other ex of hetero catalysts for bulk and fine
throughout the bulk of the solid material. highly active_fast rx rate Tersebar merata di permukaan material chemicals : rx hidrogenasi (produksi margarine); [E]
Keunggulan : easy separation of catalyst and pro-
ducts (pmisahan katalis & produk bs tjd dlm reak-
bisa membesarkan laju reaksi yang cepat support sintesis methanol; oksidasi selektif alkena;
polimerisasi olefin; hidrogenasi katalitik (produksi
[ E]0
tor/ikut tseret kluar reaktor, kmdn dipisahkan scr
relatively cheap Bisa monometalik
vitamin); proses oksidasi (ex: citral production); [ E ]=
sentrifugal), low sensivity to H2O & O2, high tem-
katalis heterogen :
harus memiliki konduktivitas termal yang tinggi
Bisa menyerap molekul reaktan secara catalytic C-C linkage (ex: produksi ibuprofen 1+ K [S ]
perature stability, shape selectivity (zeolites) berbeda-beda (analgesic))
=untuk menghindari hot spot karena jika Tempat dimana cemisoprtion dapat
Kelemahan : kinetics can be complex, often high P Note:
and T required, catalyst poisoning by sulfur
terlampau panas, katalis akan rusak. terjadi Sinterik: pengurangan/kehilangan pusat aktif r p=k R . [ SE ] =k R . K . [ S ][ E ]
Terlampau panas-> karena banyak reaktan
Dapat secara sementara dinonaktifkan.
compounds (
H S 2 , snyawa belerang organik
eksotermis. Kalo endo->kesetimbangan harus secara perlahan-lahan
Cracking(katalis): biasa diatur produknya apa
bergeser ke kanan(butuh T tinggi)
Promotor Hidrogenolysis: berapa hidrolitik membutuhkan
[E ]0
& non-organik), sintering (hilangnya pusat aktif krn
memberikan cairan yang seragam dan hilang
r p=k R . K . [ S ] .
katalis tekspos pd T tggi), heat transfer sulit shg T
tekan yang tinggi ukuran, btuk, pori hrs
diatur spy fluida yg ngalir ke dlmnya tdistribusi Memperlambat sintering
hidrogen. Semakin sedikit, nilai oktan semakin
tinggi. semakin lurus rantai, nilai oktan
1+ K [S ]
nya naik terus katalisnya bisa rusak. merata ke sluruh bag katalis, skligus spy hilang semakin rendah
Meningkatkan daya tahan katalis dari
Heterogeneous catalysts have their acive sites tekannya ga trlalu bsar. Kalo tidak, sebagian Hidrolitik(reaksi): untuk menghilangkan sulfur dan disdrhanakan dgn cara dibagi K:
on the surface. High surface area materials produce racun
katalis tidak bisa kontak dengan bahan maka hidrogen organik. Sulfur harus dikurangin, kalo
better catalysts. Typically, very high surface area katalis tidak akan berfungsi.
Meningkatkan ketahanan mekanik
ga bisa ujan asam. V max [ S ]
supports (sillica gel, gamma alumina, etc) are used Perubahan tekanan yang terlalu tinggi akna
Adiktif(aktif secara katalitik)
K2O: bisa mempermudah, disosiasi idrogen-> T ga r p=
to support very small particies of active material.
Zeolite are porous and have a lot of accesible
menyebabkan pemborosan dan butuh rekator
Dibutuhkan kalo kita membutuhkan
tekanan yang tinggi(katalis tidak mudah
harus tinggi, 400oC uda uap. K m +[ S ]
yang besar. Perubahan tekanan yang inggi,
internal surface. panjang dan diameter tinggi maka makin rapuh dan hancur)
Reactions on metal surfaces molekul dpt nempel susah untuk seragam. Bisa memperbaiki struktur CHAPTER 7 1
krn ada gy trik-mnarik molekul mbntk iktn kim Secara elektronik bisa memodifikasi Enzyme-catalyzed reactions: V m=k R [E ]0 , K m=
(chemi-sorption) ato cm nempel aja (physisorption). Katalis Padat->susah memindahkan struktur e- * lock-key mechanism sgt spesifik. dgn K
Ada kesa-maan katalis homogen organometalik dgn panas reaksi, adanya difusi. Membut karbon tidak mudah menempel * enzyme = protein (amino ac. polymer MW 6.10 3
kompleks tkoordinasi. Katalis padat(heterogen) biasanya mengandung :
Adiktif, jadi tekanan sedikit saja 6.105) in colloidal size (1nm-1m)
Katalias yang bagus: Ea<170kj/mol; ordenya1. Fasa pusat aktif: speed-up&direct desirable rx. Btk linearisasi (lineweaver-Burk-equation):
* yg mpngaruhi aktivitas enzim: sifat alam enzim
35-50kj/mol; harus selektif; hanya dibutuhkan dalam Mempercepat dan menyeleksi reaki
Media support
tsb (inhibitor & ko-enzim), sifat substrat, konsentrsi 1 Km 1 1
julah kecil(katalis meruoaaka suatu siklus, bisa Logam transisi banyak memiliki fasa pusat E dan S, pH, temperatur. = . +
digunakan kembali, katalis digunakan secukupnya). aktif(sulfida dan oksida, vanadium)

