Calorimetric Measurements of The Molar H

CALORIMETRIC MEASUREMENTS OF THE MOLAR
HEAT CAPACITY AND THE MOLAR EXCESS
ENTHALPY FOR VARIOUS ALKANOLAMINES IN
AQUEOUS SOLUTIONS
A Thesis
Submitted to the Faculty of Graduate Studies and Research
In Partial Fulfillment of the Requirements
for the Degree of
Master of Applied Science
in Industrial Systems Engineering
University of Regina
by
Mayur Mundhwa
Regina, Saskatchewan
February, 2007
Copyright © 2007: M. Mundhwa

ABSTRACT
The experimental measurements of the molar heat capacity and molar excess enthalpy
for 2-((2-Aminoethyl)amino)ethanol, 3-Amino-1-Propanol, 2-(Methylamino)ethanol, 1-
Amino-2-Propanol, and N-N-Dimethylethanolamine in water were carried in a C80 heat
flow calorimeter at different temperatures and for the entire range of the mole fractions.
The estimated uncertainty in the measured values of the molar heat capacity and molar
excess enthalpy was found to be ± 2 %.
Among the five studied alkanolamines, 2-((2-Aminoethyl)amino)ethanol exhibited
the highest molar heat capacity values and 2-(Methylamino)ethanol exhibited the lowest.
The same solvent also exhibited the highest molar excess enthalpy values on the negative
side (exothermic mixing process), followed by N-N-Dimethylethanolamine, 2-
(Methylamino)ethanol, 3-Amino-1-Propanol, and 1-Amino-2-Propanol.
The molar excess heat capacities were calculated from the experimental molar heat
capacities and correlated as a function of the mole fractions employing the Redlich-Kister
equation. The molar excess enthalpy values were also correlated as a function of the mole
fractions employing the Redlich-Kister equation. The molar enthalpies were also
calculated at infinite dilution.
The molar excess enthalpy values were modeled using the solution theory models:
NRTL (Non Random Two Liquid theory) and UNIQUAC (UNIversal QUAsi Chemical
theory). The molar excess enthalpy values were also modeled using the group
contribution model: modified UNIFAC (UNIversal quasi chemical Functional group
Activity Coefficients - Dortmund). The modified UNIFAC was found to be the most
i
accurate and reliable model for the representation and prediction of the molar excess
enthalpy values.
The present study confirms that the molar heat capacities of alkanolamines are
dominated by –CH2, –OH and amine group contributions which increase with increasing
temperature. The study also confirmed that the molar excess enthalpy values are
dominated by the interaction between –OH and amine groups. The study observed the
molar excess enthalpy values also depend upon the positions of the –OH and –NH2
groups in the primary alkanolamines. Finally, this study confirmed by studying the molar
excess enthalpies of MAE and DMEA that the –CH3 group corresponds to the higher
molar excess enthalpy values on the negative side.
ii
ACKNOWLEDGEMENTS
I would like to express my gratitude to my supervisor, Dr. Amr Henni, whose
guidance, thought provoking suggestions, encouragement and financial assistance
supported me throughout my research. I would also like to thank all the people, who in
different ways helped me with my work on this Master’s thesis.
iii
DEDICATION
I would like to dedicate my thesis to my mother Rajeshriben, who taught me even the
largest task can be accomplished if it is done one step at a time and to my father
Arjunbhai, who taught me the best kind of knowledge to have is that which is learned for
its own sake. This thesis is also dedicated to my brother Himanshu.
Finally, this thesis is dedicated to all those who believe in the richness of learning.
iv
TABLE OF CONTENTS
ABSTRACT i
ACKNOWLEDGEMENT iii
DEDICATION iv
TABLE OF CONTENTS v
LIST OF TABLES viii
LIST OF FIGURES xiii
LIST OF SYMBOLS xvi
1. INTRODUCTION 1
1.1 Objectives 2
1.2 Systems studied 3
1.2.1 2-((2-Aminoethyl)amino)ethanol 4
1.2.2 3-Amino-1-Propanol 4
1.2.3 2-(Methylamino)ethanol 5
1.2.4 1-Amino-2-Propanol 5
1.2.5 N-N-Dimethylethanolamine 6
2. THERMODYNAMICS 8
2.1 Calorimetric methods 10

2.1.1 Adiabatic calorimeter 10
2.1.2 Isothermal calorimeter 11
2.1.3 Isothermal dilution calorimeter 12
2.1.4 Flow calorimeter 13
2.2 Correlation and prediction approaches 15
2.2.1 Empirical expressions 15
2.2.1.1 Molar excess heat capacity 15
v
2.2.1.2 Molar excess enthalpy 15
2.2.2 Solution theory methods 16
2.2.3 Group contribution methods 18
2.3 NRTL (Non-Random Two Liquid) model 19
2.4 UNIQUAC (UNIversal QUAsi-Chemical Theory) model 20
2.5 Modified UNIFAC (Dortmund) model 23
2.6 Determination of the parameters 25
3. EXPERIMENTAL STUDIES 27
3.1 Experimental apparatus 27

