A short notes of Adsorption

© All Rights Reserved

Просмотров: 13

A short notes of Adsorption

© All Rights Reserved

- Interaction of Hydrogen Chloride with Alumina
- Performance of a Dual_purpose Solar Continuous Adsorption System
- C4 Hydrate and Gas Dehydration
- Thesis Yudong Zhang
- 12
- bet-130102024849-phpapp02
- InTech-Dyeing in Computer Graphics
- Comparison of the kinetics of methanol adsorption in static and continuous flow conditions on activated.pdf
- 2015 Mangrove Paper
- Gascon d Conf
- Development of Adsorption Isotherm for Enrichment of Biogas (0th)
- 0000037
- Petelska y Figaszewski - 2003 - Acid–base equilibria at interface separating elect
- kltn newest Thủy.pdf
- isotermas.pdf
- 3 Adsorptive Removal of Basic Dye
- Summary of Physical and Analytical Chemistry 2
- JSEMAT_2014071713580889
- Adsorption Isotherms Kinetics and Column Operations for the Removal of Hazardous Dye Tartrazine From Aqueous Solutions Using Waste Materials Bottom As
- A new methodology of studying the dynamics of water sorption/desorption under real operating conditions of adsorption heat pumps: Experiment

Вы находитесь на странице: 1из 10

CHEMICAL ENGINEERING

of adsorption has been put forward which satisfactorily explains all systems. Fortunately

for the engineer, what is needed is an accurate representation of equilibrium, the theoretical

minutiae of which is not of concern. For this reason, some of the earliest theories of

adsorption are still the most useful, even though the assumptions on which they were

based were seen in later years to be not entirely valid. Most theories have been developed

for gassolid systems because the gaseous state is better understood than the liquid.

Statistical theories are being developed which should apply equally well to gassolid and

liquidsolid equilibria, though these are not yet at a stage when they can be applied easily

and confidently to the design of equipment.

The capacity of an adsorbent for a particular adsorbate involves the interaction of three

properties the concentration C of the adsorbate in the fluid phase, the concentration Cs

of the adsorbate in the solid phase and the temperature T of the system. If one of these

properties is kept constant, the other two may be graphed to represent the equilibrium.

The commonest practice is to keep the temperature constant and to plot C against Cs

to give an adsorption isotherm. When Cs is kept constant, the plot of C against T is

known as an adsorption isostere. In gassolid systems, it is often convenient to express

C as a pressure of adsorbate. Keeping the pressure constant and plotting Cs against T

gives adsorption isobars. The three plots are shown for the ammonia-charcoal system in

Figure 17.4 which is taken from the work of BRUNAUER(10) .

Most early theories were concerned with adsorption from the gas phase. Sufficient was

known about the behaviour of ideal gases for relatively simple mechanisms to be postulated, and for equations relating concentrations in gaseous and adsorbed phases to be

proposed. At very low concentrations the molecules adsorbed are widely spaced over the

adsorbent surface so that one molecule has no influence on another. For these limiting

conditions it is reasonable to assume that the concentration in one phase is proportional

to the concentration in the other, that is:

Cs = Ka C

(17.1)

This expression is analogous to Henrys Law for gasliquid systems even to the extent

that the proportionality constant obeys the vant Hoff equation and Ka = K0 eH /RT

where H is the enthalpy change per mole of adsorbate as it transfers from gaseous

to adsorbed phase. At constant temperature, equation 17.1 becomes the simplest form of

adsorption isotherm. Unfortunately, few systems are so simple.

At higher gas phase concentrations, the number of molecules absorbed soon increases to

the point at which further adsorption is hindered by lack of space on the adsorbent surface.

The rate of adsorption then becomes proportional to the empty surface available, as well

as to the fluid concentration. At the same time as molecules are adsorbing, other molecules

ADSORPTION

(a) Adsorption isotherm (b) Adsorption isobar (c) Adsorption isostere

981

982

CHEMICAL ENGINEERING

will be desorbing if they have sufficient activation energy. At a fixed temperature, the rate

of desorption will be proportional to the surface area occupied by adsorbate. When the

rates of adsorption and desorption are equal, a dynamic equilibrium exists. For adsorption

which is confined to a mono-molecular layer, the equilibrium may be written as:

k0 a0 C = k0 (1 a1 )C = k1 a1

or:

a1 =

where: a0

a1

B0

k0

k1

B0 C

1 + B0 C

(17.2)

is the fraction of surface occupied by a monolayer of adsorbed molecules,

= k0 /k1 ,

is the velocity constant for adsorption on to empty surface, and

is the velocity constant for desorption from a monolayer.

