CHAPTER 5

1.
Introduction to reaction kinetics:
Energi Aktifasi adalah energi minimum agar partikel
dapat bertumbukan scr sempurna, tumbukan bisa
sering terjadi jika: frekuensi tumbukan partikelny
2.
bertambah banyak, energi aktifasiny naik.
Laju reaksi akan bertambah jika: fraksi reaktan
dinaikkan, tekanan parsial reaktan
dinaikkan,temperatur dinaikkan (lebih sering
3.
bertumbukan karena energi kinetik bertambah.).
1. Pemilihan bentuk partikel katalis:
Pemilihan bentuk dan partikel katalis dipengaruhi
oleh area pusat aktif per unit volume, struktur
ketahanan/
Strength,
kemudahan
konstruksi,
manufacturing cost, bed voidage, pressure drop, dan
transport properties. Partikel dengan struktur ekuatan4.
yang lemah akan mudah rusak saat proses
berlangsung, untuk mengantisipasi kerusakan katalis
selama loading ke reaktor, saat packing awal reaktor
empty container diisi dengan air setelah itu baru
katalis sdimasukkan secara perlahan kedalam
reaktor.Surface aktif area per unit volume, voidage,
streangth dan transport koefisien harus bernilai
besar. Pressure drop dan cost nya harus kecil.
Untuk regenerator thermal,karena packing matrix nya
bertindak sebagai heat storage, non poros bulat dan
persegi panjang umumnya yg dpilih.
Pada penentuan design katalis yg paling diutamakan
surface area per unit volum dan reduced pressure
drop karena surface area semakin besar, reaktor
yang dibbutuhkan menjadi kecil. (Surface area
silinder lebih besar daripada bulat). ( di industri

methanol, four-hole cylinder surface areanya lebih

besar daripada silinder pejal).

Pringkat bhn kimia yg plg bnyk diproduksi:

1. Ethene/etilen: lwt hydrocarbon cracking,
katalis
heterogen.
2. As. sulfat: lwt oksidasi SO2, ktalis heterogen.
3. Propana: lwt hydrocarbon cracking, ktalis hterogen
Importance
of
catalysis
:
selectivity
issues(esp.finechemicals),T&P lbh rendah jd konsumsi
energy rndh,efisien(laju rx dipcepat),produksi hightech produk:teflon,kevlar,nylon,clean processed(less
waste),proteksi lingk.(green chemistry&catalysts)
Khiral catalyt utk obat obatan.
PRINSIP KATALISIS
Katalis
ubah
kinetiknya(mekanisme,dan
laju
reaksi),tp ga termodinamika reaksi tsb.in case of
equilibrium
rxn,katalis
mpercepat
both
forward&backward rxn to the same extent.in order to
function,katalis
should
make
a
chemical
bonding,normally dative bonding,w/the reactants.
Rx tnpa katalis butuh suhu tinggi shg tumbukan
yg tjd mkin bnyak & cpat, rx yg blangsung mkin
cepat shg butuh Ea yg lbih besar. Dgn katalis, energi

Ea
utk rx jadi lebih sdikit.

K= A 0 . e

RT

. Pd

suhu konstan, rx dgn katalis mbentuk senya-wa

kompleks shg butuh energi lbih rendah utk menghasilkan produk. Kalo ga pke katalis, rx dpat dipercepat dgn mekan suhu shg frekuensi tumbukan lbih
banyak, rx lebih cepat (Ea diperkecil). Kunci
keberhasilan katalis: ikatan dgn reaktan hrs ckp kuat,
reaktan dpt bentuk ikatan stabil, hrs dpt dilepaskan
dgn mudah dr katalis, produk tdk boleh terikat kuat.
Syarat pake katalis (masuk prinsip)
1. Reaktan & katalis harus cukup kuat ikatannya agar
tidak lepas sebelum bereaksi
2. Produk P hrs bisa tlepas dr katalis klo ga katalisnya
akn tracuni shg tdk dpt dipke lagi. Makanya katalis
yg diperlukn sedikit krn bisa trus dipae ulang
3. Katalis cm ngubah kinetika reaksi tp termodinamika
rx tdk diubah (Hrx,&Grx menen-tukan konstanta
kstimbangan
rx,
tdk
ngubah
kon-versi
kstimbangan, cm mpercepat aja). Dgn menggunakn katalis, rx-nya akn blgsung jauh lbih cpat.
Katalis mpercepat rx mju&mndur dgn bsar yg sma.

Important catalyst properties:

KATALIS MERUBAH LAJU KINETIK, BUKAN
Harus aktif : klo rx cpat, wktu lbih singkat TERMODINAMIK
produksi-nya bsa lbih bnyk, kal pke reaktor Homogeneous catalysis:
kontinu reaktor-nya tdk bsar krn wktu tinggal di Generally homogeneous catalysis refers to the
reaktor singkat.
use of organometalic complexes as the catalysts.
Selektivitas tinggi :selektifitas harus besar, bisa Homogenous catalysis often involves changes in
mengecilkan produk samping. mngarahkan rx oxidation number of the ions involved in catalysis
ke produk yg diinginkan (biasanya rx-nya ex:
paralel, ada limbah), menekan produk samping
H2O2 + I- H2O + IOUmur katalis : Harga daur ulang katalis sangat H2O2 + IO- H2O + I- + O2
diperhitungkan. klo pabrik bulk chem, rx-ny katalis homogen dibagi 2 yaitu :
kontinu, wktu operasiny pnjang &non-stop shg Hard catalyst:
saat operasi, katalis hrs tetap aktif spy biaya
- With H+ ortransition metal ions in high oxidation
operasiny ga bsr. Tiap kali pbrik start-up akn
states, Mo6+, VO2+, FeCl3,TiCl4, Zn2+
mhabiskan bnyk biaya, energi &bahan, jd
- Acid
base
catalysis:
generation
of
sbaiknya tdk sering di start up.
electrophylicand nucleophilic centers
Biaya katalis harus hemat : katalis semakin bagus,
Hard catalyst:
harganya semakin mahal & selektifitas makin
complexes in low oxidation
tinggi tapi jangan sampai biaya untuk katalis - With transition- metal
states. Co , Rh+,Ni0Fe0,Cu+,Ir+
lebih besar daripada income
- Goodelectron exchange between metal and
Types of catalysis :
substrate
Homogeneous
catatalysis
:
katalis&reaktan
- Soft ligand and reagent H2, CO,CN-,PR3, SNClfasanya sm(cair/gas).katalis yang mempunyai
- Softsolfents (benzene,acetone, Me2SO
fasa sama dengan campuran reaksi. Campuran
Contoh katalis homogen :
rx:
reaktan,
produk,
katalis,
komponen
General aci& base catalysis (ester hydrolisis),
pelarut(inert). ( logam transisimbntuk kompleks,
Lewis acids as catalysts (diels-alder rx), Organic
krn pny tempat kosong di kulit atau orbital D
catalysts (ion thiazolium di rx Cannizzaro),
dan bias diisi oleh elektron). Pusat aktif
zeolite:Asam
lewis:
melibatkan
transfer Kmplks prophyrin(epoxidations, hydroxylation)
elektron, ada ikatan kovalen koordinasi ada yg Proses enzimatik, Carbonilasi, hidrogenasi
memberikan pasangan elektron bebas, ada yg Olefin oligomerasi
Coordination cmplex(polyester condensetion)
menerima.
contoh: Asam bronsted: melibatkan transfer Catalytic antibodies, friedel craft reaction
+
Keuntungan : kinetikanya mudah dipahami, reproton (H )
producibility, relatively mild reaction conditions,
Co: CH3COOC2H5 + H2O CH3COOH + C2H5OH
INGET REAKSI DI KINREK FASA CAIR (I - dengan high selectivity, easy modification of catalyst properties, efficiency (all molecules are accessible),
S2O82- katalisnya Fe3+ dan Fe2+)
Heterogeneous catalysis : reactant & catalyst bda mechanistic studies are relatively easy to perform
fasa (kat : solid/liq, rxtan : liq/gas). Ada logam (complex identification by IR,NMR,UV,etc)
yg terdispersi(tersebar merata) sbg material Kerugian : water and oxygen sensitivity (jd saat
support.Contoh: zeolite, didalam katalis ada rx dilangsunkan tdk boleh kontak dengan udara),
komponen zeolite sbg inert dimana padatannya separation of catalyst and products often difficult
berbentuk
kristal
(terstruktur)
atomnya. Tahapan rx katalis homogen :
1. Asosiasi / disosiasi ligan (ligan dan pusat
Komponen zeolite (alumina & silika). Yg dipake
berikatan dengan ikatan koordinasi, ligan harus
zeolite sintetik agar pusat aktif ny bisa
punya minimal 1 elektron bebas)
diaturLogam
yg
digunakan
adalah
yg
2.
Rx
insersi dan eliminasi
mempunyai biloks >> 1, mudah mentransfer
Serangan nukleofilik pada ligan koordinasi
elektron shgga biloks bisa berubah. 2H 2O3.
2
4. Oksidasi dan reduksi pada pusat logam
2H2O + O2 katalis: MnO2. Many are multiphasic5. Adisi oksidatif / eliminasi reduktif
dispersed metals on a supportautomobile
catalytic
converters.
Some
are
uniform
catalysts:acid catalysts ZSM5 is porous&active
throughout the bulk of the solid material. Good
activity requires very high accessible surface
area as the reaction take place on the surface.
Biocatalyst : enzim mrpkn katalis alami yg komponen utmanya brp protein.(asam amino yg
berikatan membentuk peptida) Enzim mrpkan
ka-talis plg efisien:highly active (10 8-1011- fold
rate increase) & extremely selective. They work
under mild conditions of temperature & pH.
Homog
en(co:
Heterogen
H+,
(co:
organo
zeolite,
katalis
Properties
copper,
zincorgano
cyrstallite
metali
on silica)
ccompl
ex
Activity
Varying
Varying
Selectivity
High
Low
Reaction
Mild
Drastic
conditions
Variasiaplikasi
Limited
High
Permisahankatali
Difficult
Easy
s

Physisorption

Heterogeneous catalysis:
Heterogenous catalysis often involves gaseous
molecules reacting at the surface of a solid catalyst.
Chemisorption occurs when molecules become
bonded to atoms on the surface of a solid). Pusa aktif
di permukaan.very high surface area supports(silica
gel,gamma alumina)used to support very small
1.
particles of active material. Zeolit bpori&punya
banyak accessible internal surface.
Langkah2 dari reaksi pada katalis heterogen:
Difusi: reaktan terdifusi ke permukaan katalis
Adsorpsi: Molekul reaktan secara kimia teradsorp
kedalam katalis.
2.
Ikatan yang terbentuk antara reaktan dan katalis
(HABER):
- Ikatan antara katalis dan reaktan terlalu kuat untuk
dipecah sehingga reaktan tetap berada di pusat
aktif
- Terlalu mudah untuk di pecah oleh produk sehingga
produk bisa terlepas dari katalis
Reaksi: reaktan di permukaan katalis bereaksi
3.
membentuk ammonia
Desorpsi: ikatan antara amonia dengan katalis
melemah dan terpecah
4.
Difusi: amonia terdifusi keluar dari pusat aktif katalis
Co: catalytic converter mengubah NOdan CO jadi N 2
dan CO2.
Many heterogeneous catalyst are multiphasic
(komponen >1). Some are uniform catalyst. Contoh :
ZSMS (zeolit) acid catalystporous & active
throughout the bulk of the solid material.
5.
Contoh: copper-zinc-crystallites on silica. Fasanya :
silica, cu, zn. Keunggulan : easy separation of catalyst
and pro-ducts (pmisahan katalis & produk bs tjd dlm
reak-tor/ikut tseret kluar reaktor, kmdn dipisahkan
scr sentrifugal), low sensivity to H 2O & O2, high tem6.
perature stability, shape selectivity (zeolites)
Kelemahan : kinetics can be complex, often high P
and T required, catalyst poisoning by sulfur
7.

Chemisorpti
on
Cause 1. Vander wals
covalent/elect
forces, no
rostatic
electron
forces,
Adsorb
transfer
electron trans
en
2. All solids
some solid
Adsorb3. All gases below some
at
the critical
chemically
point, intact
reactivegases,
molecules
dissosiation
T
4. low temp
into at
Range5. low heat of
High
Heat
fusion
high~heat of
ads 6. very fast
rx, exo
rate 7. low
tergantung T
Ea
8. multilayers
high
pust 9. highly
monolayer
aktf
reversible
often reversible
reversibilt 10.determinati determination
y
on of surface
of surface
Appliccati area and pore
consentration
on
size

Co chemisorption: H2 on grapite, CO on Cr2O3,

N2 on Fe, Co on Pd, H2 on W powders

H2 S

compounds (

, snyawa belerang organik

& non-organik), sintering (hilangnya pusat aktif krn

katalis tekspos pd T tggi), heat transfer sulit shg T
nya naik terus katalisnya bisa rusak.
Heterogeneous catalysts have their acive sites
on the surface. Pusat aktif asam dan basa: dehidrasi
alumina dan produk zeolite dengan pusat aktif asam
dan basa. Temperatur rendah untuk produksi asam
OH di alumina. High surface area materials produce
better catalysts. Typically, very high surface area
supports (sillica gel, gamma alumina, etc) are used to
support very small particies of active material. Zeolite
are porous and have a lot of accesible internal
surface.
Acid&base sites
Katalis
heterogen
pakai
pusat
aktif
basa/asam:alkilasi,isomerisasi alkana.dehydration of

