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1.

Introduction

Presently, 70% of the existing chemical processes employ a catalyst, whereas over 90%
of the newly developed processes contain a catalytic process as one of its crucial step.
Catalysis is therefore an essential technology to improve the efficiency of chemical
processes (especially selectivity) and thereby helping to improve living standards for the
world population. Catalysts are being used for the manufacture of chemicals/materials,
for energy transformation processes, in fuel cells, in combustion devices, and for
pollution control systems. Catalysts are also widely used in production of day-to-day
chemicals, such as pharmaceuticals, food processing, and detergents. Novel
applications of catalysts involve their use in sensor devices.

Berzelius first recognized the phenomenon of catalysis in 1836


[1]. He named it catalysis (which means breaking down in Greek),
since the examples of catalytic reactions known up to that point
involved (oxidative) cleavage of the starting material [2]. Berzelius
defined catalysis as “the action of a catalytic force”. The action of
a catalytic force was strongly opposed by Ostwald [3], who
proposed that catalysts are involved in the energetics of the
reaction. Catalysis can thus be defined as:
J.J. Berzelius
The acceleration of the rate of a process or reaction, brought about by a catalyst,
which changes the reaction pathway, but is unaffected at the end of the reaction.

Catalysis has classically been subdivided into homogeneous catalysis and


heterogeneous catalysis. In homogeneous catalysis the catalyst is in the same phase as
the reactants. Examples of this can be found in many chemistry textbooks. The
examples in organic chemistry textbooks on acid catalyzed reactions using sulphuric
acid, hydrochloric acid or aluminium trichloride are classical examples of homogeneous
catalytic systems. Metal complexes are also being used as catalysts, e.g. the use of
metallocene in the polymerization of propene yielding syndiotactic polypropylene [4], the
use of metal carbonyls for the hydroformylation of olefins with synthesis gas yielding
alcohols/aldehydes, homogeneously initiated cyclohexane oxidation yielding
cyclohexanol and cyclohexanone. It should however be noted that this is an artificial
separation since the basic concepts of catalytic reactions do apply to both
homogeneously and heterogeneously catalyzed reactions.

Table 1.1: Examples of homogeneously and heterogeneously catalyzed reactions


Homogeneous catalysis Heterogeneous catalysis
Acid catalyzed organic reactions using Reactions catalyzed by solid acids, such
H2SO4, HF, AlCl3, etc. (e.g. alkylation) as resins, zeolites, etc. (e.g. alkylation of
aromatic compounds, cracking,
isomerisation
Metal catalyzed polymerization (e.g. using Metal catalyzed polymerization (e.g.
zirconocene compounds Zr(CP)2(PPh3)4) Philips catalyst CrOx/SiO2)
Metal catalyzed hydrogenation reactions
Metal catalyzed conversion of synthesis Metal catalyzed conversion of synthesis
gas (e.g. hydroformylation using Co2(CO)8) gas
Cyclohexane oxidation using cobalt salt Metal and metal oxide catalyzed oxidation
reactions
Metal sulphide catalyzed dehydrogenation

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Heterogeneous catalysts are typically solids. They have been preferred industrially over
homogeneous catalyst, because of the ease of separation of the catalyst from the
product stream. The functionality associated with typical homogeneous catalysts can
also be found in heterogeneous catalysts.

Homogeneous catalysts are typical examples of molecular catalysts, i.e. catalysts with
sites that are identical in activity and selectivity [5]. In heterogeneous catalysis a variety
of sites can co-exist resulting in lower selectivity in specific catalytic reactions.

1.1 Historical development of catalytic processes


Catalytic reactions have been applied since the early days of humanity, e.g. the use of
yeast in beer brewing. In those days the catalytic phenomenon was not understood. That
came only by the end of the 19th century. Catalytic phenomena were initially mainly
described in connection with combustion processes, which were facilitated by the
presence of platinum [2]. This led to the first commercial utilisation of a heterogeneous
catalyst in lighters. Table 1.2 sketches the historical trend in the development of catalytic
processes over the last 2 centuries.

