20 views

Uploaded by cymy

nbps

- AP Statistics Practice Exam
- Binary Distillation Manual
- sweetening LPG with Amines
- A Fast Method To Calculate Residue Curve Maps
- Humidity Handbook
- Term Paper
- EquationOfState-DerivativesOfPR
- Vessel Design
- Lect36 42 Gibbs
- VLE Consistency Pitfalls
- Desti Las i Alkohol
- BASICapricot kernel oil.pdf
- kardos1986 - Void growth and resin transport during processing of thermosetting matrix composites.pdf
- Class Notes Sessions5-6
- TEG paper
- Condensate Recovery by Cycling at Declining
- Solved Problems in Heat Transfer
- 140990105009_vle & diff dist.pptx
- Fluid Mechanics (3)
- Www.unitoperation Th1

You are on page 1of 25

point of non-electrolyte organic compounds

Wilfried Cordes

a

, Jrgen Rarey

a,b,

a

DDBST GmbH, Industriestr. 1, 26121 Oldenburg, Germany

b

Industrial Chemistry, Carl von Ossietzky University Oldenburg, Fachbereich 9, Postfach 2503, 26111 Oldenburg, Germany

Received 3 September 2001; accepted 21 February 2002

Abstract

Agroup contribution method for the estimation of the normal boiling point of non-electrolyte organic compounds

was developed using experimental data for approximately 2500 components stored in the Dortmund Data Bank

(DDB). Predictions are based exclusively on the molecular structure of the compound. The results of the newmethod

are compared to currently-used methods and are shown to be far more accurate. Structural groups were dened in a

standardized form and the fragmentation of the molecular structures was performed by an automatic procedure to

eliminate any arbitrary assumptions.

2002 Elsevier Science B.V. All rights reserved.

Keywords: Vapor pressure; Model; Method of calculation; Normal boiling temperature; Group contribution

1. Introduction

Pure component vapor pressures of liquid (and solid) compounds are of great importance for many

practical applications in chemical and biochemical engineering as well as for environmental and safety

problems. Vaporliquid equilibria of mixtures, which are for example employed for the design and

simulation of distillation processes, are usually described on the basis of the pure component vapor

pressures of the components in the mixture and a correction term (activity coefcient), which accounts

for the real behavior of the mixture. If an equation-of-state is used for the calculation of the phase

equilibrium, both pure component vapor pressure and real mixture behavior are described by the fugacity

coefcients of the components in the mixture.

While pure component vapor pressures are in most cases accessible by rather simple experimental

techniques and are available for nearly all components of industrial importance, great effort was invested

into the development of methods for the correlation and prediction of the real behavior of liquid mixtures

(Wilson, NRTL, UNIQUAC, UNIFAC, modied UNIFAC, PSRK, . . . ).

E-mail address: rarey@ddbst.de (J. Rarey).

0378-3812/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.

PII: S0378- 3812( 02) 00050- X

410 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

However, with the wide availability of computers and software for the simulation of chemical processes

and environmental simulations (e.g. compartment models for the estimation of the distribution of chemi-

cals in the environment), today we face a great need for physical properties, especially vapor pressures of

a large number of rather exotic compounds (by-products, trace impurities, additives in resign production,

pesticides, . . . ), which are not easily available from literature or experiment.

Another evolving application for accurate physical property estimation methods is computer aided

molecular design (CAMD), which is focused on generating molecular structures for components with

specic properties (vapor pressure, viscosity, polarity, . . . ). During the optimization process, the computer

will generate a large number of structures, for which experimental data are not available and the program

has to rely on the accuracy of the predictive methods employed.

Due to theoretical considerations, physical property estimation usually starts with the estimation of

the critical point, which is directly linked to the molecular parameters of the intermolecular potential. At

the critical point, physical properties of components are not yet strongly inuenced by the formation of

short-range structures, which tend to signicantly complicate property estimation.

Development of estimation methods for critical data with broad applicability is limited by the fact, that

the critical point is difcult to determine and that most of the more complex molecules are not stable at

the critical temperature. Currently, reliable data for less than 600 components are available in literature.

Normal boiling points on the other hand are available for a large number of compounds and are of

special practical importance, but are inuenced signicantly by short-range structures in the liquid phase,

which are difcult to describe by group contributions. This paper presents a method for the estimation of

normal boiling points by group contribution based on a large number of experimental data without the

need for experimental or estimated critical data.

2. Available methods for the prediction of normal boiling points

A variety of estimation methods for normal boiling points from molecular structure are available. A

broad overview on these methods was given by Prausnitz et al. [1]. Several methods are restricted to

individual classes of substances, others require the knowledge of molecular descriptors usually obtained

from quantum mechanical methods. In this work, we will compare our results with those of Constantinou

and Gani [2], Joback and Reid [3], Stein and Brown [4] and Marrero-Morejon and Pardillo-Fontdevila

[5]. All of these methods have in common, that they only require the knowledge about the molecular

structure and therefore are comparable. As the original paper of Marrero-Morejon and Pardillo-Fontdevila

[5] contains several misprints, in this work, we use the corrected parameters supplied by the authors and

published by Prausnitz et al. [1].

3. Theoretical considerations

From the ClausiusClapeyron equation, the normal boiling point can be calculated via the ratio of

H

vap

and S

vap

:

T

b

=

H

vap

S

vap

(1)

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 411

At the normal boiling point, the total interaction between the molecules in the vapor phase is small

compared to that in the liquid phase and the enthalpy of vaporization can be approximated by the total

intermolecular interaction in the liquid phase.

In a homologous series, in which the individual members of the series differ by one CH

2

group, the

volume of the molecule increases linearly. Because molecules are usually not stiff, but tend to tangle to a

more or less spherical form, their outer surface should increase with approximately n

2/3

CH

2

once a certain

length is reached. In case of short chains, however, the gain in entropy is probably not large enough to

favor a spherical form.

As molecular interaction in organic liquids is dominated by nearest neighbor contacts, it should also be

proportional to the molecular surface. Fig. 1a shows H

vap

(J/(mol K)) at the normal boiling for n-alkanes

as function of molecular weight together with a correlation using the expression:

H

vap

= 4067.5 +1738.8M

0.6248

(2)

The exponent of 0.6248 is close the estimated value of 2/3. In case of small chains (14 CH

2

groups),

H

vap

increases linearly with the number of CH

2

groups as expected (Fig. 1b). For very large molecules,

a mutual contact of the complete outer surface becomes more difcult (increasing free volume) and the

increase of H

vap

is less than estimated.

Fig. 1. (a and b) Enthalpy of vaporization of n-alkanes at the normal boiling point as function of the molecular weight (data

taken from Dortmund Data Bank, 2001).

412 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

For the estimation of the normal boiling temperature also knowledge of the entropy change with

vaporization is required. Following Troutons rule, the molar entropy of vaporization of a non-associated

liquid at standard boiling point is approximately constant, about 8288 J/(mol K). Different approaches are

available for a more sophisticated estimation. Different effects contribute to the entropy of vaporization,

e.g.

(a) Generally, external movement (translation) of the molecule is conned to the molar volume minus the

volume occupied by the molecule itself. For an ideal gas, at 1 atmand 273.15 KV

V

trans

amounts to nearly

22.414 dm

3

/mol. In the liquid phase, the available volume V

L

trans

is usually less than a few percent of

the total liquid volume. The translational part of the entropy of vaporization can be calculated via

S

vap, trans

= Rln

V

V

trans

V

L

trans

(3)

V

L

trans

should decrease with increasing attractive forces (i.e. increasing enthalpy of vaporization) and

be inuenced by structural effects.