alumina&various zeolites produces materials

w/ acidic&in some cases basic siteslow T produce

acid OH on

alumina,high T produce lewis acid

sites.
Reactions on metal surfaces many molecules react
or coordinate to metal surfaces. Formation of a
chemical bond w/ the surface: chemisorptions. If no
chemical bonds to the surface the species is
physisorbed. The surface bonded species are similar
to organometallics/coordination complexes.
Banyak industry gunakan katalis heterogen dgn pusat
aktif asam/basa co: nikel, palladium, platinum, Zn.
Pusat aktif: berfungsi jk chemisorptions kuat.
Kemisorp: ikatan kovalen koordinasi, fisisorp: VDW.
Spesies yang telah terkemisorp menghasilkan spesies
netral. Katalis heterogen tidak terlalu selektif karena

kristal, bentuknya bedabeda jadi fasa pusat

aktifnya bedabeda)
Early&mi
transition
metals
have
good
chemisorptions ability:Ti,Zr,V,Fe,
Sintesis amonia umumnya dilakukan pada tekanan
100 250 bar. Mekanismenya:
Feedstock desulphurisation
Feed dipanaskan hingga 350-400 C,
menggunakan katalis cobalt molybdenum ( agar
feed bebas sulphur)
Reaksi:
R-SH + H2 H2S + RH
H2S + ZnO ZnS + H2O
Primary reforming
Di bagian ini metana di bakar dengan steam
pada temperatur dan tekanan tinggi untuk
memproduksi CO2 dan H2. Katalis yang dipakai
adalah nickel chromium catalyst, reaksi
endoterm pada temperatur 780-830 C .Reaksi:
CH4 + H2O CO + 3H2
CO + H2O CO2 + H2
Secondary reforming
Karena konversi dari primary cuman 30-40%
reformingnya dua kali
Shift conversion
Dalam shift conversion, feed untuk reaksi
amonia masih mengandung CO, CO diubah dulu
ke CO2. Kalo High temp Shift pake katalis iron
oxide/ chromium oxide pada suhu 400 C. Kalo
Low tem shift pake katalis copper oxide/ zinc
oxide-based catalyst pada T 200-220 C
CO2 Removal
CO2 removal diabsorpsi kalo secara kimia pake
solvent mono ethanolamine (MEA), Active
methyl dietanol amine (aMDEA), atau potasium
karbonat panas. Kalo fisika pake selexol
Methanation
Sisa CO2 di feed yg gabisa diekstrak dibalikin
jadi metan dengan bantuan katalis Nickel
Synthesis gas compression and ammonia synthesis
Di tahap operasi nya, katalis yang dipake Iron di
tekanan 100-250 bar suhu 350-550 C
N2 + 3 H2 2 NH3.
Kalo pake teknologi yang baru katalisnya
ruthenium dengan graphite support

Catalytic reaction
sharpless oxidation,
epoxidation
selective oxidation
with H2O2
hydroformilation
polymerization
olevines
selective catalic
reduction
acetic acid

catalyst
Ti.ROOH/Tartarat
e
titanium zeolite
(TS-1)
Rh/Phospine/aqu
eous
zirconocen/MAO
V,W,Ti
oxides/monolith
Ir/Ru

CHAPTER 6

Karakteristik laju reaksi:

Laju reaksi berpengaruh terhadap temperatur,
temperatur naik maka Ea turun(boltzman
distribution)
Katalis. Katalis menurunkan Ea dan (mempercepat
lajureaksi)(boltz man distribution)
Enzim menurunkan harga Ea dan dapat membua
reaksi berlangsung pada suhu rendah.(boltzman
distribution)
Enzim seperti lock and key, hanya aktif pada reaksi
tertentu
Pada industri kimia, rx kimia berperan penting :
Bahan baku dr alam (brp air,udara,bhn tambang)
proses2 pretreatment rx kimia pemurnian/
separasi
(bisa
recycle)
product
&
by
product/waste.

Proses2 pretreatment : pengolahan utk menghilangkn

poisons cake formation on active centers),
kotoran yg dpt mganggu rx2 berikutny (CO, CO 2, S)
HCl
(mningkatkankeasaman),MgO
(slows
ter-utama rx yg melibatkn katalis (racun katalis hrs
sintering of active com-ponents),Pt (increase
dibuang dlu). Rx kim di industri kbanykn mrpkn rx
CO
oxidations),
ZnO
(de-creased
Cu
kstimbangan, walaupun sdah diatur T & P-nya, tp
sintering), Re (lower hidrogenolisis activity
konversinya tdk bisa 100%. Saat kluar dr reaktor,
and
synthering,
Ni,Co
(meningkatkan
produk bcmpur dgn katalis, sisa reaktan, prduk
hidrogenolisis
C-S
dan
C-N),
P,B
samping,dll, jd hrus dimurnikn. Bbrp by-product dpt
(meningkatkan dispersi, K ( improve coke
lgsg digunakn. Pran katalis sgt pnting krn by-product
removal), K2O electron donor meningkatkan
& waste bsa di-min & produk dpt di-max.
disosiasi
N2),
Alkali
metal
(increase
Dlm industri kim, rx hrs dikontrol utk mendptkn:
selectivity, hinder crystal growth, stabilize
high yield : high conversion & selectivity
oxidation states)
reasonably fast rate make conversion bigger
Bersifat aditif( hny ditambahkan sedikit saja,
milder (T,P) conditions
sisanya support). Inert,kuat di bwh tekanan
Ini smw dpt diperoleh dg menggunakan katalis yg
reactor,stabil
pd
kondisi
reaksi,dpt
cocok.
diregenerasi kalau keracunan sementara
Karakteristik pntg katalis industri:
tjd,area permukaan luas,berpori,terjangkau
hrganya.
Ea<170 kJ/mol even lower for enzyme catalyzed
3. Support: gives high surface area & increase active
reactions (35-50 kJ/mol)
sites reactivity.
spesifik/selektif
- harus inert (tdkblhbrx)
only need a relatively small amount
ckup
kuat di bwah tkanan reaktor yg tggi.
homogeneous dan heterogenous
- stableon reaction condition (T,P) range
Katalis industri ideal:
- bsdiregenerasijikakeracunan semntaratjd
selektif
- very high surface area; porosity; and cost
stabil (long lifetime)
Order of
- Ex of good support : alumina,silica, alumina-silika
prority
highly active_fast rx rate
(zeolit), karbon aktif
relatively cheap
- Other supports : MgO (rather poor mechanical
For heterogeneous catalyst :
strength),ZnO (poor stability as prone to
high thermal conductivity=mudah memindahkan
reduction),Cr2O3(acid sites cause undesirable
panas
reactions), TiO2(highly stable at T tinggi,
gives uniform fluid flow & low pressure drop
mahal)
ukuran, btuk, pori hrs diatur spy fluida yg ngalir ke
Contoh:material yang sgtberporispt silica,
dlmnya tdistribusi merata ke sluruh bag katalis,
karbonaktif. Kalopusataktiflogam, bisapake
skligus spy hilang tekannya ga trlalu bsar.
monometallic atau bimetallic.
BIMETALLIC CATALYST ON INDUSTRY

Catalist
1. Ni/Cu.SiO2
2. Pd/Fe.S
iO2
3. Rh, Ru, Ni+
Sn
4. Rh/Mo-Si.O2
atau
Al2O3
5. Ni/Sn ;
Rh/SnSiO2
6. Pt/Sn