3.1.1 Overview of the C80 calorimeter 27
3.2 Calibration of the C80 calorimeter 31
3.2.1 Sensitivity calibration 31
3.2.2 Temperature calibration 32
3.3 Molar heat capacity (Cp) measurements 36
3.3.1 Methods of molar heat capacity (Cp) measurement 36
3.3.1.1 Continuous two steps method 38
3.3.1.2 Continuous three steps method 38
3.4 Molar excess enthalpy (HE) measurements 39
3.4.1 Membrane mixing cell 41
3.5 Sources of error 44
3.6 Verification of the C80 heat flow calorimeter 44
3.6.1 Molar heat capacity measurements 44
3.6.2 Molar excess enthalpy measurements 45
3.7 Solution preparation 50
4. EXPERIMENTAL RESULTS AND DISCUSSION 52
4.1 Materials 52
4.2 Molar heat capacity measurements 52
vi
4.2.1 2-((2-Aminoethyl)amino)ethanol (AEEA) 53
4.2.2 3-Amino-1-Propanol (AP) 57
4.2.3 2-(Methylamino)ethanol (MAE) 60
4.2.4 1-Amino-2-Propanol (MIPA) 64
4.2.5 N-N-Dimethylethanolamine (DMEA) 67
4.3 Comparison of Cp values of alkanolamines 71
4.4 Molar excess enthalpy measurements 73
4.4.1 2-((2-Aminoethyl)amino)ethanol (AEEA) 73
4.4.2 3-Amino-1-Propanol (AP) 81
4.4.3 2-(Methylamino)ethanol (MAE) 88
4.4.4 1-Amino-2-Propanol or Monoisopropanolamine (MIPA) 95
4.4.5 N-N-Dimethylethanolamine (DMEA) 102
4.5 Comparison of HE values of alkanolamines 109
5. CONCLUSION AND RECOMMENDATIONS 113
5.1 Conclusion 113

5.2 Recommendations 114
6. REFERENCES 115
7. APPENDICES 123
7.1 APPENDIX-A: Experimental data 123

7.2 APPENDIX-B: Molecular area and volume parameters 138
vii
LIST OF TABLES
Table (3.1) Sensitivity constants…………………………………………………………….…………………...32

Table (3.2) Temperature correction coefficients……………………………………………..…………..36
Table (3.3) Molar heat capacity data of MEA and MDEA………………………………..………..46
Table (3.4) Molar excess enthalpies of (DEA + H2O) and (MDEA + H2O)
systems..........................................................................................................................................................48
Table (4.1) Redlich-Kister equation fitting coefficients for the molar excess heat
capacity ( C pE ) (equation (4.3)), for AEEA (1) + water (2) mixtures from
(303.15 to 353.15) K……………………………………………………………….………………..56

capacity ( C pE ) (equation (4.3)), for AP (1) + water (2) mixtures from
(303.15 to 353.15) K………………………………………………………………….……………..59

Table (4.3) Comparison of the molar heat capacity (Cp) values for pure MAE……….....63
capacity ( C pE ) (equation (4.3)), for MAE (1) + water (2) mixtures from
(303.15 to 353.15) K………………………………………………………….……………………..63

capacity ( C pE ) (equation (4.3)), for MIPA (1) + water (2) mixtures from
(303.15 to 353.15) K…………………………………………………………………….…………..66

Table (4.6) Comparison of the molar heat capacity (Cp) values for pure DMEA………70
capacity ( C pE ) (equation (4.3)), for DMEA (1) + water (2) mixtures from
(303.15 to 353.15) K……………………………………………………….………………………..70

Table (4.8a) Redlich-Kister equation fitting coefficients for the molar excess enthalpy
(HE) (equation 4.8), for AEEA (1) + water (2) mixtures for (298.15,
313.15, and 323.15) K………………………………………………………………………………77
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Table (4.8b) Molar enthalpies of AEEA at infinite dilution in water, ( ΔH 1∞ ), and of
water at infinite dilution in AEEA, ( ΔH 2∞ ), for (298.15, 313.15, and

323.15) K……………………………………………………………………………..…………………...77
Table (4.9a) NRTL and UNIQUAC equations parameters for the molar excess enthalpy
data of AEEA (1) + water (2) for (298.15, 313.15, and 323.15) K……..…...80
Table (4.9b) Modified UNIFAC (Dortmund) equation parameters for the molar excess
enthalpy data of AEEA (1) + water (2) for (298.15, 313.15, and 323.15)
K……………………………………………………………………………………………………………….80
(HE) (equation (4.9)), for AP (1) + water (2) mixtures for (298.15, 313.15,
and 323.15) K…………………………………………………………………………..……………….83
Table (4.10b) Molar enthalpies of AP at infinite dilution in water, ( ΔH 1∞ ), and of water
at infinite dilution in AP, ( ΔH 2∞ ), for (298.15, 313.15, and 323.15) K…...83

Table (4.11a) NRTL and UNIQUAC equations’ parameters for the molar excess
enthalpy data of AP (1) + water (2) for (298.15, 313.15, and 323.15)
K.........................................................................................................................................................................87
Table (4.11b) Modified UNIFAC (Dortmund) equations’ interaction parameters for the
molar excess enthalpy data of AP (1) + water (2) for (298.15, 313.15, and
323.15) K………………………………………………………………………..………………………...87
(HE) (equation (4.10)), for MAE (1) + water (2) mixtures for (298.15,
313.15, and 323.15) K………………………………………………………………………………91
Table (4.12b) Molar enthalpies of MAE at infinite dilution in water, ( ΔH 1∞ ), and of
water at infinite dilution in MAE, ( ΔH 2∞ ), for 298.15 K……………….………...91
Table (4.12c) Molar enthalpies of MAE at infinite dilution in water, ( ΔH 1∞ ), and of
water at infinite dilution in MAE, ( ΔH 2∞ ), for (298.15, 313.15, and

323.15) K……………………………………………………………………………..…………………...91
data of MAE (1) + water (2) for (298.15, 313.15 and 323.15) K………...…..94
ix
molar excess enthalpy data of MAE (1) + water (2) for (298.15, 313.15
and 323.15) K…………………………………………………………………………..……………….94
(HE) (equation 4.11), for MIPA (1) + water (2) mixtures for (298.15,
313.15, and 323.15) K………………………………………………………………………………97
Table (4.14b) Molar enthalpies of MIPA at infinite dilution in water, ( ΔH 1∞ ), and of
water at infinite dilution in MIPA, ( ΔH 2∞ ), for (298.15, 313.15, and