(b) Due to close packing in the liquid phase, a difcult to estimate part of the internal movements can be

conned. This effect is considered to be very small and generally not of further importance. In case of,

e.g. cyclohexane and n-hexane, the difference in the entropy of vaporization is only approximately

0.4% which is nearly solely due to the increase in molar vapor volume due to the higher boiling

temperature of cyclohexane.

(c) In case of association, the number of particles is changed when going from the liquid phase (nearly

complete association) to the vapor phase (partial association).

Instead of separately estimating H

vap

and S

vap

, a correlation expression for T

b

based on group

contributions and other easy to obtain quantities will be sought for as a certain correlation between H

vap

and S

vap

can be expected. If both properties would depend very differently on molecular structure, two

sets of group contributions would be required.

In order to accomplish this, the typical dependence of T

b

on the number of groups in different homol-

ogous series will rst be compared to the results of methods previously published.

Figs. 2 and 3 show the normal boiling points of n-alkanes and n-alkanols as a function of chain length

together with the predicted values from different group contribution methods.

Joback and Reid [3] employed a linear relationship between the sum of group increments and the

boiling point, which is only adequate to describe the experimental data over a small range of normal

boiling temperatures. Because the method is based on a rather limited database of only 438 components,

this deciency may not have become apparent to the authors.

Stein and Brown employed the same linear relationship, but their method is based on a much larger set

of data (4426 components from the Aldrich Chemical Catalog [6] and 6584 different compounds from

the HODOC[7] database, normal boiling temperatures were partly extrapolated fromvapor pressure data

at low pressures using the LeeKesler [8] equation). In this case, large systematic deviations became

apparent and the authors applied a correction to the estimated values:

T

b

(corrected) = T

b

+A +BT

b

+CT

2

b

(4)

As the polynomial parameters A, Band Cand the group contribution parameters were regressed separately,

they do not give the best results possible with this type of mathematical expression.

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 413

Fig. 2. Normal boiling points of n-alkanes as a function of the number of CH

2

groups.

Constantinou and Gani [2] greatly improved the method of Joback and Reid [3] by using a logarithmic

dependence of the boiling point on the sum of the group contributions:

T

b

= 204.359 ln

N

i

C

i

+

M

i

D

i

(5)

with N

i

is the number of rst-order groups of type i, C

i

the group contribution of rst-order group i, M

i

the number of second-order groups of type i, and D

i

is the group contribution of second-order group i.

The second-order groups are only used as a correction to the rst-order estimations for a limited number

of special structures.

Marrero-Morejon and Pardillo-Fontdevila [5] employed the equation:

T

b

= M

0.404

N

i

C

i

+156.00 (6)

where N

i

is the number of rst-order groups of type i, C

i

the group contribution of rst-order group i,

and M is the molecular weight (g/mol).

Fig. 3. Normal boiling points of n-alkanols as a function of the number of CH

2

groups.

414 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

In contrary to the other methods, Marrero-Morejon and Pardillo-Fontdevila use bond contributions

instead of group contributions.

From Figs. 2 and 3, it can be seen that, although much better than the linear assumption of Joback and

Reid, neither the logarithmic dependence nor the term M

0.404

are able to describe the dependence of T

b

on chain length in the two homologous series.

For the correlation of group contribution parameters Constantinou and Gani as well as Marrero-Morejon

and Pardillo-Fontdevila used only a limited set of data (392 and 507 components, respectively).

4. Development of the new method

From the analysis of the different estimation methods, it is obvious that a signicantly better method

could be developed based on an improved expression for the dependence of the normal boiling point

on the sum of group increments and a signicantly larger set of reliable experimental information. In

addition, all parameters should be regressed simultaneously in order to nd the optimum value of the

objective function.

4.1. Group denitions and equations

To describe the normal boiling point for a large number of molecules greatly differing in size the

following expression was employed:

T

b

=

N

i

C

i

n

a

+b

+c (7)

where a, b and c are the adjustable parameters, N

i

the number of groups of type i, C

i

the group contribution

of group i (K), and n is the number of atoms in the molecule (except hydrogen).

While this expression gives a good description of the dependence of T

b

on molecular size, it carries the

additional advantage, that via the number of atoms in the molecule, an additional and readily available

quantity more or less independent from the sum of the increments is introduced. The number of atoms or

the molecular weight have been successfully employed by numerous other authors in the past (e.g. Joback

and Reid [3], Marrero-Morejon and Pardillo-Fontdevila [5]) to improve the results of group contribution

methods for various properties.

Correlation of data for 2550 components lead to the following values for the constants:

a = 0.6713, b = 1.4442, c = 59.344 (K)

Results for the new model for n-alkanes and n-alkanols are given in Figs. 4 and 5.

Denition of the structural groups was approached by an iterative procedure. Starting off from the

groups used in the method by Joback and Reid, the adjustable parameters a, b and c as well as all the

group contributions were tted to the experimental data. The results were then carefully analyzed and

the group denitions were revised in order to take into account special effects, which otherwise led to

large deviations. This had to be repeated several times. In the second step, all the molecules, which could

not be fragmented into the structural groups available were reviewed and new groups were dened for

all cases in which enough experimental information was available for the correlation of reliable group

parameters.

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 415

Fig. 4. Normal boiling points of n-alkanes as a function of the number of CH

2

groups together with the results for the proposed

method.

In this procedure, each redenition of molecular groups required the re-fragmentation of about 2550

components. This was made possible by employing an automatic fragmentation algorithm (AutoInkr)

and a data bank with the molecular structures of all components (ChemDB) (Cordes et al. [9]).

In order to perform group fragmentation consistent with the chemical knowledge usually required for

this task, not only the structure of the groups themselves but also their chemical neighborhood had to be

included in the group denition.

Fig. 5. Normal boiling points of n-alkanols as a function of the number of CH

2

groups together with the results for the proposed

method.

416 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

The list of groups, explanations as well as examples for molecules containing these groups are given

in Table 1. The group contributions, the number of components used for regressing these values and the

mean absolute deviation in temperature for these components are given in Table 2.

In the approach used for the development of the new method specication of the chemical neighbor-

hood of a structural group plays a very important part. The correct specication of this neighborhood is

especially critical, because in our approach the fragmentation of molecules is performed by an automatic

algorithm rather than a chemist with his understanding of the electronic structure.

During the development of the method, it became apparent that:

there is no need to distinguish between carbon or silicon as a neighbor atom;

veryelectronegative (N, O, FandCl) or aromatic neighbors oftensignicantlyinuence the contribution

of a structural group;

it is usually of great importance whether a group is part of a chain, ring or aromatic system.

In addition, strong steric or mesomeric effects signicantly worsen the results of the new method. This

is discussed in detail later on.

In a number of cases, for a computer software, it is not as obvious as for a chemist which group to use.

