Hydrogen Sulfide Solubility in Weak Electrolyte Solutions

Thermodynamic Modeling of
Hydrogen Sulfide Solubility in Weak

Electrolyte Solutions

Master Thesis

The Technical University of Denmark

Date of delivery: 31
st
of January 2008

Asger Lindholdt (s021870)

Supervisor: Kaj Thomsen

Problem formulation

I

Problem formulation
The title of the projects is: Thermodynamic Modeling of H
2
S in Weak Electrolyte
Solutions.
The project consists of a theoretical and practical part where the systems H
2
S, H
2
S-H
2
O,
H
2
S-H
2
O-NH
3
and H
2
S-H
2
O-CO
2
are treated.
Theoretical part
The theoretical part consists of a literature study with focuses on vapor-liquid equilibrium
(VLE) and gas hydrate formation for the treated systems. General gas hydrate theory
and thermodynamic modeling of gas hydrate formation described by Munck (1988) with
emphasis on hydrogen sulfide is described. The Extended UNIQUAC model is
described. Phase diagrams are described with emphasis on the H
2
S and H
2
S-H
2
O
systems.
Practical part
The practical part consists of estimating parameters for hydrogen sulfide in the gas
hydrate model and estimating parameters for hydrogen sulfide species in the Extended
UNIQUAC for the systems H
2
S, H
2
S-H
2
O, H
2
S-H
2
O-NH
3
.
Time schedule and content of status reports
The project starts the 3
rd
of September 2007 and is to be handed in the 31
st
of January
2008. Through out the period of the project three status reports are to be handed in.
Status report 1
The date of delivery is the 12
th
of October. A literature survey is carried out with focuses
on the H
2
S and H
2
S-H
2
O systems. A general description of gas hydrates, modeling of
gas hydrate formation and VLE for the H
2
S and H
2
S-H
2
O systems are described. The
Extended UNIQUAC model and the article Computations of the formation of gas
hydrates by Munck (1988) are described.
Status report 2
th
of November. The parameter estimation in the gas
hydrate model and the Extended UNIQUAC is estimated for H
2
S and HS
-
by using
experimental data from the systems H
2
S and H
2
S-H
2
O. The Langmuir constants in the
Problem formulation

II

gas hydrate model are estimated for H
2
S and for the Extended UNIQUAC model the
volume, surface and interaction parameters are estimated for the H
2
S species.
Status report 3
th
of January. The parameter estimation in the Extended
UNIQUAC model is carried out for the H
2
S species in the systems H
2
S-H
2
O-NH
3
and
H
2
S-H
2
O-CO
2
.
Preface

III

Preface

This thesis of 30 ECTS points is submitted as partial fulfillment of the requirements for
the Masters degree at the Technical University of Denmark. The work was carried out at
the Department of Chemical Engineering, from September 2007 to January 2008 under
the supervision of Associate Professor Kaj Thomsen.
This thesis deals with thermodynamic modeling and a standard graduate course in
thermodynamics should be sufficient to easily understand the major contents of the
report. The different chapters can be read independently, but in most cases the best
understanding is obtained when the previous chapters have been read.
In this work the references used are presented by their last name and year of
publication. The complete reference is then found in the list of references, which is at the
end of the thesis.
I thank my supervisor for guidance as well as all the time he used to discuss matters
concerning my project.
I would also like to thank Post Doc. Philip L. Fosbl for helping me with the thesis and
my friend Kristian E. Nrgaard for assisting in the proof reading process.

Lyngby, January, 2008

Asger Lindholdt
Abstract

IV

Abstract

The Extended UNIQUAC model and the SRK EoS were successfully applied to the
systems H
2
S, H
2
S-H
2
O, H
2
S-H
2
O-gas hydrates, and H
2
S-H
2
O-NH
3
. Extended UNIQUAC
parameters for H
2
S and HS
-
were successfully estimated in the systems H
2
S, H
2
S-H
2
O,
H
2
S-H
2
O-NH
3
.
Langmuir constants in the gas hydrate model presented by Munck (1988) were
estimated for H
2
S. The gas hydrate model, the Extended UNIQUAC model and the SRK
EoS were applied and successfully correlate the experimental data points found in the
literature for the system H
2
S-H
2
O where gas hydrates are present.
A major review of the open literature for the systems H
2
S, H
2
S-H
2
O (with and without
gas hydrates), H
2
S-H
2
O-NH
3
, and H
2
S-H
2
O-CO
2
were carried out. The review includes
collection of a large amount of experimental data and a presentation of the most
important VLE models. A presentation of the differences between the gas hydrate model
presented by Munck (1988) and other authors in the open literature are presented.

Nomenclature

V

Nomenclature
Notation
Symbol Explanation Unit
A Avogadros number mol
-1
A Debye-Hckel parameter kg
1/2
mol
1/2
A, B Langmuir parameters K
b Constant kg mol
-1

C Chemically independent
number of components
-
C Langmuir adsorption
constant
-
C
p
Heat capacity difference
CP Pure component critical
point
-
d Density kg m
-3

f Fugacity Pa
1
f ,
2
f Functions in Pitzers
equation
-
F Degrees of freedom -
F Faradays constant C mol
-1

H Hydrate -
H Enthalpy difference J
I Ionic strength mol kg water
-1

I Ice -
K Three-phase critical end
point
-
L
A
Aqueous liquid -
L
S
H
2
S-rich liquid
m Molality mol kg water
-1

M Molecular weight Mol kg
-1

n Number of moles mol
P Pressure Pa
P Number of phases -
Q Quadruple point -
R Universal gas constant
-1 -1
J mol K
S Solid -
T Temperature K
TP Pure component triple
point

V Molar volume of water
(ice or liquid)
m
3
mol
-1

V Volume difference m
3
Y Probability of a filled
cavity
-
Nomenclature

VI

Z Coordination number -

Greek letters
Symbol Explanation Unit
( ) ( ) 0 1
,
Binary interaction parameters in
Pitzers equation
-
r
Relative permittivity -
0
Vacuum permittivity C
2
J
-1
m
-1

Mathematical constant -
Standard deviation -
Ternary interaction parameters

Chemical potential J
Number of cavities -

Activity coefficient -
Subscripts
Symbol Explanation
A Aqueous Liquid
C Combinatorial
i Type of cavity
K Component
L Large cavity
m molar
0 Reference temperature
273.15 K
R Residual
S Small cavity
S Sulfide rich liquid
w Water
Superscripts
Symbol Explanation
Non-hydrate phase
Hypothetical empty lattice
H Hydrate
, , i j k Component , , i j k
0 Pure ice or liquid water
0 Reference temperature
298.15 K
Infinite solution
* Rational, unsymmetrical
Nomenclature

VII

Abbreviation
EoS Equation of state
LLE Liquid-liquid-equilibrium
LM Levenberg-Marquardt
NM Nelder-Mead
NP Number of experimental data points
PR Peng-Robinson
SLE Solid-liquid-equilibrium
SLVE Solid-liquid-vapor-equilibrium
SRK Soave-Redlich-Kvong
VLE Vapor-liquid-equilibrium

Summary

VIII

Summary

This thesis deals with thermodynamic modeling of hydrogen sulfide systems containing
the weak electrolyte solutions CO
2
and NH
3
. The Extended UNIQUAC model is used to
describe the excess Gibbs energy in these systems. The Extended UNIQUAC
parameters are estimated for H
2
S and HS
-
in the systems H
2
S, H
2
S-H
2
O, H
2
S-CO
2
-H
2
O,
H
2
S-NH
3
-H
2
O.
Langmuir gas hydrate parameters for the model presented by Munck (1988) were
estimated for H
2
S in the system H
2
S-H
2
O.

Chapter 1: Introduction to aqueous electrolytes and the importance of thermodynamic
models containing H
2
S and weak electrolytes are presented.
Chapter 2: Thermodynamic concepts pertinent to thesis including the chemical potential,
activity coefficients and the Extended UNIQUAC model are described.
Chapter 3: General gas hydrate theory including structures, characteristics of guest
molecules, H
2
S gas hydrates and thermodynamic models for gas hydrates are
presented.
Chapter 4: Phase diagrams for the systems H
2
S and H
2
S-H
2
O and Gibbs phase rule are
presented.
Chapter 5: Different thermodynamic VLE models from the literature used to describe
weak electrolytes systems containing H
2
S is described.
Chapter 6: Calculations of approximate concentrations of H
2
S species in the H
2
S-H
2
O
system are presented.
Chapter 7: The principal method used to estimate the Extended UNIQUAC parameters
including description of the objective functions, the Levenberg-Marquardt and the
Nelder-Mead algorithms are presented
Chapter 8: Estimated Extended UNIQUAC parameters for H
2
S species for the systems
H
2
S and H
2
S-H
2
O are presented
Chapter 9: Estimated Langmuir gas constants for H
2
S for the H
2
S-H
2
O system are
presented.
Chapter 10: The Extended UNIQUAC parameters estimated for the H
2
S-NH
3
-H
2
O
system are presented. It is argued that the very scarce experimental data points for the
system H
2
S-CO
2
-H
2
O are wrong.
Summary

IX

Chapter 11: Is the conclusion, summarizing the results of the project.
Chapter 12: Future work related to the project, which is relevant to investigate is
presented.

Table of Contents

X

Table of Contents
Problem formulation............................................................................................................ I
Theoretical part ............................................................................................................ I
Practical part ................................................................................................................ I
Time schedule and content of status reports ................................................................ I
Status report 1 .............................................................................................................. I
Status report 2 .............................................................................................................. I
Status report 3 .............................................................................................................II
Preface............................................................................................................................... III
Abstract ............................................................................................................................. IV
Nomenclature..................................................................................................................... V
Notation.......................................................................................................................... V
Greek letters .................................................................................................................. VI
Subscripts...................................................................................................................... VI
Superscripts................................................................................................................... VI
Abbreviation ................................................................................................................ VII
Summary.........................................................................................................................VIII
Table of Contents............................................................................................................... X
1 Introduction................................................................................................................. 1
2 Thermodynamic model ............................................................................................... 2
2.1 Chemical potential and activity coefficients....................................................... 2
2.1.1 Chemical potential ...................................................................................... 2
2.1.2 Excess chemical potentials and activity coefficients.................................. 3
2.2 The Extended UNIQUAC model........................................................................ 4
3 Gas hydrates................................................................................................................ 9
3.1 General gas hydrate theory ................................................................................. 9
3.1.1 Structure.................................................................................................... 10
3.1.2 Characteristics of Guest Molecules .......................................................... 12
3.2 Hydrogen Sulfide.............................................................................................. 13
3.3 Thermodynamic model for gas hydrates........................................................... 13
4 Phase diagrams.......................................................................................................... 22
4.1 Phase rule.......................................................................................................... 22
4.2 The H
2
S system................................................................................................. 23
4.3 The H
2
S-H
2
O system........................................................................................ 24
4.3.2 Summary of the three-phase loci .............................................................. 33
5 H
2
S-H
2
O-weak electrolyte systems .......................................................................... 35
5.1 Solid-liquid-vapor equilibrium......................................................................... 35
5.1.1 The H
2
S-NH
3
-H
2
O system........................................................................ 37
5.1.2 The H
2
S-CO
2
-H
2
O System....................................................................... 38
5.1.3 Vapor-liquid equilibrium models.............................................................. 39
5.1.4 Vapor-liquid equilibrium model by Edwards ........................................... 40
6 Concentration calculations for the H
2
S-H
2
O system................................................ 43
7 Parameter estimation and data description ............................................................... 46
7.1 Minimization..................................................................................................... 46
7.1.1 Levenberg-Marquardt Algorithm.............................................................. 47
Table of Contents

XI

7.1.2 Nelder-Mead Algorithm............................................................................ 47
7.2 Confidence limit for estimated parameters ....................................................... 47
7.3 Collection and review of data ........................................................................... 48
8 H
2
S and HS
-
parameter estimation............................................................................ 49
8.1.1 Objective function..................................................................................... 49
8.1.2 Vapor-liquid equilibrium data................................................................... 50
8.1.3 Estimated UNIQUAC parameters............................................................. 51
9 Gas hydrate parameter estimation............................................................................. 60
10 Parameter estimation for ternary systems ............................................................. 65
10.1 Description of the H
2
S-CO
2
-H
2
O system ......................................................... 65
10.2 Parameter estimation of the H
2
S-NH
3
-H
2
O system.......................................... 67
11 Conclusion ............................................................................................................ 79
12 Future work........................................................................................................... 81
References.......................................................................................................................... A
13 Appendices............................................................................................................... i
13.1 Appendix A.......................................................................................................... i
13.1.1 Concentration calculations for the H
2
O-H
2
S system................................... i

Introduction

1

1 Introduction

Accurate knowledge of the phase behavior in aqueous systems containing weak
electrolytes like hydrogen sulfide, ammonia and carbon dioxide is crucial, since these
systems are encountered in a variety of fields. Typical examples are the cleaning of raw
gases in power stations, the production of fertilizers, the oil industry, and in the field of
environmental protection. The volatile weak electrolytes of greatest industrial importance
are ammonia, carbon dioxide and hydrogen sulfide and good models are therefore of
industrial importance for these components. A typical example is the process of
gasification of coal where nitrogen, sulfur and carbon are liberated as ammonia,
hydrogen sulfide and carbon dioxide. The investigated phase equilibrium of these weak
electrolyte gases in aqueous solutions is of interest to the industry when designing the
separation process of these pollutant components.
Many sour reservoir fluids contain hydrogen sulfide and it is in general desirable to avoid
the formation of condensed water to reduce the risk of gas hydrate formation and ice
formation. It is therefore important to have a reliable model to predict the gas hydrate
formation for the binary system hydrogen sulfide and water.
Furthermore, hydrogen sulfide and water are encountered in many natural hydrocarbon
reservoirs. The phase equilibrium of mixtures of these two components is therefore
important in petroleum systems in general. The H
2
S-H
2
O system is also encountered in
the important field of geochemistry. Hot, aqueous (hydrothermal) reservoirs that contain
hydrogen sulfide are important in the formation of some sulfide and sulfate minerals. The
hydrogen sulfide-water system is also used to produce heavy water (D
2
O).
Thermodynamic models describing the phase equilibrium for systems containing weak
electrolytes like hydrogen sulfide, ammonia and carbon dioxide are therefore important
in a wide variety of areas in the chemical industry.

Thermodynamic model

2

2 Thermodynamic model

The thermodynamic models used in this work are the Extended UNIQUAC (Universal
Quasi Chemical), the Soave-Redlich-Kvong (SRK) equation of state (EoS) and the gas
hydrate model presented by Munck (1988).
The Extended UNIQUAC model is used to calculate the activity coefficient in the liquid
phase, the SRK EoS is used to calculate the fugacity in the gas phase and the gas
hydrate model presented by Munck (1988) is used to calculate the gas hydrate formation
(solid). The gas hydrate model is presented in details in section 3.3 (Thermodynamic
model for gas hydrates) even though it is part of the thermodynamic model. The SRK
EoS is not described further in this work, because it is well described in the literature and
an already well-know EoS.
A review of the Extended UNIQUAC model and a minor review of the chemical potential
and activity coefficients are presented in this section.
2.1 Chemical potential and activity coefficients
2.1.1 Chemical potential

For a substance i in a mixture its chemical potential
i
is defined as the partial molar
derivative of the total Gibbs energy G where the temperature T, pressure P, and amount
of j are held constant.

, ,
j
i
i
T P n
G
n

(2-1)

The chemical potential is used to determine if the system is at a state of equilibrium
since the chemical potential of each substance is the same at equilibrium. For ideal
solutions the chemical potential is

( )
id
,0
ln
i
i i
RT x = +
(2-2)

Thermodynamic model

3

where
,0 i
is the chemical potential of component i at standard state, R is the gas
constant, T is the absolute temperature, and
i
x is the mole fraction of component i .
2.1.2 Excess chemical potentials and activity coefficients

Mixtures deviate from ideality, and in order to describe this deviation the excess Gibbs
energy is used. Gibbs excess energy is the difference between the chemical potential of
a real solution and that of an ideal solution. The excess chemical potential for
component i is

( )
E
ln
i
i
RT =
(2-3)

where
i
is the symmetrical activity coefficient of i .

