SURFACE PHENOMENA,

ADSORPTION AND
CATALYSIS
RESTU - 2015

INTRODUCTION TO SURFACE
PHENOMENA
THE SURFACE TENSION OF LIQUIDS

Why do some insects succeed in skating

on water instead of sinking?
Why does water climb up a thin tube?
Why can you make bubbles with soapy
water and not with tap water?

The surface of a substance has special properties.

These surface properties are what allow these
strange phenomena we have mentioned.
Not only that, but the surface is also the place of
contact among different substances.
In short, the properties of surfaces are so special
and important that there is a branch of science, the
physics of surfaces, devoted to the study of
surface phenomena.

SURFACE TENSION
A molecule of a liquid attracts the molecules which surround
it and in its turn it is attracted by them

GAYA TARIK ANTAR MOLEKUL liquid. Molekul di dalam mempunyai

gaya tarik yang seimbang. Tapi gaya tarik molekul permukaan tidak
seimbang. Selain itu gaya kohesi antar molekul menghasilkan tegangan
tangential pada permukaan, sehingga permukaan liquid bersifat seperti
membran elastis

Beberapa contoh fenomena tegangan muka

l
B

x
C

Misalkan terdapat lapisan

tipis liquid di antara kawat
seperti gambar di samping

Jika terdapat gaya f yang menggerakkan kawat CD sepanjang x, dari

CD ke EG, maka kerja yang dilakukan adalah
W = fx
Gaya f akan diimbangi oleh gaya tegangan muka, , shg f = 2 l
Shg w = 2 l x = A
= w/A

Metode penentuan tegangan muka

Tensiometer
Drop weight
Bubble pressure
Capillary rise method

Metode terakhir didasarkan pada kenyataan bahwa

kebanyakan liquid bila dimasukkan dalam gelas kapiler
akan naik permukaannya sampai di atas permukaan luar

Ketika pipa kapiler dimasukkan ke liquid,

permukaan dalam kapiler basah shg
permukaan liquid naik. Utk menurunkan
permukaan bebasnya, liquid harus naik
dalam kapiler. Hal ini akan berhenti apabila
gaya tegangan muka (yg mengarah ke atas)
sama dengan gaya liquid yang mengarah ke
bawah (karena pengaruh gravitasi)

f1 (gaya karena tegangan muka) = 2 r cos

f2 (gaya penyeimbang) = r2hg
f1 = f2 shg 2 r cos = r2hg
=

rhg
2 cos

(h + r/3)(l - v) rg
2

Drop weight
=

W = berat tetesan liquid

Wg

= r/V1/3, V = volume tetesan liquid

2 r

Ramsay-Shields
Menentukan surface tension terhadap suhu

M
l

2/3

= k (tc t 6)

Modifikasi Katayama
M

l - v

2/3

= k (tc t)

Molar surface energy

Zat cair yang

bersentuhan dengan udara

Suhu (oC)

Tegangan Permukaan
(mN/m = dyn/cm)

Air

75,60

Air

20

72,80

Air

25

72,20

Air

60

66,20

Air

80

62,60

Air

100

58,90

Air sabun

20

25,00

Minyak Zaitun

20

32,00

Air Raksa

20

465,00

Oksigen

-193

15,70

Neon

-247

5,15

Helium

-269

0,12

Aseton

20

23,70

Etanol

20

22,30

Gliserin

20

63,10

Benzena

20

28,90

Interfacial tension and spreading of liquids

2 liquids yg tidak saling larut atau larut sebagian bercampur maka
interfacial tension, AB terjadi pada batas antara 2 lapisan
Jika sebuah kolom liquid 1 cm 2 ditarik sebagian, 2 permukaan akan
terbentuk, masing2 1 cm2. krn tegangan muka adalah juga kerja untuk
membentuk unit area permukaan, maka kerja (kohesi)
Wc = 2
Jika kolom tersebut berisi 2 liquids yg tidak saling larut atau larut
sebagian, maka kerja (Wa, kerja adesi) yg diperlukan utk memisahkan
2 liquid dlm melawan interfacial tension
Wa = A + B - AB
Akan menghasilkan pers. utk spreading coefficient (SBA) utk liquid B
pada permukaan A
SBA = Wa Wc atau
SBA = A - B - AB
SBA + = spreading terjadi; - = no spreading

