Effect of temperature on sorption equilibrium and sorption kinetics of organic micropollutants - a review

PergBlllOIl

Chenwsphcre. Vol. 32, No. 4, pp. bW-b26, 1996 Copyright 8 1996 Ekvier Science Ltd Printed in Great Britain. All rights reserved 004%6535/96 $15.00+0.00

?45-6535(95)00345-2

Effect of temperature sorption

on sorption

equilibrium

kinetics of organic micropollutants

RIZA,

Th.E.M.

ten Hulscher’

P.O.Box

17, 8200

(Received in Gemany

and

- a review

and G. Cornelissen

AA Lelystad,

The Netherlands

I June 1995; accepted 30 October 1995)

Abstract

Temperature environmental sorption slow

is an important

processes.

equilibrium

process

In the present

and sorption

can

be

decreases

with

increasing

temperature

on the rates of fast adsorption In Literature structures

the present on

with increasing

the

paper,

effect

is summarized.

reported

values

diffusion

of organic

and desorption

of

the slow

Activation

for the activation micropollutants

causes nonequilibrium

sorption

on

the

energies

energy

step

of temperature

equilibrium

Calculated

of on

A fast and a

equilibrium

equilibrium

sorption

sorption

with

were also found. activation

of no influence

is assumed

diffusion

energies

of temperature

to be a diffusion

of organic

for diffusion

of slow

through

examples

rates

were reported.

desorption

temperature

of increasing

temperature.

and

is presented.

compounds,

on sorption

Also,

equilibria

the influence

most

examples

kJ/mol.

of

the

micropollutants For

of temperature

were in the range of lo-50

influence

a review

sorption. Some

and of no effect increased

can

for organic

for

temperature.

The rate of fast desorption

that

paper,

kinetics

distinguished

increasing

for desorption

parameter

compounds

in polymers

desorption

average

are comparable

organic polymers.

process.

in polymeric

60 kJ/mol.

to those

This is an indication

found

The for

that diffusion

effects.

Introduction

The sorption

of hydrophobic

organic

and terrestrial

environment.

It affects

the availability

for uptake,

degradation,

compounds

the transport

is an important

of these

and volatilization.

609

process

compounds

Many

factors

in both the aquatic

in aquatic

systems

can influence

and

the extent

610 and rate of the sorption the organic term

carbon

“sorption”

“solute”

content is used

influence

of the

existence

of

1979;

Steinberg

sorption.

The

diffusion

(Brusseau

combination

which

most

and

kinetics

paper

and

and

equilibrium The

the

sorption

summarizes of

the properties

experimental and activation

of the

The data dependence

of the

used

coated

silica was

matter

Rao, diffusion

structure. Therefore,

1989)

or a

along the

diameters.

Intra-

matter

matrix,

The latter

process

attention

is given

to

summarized

and

effect

on

interpreted

in

variation sorption

is

terms

of

kinetics.

variation

at room temperature

e.g.:

of temperature

process the type

on sorption (20-25OC) could

also

equilibrium

and

to environmental be used to reveal

of sorptive

interactions

and

matter.

for the

(Matzner

If necessary,

present

equilibrium

and materials

silica

intra-organic

organic

temperature

of sorption

involved,

on

for slow

slow

the

et

of temperature

to solute

through

the

on the sorption

process

processes:

Karickhoff

is responsible

and

on the effect

of temperature

of temperature

effect

equilibrium

materials.

of

are

1989;

and

comparable

literature

energies

(delayed

Brusseau

materials.

theory

obtained

the

and interpretation

of the

porous

values

two

polymer

data

influence

to translate

polymer

The

available

of the organic

Data selection

sorption.

to soils and sediments,

process

macromolecular

the available

the

on the

1991 b;

in and diffusion

through

describes

on sorption

diffusion

diameters

through

enthalpies

information

Rao,

and heterogeneous

term

Pignatello,

rate-limiting

can involve

with

on diffusion

The influence

(thermodynamic)

and

penetration

of diffusion

understanding

temperatures.

in pores

flexible

kinetics

is important

sediments

diffusion

the process

equilibrium

explained

Micropore

of temperature

The present on

two.