Equation 17.2 has been developed for adsorption from the gas phase. It is convenient to

also express it in terms of partial pressures, which gives:

B1 P

Cs

=

Csm

1 + B1 P

where: Cs

Csm

B1

P

(17.3)

is the concentration of the adsorbed phase when the monolayer is complete,

= B0 /RT ,and

is the partial pressure of adsorbate in the gas phase

.

Equations 17.2 and 17.3 have the form of the LANGMUIR(11) equation, developed in 1916,

which describes the adsorption of gases on to plane surfaces of glass, mica and platinum.

A number of assumptions is implicit in this development. As well as being limited to

monolayer adsorption, the Langmuir equation assumes that:

(a) these are no interactions between adjacent molecules on the surface.

(b) the energy of adsorption is the same all over the surface.

(c) molecules adsorb at fixed sites and do not migrate over the surface.

When B1 P 1, equation 17.3 reverts to the form of Henrys Law, as given in

equation 17.1. Equation 17.3 can be rewritten in linear form to give:

P

P

1

=

+

Cs

Csm

B1 Csm

(17.4)

so that a plot of P /Cs against P will be a straight line when applied to a system that

behaves in accordance with the Langmuir isotherm.

It has been shown experimentally, however, that many systems do not follow this

isotherm and efforts continue to find an improved equation.

ADSORPTION

983

In 1938, BRUNAUER, EMMETT and TELLER(12) and EMMETT and DE WITT(13) developed what

is now known as the BET theory. As in the case in Langmuirs isotherm, the theory is

based on the concept of an adsorbed molecule which is not free to move over the surface,

and which exerts no lateral forces on adjacent molecules of adsorbate. The BET theory

does, however, allow different numbers of adsorbed layers to build up on different parts

of the surface, although it assumes that the net amount of surface which is empty or

which is associated with a monolayer, bilayer and so on is constant for any particular

equilibrium condition. Monolayers are created by adsorption on to empty surface and by

desorption from bilayers. Monolayers are lost both through desorption and through the

adsorption of additional layers. The rate of adsorption is proportional to the frequency

with which molecules strike the surface and the area of that surface. From the kinetic

theory of gases, the frequency is proportional to the pressure of the molecules and hence:

The rate of adsorption on to empty surface = k0 a0 P , and

the rate of desorption from a monolayer = k1 a1

Desorption is an activated process. If E1 is the excess energy required for one mole in the

monolayer to overcome the surface forces, the proportion of molecules possessing such

energy is eE1 /RT . Hence the rate of desorption from a monolayer may be written as:

A1 eE1 /RT a1

where A1 is the frequency factor for monolayer desorption.

The dynamic equilibrium of the monolayer is given by:

k0 a0 P + A2 eE2 /RT a2 = k1 a1 P + A1 eE1 /RT a1

(17.5)

where A2 is the frequency factor for description from a bilayer, thus creating a monolayer.

Applying similar arguments to the empty surface, then:

k0 a0 P = A1 eE1 /RT a1

(17.6)

k1 a1 P = A2 eE2 /RT a2

and:

a1 =

k0 E1 /RT

e

a0 P = 0 a0

A1

(17.7)

a2 =

k1 E2 /RT

e

a1 P = a1

A2

(17.8)

The BET theory assumes that the reasoning used for one or two layers of molecules may

be extended to n layers. It argues that energies of activation after the first layer are all

equal to the latent heat of condensation, so that:

E2 = E3 = E4 = = En = M

984

CHEMICAL ENGINEERING

Hence it may be assumed that is constant for layers after the first and:

ai = i1 a1 = B2 i a0

where B2 = 0 /, and ai is the fraction of the surface area containing i layers of adsorbate.