Process
industri olefin
hidrogenasi 2,4
dinitrotoluene jadi 2,4
diaminotoluene
hidrogenasi ester
menjadi alkohol/asam
hidrogenasi CO dan
CO2 jadi metanol/
dimethyl eter
hidrogenasi dimetil
asetat jadi etanol
dehidrogenasi and
cracking alkana

SOLID CATALYSTS
A solid (hetero) katalis biasanya mengandung :
1. Active site(phases): speed-up&direct desirable rx.
- active metal (normally transitional group) atom
dispersed over the surface of the support
- bisamonometalik/bimetalik
- adsorb reactant molecules differently (some molcules
are adsorbed more strongly than others)
- place where chemisorptions &surface rx occurs
- can be temporarily/permanently deactivated (catalyst
poisoning)
biasanyalogamtransisi&oksidalogam,sulfideatau
asambronstenataulewis.Merupakancehmisorpda
nreaksipermukaan.
2. Promoters:increase catalysts performance by physical
(textural) or chemical (structural) interaction.
- Increase catalyst activity but they are not
catalytically active
- types: physical(textural)mbutuhkan tekanan tinggi
u/ kuatkan katalis, chemical(stuctural) electronicmemodifikasi
sifat
elektron,catalystpoison-resistantmeningkatkan tahanan pada
racun.
- Ditmbhkan ke katalis dgn persentasi kecil
- Contoh
promoter
:
SiO2,ZrO2,P
(mningkatkanstabilitastermal),K2O
(mencegah

Effectivit
y
1.Active
Center
2.
Concentra
tion
3.
selectivity
4.
Diffusion
problem

Homogenous

Heterogen
ous

All metal atom

Only
surface
atom
High

Low
High
Practicatlly
absent

Mild (50-200)
Limited

5.
Reaction
condition
6.
Applicabili
ty
7. activity
loss

katalis
prop
1.struktur/
stoikiomet
ri

Irreversible
with
products
;poisoning

Lower
Present(m
asstransfercontrolled
reaction)
Severe>2
50oC
Wide
Sintering
of
metal
crystallitie
s
poisoning

Defined

Undefined

High

Low

Low

High

2.modif
possibilitie
s
3.thermal
stability
4.catalyst
separation
5.catalyst
recycling
6.cost of
catalyst
losses

KATALIS
hetero
Al2O3

produksi acrylamide dariadisi air ke acrylonitrile

Sometimes
laborious
Possible
high

low

Promotor

Fungsi

SiO2,
ZiO2, P

Increase
thermal
stability
Poison coke
formation
on active
center
Increase
acidity
Slows
sinthering
on active
component
Increase CO
oxidation
Lowers
hydrogenoly
sis, activity
& sintering
Increase
hydrogenoly
sis activity
& sinthering
Increased
hydogenoly
sis of C-S
and C-N
bond
Improved
coke metal
Decrease
Cu
sinthering
Electron
donor,
favors N2
dissociation
Structure
promoter

K2O

SiO2/Al2O3/
(cracking
cat)
Pt/Al2O3
MoO3/Al2O3
(hydrotreat
ng,
HDS,HDN)

HCl
MgO

Pt
Re

Ni,Co

Ni/Ceramic
support
(steam
CuO/ZnO/Al2
O3
Fe2O3
(NH3
sinthesis)

menggunakan nitrile hydratase enzyme

Fixed bed/
sintesis aspartame, a widely used artificial low-calorie
filtration
sweetener using thermolysin enzyme
Unnecesa Contoh racun Katalis:
ry

P,B

K
ZnO
K2O
Al2O3

Sintering:kehilanganpusataktifsecaraperlahan
(krn T tinggi)
Sintesisaspartan:
enzyme
thermolycin.
u/
hidrogenasi, oksidasi, oligomerasi, polimerasi,
rxdgn CO2:semua dikatalisdgnkatalis homogeny.
Some industrial ex of enzyme catalysed reactions
:

Proses

catali
st
Fe

Tempat dimana cemisoprtion dapat terjadi

Dapat secara sementara dinonaktifkan.

Promotor

Memperlambat sintering

mode
of

Meningkatkan daya tahan katalis dari racun

action

Meningkatkan ketahanan mekanik

NH3
S,Se,Te,P, Poison: strong

Adiktif(aktif secara katalitik)

Dibutuhkan kalo kita membutuhkan tekanan

sintet
As,Haloge chemisorption
yang tinggi(katalis tidak mudah rapuh dan
sis
n
or formation
hancur)
compounds

Bisa memperbaiki struktur

O2.H2O,N Weak poison:

Secara
elektronik
bisa
memodifikasi
O
oxidation of Fe
struktur e
Membut
karbon
tidak
mudah
menempel
surface;

Adiktif, jadi tekanan sedikit saja

reductioin
possible but
Media support
cause sintering
CO2
Inhibitor:

Harus bisa menahan kondisi reaksi

Reaction with
CO

Stabil
alkaline

Luas permukaan tinggi

promoter

Harus
sangat
berpori(makan
berpori,
Poisin and
luasmakin tinggi)

Biaya harus terjangkau

inhibitor:strong
chemisorption,
The use of hetero industrial catalysts, based on
Unsaturat
Ni,Pt
reduction to
product types :
ed
Hydrogen ,Pd, hidrocarb metan,memper produksibhnkimia organic &anorganik

crude oil refinery and petrochemical industries

Cu
cepat sintering
atiion
on
Prduction of industrial gases and inorganic
Inhibitor: strong
chemicals :
chemisorption,
steam reforming of methane: H2O+ CH43H2+CO,
kat: Ni/Al2O3, 750-950C, 30-35bar
S,Se,Te,P, slow reduction
CO conversion, kat: Fe/Cr oxides (350-450C),
As,Haloge Poison: strong
Cu/Zn oxides(140-260C)
chemisorption
n
Methananization (SNG): CO + 3H2 CH4 + H2O,
Catalyti Alu
Poison:
alloy
kat: Ni/Al2O3 ,500-700C, 20-40bar
min -Hg and
c
form
Sintesis ammonia, kat: Fe2O3(K2O, Al2O3), 450Pb
ocracking
500C, 250-400bar
Poision: surface
silik -O2
Oks SO2SO3, kat: V2O5/support, 400-500C
oxide film

OksNH
3NO (as nitrit), kat:Pt/Rh nets,900C
a
Ni forms volatile
CO
Clauss process (sulfur): 2H2S + SO2 3S +2H2, kat:
carbonyl
NH3
bauksit, Al2O3, 300-350C
Pt/R
inhibitor:
amina,
NH3/urea plant
oxidatio
h
*primary reformer-Ni based
H2O, Ni, blocking of
n
*water gas shift rxtor (HTSC:Fe-based, LTSC:Cuactive sites
Fe, V,
based)
SO2 oks V2O
5/K2
S2O
7
etilen
Ag
okside
sintesis

poison

poison: SAMA
Coke
P,As,Sb,P Poison: alloy
b, Zn, Cd, form, catalyst
net becomes
Bi
brittle
Alkali
React with Rh
As
Inhibitor:
poison,
compound
Halogena
formation
ted
hydrocar inhibitor:
bon
increase
selectivity