1989;

micropore

the

The

fractions

literature

paper,

process.

desorbing

any

pH, salts),

at equilibrium.

chemicals

and Rao,

are

Brusseau

involves

and

is hardly

explanations

hindrance

of organic

(humics,

In the present

of temperature

It is not clear which

1991a;

of a rather

may resemble the influence

There

phase

processes

in the sorption

influence

(Brusseau

et al.,

diffusion

consists

1987).

processes.

steric

matter

the

sorbing

reported

surface

involved

with

slowly

plausible

of these

walls

organic

et al,

and

For the sorption

and been

of sorptive

partitioning

dealing

of the water

or soil, and the temperature.

the compound

fast

has often

the kinetics

for

equilibrium.

both

achievement)

pore

both

literature

on sorption

i.e. the composition

of the sediment

is used to describe

Most

al.,

to sediments

and

study the

kinetics

closely

resembling

and Bales,

1994)

(Szecsody

and Bales,

calculations

include

the ones

of the

sorption

soil or sediment.

was

not taken

which

into

reported

of organic

For example, account,

on the temperature compounds

a study

whereas

to soils,

carried

a study

out on

on phenyl

1991).

of sorption

enthalpies

or activation

energies

were

carried

out by

611 the present these

authors.

calculations

The legends have

been

underneath

carried

out.

reported

values,

giving

different

solutes,

these were averaged

Temperature

The partition usually

reference

dependence

short term

coefficient

solubility

of the compounds

nonpolar

The variation

partitioning:

thermodynamic

quantities

when the free energy

AG”

When

chemicals

are overall

a reference

carbon.

studied

Gibbs give

The

(Hassett

organics

reports

ways

averages

of

more values

for

of the overall average

(Hassett

assumption

linear

isotherms

value.

insight

in the

exchange

Karickhoff

up to

and water.

60

to

80%

K, is

isotherm

has

1979).

The

et al.,

of the

about the thermodynamic

(AH"),and entropy

(AGO), enthalpy sorption

sediment

by a linear

water

1989).

gives information

energy

described

of a linear sorption

1989;

and Banwart,

free

is often

ratio between

and Banwart,

shows

of the sorptive

in sediment

the concentration

of K, with temperature

of equilibrium

AG” is related to

of organic

researchers

of many

cases and in what

in the tables

before use in the calculation

per unit of organic

sorption

values

in which

of sorption equilibrium

sorption

by several

Average

equal weight.

K,, which describes

expressed

been tested

each

the tables indicate

process

is negative

involved.

(Hassett

quantities (AS”).

A net sorption

and Banwart,

These occurs

1989).

AH" and AS” through

= AH"

in which:

- TM"

AG” = change

(1)

in Gibbs free energy

(kJ- mol.‘)

AH“ = change in enthalpy (kJ. mol.‘1 AS” = change

At equilibrium,

K, (expressed

in entropy

in mol fraction

(kJ. mol“-K.‘)

units)

is related

to the standard

free energy

change

by:

AG”

= -RT/n

in which:

K,”

(2)

R

= gas constant

T

= absolute

(8.31441

temperature

K,” = mol fraction

combination

change

. K-‘. mol.‘)

(K)

based partition

(mol water/mol

The enthalpy

. 1O-3 kJ

organic

coefficient

carbon)

(AH")can thus be obtained from the variation of K, with temperature,

of equations

1 and 2 (equation

3).

AH" is independent

of the units of K,.

i.e. by

612

d lnKJd(l/T)

= -AH”/R

Two types of driving forces that affect solvent

the relative

affinity

and entropy-related

ment/water

system

Examples induced increasing

solute

related

dipole

molecular

the

dissolved

1989).

The entropy-related

nature

forces

of a covalent disorder

force

are:

bond).

and

in the sediment (mixing

of itself, the former

phase

der Waals

disorder

As the undisturbed

force in the

and

water

Banwart,

in the organic

organic

force is much stronger

with

interactions

of the highly structured

is the increasing

(weak

increase

dipole-dipole

Hassett

entropy).

forces

that

1972;

entropy-related

of the sedi-

The entropy-related

Thompson,

to the

1989).

matrix

ligand exchange,

chemical

(Hamaker

or disorder

London-van and organic

forces

of the chemical

and Banwart,

due to the disappearance

chemical

enthalpy-related

in randomness

solute

bonds,

process:

vs. the affinity

Hassett

between

hydrogen

matrix that results from solute inclusion highly disordered

1972;

adsorption

weight),

(the formation

around

include the change

interactions

phase is the increasing

mantle

to the sorbent

and Thompson,

of enthalpy

and chemisorption aqueous

ones that

(Hamaker

dipole-induced

can play a role in the sorption

of a chemical

matrix has a

than the latter

one. For hydrophobic behind the sorption of London-Van resulting

process

der Waals

forces

polar group

that

the

additional

equilibrium

contribution

of temperature For weaker

sorption

are presented.

matrix.