323.15) K…………………………………………………………………………………..……………...97
data of MIPA (1) + water (2) for (298.15, 313.15, and 323.15) K…….…..101
molar excess enthalpy data of MIPA (1) + water (2) for (298.15, 313.15,
and 323.15) K………………………………………………………………………….……………...101
Table (4.16a) Redlich-Kister equation fitting coefficients for the excess enthalpy (HE)
(equation 4.12), for DMEA (1) + water (2) mixtures for (298.15, 313.15,
and 323.15) K…………………………………………………………………………….…………...104
Table (4.16b) Molar enthalpies of DMEA at infinite dilution in water, ( ΔH 1∞ ), and of
water at infinite dilution in DMEA, ( ΔH 2∞ ), for 298.15 K………...…………..104
Table (4.16c) Molar enthalpies of DMEA at infinite dilution in water, ( ΔH 1∞ ), and of
water at infinite dilution in DMEA, ( ΔH 2∞ ), for (298.15, 313.15, and

323.15) K……………………………………………………………………….……………………….104
data of DMEA (1) + water (2) for (298.15, 313.15, and 323.15) K…….…108
molar excess enthalpy data of DMEA (1) + water (2) for (298.15, 313.15,
and 323.15) K……………………………………………………………….………………………...108
Table (A1) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for AEEA (1)
+ water (2) mixtures from (303.15 to 353.15) K……………………...…………….123
x
Table (A2) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for AP (1) +
water (2) mixtures from (303.15 to 353.15) K……………………………………….124

Table (A3) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for MAE (1) +
water (2) mixtures from (303.15 to 353.15) K……………………………………….125

Table (A4) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for MIPA (1)
+ water (2) mixtures from (303.15 to 353.15) K…………………………...……….126

Table (A5) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for DMEA (1)
+ water (2) mixtures from (303.15 to 353.15) K…………………………...……….127

Table (A6) Molar excess heat capacity ( C pE /J·mole-1·K-1), for AEEA (1) + water (2)
mixtures from (303.15 to 353.15) K………………………………………………………129

Table (A7) Molar excess heat capacity ( C pE /J·mole-1·K-1), for AP (1) + water (2)

Table (A8) Molar excess heat capacity ( C pE /J·mole-1·K-1), for MAE (1) + water (2)

Table (A9) Molar excess heat capacity ( C pE /J·mole-1·K-1), for MIPA (1) + water (2)

Table (A10) Molar excess heat capacity ( C pE /J·mole-1·K-1), for DMEA (1) + water (2)

Table (A11) Molar excess enthalpy (HE/J·mole-1), for AEEA (1) + water (2) mixtures
for (298.15, 313.15, and 323.15) K…………………………………………….…………..133
Table (A12) Molar excess enthalpy (HE/J·mole-1), for AP (1) + water (2) mixtures for
(298.15, 313.15, and 323.15) K……………………………………………………………...134
Table (A13) Molar excess enthalpy (HE/J·mole-1), for MAE (1) + water (2) mixtures for
(298.15, 313.15, and 323.15) K……………………………………………………………...135
Table (A14) Molar excess enthalpy (HE/J·mole-1), for MIPA (1) + water (2) mixtures
for (298.15, 313.15, and 323.15) K…………………………………………….…………..136
Table (A15) Molar excess enthalpy (HE/J·mole-1), for DMEA (1) + water (2) mixtures
for (298.15, 313.15, and 323.15) K…………………………………………….…………..137
xi
Table (B1) Molecular surface area and volume parameters for the UNIQUAC
Model……………………………………………………………………………………………………...138
Table (B2) Main groups and subgroups and the corresponding van der Waals
quantities for the modified UNIFAC (Dortmund) model………………………139
xii
LIST OF FIGURES
Figure (1.1) Chemical structures of the selected alkanolamines……………………………...…….7