As there are only two avors of the CH

2

group (ring and chain), one could use the chain CH

2

group

(identication number (ID) 4, priority (PR) 82) for the phenylic carbon in ethylbenzene. In this case, the

C(c) (a)-group (phenylic carbon, ID 8, PR 79) would be the correct choice as the neighboring aromatic

carbon is of greater importance than the two hydrogen atoms. To solve this problem, the different groups

were sorted by priority. In case of the automatic algorithm structural groups are matched in the order of

their respective priority. In this way, it is guaranteed that always the group with the lower priority number

(higher priority) is used to estimate the normal boiling point. The priority numbers are given in Tables 1

and 3 in order to allow the reader to correctly apply or program the method.

As was also observed by other authors, the short chain alkanols do not t into the group contribution

scheme. For this reason, special groups are used for short-chain (ID 36) and long-chain (ID 34 and 35)

alkanols. In some cases a larger group could be but should not be constructed of smaller groups (e.g. the

carbamat-group, the CCOCOC group, . . . ). Some of these groups are given at the end of Table 1

as excluded groups with a group ID of 1. Whenever one of these groups is found in a molecule, the

method cannot be applied as no group parameters are available for excluded groups.

4.2. Second-order corrections

In addition to the group increments given in Table 1, special second-order corrections were applied.

A list of these special corrections together with examples is given in Table 3. Table 4 contains the

second-order contributions, the number of components used for regressing these values and the mean

absolute deviation in temperature for these components.

4.3. Database

Normal boiling temperature data for approximately 2800 components are available in the Dortmund

Data Bank (DDB), out of which 2550 components are constructed of the structural groups proposed in

this work. These data were entered since work on the data bank started in 1973 and were extensively

used, e.g. for the calculation of phase equilibrium data. This is the reason why this set of data may be

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 417

Table 1

Group denitions (ID, identication number; PR, priority)

Group Description Name ID/PR Occurs

Periodic group 17

Fluorine

F F connected to C or Si F(C,Si) 19/59 2-Fluoropropane,

trimethyluorosilane

F connected to a C or Si

already substituted with

one F or Cl and one other

atom

F(C([F,Cl]))a 22/56 1-Chloro-1,2,2,2-tetra-

uoroethane[R124],

diuoromethylsilane

F connected to C or Si

already substituted with at

least one F or Cl and two

other atoms

F(C([F,Cl]))b 21/54 Trichlorouoromethane

[R11],

2,2,3,3-tetrauoropropionic

acid

F connected to C or Si

already substituted with

two F or Cl

F(C([F,Cl]

2

)) 23/55 1,1,1-Triuorotoluene,

2,2,2-triuoroethanol,

triuoroacetic acid

F connected to an

aromatic carbon

F(C(a)) 24/58 Fluorobenzene,

4-uoroaniline

F on a C=C (vinyluoride) CF=C 20/57 Vinyl uoride,

triuoroethene,

peruoropropylene

Chlorine

Cl Cl connected to C or Si

not already substituted

with F or Cl

Cl(C,Si) 25/47 Butyl chloride,

2-chloroethanol,

chloroacetic acid

Cl connected to C or Si

already substituted with

one F or Cl

Cl((C,Si)([F,Cl])) 26/46 Dichloromethane,

dichloroacetic acid,

dichlorosilane

Cl connected to C or Si

already substituted with at

least two F or Cl

Cl((C,Si)([F,Cl]

2

)) 27/44 Ethyl trichloroacetate,

trichloroacetonitrile

Cl connected to an

aromatic C

Cl(C(a)) 28/48 Chlorobenzene

Cl on a C=C

(vinylchloride)

CCl=C 29/45 Vinyl chloride

COCl COCl connected to C

(acid chloride)

COCl 77/13 Acetyl chloride,

phenylacetic acid chloride

Bromine

Br Br connected to a

non-aromatic C or Si

Br(C/Si(na)) 30/41 Ethyl bromide,

bromoacetone

Br Br connected to an

aromatic C

Br(C(a)) 31/42 Bromobenzene

Iodine

I I connected to C or Si I(C,Si) 32/39 Ethyl iodide 2-iodotoluene

418 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

Table 1 (Continued)

Group Description Name ID/PR Occurs

Periodic group 16

Oxygen

OH OH for aliphatic chains with

one or two C (even if connected

to aromatic fragments, used in

particular for methanol and

ethanol and their derivatives)

OH short chain 36/64 Ethanol, benzyl alcohol

OH connected to C which has

four non-hydrogen neighbors

(tertiary alcohols)

OH tert 33/63 Tert-butanol, diacetone

alcohol

OH connected to C or Si

substituted with one C or Si in an

at least three C or Si containing

chain (primary alcohols)

HO((C,Si)H

2

(C,Si)

(C,Si))

35/60 1-Nonanol,

tetrahydrofurfuryl alcohol,

ethylene cyanohydrin

OH connected to an aromatic C

(phenols)

OH (Ca) 37/62 Phenol, methyl salicylate

OH connected to a C or Si

substituted with two C or Si in a

at least three C or Si containing

chain (secondary alcohols)

HO((C,Si)

2

H(C,Si)

(C,Si))

34/61 2-Butanol, cycloheptanol

O O connected to two neighbors

which are each either C or Si

(ethers)

(C,Si)O(C,Si) 38/66 Diethyl ether, 1,4-dioxane

O in an aromatic ring with

aromatic C as neighbors

(C(a))O(a)(C(a)) 65/65 Furan, furfural

CHO CHO connected to C

(aldehydes)

CHO(C) 52/29 Acetaldehyde, benzaldehyde

C=O CO connected to two C

(ketones)

O=C (C)

2

51/30 Acetone, methyl

cyclopropyl ketone

O=C(O)

2

Non-cyclic carbonate O=C(O)

2

79/9 Dimethyl carbonate

COOH COOH connected to C COOH(C) 44/18 Acetic acid

COO HCOO connected to C (formic

acid ester)

HCOO(C) 46/21 Ethyl formate, phenyl

formate

COO connected to two C

(ester)

(C)COO(C) 45/19 Ethyl acetate, vinyl acetate

COO in a ring, C is connected

to C (lactone)

C(c)OO 47/20 -Caprolactone,

crotonolactone

(OC

2

) (OC

2

) (epoxide) (OC

2

) 39/27 Propylene oxide

COOCO Anhydride connected to two C COOCO 76/6 Acetic anhydride, phthalic

anhydride

Sulphur

SS SS (disulde)

connected to two C

(C)SS(C) 55/28 Dimethyldisulde,

1,2-dicyclopentyl-1,2-disulde

SH SH connected to C

(thiols)

SH(C) 53/49 1-Propanethiol

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 419

Table 1 (Continued)

Group Description Name ID/PR Occurs

S S connected to two C (C)S(C) 54/50 Methyl ethyl sulde

S in an aromatic ring S(a) 56/51 Thiazole, thiophene

SO

2

Non-cyclic sulfone

connected to two C

(sulfones)

(C)SO

2

(C) 82/12 Sulfolane, divinylsulfone

SCN SCN (thiocyanate) connected to C SCN(C) 81/14 Allyl isothiocyanate

Periodic group 15

Nitrogen

NH

2

NH

2

connected to either

C or Si

NH

2

(C,Si) 40/68 Hexylamine, ethylenediamine

NH

2

connected to an

aromatic C

NH

2

(Ca) 41/67 Aniline, benzidine

NH NH connected to two

neighbors which are each

either C or Si (secondary

amines)

(C,Si)NH(C,Si) 42/71 Diethylamine, morpholine

N N connected to three

neighbors which are each

either C or Si (tertiary

amines)