According

for

solubility

to the sorption

on the sorption

bonds,

tables,

organic

or that organic

(Hamaker,

can donate

Hamaker is a direct

of temperature

main

driving

and the large entropy

chemicals.

matrix

enthalpy.

the

force

a term used for the combination

and sediment

equilibrium

less influence

literature

1 data

data on the effect

are presented

and

1972).

change

The other

For chemicals or accept

the

solute

and Thompson indication

is expected

to Chiou et al.( 1979) for which

but

of PCB-congeners whereas

solubility

for compounds

sorption

increased

decreases

is in contrast

(Tateya

sorption

of temperature that

that may show electrostatic

values for equilibrium

1 ,l ,l-trichloroethane

temperatures,

sorption”,

groups,

with a

a hydrogenprovides (1972)

an state

of the strength

because

of

of the lower

enthalpy.

In table

The average

the

polar

from the solution

electrostatically between

Table 2 deals with compounds

for compounds

solute

of the sorbing chemical

interaction

In the following

sorption.

any

“hydrophobic

between

are able to interact

exothermic

the sorption.

is so-called

without

only play a minor role for hydrophobic

electrostatic

that the effect

compounds

interactions

from the removal

adsorption

bond,

organic

et al.,

decreased.

enthalpies

sorption

1988).

the

can only

Solubility

equilibrium hydrophobic

with the sorbent

in both tables.

at higher temperatures

reported

show

interactions

are presented

at higher temperatures. with

on sorption

can be expected

This was observed

temperature

was observed

dependence to increase

by Chiou of the at higher

613 Table

The influence

1.

of temperature

compound

on sorption

equilibrium:

hydrophobic

interactions

AH0

temperature

(kJ*mol”)

range

-17.7’

5-25

soil,

1.08%

-7.1

6.5-37

soil,

1%

-1.7

7.5-37

soil,

3.8

6.5-37

soil,

1.2.3.4~tetrachlorobenzene

-163

24-55

sediment

DDT

-8

5-25

marine

DDT

12

5-25

humic

1,2-dichlorobenzene

-0

3-20

soil,

1,4-dichlorobenzene

-12

to -16

3-48

phenyl

coated

silica

1.6%

oc

-12

1,2,4-trichlorobenzene

-13

to 17

3-48

phenyl

coated

silica

1.6%

oc

-12h

1,2,4,5-tetrechlorobenzena

-12

to -25

3-48

phenyl

coated

silica

1.6%

oc

-12

j-HCH

-3s

fluoranthene

naphthalene IO-’ mol/kg

type

of adsorbent’

10.’ mollkg

10.’ mollkg

n.i.’

1

om

n.i.

2

1%

om

n.i.

2

1%

om

n.i.

2

om

y_HCH

20-30

1 O-30

-13

-8%

acid,

peat

22%

clay

6%

peat

22% 6%

silt loam,

2,2’,5,5’-tetrachlorobiphenyl

0

5-33

Aldrich

Aroclor

283

12-22

sediment,

% organic

2References: 5=Jota

and Con”, 3 calculated reliable ’ n.i.

carbon; et

Hassett,

om al.,

1991;

% organic

10 = Weber present

et al.,

study

measurements

matter

Z=Wauchope

6=Szecsody

1992;

= not indicated

=

1995;

in the because

oc

% oc

3

42-66

h

4

42-66

h

4

n.i.

om;

5

h

6

6

h

6

70 h

7

om;

70

7

h

om

1.6%

humic

om

acid

2.61%

oc

n.i.

8

3h

9

24

h

10

-0.25

1 =He

and

2.7%

h

om

clay

3.5-20

VALUE

57

-2

sediment

23’

1254

oc

sediment,

1 ,I ,I trichloro-ethane

=

oc

om

naphthalene

’ oc

ref.’

time

om

naphthalene

AVERAGE

equilibration

IOC)

from have

and

(= et

Bales,

1.7

. ad

el.,

1983;

1991:

3=Wu

7=Mills

and

Gschwend,

and Bigger,

1969;

using

Van

1986; 8=Chiou

4=Pierce et al.,

et 1979;

al.,

1974;