Figure (3.1) Block diagram of C80 heat flow calorimeter………………………………..………….28
Figure (3.2) Sectional view of the C-80 heat flow calorimeter…………………………...……….29
Figure (3.3) Sensitivity calibration curve……………………………………………………………………..33
Figure (3.4) Temperature calibration with Indium at 0.4 K/min of scanning rate……….35
Figure (3.5) Standard cell for the molar heat capacity (Cp) measurement…………………...37
Figure (3.6) Three steps method for determination of molar heat capacity signals…......40
Figure (3.7) Molar excess enthalpy graph……………………………………………………………...…….42
Figure (3.8) Membrane mixing cell for the molar excess enthalpy measurement……….43
Figure (3.9) Comparison of the molar heat capacity data of pure MEA……………………...47
Figure (3.10) Comparison of the molar heat capacity data of pure MDEA………………..….47
Figure (3.11) Molar excess enthalpies of DEA (1) + water (2) system at 298.15 K……...49
Figure (3.12) Molar excess enthalpies of MDEA (1) + water (2) system at 313.15 K…..49
Figure (4.1) Molar heat capacity of AEEA in aqueous solution at various
temperatures……………………………………………………………………………………………...54
Figure (4.2) Molar excess heat capacity of AEEA in aqueous solution………………….……54
Figure (4.3) Molar heat capacity of AP in aqueous solution at various temperatures...58
Figure (4.4) Molar excess heat capacity of AP in aqueous solution.............................................58
Figure (4.5) Molar heat capacity of MAE in aqueous solution at various
temperatures……………………………………………………………………………………………...61
Figure (4.6) Molar excess heat capacity of MAE in aqueous solution…………………….…..61
Figure (4.7) Molar heat capacity of MIPA in aqueous solution at various
temperatures……………………………………………………………………………………………...65
Figure (4.8) Molar excess heat capacity of MIPA in aqueous solution………………….…….65
Figure (4.9) Molar heat capacity of DMEA in aqueous solution at various
temperatures……………………………………………………………………………………………...68
Figure (4.10) Molar excess heat capacity of DMEA in aqueous solution……………………...68
Figure (4.11) Comparison of Cp values for the five selected alkanolamines………………....72
xiii
Figure (4.12) Molar excess enthalpies for AEEA (1) + water (2) mixtures……………...……74
Figure (4.13) Molar excess enthalpies of binary mixtures AEEA, diethylamine, MEA,
diethanolamine and ethanol, in water at 298.15………………………………….……74
Figure (4.14) Molar excess enthalpy of AEEA (1) + water (2) represented by the NRTL
Model…………………………………………………………………………………….………………….78
Figure (4.15) Molar excess enthalpy of AEEA (1) + water (2) represented by the
UNIQUAC Model.................................................................................................................................78
UNIFAC Model………………………………………………….…………………………………….79
Figure (4.17) Molar excess enthalpies for AP (1) + water (2) mixtures……………….………..82
Figure (4.18) Molar excess enthalpy of AP (1) + water (2) represented by the NRTL
Model……………………………………………………………………………….……………………….85
Figure (4.19) Molar excess enthalpy of AP (1) + water (2) represented by the
UNIQUAC Model.................................................................................................................................85
Figure (4.20) Molar excess enthalpy of AP (1) + water (2) represented by the UNIFAC
Model………………………………………………………………………….…………………………….86
Figure (4.21) Molar excess enthalpies for MAE (1) + water (2) mixtures.................................89
Figure (4.22) Molar excess enthalpies for MAE (1) + water (2) mixtures at 298.15
K.........................................................................................................................................................................89
Figure (4.23) Molar excess enthalpy of MAE (1) + water (2) represented by the NRTL
Model…………………………………………………………………………………….………………….92
Figure (4.24) Molar excess enthalpy of MAE (1) + water (2) represented by the
UNIQUAC Model.................................................................................................................................92
UNIFAC Model…………………………………………………………………….………………….93
Figure (4.26) Molar excess enthalpies for MIPA (1) + water (2) mixtures………………...….96
Figure (4.27) Molar excess enthalpy of MIPA (1) + water (2) represented by the NRTL
Model…………………………………………………………………………….………………………….99
Figure (4.28) Molar excess enthalpy of MIPA (1) + water (2) represented by the
UNIQUAC Model.................................................................................................................................99
xiv
UNIFAC Model……………………………………………………………………………………...100
Figure (4.30) Molar excess enthalpies for DMEA (1) + water (2) mixtures………….…….103
Figure (4.31) Molar excess enthalpies for DMEA (1) + water (2) mixtures at 298.15
K......................................................................................................................................................................103
Figure (4.32) Molar excess enthalpy of DMEA (1) + water (2) represented by the NRTL
Model……………………………………………………………………………………………………...106
Figure (4.33) Molar excess enthalpy of DMEA (1) + water (2) represented by the
UNIQUAC Model………………………………………………………………..…………………106
UNIFAC Model……………………………………………………………………………………...107
Figure (4.35) Comparison of the molar excess enthalpies of the five studied
alkanolamines at 298.15 K..........................................................................................................111
xv
LIST OF SYMBOLS
a NRTL and UNIQUAC energy interaction parameter
ai Redlich-Kister equation parameters
anm UNIFAC group interaction parameter between groups n and m, K
b NRTL and UNIQUAC energy interaction parameter, K
bnm UNIFAC group interaction parameter between groups n and m
cnm UNIFAC group interaction parameter between groups n and m, K-1
Cp molar heat capacity, J/mole/K
C p (T ) molar heat capacity of the substance at the desired temperature T,
J/mole/K
C p, reference (T ) molar heat capacity of the reference substance (sapphire) at the desired
temperature T, J/mole/K
C pE molar excess heat capacity, J/mole/K
G parameter in NRTL model
gE excess Gibbs free energy, J/mole
H molar enthalpy, J/mole
ΔH E change in molar excess enthalpy, J/mole
ΔH 1∞ molar enthalpy of alkanolamine at infinite dilution
ΔH 2∞ molar enthalpy of water at infinite dilution
HE molar excess enthalpy, J/mole
xvi
F
H blank heat flow of the blank cells
F
H reference heat flow of the reference material (sapphire)
F
H sample heat flow of the sample
mreference mass of the Reference (Sapphire)
msample mass of the Sample
M Solvent mass of alkanolamine
M Water mass of water
MWSolvent molecular weight of alkanolamine
MWWater molecular weight of water
N number of moles
q, q’ surface area parameter