The chemical potential of component i , in a real solution (not ideal), is the summation of
the excess and ideal Gibbs energy

( )
id E
,0
ln
i i
i i i i
RT x = + = +
(2-4)

where
E
i
is the excess chemical potential. For pure solutions, the mole fraction and the
symmetrical activity coefficient is unity, and the excess term therefore vanishes for pure
solutions. In general the purer the solution is, the more ideal the behavior is (e.g. the
symmetrical activity coefficient equal to unity).

The chemical potential of water in an aqueous solution, expressed by equation (2-4), is
given below.

( )
,0
ln
w w w w
RT x = +
(2-5)

The chemical potential for the ion i , expressed by equation (2-4), is as follows.

Thermodynamic model

4

( )
,0
ln
i i i i
RT x = +
(2-6)

The activity coefficients of a solute, for example ions, are normalized so that the activity
coefficient is unity at infinite dilution. This is achieved by defining a rational,
unsymmetrical activity coefficient
i

i
i
i
=

(2-7)

where
i
is the symmetrical activity coefficient at infinite solution and

i
is the
previously introduced symmetrical activity coefficient. The adjective unsymmetrical
refers to the fact that this activity coefficient is unity at infinite dilution where as the
symmetrical activity coefficient is unity for the pure component state.
The excess chemical potential of ion i expressed so that the activity coefficient is unity
at infinite dilution is

( )
( ) ( )
( )
,0
,0
,0
ln
ln ln
ln
i
i i i i
i i i i
i i
RT x
RT RT x
RT x

= +
= + +
= +

(2-8)

where
,0 i
is rational, unsymmetrical chemical potential of component i .

2.2 The Extended UNIQUAC model

The Extended UNIQUAC model is a local composition model. It is identical to the
original UNIQUAC model (Abrams and Prausnitz 1975, Maurer and Prausnitz 1978) with
the difference that a Debye-Hckel term has been added (Sander 1984, 1986a, 1986b).
For local composition models it is assumed that the composition on a molecular level is
different from the bulk composition. It is assumed that the molecules sizes, shapes, and
interaction energies determine the microscopic (local) composition. The Extended
UNIQUAC model consists of a combinatorial or entropic term, residual or enthalpic and
Debye-Hckel or electrostatic term, where the molecules sizes, shapes and interaction
Thermodynamic model

5

energies are included. The excess Gibbs energy is calculated by addition of the three
terms.

E E E E
Combinatorial Residual Debye-Hckel
G G G G = + +
(2-9)

The combinatorial and the residual terms are identical to the terms used in the traditional
UNIQUAC equation. The combinatorial (entropic) term is

E
Combinatorial
G
ln ln
2
i i
i i i
i i
i i
z
x q x
RT x

| | | |
=
| |
\ \

(2-10)

where z=10 is the co-ordination number (assumption),
i
x is the mole fraction,
i
is the
volume fraction, and
i
is the surface area fraction of component i .
The volume and surface fraction of component i is given by the following expressions

i i
i
l l
l
x r
x r
=
;

i i
i
l l
l
x q
x q
=

(2-11)

where
i
r and
i
q respectively are volume and surface parameters for component i .

The residual (enthalpic) term is

E
Residual
G
ln
i i k ki
k
x q
RT

| |
=
|
\

(2-12)

The shape parameter
ki
is given by

u u
exp
ki ii
ki
T
| |
=
|
\

(2-13)

where u
ki
and u
ii
are interaction energy parameters. The interaction energy parameters
temperature dependence is

Thermodynamic model

6

( )
0
u u u 298.15
ki ki
t
ki
T = +
(2-14)

where
0
u
ki
is the temperature independent interaction parameter at 298.15 K and u
ki
t
is
the temperature dependent parameter. Equation (2-14) is also used for the case i k = .

The electrostatic Debye-Hckel term is

( )
E
2
Debye-Hckel 1 2 1 2
3
G
4A b I
ln 1 bI bI
b 2
w w
x M
RT
(
= + +
(

(2-15)

where
w
x is the mole fraction of water,
w
M is molar mass of water, I is the ionic strength
(def. in eq.(2-18)), b is considered a constant of 1.50 (kg mol
-1
)
1/2
,and A is the Debye-
Hckel parameter.
The Debye-Hckel parameter A is calculated from the following equation

( )
1 2
3
3
0
4
2
A
r
F d
A
N
RT

(
= (
(

(2-16)

where F (C mol
-1
) is Faradays constant, N
A
(mol
-1
) Avogadros number,
0
the vacuum
permittivity (C
2
J
-1
m
-1
), R the gas constant (
-1 -1
J mol K ), T is the temperature (K), d is
the density (kg m
-3
) and
r
the relative permittivity (dielectric constant, dimensionless) of
the solution. The temperature dependent parameters are the density and the relative
permittivity.
Based on the density and the relative permittivity of pure water, the Debye-Hckel
parameter A has been approximated in the temperature range 273.15 K - 383.15 K as
follows.

( ) ( )
2
3 5 1 2 1 2
1.131 1.335 10 273.15 1.164 10 273.15 A T T kg mol

(
= + +

(2-17)

The ionic strength is

Thermodynamic model

7

2
1
2
i i
i
I m z =

(2-18)

where
i
m is the molality of ion i .

By partial molar differentiation of the combinatorial and the residual UNIQUAC terms, the
combinatorial and residual parts of the rational, symmetric activity coefficients are
obtained:

( )
ln ln 1 ln 1
2
C i i i i
i i
i i i i
z
q
x x

( | | | |
= + +
( | |
\ \

(2-19)

( )
ln 1 ln
R k ik
i i k ki
k K
l lk
l
q

(
| |
(
=
|
(
\
(

(2-20)

The infinite dilution terms are obtained by setting 1
w
x =

( )
ln ln 1 ln 1
2
C i i i w i w
i i
w w w i w i
r r rq r q z
q
r r r q r q

( | | | |
= + +
( | |
\ \

(2-21)

( ) ( ) ln 1 ln
i i wi iw
R
q
= (

(2-22)

The electrostatic contributions to the symmetric water activity coefficients and the
unsymmetrical ionic activity coefficients are obtained by partial molar differentiation of
the extended Debye-Hckel term, giving the following expressions.

( ) ( )
( ) ( )
DH 3 2 1 2
w w
3
2
ln
3
3 1
1 2ln 1
1
M AI bI
x x x
x x

=
| |
= + +
|
+
\

(2-23)

Thermodynamic model

8

( )
1 2
DH 2
1 2
ln
1
i i
AI
z
bI
=
+

(2-24)

The activity coefficient for water in the Extended UNIQUAC model is calculated by
summation of the combinatorial, residual and Debye-Hckel term.

( ) ( ) ( ) ( )
w w w
C R DH
w
ln ln ln ln = + +
(2-25)

The activity coefficient for ion i , obtained as the rational unsymmetrical activity
coefficient, is found by summation of the different contributions.

( ) ( ) ( ) ( ) ( ) ( )
w
C C R R DH
ln ln ln ln ln ln
i i i i i

= + +
(2-26)

To summarize, the activity coefficients for water and ions in the liquid phase are
calculated by use of the Extended UNIQUAC model, that is a local composition model
based on size, volume and interaction parameters (Thomsen 2005).

Gas hydrates

9

3 Gas hydrates

Systems containing hydrogen sulfide and water form gas hydrates under specific
conditions and this give rise to engineering problems in the chemical industry. Gas
hydrates can for example cause problems when plugging transmission lines and process
equipment. The system H
2
S-H
2
O is often encountered as a part of the natural gas
systems (Guo et al. (2003) and exhaustion gas of coal-fired power plants. A reliable
model able to predict the formation of gas hydrates is therefore important when, for
example, designing processing equipment and preventing plugging of pipelines.
In this section a general introduction to gas hydrates, with emphasis on hydrogen sulfide
gas hydrates, and the model used to calculate the gas hydrate formation by Munck
(1988) are presented.
3.1 General gas hydrate theory

Gas hydrates are ice-like crystalline compounds of water and gases of a rather modest
size such as, for example, light natural gas components. Many gases of small molecular
size form hydrates by becoming trapped in cavities in solid water. The crystal is held
together by hydrogen bonding between the water lattice and the trapped molecules. The
gas hydrates belong to a group called Clathrate hydrates. The name comes from
clathratus meaning enclosed or protected by cross bars of grating (Cady 1983).
The formation of gas hydrates is favored at high pressures and low temperatures. The
gas hydrates may form at temperatures below approximately 310 K. There must be a
sufficient amount of water of water present, but also not too much water present, in order
for gas hydrate formation to occur. Some of the most common gas hydrates formers, or
guest molecules as they are often named, are methane, ethane, propane, iso-butane,
butane, nitrogen, carbon dioxide, and hydrogen sulfide. Highly soluble gases such as for
example ammonia are not known to form gas hydrates. As gas hydrates may exist far
above the freezing point of water they can cause plugging in transmission lines and
production processing equipment. Adding an inhibitor may lower the hydrate formation
temperature. Inhibition is quite analogous to freezing point depression and the
compounds causing the largest freezing-point depressions for water are also the most
powerful inhibitors. Alcohols, glycols and salts are examples of good inhibitors (Munck
1988; Sloan 1990).
Gas hydrates

10

3.1.1 Structure

The hydrates are known to form the more common cubic structures I and II and the more
rare hexagonal structure H. The hydrate structure is stabilized by the van der Waals
forces arising from the guest molecule that occupies the cavity in the ice-like structure of
the hydrate. The pure natural gas components nitrogen, propane, and isobutene are
known to form structure II while methane, ethane, carbon dioxide, and hydrogen sulfide
all form structure I.

The unit cell of structure I contains 46 water molecules and has form as a cube with side
length of 12 . The total number of cavities is eight per unit cell. It is comprised of two
small 12-hedral and six large 14-hedral cavities per unit cell. The 12-hedral cavity
consists of all regular pentagons while the 14-hedral cavity consists of twelve sides that
are pentagonal and two (oppositely positioned) hexagonal sides. The 12-hedral and 14-
hedral are therefore respectively denoted 5
12
and 5
12
6
2
. If all eight cavities of the unit cell
were filled with the guest molecule M, the ratio of water and guest molecules would be
46 8 5.75 = . The empirical formula for the structure I is therefore
2
M 5.75H O .
The unit cell of structure II contains 136 water molecules and has form as a cube with
side length 17.3 . The total number of cavities is 24 per unit cell. It is comprised of
sixteen small 12-hedral cavities and eight 16-hedral cavities. The former are like those
in structure I. The latter consists of four hexagonal sides and twelve pentagonal sides
and denoted 5
12
6
4
. If all of the cavities were filled with the guest molecules, the ratio of
water and guest molecules would be
2
24M 136H O . The empirical formula is therefore
2
24M 136H O or
2
2
M 5 H O
3
(Sloan 1990).

Gas hydrates

11

Table 3-1. Description of gas hydrates with structure I and II (Sloan 1990).
Property Structure I Structure II
Cavity Small Large Small Large
Description 5
12
6
2
5
12
6
4

Number of
Cavities per unit
cell

2

6

16

8
Average Cavity
Radius / []
3.91 4.33 3.902 4.683
Number of H
2
O
molecules per
unit cell

46

136
Crystal System Cubic Cubic
Lattice
Description
Body Centered Diamond

The unit cell of structure H contains 34 water molecules and the total number of cavities
is 6 per unit cell. It is comprised of three smaller 12-hedral cavities, two intermediate
cavities formed of three squared sides, six pentagonal sides and three hexagonal sides
and a large cavity comprised of twelve pentagonal sides and eight hexagonal sides. The
smaller cavity is identical to the one in structure I. The intermediate structure and the
larger structure are respectively denoted 4
3
5
6
6
3
and 5
12
6
8
. The empirical formula
is
2
2
M 5 H O
3
.
The structure of the different hydrate types and the number of times each cavity occurs
in the complete structure is seen in Figure 3-1. Structure I is for example comprised of
the cavity 5
12
two times and six times the cavity 5
12
6
2
(Sloan 1998).
Gas hydrates

12

Figure 3-1. The structure of the different hydrate types and the number of times each
cavity occurs in the complete structure is seen. For example is structure I comprised of
two times 5
12
and six times 5
12
6
2
. A guest molecule in the form of methane is seen
occupied in a 12-hedral cavity (Sloan 1998).

3.1.2 Characteristics of Guest Molecules

The guest molecule is classified by its chemical nature, its size and to a lesser extent its
shape. The size of the guest molecule is directly related to the hydrate number and, in
most cases, to its non-stoichiometric value. Gas hydrates are non-stoichiometric and the
degree of saturation depends (number of guest molecules per cavity) on the temperature
and pressure (Carroll 1991). The fractional occupancy for the smaller cavities (5
12
) from
structure I and II usually varies between 0.7 and 0.9. The gas hydrates stoichiometric
variation causes them to be called non-stoichiometric in order to distinguish them from
the stoichiometric salt hydrates.
The guest molecule must not contain either a single strong hydrogen-bonding group or a
number of moderately strong hydrogen bonding groups if gas hydrates are to be formed.
The natural gas components do not make hydrogen bonds (Sloan 1990).

Gas hydrates

13

3.2 Hydrogen Sulfide

Hydrogen sulfide forms structure I. Hydrogen sulfide is of such a size that it can occupy
both cavities (5
12
and 6
2
) in structure I. If there is a mixture of gases forming structure II
then hydrogen sulfide can also be part of structure II. Of the components commonly
found in natural gas the hydrate of hydrogen sulfide forms at the lowest pressure and
persist to the highest temperature.
Hydrogen sulfide can be classified as a water-soluble acid gas and not a hydrophobic
compound like most other guest molecules. The hydrogen sulfide gas hydrate properties
are summarized in Table 3-2 (Sloan 1990).

Table 3-2. Hydrogen sulfide gas hydrate properties (Sloan 1990).
Component Hydrogen sulfide gas hydrate
Hydrate structure Structure I
Crystal System Cubic
Lattice Structure Diamond
Compound classification Water-soluble acid gas
Theoretical structure
2 2
H S 5.75H O
H
2
S diameter [] 4.58

3.3 Thermodynamic model for gas hydrates

The thermodynamic model presented by Munck (1988) is used in this work to compute
the gas hydrate formation. A review of the relevant parts of the article is therefore
presented in this section.
The condition for phase equilibrium in a closed system is that each component must
have the same chemical potential. The equilibrium condition of the model is based on
the chemical potentials of the hydrate phase H and a non-hydrate -phase, which is
either ice (I) or an aqueous solution (L
A
).

Gas hydrates

14

H
=
(3-1)

The chemical potential of water in the hydrate phase is calculated from the van der
Waals and Platteeuw (1959) adsorption model

H
i
i
RT ln 1 Y
1, 2,..., Number of cavities
1, 2,..., Number of components
i K
K
i
k

| |
= +
|
\
=
=

(3-2)

where refers to a hypothetical empty lattice state,
i
is the number of cavities of type
i , and
K
Y
i
denotes the probability of a cavity of type i being occupied by a hydrate-
forming molecule of type k.
The probability is calculated according to the Langmuir adsorption theory

K
k
j j
j
C
Y
1 C
j=1,2,...,Number of components
i k
i
i
f
f
=
+

(3-3)

where
k
f is the fugacity of hydrate-forming component k ,
K
C
i
is the adsorption
constant at the specified temperature, and j is the number of hydrate forming
components.

The Langmuir constants are considered to be temperature-dependent and are
calculated from a two-parameter approach

Ki Ki
Ki
A B
C exp
T T
| |
=
|
\

(3-4)

where
Ki
A and
Ki
B are constants for cavity of type i and molecule of type k . The
parameters
Ki
A and
Ki
B are estimated from experimental data points.
Gas hydrates

15

There are other existing methods to estimate the adsorption coefficient
Ki
C such as, for
example, the Kihara potential model used by John et al. (1985). The Kihara potential
model has a more theoretical approach, but it is somewhat more complicated than the
convenient two-parameter approach presented here and used by Munck (1988).