Since a0 , a1 , . . . are fractional areas, their summation over n layers will be unity and:

1 = a0 +

n

ai

i=1

= a0 +

n

B2 i a0

(17.9)

i=1

The total volume of adsorbate associated with unit area of surface is given by:

vs = vs1

n

iai = vs1

i=1

n

iB2 i a0

(17.10)

i=1

Since vs1 does not change with n, a geometrically plane surface is implied. Strictly,

equation 17.10 is not applicable to highly convex or concave surfaces. Equations 17.9

and 17.10 may be combined to give:

n

vs

=

vs1

iB2 i a0

i=1

a0 +

n

(17.11)

i

B2 a0

i=1

n

d i

d

1 n

= B2 a0

B2 a0

d i=1

d

1

and the denominator as:

1 n

a0 1 + B2

1

B2 [1 (n + 1) n + n n+1 ]

vs

=

vs1

1 [1 + (B2 1) B2 n+1 ]

(17.12)

On a flat unrestricted surface, there is no theoretical limit to the number of layers that

can build up. When n = , equation 17.12 becomes:

B2

vs

=

1

vs

(1 )(1 + B2 )

(17.13)

ADSORPTION

985

When the pressure of the adsorbate in the gas phase is increased to the saturated vapour

pressure, condensation occurs on the solid surface and vs /vs1 approaches infinity. In

equation 17.13, this condition corresponds to putting = 1. It may be noted that putting

= 1/(1 B2 ) is not helpful.

Hence from equation 17.8:

k1

1 = eM /RT P 0

A2

where: M is the molar latent heat and

P 0 is the saturated vapour pressure.

Hence, from equation 17.8, = P /P 0 .

Equation 17.12 may be rewritten for unit mass of adsorbent instead of unit surface.

This is known as the limited form of the BET equation which is:

Vs

P

[1 (n + 1)(P /P 0 )n + n(P /P 0 )n+1 ]

=

B

2 0

Vs1

P (1 P /P 0 )[1 + (B2 1)(P /P 0 ) B2 (P /P 0 )n+1 ]

(17.14)

where Vs1 is the volume of adsorbate contained in a monolayer spread over the surface

area present in unit mass of adsorbent.

When n = 1, adsorption is confined to a monolayer and equation 17.14 reduces to the

Langmuir equation.

When n = , (P /P 0 )n approaches zero and equation 17.13 may be rearranged in a

convenient linear form to give:

1

P /P0

B2 1 P

= 1 + 1

(17.15)

V (1 P /P0 )

V B2

V B2 P 0

where V and V 1 are the equivalent gas phase volumes of Vs and Vs1 .

If a plot of the left-hand term against P /P 0 is linear, the experimental data may be

said to fit the infinite form of the BET equation. From the slope and the intercept, V 1

and B2 may be calculated.

The advantage of equation 17.14 is that it may be fitted to all known shapes of

adsorption isotherm. In 1938, a classification of isotherms was proposed which consisted

of the five shapes shown in Figure 17.5 which is taken from the work of BRUNAUER

et al.(14) . Only gassolid systems provide examples of all the shapes, and not all occur

frequently. It is not possible to predict the shape of an isotherm for a given system,

although it has been observed that some shapes are often associated with a particular

adsorbent or adsorbate properties. Charcoal, with pores just a few molecules in diameter,

almost always gives a Type I isotherm. A non-porous solid is likely to give a Type II

isotherm. If the cohesive forces between adsorbate molecules are greater than the adhesive

forces between adsorbate and adsorbent, a Type V isotherm is likely to be obtained for a

porous adsorbent and a Type III isotherm for a non-porous one.

In some systems, three stages of adsorption may be discerned. In the activated aluminaair-water vapour system at normal temperature, the isotherm is found to be of Type IV.

This consists of two regions which are concave to the gas concentration axis separated

by a region which is convex. The concave region that occurs at low gas concentrations

is usually associated with the formation of a single layer of adsorbate molecules over the

986

Figure 17.5.

CHEMICAL ENGINEERING

Classification of isotherms into five types of BRUNAEUR, DEMING, DEMING and TELLER(14)

surface. The convex portion corresponds to the build-up of additional layers, whilst the

other concave region is the result of condensation of adsorbate in the pores so called

capillary condensation as discussed earlier in this Section.