Q objective function to be minimized by data regression in equation (2.27)
Q heat transfer, J/mole
Qk relative van der Waals surface area of subgroup k
r volume parameter
R universal gas constant, 8.314472(15) J/K/mole
ΔT difference between the final (Tf) and initial (Ti) temperatures, K
Tf final temperature, K
Ti initial temperature, K
x mole fraction
x1 mole fraction of alkanolamine
x2 mole fraction of water
xvii
Xm group mole fraction of group m in the liquid phase
z coordination number
Z variables in equation (2.27)
Acronyms
AAD average absolute deviation
AEEA 2-((2-aminoethyl)amino)ethanol
AP 3-amino-1-propanol
DEA diethanolamine
DEA diethylamine
DMEA dimethylethanolamine
MAE 2-(methylamino)ethanol
MEA monoethanolamine
MDEA methyldiethanolamine
MIPA monoisopropanolamine or 1-Amino-2-Propanol
NRTL non random two liquid
UNIFAC universal quasi chemical functional group activity coefficients
UNIQUAC universal quasi chemical
Greek Letters
α randomness factor in NRTL model
Γk group activity coefficient of group k in the mixture
Γk(i ) group activity coefficient of group k in the pure substance
γ activity coefficient
θ area fraction in UNIQUAC model
xviii
θm surface fraction of group m in the liquid phase
ν k(i ) number of structural groups of type k in molecule i
σZ standard deviation of the indicated data in equation (2.27)
σ standard deviation
τ energy interaction parameters in NRTL and UNIQUAC models
Φ* segment fraction in UNIQUAC model
Ψnm UNIFAC group interaction parameter between groups n and m
Superscripts
c combinatorial
cal calculated value
E excess property
exp experimental value
r residual
Subscripts
1 alkanolamine
12 interactions between alkanolamine and water
2 water
21 interactions between water and alkanolamine
e estimated data in equation (2.27)
i number of variables in equation (2.27)
i, j any species
ij interactions between i and j component
j number of data points in equation (2.27)
xix
ji interactions between j and i component
k number of data sets in equation (2.27)
m measured data in equation (2.27)
nm groups n and m
xx
1. INTRODUCTION
Alkanolamine solutions have been extensively studied over the last 25 years due to
their industrial importance with regard to natural gas, synthetic ammonia plants, fossil-
fuel-fired power plants, chemical and petrochemical industries and the removal of acid
gas impurities such as carbon dioxide (CO2), hydrogen sulfide (H2S) and sulfur dioxide
(SO2) from gas streams (Astarita et al., 1983).
It is very important to capture CO2 and other acid gases to minimize the possible
threat of Greenhouse Effect but it presents technological challenges. The main challenge
for CO2 capture is in the reduction of the overall cost by reducing both the energy and
capital costs (Astarita et al., 1983). The United States Department of Energy noted
existing technology for CO2 capture is very expensive (on the order of $ 150 per ton of
carbon). They also noted analysis performed by SFA Pacific, Inc. that capture CO2 by
existing technologies could increase the cost of electricity by 2.5 cents to 4 cents/kWh.
Recent investigations (Kvamsdal et al., 2004; de Koeijer, 2004) indicate that acid-
gases capture technology will remain competitive in the future. To make this technology
more competitive, it is important to find new, faster and more energy-efficient solvents.
These commercial solvents must have a high net cyclic capacity, high absorption rate for
acid-gases and good chemical stability. In order to minimize the absorption of
components other than the acid-gases by the solvent, it is important to control the solvent
distribution, water content and operating conditions of the process. Because the
efficiency and the cost of any absorption process depend directly on the various
thermodynamic properties of the solvent, investigation of these properties is crucial (Kirk
1
and Othmer, 1992). Some of the most important thermodynamic properties are the molar
heat capacity (Cp) and molar excess enthalpy (HE).
The molar heat capacities (Cp) of alkanolamine solutions are required for the
calculation of the heat duty in condenser, heat exchanger and reboiler used in the gas-
treating processes. In addition, Cp is directly linked with temperature derivatives to basic
thermodynamic functions like enthalpy and entropy. Cp values are also necessary in
evaluating the effect of temperature on phase and reaction equilibria. They also serve as a
sensitive indicator of phase transitions and assist in the understanding of changes in the
structure of liquid solutions (Sandler, 1999; Perry et al., 1999; Prausnitz et al., 1999).
The molar excess enthalpy (HE) values of alkanolamine solutions are required to test
the feasibility of existing solution theories as well as in formulating new solution
theories. The HE values are also used for modeling the multistage, multi-component
equilibria in absorption and stripping columns (Sandler, 1999; Perry et al., 1999;
Prausnitz et al., 1999).
1.1 Objectives
This study focused on the experimental findings of the molar heat capacity (Cp) and
molar excess enthalpy (HE) of five alkanolamines.
The objectives of this study include:
• To determine experimentally the molar heat capacity and molar excess enthalpy for
the following five alkanolamines:
1) 2-((2-Aminoethyl)amino)ethanol (H2N(CH2)2NH(CH2)2OH, AEEA)
2) 3-Amino-1-Propanol (H2NCH2CH2CH2OH, AP)
3) 2-(Methylamino)ethanol (CH3NHCH2CH2OH, MAE)
2
4) 1-Amino-2-Propanol (CH3CH(OH)CH2NH2, MIPA)
5) N-N-Dimethylethanolamine ((CH3)2NCH2CH2OH, DMEA)
The measurements for the molar heat capacity of the above mentioned five
alkanolamines in water were carried out at eleven different temperatures ranging
from (303.15 to 353.15) K and for the entire range of mole fractions. The
experimental measurements of the molar excess enthalpy for the above mentioned
five alkanolamine + water systems were carried out at three different temperatures
(298.15, 313.15 and 323.15) K and for the entire range of mole fractions.
• To calculate the molar excess heat capacities from the experimental molar heat
capacities and to correlate them as a function of the mole fractions employing the
Redlich-Kister equation.
• To correlate the experimental molar excess enthalpies as a function of the mole
fractions employing the Redlich-Kister equation and the solution theory models:
NRTL (Non Random Two Liquid theory) and UNIQUAC (UNIversal QUAsi
Chemical theory) and the Modified UNIFAC (UNIversal quasi chemical Functional
groups Activity Coefficient, Dortmund).
1.2 Systems studied
The thermodynamic properties of five solvents were studied. Among them, two were
primary, one secondary, one tertiary, and one with primary and secondary amine. The