The chemical potential of water in the -phase (ice or an aqueous solution) may in
general be written as

0 w
0
w
RTln
f
f

| |
= +
|
\

(3-5)

where
0
is the chemical potential of pure water as ice, liquid water or gaseous water at
temperature T and pressure P,
w
f

is the fugacity of water in the -phase and
0
w
f is the
fugacity of pure ice, liquid water or gaseous water at the reference temperature.

The difference between the chemical potentials of pure water, as an empty lattice, and
as ice or liquid water at pressure P and temperature T is obtained by combining equation
(3-1), (3-2) and

(3-5).

0 w
Ki 0
i K
w
ln ln 1 Y
i
f
RT RT
f

| |
| |
=
|
|
\
\

(3-6)

The temperature and pressure dependence for the chemical potential of pure water, as
an empty lattice, and liquid water (equation (3-6)) can be derived from the well-known
Gibbs-Helmholtz equation. The Gibbs-Helmholtz equation is as follows (Atkins 2002).

2
P
G H
T T T
( | |
=
| (
\

(3-7)

The temperature dependence of H between the empty hydrate lattice and the non-
hydrate phase as a function of the difference of the heat capacity C
p
is as follows.

Gas hydrates

16

p
p
H
C
T
(
=
(

(3-8)

By integration of equation (3-8) from the reference temperature T
0
to temperature T, the
temperature dependence of the enthalpy difference of the system is obtained. The
enthalpy difference is assumed to be of linear dependence and is

( )
0 0 p
H H C T T = +
(3-9)

where T
0
represents the reference temperature 273.15 K.

By substitution of equation (3-9) in to the Gibbs-Helmholtz equation (equation (3-7)) and
integration with respect to temperature, the following temperature dependence of Gibbs
energy is obtained.

( )
0
0 0
2
T
p
T
H C T T
G
dT
T T
+

(3-10)

By setting 0 dT = the pressure dependence for a closed system in the absence of non-
expansion work and at constant composition can be derived from the following well-
known thermodynamic function

dG Vdp SdT =
(3-11)

where S is the entropy and V is the volume of the system (Atkins 2002).

By integration with respect to pressure the following pressure dependence for the
system with respect to Gibbs energy is obtained

0
p
p
G Vdp =

(3-12)

Gas hydrates

17

where V is the volume difference and
0
p is the vapor pressure at the reference
temperature.

Equation (3-12) is expanded with the gas constant and a temperature parameter.

0
p
p
G V
dp
RT RT

=

(3-13)

An average temperature T is introduced where
0
T is the reference temperature.

The difference in volume ( V ) between the hydrate phase and the non-hydrate phase
at the average temperature T is used to calculate the difference in Gibbs energy
between the hydrate and non-hydrate phase.

0
p
p
G V
dp
RT RT

=

(3-15)

The temperature and pressure dependence for Gibbs energy is expressed in
respectively equation (3-10) and (3-15). By applying the definition
m
G = to these
equations a general expression for the difference between the chemical potentials of
pure water, as an empty lattice, and as ice or liquid water at pressure P and temperature
T is obtained.

( )
0 0
P 0
0 p 0
0
2
0 P
V
dT+ d
R
T
T
H C T T
P
RT RT RT T

+

=

(3-16)

0
denotes the difference between the chemical potential of water in the empty hydrate
lattice and ice or liquid water at reference temperature
0
T (273.15 K).
0
H is the
corresponding enthalpy difference,
p
C the heat capacity difference and V the volume
( )
0
2 T T T = +
(3-14)

Gas hydrates

18

difference. P
0
is the vapor pressure at reference temperature T
0
and since it is very small
compared to the pressure P it can be set to zero (
0
0 P = ).
V and
0
H are both considered to be pressure-independent because the pressure
effects on condensed phases are small. V is also considered to be temperature-
independent, while the temperature dependence of the enthalpy term is taken into
account by means of a constant molar heat capacity difference C
p
.
The gas hydrate model is obtained by combining equations (3-6) and (3-16).

( )
0 0
P
0 p 0
0 w
Ki 2 0
i K
0 w P
V
dT+ d ln ln 1 Y
R
T
i
T
H C T T
f
P
RT RT f T
+ | | | |
=
|
|
\
\

(3-17)

The mole fraction and the activity coefficient, for the solid or liquid phase, replace the
respective fugacity and equation (3-17) is given by the following equation.

( )
0 0
P
0 p 0
0 w w
Ki 2 0 0
i K
0 w w P
V
dT+ d ln ln 1 Y
R
T
i
T
H C T T
x
P
RT RT x T

+ | | | |
=
|
|
\
\

(3-18)

The fugacity of the -phase consisting of ice is unity by definition of a solid and the
fugacity of a liquid phase without inhibitor is pure and therefore also unity. The first term
on the right side of equation (3-18) in these cases therefore cancels out. By including the
term describing the probability of cave Y
Ki
being occupied the complete gas hydrate
model is derived when no inhibitor is added.

( )
0 0
Ki Ki
P
0 p 0
0 0
2
i K ji ji 0 P
j
j
A B
exp
V T T
dT+ d ln 1
A B
R
1 exp
T T
T k
i
T
f
H C T T
P
RT RT T
f
| |
| |
|
|
+

\
|
=
|
| |
+
|
|
\ \

(3-19)

The physical properties used in the gas hydrate model are seen in Table 3-3 and are
taken from Munck (1988). Only the physical properties for the liquid phase in this project
were used to estimate the Langmuir parameters, but the properties of ice are presented
Gas hydrates

19

for completeness. The physical properties used by Munck (1988) are not treated in the
article and the correctness of these parameters is therefore uncertain. The properties
used by Munck (1988) seem to be taken from Parrish and Prausnitz (1972), although
they are not referred to directly in the article, but listed in the reference list.

Table 3-3. Physical properties used in the gas hydrate model (equation (3-19)).
0

denotes the difference in the chemical potential of water in the empty hydrate lattice and in
the liquid state (liq) or solid state (ice) at 273.15 K. H
0
and V
0
is the corresponding
enthalpy difference. C
p
is the molar heat capacity difference (Munck 1988).
Property Structure I Unit
0
(liq) 1264 J mol
0
(liq) H - 4858 J mol
0
(liq) V 4.6
3
cm mol
p
(liq) C 39.16 J (mol K)
0
(ice) 0 J mol
0
(ice) H 1151 J mol
0
(ice) V 3.0
3
cm mol
p
(ice) C 0 J (mol K)

In Table 3-4 the values of the physical properties used in the gas hydrate model are
seen from several different authors. It is seen that there is a great deal of uncertainty of
the correct values. It is therefore important to investigate the physical properties, not only
for systems containing water and hydrogen sulfide, but also for gas hydrate systems with
structure I. However, investigating these physical properties further is beyond the scope
of this project.

Gas hydrates

20

Table 3-4. Physical properties used in the gas hydrate model from different sources in the
literature.
0
denotes the difference in the chemical potential of water in the empty
hydrate lattice and in the liquid state (liq) or solid state (ice) at reference temperature. H
0

and V
0
is the corresponding enthalpy difference. C
p
is the molar heat capacity
difference. T
0
I is the reference temperature 273.15 K. (Parrish et al. 1980; Parrish 1972;
Holder 1980).
Property Value Reference Unit
0
(liq) 123510 Holder (1980) J mol
1297 Parrish (1980)
1155 Holder (1976)
1264 Parrish (1972)
1255 Child (1964)

a
1264 Munck (1988)

0
(ice) H 1684 Holder (1980) J mol
1389 Parrish (1980)
381 Holder (1976)
1151 Parrish (1972)

a
1151 Munck (1988)

0
(liq) H -4327 Holder (1980) J mol
- 4860 Parrish and Prausnitz
(1972)

- 4858 Munck (1988)

0
(ice) V 3.0 Stackelber and Mller

a
3.0 Munck (1988)

p
(liq) C -37.32+0.179(T-T
o
) Holder (1980) J (mol K)
0.565+0.002(T-T
o
) Holder (1980)
9.11-0.0336(T-T
o
) Weast (1968)

a
39.16 Munck (1988)
a
Used by Munck (1988) and in this work.

A short summary of the complete gas hydrate model (equation (3-19)) is given here. The
gas hydrate model is used to describe the SLVE between the gas hydrates (solid), the -
phase that is a non-hydrate phase that is either ice (I) or a liquid aqueous phase (L
A
),
and the gas phase.
is the number of cavities, A and B are Langmuir constant that are estimated from
experimental data points, f is the fugacity, T is the average temperature and T
0
is the
reference temperature.
Gas hydrates

21

For the -phase consisting of ice,
0
,
0
H ,
p
C and V denotes the differences
between the empty lattice and ice at reference temperature.
For the -phase consisting of a liquid aqueous phase (L
A
),
0
,
0
H ,
p
C and
V denotes the differences between the empty lattice and liquid water at reference
temperature (Munck 1988).

Phase diagrams

22

4 Phase diagrams

A phase of a substance is a form of matter that is uniform throughout in chemical
composition and physical state (Atkins 2002). In order to describe a given substance
phase diagrams are used to visualize the physical state and composition of a given
system. In this section an introduction to phase diagrams is presented with emphasis on
the H
2
S and H
2
S-H
2
O phase diagrams. No information concerning phase diagrams for
the ternary systems H
2
S-H
2
O-NH
3
and H
2
S-H
2
O-CO
2
was found in the literature.
4.1 Phase rule

The phase rule deduced by J.W. Gibbs is a general relation between the degrees of
freedom (F), the number of independent components (C), and the number of phases at
equilibrium (P) for a system of any composition.

F=C-P+2
(4-1)

The degrees of freedom F for a system are the number of variables that can be changed
independently without disturbing the number of phases in equilibrium. For a single-
component, single-phase system (C=1, P=1) such as pure water, the pressure and
temperature may be changed independently without changing the number of phases, so
the degrees of freedom is 2 (F=2). For pure water at conditions where water is in
equilibrium with vapor there is only one degree of freedom. Therefore, if the pressure is
fixed the temperature will automatically be determined and vice-versa. At the triple point
of pure water, ice, water, and steam are in equilibrium. According to the phase rule, a
one component system has zero degrees of freedom when three phases are in
equilibrium (F=0) and the system is by definition at an invariant point.
The number of components C in a system is the minimum number of independent
species necessary to define the composition of all the phases present in the system. An
aqueous solution of a pure salt contains three species which are water, cations and
anions. The number of chemically independent components is two because the charge
of the cations has to be balanced with an equivalent charge of the anions. The number
of cations is therefore depended on the number of anions. The solution is therefore
Phase diagrams

23

considered a binary solution, a solution of two chemically independent components
(Atkins 2002).
4.2 The H
2
S system

The understanding of the pure component system H
2
S is of importance for
understanding the more complex systems H
2
S-H
2
O, H
2
S-H
2
O-NH
3
, and H
2
S-H
2
O-CO
2
.
For the pure component system H
2
S there is only one component, which yields the
following phase rule for the H
2
S system.

F = C-P+2 = 3-P
(4-2)

From equation () it is seen that the invariant point (F=0) is a triple point, since there are
three co-existing phases (P=3) when the degrees of freedom is zero. The three co-
existing phases are L-S-V (V is vapor, S is solid and L is liquid hydrogen sulfide). For the
system, where only two phases exist, there is one degree of freedom and the loci are S-
V, L-S and L-V. For the system with one degree of freedom there is only one phase
which is solid, liquid or vapor.

Table 4-1. The degrees of freedom, number of phases and loci for the pure component
system H
2
S. L is the liquid phase, S is the solid phase and V is the vapor phase.
Degrees of freedom Number of phases Loci
0 (Triple point) 3 L-S-V
1 2 S-V
L-S
L-V
2 1 S
V
L

The vapor pressure of pure H
2
S was measured by Cardoso (1921), Reamer (1950),
Clarke (1970), and Klemenc (1932). There is good agreement between the vapor
pressure obtained by Cardoso (1921), Reamer (1950) and Clarke (1970). Klemenc
(1932) measured the vapor pressure at a lower temperature than Cardoso (1921),
Phase diagrams

24

Reamer (1950) and Clarke (1970), so direct comparison is not possible. The vapor
pressure of pure H
2
S is seen in
Figure 4-2.

0
10
20
30
40
50
60
70
80
90
150 200 250 300 350 400
Temperature [K]
P
r
e
s
s
u
r
e

[
a
t
m
.
]
0
0,2
0,4
0,6
0,8
1
1,2
P
r
e
s
s
u
r
e

[
a
t
m
.
]
Cardoso (1921) Clarke (1970)
Reamer(1950) Klemenc (1932)

Figure 4-2. Vapor pressure as a function of the temperature for pure H
2
S. The vapor
pressure measured by Cardoso (1921), Reamer (1950) and Clarke (1970) are represented
by the left axis (bigger scale) and the vapor pressure from Klemenc (1932) are represented
by the right axis (smaller scale).

4.3 The H
2
S-H
2
O system

The H
2
S-H
2
O system has been studied extensively due to its importance in the chemical
and petrochemical sector. A review of the most important discoveries for the H
2
S-H
2
O
system is presented in this section.
Hydrogen sulfide is a weak diprotic acid that dissociates in two steps as shown in the
following reactions together with the ionic equilibrium of water.

Phase diagrams

25

( ) ( ) ( )
1
+ - 7
2 a
H S aq H aq +HS aq K 10 (25 ) C
=

(4-1)

( ) ( ) ( )
2
- + 2- 19
a
HS aq H aq +S aq K 10 (25 ) C

(4-2)

+ - 14
2 w
H O H +OH 10 (25 ) K C
=

(4-3)

From the small
2
a
K value it is seen that sulfide ion
2-
S has a high affinity for protons. In
an acidic solution where the concentration of protons is high the concentration of sulfide
ion will be relatively small, since under these conditions the dissociation equilibrium will
lie far to the left. On the contrary, in basic solutions the sulfide ion will be relatively large,
since the small proton concentration will be responsible for producing relatively large
amounts of sulfide ions (Zumdahl 2002).
In Figure 4-3 the phase diagram for hydrogen sulfide-water is seen. It must be noticed
that the diagram is not scaled and several of the three-phase loci are speculation by the
authors (Carroll 1991) and included for completeness.
The pure component two-phase loci, denoted by the solid lines, are well established for
hydrogen sulfide and water (Carroll 1991). Of the three-phase loci the L
A
-H-V (Aqueous
liquid-Hydrate-Vapor), L
S
(Hydrogen sulfide rich liquid)-H-V, L
A
-L
S
-H, H-I-V and L
A
-L
S
-V
loci have been determined.
The first and second quadruple points have been well determined, while the third and
fourth quadruple points have not and it is not sure they exist.

Phase diagrams

26

Figure 4-3. Pressure-temperature diagram for the H
2
S-H
2
O system. The diagram is not
scaled. The pure component loci are represented by the solid lines. The three-phase loci
are represented by the dotted lines. The three-phase loci L
A
-H-V, L
S
-H-V, L
A
-L
S
-H, H-I-V,
and L
A
-L
S
-V have been determined while the others are speculation. The quadruple points
Q
1
and Q
2
have been determined while Q
3
and Q
4
are believed to exist but not determined
(Carroll 1991).

For the H
2
S-H
2
O system there are two components, which yield the following phase rule
for the system.

F = C-P+2 = 4-P
(4-4)

From the phase rule it is seen that the invariant points (F=0) are quadruple points, since
there are four co-existing phases when there is zero degrees of freedom. For the system
where only three phases exist there is one degree of freedom. For the system where two
phases exist there are two degrees of freedom and for the system with one phase there
are three degrees of freedom.