Klas rx enzimatik: r p V m [S] V m
Bisa berupa asam Harus bisa menahan kondisi reaksi Oxidoreductases: rx redoks
CHAPTER 6 Temperatur tinggi=H+; temperatur Stabil [ AH2+B+EA+BH2+E ]
Pada industri kimia, rx kimia berperan penting : rendah=lewis dan H+ Luas permukaan tinggi Transferases: trnsfer gu2s kim dr 1sbstrat k subs- y = a x + b
Bahan baku dr alam (brp air,udara,bhn tambang) 2. Promotor: meningkatkan performa katalis secara Harus sangat berpori(makan berpori, trat ln/dr 1bag sbstrat ke bag ln. Nilai Vm & Km bgntung pd konsentrasi enzim
proses2 pretreatment rx kimia pemurnian/ physica(tekstur dan struktur kimia). luasmakin tinggi) [AB+C+EAC+B+E] awal, T, dan pH (diluar pH yg sesuai, enzim gmw
Semacam aiktif dan ditambahkan beberapa % Hydrolases: rx hidrolisis kerja). Enzim bkerja pd pH & T optimum, diluar itu
separasi (bisa recycle) product & by Biaya harus terjangkau
product/waste. saja, sisanya adalah material support(tempat [ AB+H2O+EAH+BOH+E ] kerjanya ga max.
Proses2 pretreatment : pengolahan utk fasa pusat aktif). Material support memberikan Isomerases: pnyusunan ulang atom dlm swt Integral method:
Some industrial ex of enzyme catalysed
menghilangkn kotoran yg dpt mganggu rx2 luas permukaan seluas mungkin. struktur molekul [ A + E A + E ]
- mekn keaktifan ktalis tp dy sdr ga aktif dlm rx
reactions :
dC s V .C
Titin Mardiana Anggraini tsb
produksi acrylamide dari adisi air ke acrylonitrile
menggunakan nitrile hydratase enzyme
Lyases: eliminasi dr grup adjacent atoms / addition
of groups to double bonds _ penguraian = (r s )= m s
6211113/F - types: physical(textural), chemical(stuctural),
sintesis aspartame, a widely used artificial low- [ AB+EA+B+E ] dt K m +C s
elec-tronic, catalyst-poison-resistant.
berikutny (CO, CO2, S) ter-utama rx yg melibatkn - ditmbhkan ke katalis dgn persentasi kecil calorie sweetener using thermolysin enzyme Ligases: pgbungan iktn mllui
katalis (racun katalis hrs dibuang dlu). Rx kim di - Contoh promoter : SiO2,ZrO2,P (mningkatkan The use of hetero industrial catalysts, based on hdrolisis[ A+B+EAB+E ] integralkan pd t=0 & Cs=0 :
Mekanisme reaksi berkatalis enzim Michaelis-
industri kbanykn mrpkn rx kstimbangan, walaupun stabilitas termal),K2O (mencegah poisons product types : CS
sdah diatur T & P-nya, tp konversinya tdk bisa 100%. produksi bhn kimia organic & anorganik Menten:
Saat kluar dr reaktor, produk bcmpur dgn katalis,
cake formation on active centers), HCl
crude oil refinery and petrochemical industries k ln
(mningkatkan keasaman),MgO (slows CS 0 1 V t
sisa reaktan, prduk samping,dll, jd hrus dimurnikn. sintering of active com-ponents), Pt Prduction of industrial gases and inorganic S + E 1 ES = m.
Bbrp by-product dpt lgsg digunakn. Pran katalis sgt
pnting krn by-product & waste bsa di-min & produk
(increase CO oxidations), ZnO (de-creased chemicals :
steam reforming of methane: H2O+ CH4 3H2 +
(1) k1 ...... fast
C S 0 C s K m K m ( C S 0C s )
Cu sintering)