9=Graham

1983 data only

presented been

carried

in the

reference,

out at two

temperatures

the

‘t Hoff

equation;

the

data

are

less

614 The influence

Table 2.

of temperature

AH"

compound

temperature

(kJ.mol

picloram. (pKa

=

pH=4.2

on sorption

‘I

equilibrium:

range

type

possible specific

of adsorbent’

interactions

equilibrat

ref.’

ion tame

(“Cl

-22

15-35

clay

loam,

0.9%

om

24 h

1

loam,

0.9%

om

24 h

1

24

h

1

24 h

1

3.6)

picloram,

pH = 1 .2

-84

1 O-30

clay

picloram,

pH = 7.2

-38

15-35

sandy

plcloram,

pH = 5.9

-17

15-35

silty

pentachlorophenol

-28.6

p-chloroamlww

8 to 27

loam,

loam,

0.7%

3.0%

om

om

2

clay

4-40

soil,

2.49%

<

oc and 8.52%

16h

3

OC

aniline

14to28

4-40

SSlllS

diuron

-14

1 O-40

soil,

diuron

0

5-45

clay,

fluridone

-7 to -15

6-44

soil,

flwdone

1 to 8

6-44

clay,

trlorganotins

0

16-50

sediment,

ametryne

0

5-45

clay,

3.2%

carbofuran

-22

26-50

loam

0.59%

slmazine

0.2

3-50

24 h

9

atrazine

-0.2

to -0.3

0.5-40

2h

9

metolachlor

3to

10

5-28

silt loam,

3.8%

metolachlor

0

5-28

s!lt loam,

0.69%

to -28

0.31-0.85%

3.2%

4%

oc

om

om 1.7%

1.8%

om

om

2.5%

oc

om

same

3

6d

4

24 h

5

24 h

6

24 h

6

3d

7

24

om

-20

oc, 6.4%

oc

oc, 0.74%

5

h

h

3-24

h

8

10

11

24 h

OC

metnbuzin

0

5-28

same

metribuzin

-5 to -9

5-28

silt loam,

AVERAGE

1992;

5=L1u

Thompson,

1972;

3 direct

calorimetric

4 not relevant

3.8%

6.4%

oc

24

h

h

11

10

-8

VALUE

’oc = % organic carbon; or” = % ’References: 1= Biggar and Cheung, al.,

3-24

et al.,

1970;

lO=Graham

organic

matter

and Con”.

measurement

(5 1.7

2 =Xing

6=McCloskey

measurement

for a direct

1973;

and 1992;

oc)

et al.. Bayer,

11 =Chiou

1993;

3 = Moreale

1987; et al.,

7=Tas, 1979

and van 1993;

Bladel,

8=Singh

1979; et al.,

4 =Gonzdlez-Pradas 1994:

9=Hamaker

et and

615

Temperature

dependence

The sorption

kinetics

of fast sorption kinetics

of organic

micropollutants

steps with different

rates: a fast process that reaches

slow

may

process

Brusseau

that

take

and Rao, 1989;

the fast process. fast sorption

months

Pignatello,

The discussion

process.

to 1989).

years Many

in this section

The influence

to

has been shown equilibrium reach

experiments

is restricted

of temperature

within

equilibrium

to occur

in at least two

a minutes to hours, and a (Karickhoff

et

with soil and sediment

to the influence

on the slow sorption

al.,

only study

of temperature process

1979;

on the

is discussed

in

the next section. The temperature an Arrhenius-type

dependence

of the rate of fast adsorption

and desorption

is described

by

equation:

in which:

E”

= activation

energy

for adsorption

or desorption

(kJ. mol.‘) A

= constant

k

= rate constant

(h-l) of fast sorption

(h-‘)

rewritten:

d lnk/d(l/T)

Through

a combination

= -E*/R

of equations

difference

of activation

illustrated

in figure

energies

3 and 5 and defining

for adsorption

K, as kads/kdesit can be shown

and desorption

is the sorption

enthalpy.

that the This is

1.