Phase diagrams

27

Table 4-2. The degrees of freedom, number of existing phases, the three and four phase
loci and the physical occurrence for the quadruple points for the H
2
S-H
2
O system (Carroll
1991).
Degrees of freedom Number of phases Loci Physical occurrence
0 (Quadruple point) 4 L
A
-L
S
-H-V
H-I-V- L
A
H-I-S-V*
H-S-L
S
-V*
29.4C and 2.24 MPa
-0.4C and 93.1 kPa
1

3

L
A
-H-V
L
S
-H-V
L
A
-L
S
-H
H-I-V
L
A
-L
S
-V
S-I-V*
S-I-H*
H-S-V*
L
S
-S-V*
L
A
-I-V*
L
S
-H-S*
L
A
-I-H*

2 2
1 3
*
Locus not measured, but believed to exist (Carroll 1991).
4.3.1.1 The L
A
-H-V locus

Several people have determined the L
A
-H-V locus. Carroll (1991) have collected data
from several sources and correlated this locus from a Clausius-Clapeyron type equation

( ) ( )
2788.88
ln 26.8952 0.15139 3.5786ln P T T
T
= + +

(4-5)

where P is the total pressure in kPa and T is the temperature in Kelvin.

Phase diagrams

28

The data points for the L
A
-H-V locus from the different sources used to make the
Clausius-Clayperon type correlation (equation (4-5)) are seen in Figure 4-4.

Figure 4-4. The aqueous liquid-hydrate-vapor locus for the H
2
S-H
2
O system. Equation (2)
on the figure corresponds to equation (4-5) in this work. Data from several authors are
included: Forcrand (1882a,b), Cailletet (1882), Wright (1932), Bond (1949), Selleck (1951),
Carroll (1990). The figure is taken from Carroll (1991).

The composition of the co-existing phases along the L
A
-H-V locus with varying
temperature and pressure is seen in Table 4-3.

Table 4-3. Compositions of the co-existing phases along the L
A
-H-V locus for the system
hydrogen sulfide-water (Carroll 1991).
Mole Percent Hydrogen Sulfide
Temp [C] Pressure
[kPa]
(1)
Aqueous
(2)
Hydrate
(3)
Vapor
(2)

0 98.6 0.366 14.3 99.373
5 163.9 0.511 14.4 99.458
10 274.7 0.725 14.5 99.539
15 463.6 1.053 14.6 99.613
20 787.9 1.525 14.6 99.676
(1) from equation (4-6).
(2) from the model presented by Carroll (1988c).
(3) from a modified van der Waals-Platteeuw (1959) model using the parameters from Munck
(1988) and the hypothesis of Cady (1981).

Phase diagrams

29

4.3.1.2 The L
s
-H-V locus

The L
s
-H-V locus was correlated as a Clausius-Clapeyron type equation by Carroll
(1991) with experimental data points from several sources (see also Figure 4-5)

( )
2061.05
ln 14.5229 P
T
=

(4-6)

where P is the total pressure in kPa and T the temperature in Kelvin.

The vapor pressure for the L
s
-H-V locus for the H
2
S-H
2
O system is seen in Figure 4-5
and the vapor pressure for pure H
2
S is also presented by Goodwin (1983). After a
thorough study of Goodwins article (1983) I concluded that the vapor presented by
Goodwin (1983) is doubtful and it is therefore advised to be used with caution. The major
concern regarding Goodwins article (1983) is whether he actually measured the vapor
pressure or calculated it. This is not presented clearly.

Figure 4-5. The L
s
-H-V locus for the H
2
S-H
2
O system. The solid line is the correlation
expressed in equation (4-6). The data points are from Carroll (1990), Scheffer (1913),

and
Selleck (1951). The dotted line is the vapor pressure of pure H
2
S presented by Goodwin
(1983)
*
. Q
1
represents the quadruple point at 29.4C and 2.24 kPa. The figure is taken from
Carroll (1991).

*
Argued in section 4.3.1.4 that the vapor pressure presented by Goodwin (1983) is doubtful.
Phase diagrams

30

4.3.1.3 The L
A
-L
s
-H locus

Only very limited data was available for the L
A
-L
s
-H locus. Two data points from Scheffer
(1913) and three data points from Selleck (1951) are found in the literature. From the
data points Carroll (1991) obtained the following correlation,

11.083 3352.515 P T =
(4-7)

where P is the total pressure in MPa and T is the temperature in Kelvin.

A graphical presentation of the experimental data points and the correlation (Equation
(4-7)) for the L
A
-L
s
-H locus are seen in Figure 4-6.

Figure 4-6. The L
s
-L
a
-H locus for the H
2
S-H
2
O system. Equation 4 on the figure
corresponds to the correlation given in equation (4-7) with data points from Scheffer
(1913) and Selleck (1951). Q
1
represents the quadruple point at 29.4C and 2.24 kPa. The
figure is taken from Carroll (1991).

4.3.1.4 The H-I-V locus

Experimental data points from Scheffer (1913) and Meyer (1919a, b) were correlated by
Carroll (1991). The following Clausius-Clapeyron type equation was obtained
Phase diagrams

31

( )
3070.13
ln 15.8059 P
T
=
(4-8)

where P is the total in pressure kPa and T is the temperature in Kelvin.

A graphical presentation of H-I-V locus is seen in Figure 4-7 and the respective
correlation (Equation (4-8)).

Figure 4-7. The H-I-V locus for the H
2
S-H
2
O system. Equation 5 on the figure corresponds
to the correlation given in equation (4-8). Q
2
represents the quadruple point at -0.4C and
93.1 kPa. The figure was taken from Carroll (1991).

4.3.1.5 The L
A
-L
s
-V locus

The L
A
-L
s
-V locus was determined by Carroll (1989a). From the experimental data points
a Clausius-Clapeyron-type equation was obtained

( )
2156.9
ln 7.928 P
T
=
(4-9)

Phase diagrams

32

where P is the total pressure in kPa and T is the temperature in Kelvin.

A graphical presentation of the experimental data points for the L
A
-L
S
-V locus and the
correlation (equation (4-9)) is seen in Figure 4-8. The vapor pressure of pure H
2
S is also
presented by Goodwin (1983), but it was earlier concluded that correctness of the vapor
pressure is doubtful (see section 4.3.1.2).

Figure 4-8. The liquid-liquid-vapor locus for the system hydrogen sulfide-water. K is the
three-phase critical end point. The vapor pressure of pure H
2
S is from Goodwin (1983). The
correlation denoted by a solid line corresponds to equation (4-9). Q
1
represents the
quadruple point at 29.4C and 2.24 kPa. The figure was taken from Carroll (1991).

The composition given as mole fraction of H
2
S of the co-existing phases along L
A
-L
s
-V
locus is seen in Table 4-4.

Phase diagrams

33

Table 4-4. The composition given as mole fraction of H
2
S of the co-existing phases for the
L-L-V locus. The + in the first rows under the vapor compositions denotes that the
composition could not be determined more accurately than within two decimals (Carroll
1989a).
Mole fraction of H
2
S
Temp [C] Aqueous liquid H
2
S-Rich liquid Vapor
40 0.0335 0.987 0.99+
60 0.0341 0.973 0.99+
80 0.0385 0.965 0.987
100 0.0440 0.951 0.975
105 0.0451 0.955 0.973
4.3.2 Summary of the three-phase loci

The three-phase loci for the complex H
2
S-H
2
O system are summarized in this section. In
Table 4-3 the earlier presented correlations and the loci that are believed to exist, but not
determined are presented.

Table 4-5. Correlations for 5 known three-phase loci for the H
2
O- H
2
S system. Three-phase
loci that are believed to exist, but not determined are also included (Carroll and Mather
1991, 1989a).
Locus Correlation
L
A
-H-V
( ) ( )
2788.88
ln 26.8952 0.15139 3.5786ln P T T
T
= + +
L
S
-H-V
( )
2061.05
ln 14.5229 P
T
=
L
A
-L
S
-H 11.083 3352.515 P T =
H-I-V
( )
3070.13
ln 15.8059 P
T
=
L
A
-L
S
-V
( )
2156.9
ln 7.928 P
T
=
S-I-V Not determined
S-I-H Not determined
H-S-V Not determined
L
S
-S-V Not determined
L
A
-I-V Not determined
L
S
-H-S Not determined
L
A
-I-H Not determined

Phase diagrams

34

A thorough review of the literature regarding the pure H
2
S system and the binary system
H
2
S-H
2
O was presented in this section. It is concluded that much research has been
carried out and that the phase behavior for several loci are well described, but still much
research must be carried out in order to increase the current knowledge of the important
systems H
2
S and H
2
S-H
2
O, which is of great importance in the petrochemical and
chemical sector.

H
2
S-H
2
O-weak electrolyte systems

35

5 H
2
S-H
2

A review of the most important earlier works from the literature describing the H
2
S-H
2
O-
NH
3
and H
2
S-H
2
O-CO
2
systems together with the important equilibrium in the ternary
system is presented in this section.
In the literature very scarce information concerning the SLVE for the H
2
S-NH
3
-H
2
O and
H
2
S-CO
2
-H
2
O systems where the solid is ice or gas hydrates were found.
The Extended UNIQUAC model has successfully been applied for the H
2
O-NH
3
-CO
2

system by Thomsen (1999). The work presented here can be seen as a continuation
and the Extended UNIQUAC model in this work is applied to the ternary system H
2
S-
H
2
O-NH
3
. The system H
2
S-H
2
O-CO
2
is also described, but the lack of experimental data
made it impossible to estimate the parameters.
5.1 Solid-liquid-vapor equilibrium

The solubility of volatile weak electrolytes in water results from two equilibrium: Vapor-
liquid and ionization. In the case of hydrogen sulfide, for instance the following
equilibrium exists.
( ) ( ) ( ) ( )
VLE Ionization
- +
2 2
H S g H S aq HS aq +H aq
(5-1)

A more general form for the VLE and ionization for electrolyte systems for single solute
systems are seen in Figure 5-1. The weak electrolyte in the liquid phase exists in two
forms which are the molecular (VLE) and ionic form. The equilibrium depends on
pressure and temperature.
H
2
S-H
2

36

Figure 5-1. Equilibrium for vapor-liquid and ionization for a single-solute system (Edwards
et al. 1975).

In the systems H
2
S-NH
3
-H
2
O and H
2
S-CO
2
-H
2
O several equilibrium exist. Due to the
chemical reactions in the liquid phase and a strong deviation from ideality, correlating
and predicting the thermodynamic properties of aqueous systems containing ammonia
and sour gases is an extremely difficult task (Beatier 1978 and Rumpf 1998).

Figure 5-2. The temperature dependence for the first dissociation equilibrium constant for
ammonia, carbon dioxide and hydrogen sulfide in water (Edwards et al. 1978).

For systems with only a single weak electrolyte the only chemical reaction occurring is
ionic dissociation. For very dilute concentrations this effect is appreciable. At more
H
2
S-H
2

37

moderate concentrations the effect is less appreciable and only a relatively small fraction
of the weak electrolyte is in ionic form. For example, for the single solute system
hydrogen sulfide, the vast majority of electrolyte in the solution exists in molecular form
and not ionic. However, by for example adding ammonia to the solution the
concentration of the molecular form decreases significantly and the concentration of the
ionic form increases significantly. Depending on the concentration of the weak acid and
weak base in the solution, the fraction of weak electrolyte in molecular form may be
greatly reduced. Since it is the molecular species that are in equilibrium with the vapor
phase, the partial pressure of the weak electrolyte in the vapor phase may also be
greatly reduced (Edwards et al. 1975; Edwards et al. 1978; Beutier 1978).
5.1.1 The H
2
S-NH
3
-H
2
O system

In this section the equilibrium of importance, which are later used to estimate the
Extended UNIQUAC parameters, are presented for the H
2
S-NH
3
-H
2
O system. The
following VLE, LLV and SLE are considered for the system.

Vapor-liquid equilibrium:

( ) ( )
3 3
NH g NH aq
(5-2)

( ) ( )
2 2
H S g H S aq
(5-3)

( ) ( )
2 2
H O g H O l
(5-4)

Speciation equilbria (Ionization):

( ) ( )
+ -
3 2 4
NH aq +H O l NH +OH
(5-5)

( )
+ -
2
H S aq H +HS
(4-1)

+ -
2
H O H +OH
(5-6)

Solid-liquid equilibrium:
- + 2-
HS H +S
(4-2)
H
2
S-H
2

38

( ) ( )
2 2
H S aq + H O s Gas hydrate
(5-13)

( ) ( )
2 2
H O s H O l
(5-7)

At sufficiently low temperatures solid phases of water and ammonia exist where x is a
not specified stoichiometric coefficient (Thomsen, not in the reference list). The
equilibrium condition 5-8 does not have importance in this work, since the temperature
used to estimate the Extended UNIQUAC parameters is not sufficiently low to make the
equilibrium have any influence, but presented here for completeness.

( )
2 3 2 3
H O l NH (aq) H O XNH ( ) s +
(5-8)

5.1.2 The H
2
S-CO
2
-H
2
O System

In this section important VLE, LLV and SLE equilibrium for the H
2
S-CO
2
-H
2
O system are
presented. The behavior of the solubility of carbon dioxide is very similar to that of
hydrogen sulfide in many systems. Carbon dioxide also forms a weak diprotic acid when
dissolved in water. Many of the H
2
S observations can be directly translated to the
behavior of CO
2
although the results will be different for the two gases, but the
qualitative phenomena are often the same (Carroll 1998).

Vapor-liquid equilibrium:

( ) ( )
2 2
CO g CO aq
(5-9)

( ) ( )
2 2
H S g H S aq
(5-3)

( ) ( )
2 2
H O g H O l
(5-4)

Speciation equilibrium:

( ) ( )
+ -
2 2 3
CO aq +H O l H +HCO
(5-10)
H
2
S-H
2

39

( )
+ -
2
H S aq H +HS
(4-1)

( )
+ -
2
H O l H +OH
(4-3)

Solid-liquid equilibrium:

( )
2 2
H S aq + H O(s) Gas hydrate
(5-12)

( )
2 2
CO aq +H O(s) Gas hydrate
(5-13)

( )
2 2
H O l H O(s)
(5-14)

5.1.3 Vapor-liquid equilibrium models

In the literature a number of different models have been applied to describe the VLE for
the H
2
S-NH
3
-H
2
O system and the NH
3
-CO
2
-H
2
O system. The Pitzer equation (Pitzer
1973) has been widely applied for these systems and the authors Edwards et al. (1975;
1978), Beutier (1978) and Rumpf (1999) use it directly or in a modified form. Models
published by Krevelen (1949), Wilson (1980), Leyko (1964a), Leyko (1964b) and
Ginzburg (1965) are widely empirical. Wilson (1980) and Krevelen (1949) base their
models on equilibrium constants and Henrys law coefficients with out taking the ionic
activity into account. Daumn (1986) have developed an EoS for weak electrolyte VLE
behavior. All of the mentioned methods are quite complex and require a lot of
information.
The most applied models used to describe the vapor phase for the systems H
2
S-NH
3
-
H
2
O and H
2
S-CO
2
-H
2
O are the SRK, Peng-Robinson (PR), Nothnagel et al. (1973) and
Nakamura et al. (1976).
In the literature no information concerning the H
2
S-NH
3
-H
2
O and H
2
S-CO
2
-H
2
O systems
modeled with the Extended UNIQUAC was found.
- + 2-
3 3
HCO H +CO
(5-11)
- + 2-
HS H +S
(4-2)
H
2
S-H
2

40

A minor review of the article published by Edwards et al. (1978) is presented here,
because of its importance in describing the H
2
S-NH
3
-H
2
O and NH
3
-CO
2
-H
2
O systems.
For more details the reader is referred to the literature.
5.1.4 Vapor-liquid equilibrium model by Edwards

The model describing the VLE based on the Pitzer equation used by Edwards et al.
(1975; 1978) is presented in this section.
The liquid phase activity is calculated from the Pitzer equation and the vapor phase
activity is calculated by an extended Henrys law. The Pitzer equation is a semi-empirical
virial type model.
The Pitzer equation is used to calculate the activity coefficients of both neutral and ionic
species and the excess Gibbs energy of an aqueous electrolyte mixture is

( )
( ) ( )
( )
( )
( ) ( )
Bin, 0 Bin,1
1 2
, , ,
E
i j ij ij i j k ijk
i j w i j k w
w w
G
f I mm f I mm m
RTn M

= + + +

(5-15)

where
1
f and
2
f are functions of ionic strength I,
( ) Bin,0
, i j
,
( ) Bin, 1
, i j
and
, , i j k
are
respectively binary and ternary interaction parameters, m is the concentration in molality
of other species than water, R is the gas constant, T the temperature in Kelvin,
w
M the
molecular weight of water, and
w
n the number of moles of water.