selection criteria and background information are given in the following sections. No
literature data of the molar heat capacity are available for the five selected alkanolamines,
except for the pure MAE and pure DMEA at selective temperatures. Also, no literature
3
data of the molar excess enthalpy are available for the five selected (alkanolamine +
water) systems, except the MAE + water and DMEA + water systems at 298.15 K.
1.2.1 2-((2-Aminoethyl)amino)ethanol
2-((2-Aminoethyl)amino)ethanol (H2N(CH2)2NH(CH2)2OH, AEEA) is commonly
used in the production of fuel additives, lube oil additives, chelating agents, surfactants
and fabric softeners among other applications. AEEA is an organic compound with
primary and secondary amine groups, which together with a hydroxyl group, combine the
features of an ethyleneamine and an ethanolamine.
In 2006, Ma’mun et al. found in a screening test AEEA could be a potential absorbent
for capturing CO2 from post-combustion exhaust gases as it displays a high absorption
rate combined with high net cyclic capacity. The net cyclic capacity of AEEA is
significantly higher than that of the well known monoethanolamine (MEA). It maintains
its absorption power at higher loadings. In terms of vapor pressure, AEEA has a much
lower vapor pressure (0.969 kPa) as compared to the industry standard MEA (15.9 kPa)
at the regeneration temperature of 393.15 K (Wilson et al., 2002). No published data was
available for the molar heat capacity and molar excess enthalpy of AEEA + water
systems.
1.2.2 3-Amino-1-Propanol
3-Amino-1-Propanol (H2NCH2CH2CH2OH, AP) is a primary amine, and is
commonly used as an intermediate in the production of pharmaceuticals, cosmetics,
corrosion inhibitors, synthetic resins and plasticizers. Bavbek et al. (1999) studied the
kinetics between AP and CO2 at 303.15 K and found higher reaction rates for AP with
CO2. The main reason for selecting this amine was to investigate the effects of the
4
primary amine group and hydroxyl group on the thermodynamic properties in
comparison with the other selected alkanolamines. No literature data for molar heat
capacity and molar excess enthalpy were found for the AP + water systems.
1.2.3 2-(Methylamino)ethanol
2-(Methylamino)ethanol (CH3NHCH2CH2OH, MAE) is a secondary amine in which
a methyl group substitutes a hydrogen atom of amino group of monoethanolamine (MEA,
a primary amine). The methyl group theoretically enhances the reaction kinetics because
it increases the basicity of the amine, while not appreciably increasing hindrance around
the nitrogen atom. In 2002, Ali et al. showed that the electron donating methyl group on
the nitrogen atom increases the reaction rate between CO2 and MAE. MAE demonstrated
high absorption rates and CO2 capacities based on performance tests on a pilot plant
scale. In addition, it has excellent regeneration characteristics. Compared with MEA,
20% less regeneration energy is required (Mimura et al., 1997). Maham et al. (1997)
measured the molar heat capacities of 99 % pure MAE at (299.1, 322.8, 348.5, 373.2, and
397.8) K. The molar heat capacities measured in the present study at (299.11, 322.80, and
348.50) K were compared with those measured by Maham et al. (1997). The molar
excess enthalpies measured here at 298.15 K were compared with those measured by
Touhara et al. (1982) under the same temperature condition.
1.2.4 1-Amino-2-Propanol
1-Amino-2-Propanol or monoisopropanolamine (CH3CH(OH)CH2NH2, MIPA) is a
primary amine used as an absorbent of acid gases in the refinery of natural gas and
purification of ammonia. It is also used as an emulsifying agent due to its solubility in
water and low alkalinity, and as a component of insecticides, surfactants, rubber
5
chemicals, corrosion inhibitors and pigment dispersants. Camacho et al. (1997) analyzed
the process of CO2 absorption at high pressures in aqueous MIPA, in relation to the
thermal effects. Bavbek et al. (1999) studied the kinetics between MIPA and CO2. They
found the reaction rate of MIPA is high compared to secondary MAE. No published data
for molar heat capacity and molar excess enthalpy were located for MIPA + water
systems.
1.2.5 N-N-Dimethylethanolamine
Dimethylethanolamine ((CH3)2NCH2CH2OH, DMEA) is a tertiary amine used in the
synthesis of dyestuffs, pharmaceuticals and emulsifiers. The key purpose for selecting
DMEA was to investigate the effects of the different groups (amine, methyl, and
hydroxyl) on the thermodynamic properties in comparison to the selected primary and
secondary alkanolamines. Maham et al. (1997) measured the molar heat capacities of 99
% pure DMEA at (299.1, 322.8, 348.5, 373.2, and 397.8) K. The molar heat capacities
measured in this study at (299.11, 322.80, and 348.50) K were thus compared to those
measured by Maham et al. (1997). The molar excess enthalpies measured in this study at
298.15 K were compared with those measured by Touhara et al. (1982) at the same
temperature.
6
2-((2-Aminoethyl)amino)ethanol 3-Amino-1-Propanol
2-(Methylamino)ethanol
1-Amino-2-Propanol N-N-Dimethylethanolamine
Figure (1.1) Chemical structures of the selected alkanolamines
7
2. THERMODYNAMICS
This chapter discusses calorimetry, molar heat capacity and molar excess enthalpy, as
well as calorimetric methods and an evaluation of a number of existing approaches for
correlating the experimental molar excess heat capacity and molar excess enthalpy
values. There are a number of ways the experimental molar excess heat capacity and
molar excess enthalpy values are correlated and represented, e.g., by empirical
representations, solution theory and group contribution methods. Three selected models
(NRTL, UNIQUAC and Modified UNIFAC-Dortmund) are also presented.
The word calorimetry comes from the Latin word for heat and the Greek word for
measure. A calorimeter is an instrument in which a chemical or physical process takes
place, and by which the heat flow to or from the process is measured to obtain the
required thermodynamic properties. The calorimeter is well-insulated so ideally no heat
interacts with the surroundings. Thus, any heat liberated or absorbed during the studied
process must be measured by the calorimeter. The process of measuring the quantity of
heat exchanged during a chemical or physical process is known as calorimetry.
Thermodynamically, the relationship between the changes in temperature (ΔT) and heat
(Q) transferred during the process is given by:
Q = CpΔT = C (Tf - Ti) (2.1)
Where Q is the heat transfer as a result of change in temperature, the proportionality
constant Cp is the molar heat capacity of a substance, which is defined as the amount of
heat required to change the temperature of the substance by one degree, and ΔT is the