dpt di-max. 3. Support: gives high surface area & increase CO, kat: Ni/Al2O3, 750-950C, 30-35bar
Dlm industri kim, rx harus dikontrol untuk
mendptkn:
active sites reactivity. CO conversion, kat: Fe/Cr oxides (350-450C), SE k R P+ E y = c + m x
- harus inert (tdk blh brx) Cu/Zn oxides(140-260C) (2) ....... slow
- high yield : high conversion & selectivity - ckup kuat di bwah tkanan reaktor yg tggi. Methananization (SNG): CO + 3H2 CH4 + Initial rate method:
- reasonably fast rate
- milder (T,P) conditions
- stable on reaction condition (T,P) range H2O, kat: Ni/Al2O3 ,500-700C, 20-40bar
Rx (1) cpat mncapai kstimbangan: 1 K 1 1
Ini smw dpt diperoleh dg menggunakan katalis yg
- bs diregenerasi jika keracunan semntara tjd
- very high surface area; porosity; and cost
Sintesis ammonia, kat: Fe2O3(K2O, Al2O3), 450-
K1[S][E] = k-1[SE] [SE] = K[S][E] = m. +
cocok.
500C, 250-400bar
(r s )0 V m [S]0 V m
Karakteristik pntg katalis industri:
- Ex of good support : alumina,silica, alumina-silika Oks SO2SO3, kat: V2O5/support, 400-500C k1
Ea<170 kJ/mol even lower for enzyme catalyzed
(zeolit), karbon aktif Oks NH3NO (as nitrit), kat: Pt/Rh nets, 900C
- Other supports : MgO (rather poor mechanical Clauss process (sulfur): 2H2S + SO2 3S +2H2, dgn
K=
reactions (35-50 kJ/mol) strength),ZnO (poor stability as prone to
k 1 Inhibisi & aktivasi dlm rx bkatalis enzim
dihasilkan oleh efek internal (single/multi-ple
kat: bauksit, Al2O3, 300-350C
spesifik/selektif reduction),Cr2O3(acid sites cause NH3/urea plant substrat) & efek xternal (racun-inhibitor &
only need a relatively small amount undesirable reactions), TiO2(highly stable at *primary reformer-Ni based Neraca enzim: koenzim-aktivator). Tiga tipe inhibisi:
homogeneous dan heterogenous T tinggi, mahal) *water gas shift rxtor (HTSC:Fe-based, 1. Inhibisi kompetitif : inhibitor (I) bkmpetisi dgn
Katalis industri ideal: ................... LTSC:Cu-based) substrat mdptkn molekul enzim utk mbtuk
 kompleks I-E. Inhibi-tor pnya struktur yg mirip dgn
substrat shg bsa mbtk kompleks dgn enzim.
5. Desorption of the product from the active.
6. Internal counter-difussion:transport of the
J=mass flux (d moles transported per unit of time
and per unit of surface perpendicular to the k a.
r=a . Cb
Reaction steps: sd product through the pores to the external diffusive movement)
E+ S k 1 E . S surface
3. Inhibisi NonKompetitif(mixed): substrat & inhibitor 7. External counter-difussion:transport of the
C=concentration of the diffusing substance
D=diffusion coefficient
External effectiveness factor (e)
(1) berx dgn sisi yg molekul enzim. Reaction Steps: pro-duct from the xternal surface to bulk fluid The negative sign indicates that d diffusion occurs observed reaction rate
E+ S E . phase. in d opposite direction of d C gradient (dC/dx) e =
E . S k 2 E+ S (1) Steps 1,2,6,7 are strictly physical External diffusion reactionrate at bulk fluid cond
(2) rx michaelis- steps(transport phe-nomena). Steps 3,4,5 are Ada 2 pristiwa yg tjd:

(2)
E+ I I . E (inactive)
purely chemical phenomena (microkinetics). The1.
transfer steps 1 & 7 depend upon the2.
difusi ke perm padt katalis (nembus film)
rx yg dktalisis pusat aktif katalis padat
menten flowdynamics of the system. The transport steps ficks law: * utk orde 1 kasus (2)&(3) :
E . S k 3 E+ P I+E. SI .E.S 2 & 6 are represent only with porous catalysts &
D a
(3)
(3) (inactive) depend on the geometry of catalyst particles. J= ( C bC s )= ( Cb C s ) r obs =e kC b , < e <1
Steps 1&7 (xternal diff.) are in series with steps k
S+I . E I .E .S 3-5 (chemical steps): the xternal trasfer occurs
E+ I k 4 E . I Muncul krn
(4) (inactive) separate-ly from the chemical reaction. Steps Internal diffusion
(4) (inactive)
ada 2&6 (internal diff.) occur simultaneously with [mol m-2s-1]
inhibitor Ada 2 pristiwa yg tjd pd katalis padat bpori:
(5)
E.S P chemical reaction. D=koef difusivitas molecular_camp
=thickness of d external film 1. difusi film/ difusi external
Difusi pori : ppindahan massa bdasatkn pbdaan
E .I k 5E +I kon-sentrasi, dmn fluida tsb melalui fluida diam.
=koef ppindahn massa 2. difusi dlm pori (rx tjd bersama2 dg difusi
pori)
[I] 1 K [I ]
( ) ( )
At steady state, the rate of mass transfer must be
(5) 1 1 m Klo sistem sdh steady state, maka laju
= 1+ + 1+adsorption Strong atomic e-qual to the rate of the surface rx, expressed per
difusi film = laju difusi external + laju difusi
1 K 1 [I ] 1 ( r s ) V m K I [ s ] V m Easy
Kdissociation
Cr I Mn Fe Co Ni Cu
unit external surface area:
dlm pori