The first commercial, catalytic process (the lead chamber process for the production of
sulphuric acid) was operated without knowing the presence of the homogeneous
catalyst. Research in the properties of platinum in the 19th century led to the
development of platinum as a catalyst for the SO2 oxidation (an important intermediate
step in the synthesis of sulphuric acid).

Around the turn of the 19th/20th century the presence of many substances on the activity
in a variety of reactions was investigated. Those reactions were performed at or close to
atmospheric pressure. High-pressure processes could only be investigated after the
technology of high-pressure reactions had been developed around 1910. The most
important development is here the commercialisation of the ammonia synthesis, which
was driven by the need in Germany for a nitrate source for explosives production in
World War I.

Table 1.2: Sketch of historical development of catalytic processing


Year Process Catalyst
1750 H2SO4 lead chamber process NO/NO2*
1879 SO2 oxidation Pt
1880 DEACON Process (Cl2 from HCl) ZnCl2/CuCl2
CLAUS Process (H2S + SO2  S) Bauxite (Al2O3)
1900 Hydrogenation of fatty oils Ni
Methane from synthesis gas (CO + H2) Ni
1910 Coal Liquefaction Fe
Upgrading of liquefied coal WS2
Ammonia synthesis Fe/K
Ammonia oxidation Pt
1920 Methanol synthesis Zn/Cr
Fischer-Tropsch synthesis Fe, Co
SO2 oxidation V2O5

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Table 1.2 (continued)
Year Process Catalyst
1930 Catalytic cracking Acid clays
Ethene oxidation to ethylene oxide Ag
Oxidation of benzene to maleic anhydride V2O5
Alkylation of isobutane/olefin HF/H2SO4*
1940 Hydroformulation Co*
Reforming (n-hexane  benzene) Pt
Cyclohexane oxidation Co
1950 Ethene polymerization Ti
Propene polymerization Ti
Hydrodesulphurisation (HDS) CoMo
1960 Propene oxidation to acrolein BiMo
Propene ammoxidation to acrylonitrile BiMo
Propene metathesis Re, W, Mo
Improved reforming Pt,Re/Al2O3
Improved catalytic cracking Zeolite HUSY
Propene oxidation to propene oxide Mo
Hydrocracking NiW/Al2O3
1970 Improved methanol synthesis Cu/ZnO-Al2O3
Xylene isomerisation Zeolites
Auto exhaust gas catalysts Pt/Rh
Hydro-isomerisation Pt/zeolite
(Mordenite)
Selective catalytic reduction V2O5/TiO2
(SCR: NO + NH3  N2 + H2O)
1980 Methanol to gasoline (MTG) Zeolite ZSM-5
Vinylacetate from ethene and acetic acid Pd
n-Butane oxidation to maleic anhydride V-P
t-Butanol oxidation to methylacrylate Mo-oxide
1990 CO/ethene co-polymerisation (polyketone) Pd
VOC oxidation Au
Phenol hydroxylation TS-1
2000 Ammonia synthesis Ru
* Homogeneous catalysts

The ability to investigate reactions under pressure opened a new field of research. One
of the reactions, which were re-investigated, was the conversion of synthesis gas (a
mixture of H2 and CO, which was readily available in the early part of the 20th century
from coal gasification). It was found that the combination of these reactants at elevated
pressures yielded a mixture of hydrocarbons and oxygenates [6]. It must however be
noted that the initial reaction conditions were far from those which were commercially
applied. The initial studies dealt with the conversion of synthesis gas at temperatures
between 700 and 750 K and pressures in excess of 100 bar. Nowadays, the commercial
operation of this reaction (Fischer-Tropsch synthesis) is typically performed at
temperatures between 500 and 650K and pressures up to 40 bar.

Serendipity played a large role in the development of catalytic processes. For instance,
Houdry discovered catalytic cracking reaction by letting oil standing over acid clay and
after returning from holiday observing the formation of a clear liquid. This process
developed in France was only commercialised in America, and was the first process in

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oil refining. Subsequent other processes needed in oil refining and down stream
processes were developed. The end of World War II saw the rise of the polymer
industry, which was aided by the development of a catalyst for ethene and propene
polymerisation. The discovery of the Ziegler-Natta catalysts was also serendipitously.