(C,Si)

2

N(C,Si) 43/72 N,N-dimethylaniline,

nicotine

=N aromatic =N in a

ve-membered ring

=N(a)(r5) 66/70 Piperidine, thiazole

=N aromatic =N in a

six-membered ring

=N(a)(r6) 67/69 Pyridine, nicotine

C

N C

N (cyanide)

connected to C

C

-dicyano

diethyl sulde

CONH CONH

2

(amide) CONH

2

50/22 Acetamide

CONH (monosubstituted amide) CONH 49/25 N-methylformamide,

6-caprolactam

CON (disubstituted

amide)

CON 48/26 N,N-dimethylformamide

(DMF)

OCN OCN connected to C or

Si (cyanate)

OCN 80/23 Butylisocyanate,

hexamethylene

diisocyanate

ONC ONC (oxime) ONC 75/24 Methyl ethyl ketoxime

NO

2

Nitrites (esters of nitrous

acid)

O=NO(C) 74/17 Ethyl nitrite, nitrous acid

methyl ester

NO

2

connected to aliphatic C NO

2

(C) 68/15 1-Nitropropane

NO

2

connected to

aromatic C

NO

2

(C(a)) 69/16 Nitrobenzene

NO

3

Nitrate (esters of nitric acid) NO

3

72/8 N-butylnitrate,

1,2-propanediol dinitrate

Phosphorous

PO(O)

3

Phosphates with three

substituents

PO(O)

3

73/5 Triethyl phosphate,

tris-(2,4-dimethylphenyl)

phosphate

420 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

Table 1 (Continued)

Group Description Name ID/PR Occurs

Arsine

AsCl

2

AsCl

2

connected to C AsCl

2

84/11 Ethylarsenic dichloride

Periodic group 14

Carbon

CH

3

CH

3

not connected to either N,

O, F or Cl

CH

3

(ne) 1/75 Decane

CH

3

connected to either N, O, F

or Cl

CH

3

(e) 2/73 Dimethoxymethane,

methyl butyl ether

CH

3

connected to an aromatic

atom (not necessarily C)

CH

3

(a) 3/74 Toluene, p-methyl-styrene

CH

2

CH

2

in a chain C(c)H

2

4/82 Butane

CH

2

in a ring C(r)H

2

9/83 Cyclopentane

CH CH in a chain C(c)H 5/88 2-Methylpentane

CH in a ring C(r)H 10/87 Methylcyclohexane

C C in a chain C(c) 6/90 Neopentane

C in a chain connected to at

least one aromatic carbon

C(c) (a) 8/79 Ethylbenzene, diphenylmethane

C in a chain connected to at

least one F, Cl, N or O

C(c) (e) 7/78 Ethanol

C in a ring C(r) 11/89 Beta-pinene

C in a ring connected to at

least one aromatic carbon

C(r) (Ca) 14/77 Indene, 2-methyl tetralin

C in a ring connected to at

least one N or O which are not

part of the ring or one Cl or F

C(r) (e,c) 12/80 Cyclopentanol, menthol

C in a ring connected to at

least one N or O which are part

of the ring

C(r) (e,r) 13/81 Morpholine, nicotine

=C(a) Aromatic =CH =C(a)H 15/76 Benzene

Aromatic =C not connected to

either O, N, Cl or F

=C(a) (ne) 16/86 Ethylbenzene, benzaldehyde

Aromatic =C with three

aromatic neighbors

(a)=C(a) 2(a) 18/85 Naphthalene, quinoline

Aromatic =C connected to

either O, N, Cl or F

=C(a) (e) 17/84 Aniline, phenol

C=C H

2

C=C (1-ene) H

2

C(c)=C 61/33 1-Hexene

C=C (both C have at least one

non-H neighbor)

C(c)=C(c) 58/38 2-Heptene, mesityl oxide

Non-cyclic C=C connected to

at least one aromatic C

C(c)=C(c) (C(a)) 59/35 Isosafrole, cinnamic alcohol

Cyclic C=C C(r)=C(r) 62/36 Cyclopentadiene

Non-cyclic C=C

substituted with at least

one F, Cl, N or O

(e)C(c)=C(c) 60/34 Trans-1,2-dichloroethylene,

peruoroisoprene

C

C HC

C (1-ine) HC

C 64/32 1-Heptyne

C

C C

C 63/37 2-Octyne

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 421

Table 1 (Continued)

Group Description Name ID/PR Occurs

Silicon

Si Si Si 70/53 Butylsilane

Si Si connected to at least

one O, F or Cl

Si (e) 71/52 Trichlorosilane,

hexamethyl disiloxane

Germanium

Ge Ge connected to four

carbons

(C)

2

Ge (C)

2

86/43 Tetramethylgermane

GeCl

3

GeCl

3

connected to

carbons

GeCl

3

85/7 Fluorodimethylsilyl-

(trichlorogermanyl)methane

Stannium

Sn Sn connected to four

carbons

(C)

2

Sn (C)

2

83/40 Tetramethylstannane

Periodic group 13

Bor

B(O)

3

Non-cyclic boric acid ester B(O)

3

78/10 Triethyl borate

Excluded groups

OCON Carbamat OCON 1/1 N-propylcarbamate

CO(NH

2

)

2

Urea and derivatives CO(NH

2

)

2

1/2 Urea

CCOCOC Neighboring keto groups CCOCOC 1/3 2,3-Butanedione

Imidazol Imidazol Imidazol 1/4 Imidazol

Abbreviations: e, very electronegative neighbors (N, O, F, Cl); ne, not very electronegative neighbors (not N, O, F, Cl); a, aromatic

atom or neighbor; c, atom or neighbor is part of a chain; r, atom or neighbor is part of a ring.

regarded as very reliable. In addition, molecular structures for approximately 16000 components were

stored in form of connection tables, so that the molecules may easily be fragmented into groups by the

automatic procedure described before. The components in the DDB comprise a set of substances for

which experimental thermophysical data are available in literature and which are therefore of importance

to science or industry. The frequency of occurrence of the individual structural groups and second-order

corrections in a database of 2550 components is given in Tables 2 and 4, respectively.

4.4. Regression of the group constants

For the simultaneous regression of the model parameters, a special algorithm was developed consisting

of an inner and outer regression loop. In the outer loop, the coefcients a, b and c are optimized in order

to minimize the mean absolute deviation in normal boiling temperature times the square of the standard

deviation with the help of a non-linear regression using a simplex algorithm. Using this, rather uncommon

objective function decreases the number of large deviations while leading to a slightly increased mean

deviation. The inner loop incorporates a multilinear least squares regression of the equations:

i

N

i,j

C

i,j

= T

b,j

(n

b

j

+c) a (for all components j) (8)

422 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

Table 2

Group contributions, number of components used for regressing these values and mean absolute deviation in temperature for

these components

Group Group Mean Standard Mean Standard Number of

number contribution absolute deviation absolute deviation components

(K) error (%) (%) error (K) (K)