( )
n
= m 1+ + Mo Tc Ru Rh Pd Ag r= . a . ( C C ) =k C
b s s Tahanan(resistance): tumbukan antar
W Re Os Ir Pt Au
(r s ) V m [S ] KI Vm Weaker atomic
molekul atau tumbukan antara molekul dgn
dinding pori katalis.
adsorption laju ppindahan = flux. area ppindahan ficks law:
[I]: baik gradien & Early&mid-trasition
No dissociation
metals have goodlaju ppindahan = J.a [mol. s-1. vol unggun-1]
[I]=konsentrasi inhibitor dlm cmpuran intercept brubah k= kinetic constant referred to the unit of vol dC
chemisorption abilities. Thermodinamically they
catalyst J =D e
[I] : garis mkn dkt sb.y, tp are capable of forming bonds that make it
dx [mol m-2 s-1]
intercept ga brubah. worthwhile for the molecule to break up. Ap(luas area pdtan katalisdlm unggun)
[I] : rx mkin lambat Classifications of heterogeneous catalysts : a=
1. Metalshydrogenation, dehydrogenation,
hydro-genolysis (oxidation). ex:Fe,Ni,Pd,Pt,Ag
V unggun x= jarak yg tgk lurus dr pusat partikel
D = koef difusi efektife
Lineweaver-Burk plots for three types of enzyme2.
2. Inhibisi Unkompetitif : inhibition:
Semiconducting oxides & sulphides
oxidation, dehydrogenation, desulphurization Cb=konsentrasi rxtan pd fasa curah/bulk 1 p
Inhibitor (I) mikat sbstrat-enzim dgn mbntk
(hydrogena-tion)
De=
Cs=konsentrasi rxtan pd fasa solid (pd
kmpleks I-E-S yg inaktif. Reaction steps: katalis) 1 1
E+ S k 1 ES
ex:Nio,ZnO,MnO2,Cr2O3,Bi2O3-MoO3,Ws2
1st order reaction +
3. Insulator Dm D k
(1)
4.
oxidesdehydration.ex:Al2O3,SiO2,MgO
Acidspolymerization,isomerization,cracking,al
r= . a . ( C C ) =k C
b s s ;
kylation. ex:H3PO4,H2SO4,SiO2-Al2O3,zeolites diperhitungkan jika:
E . S k 2 E+ S Rate determining steps (rds) if the rate
1 p = porosity of the catalyst particle
(2)
Utk tau inhibitor apa yg tdpt dlm suatu bhn,
constant of 1 of these steps is markedly smaller r= C b
(characteristic values: 0,2< p <0,7)
lakukan pcobaan dgn dan tnpa inhibitor, lalu
than other, the overall rate is determined by this 1 1 = tortuosity of the pores (characteristic
E . S k 3 P+ E step. + values: 3< <7): nunjukin rumit tdknya
(3)
1 Regimes k a.
bandingkan garisnya dlm kurva kinetic regime: rds = chem rx (chem regime) swt struktur katalis. struktur
rs external diffusion regime: rds= external diffusion 1/k= chemical resistance
1+ E . S k 4 I . E . S (film diffusion, external mass transfer 1/: external mass transfer resistance mkin rumit
mkin sulit brpindah/
(4) (inactive) 1
limitation)
internal difusion regime: rds= internal difusion
Limit case
berdifusi.
terhadap
s . (pore difusion, internal mass transfer
I . E.Sk 5 I. E.S limitation)
The resistance towards transport originates
from colli-sion of the molecules either
(5) Convective & diffusive transport
with each other (Dm = mo-lecular
convection: transport by bulk motion of the fluid
CHAPTER 8 diffusivity) / with the pore walls (Dk =
(krn ada pngadukn)
[I ] 1 K m Knudsen diffusivity). Dm tergantung dr
1 1
= + 1+
( r s ) V m
+
( )
KI [s] Vm
Steps in a heterogeneously-catalyzed reactions:
1. External difussion:transfer of the reactants
from the fluid phase surrounding dcatalyst
particle(bulk fluid phase)to the external surface
diffusion: transport due to gradients
(concentration gradients if the transported
property is d mass, temperative gradients if d
transported property is d thermal energy)
(1) No limitation by film diffusion (kinetic
regime) no gradient concentration
(Cs=Cb)
molekul & komposisi molekul. Dk berhub
dg tumbukan molekul reaktan wkt dia
pindah dg dinding porinya. Dk tgantung
of the catalyst Mass transport by diffusion: the Ficks law k a.
r=k .C b
dr factor kkuatan material dinding
porinya.
2. Internal difussion:transport of the reactants
dC Internal effectiveness factor (i)
[I]: Gradien garis tdk
brubah, tp intercept brubah
from the external surface of the particle J =D (2)
through the pores to the active sites on the
interrior surface
dx [mol m-2 s-1] (3)
Film diff & reaction e diphitungkn
bwt nyari r
(4) Maximum limitation by film diffusion
3. Adsoption on the reactant on the active site
(xternal diff regime) Cs 0
4. Surface reaction
substitu
si
observed reaction rate k =k 0 exp(E r / RT ) v ( K A C A +1 )=1 @ equilib:
SA k 2 SP
i = = obsnatt AX =K A C A vx ; BY =K B CB vy (surface reaction)
reaction rate at xternal surface conditions kC s
E 1 1
ln k =ln k 0 v = K A CA 75% sbg rds