At low gas concentrations, whilst the monolayer is still incomplete, the absorbed

molecules are relatively immobile. In the multilayer region, the adsorbed molecules behave

more like a liquid film. The amount of capillary condensation that occurs depends on the

pore sizes and their distribution, as well as on the concentration in the gas phase.

When n = 1, equation 17.14 represents a Type I isotherm.

When n = , equation 17.14 represents a Type II, and the rarer Type III isotherm by

choosing a suitable value for B2 . As B2 is increased, the point of inflexion or knee

of Type II becomes more prominent. This corresponds to an increasing tendency for the

monolayer to become complete before a second layer starts. In the extreme case of an

adsorbent whose surface is very uniform from an energy point of view, the adsorbate

builds up in well-defined layers. This gives rise to a stepped isotherm, in which each

step corresponds to another layer. When B2 is less than 2, there is no point of inflexion

and Type III isotherms are obtained. The condition 1 > B2 > 0 often corresponds to a

tendency for molecules to adsorb in clusters rather than in complete layers.

The success of the BET equation in representing experimental data should not be

regarded as a measure of the accuracy of the model on which it is based. Its capability

of modelling the mobile multilayers of a Type IV isotherm is entirely fortuitous because,

in the derivation of the equation, it is assumed that adsorbed molecules are immobile.

Example 17.1

Spherical particles of 15 nm diameter and density 2290 kg/m3 are pressed together to form a pellet.

The following equilibrium data were obtained for the sorption of nitrogen at 77 K. Obtain estimates

987

ADSORPTION

of the surface area of the pellet from the adsorption isotherm and compare the estimates with the

geometric surface. The density of liquid nitrogen at 77 K is 808 kg/m3 .

P /P 0

m3 liq N2 106 /kg solid

0.1

66.7

0.2

75.2

0.3

83.9

0.4

93.4

0.5

108.4

0.6

130.0

0.7

150.2

0.8

202.0

0.9

348.0

Use the following data:

density of liquid nitrogen = 808 kg/m3

area occupied by one adsorbed molecule of nitrogen = 0.162 nm2

Avogadro Number = 6.02 1026 molecules/kmol

Solution

For 1 m3 of pellet with a voidage , then:

Number of particles = (1 )/(/6)(15 109 )3

Surface area per unit volume = (1 )(15 109 )2 /(/6)(15 109 )3

= 6(1 )/(15 109 ) m2 /m3

1 m3 of pellet contains 2290 (1 ) kg solid and hence:

specific surface = 6(1 )/[(15 109 (1 )2290]

= 1.747 105 m2 /kg

(a) Using the BET isotherm

(P /P 0 )/[V (1 P /P 0 )] = 1/V B + (B 1)(P /P 0 )/V B

(equation 17.15)

From the adsorption data given:

(P /P 0 )

V (m3 liquid N2 /kg solid 106 )

((P /P 0 )/V ) 106

(P /P 0 )/[V (1 P /P 0 )]

0.1

66.7

1500

1666

0.2

75.2

2660

3333

0.3

83.9

3576

5109

0.4

93.4

4283

7138

0.5

108.4

4613

9226

intercept, 1/V B = 300, and slope, (B 1)/V B = 13,902

0.6

130.0

4615

11538

988

CHEMICAL ENGINEERING

12000

10000

(BET isotherm)

V (1 P /P 0)

P /P 0

or

P /P 0

8000

6000

(Langmuir isotherm)

4000

2000

0

0.2

0.4

0.6

0.8

P /P 0

Figure 17.6.

from which:

B = (13,902/300) + 1 = 47.34

and:

V = 1/(300 47.34) = 70.4 106 m3 /kg.

The total surface area = [(70.4 106 808 6.2 1026 0.162 1018 )]/28

= 2.040 105 m2 /kg .

ADSORPTION

989

Assuming this applies at low concentrations then, expressing pressure as the ratio P /P 0 , and the

amount adsorbed as a volume of liquid adsorbate, equation 17.4 becomes:

(P /P 0 )/V = (P /P 0 )/V + 1/(B2 V )

Thus, a plot of (P /P 0 )/V against (P /P 0 ) will have a slope of (1/V ).