In the 1960s catalysts for the bulk petrochemical industry were developed. Furthermore,
the development of improved process was seen in this period (catalyst with higher
activity, better selectivity and/or better stability). During this decade the synthesis of
zeolites started taking off. The first zeolite to be applied in a commercial process as a
catalyst was HY for catalytic cracking.

The development in the last 40 years was aimed at the introduction of heterogeneous
catalysts in domains classically using homogeneous catalysts (e.g. synthesis of fine
chemicals), the use of catalysts for environmental clean-up, and a deep understanding in
the working of catalysts to improve them.

1.2 Basic rules in catalysis


People working in the area of catalysis and catalytic processes need to keep a few basic
concepts in mind.

Rule 1: Catalysts do not change the position of thermodynamic equilibrium1

This first rule is a re-formulation of the thermodynamic rule that the equilibrium position
is independent of the path, which was followed, to come to the equilibrium position. This
formulation can easily be visualized by taking 3 equally sized, metal blocks with block A
at temperature T1 and the blocks B and C at temperature T2. I can put the three metal
blocks together in various ways and observe their final temperature.

Block A Block B Block C


T1 T2 T2

Block B Block A Block C


T2 T1 T2

In all cases the final temperature (equilibrium state) will be the same (i.e. (2T 2 + T1)/3).

A similar conclusion can be made for catalytic reactions.


Take the reversible reaction A B. The equilibrium for this reaction is given by:

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It should be realized that this statement is only true for an overall equilibrated system. Exceptions can be
expected when the catalyst can be considered to be a separate phase (e.g. zeolites), in which the
equilibrium position differs from the equilibrium position in the bulk fluid phase, which is not in equilibrium
with the bulk fluid phase. This situation is analogue to a situation where a reaction reaches equilibrium in
the liquid phase, but is not in equilibrium with the vapour phase. The equilibrium ratio of products to
reactants will then correspond to the equilibrium of the liquid phase, but not to the equilibrium of the vapor
phase.

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 (ΔGBf  ΔG fA )
RT
C 
K(T)  e K(T)   B 
 CA  eq
Suppose that over a catalyst the reaction proceeds via following reactions steps:
 C 
A + cat A.cat K1   A  cat 
 C A  Ccat  eq
C 
A.cat B.cat K 2   B  cat 
 C A  cat  eq
 C C 
B.cat B + cat K 3   B cat 
 CB  cat  eq

In equilibrium all species are in equilibrium and therefore:


 CB  K C C 

C 
   3 B  cat cat   K1  K 2  K 3
 A  eq  C A  cat K1  Ccat  eq
Since the position of the equilibrium is independent of the pathway, which was followed
to come to equilibrium, and therefore the ratio of the equilibrium concentrations:
K1  K 2  K3  K

This leads immediately to rule 2 in catalysis.

Rule 2: Catalysts accelerate reactions by providing an alternative reaction pathway

The provision of an alternative reaction pathway as the way to accelerate a reaction can
be illustrated with the hydrogenation of ethene [7]. The homogeneous hydrogenation of
ethene proceeds via an activated complex, C2H4.H2:

C2H4 + H2 C2H4.H2
C2H4.H2 C2H6

-85 500
with a rate of: rhomogeneou s  10 27
 e RT

The heterogeneous the reaction over CuO-MgO proceeds via a number of elementary
reactions on the catalyst surface
C2H4 + * C2H4*
H2 + 2* 2 H*
C2H4* + H* C2H5* + *
C2H5* + H* C2H6* + *
C2H6* C2H6 + *
(* denotes an active site on the catalyst)
-25 900
with a rate of: rheterogene ous  2  10 27  e RT

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The main difference between the homogenous and heterogeneous reaction is the
activation energy (much lower for the heterogeneous reaction due to the different
reaction pathway). Figure 1.1 compares the rate of the homogeneous reaction relative to
the rate of the homogeneous reaction as a function of temperature. At 600 K is the rate
of the heterogeneous reaction is a factor 105 faster. The heterogeneous reaction is thus
much faster, especially at lower temperatures and the advantage disappears at high
temperatures (as could be expected based on the activation energies).