Pusat

aktif:
Bersifat logam
Dalam bentuk atom, terdispersi
Tersebar merata di permukaan material
support
Bisa monometalik
Bisa menyerap molekul reaktan secara
berbeda-beda

* NH3 reactor : promoted Fe

* methanator : Ni-based
Other ex of hetero catalysts for bulk and fine
chemicals :rx hidrogenasi (produksi margarine);
sintesis methanol; oksidasi selektif alkena;
polimerisasi olefin; hidrogenasi katalitik (produksi
vitamin); proses oksidasi (ex : citral production);
catalytic C-C linkage (ex : produksi ibuprofen
(analgesic))
HOMOGENOUS INDUSTRIAL CATALYSTS
Co: enzim, katalis asam/bs, organometallikompleks
Organometallik kompleks: katalis homogen dgn
metal-C bonds. Komponen reaktifny dari organik
ligan seperti H,CO, alkena, metal center(d orbital)
Molecular
transformation
require
aloose
coordination of the reactants to meeta(central) and
easy release of the products from the coordination
sphere.
Extremely labile metal complexes are required
which have a vacant coordination site or at least
one weakly bond ligan.
Some key reaction in homogenous catalysis is
etensuvelu discussed complex formation, acidbase (Bronsted & Lewis) reaction, redox reaction,
insertion & elimination reaction reactions at
coordinated ligans

Hydrocyanation
Oxidation

Isomeration

Metathesis
Hydrogenation

Hco(CO)4 : punya 5 ligan, adanya ikatan kovalen

koordinasi antara ligan dgn atom pusat. (Ligan (CO)
punya 2 psg elektron bebas dan atom pusat (Co)
punya 5 orbital kosong (3d1orbtl, 4s, 4p)
HCO(CO)3 : 1 ikatan kovalen koordinasi (CO) tercopot
krn tidak stabil. Jadi spare 1 orbital.
HCO(CO)3CH2CHR : atom pusat yg orbitalny masih
kosong berikatan dgn CH2=CHR
RCH2CH2Co(CO)3 : H pindah ke CH2=CHR jadi CH2CH2.
1 orbital kosong lg
RCH2CH2Co(CO)4:CO masuk lagi mengisi 1 orbital
kosong.
RCH2CH2COCo(CO)3: CO berikatan dgn RCH 2CH2 jadi
RCH2CH2CO ada 1 orbital kosong lg
RCH2CH2COCo(H2)(CO)3: H2 masuk ke katalis lalu tjd rx
hidrogenasi. Terakhir RCH2CH2CHO lepas.
Rx coupling:
Rx organometallic dgn halida coupling product +
metal halida.
Co industri yg pake katalis homogen transisi

Unit Operation
Dimerization
olefins

Oligomerization
olefin

Polymerization
CO reaction

of

Process/Product
Dimerization
of
mono
olefins
(dimersol process),
synthesis of 1,4hexadiene
from
butadiene
and
ethylene(DuPont)
Trimerization
of
butadiene
to
cyclododecatriene;
oligomerization of
ethylene to olefin
Polymers
from
olefin and diene

Transferases: trnsfer gu2s kim dr 1sbstrat k

subs-trat ln/dr 1bag sbstrat ke bag ln.
[AB+C+EAC+B+E]
Hydrolases:
rx
hidrolisis
[ AB+H2O+EAH+BOH+E ]
Isomerases: pnyusunan ulang atom dlm swt
struktur molekul [ A + E A + E ]
Lyases: eliminasi dr grup adjacent atoms /
addition of groups to double bonds _
penguraian [ AB+EA+B+E ]
Ligases:
pgbungan
iktn
mllui
hdrolisis[ A+B+EAB+E ]
Mekanisme reaksi berkatalis enzim MichaelisMenten:

Carbonylation
(hydroformilation,
hydrocarboxylation
, reppe reaction
Carbonylation
of
methanol to acetic
acid, carbonylation
of methyl acetate.
Adiponitrile
from
butadiene and HCN
Cyclohexane
oxidation;
production
of
carboxylic
acids
(adipic
and
terephtalic acid) ,
epoxides
(propylene
oxide,
halcon
process),
epoxyalcohols;
aetaldehyde
Isomeration
of
double
bonds;
conversion of 1,4dichloro-2-butene
to
3,4-dichloro-1butene
Octonamer
from
cyclooctene
Asymetric
hydrogenation,
benzene
to
cyclohexane,
Lmenthol

Contoh katalis industri homogen yg tmasuk

ENZYME catalyzed reactions.(6 tipe enzim based
on tipe reaksi)
Oxidoreductase (rx oksidasi-reduksi)
Transferase (transfer chemical grupdari satu
substrat ke substrat lain atau fromone part of
substrat to another.
Hydrolase (hydrolysis reaction)
Lyases (elimination of group from adjacent atoms
or addition of groups to double bonds
Isomerase (rearrangement of atom in a molecular
structure)
Ligase (formation of bonds to group with
hydrolysis
Production of acrylamide from water addition to
acrylonitrile usiing nitrile hydratase enzyme.
Sintesis aspartame

(1)

S+E

k1
ES
k1

SE k R P+ E

(2)

...... fast

Integral method:

dC s
V .C
= (r s )= m s
dt
K m +C s

integralkan pd t=0 & Cs=0 :

CS
CS 0
1 V
t
= m.
C S 0 C s K m K m ( C S 0C s )
ln

= c + m

Initial rate method:

K
1
1
1
= m.
+
(r s )0 V m [S]0 V m

....... slow

Rx (1) cpat mncapai kstimbangan:

K1[S][E] = k-1[SE] [SE] = K[S][E]

dgn

k
K= 1
k 1

Neraca enzim:

[E]=[E]0-[SE]

[ E ]=
Other
examples
of
heterogeneous
industrial catalysts, for bulk and fine
chemicals:Hydrogenation reactions, egin
margarine
production,Methanol
synthesis,Selective oxidation of alkene,
egethylene
oxide,
acrolein,
maleicanhydride and phthalicanhydride
production,Olefin polymerization,Catalytic
hydrogenation
in
vitamin
productions,Oxidation
process,
egcitralproduction (an intermediate for
fragnancesand vitamins A & E)

[ E]0
1+ K [S ]

Inhibisi & aktivasi dlm rx bkatalis enzim

dihasilkan oleh efek internal (single/multiple substrat) & efek xternal (racun-inhibitor
& koenzim-aktivator).Tiga tipe inhibisi:
1. Inhibisi kompetitif : inhibitor (I) bkmpetisi
dgn substrat mdptkn molekul enzim utk
mbtuk kompleks I-E. Inhibi-tor pnya
struktur yg mirip dgn substrat shg bsa
[E] = [E]0 - K[S][E]
mbtk kompleks dgn enzim. Reaction
steps:
(1)

r p=k R . [ SE ] =k R . K . [ S ][ E ]
[E ]0
r p=k R . K . [ S ] .
1+ K [S ]

disdr

hanakan dgn cara dibagi K:

1
K

1 K
1
1
=
.
+
r V [S] V

Oxidoreductases:
rx
[ AH2+B+EA+BH2+E ]

redoks

y =

(3)

(4)

V [S]
r p= max
K m +[ S ]

V =k [ E ] , K =

(2)

E+ S k 1 E . S

E . S k 2 E+ S

rx michaelis-

menten

Catalytic
C-C
linkage,
egibuprofen
(analgesic) production
CHAPTER 7
Enzyme-catalyzed reactions:
m
R
0
m
dgn
* lock-key mechanismsgtspesifik.
* enzyme = protein (amino ac. polymer
MW 6.103 6.105) in colloidal size (1nmBtk linearisasi (lineweaver-Burk-equation):
1m)* ygmpngaruhi aktivitas enzim: sifat
alam enzim tsb (inhibitor & ko-enzim),
m
sifat substrat, konsentrsi E dan S, pH,
temperatur.
p
m
m
Klas rx enzimatik:

gmw kerja). Enzim bkerja pd pH & T

optimum, diluar itu kerjanya ga max.

(5)

E . S k 3 E+ P

E+ I k 4 E . I

Muncul krn

ada
(inactive)
inhibitor

E.I k 5E+I

K 1
[I ]
1
1
= m
1+
+
(r s ) V m [S ]
KI Vm

[I]=konsentrasi inhibitor dlm cmpuran

[I] : garis mkn dkt sb.y,
tp intercept ga brubah.
[I] : rx mkin lambat

x + b

Nilai Vm& Km bgntung pd konsentrasi enzim

2.
awal, T, dan pH (diluar pH yg sesuai, enzim

Inhibitor

(I)

Inhibisi Unkompetitif :
mikat sbstrat-enzim dgn

mbntk kmpleks I-E-S yg inaktif. Reaction

steps:
(1)

(2)

(3)

(4)

(5)

E+ S k 1 ES

E . S k 2 E+ S

Utk tau inhibitor apa yg tdpt dlm suatu

bhn, lakukan pcobaan dgn dan tnpa
inhibitor, lalu bandingkan garisnya dlm
kurva

E . S k 3 P+ E

terhadap

1
s

CHAPTER 8

1+ E . S k 4 I . E . S

(inactive)

I . E.Sk 5 I. E.S

[I ] 1 K m
1
1
= + 1+
+
KI [s] Vm
( r s ) V m

( )

[I]: Gradien garis tdk

brubah, tp intercept
brubah

sd
3. Inhibisi
NonKompetitif(mixed):
substrate&inhibitor react w/ diff types of
sites on the enzyme molecule..Reaction
Steps:
(1)

E+ S E .

(2)

E+ I I . E

(3)

I+E . SI .E .S

(4)

S+I . E I .E .S

(5)

E.S P

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
of the catalyst
2. Internal difussion:transport of the reactants
from the external surface of the particle through
the pores to the active sites on the interrior
surface
3. Adsoption on the reactanton the active site
4. Surface reaction
5. Desorption of the product from the active.
6. Internal counter-difussion:transport of the
1.
product through the pores to the external
2.
surface
7. External counter-difussion:transport of the
pro-duct from the xternal surface to bulk fluid
phase.
Steps 1,2,6,7 are strictly physical steps(transport
phe-nomena). Steps 3,4,5 are purely chemical
phenomena (microkinetics). The transfer steps 1 &
7 depend upon the flowdynamics of the
system.The transport steps 2 & 5 are present only
with porous catalysts & depend on the geometry
of catalyst particles.
Steps 1&7 (xternal diff.) are in series with steps 35 (chemical steps): the xternal trasfer occurs
separate-ly from the chemical reaction. Steps 2&6
(internal diff.) occur simultaneously with chemical
reaction.
Umumnya utk laju kinetika intrinsiknya dicoba di
reaktor skala lab. Utk rx cepat pake reaktor
kontinyu, kalo lambat pake reaktor batch.

Difusi pori : ppindahan massa bdasatkn pbdaan

kon-sentrasi, dmn fluida tsb melalui fluida diam.

(inactive)

Strong atomic
adsorption
Easy
Cr dissociation
Mn Fe

(inactive)
(inactive)

Co Ni Cu
Mo Tc Ru Rh Pd Ag
W Re Os Ir Pt Au

[I]: baik gradien &

intercept brubah

Lineweaver-Burk plots for three types of

enzyme inhibition:

Weaker atomic
adsorption
No dissociation

Classifications of heterogeneous catalysts :

1. Metalshydrogenation,
dehydrogenation,hydrogenolysis(oxidation).ex:Fe,Ni,Pd,Pt,Ag
2. Semiconducting
oxides&sulphidesoxidation,
dehydrogenation,desulphurization(hydrogenation)ex:Nio,ZnO,MnO2,Cr2O3,Bi2O3-MoO3,Ws2
3. Insulator oxidesdehydration.ex:Al2O3,SiO2,MgO
4. Acidspolymerization,isomerization,cracking,alkyl
ation.ex:H
3PO4,H2SO4,SiO2-Al2O3,zeolites
I
Rate determining steps (rds) if the rate constant
of 1 of these steps is markedly smaller than other,
the overall rate is determined by this step.
Regimes
kinetic regime: rds = chem rx (chem regime).
external diffusion regime: rds= external diffusion
(film diffusion, external mass transfer
limitation)KALO LAJU DIFUSI PORI NY PELAN
internal difusion regime: rds= internal difusion
(pore difusion, internal mass transfer limitation)
Convective & diffusive transport
convection: transport by bulk motion of the fluid
(krn ada pngadukn)
diffusion: transport due to gradients
(concentration gradients if the transported

[ I ] 1 Km
[I ]
1
1
=
1+
+
1+
KI [s] V m
K
( r s ) V m

1
rs

( )

property is d mass, temperative gradients if d

transported property is d thermal energy)
Mass transport by diffusion: the Ficks law

J =D

dC
dx

(1)

regime)

[mol m s ]
-2

-1

r=k .C b

,surrounding external surface

catalyst, dimana terdapat gradient kons. Dlm

fasa cair curah, kons konstan
Ada 2 pristiwa yg tjd:
difusi ke perm padt katalis (nembus film)
rx yg dktalisis pusat aktif katalis padat
ficks law:

rezim kinetik. r=

k .Cb
=1
k .Cb '

mkin rumit

Film diff & reaction e diphitungkn

bwt nyari r
Maximum limitation by film diffusion
(xternal diff regime) Cs 0

k a.

r=a . Cb

. 1/k

kecil jd diabaikan. Difusi lambat, ad dlm

rezim difusi film.

e =

= tortuosity of the pores (characteristic

values: 3< <7): nunjukin rumit tdknya
swt struktur katalis.