AH o = E”,,

- E*des

with:

= activation

energy

for adsorption

5 ?? des = activation

energy

for desorption

EX,,,

In table 3, the available sorption

(5)

are presented.

literature

data on the influence

Most data were obtained

in all cases and range between

40 and 50 kJ/mol.

of temperature

for desorption

experiments.

on the kinetics of fast E’-values

are positive

616 Table 3. The influence

of temperature

on fast sorption

kinetics

type

of adsorbent’

E’

temperature

(kJ.mol’I

range

1,2,3,4-tetra-chlorobenzene

63

23-54

sediment,

- 8%

naphthalene

354

15-35

soil,

1 .6%

494

15-35

soil,

1 .6%

-0

3-48

phenyl

compound

adsorption

ref.’

or

desorption

IOCI

desorption

1

oc

desorption

2

oc

desorptlon

2

silica

both

3

stlica

both

3

silica

both

3

silica

both

3

oc

1 d incubation

naphthalene 6 d incubation

1,4-dichlorobenzene

1.6%

1.2.4.trichlorobenzene

-0

phenyl

3-48

1.6%

1,2,4,5-tetrachlorobenzene

oc

1.6%

pentachlorobenzene

coated oc

phenyl

3-48

-0

coated

phenyl

3-48

-0

coated oc

1.6%

coated oc

dichlorobenzenes

175

4-40

sediment,

3.9%

oc

desorptio”

4

trichlorobenzenes

185

4-40

sediment,

3.9%

oc

desorption

4

tetrachlorobenzenes

195

4-40

sediment,

3.9%

oc

desorption

4

pentachlorobenzene

25’

4-40

sediment,

3.9%

oc

desorption

4

hexachlorobenzene

295

4-40

sediment,

3.9%

oc

desorptlon

4

hexachlorobutadiene

155

4-40

sediment,

3.9%

oc

desorption

4

trichlorotoluenes

215

4-40

sediment,

3.9%

oc

desorption

4

pentachlorotoluene

535

4-40

sediment,

3.9%

oc

desorption

4

AVERAGE

18

’ oc =

VALUE

% organic

’ References:

carbon

1 =Wu

and Gschwand,

3 Calculated

from

a factor

4 Calculated

from

the

difference

’ Calculated

from

%

desorbed

fast

and slow

desorption

1966;

2 difference in time after

Z=Podoll

in desorption needed

930

et al., rates

to desorb

hrs for

1989;

3=Szecsody

over the temperature 70%

3 temperatures.

of naphthalene Influence

and Bates, range added

1991;

4=Oliver,

1985;

studled to the soil for 2 temperatures

of temperature

is caused

by

influence

on both

617 Energy

A

Sorption Progress

Figure 1. Relationship

Temperature

Until rapid

dependence

1980,

most

equilibrium

Karickhoff identify

both

on slow

that were

sorption

and slow sorption

the sorption

the first to study

component have

of organic

by first

order

sorption

in the sorption

been

published.

pollutants

kinetics

process.

These

to sediments

processes

in both

with

sediments

In the past

have

been

as a

directions. and to

15 years

reviewed

many

elsewhere

and Rao, 1989). matter

is probably structure,

matter.

a short

Therefore,

compounds

through

organic

the temperature information

Polymers high degree chains

EXdes

be described

among

kinetics

is a macromolecular

detailed

treated

can

a fast and a slow

Organic

which

of diffusion

researchers

process

et al. (1979)

studies

(Brusseau

AH",ECads, and

between

polymer review

dependence

states:

and freedom,

rigid.

The

the

present

in slow sorption.

may resemble

temperature

is presented

of pore diffusion

on the temperature

of flexibility

determinant

diffusion on

polymers

can exist in two

are relatively

an important

dependence

here.

slow diffusion

dependence Only

a few

was studied.

of

through

the organic

diffusion

studies

could

This section

matrix

of

organic

be found

in

does not present

of pore diffusion.

a high temperature and a low temperature study

As the organic

is concerned

elastomeric glassy with

state

in which

state in which

diffusion

through

there

is a

the polymer elastomeric

618 polymers, (Barrer,

as these

resemble

et al. 1958))

polymer

sorption

the

creation

molecule

in that

hole.

polymers

upon solute penetration

(Hayashi,

et al. 1994;

thus

of a hole It is the

Fujita,

do not preexist.

interactions

between

polymer

formation

the absence

highly positive

The

because

diffusion with

dependence

of organic

which

or more branched rigid (Aminabhavi Diffusion

make

1995).

or as the polymer

activation

energy

Pignatello,

1989):

the

of most

of diffusion 1995)

and

of weak

and/or

whereas

H-bridge

bonds),

Van der Waals

In cases

where

interactions

holes preexist,

they do not. The reason for this is The sorption

water

of organic

the entropy mantle

solutes

to

of sorption

is

around the dissolved

through

polymers

“jump”

from

is controlled

energy

that

space in the polymer

forces in the polymer energy

by the ease

one hole to another. is required matrix,

structure

for the solute

its activation

(Rogers,

1965;

will be larger as the solute is larger,

cohesive

energies

described

by the diffusion

and the

The temperature

are larger or the polymer

in

energy

Stannett,

less flexible

segments

more

1995).

