Kesetimbangan Adsorbsi

Single gases and vapors

In many respect the equilibrium adsorption characteristic of a gas or vapor upon
a solid resemble the equilibrium solubility of a gas in a liquid. Figure 11.1 shows
several equilibrium adsorption isotherms for a particular activated carbon as
adsorbent, where the consentration of adsorbed Gas (the adsorbate) on the solid
is ploted against the equlibrium partial pressure P* of the vapor or gas at
constant temperature.
As ageneral rule, vapors and gases are more readily adsorbed the higher ttheir
moleculer and the lower their critical temperature, although chemical differences
such as the extent of unsaturation in the molecule also influance the extent of
adsorption. The so-called permanent gases are usually adsorbed only to a
relatively small extent, as the methane isotherm of fig. 11.1 indicates.
There are three commonly used mathematical expression to discribe vapor
adsorption equilibria: the languir .......
Adsorption Hysteresis
Ocasionally, however different equilibria result at least over a part of an
isotherm, depending upon whethere the vapor is adsorbed or desorbed, and this
gives rise to the hysteresis phenomenom indicated in fig. 11.4. this may be the
result of the shape of the openings to the capillaries and pores of the solid or of
the complex phenomena of wetting of the solid by the adsorbate. In any case,
when hysteresis is observed, the desorption equilibrium preassure is always
lower than that obtained by adsorption.
Heat of adsorption
The diferntial heat of adsorption (-H) is defined as the heat liberated at constant
temperature when unit quantity of vapor is adsorbed upon a large quantity of
solid already containing adsorbate. The integral heat of adsorption at any
consentration X of adsorbate upon the solid is defined as the enthalpy of the
adsorbate adsorbent combination the sum the enthalpies of unit weight of
pure solid adsorbent and sufficient pure adsorbed substance (before adsorption)
to provide the required consentration X, all at the same temperature. Thus, the
slope of an isostere is (rumus 11.1)
Where H energy per mass of vapor adsorbed, is refered to the pure vapor and
lamda is the latent heat of vaporization of the reference substance at the same
temperature, energy per mass. M and MR are the molecular weight of the vapor
and reference substance, respectively. If H is computed at constant temperature
for each isostere, the integral heat of adsorption at this temperature can be
computed from the relation (rumus 11.2)
deltaH, energy per mass of adsorbate free solid, is refered to the pure vapor
and X is the adsorbate consentartion, mass adsorbate / mass solid. The integral

heat of adsorption refered to solid and the adsorbed substance in the liquid state
is (rumus), energy per mass solid.
Vapor and gas mixture
One component adsorbed
In the case of many mixtures, particularly vapor gas mixture only one
component is appreciably adsorbed. In such instances the adsorption of the
vapor will be substantially unaffectived by the presences of the poorly adsorbed
gas , and the adsorption isotherm for the pure vapor will be aplicable provided
the equilibrium presure is taken as the partial pressure of the vapor in the vapor
gas mixture.
Binary gas or vapor mixture, both components apricable absorbed
When both componnets of a binary gas or vapor mixture are seperately adsorbed
to roughly the same extent, the amount of either one adsorbed from the mixture
will be affected by the presence of the other. However adsorption is greatly
influenced by both temperature and pressure under ordinary circumtances.
Equilibrium diagrams are cosequenly best plotted ad constant temperature and
constant total pressure, and they are therefor simultanously isotherms and
isobars.
Effect of change of pressure or temperature
In several cases investegated over any appricable range the relative adsorptivity
of parafin hydrocarbons on carbon decrease at increased pressure, as shown is
the lower part of this figure, just at it does in distilation. Increasing the
temperature at constant pressure will decrease the amount adsorbed from a
mixture and will influence the relative adsorptivity as well but in a manner for
wich no generalizations can now be made.
Liquid
When an adsorbent solid is immersed solid in pure liquid, the evolution of heat,
known as the heat of wetting is evidence that adsorption of the liquid does occur.
But immertion does not provide an effective method of measuring the extent of
adsorption.
Adsorption of solute from dilute solution
The apperent adsorption of solute, neglecting any volume change in the solution,
is then V(co c) mass solute adsorbed / mass adsorbent. Isotherms of all the
indicated forms have been observed, for example, when a given solute is
adsorbed on the same adsorbent, but from differnt solvents. The extent of
adsorption of a given solute partically always decreases at increased
temperature and usually is greater the smaller the solubility in the solvent. It is
usually reversible, so that the same isotherm result whether solute is disolved or
adsorbed.