1.E+10
rheterogeneous/rhomogeneous

1.E+08

1.E+06

1.E+04

1.E+02
200 400 600 800 1000
Temperature, K
Figure 1.1: Comparison of the rate of the heterogeneous hydrogenation of ethane
relative to the rate of the homogeneous hydrogenation of ethane [7]

A catalyst provides thus an alternative pathway without changing the overall energetics
of the reaction. Figure 1.2 shows qualitatively the energy profile for a catalyzed and a
non-catalyzed reaction. The heat of reaction is given by the difference in the energetics
of the products and the reactants. An energy barrier has to be overcome, before a
reaction takes place. For the non-catalytic reaction the energy barrier is high. For the
catalytic reaction a number of energy barriers have to be overcome, but each of them is
lower than the one for the non-catalytic reaction. The difference between the highest
energy for all reaction steps and the energy of the reactant can be considered to be the
activation energy for the catalyzed reaction for catalysts with a low surface coverage.

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EA,non-catalytic
Energy, a.u.

EA,catalytic
A
H
rxn

Reaction pathway
Figure 1.2: Comparison of the energy profile for non-catalytic reactions and
catalytic reactions as a function of the reaction pathway

Rule 3: Forward and reverse reactions are catalysed to the same extent

This rule can be demonstrated by considering a simple non-catalytic reaction that can
also proceed in the presence of a catalyst. Take the elementary reaction:
A B
Rate of forward non-catalytic reaction: rf  k f  C A
Rate of reverse non-catalytic reaction: rr  k r  CB
The equilibrium constant for the non-catalytic reaction is thus given by:
k
Knon-catalytic  f
kr
Suppose the reaction can also be performed catalytically and the catalyzed reaction can
be represented by the following elementary reaction:
A + cat B + cat
Rate forward catalyzed reaction: rf,cat  k f,cat  C A  Ccat
Rate reverse catalyzed reaction: rr,cat  k r,cat  CB  Ccat

k f,cat
The equilibrium constant for the gas phase reaction is thus given by: K catalytic 
k r, cat

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The equilibrium constant is not affected by the pathway by which the equilibrium was
obtained: K non -catalytic  K catalytic
k f k f,cat
Therefore, 
k r k r,cat
Thus, if kf,cat = 10 kf, then kr,cat = 10 kr

The conclusion from this rule is that a good catalyst for a forward reaction must be a
good catalyst for the reverse reaction. This is useful for in the development of novel
catalysts, if catalysts are known for particular parts of the reaction or for the reverse
reaction. The application of this rule is also found in practice.
Methanation - steam reforming:
CO + 3 H2 CH4 + H2O + 167 kJ/mol
Nickel (supported on alumina) is a good catalyst for the formation of methane from
synthesis gas. This reaction takes place at moderate temperatures (ca. 500 K) and
relatively high pressures. Nickel is also a good catalyst for the reverse reaction, i.e.
steam reforming of methane. Of course, this reaction, which is endothermic, must be
performed at higher temperatures (ca. 1300 K) and lower pressures (Le Chatelier’s
principle)

Rule 4: Catalysts may alter the selectivity of a reaction

A reactant has typically a multitude of possible reaction pathways, which it can follow.
Catalysts can selectively allow certain reactions to take place. This characteristic is
sometimes used to probe catalysts. For instance, the conversion of iso-propanol over an
acid yields the dehydration product propene. The conversion of the same reactant at
approximately identical conditions over a metal or a base yields the dehydrogenation
product acetone.

Another example is the conversion of synthesis gas (CO plus H2), which can yield
methanol, methane, higher hydrocarbons and even ethylene glycol over appropriate
catalysts.

Rule 5: Catalysts take part in a catalytic cycle

The catalyst is not supposed to be consumed in the reaction. At the end of reaction the
catalyst is to be found in its original state. Because of the cyclic nature of the catalyst a
relatively small amount of catalyst is needed to convert the reactant feed.