can be quantitatively From

swelling

mesh.

requires

The activation

the

of a solute

and Phayde,

thermodynamically:

of the structured

the

or not;

of two

due to the dissociation

segments.

of hole-creation.

by the activation

As this jump

forces

than in cases where

in the polymer

is governed

and Phayde,

1975).

as well

a sequence

during the process

of the hydrophobic

solute and polymer

on intra- and interchain

Aminabhavi,

(Crank,

because

substances

molecules

of diffusion

will be dependent

of flexibility

accommodation

Aminabhavi

process

(Van der Waals

contribution

disorder

preexist

1994;

is an endothermic

of the disappearance

order to make this jump.

1968;

holes

through

and the

that holes are created

is a process that is highly favoured

solute and the increasing

frequency

whether

to be more exothermic

of the endothermic

organic polymers

is a high degree

proceed

matrix

Sun and Chen,

process

between

to

polymer

indicates

segments

and/or

is expected

there

is regarded

question

Hole creation

is an exothermic

sorption

(in which

in the

1968;

hole occupation H-bridge

matter

in a better way than glassy polymers.

Mechanistically, processes:

organic

temperature

E,’ for diffusion

dependence

in a polymer

of this

coefficient diffusion

can be determined

D in Fick’s second coefficient,

(Rogers,

1965;

an

law

apparent

Stannett,

1968;

(7)

in which:

D

= diffusion

DO

= preexponential

E,’

= activation

coefficient factor

energy

(cm’. sec.‘) (cm2. sec.‘)

for diffusion

in a polymer

(kJ . mol”)

in which the preexponential

factor

D, is related to the number of holes in which

the penetrant

can

619 be accommodated energy

(dependent

of diffusion)

depends

on polymer

and solute

on the ease with which

temperature-independent

D, thus includes

E,’ includes the enthalpic

factors.

Diffusion-determining (Rogers,

density

polymer

entropic

1)

and

crosslinking,

which

crosslinking:

because

diffusivity

the number

decreases

whereas

the temperature-dependent

are influenced

by temperature

include

chain

riaidity:

becomes

more

elastomeric

state,

polymer

to transfer

addition,

the

rendering

temperature-dependent

activation

energy

curve

(Rogers,

longer

been reported;

these

Diffusion

solutes.

(Karickhoff

As the

solutes

apparently

more

In

Table

polymers

4a,

of slow

temperature

from

1985;

the

polymer

diffusion

1993). and

density

because

chains.

it

In the

and thus higher diffusivities.

may

however,

diffusivity

rigid polymer

be affected

in nonlinear

can be determined

law constants

from water

to gas were calculated.

which

to the

from water

in synthetic

In

by temperature,

In D-l/T

curves.

The

by the slope of the In D-l/T

usually remain

polymers,

to 1013 cm’/sec, sediments

in the same order of

sediment

many different

lower

are lower 1986;

the lower values

to diffuse

activation

values

values

generally

still, ranging

Steinberg

have

being

from

10-‘-l

et al., 1987;

for 0.”

Rijnaarts

again being for the larger solutes.

experiments through

were

energies

of solutes.

are presented.

of Henry’s

of sorption

decreases

are of comparable

the

natural

organic

size,

it is

macromolecular

polymer.

for a number

desorption

contribution

more

This results

Wu and Gschwend,

for substances

a synthetic

lo”

in natural

sorption from the gas and not the aqueous

endothermic

between

be made

of E’,,

of solutes

range

in the

are presented

can

E’,-values.

and Reinhard,

difficult

mesh than through

in a decreasing

cause lower rigidities

“jumps”

coefficients

and Morris,

used

temperature

1965).

values

Grathwohl

Increasing

result

a molecule

The values

coefficients

larger

et al., 1990;

which

at a certain

For the diffusion

cm’/sec

by

at that temperature.

magnitude

chains

higher temperatures

ease

and

diffusion.

rigid

more difficult

density

of a “jump” from one hole to another

makes the jump more difficult.