Thus, from Figure 17.6:

1/V = 13,902

V = 71.9 106 m3 /kg

and:

It may be noted that areas calculated from the isotherm are some 20 per cent greater than the

geometric surface, probably due to the existence of some internal surface within the particles.

An entirely different approach to equilibrium adsorption is to assume that adsorbed layers

behave like liquid films, and that the adsorbed molecules are free to move over the surface.

It is then possible to apply the equations of classical thermodynamics. The properties which

determine the free energy of the film are pressure and temperature, the number of molecules

contained and the area available to the film. The Gibbs free energy G may be written as:

G = F (P , T , ns , As )

(17.16)

Hence:

G

G

G

G

dG =

; dP +

; dT +

; dns +

dAs

P T ,ns ,As

T P ,ns ,As

ns T ,P ,As

As T ,P ,ns

(17.17)

At constant temperature and pressure this becomes:

G

G

dG =

dns +

dAs

(17.18)

ns

As

= s dns % dAs

(17.19)

where: s is the free energy per mole or chemical potential of the film, and

% is defined as a two-dimensional or spreading pressure.

The total Gibbs free energy may be written as:

G = s ns %As

so that:

dG = s dns + ns ds % dAs As d%

ns

d% =

ds

As

(17.20)

(17.21)

- Interaction of Hydrogen Chloride with AluminaЗагружено:iMiklae
- Performance of a Dual_purpose Solar Continuous Adsorption SystemЗагружено:myusof_sulaiman
- C4 Hydrate and Gas DehydrationЗагружено:Faidhi Fahmi
- Thesis Yudong ZhangЗагружено:Pham Thi Thu Hong
- 12Загружено:Alexis Hernandez
- bet-130102024849-phpapp02Загружено:Lương Ngọc Thái
- InTech-Dyeing in Computer GraphicsЗагружено:Anne Calyx
- Comparison of the kinetics of methanol adsorption in static and continuous flow conditions on activated.pdfЗагружено:ali105
- 2015 Mangrove PaperЗагружено:Dr. Thadikamala Sathish
- Gascon d ConfЗагружено:mostafa_1000
- Development of Adsorption Isotherm for Enrichment of Biogas (0th)Загружено:JaanVar
- 0000037Загружено:Penny Gildo
- Petelska y Figaszewski - 2003 - Acid–base equilibria at interface separating electЗагружено:NadieningunoNadieNad
- kltn newest Thủy.pdfЗагружено:Trương Tuấn Vũ
- isotermas.pdfЗагружено:Andres Felipe Perez
- 3 Adsorptive Removal of Basic DyeЗагружено:AprilianhaNur
- Summary of Physical and Analytical Chemistry 2Загружено:Nur Amanina
- JSEMAT_2014071713580889Загружено:Gladys Gabriela Quispe Ramos
- Adsorption Isotherms Kinetics and Column Operations for the Removal of Hazardous Dye Tartrazine From Aqueous Solutions Using Waste Materials Bottom AsЗагружено:LuanaMirtes
- A new methodology of studying the dynamics of water sorption/desorption under real operating conditions of adsorption heat pumps: ExperimentЗагружено:Ngọc Vi Cao
- Caracterizaçao e uso das sementes de Noni para remoçao de Cr VI de soluçoes aquosas.pdfЗагружено:Flávio Freitas
- Adsorption - Article _ Bry-AirЗагружено:oooZ
- adsorption-150713102637-lva1-app6891Загружено:cgajendran_56098156
- Journal of Environmental Chemical Engineering Volume Issue 2017 [Doi 10.1016_j.jece.2017.11.024] Modwi, A.; Abbo, M.a.; Hassan, E.a.; Al-Duaij, O.K.; Houas, Amma -- Adsorption Kinetic and PhotocatalЗагружено:nezarahayu
- Facile fabrication and characterizations of nanostructured Fe2O3-TiO2 composite from Ilmenite oreЗагружено:Ijaems Journal
- VideoЗагружено:devil cry
- eutrofizacionЗагружено:Monica Choque
- Experimental Investigation of Solar Adsorption Refrigeration SystemЗагружено:Nelson Tacy
- Adsorbent selection.pdfЗагружено:Jian Liu