1 188.555 1.71 2.42 7.42 10.69 1468

2 282.015 2.3 3.02 9.67 13.11 199

3 176.705 2.01 2.78 9.63 13.41 153

4 250.119 1.58 2.26 7.24 10.66 956

5 260.938 1.48 2 6.83 10.11 310

6 273.544 2.15 2.83 8.56 11.37 66

7 278.135 2.14 3.42 8.97 14.35 820

8 210.93 1.5 2.12 7.85 11.71 124

9 246.871 2.07 2.77 8.71 11.65 270

10 241.804 1.55 2.11 6.84 9.43 137

11 265.032 1.72 2.15 7.47 9.24 35

12 264.839 1.95 4.01 8.05 14.93 67

13 304.422 2.49 3.26 10.32 13.21 64

14 281.964 1.73 2.22 9.07 11.52 22

15 245.521 2.32 3.4 11.73 17.5 558

16 322.825 2.08 2.99 10.57 15.65 421

17 377.988 2.79 3.94 13.88 19.82 247

18 386.361 1.68 2.28 9.81 13.89 65

19 129.511 1.95 2.72 6.58 9.44 38

20 73.5088 2.92 4.31 6.69 9.29 9

21 65.9125 2.95 5.04 9.58 15.07 132

22 111.411 2.36 3.24 7.12 9.63 21

23 144.464 3.95 5.7 9.38 12.9 3

24 21.348 2.35 2.78 9.04 10.85 25

25 327.158 2.01 2.89 8.58 12.59 108

26 300.288 1.73 2.23 6.66 8.63 47

27 275.233 2.79 3.98 10.37 14.3 55

28 204.105 2.1 2.75 10.2 13.55 63

29 299.52 1.69 2.21 5.87 7.79 34

30 427.56 2.23 2.94 8.45 11.31 65

31 351.895 1.36 1.85 6.51 8.83 21

32 564.102 1.89 2.35 7.71 9.73 28

33 401.033 1.97 2.81 8.51 11.66 43

34 411.08 1.81 2.43 8.31 11.4 73

35 477.583 2.33 3.1 11.04 14.65 68

36 515.544 2.47 3.01 10.6 12.65 65

37 354.061 3.28 4.05 16.86 21.4 63

38 158.793 2.11 3.14 8.91 13.31 283

39 861.138 2.18 2.66 8.88 11.24 15

40 361.207 2.31 2.97 9.44 12.75 51

41 468.458 2.04 2.83 11.29 15.96 31

42 259.446 2.18 2.93 9.21 12.04 58

43 121.99 2.76 3.54 11.66 15.7 41

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 423

Table 2 (Continued)

Group Group Mean Standard Mean Standard Number of

number contribution absolute deviation absolute deviation components

(K) error (%) (%) error (K) (K)

44 1124.49 1.88 2.87 9.67 14.46 63

45 697.228 2.16 3.01 10.41 15.38 203

46 712.76 1.4 2.11 6.03 9.17 19

47 1230.21 4.76 6.46 20.25 27.66 5

48 1058.87 1.94 2.57 9.28 12.12 10

49 1323.88 2.72 3.29 14.71 17.99 8

50 1479.27 1.78 2.28 8.76 11.21 5

51 654.008 3.12 4.96 12.98 20.17 89

52 626.216 3.24 4.6 14.97 21.69 42

53 459.247 1.37 1.71 5.22 6.35 44

54 479.985 1.43 1.9 6.14 8.41 33

55 874.273 0.94 1.29 3.66 5.09 4

56 309.872 2.1 2.82 9.27 12.6 18

57 804.356 3.05 3.87 14.38 18.51 41

58 516.817 1.66 2.27 6.66 9.37 117

59 607.968 2.37 2.62 12.51 13.81 12

60 521.597 1.74 2.33 6.31 8.58 29

61 437.399 1.95 2.71 7.2 9.82 182

62 507.998 2.56 3.48 10.59 14.21 76

63 556.785 1.19 2.01 4.98 8.34 23

64 468.03 1.74 2.24 5.79 7.7 23

65 79.2981 2.81 3.88 12.68 17.51 11

66 430.782 3.47 4.4 15.37 19.55 15

67 282.737 2.64 4.15 12.39 19.82 36

68 907.229 10.26 16.5 40.71 65.72 9

69 775.752 5.59 7.03 28.47 35.49 37

70 294.323 1.42 2.19 4.9 7.16 33

71 219.416 2.98 4.47 10.47 13.55 70

72 964.373 0.93 1.18 3.79 4.85 6

73 1267.28 2.39 3.02 11.84 14.97 6

74 532.35 0.62 0.78 1.91 2.43 7

75 1082.68 1.95 2.51 8.64 10.9 9

76 1431.22 5.47 6.35 26.53 30.48 7

77 837.687 1.41 1.8 5.99 7.74 18

78 594.43 0.96 1.37 4.14 5.72 7

79 911.983 0.88 1.08 3.65 4.34 4

80 671.441 5.5 7.27 24.7 32.57 14

81 1002.53 1.85 2.29 8.21 10.26 5

82 1502.35 2.4 2.95 13.34 16.46 5

83 525.228 0.33 0.45 1.28 1.76 3

84 1173.13 0.43 0.59 1.97 2.7 6

85 1280.52 1

86 301.028 1

424 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

Table 3

Second-order contributions for normal boiling points

Name Description ID Occurs

Para pair(s) Para positioncounted only once and

only if there are no meta or ortho pairs

87 p-Xylene

Meta pair(s) Meta positioncounted only once and

only if there are no para or ortho pairs

88 m-Xylene

Ortho pair(s) Ortho positioncounted only once and

only if there are no meta or para pairs

89 o-Xylene

Five-ring A ve-membered non-aromatic ring 90 Cyclopentane

Three/four-ring A three- or four-membered non-aromatic ring 91 Cyclobutene

One hydrogen Component has one hydrogen 92 Nonauorobutane

No hydrogen Component has no hydrogen 93 Peruoro compounds

The main advantage of this algorithm is, that only three parameters need to be regressed using the slow

non-linear method while the large number of group increments is calculated from the fast multilinear

least squares regression. The objective function in linear regression is always the mean squared deviation

between calculated and experimental value. Partial derivation of the objective function with respect to

the n coefcients (in this case, the n individual group contributions) leads to n linear equations. At the

minimumof the objective function, all partial derivatives have to be zero. This leads to a set of n equations

with n unknowns, which can readily be solved, e.g. by the well known GaussJordan elimination. The

set of linear equations leads to exactly one solution provided all columns and rows in the coefcient

matrix are linear independent, which can be analyzed by singular value decomposition. In this work, the

ratio of experimental data (normal boiling temperatures) to adjustable parameters is about 26.61 and the

resulting matrix is not close to singular.

Once the coefcients are available from the linear regression, the mean absolute deviation in T

b

and the

squared standard deviation are calculated and their product is returned to the outer loop. Initial estimates

are only required for a, b and c, which are regressed in the outer loop. A full regression of 96 parameters

(a, b, c, 87 group contributions and six second-order corrections) to 2550 experimental normal boiling

temperatures, thus, requires only a few minutes on a regular PC. We experienced no problems with

Table 4

Second-order contributions, number of components used for regressing these values and mean absolute deviation in temperature

for these components

Group

number

Group

contribution

Mean

absolute

error (%)

Standard

deviation

(%)

Mean

absolute

error (K)

Standard

deviation

(K)

Number of

components

87 37.5096 2.87 4.29 14.31 21.8 81

88 3.5994 2.47 3.83 11.79 18.49 77

89 44.8024 2.85 3.82 14.53 19.52 77

90 27.0458 2.06 2.85 8.88 12.42 134

91 39.0849 3.18 5.3 11.14 17.74 50

92 131.323 2.34 3.36 7.64 11.69 36

93 167.799 3.48 7.18 11.58 24.73 97

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 425

local minima. To verify the algorithm, the nal parameters were used as starting values for a non-linear

regression of all parameters to the experimental data using the commercial GRG2 algorithm (Frontline

Systems, Inc., Incline Village, NV, USA). No further improvement was achieved.