. Difusi

mudah,cpt. Difusi film diabaikan. Ad dlm

J=mass flux (d moles transported per unit of time

and per unit of surface perpendicular to the
diffusive movement)
C=concentration of the diffusing substance
D=diffusion coefficient
The negative sign indicates that d diffusion
(2)
occurs in d opposite direction of d C gradient
(3)
(dC/dx)
(4)
External diffusion
Film model:existence of a stagnant layer(film),of
thickness

No limitation by film diffusion (kinetic

Cb
=nol
k . Cb'

struktur

mkin sulit brpindah/

berdifusi.
The resistance towards transport originates
from colli-sion of the molecules either
with each other (Dm = mo-lecular
diffusivity) / with the pore walls (Dk =
Knudsen diffusivity). Dm tergantung dr
molekul & komposisi molekul. Dk berhub
dg tumbukan molekul reaktan wkt dia
pindah dg dinding porinya. Dk tgantung
dr factor kkuatan material dinding
porinya.
Internal effectiveness factor (i)

i =

observed reaction ra
reaction rate at xternal surfac

D
( C bC s )= ( Cb C s )
r=i k C ns

External effectiveness factor ( )

observed reaction rate Limit case r obs
[mol m s ]

=
= n kasus batas yg serupa
e
D=koefdifusivitasmolecular_camp
Internal diff jga pnya
reactionrate at bulk fluid conditions
=thickness of d external film
dgn xternal kC
diff.bPada kasus (1) = 1. Pada
J=

-2 -1

=koef ppindahn massa

At steady state, the rate of mass transfer must be
e-qual to the rate of the surface rx, expressed per
unit external surface area:

r= . a . ( C b Cs ) =k C

n
s

a
< e <1
k

Internal diffusion
Ada 2 pristiwa yg tjd pd katalis padat bpori:
difusi film/ difusi external
difusi dlm pori (rx tjd bersama2 dg difusi pori)
Klo sistem sdh steady state, maka laju difusi
film = laju difusi external + laju difusi dlm pori
Tahanan(resistance): tumbukan antar molekul
atau tumbukan antara molekul dgn dinding
pori katalis.
Difusivitas dipengaruhi o/ temperature&jenis
molekul.
Difusi film dipengaruhi sifat aliran
ficks law:

Ap(luas area pdtan katalisdlm unggun)

V unggun

Cb=konsentrasi rxtan pd fasa curah/bulk

Cs=konsentrasi rxtan pd fasa solid (pd
katalis)
1st order reaction

r= . a . ( C b Cs ) =k C s
r=

* utk orde 1 kasus (2)&(3) :

r obs =e kC b ,

laju ppindahan = flux. area ppindahan

laju ppindahan = J.a [mol. s-1. vol unggun1
]
k= kinetic constant referred to the unit of1.
vol catalyst
2.

a=

kasus (4) i = 0. Pada kasus (2)&(3) 0 < i<

1.
Thiele Modulus

1
1 1
+
k a.

Cb

1/k= chemical resistance

1/: external mass transfer resistance
Limit case

J =De

dC
dx

[mol m-2 s-1]

x= jarak yg tgk lurus dr pusat partikel

De= koef difusi efektif

p
De=
1
1
+
Dm D k
1

jika:
p = vol pori/vol partikel katalis. Vol pori bsr,
difusi mudah

kCns
rate without p
De C s maximum rate o

KlokDe =0
Klo kDe =>>, makai<< regime
difusi internal (robs<< Cs)
Small : rx rate is smallrx limits the
overall rate (kinetic regime)
Large : diffusion rate is small internal
diffusion the overall rate (int. diff. regime)
Faktor yg pngaruhi i:
- bntuk &
ukuran partikel katalis
- temperatur
- orde rx
Simultaneous xternal & internal difffusion
Saat tunak (rx orde 1): laju transfer massa
external hrus sm laju reaksi permukaan dg
difusi internal
Orde 1: r (react+int diff)=

cs=
diperhitungkan

Vp
Ap

Cb
+ik

sblmnya didapat:

i.k.Cs ;

substitusikan ke pers

substitu
si

3. All adsorption occurs through the same

v
A
A
B B
mechanism.
v
A2 A 2

4. At the maximum adsorption, only a

[mol m-3 smonolayer is formed: molecules of
adsorbate do not deposit on other, already
v
1
adsorbed, molecules of adsorbate, only on
v
]
A
A
B B
the free surface of the adsorbent.
General formula for 1st order reaction.
A2 A 2
Jrg smuanya bner. Permukaan slalu ga
Rds: Surface reaction(jrg) is controlling& the sempurna,molekul teradsorb ga
concent profile across the film & inside the inert,mekanisme ga sama molekul pertama
A
A
B B
pore is flat. The Ea derived frm the rx rate teradsorb sm yg trakir.
A2 A 2
A
B
correspond to true Ea of chem rx without1. Single adsorbate case
A
A
B B
A Av
B B
mass trnsport limitation.
A2 A2
Pd T rendah : k <<< , k <<<=0& i 1,
ads
3. Single adsorbate + inert = no.2, cm B-nya
Adsorpsi :
shg:

diganti I
4. Two different adsorbates adsorbed at 2
obs
b ;
Monomolecular heterogeneous reaction [A
kind of sites
P]
des
Ads-Des of A at X :
Mekanisme reaksinya
Desorpsi :

0
a
A
1
S = pusat aktif yg msh kosong

(A
(fraksinya = v)
1
intrinsic
att b
SA = pusat aktif yg sdh ditempati A
;kapp = katt , Eapp =
(fraksinya = A)
B
Ads-Des of B at Y :
Eatt
@ equlib:
VX+ AX =
1

r obs =i k C b / 1+

i k
.a

( K C + K C +1 ) =1

1
K C + K C +1

A +Sk

r =k C

SA

k =k 0 exp(Eatt / RT )

A + X K XA

1
K C +1

k
A +S
SA
k

B+ Y K YB

r ads =r des k ads C A v =k des A

E 1
RT

A=

substitu
Rds: internal pore diff is controlling & there
si

is a concent gradient inside the pore. The E a

derived frm the observed rx rate constant
corresponds to approxi-mately of the true
Ea. Pd T sedang: i<<< , shg:

A
1
r obs =i k C b k C b p

Vp
robs= k cb

C +1 )=1

K C
K C
K C
=
K C + K C +1
K
C +=K C + 1
K C +1

=k C

ln k =ln k 0

( K

v ( K A C A + K P C P +1 ) =1
v =

1
K A C A + K P C P +1

A=

KACA
K A C A + K P C P +1

r =

SA k S + A

ln k =A exp (E / RT )
r

N.M pst aktif :

A + v = 1

k ads
C =Ksubstitu
C
k des A v si A A

K A C A v +v =1

De C s v ( KAAp C A +1 )=1
k C b = D e kC b
k Cs
Vp 1
v =
K A C A +1

K C
=
K C +1

Rds: external pore diff is controlling & there

A A
is a concent gradient across the film. The E a
A
derived frm the observed rx rate constant is
A
A
generally below 5kJ/mol. Pd T tinggi: <<<
k.i, shg:
2. Two different adsorbates case
b
; Cb makin ke bawah makin
A
Ads-Des of A :

dikit, r makin kecil. T tinggi

* utk feed batch biasanya pke rds = xternal
pore diff
B
Isotherm adsorpsi : pers yg hubungkan kons
Ads-Des of B :

reaktan teradsorb pada prmukaan katalis dan

kons reaktan fasa curah pd T tertentu
@ equilib:
Mcm2:freundlich, Langmuir, temkin, BET. Plg

r=a C

A +S K SA

B+ S K SB

umum: Langmuir(semi-empiris)
LANGMUIR ISOTHERM berhub dgn
konsentrasi rxtan dlm fasa gas & yg tlah
tadsorb oleh pdtan.
Asumsi: The surface of the adsorbent is
uniform, that is, all the adsorption sites are
equivalent.
2. Adsorbed molecules do not interact.