- Poly vinyl chlorideЗагружено:Vigneshwaran Aiyappan
- Conveyor Cleaning ScheduleЗагружено:Vigneshwaran Aiyappan
- Raw Water SpecsЗагружено:Vigneshwaran Aiyappan
- Pet Bottle FaultsЗагружено:Piyalarp Ludeelerd
- PET co2 variationЗагружено:Vigneshwaran Aiyappan
- modelling for Variable volume systemsЗагружено:Vigneshwaran Aiyappan
- Alicyclobacillus - WikipediaЗагружено:Vigneshwaran Aiyappan
- Analytical Methods in Food IndustryЗагружено:YuMdza
- Modelling & Simulation of Isothermal Batch ReactorЗагружено:Vigneshwaran Aiyappan
- Graph for Xa vs TЗагружено:Vigneshwaran Aiyappan
- Hazards in Transport of Dangerous ChemicalsЗагружено:Vigneshwaran Aiyappan
- M.tech Chemical Engg SyllabusЗагружено:Vigneshwaran Aiyappan
- Bread RollЗагружено:Vigneshwaran Aiyappan
- PHY 121Загружено:Vigneshwaran Aiyappan
- Rice MillingЗагружено:Sabyasachi Sam
- Book Review07Загружено:Vigneshwaran Aiyappan
- UnitЗагружено:Vigneshwaran Aiyappan
- chy121Загружено:Vigneshwaran Aiyappan
- DIFFRACTIONЗагружено:Vigneshwaran Aiyappan

- Removal of cadmium and nickel from wastewater using bagasse fly ash—a sugar industry waste.pdfЗагружено:olie
- SPE-140555-MSЗагружено:Hichem Fakhfekh
- Etd.aau.Edu.et Dspace Bitstream 123456789 1815 1 Admasu AdamuЗагружено:ezra
- Hexavalent Chromium Removal From Aqueous Medium by Activated CarbonЗагружено:Endah Ayuningtyas
- aipmt-1Загружено:ANUBHAVAS
- Flyash Water ManagementЗагружено:kashifwarsi
- Adsorption Isotherms[1].docxЗагружено:kumaravel_M
- AACanalysis&ConclusionЗагружено:Elsie Xiao
- FINAL LAB Report(Experiment 2)Загружено:Jonelou Cusipag
- 1-s2.0-S2213343713002662-main[1]ok teoriaЗагружено:Diego Galicia
- Sircar Ind Eng Chem Res 2007Загружено:papers2009
- Adsorption of Dichloromethane on Activated CarbonЗагружено:crisfaq
- ChBE 51 AdsorptionЗагружено:Joshua Zannoni
- Cit Iceee Peroceedings 2016Загружено:rte ghtr
- Adsorption of MercuryЗагружено:Betty Dguez
- Chemistry Question Bank 2017 NewЗагружено:அன்புடன் அஸ்வின்
- 1-s2.0-S0376738812003717-mainЗагружено:Fadhilatul Adha
- Adsorption of n-Butanol from Dilute Aqueous Solution with Grafted CalixarenesЗагружено:Matt Miles
- A performance of hybrid biosorbent ‘M-Bios’ of Pb(II) and Cu(II) in aqueous solutions.Загружено:IJSRP ORG
- A2Загружено:sdffds
- 1-s2.0-S0010938X12006269-mainЗагружено:Vijetha Sv
- Cobalt Nickel and Copper Recovery With Resin-In-pulpЗагружено:Nancy Quispe
- Hajati (2014) Competitive Adsorption of Direct Yellow 12 and Reactive Orange 12 on ZnS-Mn Nanoparticles Loaded on Activated Carbon as Novel AdsorbentЗагружено:SunilParjapati
- Unit11 Surface Chemistry QnsЗагружено:Govind Manglani
- Ads or PtionЗагружено:vzimak2355
- GATE 2014 Question Paper & Answers - CYЗагружено:aglasem
- Adsorption and Thermochemical Data of Divalent Cations Onto Silica Gel Surface Modified With Humic Acid at Solid Liquid InterfaceЗагружено:Abdullah Mofarrah
- Experiment 5 Chapter 1 and ReferencesЗагружено:Arima Kousei
- PSA3Загружено:biophr34k
- On a Theory of the van der Waals Adsorption of Gases.pdfЗагружено:JefersonCorreia