Surface tension

Surface tension of solution

II
III

- surface
activity

+ surface
activity

concentration

I = strong electrolytes, sukrosa, asam amino benzoat dalam air atau anilin
dalam hexana
II = non- or weak electrolytes in water
III = aqueous solution of soaps, sulfonic acid and sulfonates, some organic
compounds (surfactants)

Mengapa surfactant bisa menurunkan

tegangan permukaan?

Willard Gibbs: aktivitas permukaan dipengaruhi distribusi solut di antara permukaan

dan dalam larutan.
Jika solut terdistribusi shg di permukaan terdapat q mol solut per 1 cm2 pada
larutan, maka
C d
q=RT dC

C = konsentrasi larutan
d
= laju variasi tegangan muka lar. thd konsentrasi
dC

Persamaan
adsorbsi Gibbs
d
dC

+ = q akan -, shg dalam larutan lebih banyak solut

daripada permukaan ; mis. Elektrolit
Sebaliknya terjadi pada surfactant.

So, positive surface active = adsorpsi solut dari larutan oleh permukaan,
Sebaliknya karena expulsion of solute from the surface

adsorpsi
Adsorpsi = proses yg terjadi ketika solut
(gas/liquid) terakumulasi di permukaan solid
Adsorben = zat penyerap
Adsorbed phase/adsorbat = zat yg diserap
Absorbsi = zat tdk hanya di permukaan, tp
terdistribusi sampai ke dlm solid/liquid penyerap
Adsorpsi, contoh = larutan asam asetat, dan bbrp
gas oleh charcoal
Absorpsi, contoh = air oleh sponge, uap air oleh
anhydrous

Adsorpsi gas oleh solid

Scr umum semua solid bisa mengadsorp
gas, dgn syarat solid tsb mempunyai luas
permukaan yg besar.
Solid perlu diaktivasi sebelum digunakan
Jumlah gas yg diadsorp tgt sifat adsorben
dan gas, luas permukaan adsorben, P & T
gas

Types of adsorption
- Physical (Van der Waals) adsorption
# low heat adsorption (< 10,000 kal/mol
adsorbate)
# reversible
# adsorption equilibrium established rapidly

- Chemical (activated) adsorption

# high heat changes (20,000 100,000 kal)
# combination gas molecules with surface to
form surface compound

Fundamentals of adsorption and desorption

Adsorption Isotherms
Adsorpsi biasanya ditentukan pada kondisi isoterm
yaitu hubungan antara jumlah zat yg diserap
oleh adsorben dengan tekanannya atau
konsentrasinya pada suhu konstan
Secara umum ada 5 jenis adsorpsi isotermal gas
oleh solid.
Chemisorption hanya mengikuti type I, sedangkan
physisorption dapat mengikuti semua type.

Type I

Type II

Type III

Pressure
Amount adsorbed

Amount adsorbed

Type of adsorption isotherm

Type V

Type IV

Pressure

Type I

By Freundlich and Kster (1894)

x = adsorbed quantity, m = mass of adsorbent, P = the pressure of adsorbate, and

k and n = empirical constants for each adsorbent-adsorbate pair at each T
Persamaan tsb biasanya tidak sesuai pada P besar, dan juga tidak semua adsorpsi
gas akan mengikuti persamaan tsb (contoh hal. 757). Persamaan yg lebih tepat
diusulkan oleh Irving Langmuir
PERSAMAAN ADSORPSI LANGMUIR

It is based on four hypotheses:

1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equal.
2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same mechanism.
4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate
do not deposit on other, already adsorbed, molecules of adsorbate, only on the free
surface of the adsorbent.