difference between the final (Tf) and initial (Ti) temperatures of a process.
8
The molar excess enthalpy is also an important property in the field of chemical
engineering thermodynamics. It is used to calculate heat duties during mixing and
separation processes and is defined as the change in enthalpy per mole of solution formed
when the pure components are mixed at constant temperature and pressure. When defined
this way, the calorimetrically measured heat of mixing is identical to the molar excess
enthalpy (HE). The excess property of a solution is a measure of the difference between
the property value of a real solution and the value it would have as an ideal solution at the
same temperature, pressure, and composition. Mathematically the change in molar excess
enthalpy is
ΔH E = ΔH − ΔH id (2.2)
(
ΔH E = (H − ∑ xi H i ) − H id − ∑ xi H i ) (2.3)
Where, H is the enthalpy of the real solution, Hi is the enthalpy of the pure chemical
species and xi is the mole fraction of the pure components. For an ideal solution the
enthalpy, Hid, can be written as:
H id = ∑ xi H i (2.4)
The formation of an ideal solution results in no change in molecular energies i.e.,
ΔH id = 0 . Therefore, equation (2.3) is reduced to:
ΔH E = H − ∑ xi H i = ΔH (2.5)
Further, ΔH E can be reduced to HE, by the definition of an excess property:
H E = H − H id = ΔH E (2.6)
From equations (2.5) and (2.6), the enthalpy change of a mixing process, or heat of
mixing, is equal to the molar excess enthalpy of the mixing process (Smith et al., 2001;
Sandler, 1999; Perry et al., 1999).
9
The measurements of molar heat capacity and molar excess enthalpy for different
substances are accomplished by various types of calorimeters depending on the
application, availability and accuracy of the data required. These calorimeters are
classified based on the methods applied.
2.1 Calorimetric methods
2.1.1 Adiabatic calorimeter
Originally designed by McGlashan, the adiabatic calorimeter is one of the most
successful calorimeters for the measurement of heat effects of solid and/or liquid systems
over a wide range of temperatures. This heat effect includes the heats of formation, heats
of chemical reaction, latent heat of phase changes, molar heat capacity, and heats of
mixing (Larkin and McGlashan, 1961; Armitage and Morcom, 1969; Hill and Swinton,
1980; van Miltenburg et al., 1987). In an adiabatic calorimeter the two boundaries are
separated by a perfect insulator, so the majority of the heat produced is retained by the
calorimeter container causing its temperature to rise. The ΔT is measured by an
appropriate thermometer. Such calorimeters are also referred to as integrating apparatus
because they respond to the total heat produced during the reaction, stirring, evaporation
etc. The best types of adiabatic calorimeters are those in which the temperature of the
external boundary is continuously adjusted to match that of the internal boundary, so that
the net heat transfer between the two boundaries is zero and the temperature between the
two boundaries is zero. Other methods to reduce heat transfer between the two
boundaries are to minimize the heat transfer coefficient and to minimize the time for heat
exchange. The main disadvantages of adiabatic calorimeters are they have relatively large
thermal inertia and the temperature of the calorimeter changes during the course of an
10
experiment. Thus, it is not satisfactory for kinetic studies of chemical or biological
transformations.
2.1.2 Isothermal calorimeter
An alternative method to conduct calorimetric experiments adiabatically is in an
isothermal environment. The isothermal calorimeter has two advantages over the
adiabatic calorimeter: (1) No corrections are required for the change in heat content of the
mixing vessel, and (2) No compensation is needed for heat losses to the surroundings.
The isothermal calorimeter was originally developed (Mrazek and Van Ness, 1961;
Savini et al., 1966) for mixtures and has been further improved by Marsh and co-workers
(Stokes et al., 1969; Ewing et al., 1970). Malcolm and co-workers (Malcolm and
Rowlinson, 1957; Kersaw and Malcolm, 1968) described the isothermal calorimeter
based on the Bunsen calorimeter. The stability and accuracy of Bunsen type calorimeters
have been discussed by Davies and Pritchard (1972).
When using the isothermal calorimeter, the temperature of the vessel must be
constant throughout the experiment. To maintain constant temperature, the heat produced
in the vessel is transferred as rapidly as possible to the outer jacket through a high
thermal conductivity medium. This type of calorimeter is capable of producing highly
precise and accurate results for different types of heat effect and is widely used for molar
excess enthalpy measurements (Alonso et al., 1987; Lim et al., 1994). There are two
ways to achieve a constant temperature. One is based on solid-liquid or liquid vapor
phase change. For example, solid-liquid phase change is used in the ice calorimeter
(Ginnings et al., 1953). The volume change involved is used as a measure of the heat
added or removed. The main disadvantage of this calorimeter is the measurements can
11
only be carried out at the phase change temperature of the calorimeter fluid. Another way
to keep the temperature constant is to use electrical heating to balance the removal of
heat, or to use electrical cooling (Peltier effect) to balance the addition of heat (Mann,
1954; Rossini, 1956). The major advantages of this type of calorimeter include easier
control of heat leakage and independence of results from the molar heat capacity of the
calorimeter since its temperature does not change.
2.1.3 Isothermal dilution calorimeter
The isothermal dilution calorimeter provides an alternative method of measuring the
molar excess enthalpy isothermally. For endothermic systems, one component is
injected slowly into a stirred vessel in which a second component has been placed. To
maintain the isothermal condition inside the calorimeter, electrical energy is added at an
appropriate rate. The addition of the second fluid may be terminated at any desired
composition and the heat of mixing may be determined from measurements of the
amount of liquid A originally in the vessel, as well as the amount of B added and the
amount of electrical energy added. Further addition of B allows the determination of the
heat of mixing at other compositions.
Usually the full composition range may be covered in two runs. For exothermic
experiments, electrical energy may be added continuously to raise the temperature
slightly above the thermostat temperature. As the second liquid is injected, the electrical
energy addition is reduced in such a way as to maintain isothermal operation.