The activity coefficient in Pitzers theory describes the molecule-molecule, molecule-ion
and ion-ion interaction. The unsymmetrical activity coefficient
i
for solute i (ion or

molecule in molecular form) derived by Pitzers theory (Pitzer 1973) is

H
2
S-H
2

41

( ) ( )
( )
( )
( ) ( )
( )
( ) ( ) { }
2
Bin,1
Bin, 0
2
Bin,1
2
2
ln ln 1 1.2
1.2 1 1.2
2 1 1 1.2 exp 2
2
1 1 2 2 exp 2
4
i i
ij
j ij
j w
i
j k jk
j w k w
I
A z I
I
m I I
I
z
m m I I I
I

(
= + +
(
+

(
+ + +
`

)
+ +

(5-16)

where A
is a Debye-Hckel parameter and I is the ionic strength.

The activity of water is determined from the Gibbs-Duhem equation.

( )
( ) ( )
( )
3 2
Bin, 0 Bin,1
2
ln exp 2
1 1.2
w w i j ij ij w i
i w j w i w
A I
a M mm I M m
I

(
= +
`

+

)

(5-17)

An extended version of Henrys law is used to describe the solubility of the weak
electrolytes. Henrys law states that for ideal solutions that the vapor pressure of solute
i is proportional to the mole fraction of component i in the liquid phase. The
proportionality factor is an experimental constant named Henrys constant H.

i i i
p x H =
(5-18)

Henrys law is modified and the non-ideality is taking into account by introducing the
activity coefficient for the liquid phase and the fugacity coefficient for the gas phase. The
equilibrium for the molecular solute between the vapor and liquid phase is then

i i i i i
y P m H =
(5-19)

where P is the total pressure,
i
is the fugacity coefficient for component i , and
i
m is
the molality of solute i .

Henrys constant is a strong function of temperature and a weak function of pressure.
The pressure dependence is given by the following equation

H
2
S-H
2

42

( )
( )
( )
( )
w
ln ln
sat
w
sat
p a
P
P P
H H
RT
| |
= +
|
\

(5-20)

where
a
is the partial molar volume of molecular solute at infinite dilution and

w
sat
P is
the saturation pressure of water at system temperature.

The temperature dependence of Henrys constant is given by the following empirical
function

( ) ( )
2
1 3 4
ln ln
H
H H H T H T
T
= + + +
(5-21)

where
1 2 3
, , H H H , and
4
H are empirical constants.

The equilibrium constants are calculated from the following empirical correlation

( ) ( )
2
1 3 4
ln ln
C
K C C T C T
T
= + + +
(5-22)

where
1 2 3
, , C C C , and
4
C are empirical constant.

From the thermodynamic models presented in this section Edwards et al. (1978)
describe the H
2
S-NH
3
-H
2
O and NH
3
-CO
2
-H
2
O systems in the temperature range 0C to
170C. The composition range, depending on the extent ionization, may be as high as
10 to 20 molal.
Rumpf (1999) successfully describe the H
2
S-NH
3
-H
2
O system in the temperature range
40C to 120C and a total pressure up to 0.7 MPa.
Concentration calculations for the H
2
S-H
2
O system

43

6 Concentration calculations for the H
2
S-H
2
O system

Ideal concentration calculations for the H
2
S-H
2
O system are carried out in this section.
This is done in order to get an overview of the concentrations of the considered species
for different amounts of total dissolved hydrogen sulfide, which is useful when estimating
the Extended UNIQUAC parameters. The species H
2
S(aq), HS
-
, S
2-
, H
+
, OH
-
and H
2
O(l)
are considered for the H
2
S-H
2
O system.
The concentrations of the 6 species depend on the total amount of H
2
S dissolved in the
solution. There are 6 species and 6 independent equations must therefore be specified
to determine the concentration of the species. The 6 equations consist of three
equilibrium conditions, one electro-neutrality and two mass balances (sulfide and
oxygen).
The molality m, which is defined as mol pr. kg solvent, is used in the equilibrium
calculations. In order to determine the molalities of the species 1 kg water is considered.
The concentrations are relatively small and the assumption of ideality is therefore good.
The three chemical equilibrium considered are the first dissociation equilibrium constant
for H
2
S
1
K , the second dissociation equilibrium constant for H
2
S
2
K , and the equilibrium
constant for self-ionization of water
w
K . The equilibrium constants were determined
from the standard Gibbs energy of formation at 25C. The data for the species are from
the database NIST. The equilibrium constants were calculated from the following well-
known thermodynamic relation.

( ) RTln G K =
(6-1)

2
S-H
2
O system

44

Table 6-1. The standard Gibbs energy of formation at 25C for the 6 species considered in
the H
2
S-H
2
O system. The data are from the database NIST.
Specie
( )
25 C
f
G

[ KJ Mol ]
H
2
S(aq) -27.83000
HS
-
12.08000
S
2-
85.80000
H
2
O(l) -237.1290
H
+
0
OH
-
-157.2481

The 6 conditions setup to determine the concentrations in the H
2
S-H
2
O system are seen
below. The 3 calculated equilibrium constants K
1
, K
2
and K
w
are seen first, then the
electro neutrality and then the sulfide and oxygen mass balance.

2
-7 HS H
1
H S
1.019 10
m m
K
m
+
= =
(6-2)

-13 S H
2
HS
1.216 10
m m
K
m
+
= =
(6-3)

-
-14
w
OH H
1.013 10 K m m
+
= =
(6-4)

There is no net charge in the solution and an electro neutrality condition is specified.

2
H OH HS S
2 m m m m
+
= + +
(6-5)

Two mass balances are set up, which are for elemental sulfur and elemental oxygen

2
2 2
Total
H S H S
HS S
m m m m

= + +
(6-6)

where
Total
S
m is the total amount of sulfide dissolved in the solution.
2
S-H
2
O system

45

2 2
Total
H O H O
OH
m m m

= +
(6-7)

The molality of water was included, even though it is usually neglected, since it occurs in
the mass balance for oxygen.

The three equilibrium equations, the electro neutrality and the two mass balances are
solved, and the concentrations of the 6 species in the system are determined. In Table
6-2 the calculated concentrations are seen for several total amounts of dissolved
hydrogen sulfide. The equations were solved by the use of the math program Maple and
the calculation for
2
Total
H S
1 m = is as an example seen in appendix 13.1.1.

Table 6-2. Calculated concentrations for total amounts of dissolved hydrogen sulfide. The
molality of water is also included, since it was used in the mass balance for oxygen.
2
Total
H S
m
2
H S
m
HS
m

2
S
m

2
H O
m
OH
m

H
m
+

0.001
4
9.900 10

5
1.004 10

13
1.216 10

55.508
9
1.008 10

5
1.004 10

0.010
3
9.968 10

5
3.187 10

13
1.217 10

55.508
10
3.178 10

5
3.187 10

0.100 0.100
4
1.008 10

13
1.217 10

55.508
10
1.004 10

4
1.009 10

1.000 0.9997
4
3.191 10

13
1.217 10

55.508
11
3.173 10

4
3.191 10

2.000 1.9995
4
4.513 10

13
1.217 10

55.508
11
2.244 10

4
4.513 10

3.000 2.999
4
5.528 10

13
1.217 10

55.508
11
1.832 10

4
5.528 10

From Table 6-2 it is seen that the molality of S
-2
is very small and it is therefore not
considered when estimating the Extended UNIQUAC parameters.

Parameter estimation and data description

46

7 Parameter estimation and data description

The general method used to estimate the parameters in the Extended UNIQUAC model
and the gas hydrate model by Munck (1988) is presented in this section. The algorithm
used in the parameter estimation, the uncertainty of the parameters and a review of the
experimental data is also presented.
The Extended UNIQUAC parameters (r, q, u
0
and u
t
) for H
2
S and HS
-
are important for
the systems H
2
S-H
2
O, H
2
S-NH
3
-H
2
O and H
2
S-CO
2
-H
2
O. The Langmuir constants (A

and
B) in the gas hydrate model for H
2
S are important for the systems H
2
S-H
2
O, H
2
S-NH
3
-
H
2
O and H
2
S-CO
2
-H
2
O.
In order to estimate the Extended UNIQUAC parameters and the Langmuir constants, a
FORTRAN code with the Extended UNIQUAC model, SRK EoS and the gas hydrate
model was used. Kaj Thomsen (supervisor) had programmed the general code and only
minor changes were applied to the existing FORTRAN code, such as adding the
hydrogen sulfide species and adding the experimental data points found in the literature.
The task of estimating the parameters is usually quite tedious, although in theory it is
only necessary to add the data to the existing program and run the simulation until it
converges. For several reasons such as, for example, poor data and poor start guesses,
the process of estimating the parameters is often time consuming, since several start
guesses must be tried in order to obtain good parameter values. If the model for some
reason did not describe some experimental values, then I tried in the best possible way
to compare them with other experimental data from the literature in order to verify the
reliability of the data.
7.1 Minimization

In this work the Levenberg-Marquardt (LM) algorithm and the Nelder-Mead simplex
search method (NM) algorithm are combined, in order to locate the global minimum of
the specified objective function, and thereby find the best estimate of the investigated
parameters. The objective function includes the squared summation of the difference
between the experimental and calculated values. Different weighting factors can be
included in this summation in order to give different weight (importance) to the different
types of data points (for example VLE and SLVE).

47

The reason for combining the LM and the NM algorithms is because they have proven to
work well together, since they can compensate for each others drawbacks (Kaj
Thomsen, not in the reference list). A short summary of the LM and NM algorithm is
presented in the two following subsections, but for more specific information the reader
should consult the literature.
7.1.1 Levenberg-Marquardt Algorithm

The levenberg-Marquardt (LM) algorithm is an iterative technique that locates the
minimum of a multivariate function that is expressed as the sum of squares of non-linear
real valued functions. It has become a standard technique for non-linear least-squares
problems and can be thought of as a combination of steepest descent and the Gauss-
Newton method. It is sure to converge, since it uses a gradient method, but with risk of
getting trapped in local minimums. It is therefore maybe not able to find the global
minimum without very good initial guess for the parameter values (Lourakis, 2005).
7.1.2 Nelder-Mead Algorithm

The NM algorithm locates minimums with out using the gradient method, but has
difficulty in converging, which is a serious drawback. The advantage of the LM algorithm
is that it avoids getting trapped in local minimums and therefore a good method to find
the global minimum in a difficult terrain (Nelder and Mead 1965 ; Barker and Conway
2007).
7.2 Confidence limit for estimated parameters

The estimated parameter values were determined with a confidence limit of two standard
deviations (st. dev. commonly denoted ). The following probability statement for the
confidence limit for the parameter is used to determine the accuracy of the parameter
estimation

( ) P L Parameter U 1 =
(7-1)


48

where P is the probability, L is the lower confidence limit, U is the upper confidence limit,
and is the probability of rejecting the parameter value when it is true (in common
statistics called probability of type I error).
The interpretation of equation (7-1) is that the interval the parameter lies in will be true
( ) 100 1 % of the times that the statement is made. 1.96 standard deviations
correspond to a 95% confidence interval and the two standard deviations that are used
as upper and lower confidence limit, therefore correspond to a slightly higher confidence
interval than 95% (any standard book of statistics, for example Applied Statistics and
Probability for Engineers by Douglas C. Montgomery).
The estimated parameter values in the following sections are presented with many
significant digits. This means that the parameter value is often presented with more
digits than the confidence limit (for example 0.05 0.06). Many significant digits are
presented because this allows other people to easily reproduce this work.
In general it is desired to have as few as possible parameters in the model because the
significant parameters in this way are estimated more precisely (e.g. smaller confidence
limit).
7.3 Collection and review of data

The open literature was used to collect experimental data points in order to estimate
parameters in the Extended UNIQUAC model and the gas hydrate model. The process
of collecting and reviewing experimental data is time consuming, since it takes time to
find articles with experimental data and a careful examination of the experimental data
must be carried out. From articles, especially older, it is often unclear how the
experiments were carried out. Important information is sometimes missing in the articles
and assumptions must be made. For example, often only the partial pressures were
presented and the vapor pressure of water therefore had to be added in order to obtain
the total pressure. Sometimes authors refer to data in the literature and investigation of
the original article shows that the referred data had been misinterpreted. Therefore all
the experimental data used are from the original articles except from Carroll (1977). By
using the original articles misprints from other articles are also eliminated. It was not
possible to obtain the original data from Carroll (1977) and the data published by Fogg
(1988) was therefore used.
H
2
S and HS
-
parameter estimation

49

8 H
2
S and HS
-

The estimated Extended UNIQUAC parameters, which are the surface (q), volume (r)
and interaction (u
0
and u
t
) parameters, for H
2
S and HS
-
are presented in this section.
The Extended UNIQUAC model with the estimated parameters from this work and the
SRK EoS are used to correlate the experimental data points for the pure H
2
S system
and the binary H
2
S-H
2
O system.
The S
2-
specie has very low concentrations (see section 6) in the concentration range
given by the data and it was therefore decided not to estimate any parameters for this
specie. 462 experimental VLE data points from the systems H
2
S and H
2
S-H
2
O were
used to estimate the Extended UNIQUAC parameters.
8.1.1 Objective function

In order to obtain the best parameter estimate the following objective function was
minimized

( )
2
calc exp
VLEdata
exp
P -P
SSQ
0.05 P 0.01
(
= (
+
(

(8-1)

where P
calc
is the calculated total pressure and P
exp
is the experimental total pressure in
bars.
0.01 is added to the experimental pressure in the denominator to prevent giving too
much weight to the data points at very low pressures. The data points with small
pressures and relatively big pressure differences between the calculated and
experimental pressures might otherwise result in a very big contribution to the total sum
of squares compared to the data points with big pressures. However, if the factor is too
big the data points at small pressures will not have significant influence in the parameter
estimation and a value of 0.01 was therefore found appropriate. The factor 0.05 is only
important when other equilibriums than VLE exist and are used to simultaneously
estimate the parameters. The factor 0.05 is a weighting factor and can be changed in
order to decrease or increase the weight of the VLE data by respectively increase or
decrease the value of the factor.
H
2
S and HS
-

50

8.1.2 Vapor-liquid equilibrium data

Pure component data for the H
2
S system and data from the H
2
S-H
2
O system were used
to estimate the Extended UNIQUAC parameters. In Table 8-1 the range of temperature,
pressure and molality, the sources, and the number of data points used to estimate the
Extended UNIQUAC parameters are seen.
By inspection of the data from West (1948) it was seen that the data points are identical
to the earlier published data by Cardoso (1921), with the exception of 3 extra data points
published by West (1948). West (1948) does not refer to Cardoso (1921) and due to
experimental error the only reasonable conclusion is that West (1948) copied the data
from Cardoso (1921). Only data from the original article except for Lee (1977) has been
used in order to avoid misprints and wrong interpretation of the data. It was not possible
to obtain the original data, since they are in the National Depository of Unpublished
Data, Ottowa, Canada
. The data from Lee (1977) was taken from a compendium by

Fogg (1998). By comparing other experimental data presented in the compendium by
Fogg (1998) and the original articles available in the open literature there was found no
wrong presentation of the data by Fogg (1998). The data presented by Fogg (1998) is
therefore believed to be correct.