r=i k C ns RT K A C A +1 AX= k 3
K A C A +1 SP S+ P
Rds: internal pore diff is controlling & k3 (P
Limit case there is a concent gradient inside the pore. K AC A
Internal diff jga pnya kasus batas yg serupa The Ea derived frm the observed rx rate A= K B CB
dgn xternal diff. Pada kasus (1) i = 1. Pada constant corresponds to approxi-mately K A C A +1 BY = k3
kasus (4) i = 0. Pada kasus (2)&(3) 0 < i < of the true Ea. Pd T sedang: i <<< , shg: K B C B +1 desorption)
K P=
1.
r obs =i k C b 2. Two different adsorbates case
k3
Thiele Modulus
A + S K A SA 5. Single adsorbates with dissociation
V
kCns A 2 +2 S k ads 2 SA Rds : surface reaction
Ads-Des of A :
p


1 A De C s A Adsorpsi : r=k 2 A
Ap De C s k Cb p k C b= p D e kCb ; r2 <<< smntra r1 & r3
Vp k Cs Vp B+ S K B SB
Ads-Des of B : 2 SA k des 2 S+ A2 >>> shg :
@ equilib :
rate without pore diff . Desorpsi :
r intrinsic =k att Cb A =K A C A v ; P =K P C P v
maximumrate of pore diff . ; kapp < katt , Eapp = @ equilib:

Eatt
A =K A C A v ; B =K B C B v @ equlib:
Klo kDe =0 Rds: external pore diff is controlling & r ads =r des k ads C A v 2=k des A2 N.M pst aktif :
A + P + v = 1
Klo kDe =>>, maka i<< regime difusi there is a concent gradient across the film.
2
N.M pst aktif :
internal (robs<< Cs) The Ea derived frm the observed rx rate A + B + v = 1
K A C A v + K P C P v + v =1
2 2
Small : rx rate is smallrx limits the overall
rate (kinetic regime)
constant is generally below 5kJ/mol. Pd T
K A C A v + K B C B v + v =1 A =K A C A v A= v K A C A
tinggi: <<< k.i, shg: 2 2 2 2
Large : diffusion rate is small internal v ( K A C A + K P C P +1 ) =1
diffusion the overall rate (int. diff. regime) r=a C b ;
r intrinsic =k att Cb N.M pst aktif :
Faktor yg pngaruhi i: substitu
si
- bntuk & v ( K A C A + K B C B +1 ) =1
A + v = 1
ukuran partikel katalis
* utk feed batch biasanya pke rds = xternal v K A C A + v =1 1
- temperatur
pore diff
v =
- orde rx 1
2 2
K A C A + K P C P +1
Simultaneous xternal & internal difffusion Isotherm adsorpsi : pers. Yg mnunjukkan
hub antara Cs dan Cb pd T tertentu utk
v =
Saat tunak (rx orde 1):
nentuin pers laju rx-nya.
K A C A + K B C B +1 v ( K A C A +1 )=1
r obs =r ext diff =r pore diff ....................
2 2 KACA

LANGMUIR ISOTHERM berhub dgn A=
konsentrasi rxtan dlm fasa gas & yg tlah KACA 1 K A C A + K P C P +1 r

i k A= v =
( )
tadsorb oleh pdtan.
r obs =i k C b / 1+ 1. Single adsorbate case K A C A + K B C B +1 K A CA + 1
.a [mol m-3
A + S k ads SA
2 2 k2K ACA
r =
Adsorpsi : K B CB K A C A + K P C P+ 1
s-1]

B =
v =
K A C A2 2
General formula for 1st order reaction.
SA k des S + A K A C A +K B C B +1
Rds: Surface reaction is controlling & the Desorpsi :
K A CA +1 2 2
Rds : A adsorption
r=k 1 C A v
concent profile across the film & inside the 3. Single adsorbate + inert = no.2, cm B-nya ; r1 <<< smntra r2 &
pore is flat. The Ea derived frm the rx rate diganti I
S = pusat aktif yg msh kosong (fraksinya4. Two different adsorbates adsorbed at 2 Monomolecular heterogeneous reaction [A
correspond to true Ea of chem rx without mass r3 >>> shg A0 (tjd krn rx pbtkan A sgt
= v) kind of sites P]
trnsport limitation. lmbat, bgitu kebentuk A lgs dipake brx
SA = pusat aktif yg sdh ditempati A Ads-Des of A at X : Mekanisme reaksinya
Pd T rendah : k <<< , k <<< =0 & i utk jd P, shg hmpir gada A di perm pusat
(fraksinya = A)
1, shg: @ equlib: A + X K XA
A k1 aktif)
r obs =k C b r =r k C =k A +S SA P=K P C P v
; ads des ads A v des A k1 (A adsorption) @ equilib :