However, by the occurrence of side reactions may 'consume' the catalyst (poisoning). In
industrial operation stability and selectivity of catalytic reactions are of paramount
importance. Activity is also important, but can mostly be tuned using reaction variables
(e.g. temperature).

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Rule 6: Catalysis takes place on a catalytically active site

Catalytic reactions are thought to occur on active sites/active centers on the catalyst
surface [8, 9]. Reagents adsorb on active sites (form a chemical bond) and products
desorb. The active sites interact with the reactants yielding an active intermediate, which
is further transformed. In one of the steps of the catalytic cycle, the bonding between the
active sites and the products is broken and the active site is recovered. Taylor [9]
stressed that the rate of catalytic reactions is proportional to the number of atoms in the
surface that are active, but that not all atoms are necessary active or as-active.

In homogeneous the catalytic active site is generally well-known and well described. In
some heterogeneous catalysts, e.g. zeolites the location of the active sites is also well-
described. In other heterogeneously catalyzed reactions (especially metal catalyzed
reactions) active sites are less well described.

1.3 Thermodynamic limitations


Catalysts do not change the position of the overall position of the chemical equilibrium. It
is therefore useful to determine the position of the thermodynamic equilibrium of a
particular reaction prior to embarking on research for a catalyst for a particular reaction.
The equilibrium conversion can be obtained from the equilibrium constant.

As an example, the gas phase dehydrogenation of propane will be treated.


C3H8  C3H6 + H2
Suppose that the dehydrogenation of propane is carried out in a continuous flow reactor
with a feed of pure propane. The conversion of propane (Xpropene) can be defined in terms
of the molar flow rate of propane (Fpropane):
Fpropane, in  Fpropane, out
Xpropane 
Fpropane, in

In the next step a table is created, in which the molar flow rates of all compounds in
terms of conversion are listed.

Compound In Change Out


Propane Fpropane, in  Fpropane, in  Xpropane 
Fpropane, in  1  Xpropane 
Propene 0 Fpropane, in  Xpropane Fpropane,i n  Xpropane
Hydrogen 0 Fpropane, in  Xpropane Fpropane,i n  Xpropane

Now the mole fraction and the partial pressure of each component can be determined:
Fi
yi 
Ftotal and pi  y i  p total

Thus, in this example:

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Compound yi pi
Propane 1  Xpropane 1  Xpropane
 p total
1  Xpropane 1  Xpropane
Propene Xpropane Xpropane
 p total
1  Xpropane 1  Xpropane
Hydrogen Xpropane Xpropane
 p total
1  Xpropane 1  Xpropane

The equilibrium constant for the dehydrogenation of propene is given as:


 p C3H6   pH2   p total X eq   p total X eq 
       
 1bar   1 bar   1 bar 1  X eq   1 bar 1  X eq  X2
        eq p 
Kp      total 
 p C3H8 
 
 p total 1  X eq 
 
 
1  X eq  1  X eq  1 bar  

 1bar   1bar 1  X eq 
   

The equilibrium conversion can be obtained knowing the total pressure in the system
and the value for Kp. The equilibrium constant is related to the Gibbs free energy for
reaction at the specific temperature.
 Grxn T 
Kp  e RT
In tabulated works [10-13] the values of Gf at 298 K, Hf at 298 K and specific heat can
be found for a variety of compounds. These values might also be estimated using group
contribution methods (see e.g. [13]) or using molecular modelling [14]. For the
compounds of interest in the dehydrogenation of propane the values are given below:

Compound Gf (298 K) Hf (298 K) Cp, J/(mol K)


kJ/mol kJ/mol a 102.b 105.c 109.d
Propane -24.39 -104.68 -4.042 30.456 -15.711 31.716
Propene 62.15 19.71 3.151 23.812 -12.176 24.603
Hydrogen 0 0 29.088 -0.192 0.400 -0.870
cp  a  b  T  c  T2  d  T3