 Postulat Langmuir: gas yg teradsorp tdk dapat

membentuk lebih dari single layer

Proses adsoprsi: - kondensasi gas ke solid; evaporasi molekul dari permukaan ke gas
Hanya molekul yg berdekatan dgn permukaan yg
belum tertutup molekul lain yg teradsorp, so initial
rate akan tinggi dan makin menurun seiring dgn
berkurangnya pemukaan yg terbuka
Sebaliknya molekul yg telah teradsorp, dgn adanya
panas, bisa terevaporasi ke gas (desorp). The rate
depend on amount of surface covered by molecules,
and increase as surface more saturated
Laju ini suatu saat akan sama shg terjadi
kesetimbangan
A(g) + S AS, where A is a gas molecule and S is an adsorption site.

Persamaan adsorpsi Langmuir

= fraksi total permukaan yg tertutup molekul adsorbat

(1- ) = fraksi permukaan yg masih tersedia utk adsorpsi

Rate of condensation = k1(1- )P
Rate of evaporation = k2
Pada kest. k1(1- )P = k2
= k1P / (k2 + k1P) if b = k1/k2
= bP / (1 + bP)
y (jumlah gas teradsorb/unit area/unit mass adsorben) sebanding
dgn fraksi permukaan yg tertutup
y = k = kbP / (1 + bP) if a = kb
y = aP / (1 + bP) x 1/P, then taking reciprocals
P/y = 1/a + (b/a)P
Plot P/y vs P menghasilkan garis lurus dgn intercept = 1/a dan slope
= b/a
Contoh hal. 759 adsorbent is covered only by UNIMOLECULAR LAYER of gas
molecules

Types II-V isotherms

MULTIMOLECULAR, the adsorption involves the formation of many molecular

layers on the surface (BET = BRUNAUER, EMMETT, TELLER)
A(g) + S AS
Langmuir isotherm is usually better for
A(g) + AS A2S
chemisorption and BET isotherm works
better for physisorption.
A(g) + A2S A3S and so on
P
v(P P)
o

1 + c-1
vmc
vmc

P
Po

Langmuir isotherm (red) and BET isotherm (green)

v = vol. gas teradsorp pd P, T tertentu

Po = tek. uap jenuh adsorbat pd T
vm = vol. gas teradsorp ketika permukaan tertutup
dgn unimolecular layer
c = konstanta

c e ( E1 EL ) / RT

E1 = panas adsorpsi layer pertama; EL = utk layer berikutnya (= panas liquefaction gas)
E1 > EL type II; E1 < EL type III
Type IV dan V, melibatkan selain adsorpsi multilayer juga kondensasi gas dlm pori dan
kapiler adsorben
E1 > EL type IV ; E1 < EL type V

Penentuan luas permukaan adsorben

Amount adsorbed

BET method, N2 adsorption

Type II

Pressure

B = vol. adsorbat yg diperlukan utk menghasilkan

gas monolayer pd permukaan adsorben (vm)
Berlaku:

P0 vB
RT0

NS

= area in 2; P0 = 1 atm; T0 = 273.2 K;

R = kont. Gas ideal; vB = vol. di titik B; N = bil. Avogadro
S = area yg digunakan oleh single gas molekul di permukaan

Gas yg digunakan biasanya N2 pada titik didihnya (-195.8oC)

Bentuk lain

V: molar volume of adsorbent gas

a: weight of sample solid
s: adsorption cross section (kemungkinan terjadinya interaksi solid dgn nitrogen)

Adsorption of solutes by solids

Secara prinsip sama dengan adsorpsi gas
T naik adsorpsi turun;
surface area solid naik adsorpsi naik
Contoh; activated carbon lebih adsorb non-electrolytes
drpd electrolytes
inorganic solids lebih adsorb electrolytes drpd nonelectrolytes
Biasanya berlaku
y = kC1/n
ln y = ln k + 1/n ln C
y = massa zat teradsorb/unit massa adsorben
C = konsentrasi kesetimbangan solut teradsorb
k,n = konstanta empiris