4.5. Test of the predictive capability

In order to test the predictive capability of the method, experimental normal boiling temperatures for

126 components not in the database used for regression were compared with the predicted values. This

lead to a mean absolute deviation in temperature of 8.9 K (35.3 K for the Joback method, 13.1 K for Stein

and Brown, 14.5 Kfor Constantinou and Gani, and 12.3 Kfor Marrero-Morejon and Pardillo-Fontdevila).

5. Results and discussion

The results for the different group contribution methods were carefully analyzed to detect any possible

weaknesses of the new method compared to the other methods and to identify typical components for

which to expect extraordinary large deviations.

As the most important criterion for the reliability of a model the probability of a prediction failure

(extreme deviation between experimental and estimated value) was chosen. Fig. 6 shows a plot of the

part of the data with a deviation larger than a certain temperature versus the deviation in temperature.

Calculations are based on a common set of 1863 components, for which the normal boiling point can

be estimated by all models except that of Marrero-Morejon and Pardillo-Fontdevila. Including the latter

Fig. 6. Part of the data with deviations larger than a given temperature.

426 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

Table 5

Deviations of the models for different types of hydrocarbons

Components Number of

components

This work Joback and

Reid [3]

Stein and

Brown [4]

Constantinou

and Gani [2]

Marrero-Morejon

and Pardillo-

Fontdevila [5]

n-Alkanes 27 6.5 55.7 12.1 18.7 13.6

Alkanes (non-cyclic) 166 6.5 26.7 15.2 8.9 7.7

Alkanes (cyclic) 65 7.1 8.9 8.6 6.2 17.3

Aromatic hydrocarbons 112 9.4 24.3 10.7 15.7 8.3 (70)

Alkenes (HC) 167 7.4 9.4 7.7 6.0 17.8 (123)

Alkenes (cyclic C=C) (HC) 38 9.4 8.1 8.2 6.7 16.0 (24)

Alkines (HC) 33 5.4 13.1 12.1 13.5 3.8 (31)

Hydrocarbons 568 7.4 17.7 10.8 9.5 11.6 (457)

HC denotes that the components taken into account only contain the elements C and H. The numbers in brackets for the method

of Marrero-Morejon and Pardillo-Fontdevila specify the number of components to which the method was applicable.

method would have further reduced the number of components in this test signicantly. It can be seen,

that in case of the new method, only 8% of the data are estimated with a deviation larger than 20 K.

The other models range between 17% (Stein and Braun) and 36% (Constantinou and Gani). Only 14

components (0.75%) exhibited a deviation larger than 50 K. The other models range between 3.6 and

9.7%. The reasons for these failures will be discussed later. First, the behavior of the different models is

compared for different classes of compounds.

5.1. Hydrocarbons

A comparison of the different models is given in Table 5. While the new model yields small deviations

(less than 10 K) for all classes of components, in some cases the method of Constantinou and Gani

gives slightly better results. This is due to the larger number of parameters. In this work, only four

different types of alkene groups are used compared to six groups plus three second-order groups in the

ConstantinouGani method. The use of more than twice the number of parameters results in only minor

improvements. The method of Marrero-Morejon and Pardillo-Fontdevila gives, especially good results

for alkines. In case of aromatic hydrocarbons, the range of applicability is signicantly smaller (70 instead

of 112 components), which may be a reason for the good results.

Especially, large deviations (T

b,exp

T

b,calc

) were found for the following components:

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 427

5.2. Alkanols

Table 6 gives a comparison of the different models for various types of alkanols. For all 343 components,

the newmodel gives the lowest mean deviation. In case of n-alkanols and primary and secondary alkanols

the method of Stein and Brown gives slightly better results. This is due to the greater exibility of the

polynomial linearization. As shown in Fig. 7, up to about C

7

the increase of normal boiling temperature

with molecular weight is over-predicted by the new model. Especially, high deviations are found for

alkandiols, whereby geminal diols show no special behavior. If the correction function

T

b,corr

= T

b,calc

+39.3 5.26n

C

(n

C

, number of carbon atoms) (9)

is applied, the mean deviation reduces to 5.2 K (not taking into account ethanediol).

Table 6

Deviations of the models for different types of alkanols

Components Number of

components

This work Joback and

Reid [3]

Stein and

Brown [4]

Constantinou

and Gani [2]

Marrero-Morejon

and Pardillo-

Fontdevila [5]

n-Alkanols 21 10.6 29.8 7.9 11.3 17.5

Aliphatic alkanols 110 7.3 23.6 12.1 10.3 15.7 (103)

Primary alkanols 36 8.5 20.8 7.1 10.7 15.1

Secondary alkanols 35 6.0 27.7 5.3 10.7 14.7

Tertiary alkanols 21 6.4 37.9 7.0 18.1 19.1 (14)

Alkandiols 15 15.6 (5.2) 28.9 23.3 23.9 14.3

Alkanols (HC) 343 7.5 22.5 12.5 10.6 9.9 (301)

HC denotes that the components taken into account only contain the elements C and H in addition to one or more OH-groups.

The numbers in brackets for the method of Marrero-Morejon and Pardillo-Fontdevila specify the number of components to

which the method was applicable.

428 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

Fig. 7. Calculated vs. experimental normal boiling points of n-alkanols.

5.3. Other oxygenated compounds

A comparison of the different models is given in Table 7. Deviations for the new model are amongst

the lowest achieved by the different models. The method of Marrero-Morejon and Pardillo-Fontdevila

gives exceptionally good results for aldehydes.

Table 7

Deviations of the models for different types of oxygenated hydrocarbons (except alkanols)

Components Number of

components

This work Joback and

Reid [3]

Stein and

Brown [4]

Constantinou

and Gani [2]

Marrero-Morejon

and Pardillo-

Fontdevila [5]

Ethers (HC) 85 4.7 10.7 6.7 11.1 5.0 (82)

Epoxides (HC) 9 8.6 19.9 16.2 30.9 6.31 (7)

Aldehydes (HC) 17 9.9 9.8 6.3 7.8 3.0 (16)

Ketones (HC) 43 6.9 13.3 7.4 8.8 7.0 (38)

Non-cyclic carbonates (HC) 4 3.7 25.1 49.7 3.5 5.5 (4)

Carboxylic acids (HC) 32 5.7 30.2 6.0 16.4 9.3

Esters (not CHO

2

)(HC) 120 9.2 34.2 9.0 9.6 13.4 (101)

HC denotes that the components taken into account only contain the elements C and H in addition to one or more groups

containing oxygen. The numbers in brackets for the method of Marrero-Morejon and Pardillo-Fontdevila specify the number of

components to which the method was applicable.