The Freundlich Equation

Over a small consentration range, and particularly for dilute solution, the
adsorption isotherm can frequently be descibed by an empirical expression
usually atributed to Freundlich, (rumus 11.3)
Where V(co c) is the apparent adsorption per unit mass of adsorbent and K and
n are constants. Other consentration units are frequently used also, and while
they will result in different values of k, for the dilute solution for which the
equations is applicable the value of n will be unaffected. The form of the
equation indicates that ploting the equilibrium solute consentration as ordinate
against adsorbate content of the solid as abcissa on logaritmic coordinates will
provide a straight line of slope n and intercept k.
Adsorption from concentarted solutions
At increasing solute concentration, the extent of solute adsorption may actually
continue to increase; yet the cruve showing apparent solute adsorption
necessarilly returns to point E, since in a liquid consisting of pure solute alone
there will be no consentration change on addition od adsorbent.
In cases where both solvent and solute re adsorbed to nearly the same extent,
the S shaped curves of type B are produced. In the range of consentrations
from C to D, solute is more strongly adsorbed than solvent. At point D, both are
equally well adsorbed, and the apperent adsorption falls to zero. In the range of
consentrations from D to E, solvent is more strongly adsorbed.

Pengaruh perubahan tekanan atau temperatur

Dalam beberapa kondisi, pada setiap rentang nilai [24, 62] pada adsorpsivitas relatif untuk
hidrokarbon parafin pada penurunan karbon pada saat tekanan meningkat, seperti yang
ditunjukkan pada gambar, hanya terjadi pada distilasi. Peningkatan suhu pada tekanan
konstan akan mengurangi jumlah terserap dari campuran dan akan mempengaruhi
adsorpsivitas relatif juga tapi dengan cara tidak ada generalisasi yang dibuat.
Liquid
Ketika adsorben solid dicelupkan kedalam liquid murni, evolusi panas, yang dikenal sebagai
panas pembasahan adalah bukti bahwa adsorpsi liquid terjadi. Tapi pencelupan tidak
membuktikan metode yang efektif untuk mengukur tingkat adsorpsi.
Adsorpsi zat terlarut dari larutan encer
Adsorpsi nyata zat terlarut, mengabaikan setiap perubahan volume dalam larutan, lalu V (co c) massa zat terlarut yang terserap / massa adsorben. Proses Isotermal dari semua bentuk
yang ditunjukkan telah diamati, misalnya, ketika zat terlarut teradsorpsi pada adsorben yang
sama, tetapi dengan pelarut yang berbeda. Tingkat penyerapan zat terlarut yang diberikan
pada praktiknya selalu menurun pada saat suhu meningkat dan biasanya lebih besar yang
kecil kelarutannya dalam pelarut. Hal ini biasanya terjadi bolak-balik, sehingga hasil
isotermal yang sama apakah zat terlarut tadi dilepaskan atau teradsorpsi.
Persamaan Freundlich
Selama rentang konsentrasi kecil, dan terutama untuk larutan encer, adsorpsi secara isotermal
sering dapat dideskripsikan oleh persamaan empiris yang biasanya berasal dari persamaan
Freundlich, (rumus 11.3)
Dimana V (co - c) adalah adsorpsi nyata per satuan massa dari adsorben dan K dan n adalah
konstanta. Satuan konsentrasi lainnya juga sering digunakan, dan sementara mereka akan
menghasilkan nilai k yang berbeda, untuk larutan encer yang persamaan berlaku nilai n akan
terpengaruh. Bentuk persamaan menunjukkan bahwa ploting dengan konsentrasi
kesetimbangan zat terlarut sebagai ordinat terhadap kandungan adsorbat solid sebagai absis
pada koordinat logaritmik akan memberikan garis lurus slope n dan intersep k.
Adsorpsi dari Larutan yang terkonsentrasi
Untuk meningkatkan konsentrasi zat terlarut, tingkat adsorpsi zat terlarut sebenarnya dapat
terus meningkat, namun kurva yang menunjukkan zat terlarut yang teradsorpsi dikembali ke

titik E, karena dalam cairan yang terdiri dari zat terlarut murni saja tidak akan ada perubahan
konsentrasi pada saat penambahan adsorben. Dalam kasus di mana kedua pelarut dan zat
terlarut teradsorpsi ke hampir pada tingkat yang sama, kurva berbentuk S tipe b yang
dihasilkan. Dalam rentang konsentrasi dari C ke D, zat terlarut yang lebih kuat teradsorpsi
dibandingkan pelarut. Pada titik D, keduanya sama-sama teradsorpsi, dan adsorpsi yang
sebenarnya jatuh ke titil nol. Dalam rentang Pada konsentrasi D ke E, pelarut lebih kuat
teradsorpsi.