Application of adsorption
Silica is used for drying of process air (e.g. oxygen,

natural gas etc) and adsorption of higher (polar)

hydrocarbons from natural gas
Zeolites are applied in drying of process air (only traces),
CO2 removal from natural gas, CO removal from
reforming gas and air separation.
Non-polar zeolites are mostly used in non-polar organics
removal
Activated carbon is used for adsorption of organic
substances and non-polar adsorptives and it is also
usually used for waste gas (and waste water) treatment
- Ground water purification
- The de-chlorination of process water
- Water purification for swimming pools
- The polishing of treated effluent

Catalysis of gaseous reaction by solid surfaces

Banyak reaksi gas dikatalisis oleh solid

Reaksi tdk berlangsung pd fasa gas, tp pd permukaan katalis padatan
Steps in Catalytic Reaction

A
B
A

6
2

External
diffusion

Internal
diffusion

Catalytic
surface

1. Mass transfer (diffusion) of the

reactant(s) from the bulk fluid to
the external surface of the
catalyst
2. Diffusion of the reactant from
the pore mouth through the
catalyst pores to the immediate
vicinity of the internal catalytic
surface
3. Adsorption of reactant onto the
catalyst surface

4. Reaction on the surface of the catalyst (e.g., A B)

5. Desorption of the product
6. Diffusion of the products from the interior of the pellet to the pore mouth at the
external surface
7. Mass transfer of the products from the external pellet surface to the bulk fluid

Catalyst
Definition:
a substance that increases the rate without itself becoming permanently involved in
the reaction or consumed in the process
Properties:
activity (ability of the catalyst to convert reactant to product)
selectivity (ability of the catalyst to give the desired product)
lifetime (time in which a catalyst keeps a sufficient level of activity/selectivity)
Reaction:
dehydrogenation reaction (breaking C-H and forming C=C)
dehydrogenation and oxygen insertion (breaking C-H and forming C-O)
catalytic oxidation (to control the oxidation process), etc
Components:
active component (responsible for the principal chemical reaction)
support or diluents (as a physical spacer)
promoters (to support the stability of active component and/or diluents)
Deactivation:
Sintering, poisoning, coking
Process Technology:
laboratory catalytic reactor
reactor types: batch; continuous : tubular, stirred tank, recycle, raining-solid,
circulating

Determine the rate

Sebagian permukaan tertutup molekul, sebagian lagi tidak
Sebagaian yg tertutup tsb yg menghasilkan reaksi shg menentukan

laju
Yg dipertimbangkan bukan konsentrasi atau P reaktan pd fasa gas, tp
konsentrasinya di adsorben (proporsional dgn fraksi permukaan yg
tertutup reaktan = ), shg
bP

rate = k , dan dari pers. Langmuir

1 bP

Dgn b = konstanta dan P = tekanan gas yg kontak dgn adsorben

Jika gas teradsorp lemah, b = kecil, shg = bP (fraksi permukaan yg
tertutup proporsional dgn tekanan)
Jika gas teradsorp kuat, b or P besar shg bp >> 1, shg = bP/bP = 1
(semua permukaan tertutup oleh molekul gas)
Fraksi permukaan yg masih tersedia utk adsorpsi (1 - ) = 1/bP
Yaitu berbanding terbalik dgn tekanan gas teradsorp

Kinetik reaksi heterogen utk Kasus sederhana

(only single gas)

One reactant gas slightly adsorbed

A Products
rate = kA
A = fraksi permukaan yg tertutup A

dP

k ' bP kP
dt

dP
kdt
P

k = kb adalah konstanta laju reaksi

1 pi
Shg; k ln
t P

ORDER 1 REAKSI HETEROGEN

CONTOH:
Dekomposisi fosfin pd glass, porcelen, silika
Dekomposisi nitous oxide pada emas
Disosiasi HI pada Pt

Kinetik reaksi heterogen (cont)

One reactant gas strongly adsorbed

rate = kA

dP

k
dt

A = 1

laju reaksi konstant dan tdk bergantung tekanan

ORDER NOL REAKSI HETEROGEN

Pi P
t

CONTOH:
Dekomposisi ammonia pada tungsten
Dekomposisi ammonia pada Mo, Osmium
Disosiasi HI pada emas