2)

polymer

lower.

and consequentely

increases

increasing

of solute becomes

of holes makes the distance

and, as a result,

with

of holes for the accommodation

The lower number

enthalpy

E,’ (the activation

1965): densitv

energy

whereas

the solute can move from hole to hole. The factors,

characteristics

size),

and

In table

For table

4a.

sorption

4b,

it should

phase was involved.

reported

by Ashworth

enthalpies

to a polymer.

values

be mentioned

of

et al. (1988),

presented

kJ/mol.

in table

These range between

elastomeric

for the activation that

From the temperature

These were in the order of lo-40 sorption

enthalpies

reported

in all cases dependence

enthalpies

of transfer

Addition

of this large

4a gives

values

10 and 40 kJ/mol.

for the

620

Table 4a.

Diffusion

activation

energies

solutes in elastomeric

(E,

* in kJ/mol) and sorption enthalpies

(AH"in

kJ/mol)

for

polymers.

Polymer

Permeant

ED

AH"

Ref.1

santoprene

aliphatic alkanes

8-19

0.6-4

1

5 rubbers

1,2-dichlorobenzene

18-22

-1.4-2

2

chlorinated

5 rubbers

(mlethanes

n-alkanes

polyurethane methylated

polypropylene

C,,-C,,

fatty acids

15-44

-1.2-l

18-25

3-6

1

2 3

129-l 47

4

87-104

5

36

6

100-l 09

7

2-methylpropene

74.6

8

low-density-polyethylene

toluene

87.0

9

low-density-polyethylene

n-hexane

65.4

9

C,-C,, esters of 3-(3,5-di-tert-butyC4-

low-density-polypropylene

hydroxy-phenyll-propionic

acid

dimethyl-acetamide

urethane/urea/

ether copolymer polystyrene

dichloromethane

and

bromoethane polypropylene

various polymers

carbon dioxide

45i122

11

various polymers

methane

55*17’

11

natural rubber

methane

34-50

3-6

60

3.5

AVERAGE VALUE

’ References: 1991;

1 =Aminabhavi

4=Hayashi

and Phayde,

et al., 1994;

9 = Saleem. et al. 1989;

5=Mtiller

1995;

10 = Garrer and Skirrow,

’ average of 23 measurements

2 = Khinnavar

and Gevert.

(carbon dioxide);

1948;

1994:

and Aminabhavi. 6=Gou

1 1 = Stannett,

1992;

et al., 1994: 1968

average of 8 measurements

(methane)

3 = Khinnavar

7=Ryskin.

1955;

10

and Aminabhaw. FJ=Rogers,

1965;

621 Table 4b. Activation

compound

energies

(kJ/mol)

for slow sorption

E’ adsldes

temperature

(kJ.mol ‘1

range (OC)

1,2-dibromoethane

66*11

40-97

soil, loam

benzene

>o

5-45

soil, 0.16%

toluene

70

5-45

ethylbenzene

70

l,l,l-

>O

kinetics

type of adsorbent’

in soil/sediment.

adsorption or

ref.2

desorption

1.11%oc

desorption

1

om

adsorption

2

soil, 0.16%

om

adsorption

2

5-45

soil, 0.16%

om

adsorption

2

5-45

soil, 0.16%

om

adsorption

2

trichloroethane

’oc = % organic

carbon, om = % organic material

’ References: 1 = Steinberg et al.. 1967; 2 = Steinberg, 1992 3 Amounts of solute that ere ‘firmly bound’ i.e. slowly exchanging, increase with increasing temperature

Discussion

were

and conclusions

In the studies reviewed

in the present

paper,

a wide variety

used. This heterogeneity

is a common

problem

encountered

it renders the comparison data

in the

discussion

present

of the results of different

paper

are merely

deals with these general

For the thermodynamically enthalpy

changes

average

-0.25

electrostatic

interactions

accordance

with

Thompson,

1972). energies

(on the average

rates.

The fast character energies

only

enthalpies

trends.

reviews

sorption

equilibrium,

slightly

from solution to sediment are

equilibrium

involved.

sorption

The observation (Schwarzenbach

When

This

enthalpies

of an exothermic et al. 1993

temperature

implies a low “threshold” Following

are low

energy of 66 kJ/mol

and negative

should be slightly smaller than the desorption

activation

were found is in

and Hamaker

and

dependence

means

energies.

of fast sorption

adsorption

in low

energies

process.

for slow desorption.

that

0 and 50

resulting

the activation

to be higher than those for the fast sorption

activation

(on the

process

of the process

this argument,

negative

favourable

were both found to be between

leading to a positive

of the process

are expected

and

the thermodynamic general

the transfer

for fast ad- and desorption

with the observed

sorption

-8 kJ/mol).