National Depository of Unpublished Data, National Science Library, National Research Council,
Ottowa, Ontario, K1A OS2, Canada.
H
2
S and HS
-

51

Table 8-1. The references, the number of data points and the respective temperature,
pressure and molality (liquid phase) range that were used to estimate the Extended
UNIQUAC parameters for H
2
S and HS
-
. In the last row the total range of temperature,
pressure and total number of data points is included.
T, [K] P, [bar] Molality of H
2
S Source NP
273 298 1 0.10 0.21 Kiss (1937) 3
278 333
c
0.4 5 0.036 0.39 Wright (1932) 52
273 323
c
0.5 1 0.027 0.17 Clarke (1970) 36
313 5 25 0.39 1.72 Kuranov (1996) 9
311 378
c
7 69 0.43 2.70 Selleck (1952) 22
278 374 12 90
a
0.62 Reamer (1950) 9
273 370 12 85
a
0.62
b
West (1948) 19
273 374 10 89
a
0.62 Cardoso (1921) 16
245 303 4 23
a
0.62 Clarke (1970) 20
298 1 0.10 Kapustinskii (1941) 1
283 393 1.6 67 0.070 2.27 Lee (1977) 275
273 393 0.4 89 0.027 2.70 All the above sources 462
a
Pure hydrogen sulfide data.
b
The data published by West J. R. are identical to the data earlier published from Cardoso E.,
except from 3 extra data points.
c
Partial pressures or vapor phase composition measured.

8.1.3 Estimated UNIQUAC parameters

The estimated surface and volume UNIQUAC parameters for H
2
S and HS
-
are seen in
Table 8-2. The volume parameter for H
2
S has a relatively small confidence limit and the
estimate of the parameter therefore seems to be fairly accurate. A small confidence limit
for model parameters in general indicates that the parameter is very significant in the
model. From experience the confidence limit does not always mean this in the program
used in this work. By experience, parameters that are very important for the model often
have big confidence limits, although they are very important for the model to describe
the experimental data well. A measure of how important the parameters are in this
context means that the correlation decreases significantly by changing the parameter
value slightly. The confidence limit presented in the following tables with the parameter
H
2
S and HS
-

52

values should therefore not be taken as an exact estimate of how significant (important)
the parameter is.
The surface and the volume parameters for HS
-
have relatively small confidence limits
and the estimate of these parameters therefore seem to be estimated accurately. By
changing the parameter values of the HS
-
ion and the H
2
S specie it was discovered that
the ion does have significant influence when correlating the experimental data with the
Extended UNIQUAC model, but that the H
2
S specie is far more important. The H
2
S
specie is more important than the HS
-
ion, because a small change of the H
2
S parameter
values decreases the correlation with the experimental data more than the HS
-
ion does.
The confidence limit for the H
2
S and HS
-
do not show this, but as previously mentioned
the confidence limit is not necessarily a measure of how important the parameter is.
The HS
-
ion is probably less important than the H
2
S specie because of the relatively low
concentration of the HS
-

ion compared to the H
2
S specie in the H
2
S-H
2
O system. The
HS
-
ion probably has more importance when the concentration is higher as in for
example systems with more species (for example H
2
S-H
2
O-NH
3
)
More data points might give a better estimate with smaller confidence limits for the
parameters of the HS
-
ion and the H
2
S specie. Usually the surface and the volume
parameters are within the range of 0-15 and the estimated parameters are also in this
range, but since no published parameter values are available it is not possible to
compare the parameters values with the literature.

Table 8-2. Estimated surface and volume UNIQUAC parameters for the H
2
S and HS
-

species and the confidence limit. The confidence limit assigned as is two times the
standard deviation.
Species Volume parameter (r) Surface parameter (q)
H
2
S
b
0.6205 0.06
b
0.05128 0.03
HS
-

b
0.6645 0.4
b
1.0245 0.006
H
2
O
a
0.92
a
1.4
OH
- a
9.3973
a
8.8171
H
+ a
0.13779
a 16
10

a
Parameter value from literature (Thomsen 1999)
b
Estimated parameter (this work)

H
2
S and HS
-

53

In Table 8-3 the estimated Extended UNIQUAC interaction parameters from this work at
reference temperature 298.15 K (
0
u ) are seen and the temperature dependent
parameters (
T
u ) are seen in Table 8-4. The interaction parameters between the
aqueous species (OH
-
, H
+
and H
2
O) have previously been determined, but also
presented here for completeness (Thomsen 1999).
The most important parameters were estimated by minimizing the sum of squares of the
objective function (equation (8-1)). Parameters that have no significant influence were
given a very high value for temperature independent parameter and a value of 0 for the
temperature dependent parameter. Other parameters that had only little influence in the
model were given a fixed value. The fixed value was found by trying different values and
afterwards fix the parameter value when a satisfactory correlation was obtained.
It was discovered that the HS
-
own interaction does not have very much influence in the
model. This is probably due to the very low concentration in the H
2
S-H
2
O system. A
good correlation was obtained by assigning the interaction parameter between HS
-
and
H
2
S the value 1300. The interaction parameter between HS
-
and water was assigned the
value of 1100, which gives a good correlation. The true value of the interaction between
H
2
S and water could be investigated further, because there is some uncertainty of the
value.

Table 8-3. The temperature independent parameters in the Extended UNIQUAC model
(
0 0
u u
ki ik
= ) at reference temperature (298.15 K) for the system H
2
S-H
2
O system
( ( )
0 T
u u u T 298.15
ki ki
ki
= + .
H
2
S HS
-
H
2
O OH
-
H
+
H
2
S
b
-1439 815
HS
-

d
1300
d
1000

H
2
O
b
-585 120
d
1100
c
0
OH
-
a 10
10
a 10
10
c
600.5
c
1562.9
H
+
a 10
10
a 10
10
c 4
10
a 10
10
c
0
a
The parameter was assigned this value, because it does not have significant influence in the
model.
b
Estimated parameter value (this work).
c
Parameter value from literature (Thomsen 1999).
d
The parameter was assigned (not estimated) this value in order to obtain the best correlation.

H
2
S and HS
-

54

The estimated temperature dependent parameters (u
T
) in the Extended UNIQUAC
model for H
2
S and HS
-
are seen in Table 8-4. The interaction parameters between H
2
S
and H
2
S, H
2
S and HS
-
, and HS
-
and water were fixed. The final parameter values were
fixed when a relatively low sum of squares in the objective was obtained.

Table 8-4. The temperature dependent interaction parameters in the Extended UNIQUAC
model (
T T
ij ji
u u = ) for the system H
2
S-H
2
O system ( ( )
0 T
u u u T 298.15
ki ki
ki
= + .
H
2
S HS
-
H
2
O OH
-
H
+
H
2
S
d
5
HS
-

d
-15
a
0
H
2
O
b
1.99 0.8
d
12 0
OH
- a
1
a
1
c
8.5455
c
5.6169
H
+ c
1
a
1
c
0.50922
c
1
c
0
a
model.
b
c
d
The pameter was assigned (not estimated) this value.

The estimated parameters for H
2
S and HS
-
in the Extended UNIQUAC model are seen
to include a wide range of temperature (273 393 K), pressure (0.4 89 bar) and
molality (0.027 2.70 mol/kg). A total number of 462 experimental data points were
used from 11 different sources. In the following figures it is seen that the Extended
UNIQUAC model with the estimated parameters from this work and the SRK EoS
correlate the experimental total vapor pressure very well for the pure H
2
S system and
the binary H
2
S-H
2
O system.
In Figure 8-1 the experimental total pressure and the correlation of the vapor pressure of
pure hydrogen sulfide by the Extended UNIQUAC model and the SRK EoS are seen.

H
2
S and HS
-

55

0
20
40
60
80
100
240 260 280 300 320 340 360 380
Temperature [Kelvin]
P
r
e
s
s
u
r
e

[
B
a
r
]

Reamer (1950) Cardoso (1921) Clarke (1970) Model
Figure 8-1. The vapor pressure correlated by the Extended UNIQUAC model and the SRK
EoS are seen (Reamer 1950; Cardoso 1921); Clarke 1970).

In Figure 8-2 and Figure 8-3 the experimental values and the model correlation of the
total pressure of the H
2
S-H
2
O system are seen. It is seen that the Extended UNIQUAC
model with the estimated parameters from this work and the SRK EoS correlate the H
2
S-
H
2
O system very well. In Figure 8-3 a close up of Figure 8-2 is seen for the region at low
pressure and low molality of H
2
S.

H
2
S and HS
-

56

0
10
20
30
40
50
60
70
0 0,5 1 1,5 2 2,5
Molality [mol/kg]
Exp. 0C
Mod. 0C
Exp. 4.96C
Mod. 4.96C
Exp. 5C
Mod. 5C
Exp. 10C
Mod. 10C
Exp. 15C
Mod. 15C
Exp. 20C
Mod. 20C
Exp. 25C
Mod. 25C
Exp. 30C
Mod. 30C
Exp. 37.78C
Mod. 37.78C
Exp. 40C
Mod. 40C
Exp. 50C
Mod. 50C
Exp. 60C
Mod. 60C
Exp. 71C
Mod. 71C
Exp. 71.11C
Mod. 71.11C
Exp. 90C
Mod. 90C
Exp. 104.44C
Mod. 104.44C
Exp. 120C
Mod. 120C

Figure 8-2. The total vapor pressure for the system H
2
S-H
2
O with different molalities for
H
2
S at isotherms from 0C to 120C. The model (Extended UNIQUAC and SRK EoS) with
the estimated parameters for H
2
S and HS
-
is represented by the solid line and the
experimental data points are represented by dots.

0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
2
2,2
0,02 0,07 0,12 0,17 0,22 0,27
Molality [mol/kg water]
T
o
t
a
l

p
r
e
s
s
u
r
e

[
B
a
r
]
Exp. 0C
Mod. 0C
Exp. 4.96C
Mod. 4.96C
Exp. 5C
Mod. 5C
Exp. 10C
Mod. 10C
Exp. 15C
Mod. 15C
Exp. 20C
Mod. 20C
Exp. 25C
Mod. 25C
Exp. 30C
Mod. 30C
Exp. 37.78C
Mod. 37.78C
Exp. 40C
Mod. 40C
Exp. 50C
Mod. 50C
Exp. 60C
Mod. 60C

Figure 8-3. The total vapor pressure for the H
2
S-H
2
O system with different molalities for
H
2
S at isotherms from 0C to 60C. The model (Extended UNIQUAC and SRK EoS) with the
estimated parameters for H
2
S and HS
-
is represented by the solid line and the experimental
data points are represented by dots.
H
2
S and HS
-

57

The mole fraction of H
2
S in the gas phase as a function of the H
2
S molality is seen for
several isotherms in Figure 8-4 and Figure 8-5. It is seen that the prediction of the
Extended UNIQUAC model with the estimated parameters from this work for H
2
S
together with the SRK EoS correlate the vapor composition very well in a molality range
from 0 to 2 mol/kg water and a temperature range between 0C and 104.4C.

0,76
0,81
0,86
0,91
0,96
0,02 0,07 0,12 0,17
Molality (Liquid phase) [kg/mol]
M
o
l
e

f
r
a
c
t
i
o
n

(
G
a
s

p
h
a
s
e
)
0C Exp
0C Mod
4.96C Exp
4.96C Mod
10C Exp
10C Mod
15C Exp
15C Mod
20C Exp
20C Mod
25C Exp
25C Mod
30C Exp
30C Mod
40C Exp
40C Mod
50C Exp
50C Mod

Figure 8-4. The H
2
S mole fraction of the vapor phase and the H
2
S molality is seen for
several isotherms for the binary system H
2
S-H
2
O. The experimental data points are from
Clarke (1970).

H
2
S and HS
-

58

0,89
0,91
0,93
0,95
0,97
0,99
0,1 0,6 1,1 1,6 2,1 2,6
H2S molality [mol/kg water]
M
o
l
e
f
r
a
c
t
i
o
n

o
f

H
2
S

(
G
a
s

p
h
a
s
e
)
37.8 C Mod
37.8 C Exp
71.1 C Mod
71.1 C Exp
104.4 C Mod
104.4 C Exp

Figure 8-5. The correlation (Extended UNIQUAC and SRK EoS) and experimental data of
the H
2
S mole fraction in the vapor phase. The H
2
S molality is seen for 3 isotherms for the
binary system H
2
S-H
2
O. The experimental data points are from Selleck (1952).

For several isotherms the partial pressure of H
2
S as a function of the molality is seen in
Figure 8-6. It is seen that partial pressure is well described by the Extended UNIQUAC
model with the estimated parameters for H
2
S and the SRK EoS. The partial pressure is
used in Figure 8-6 because Wright (1932) presents the experimental data as the partial
pressure of H
2
S. In Figure 8-4 and Figure 8-5 the mole fraction is presented because
Selleck (1952) and Clarke (1970) present the experimental data points as the mole
fraction of H
2
S.

H
2
S and HS
-

59

0
0,5
1
1,5
2
2,5
3
3,5
4
4,5
5
0 0,1 0,2 0,3 0,4
Molality [mol/kg water]
P
a
r
t
i
a
l

p
r
e
s
s
u
r
e

[
b
a
r
]
5C Exp
5C Mod
10C Exp.
10 C Mod
15C Exp
15C Mod
20C Exp.
20C Mod
25C Exp.
25C Mod
30C Exp
30C Mod
40C Exp.
40C Mod
50C Exp
50C Mod
60C Exp
60C Mod

Figure 8-6. The partial pressure of H
2
S and the molality for the binary system H
2
S- H
2
O is
seen for several isotherms. The experimental data points are from Wright R. H. (1932).

As a conclusion of this section it is stated that the Extended UNIQUAC model and the
SRK EoS, with the estimated Extended UNIQUAC parameters from this work for H
2
S
and HS
-
successfully correlate the VLE for pure H
2
S and H
2
S-H
2
O. Some uncertainty
exists for the interaction parameters between HS
-
and water, but a good estimate of
these interaction parameters can probably be obtained by using SLE experimental data.
For industrial purposes the Extended UNIQUAC ought to be sufficiently good in most
cases to predict the VLE of pure H
2
S and the H
2
S-H
2
O system in a wide range of
temperature (273 393 K), pressure (0.4 89 bar) and molality (0.027 2.70 mol/kg).
Gas hydrate parameter estimation

60

9 Gas hydrate parameter estimation

In this section the estimated Langmuir parameters in the gas hydrate model used to
describe the phase behavior of the system H
2
S-H
2
O with gas hydrates are presented.
The gas hydrate model is presented in details in section 3.3.
The estimated parameters in the gas hydrate model are the Langmuir constants A
Ki
and
B
Ki
for hydrogen sulfide in structure I. The Extended UNIQUAC parameters estimated in
section 8 are used to calculate the activity in the liquid phase and the SRK EoS is used
to calculate the fugacity in the gas phase.
The parameter estimation was carried out by minimizing the sum of squares of the
objective function. The objective function seen below is the squared sum of all the
pressure differences between the calculated and experimental pressures in bars.

2
Calc Exp
i
ssq = P P (

(9-1)

In Table 9-1 the sources, the number of data points, the temperature and pressure range
used to estimate the Langmuir constants for hydrogen sulfide in structure I are
presented.

Table 9-1. The references, the number of data points and the respective temperature and
pressure range that were used to estimate the Langmuir parameters for hydrogen sulfide
in SLE gas hydrate model. In the last row the total range of temperature, pressure and total
number of data points is included.
T, [K] P, [bar] Source NP
273 302 0.9 22 Selleck F. T. (1952) 13
289 302 5 22 Scheffer F. E. (1913) 10
273 302 0.9 22 All the above sources 23

The gas hydrate model used to estimate the Langmuir constants A
Ki
and B
Ki
are seen in
equation (9-2). For structure I, as in the H
2
S-H
2
O system, there are 2 small cavities and
6 large cavities per unit cell (
i
).