From this set of data the Gibbs free energy for reaction Grxn and the heat of reaction
Hrxn can be calculated at 298 K:
Grxn 298K    i  Gf 298K ) Hrxn 298K    i  Hf 298K )
i and i
Thus for the propane dehydrogenation
Grxn 298K     i  G f 298K )  62.15  0   24.39   86.54
i kJ/mol
rxn 
H 298K     i  H 298K )  19.71  0   104.68   124.39
f
i kJ/mol
The Gibbs free energy and the heat of reaction can now be calculated at any other
temperature using known thermodynamic functions, since:

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  Grxn  
  
  T   rxn  rxn
     1   G   G
 T  T  T  T2
   p
 
 p

 Grxn 
   Srxn
 T 
 p
with and Grxn  Hrxn  T  Srxn
  Grxn  
  
  T  rxn
      S Hrxn  T  Srxn  Hrxn
 
 T  T T2 T2
 
 
 p
Separating the variables and integrating both sides of the equation yields:
Grxn T2  Grxn T1
T2
 Hrxn
T2

T1
  T2
 dT
T1
or in terms of the equilibrium constant
 
 Grxn T1 2 Hrxn
T

Grxn T2   T2      dT 
 T1 2 
 T1 T 

In order to evaluate the integral, we can either assume the heat of reaction to be
constant, in which case
 Grxn 298K   1 1  
Grxn T2   T2    Hrxn    
 298  T2 298  
 

The heat of reaction is however a function of temperature:


 Hrxn 
   cp
 T  cp    i  cpi
 p i
with

Now the Gibbs free energy at any temperature can be calculated at any temperature:
 Grxn T   
 1  Hrxn T   a  T  b  T 2  c  T 3  d  T 4    1  1  
 
1  T 
 T1 
1 1
2 1 3 1 4  2 T1  
Grxn T2   T2  
  T2  b
  a  ln  
 T1  2
 T2  T1  
c
6
 
 T22  T12 
d
12

 T23  T13  

 
The equilibrium conversion for the highly endothermic dehydrogenation of propane can
now be determined as a function of reaction temperature.

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100
p = 1 bar
Propane conversion, Feed: inert/C3H8=99
Xpropane, mol-% 80 p = 0.01 bar
Feed: pure C3H8

60

40
p = 1 bar
Feed: pure C3H8
20

0
400 800 1200
Temperature, K
Figure 1.3: Equilibrium conversion of propane in the propane dehydrogenation
yielding propene as a function of temperature
calculated with empirical data [13] using a feed of pure propane
at a total pressure of 1 atm
calculated with data derived from molecular modelling2 using a
feed of pure propane at a total pressure of 1 atm
calculated with empirical data [13] using a feed of propane at a
total pressure of 0.01 atm
calculated with empirical data [13] using a feed of propane and
an inert material in a molar ratio of 1:99 at a total pressure of 1
atm

With any catalyst the maximum conversion, which can for instance be obtained at 700K
(ca. 430oC) is approximately 6%. The equilibrium conversion can be increased by
increasing the temperature, by decreasing the pressure (or adding inert material – this
will result in slight differences in the resulting equilibrium conversion in comparison to a
decrease in pressure due to the expansion taking place due to the reaction) or by adding

Molecular modeling data obtained with DMOL [B. Delley, in ”Modern Density Functional Theory”, Vol. 2,
2 3

pg 221 (1995); B. Delley, J. Chem. Phys. 113 (2000), 7756; B. Delley, J. Chem. Phys. 92 (1990), 508]
using GGA-PW91 [J.P. Perdew, Physica B 172 (1991), 1; J.P. Perdew, J.A. Chevary, S.H. Vosko, K.A.
Jackson, M.R. Pederson, D.J. Singh, C. Fiolhais, Phys. Rev. B 46 (1992), 6671] with triple numerical basis
set with polarization (TNP) using an orbital cut-off of 6.0 Å. Ortho/para hydrogen equilibrium is taken into
account. Only the staggered conformer of propene and propane were taken into account, since the
eclipsed conformer are transition states.

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a component, which reacts with e.g. hydrogen (e.g. oxygen, in which case it is called an
oxidative dehydrogenation, or carbon dioxide).

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