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 429

Table 8

Deviations of the models for different types of halogenated hydrocarbons

Components Number of

components

This work Joback and

Reid [3]

Stein and

Brown [4]

Constantinou

and Gani [2]

Marrero-Morejon

and Pardillo-

Fontdevila [5]

Fluorinated saturated hydrocarbons 52 5.4 16.9 64.3 25.6 10.1 (51)

Fluorinated hydrocarbons 74 6.7 16.8 50.3 26.6 9.6 (71)

Chlorinated saturated hydrocarbons 55 8.5 27.6 12.6 9.3 13.9 (51)

Chlorinated hydrocarbons 88 7.7 23.0 12.5 10.1 13.5 (80)

Brominated saturated hydrocarbons 31 7.6 16.9 10.3 8.0 14.9 (22)

Brominated hydrocarbons 47 8.2 14.6 10.1 8.4 14.6 (33)

Iodinated saturated hydrocarbons 17 5.7 14.7 8.8 8.1 13.4 (14)

Iodinated hydrocarbons 20 5.9 13.7 8.1 7.2 11.7 (17)

The numbers in brackets for the method of Marrero-Morejon and Pardillo-Fontdevila specify the number of components to

which the method was applicable.

5.4. Halogenated hydrocarbons

A comparison of the different models is given in Table 8. In all cases, the proposed model gives the

lowest deviation, which is probably due to a stronger differentiation in the structural groups and the large

set of data used in the regression.

5.5. Isomer differentiation

The method developed here was mainly focused on covering a broad range of components also, e.g.

including germanium, silicon, tin and phosphor and very different in size. For non-cyclic saturated

hydrocarbons, only four different groups are used and a correct differentiation between alkane isomers

cannot be expected. For a list of 18 different octane-isomers, an average error of 5.1 K was obtained,

3.3 K for the method of Constantinou and Gani and 2.7 K for Marrero-Morejon and Pardillo-Fontdevila.

The latter two methods use 9, resp. 10 parameters for non-cyclic saturated hydrocarbons.

5.6. Compounds for which large deviations are observed

Although the group contribution approach for the calculation of normal boiling temperatures generally

leads to good results, the assumption of simple additivity is not always valid.

In cases, where a strong inductive effect inuences a mesomeric system, the molecule has a rather

high dipole moment or polarizability. In these cases, the estimated normal boiling temperature is sig-

nicantly too low. Typical examples are: 4-hydroxybenzaldehyde (T

b,est

= 583.20 K, T

b

= 523.78 K);

4-dimethylaminobenzaldehyde (T

b,est

= 529.86 K, T

b

= 588. K); 4-nitroaniline (T

b,est

= 551.53 K,

T

b

= 607. K); 1,4-dihydroxybenzene (T

b,est

= 512.35 K, T

b

= 558.5 K); and resorcinol (T

b,est

= 554.55 K,

T

b

= 506.16 K).

Generally, the inuence of a larger number of strong I- or M-effects on mesomeric systems may lead

to high deviations as in 2,4,6-trinitrotoluene (T

b,est

= 624.60 K, T

b

= 573.0 K), and 2,4,6-trinitrophenol

(T

b,est

= 654.12 K, T

b

= 597.0 K).

430 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

Table 9

Estimation of the normal boiling temperature (K) of ethylbenzene

Component: ethylbenzene; number of atoms: 8

Group Atoms Frequency Contribution Total

1 (CH

3

(ne)) 1 1 188.555 188.555

8 ( C(c) (a)) 2 1 210.930 210.93

15 (=C(a)H) 48 5 245.521 1227.605

16 (=C(a) (ne)) 3 1 322.825 322.825

Sum 1949.915

T

b

=

1949.915

8

0.6713

+1.4442

+59.344 = 414.98 (remark : atom2 is matched by the group C(c) (a) as the group C(c)H

2

Table 10

Estimation of the normal boiling temperature (K) of 1,1,2,2,-tetraphenylethane

Component: 1,1,2,2,-tetraphenylethane; number of atoms: 26

Group Atoms Frequency Contribution Total

8 ( C(c) (a)) 1, 2 2 210.930 421.860

15 (=C(a)H) 48, 1014, 1620, 2226 20 245.521 4910.420

16 (=C(a) (ne)) 3, 9, 15, 21 4 322.825 1291.300

Sum 6623.580

T

b

=

6623.580

26

0.6713

+1.4442

+59.344 = 699.05.

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 431

Table 11

Estimation of the normal boiling temperature (K) of N-methyl-pyrrolidon

Component: N-methyl-pyrrolidon; number of atoms: 7

Group Atoms Frequency Contribution Total

2 (CH

3

(e)) 7 1 282.015 282.015

9 (C(r)H

2

) 3, 4 2 246.871 493.742

13 ( C(r) (e,r)) 2 1 304.422 304.422

48 (CON ) 1, 5, 6 1 1058.87 1058.87

90 (ve-ring) 15 1 27.0458 27.0458

Sum 2112.0032

T

b

=

2112.0032

7

0.6713

+1.4442

+59.344 = 470.508.

A phenyl-group can be sterically hindered, so that the electron system in hardly available for inter-

molecular interaction as in the case of 1,1,2,2-tetraphenylethane (T

b,est

= 699.07 K, T

b

= 633.0 K).

Generally, results for molecules showing an extraordinary number of functional groups should be used

only with great care. This is true for all group contribution methods.

In some cases, the pure component can rather be regarded as a mixture of tautomers. A typical ex-

ample is found in case of -alkoxy-ketones: 2-butoxy-3-hexanone (T

b,est

= 421.73 K, T

b

= 494.44 K);

2-butoxy-3-pentanone (T

b,est

= 409.06 K, T

b

= 475.94 K); and 2-butoxy-3-butanone (T

b,est

= 400.62 K,

T

b

= 456.22 K).

These examples show, that the relatively few cases of high deviations can usually be contributed to

signicant sterical or electronic effects. Yet, these are not easy to integrate into a group contribution

method, where the only required input for a property estimation should be the molecular structure.

6. Examples

To illustrate the application of the proposed method, detailed procedure for the estimation of T

b

is given

for ethylbenzene, tetraphenylethane and N-methyl pyrrolidon in Tables 911.

7. Conclusion

A group contribution method for the estimation of the normal boiling point of non-electrolyte organic

compounds was developed. The predictions are based exclusively on the molecular structure of the

compound. The results of the newmethod are in most cases far more accurate and never signicantly worse

432 W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433

than previous methods. Structural groups were dened in a standardized formand the fragmentation of the

molecular structures was performed by an automatic procedure to eliminate any arbitrary assumptions.

Second-order corrections were limited to those cases, in which larger structures or structural ef-

fects could not be dened as structural groups (e.g. o-, m- and p-positions at rings, three-, four- and

ve-membered rings and molecules with only one or two hydrogen atoms).

Structural groups were usually dened including the neighboring atoms, thus, implementing knowledge

about the electronic structure in the respective context.

Currently, the database for normal boiling points is extended. In case where only low pressure data

are available, these are used for extrapolation. Once, a signicant amount of new data is available, the

method will be updated and further extended.

In addition, work has started to use the same approach for the prediction of other pure component

properties.

List of symbols

a, b, c adjustable parameters

A, B, C adjustable parameters

B second virial coefcient

H enthalpy

k Boltzmann constant

M molar mass

r distance from center of molecule

R gas constant

S entropy

T absolute temperature

V volume

Greek letters

density

(r) function for the intermolecular potential

Subscripts

b boiling

est estimated

free available for translation

vap vaporization

Superscripts

L liquid

V vapor

References

[1] J.M. Prausnitz, R.N. Lichtenthaler, E.G. de Azevedo, Molecular Thermodynamics of Fluid Phase Equilibria, 3rd Edition,

Prentice-Hall, Upper Saddle River, 1999.