ln k =A 0 exp (E a / RT ) B+ Y K B YB N.M pst aktif :

k Ads-Des of B at Y : k K P C P v + v =1
A = ads C A v =Ksubstitu
A C A v
VX+ AX =
1 K A= 1 P + v = 1
k des si
k1
r intrinsic =k att Cb ; kapp = katt , Eapp =
VX = fraksi kosong pd pusat aktif X
Ax = fraksi yg terisi A pd pusat aktif X
N.M pst aktif : VY = fraksi kosong pd pusat aktif Y
Eatt VY+ BY =

A + v = 1
K A C A v +v =1 BY = fraksi yg terisi B pd pusat aktif
1 Y
 v ( K P C P +1 ) =1 SA + B k 2 SP+ R r k 3 A =K A C A v ; P =K P C P v

(surface K B C B v + K P C P v + K R C R v +
2. Langmuir-Hinselwood mechanism : smw N.M pst aktif :
1 reaction) A + B + P + R + v = 1
v = rxtan tadsorb
v ( K B C B + K P C P+ K R C R +1 ) =1
K PCP+ 1 r k 3 k1
SP S+ P A+S SA K A C A v + K B C B v + K P C P v + K R C R v + v =1
k3 (P desorption) k1 (A

k C
r = 1 A Rds : surface reaction adsorption) v ( K A C A + K B C B + K P C P + K R C R +1 ) =1
K P C P +1 1
r=k 2 A C B k v =
B+ S 2 SB K BCB+ K P CP+ KR CR+ 1
Rds : P desorption
..... = kasus monomolekular rds surface
k 2 (B adsorption)
1
r=k3 P ; r3 <<< smntra r1 & r2 reaction..... v = r
k K C A CB SA + SB k 3 SP+ SR K A C A+ K BC B+ K P CP+ K RCR+ 1 k1C A
2 A
>>> shg P 1 (tjd krn rx penguraian P sgt
r = r =
lmbat sdgkn rx pbtuknnya sgt cpat shg P yg
trdpt di perm psat aktif mjd sgt bnyak).
K C + K P C P+1
A A &
A B r K B C B + K P C P + K R C R +1
Krn P 1, maka A = V 0. (surface reaction) k3 K A C A K B C B
r k Rds : A adsorption k 4 r = Rds : B adsorption
2 = A adsorption, A B; k 1
3
r=k C
1 A v SP S+P ( K A C A + K B C B + K P C P + K RCkR +1 ) 2

k4 (P desorption) Rds : R desorption

Bimolecular heterogeneous reaction [A + B ..... = kasus monomolekular rds A Rds : A adsorption r=k5 R ; r5 <<< smntra rothers
P + R] adsorption..... k r=k 1 C A v
Jika ada 2 atau lebih rxtan, kadang hanya
salah 1nya aja yg tadsorb oleh pst aktif dan
k C1 A SR 5 S+ R ; r1 <<< smntra rothers >>> shg R 1. Krn P 1, maka A = B

terkadang smw rxtan dpt tadsorb. Hal ini r = k5 (R desorption)

>>> shg A0
= P = V 0.

dsbabkn krn psat aktif itu selektif, artiny dy K C +1

P P @ equilib : r k 5
milih2 mana yg mo diserap, mana yg ngga.
1. Eley-Rideal mechanism : cm 1 rxtan yg
Rds : surface reaction B =K B C B v ; R=K R C R v
tadsorb
Rds : P desorption
r=k 3 A B Rds : P desorption = R desorption, R P; k-5
r=k ; r2 <<< smntra k-4
k 1
3 P
P=K P C P v
A +S SA rothers >>> shg : ;
k1 (A adsorption) ..... = kasus monomolekular rds P @ equilib :
N.M pst aktif :
desorption..... B =K B C B v ; R=K R C R v B + P + R + v = 1