A =K A C A v ; B =K B C B v

N.M pst aktif :

A + B + v = 1

K A C A v + K B C B v + v =1

VX = fraksi kosong pd pusat aktif X

Ax = fraksi yg terisi A pd pusat aktif X
VY = fraksi kosong pd pusat aktif
Y
VY+ BY =
BY = fraksi yg terisi B pd pusat aktif
Y
1
v @ equilib:

adsorption)

k
K A=
k1

SA k 2 SP

AX =K A C A vx ; BY =K B CB vy

sbg rds
(rx elementer (paling sederhana)

K A CA
K B C B k 3
AX=
BY =
SP
S+ P
K A C A +1
K B C B +1
k3
5. Single adsorbates with dissociation

A 2 +2 S k ads 2 SA

Adsorpsi :

2 SA k des 2 S+ A2

Desorpsi :

@ equlib:

desorption)

KP=

(P

k3
k3

(produk tlepas dr pst aktif)

Kdes=1/Kp=K-3/k3
Rds : surface reaction (biasa rx katalis padat
di step ini)

r ads =r des k ads C A v =k des A

r=k 2 A

2
v

A =K A C A A=
2

N.M pst aktif :

A + v = 1

v K A C A + v =1
2

shg :
@ equilib :
v
A 2 A2
A
A

C
K =K

k2KACA
K A C A + K P C P+1

K2:ind keaktifan katalis(pusat aktif),

KA:ind adsorpsi A, KP: Ind. Adsorpsi
P(desorpsi)
Rds : A adsorption

r=k 1 C A v

; r1<<< smntra r2&

P=K P C P v

@ equilib :

N.M pst aktif :

P + v = 1

K P C P v + v =1

v ( K P C P +1 ) =1
v =

1
K PCP+ 1

r =

k1 C A
K P C P +1

; r2<<< smntra r1& r3>>> Rds : P desorption

r=k3 P

r3>>> shg A0 (tjd krn rx pbtkan A sgt

lmbat, bgitu kebentuk A lgs dipake brx
utk jd P, shg hmpir gada A di perm pusat
aktif)

(surface reaction) 75%

C A v ; P =K P C P v

N.M pst aktif :

A + P + v = 1

K A C A v + K P C P v + v =1

; r3 <<< smntra r1&

r2>>> shg P 1 (tjd krn rx penguraian

P sgt lmbat sdgkn rx pbtuknnya sgt cpat
shg P yg trdpt di perm psat aktif mjd sgt
bnyak).
Krn P 1, maka A = V 0.

r k 3

Bimolecular heterogeneous reaction [A + B

P + R]
Jika ada 2 atau lebih rxtan, kadang hanya
salah 1nya aja yg tadsorb oleh pst aktif
dan terkadang smw rxtan dpt tadsorb. Hal
ini dsbabkn krn psat aktif itu selektif, artiny

dy milih2 mana yg mo diserap, mana yg

ngga.
1. Eley-Rideal mechanism : cm 1 rxtan yg
tadsorb

k
A + S 1 SA
k1

k1 C A
K P C P +1

Rds : P desorption
(A adsorption)

SA + B k 2 SP+ R

r =

(surface

SR

k 5
S+ R
k5

r=k 1 C A v

(R desorption)

r=k 3 A B

..... = kasus monomolekular rds P

desorption.....

r k 3

; r2<<< smntra

k 3
S+ P
k3

B =K B C B v ; R=K R C R v

A +S

k1
SA
k1

B+ S

k2
SB
k 2

(P desorption)

Rds : surface reaction

r=k 2 A C B
..... = kasus monomolekular rds surface
reaction.....

r =

k 2 K A C A CB
K A C A +K P C P+1

..... = kasus monomolekular rds A

adsorption.....

k
SP 4 S + P
k4

v ( K B C B + K P C P+ K R C R +1 ) =1
K A C A v + K B C B v + K P C P v +
K R C R v + v =1
1
v ( K A C A + K B C B + K P C P + K R C R+1
v =) =1
K BCB+ K P CP+ KR CR+ 1

v =

r
1
K A C A + K B C B + K P C P + K R Cr
=
R+ 1

A &B

r =

CATATAN LAIN
Katalis padat(ZEOLIT): luas permukaan
besar, uk.pori tdk seragam,aktivitas
katalitik rendah
v Katalis heterogenkomp. Aktif:
btanggung jawab thd reaksi kimia utama,
support: jaga agar luar permukaan
komponen aktif tetap besar, promoter:
tingkatkan aktivitas, selektivitas,
stabilitas katalis
Dalam proses katalisis,
katalis heterogen lebih banyak
dilakukan. Hal ini disebabkan oleh
keuntungannya, yaitu mudah dipisahkan
dari
reaktan dan produk. Selain itu, katalis
heterogen dapat dipulihkan dan digunakan
kembali dalam proses katalisis yang sama.

K B C B v + K P C P v + K R C R v + =1

(surface reaction)

(P desorption)

Rds : P desorption = R desorption, R P; k5 k-4

N.M pst aktif :

A + B + P + R + v = 1

(B adsorption)

SA + SB k 3 SP+ SR

Rds : A adsorption

r=k 1 C A v

(A adsorption)

N.M pst aktif :

B + P + R + v = 1

A =K A C A v ; P =K P C P v

2. Langmuir-Hinselwood mechanism : smw

rxtan tadsorb

r k 5

P=K P C P v

rothers>>> shg :
@ equilib :

k1 C A
K B C B + K P C P + K R C R +1

: B adsorption = A adsorption, A B; k
k 3 K A C A K B CRds
Bk
1

Rds : R desorption
2

( K A C A + K B C B + K P C P + K R C R +1 )

; r5 <<< smntra

rothers>>> shg R 1. Krn P 1, maka A

= B = P = V 0.

B =K B C B v ; R=K R C R v

reaction)

SP

; r1<<< smntra

rothers>>> shg A0
@ equilib :

Rds : surface reaction

r=k3 P

r=k5 R

Rds : A adsorption