W. Cordes, J. Rarey / Fluid Phase Equilibria 201 (2002) 409433 433

[2] L.R. Constantinou, R. Gani, AIChE J. 40 (10) (1994) 16971710.

[3] K.G. Joback, R.C. Reid, Chem. Eng. Commun. 57 (1987) 233243.

[4] S.E. Stein, R.L. Brown, J. Chem. Inf. Comput. Sci. 34 (1994) 581587.

[5] J. Marrero-Morejon, E. Pardillo-Fontdevila, AIChE J. 45 (3) (1999) 615621.

[6] Aldrich Handbook of Fine Chemicals, Aldrich Chemical Co., Milwaukee, WI, 1990.

[7] J. Graselli (Ed.), Handbook of Data of Organic Compounds (HODOC), CRC Press, Boca Raton, FL, 1990.

[8] B.I. Lee, M.G. Kesler, AIChE J. 21 (1975) 510527.

[9] W. Cordes, J. Rarey, F. Delique, J. Gmehling, in: D. Ziessow (Ed.), Software Development in Chemistry, in: Proceedings of

Computer in der Chemie, Vol. 7, Springer, Berlin, 1993.

- AP Statistics Practice ExamUploaded byldlewis
- Binary Distillation ManualUploaded byMico Anonuevo
- sweetening LPG with AminesUploaded bysizweh
- A Fast Method To Calculate Residue Curve MapsUploaded byMario Arturo Martínez Cruz
- Humidity HandbookUploaded byPedro Dutra
- Term PaperUploaded byTaufiq Us Samad Tonmoy
- EquationOfState-DerivativesOfPRUploaded byDhaval Dave
- Vessel DesignUploaded byihllhm
- Lect36 42 GibbsUploaded byCamarada Rojo
- VLE Consistency PitfallsUploaded bysnikt7863443
- Desti Las i AlkoholUploaded byDavid Lambert
- BASICapricot kernel oil.pdfUploaded byananth2012
- kardos1986 - Void growth and resin transport during processing of thermosetting matrix composites.pdfUploaded byDaniel Maldonado Forin
- Class Notes Sessions5-6Uploaded bywasimjeens
- TEG paperUploaded byMuhammad Atif
- Condensate Recovery by Cycling at DecliningUploaded bypetroleumgirl
- Solved Problems in Heat TransferUploaded byAngelica Joyce Benito
- 140990105009_vle & diff dist.pptxUploaded byChintan Modi
- Fluid Mechanics (3)Uploaded byAhmedTaha
- Www.unitoperation Th1Uploaded bymahendra shakya
- Salvioli et al 2015Uploaded byfreetime8334
- 8 SolUploaded byRuan Pretorius
- CHT-08_No.-183Uploaded byknight282009
- LecUploaded byAakanksha Mahajan
- botanical analysis.pdfUploaded bynewnomi
- Abstrak 9 Dwi SuUploaded byNur Fitria Azizah
- Msc_Stistic_Syllabus_2016_17 Batch.pdfUploaded byHarshil Dave
- 12th Footnotes Abstract and ConclusionUploaded byVarsha Gupta
- Distillation BPUploaded byRungtiwa Morasuk
- 101399 ID Pengaruh Kualitas Produk Harga Dan Promo 1Uploaded bydian

- Example15.8Uploaded bycymy
- Counter Current Heat Exchanger CarnahanUploaded bycymy
- Live Solution Tank ExampleUploaded bycymy
- Installed Flow CharacteristicsUploaded bycymy
- Example15.4aUploaded bycymy
- Heat Transfer FinUploaded bycymy
- Problem 10.9bUploaded bycymy
- Problem 8.6 BubbleUploaded bycymy
- Example 8.5a (Vapor Ethane)Uploaded bycymy
- Problem 8.6 dewUploaded bycymy
- Problem 8.6 L (160.67F)Uploaded bycymy
- Example 7.7aUploaded bycymy
- Example 7.7cUploaded bycymy
- Figure 6.3Uploaded bycymy
- Example 6.16aUploaded bycymy
- Example 6.19aUploaded bycymy
- Example 9.7aUploaded bycymy
- Example 8.6c (Vapor Condenser)Uploaded bycymy
- Example 7.4.xlsUploaded bycymy
- Example 2.14Uploaded bycymy
- Example 2.16 aUploaded bycymy
- Example 2.16 bUploaded bycymy
- Example 2.17 bUploaded bycymy
- Example 2.17 aUploaded bycymy
- Problem 4.10Uploaded bycymy
- Problem 4.7aUploaded bycymy
- Example 5.6aUploaded bycymy
- Example 5.3cUploaded bycymy

- Romanian Journal of Mineral Deposits Vol 85 Issue 1Uploaded byTzontonel
- Evaluation of Oxygen Transfer Efficiency.pdfUploaded byAlvaro Huete
- Parameters influencing boiler efficiencyUploaded byJohn Ngwoke
- Comparative Analysis of Three Commercial Saliva TeUploaded byattique_1
- 49B.docxUploaded byJamie Schultz
- Heat ExchangerUploaded byPutra Kusuma Hardito
- FluidsUploaded byHizbar Arsjad
- Conic Flow Series Silencers SpecificationsUploaded by1mmahoney
- Bbc_ Chemistry Projects on Tensile Strength of Fibres, And Quantity of Casein in Differnt Samples of MilkUploaded byAnonymous 6BtBT1Rk1
- Bab Bahasan Buku QasimUploaded byRd Nur Muhammad
- Adhesive Anchor ExamplesUploaded byJosue Lewandowski
- Aerator Indofab IndustriesUploaded byRahul Kalathil
- Chap12 - Compressed Air (1)Uploaded byManjunath Hrm
- (Popular Science) Nick Lane-Oxygen. The Molecule that Made the World-Oxford University Press (2004).pdfUploaded byStephanie L. McCampbell
- AnicutUploaded byRohit Adhikari
- motores DE12, DE12T, DE12TI DE12TIE.pdfUploaded byhecazorla
- Electroactive Polymers as Artificial Muscles – Reality and ChallengesUploaded byq12werty
- Chapter 24 ProblemsUploaded bylynette-wu
- Controlled Osmotic Pump for DiclofenacUploaded byvidur_sarma
- LAB - EMM3514 - 06 - THERMAL - TRANSIENT HEAT TRANSFER.pdfUploaded byAnonymous KCfPEg
- Pneumatic Conveying SYSTEMUploaded byShukla Suyash
- Ads or PtionUploaded byseran
- 0064_SiberianGinseng_ApplicationNote_pw.pdfUploaded byFábio Teixeira da Silva
- Duracell Silver Oxide BatteriesUploaded byRoger Babineau
- ATF-ExplosiveMaterialsUploaded byPATRIOTSKULLZ
- D. van Oosten, P. van der Straten and H.T.C. Stoof- Quantum phases in an optical latticeUploaded byKiomax
- CcdUploaded byGian Pesantes
- Types of PollutionUploaded byShah Jee
- QuestionUploaded byDiong Jayhuey
- Enzyme (1)Uploaded bycrazymax90