Kinetik reaksi heterogen (cont)

One reactant gas moderately adsorbed

laju reaksi sebanding dgn fraksi yg tertutup

dP
kP
bP

k '

dt
1 bP 1 bP

disederhanakan

CONTOH:
Dekomposisi stibine pada antimony
Dekmposisi nitrous oxide pada indium oxide

dP

kP n
dt

Retarded reaction
Bbrp kasus katalis juga mengadsorp produk (selain reaktan)
Mungkin adsorp produk lebih kuat, shg makin banyak permukaan tertutup,
shg rate juga turun, akibatnya juga menghambat (retard) produksi produk
misal:

A B + C

A kurang diadsorp dibanding B

Jika PA, PB = tek. gas A dan B pd waktu t, (1 - B) fraksi yg tidak tertutup B,
maka laju reaksi sebanding dg fraksi permukaan yg terekspos A dan tek. A

dPA

k ' 1 B PA
dt

Krn B sangat kuat

teradsorp
(1 - B) = b/PB

dPA k ' b' PA

kPA

dt
PB
PB

Contoh: dekomposisi ammonia pd Pt di 1138 deg C

Jika B moderately adsorbed, maka:

dPA
kPA

dt 1 bPB

contoh: dekomposisi nitrous oxide pd Pt, Cd-oxide,

Cupric oxide, nickel oxide (retarding gas is O2)

Kinetik reaksi heterogen (cont)

Summary (rate-limiting or rate-controlling)

6

0. 4

0. 3 5

initial rate

0. 2 5

0. 2

0. 15

0. 1

0. 0 5

0. 0 9

2. 0 9

4. 0 9

6. 09

Adsorption-limited reaction

10 . 09

Surface-reaction-limited

3. 5

2. 5

1. 5

0. 5

0
0

8. 0 9

initial concentration of reactant

initial concentration of reactant

initial rate

initial rate

0. 3

initial concentration of reactant

Desorption-limited reaction

12 . 09

The order of heterogeneous reaction

Sangat bergantung dgn kuat lemahnya adsorpsi molekul reaktan
ataupun produk pada permukaan catalyst
Jika sangat lemah diadsorp, maka seperti reaksi tanpa melalui proses
adsorpsi, jika sangat kuat diadsorp, maka laju reaksi tdk bergantung
pada tekanan gas (order nol)

Pengaruh temperatur pd reaksi heterogen

Mengikuti persamaan Arrhenius

k 2 Ea 1 1

ln

k1
R T1 T2

d ln k
Ea

dT
RT 2

Ea = energi aktivasi, energi minimum yg harus dimiliki rekatan agar

reaksi dapat berlangsung
Energi ini tidak harus mrp energi yg diperlukan utk mengaktivkan
rekatan pada permukaan

The role of catalyst

PE

Ea
Ea

Hc

Adsorption exothermic
Ea

Hreact

Desorption endothermic

product

desorption

Reaction path

heat of chemisorption, Hc decrease the potential energy of activated complex,

means chemisorption supplies some of the energy required to form the activated
complex, energy that would otherwise only be available by raising the
temperature of the system

Catalytic deactivation
Deactivation of catalyst is a loss of catalytic activity. A clean catalyst surface
begins to deactivate as soon as it encounters reactant molecules. Activity
declines with process time at a rate that depends on prevailing conditions.
The most important reasons for deactivation

sintering

poisoning

coking
Temporary: aktivitas permukaan katalis turun/hilang utk
sementara sampai poison hilang dari permukaan
Permanent: biasanya melibatkan chemical interaction abtara
surface dan poison shg terbentuk permukaan baru yg inert

Self-poisoning occurs where the product is adsorbed too strongly to permit further
reaction

Experimental Laboratory Catalytic Reactors

Catalytic reactor configurations, (a) Batch reactor; and

continuous reactors: (b) continuous tubular; (c) continuous stirred tank;
(d) recycle; (e) raining-solid; (f) circulating-solids catalytic reactor-generator