61

( )
0
Ki Ki
0 p 0
0 0
2
i K ji ji 0
j
j
A B
exp
V T T
P dT ln 1
A B
R
1 exp
T T
T k
i
T
f
H C T T
RT RT T
f
| |
| |
|
|
+

\
|
=
|
| |
+
|
|
\ \

(9-2)

The pressure P, calculated by eq. (9-2), was used to estimate the Langmuir constants so
that the sum of squares for the objective function was minimized.
During the estimation process of the Langmuir constants it was found that both of the B
(large and small cavity) Langmuir constants changed less than 1% and it was therefore
decided to keep them at the initial value, as presented by Munck (1988), and only fit the
A parameters.
During the estimation process of the A parameters it was found that best estimate (e.g.
smallest ssq.) of the A
s
(s represents the small cavity) parameter value was obtained
with a small negative value of A
s
. A negative value of A
s
does not have any physical
significance, since the probability of cave Y
s
being occupied by a hydrogen sulfide
molecule then would be negative according to the gas hydrate model.
The value of A
s
was therefore assigned the very low value of 10
-6
. The reason for the
negative A
s
value without constrains can be investigated further, but it is beyond the
scope of this work. A possible reason for the negative A
s
value could be poor
experimental data or model flaws.
The constant A
l
(l represent the large cavity) for hydrogen sulfide was estimated to a
value of 0.025339 0.05 (two standard deviations). It is seen that the parameter value
is approximately two times smaller than the standard deviation and a big uncertainty is
therefore connected to parameter value A
Kl
. Possible reasons for the big uncertainty
could be the use of only 23 data points or that the parameter is not very important in the
model.
The estimated Langmuir constants from this work and by Munck (1988) for the small and
large cavity for hydrogen sulfide are seen in Table 9-2. It is seen that parameter values
differ significantly for the A
s
parameter compared to Munck (1988), but as previously
mentioned some uncertainty is connected to the estimated parameter value A
s
. The
parameter value A
L
differ significantly from the value by Munck (1988), but the estimated
A
L
value is still within 2 standard deviations. Munck (1988) uses 10 fewer experimental
data points than in this work (23). In this work two sources were used (Scheffer (1913)
and Selleck (1952)) while Munck only uses one source (Selleck (1952)). The values in

62

this work therefore ought to correlate the system H
2
S-H
2
O where gas hydrates are
present better than the work by Munck (1988).

Table 9-2. The estimated Langmuir constants A and B, from this work and the work by
Munck (1988), in the gas hydrate model for hydrogen sulfide in aqueous solution in small
(S) and large cavities (L) are seen.
Parameter Estimated Value (This work) Value from Munck (1988)
A
L

b
0.025339 0.05 0.01634
B
L

a
3737 3737
A
S

c
10
-6

5
2.5 10

B
S

a
4568 4568
a
These parameter values were estimated very close to the values of Munck and therefore kept
equal to estimated parameter values of Munck (1988).
b
Estimated parameter value
c
The parameter was assigned a fixed value, because it otherwise gave negative probabilities of
H
2
S being trapped in the ice structure (gas hydrate).

From a statistical analysis it was found that the four Langmuir constants for hydrogen
sulfide are highly correlated. The statistical analysis is based on the Durbin-Watson test,
which is also often referred to as D-test. The D-test is very complex and it is therefore
beyond the scope this report to treat it in details. The reader can for example consult the
following relevant literature regarding the D-test (Durbin and Watson 1950; Durbin and
Watson 1951). Due to the high correlation it is justified to keep B
Kl
and B
Ks
constant and
only fit the A
Kl
and A
Ks
. The high correlation might be because of the few data points or
also have a physical explanation. A physical explanation could be that probability of the
small and the large cavity being occupied by hydrogen sulfide is constantly proportional
and does not depended on for example pressure and temperature. However, this is
doubtful speculation and should be investigated further to make better conclusions.

In Figure 9-1 it is seen that the gas hydrate model with the estimated Langmuir gas
hydrate parameters from this work, the Extended UNIQUAC parameters presented in
section 8, and the SRK EoS correlate the experimental data points very well.

63

0
5
10
15
20
25
270 280 290 300
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
Experiment Model

Figure 9-1. The experimental data points correlated by the gas hydrate model, with
estimated Langmuir parameters from this work, the SRK EoS, and the Extended UNIQUAC
model, with the parameters estimated in section 8 (Selleck (1952) ; Scheffer (1913)).

In Table 9-3 Langmuir constants estimated by Parrish (1972) for structure I for hydrogen
sulfide are seen. The physical properties used in the model are seen in Table 3-4.
Parrish (1972) uses different values for the physical properties and he uses the Kihara
potential to calculate the adsorption coefficient
Ki
C where as in this work a simple two
parameter approach is used. It is seen by comparing the estimated parameter values
that there is relatively good agreement for the A parameters, while the B parameters
differ significantly. Due to the use of different physical properties the parameter values
from this work is not completely comparable to the ones obtained by Parrish (1972).

Table 9-3. Estimated Langmuir constants between 260 K and 300 K by Parrish (1972) for
hydrogen sulfide in structure I.
Parameter Value
A
L
0.01674
B
L
3610.9
A
S

3
3.0343 10

B
S
3736.0

The physical properties used in the gas hydrate model by Munck (1988) are not treated
in the article and these properties could also be investigated further in order to obtain a

64

better model. The physical properties presented by Munck (1988) and several other
authors are seen in Table 3-4 and significant differences are seen. Especially does the
molar temperature dependent enthalpy difference between the empty hydrate lattice and
the liquid state (
p
(liq) C ) differ and the correct value of the physical properties is
therefore uncertain. The difference in the physical properties would be of interest to
investigate in order to determine what the correct values of the physical properties are,
but it is beyond the scope of this project.

As a conclusion for this section it is stated there is some uncertainty of the estimated
Langmuir parameters A. More data points might help to estimate these parameters
better. The estimated B parameters are in very good agreement with Munck (1988). The
estimated parameters also agree fairly with Parrish (1972), although they use other
values for the physical properties and some other experimental data points.
From Figure 9-1 it is seen that the 23 data points are correlated very well by the gas
hydrate model with the estimated Langmuir parameters from this work, the Extended
UNIQUAC model with the parameters from section 8, and the SRK EoS. The good
correlation of the experimental data points could therefore be of interest, to for example
the industry, when designing process equipment and preventing plugging of pipelines
when water and hydrogen sulfide are present at relatively low temperatures and high
pressures.

Parameter estimation for ternary systems

65

10 Parameter estimation for ternary systems

In this section the estimated Extended UNIQUAC parameters for H
2
S and HS
-
in the
ternary systems H
2
S-NH
3
-H
2
O are presented. In section 8 the surface (q) and volume (r)
parameters were estimated for H
2
S and HS
-
and the interaction energy between H
2
S-
H
2
S and H
2
S-H
2
O were also estimated. In this section these parameters are estimated
again with all the experimental data collected (639 data points), which include the
systems H
2
S, H
2
S-H
2
O, H
2
S-NH
3
-H
2
O, and H
2
S-H
2
O-gas hydrates. The interaction
parameters in the ternary system H
2
S-NH
3
-H
2
O are also estimated. Due to the lack of
good experimental data it was not possible to estimate the Extended UNIQUAC
interaction parameters for H
2
S and HS
-
in the ternary system H
2
S-CO
2
-H
2
O.

10.1 Description of the H
2
S-CO
2
-H
2
O system

The important ternary system H
2
S-CO
2
-H
2
O is often encountered as a part of the natural
gas systems (Guo et al. (2003) and exhaustion gas of coal-fired power plants and
predictive methods to describe the phase behavior is therefore of importance when for
example designing processing equipment and preventing plugging of pipelines.
Despite the importance of this system experimental data is extremely scarce in the open
literature and only a single author (Golutvin (1958)) was found to present experimental
data for the H
2
S-CO
2
-H
2
O system. The data could not be used to estimate the Extended
UNIQUAC parameters in the system, since after reviewing the data it was concluded
that the data is very inconsistent with well established experimental data from the binary
systems H
2
S-H
2
O and H
2
O-CO
2
.
In Table 10-1 3 experimental data points, for the H
2
S-CO
2
-H
2
O system, measured by
Golutvin (1958) is presented together with experimental data points for the H
2
S-H
2
O
system from Wright (1932) and Clarke (1970). The experimental data points chosen for
the H
2
S-H
2
O system have almost the same molality of H
2
S as in the H
2
S-CO
2
-H
2
O
system. This is done in order to compare the H
2
S-CO
2
-H
2
O system and the H
2
S-H
2
O
system. The difference in vapor pressure between the systems H
2
S-CO
2
-H
2
O and H
2
S-
H
2
O should mainly be due CO
2
, if the data is correct.
In Table 10-2 the H
2
S molality difference is seen for the different experimental data sets
and the experimental total pressure given in Table 10-1. For example is operation a-d

66

equal to the H
2
S molality difference between the data sets a and d, and likewise for the
total pressure difference. For example, for operation a subtracted by d (a-d) in Table
10-2 it is seen that the pressure difference is approximately 0.53 bar. This means that
the very small concentration of CO
2
of 0.00686 mol/kg should contribute with
approximately 0.53 bar. Because CO
2
in pure water at 20C does not even closely
contribute to a partial pressure of 0.5 bar (Novak 1961) and the partial pressure of water
is negligible it is together with analog observations for the other experimental data points
concluded that the data set from Golutvin (1958) does not satisfactorily describe vapor
pressure of the H
2
S-CO
2
-H
2
O system.

Table 10-1. A sample of experimental data from Golutvin (1958), Wright (1932) and Clarke
(1970). The data sample is used to justify that the experimental data Golutvin (1958) are
incorrect. All data points are measured at 20C.
Molality CO
2
[mol/kg] Molality H
2
S [mol/kg] Exp. Pres. [Bar] Source
a
0.00686 0.05265 1.01325 Golutvin (1958)
b
0.00229 0.08263 1.01325 Golutvin (1958)
c
0.00150 0.09171 1.01325 Golutvin (1958)
d
0.05304 0.48369 Wright (1932)
e
0.08036 0.72623 Clarke (1970)
f
0.10617 0.95362 Clarke (1970)
g
0.10807 0.96525 Wright (1932)

In Table 10-2 the H
2
S molality difference is seen for the different experimental data set
and the experimental total pressure is given in Table 10-1.

Table 10-2. The difference in H
2
S molality and experimental pressure refers to the
difference between the data sets from Table 10-1. All data points are measured at 20C.
H
2
S Molality
[mol/kg]
Exp. pres. [Bar] CO
2
Molality
[mol/kg]
Operation
-0.00039 0.5488 0.00686 a-d
0.00227 0.30627 0.00229 b-e
-0.01447 0.0789 0.00150

c-f
-0.01636 0.0673 0.00150 c-g

In the literature a wide range of experimental data for the system H
2
O-CO
2
is available.
For the H
2
O-CO
2
system Novak (1961) measured a pressure of 0.52 bars with a

67

molality of 0.04199 mol/kg at 20C. By comparing operation a-d in Table 10-2 with the
measured pressure from Novak (1961) it is seen the low molality of 0.00686 can not give
a pressure of approximately 0.55 bars. The molality should be in the order of 0.04 mol/kg
in order to give a pressure of approximately 0.55 bars. The pressure measured by
Golutvin (1958) is therefore too low. The trend with too low pressure was also observed
for the other experimental data points by Golutvin (1958) and comparison to the
literature. It is therefore safe to conclude the experimental data from Golutvin (1958) is
not correct.
To summarize, it was not possible to estimate the Extended UNIQUAC interaction
parameters between H
2
S and CO
2
due to the very scarce experimental data. It was
argued that the only found experimental data set describing the H
2
S-CO
2
-H
2
O system is
incorrect and therefore could not be used to estimate the Extended UNIQUAC
parameters.

10.2 Parameter estimation of the H
2
S-NH
3
-H
2
O system

In this section the Extended UNIQUAC model parameter estimation for the ternary
system H
2
S-NH
3
-H
2
O are presented. The collected data for the systems H
2
S, H
2
O-H
2
S,
H
2
S-NH
3
-H
2
O and H
2
S-H
2
O-gas hydrates were used to estimate the parameters for H
2
S
and HS
-
. A total number of 639 experimental data points were used.
In order to determine which interaction parameters that are of possible importance in the
H
2
S-NH
3
-H
2
O system a Bjerrum diagram was made for the system. The equilibrium
constants were calculated as described in section 6 with Gibbs energy of formation seen
in Table 10-3.

Table 10-3. The standard Gibbs energy of formation at 25C for the ammonia species
considered in the H
2
S-H
2
O-NH
3
system. The other standard Gibbs energy of formation are
seen in Table 6-1.
Specie
( )
25 C
f
G

[ KJ Mol ]
NH
3
(aq) -26.5
+
4
NH
-79.31

It is seen in Figure 10-1 that the interaction parameters for H
2
S and HS
-
that might have
big importance in the Extended UNIQUAC model are H
2
S-HS
-
, H
2
S-
+
4
NH , H
2
S-NH
3
, HS
-
-

68

+
4
NH , and HS
-
-NH
3
. The S
2-
ion is not considered, because it is believed not to be
present at the conditions specified for the collected data.

0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
3 5 7 9 11 13 15
pH
M
o
l
e
f
r
a
c
t
i
o
n
NH3 H2S HS-
3
NH
HS
2
S

2
H S
+
4
NH

Figure 10-1. Bjerrum diagram for the system H
2
S-NH
3
-H
2
O at 25C. The diagram can be
used to exclude interaction parameters with no influence.

In Table 10-4 the experimental data points that were collected for the ternary systems
H
2
S-NH
3
-H
2
O with the temperature, pressure and molality range together with the
sources and the number of data points are seen. 5 data points from Terres (1957) were
excluded from the collected data because the Extended UNIQUAC model gave a very
bad correlation of these data points. In general very good correlations were obtained
with the Extended UNIQUAC model and a large amount data was used. The reason for
these data points giving a bad correlation could be that the data is not very good.


69

Table 10-4. Experimental data points collected for the H
2
S-NH
3
-H
2
O system from several
different sources, the temperature, pressure, molality range and the number of data
points.
Molality [mole/kg water]
T [K] P [bar] H
2
S NH
3
Source NP
293 333
a
0.48 3.40 3.40 - 0.42 0.48 6.8
c
Terres
(1957)
16
353 373
a
1.67 4.60 2.4 7.8 Leyko
(1964b )
4
313 393
b
0.16 6.85 0.22 5.40 3.0 6.0 Rumpf
(1999)
64
293 323
a
0.044
0.78
1.1 9.1 2.3 19.1 Leyko
(1959)

14
313 373
b
0.9 19.3 1.14 7.9 53.3 Stimming
(1985)
14
273 364
a
1.01 0.27 3.3 0.21 7.3 Ginzburg
(1963)
27
353 393
a
1.06 16.9 1.1 7.9 0.11 22.6 Miles
(1974)
19
273-393 0.16 16.9

0.22 9.1 0.11 53.3 All sources 158
a
) All partial pressures or mole vapor fractions were measured
b
) Only the total pressure was measured

c
) 5 data points were not used in the parameter estimate since they deviate significantly from the
model correlation.

The estimated UNIQUAC parameters from this work and the parameters used for the
ammonia species are seen in Table 10-5.

Table 10-5. The UNIQUAC parameters estimated in this work. Data from the systems H
2
S,
H
2
S-H
2
O, H
2
S-H
2
O-NH
3
, and H
2
S-H
2
O-gas hydrates were used.
Species Volume parameter (r) Surface parameter (q)
H
2
S
a
3.951 0.9
a
1.290 0.7
HS
-

a
7.023 3
a
15 4
NH
3
b
1.435
b
2.092
+
4
NH
b
4.815
b
4.603
a
Parameters estimated in this work
b
Parameters from the literature (Thomsen 1999)


70

The estimated temperature independent Extended UNIQUAC parameters are seen in
Table 10-6. Some parameters were assigned a fixed value, which was done in order to
estimate other parameters better. If too many parameters are estimated in the same
parameter estimation the best correlation is not always obtained. By fixing some
parameters often better correlations are obtained than if the fixed parameters are also
estimated. Some parameters were therefore fixed. The parameters that were given a
fixed value were not of big importance in the model (e.g. influence on the ssq. in the
objective function). The most important parameters were estimated.