in previous

18 kJ/mol),

Therefore, do reflect

science

interactions

are possible,

for fast ad- and desorption.

slow ad- and desorption

probably

sediment-water

hydrophobic

(on the average

kJ/mol

equilibrium

controlled

(e.g. H-bonding)

conclusions

The activation

in accordance

when

in soil and sediment

studies difficult. They

and sorbing materials

trends.

were usually found to accompany kJ/mol)

to be more exothermic

activation

indicative.

of solutes

This

for is

The fact that

activation

energies

622 Fast equilibrium temperature

dependence

this sorption increasing

enthalpy

process

is negative,

process

have positive

From all this,

a reason

times is nearly

dependence

of the

of slow

advanced

(the slowly

decreases) When

equilibrium

sorption.

whereas

sorbing

these two contributions

(which

average

3.5

60 kJ/mol.

kJ/mol,

i.e. slightly

polymer

stronger

Van der Waals

solute

and

the

interactions

the

endothermic Apart

enthalpy from

energies silicalite

of slow sorption dependence kJ/mol

lower

degree effect

through

for

membranes kinetics

(Kapteijn

organic

is smaller than the substances From the polymer Activation diffusion

data

diffusion energies

presented

for both

in soil and

with

short

temperature

equilibrium

“degree

of the is more

of nonequilibrium” phase) decreases.

sign, they cancel out and

have been observed for polymer

average

is a slightly exothermic

process

beneficial

and higher

slow

Thus,

present

paper

are positive

of relevance.

interactions than

show

between

intra-organic

the

matter

in sediments.

For

is not able to overcome

the

and

desorption

energies

positive

have

for polymer

(30-40

the observed

kJ/mol

also

been

diffusion, for

the

n-butane

temperature

dependence

of pore diffusion.

Temperature

of the lower E,‘:

This may also be caused

processes

probably

it is.

by the mechanism

diffusion

segments

heterogeneity thus

sorption

are

(on the

diffusion

pure polymer

may be lower because

processes

may also be a mechanism

sorption

Like the activation

polymers.

to the

sorption

dependence

slow

the

energies

for sediments

et al., 1994).

in the

slow

sorption

temperature

enthalpies

more

micropores

used in polymer

is comparable

be

of order

can also be explained

through

the

with the aqueous

of hole occupation

matter,

through

in case of pore diffusion

for diffusion

may

whereas

micropores.

diffusion

sorption

one is that

however,

in organic

it follows

of a negative

but with opposite

that sediment

enthalpy

diffusion

structures,

overall

with each other than with a solute;

of hole creation,

by diffusion

activation through

of the

that

because

Activation

is an endothermic

exothermic

with

diffusion-

and desorption

temperatures

is at equilibrium

endothermic).

matter,

phase

is probably

energy:

a combination

increases

equilibrium

interactions

organic

because

polymers,

explained

sorption

As

dependence.

One reason for the observation

whereas

polymer

sorption

and a positive

are equal in magnitude

positive

enthalpy.

to the water

activation

observation

at higher

fraction

result in hardly any or no net temperature materials,

through

of slow

for the

is that

solute

sorption

the

as well.

sorption

result

the fast fraction

For polymer

Rates

thermodynamics,

as this process

by a positive

of temperature:

of fast

The

will be shifted

of diffusion

can be found

independent

by the equilibrium

equilibrium

temperatures. energies

by equilibrium

this is different,

dependence

activation

equilibration

kinetics

sorption

is accompanied

is more rapid at higher

sediment

controlled

is thus governed

For slow sorption,

From the temperature

the diffusional

is probably

of this process

temperatures.

controlled. that

establishment

30-40

kJ/mol

vs 60

by the fact that n-butane

experiments. it can

involved

be concluded in slow

and of the

same

that

adsorption order

the

process

of

and desorption.

of magnitude.

Pore

623 Acknowledgements

Drs.

R. Bouma

polymers

and

science.

their constructive her linguistic

Dr. Th.

van den

We thank

prof.dr.

comments

during

Boomgaard

H.A.J.

are thanked

Govers,

manuscript

for introducing

Dr. P.C.M.

preparation.

van Noort,

We thank

us to the field of

and dr. S.M.

Drs.ing.

P.M.

Schrap for Knaapen

for

and permeation

of

advice.

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