Table 10-6. The temperature independent Extended UNIQUAC parameters with reference
temperature 298.15 K. Data from the systems H
2
S, H
2
S-H
2
O, H
2
S-H
2
O-NH
3
, and H
2
S-H
2
O-gas
hydrates were used.
H
2
S HS
-

+
4
NH
NH
3

H
2
O

OH
-
H
+

H
2
S
b
-730 186
HS
-

d
1100
d
1000

+
4
NH
b
-1113
142

d
-15
c
0
NH
3

d
200
b
522 68
c
359.9
c
1140.2
H
2
O
b
-614 106
b
292 67
c
52.730
c
371.60
c
0
OH
-
a 10
10
a 10
10
1877.9
c
359.9
c
600.5
c
1562.9
H
+
a 10
10
a 10
10
a 10
10
a 10
10
c 4
10
a 10
10
c
0
a
The parameter was assigned this high value, because it does not have significant influence in
the model.
b
c
d
The parameter was assigned (not estimated) this value in order to obtain a good correlation.

The estimated temperature dependent Extended UNIQUAC parameters are seen in
Table 10-7. Some parameters were assigned a fixed value, which was done in order to
estimate other parameters better. The parameters that were given a fixed value were not
of big importance. The most important parameters were estimated.


71

Table 10-7. The temperature dependent Extended UNIQUAC parameters with reference
temperature is 298.15 K. Data from the systems H
2
S, H
2
S-H
2
O, H
2
S-H
2
O-NH
3
, and H
2
S-H
2
O-
gas hydrates were used.
H
2
S HS
-

+
4
NH
NH
3

H
2
O

OH
-
H
+

H
2
S
b
3.80 3
HS
-

d
1
d
0
+
4
NH
b
-0.956 1
d
1
c
0
NH
3

d
-4.5
b
6.18 1
c
6.54
c
4.02
H
2
O
b
-1.26 0.3
b
1.51 0.2
c
0.509
c
6.19
c
0
OH
- a
1
a
1
a
1
c
0.0904
c
8.55
c
5.62
H
+ c
0
a
1
c
0
c
0
c
0
a
0
c
0
a
model.
b
c
d
The parameter was assigned (not estimated) this value in order to obtain a good correlation.

The correlation of the experimental data with the Extended UNIQUAC model, with the
parameters in Table 10-5, Table 10-6 and Table 10-7, the SRK EoS, and gas hydrate
model are seen in the following figures. The correlation of the ternary system H
2
S-H
2
O-
NH
3
, the pure component H
2
S, and the H
2
O-H
2
S system including gas hydrates are
presented.
In Figure 10-2 the total vapor pressure for the ternary system H
2
S-H
2
O-NH
3
is seen for
isotherms at 40C, 70C and 100C with a constant H
2
S concentration of 1.137 mol/kg
water. It is seen that the correlation is good, although the models correlate the vapor
pressure a little bit too low.

72

.
Molality H2S=1.137 m
0
5
10
15
20
5 15 25 35 45 55
Molality of NH3 [mol/kg water]
P
r
e
s
s
u
r
e

[
b
a
r
]
40C Mod
40C Exp
70C Mod
70C Exp
100C Mod
100C Exp

Figure 10-2. The total vapor pressure for the ternary system H
2
S-H
2
O-NH
3
for three
isoterms with a constant H
2
S molality of 1.137 m (Stimming 1985).

In Figure 10-3 the vapor pressure for the ternary system H
2
S-H
2
O-NH
3
is seen for
isotherms at 20C, 30C and 40C with different with molality ratios of
3 2
NH H S. The
models correlate the experimental well, except for the data at 40C and a ratio of 2.


73

0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0 5 10 15 20
Molality NH3 [mol/kg water]
P
r
e
s
s
u
r
e

[
b
a
r
]
20C NH3/H2S=2.1 Mod 20C NH3/H2S=2.1 Exp

Figure 10-3. The vapor pressure for the ternary system H
2
S-H
2
O-NH
3
for isotherms at 20C,
30C and 40C with different with molality ratios of
3 2
NH H S (Terres 1957; Leyko 1959).

In Figure 10-4 the vapor pressure is seen for the ternary system H
2
S-H
2
O-NH
3
for
isotherms at 40C, 80C and 120C with constant ammonia concentrations of 3.2, 5, 5.8
and 6 molality and varying concentration of H
2
S. The models correlate the experimental
data very well.

74

0
1
2
3
4
5
6
7
8
0 1 2 3 4 5
Molality of H2S [mol/kg water]
P
r
e
s
s
u
r
e

[
b
a
r
]
40C NH3=3.2 Mod 40C NH3=3.2 Exp 40C NH3=5 Mod
40C NH3=5 Exp 80C NH3=3.2 Mod 80C NH3=3.2 Exp
80C NH3=6 Exp 80C NH3=6 Mod 120C NH3=3.2 Mod
120C NH3=3.2 Exp 120C NH3=5.8 Mod 120C NH3=5.8 Exp

Figure 10-4. The vapor pressure for the ternary system H
2
S-H
2
O-NH
3
with isotherms at
40C and 80C with constant ammonia concentrations of 3.2, 5, 5.8 and 6 molality and
varying concentration of H
2
S (Rumpf 1999).

In Figure 10-5 the vapor pressure for the ternary system H
2
S-H
2
O-NH
3
with isotherms at
50C and 60C with different molality ratios of
3 2
NH H S is seen. The models correlate
the experimental data very well.


75

0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1 3 5 7 9 11
Molality of NH3 [mol/kg water]
P
r
e
s
s
u
r
e

[
b
a
r
]
50C NH3/H2S=2.1 Mod
50C NH3/H2S=2.1 Exp
60C NH3/H2S=2.0 Mod
60C NH3/H2S=2.0 Exp

Figure 10-5. The vapor pressure for isotherms at 50C and 60C with different molality
ratios (Terres 1957; Leyko 1959).

In Figure 10-2, Figure 10-3, Figure 10-4 and Figure 10-5 it is seen that the Extended
UNIQUAC model, with the estimated parameters for H
2
S and HS
-
, and the SRK EoS
correlate the experimental data very well. Few data points are not correlated very well
and this can be due to model flaws or poor experimental data. Some variation of the
experimental data must be expected and it is therefore safe to conclude that the
Extended UNIQUAC model and the SRK EoS used together are able to correlate the
experimental data well for the ternary system H
2
S-H
2
O-NH
3
.

The gas hydrate data from the system H
2
S-H
2
O was also used when estimating the
parameters in the ternary system. A good correlation of the gas hydrate data is again, as
in section 9, obtained. It is seen that the gas hydrate model, with the already estimated
Langmuir constants, the SRK EoS and the Extended UNIQUAC model in general
correlate the vapor pressure well. The vapor pressure is correlated a little bit too low
from approximately 297-303 K.


76

0
5
10
15
20
25
270 275 280 285 290 295 300 305
Temperature [K]
P
r
e
s
s
u
r
e

[
b
a
r
]
Model
Experimental value

Figure 10-6. The vapor pressure of the system H
2
S-H
2
O where gas hydrates are present
correlated with the estimated Extended UNIQUAC parameters from all the collected data
(Scheffer 1913; Selleck 1952).

The vapor pressure of pure H
2
S correlated with the estimated Extended UNIQUAC
parameters where all the collected data is used is seen in Figure 10-7. It is seen that
correlation of the Extended UNIQUAC model and the SRK EoS correlate the
experimental data very well.
0
10
20
30
40
50
60
70
80
90
100
230 250 270 290 310 330 350 370 390
Temperature [K]
P
r
e
s
s
u
r
e

[
b
a
r
]
Model
Experimental value

Figure 10-7 The vapor pressure of pure H
2
S correlated with the estimated Extended
UNIQUAC parameters with all the collected data used.

In Figure 10-8 the vapor pressure for the binary system H
2
S-H
2
O is correlated by the
Extended UNIQUAC model with the estimated parameters for H
2
S and HS
-
and the SRK

77

EoS. The parameters estimated are with use of all the experimental data collected from
all the system investigated in this work. In Figure 10-9 a close up of Figure 10-8 is seen
at the region with low pressure and low molality of H
2
S. By comparing the correlation
obtained in section 8 it is seen that the correlation presented in this section (9) is not as
good as in section 8. The correlation is in general good, but the isotherms 90C,
104.4C, and 120C are not correlated well. The other isotherms at temperatures lower
than 90C are correlated well.

0
10
20
30
40
50
60
70
0 0,5 1 1,5 2
P
r
e
s
s
u
r
e

[
b
a
r
]
0C Mod
0C Exp
5C Mod
5C Exp
10C Mod
10C Exp
15C Mod
15C Exp
20C Mod
20C Exp
25C Mod
25C Exp
30C Mod
30C Exp
37.8C Mod
37.8C Exp
40C Mod
40C Exp
50C Mod
50C Exp
60C Mod
60C Exp
71C Mod
71C Exp
71.1C Mod
71.1C Exp
90C Mod
90C Exp
104.4C Mod
104.4C Exp
120C Mod
Figure 10-8. The vapor pressure for the binary system H
2
S-H
2
O correlated by the Extended
UNIQUAC parameters with the estimated parameters where all the collected was used.

In Figure 10-9 the vapor pressure for the binary system H
2
S-H
2
O is correlated by the
2
S and HS
-
and the SRK
EoS. The parameters estimated in this section are with use of all the experimental data
collected from all the system investigated in this work.

78

0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
2
2,2
0,02 0,07 0,12 0,17 0,22 0,27
P
r
e
s
s
u
r
e

[
b
a
r
]
0C Mod
0C Exp
5C Mod
5C Exp
10C Mod
10C Exp
15C Mod
15C Exp
20C Mod
20C Exp
25C Mod
25C Exp
30C Mod
30C Exp
37.8C Mod
37.8C Exp
40C Mod
40C Exp
50C Mod
50C Exp
60C Mod
60C Exp
Figure 10-9. The vapor pressure for the binary system H
2
S-H
2
O correlated by the Extended
UNIQUAC parameters with the estimated parameters where all the collected was used.

As a conclusion of this section it is concluded that the Extended UNIQUAC model with
the estimated parameters for H
2
S and HS
-
, the SRK EoS and the gas hydrate model
correlate the systems H
2
S, H
2
S-H
2
O, H
2
S-H
2
O-gas hydrates, and H
2
S-H
2
O-NH
3
well.
The ternary system H
2
S-H
2
O-NH
3
, the pure H
2
S system and the H
2
S-H
2
O-gas hydrate
system are correlated very well. The H
2
S-H
2
O system is in general correlated well, but
the isotherms at 90C, 104.4C, and 120C are not correlated well. The best correlation
for this system is obtained by using the parameters presented in 8.

Conclusion

79

11 Conclusion

Parameters for the Extended UNIQUAC model have successfully been estimated for the
hydrogen sulfide species H
2
S and HS
-
. Interaction parameters for H
2
S and HS
-
in the
systems H
2
S-H
2
O and H
2
S-H
2
O-NH
3
were successfully estimated. The parameters were
estimated from a large amount of collected experimental data (639 data points). The
2
S and HS
-
and the SRK
EoS correlate the pure H
2
S system, the binary H
2
S-H
2
O system, and the ternary H
2
S-
H
2
O-NH
3
systems very well. The Extended UNIQUAC model could therefore prove
useful when designing process equipment for these systems.
Langmuir parameters for hydrogen sulfide in the system H
2
S-H
2
O were estimated by
using the gas hydrate model presented by Munck (1988). A minor number of
experimental data points (23) were collected and some uncertainties of the parameters
exist. However, the gas hydrate model, the Extended UNIQUAC and the SRK EoS
correlate the experimental data very well with the estimated Langmuir parameters and
the estimated Extended UNIQUAC parameters.
In this work a comprehensive review of the literature for the systems H
2
S, H
2
S-H
2
O (with
and without gas hydrates), H
2
S-CO
2
-H
2
O and H
2
S-NH
3
-H
2
O was carried out. The review
included collection of a large number of VLE and a minor number of SLVE (gas hydrate
data) experimental data. The most important VLE models were presented and the gas
hydrate model presented by Munck (1988) was presented and discussed. Some
uncertainty of the physical properties in the gas hydrate model was discovered.
It was argued that the very scarce experimental data found in the literature for the
system H
2
S-CO
2
-H
2
O was wrong. The data could therefore not be used to estimate the
parameters in the Extended UNIQUAC model.
The successful correlation of the VLE for the systems H
2
S, H
2
S-H
2
O and H
2
S-CO
2
-H
2
O
by use of the Extended UNIQUAC model and the SRK EoS can be used to describe the
phase behavior in a wide range of temperature, pressure and molality. This means that
the model most likely can be useful when designing separation equipment and
separation processes in order to minimize the outlet of these undesirable compounds
from for example the exhaust gas of coal-fired power plants.
In this work a successful correlation of the phase behavior for the system H
2
S-H
2
O
where gas hydrates are present was obtained. The work presented here can therefore
Conclusion

80

prove useful when for example preventing plugging of transmission lines and designing
process equipment.
Future work

81

12 Future work

The parameters in the Extended UNIQUAC model could most likely be estimated more
accurately resulting in an even better description of the phase behavior of the treated
systems. Especially would it be of interest to estimate the HS
-
ion more accurately. A
better estimate of the HS
-
ion could most likely be obtained by using SLE experimental
data from, for example, the systems NaOH-H
2
S-H
2
O and KOH-H
2
S-H
2
O.
Due to the lack of experimental data for the H
2
S-CO
2
-H
2
O system experimental data
could be obtained in order to estimate the interaction parameters between H
2
S species
and CO
2
species in the Extended UNIQUAC model. A natural continuation of this work
would be to estimate the interaction parameters in the Extended UNIQUAC model
between the H
2
S species and the species SO
2
and HCN, since these components are
often present in the process of gasification of coal.
The estimated Langmuir constants for H
2
S could be investigated further, since there is a
relatively big uncertainty connected to these parameters. Experimental data for the
system H
2
S-H
2
O at gas hydrate conditions could be obtained and thereby estimate the
Langmuir parameters better for H
2
S in structure I.
The quaternary system H
2
S-H
2
O-NH
3
-CO
2
could be investigated.
References

A

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Appendices

i

13 Appendices
13.1 Appendix A
13.1.1 Concentration calculations for the H
2
O-H
2
S system
In this appendix the equations used to estimate the concentrations of hydrogen
sulfide species with the assumption that the system is ideal is presented.
The equations used to determine the concentrations of the species in the H
2
S-
H
2
O system were set up and solved in the math program Maple 11. The Maple
output that is presented further down corresponds to a total molality of 3 for
hydrogen sulfide. The program gave four solutions (separated by the curly
brackets), but only the first one is valid since the other solutions have no physical
meaning (negative molality).
The first three equations (1, 2 and 3) are equilibrium equations. Equation 4 is a
mass balance for sulfide. Equation 5 is the electro neutrality condition that
implies no net charge in the solution. Equation 6 is a mass balance for oxygen.
The molality of water is the reciprocal of the molar mass of water (eq. 6). 1 kg of
water is considered in the calculations.

The value of respectively the first and second dissociation equilibrium constant
for hydrogen sulfide and equilibrium constant for water are as follows.

k1=1.01877132e-7

k2=1.21569950e-13

kw=1.012707941965e-14

> eq1 := 1.01877132e-7 = (HS*H)/(H2S);

> eq2 := 1.21569950e-13 = (S*H)/HS;

> eq3 := 1.012707941965e-14 = OH*H;

Appendices

ii

> eq4 := 3=H2S+HS+S;
> eq5 := H=OH+HS+2*S;

> eq6 := 1/0.01801528 = H2O+OH;

Determination of concentrations (solving equations) and the output is seen.

> solve( [eq1, eq2, eq3, eq4, eq5, eq6], [H2S, HS, S, OH,
H, H2O] );

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Thermodynamic Modeling of

Hydrogen Sulfide Solubility in Weak

is the symmetrical activity coefficient at infinite solution and

is rational, unsymmetrical chemical potential of component i .

for solute i (ion or

is a Debye-Hckel parameter and I is the ionic strength.

is the partial molar volume of molecular solute at infinite dilution and

. The data from Lee (1977) was taken from a compendium by

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