An alternative method, and one which is vastly superior, is to use a Peltier
thermoelectric cooler to withdraw heat at a constant rate. In this method isothermal
conditions are maintained by continuously supplying electrical energy.
12
Dilution calorimeters normally use approximately 50 ml of each component to
cover the entire composition range. The precision of the measurements is about 0.2 %
of the maximum value of HE. A more detailed discussion of the various types of
isothermal dilution calorimeters is presented by Marsh (1978).
2.1.4 Flow calorimeter
The dilution calorimeter has one fluid flowing into a reservoir of another. The flow
calorimeter has both liquids injected into a mixing chamber at a steady and known rate.
Isothermal operation is achieved the same way for dilution calorimeter. The major
problem with the flow calorimeter lies in producing a steady, non-pulsed, but readily
variable flow rate. McGlashan and Stoeckli (1969) used a vapor pressure driven flow
system and achieved reproducibility of 0.25 % in the flow rates. They measured HE with
an accuracy of about one percent. The major drawback was their requirement of about
200 cm3 of each component.
Sturevant and Lyons (1969) developed a calorimeter requiring much smaller
samples but had a reproducibility of only two percent. Eliott and Wormald (1976)
constructed a flow calorimeter with a stated reproducibility of 0.2 %. Various
researchers have used modifications of the commercial isothermal flow calorimeter
(Gustin and Renon, 1973; Goodwin and Newshar, 1971; Harsted and Thomson, 1974).
Christensen et al. (1976) developed an isothermal flow calorimeter capable of
measuring both exothermic and endothermic heats capable of mixing over a large range
of pressures. Their modifications included the addition of a Peltier cooler and using a
long flat coil as the mixing vessel. Their precision was stated to be 0.4 percent.
13
Flow calorimeters have the advantage of being easily adaptable to measurements over
a wide range of temperatures and pressures and of being able to cover the full
composition range in only a few hours. The flow calorimeter is one of the best choices
for determining the heat of mixing for most liquid systems. The flow rates can be varied
in a continuous, known manner so that a complete HE composition curve can be produced
quickly with a precision of around 1 % (Rowlinson and Swinton, 1982). With flow
techniques, it is possible to avoid several of the difficulties that may arise in batch
calorimeters of more conventional design. In particular, it is unnecessary to use mercury
to separate the component liquids before mixing and the mixing can readily take place in
the absence of any vapor space. In addition, any desired composition is obtained directly
by setting the relative flow-rates of the components. Also, transient effects during the
initial formation of the mixture are unimportant (Tanaka et al., 1975). Typically, one
mole of each of the pure components is required to produce a complete set of results.
This type of calorimeter is not suitable for viscous fluids or for liquids with large
differences in density.
In practice, the choice of calorimeter depends on the research requirements. As for
the nature of the calorimetric experiment, a batch type calorimeter is usually suitable for
processes such as chemical reaction, phase change, and bio-processes; while a flow
calorimeter is much more efficient in measuring the heat of mixing of liquid systems.
This advantage appears to be especially important when the experiments involve multi
component systems.
14
2.2 Correlation and prediction approaches
The primary aim of the correlation is to maximize the extent of usage of the
experimental data. In addition to this, due to the difficulties involved in the experimental
measurements and the increasing time consumption with each additional component of a
multi-component mixture, it is highly desirable to develop practical approaches capable
of predicting the physical and chemical properties of multicomponent systems.
2.2.1 Empirical expressions
2.2.1.1 Molar excess heat capacity
In this study, the experimental molar excess heat capacity data of the aqueous
alkanolamines were correlated as a function of the mole fractions using the Redlich-
Kister equation (Redlich and Kister, 1948). This equation has the following form for
binary systems:
n
C pE /J·mole -1 ·K -1 = x1 x 2 ∑ a i ( x1 − x 2 )
i
(2.7)
i =0
Where, C pE is the molar excess heat capacity, x1 and x2 are the mole fractions of
alkanolamines and water respectively, and ai are the coefficients that are obtained from
least squares analysis of the dependence of C pE on x1 or x2.
2.2.1.2 Molar excess enthalpy
Molar excess enthalpy or heat of mixing values of the alkanolamine + water systems
were also correlated as a function of the mole fractions using the Redlich-Kister equation:
n
H E / J·mole -1 = x1 x 2 ∑ ai ( x1 − x 2 )
i
(2.8)
i =0
15
Where, H E is the molar excess enthalpy, x1 and x2 are the mole fractions of
alkanolamines and water respectively, and ai are the coefficients that are obtained from
least squares analysis of the dependence of H E on x1 or x2.
The most popular approaches for the heat of mixing correlation and prediction are
based on solution theory and group contribution models.
The majority of the following discussions have been presented by Prausnitz et al.
(1999).
2.2.2 Solution theory methods
Well known solution theories are the regular theory, the quasi-lattice theory, the two-
liquid theory, and the associated solution theory. Solution theories represent the behavior
of a solution in terms of its intermolecular forces and structure. This approach involves
one or more characteristic parameters which are fitted to the experimental data.
In 1946 and 1953 Wohl developed an equation based on the regular solution theory,
which is defined as one in which the components mix with no excess entropy, SE,
provided that there is no volume change upon mixing, i.e., SE = 0 and VE = 0. The main
advantage of this equation is that some rough physical significance can be assigned to the
equation parameters. This type of equation provides a good representation of interactions
of the molecules. Because all its parameters contribute different groups of molecules, this
equation is viewed as an empirical or semi-empirical equation. In other words, the greater
the number of molecules in a group, the greater the number of parameters are required.
Also, Wohl’s expansion for the excess Gibbs energy can be extended systematically to
multicomponent solutions.
16
In 1964, Wilson proposed an equation based on the local composition concept. He
replaced the mole fractions in Flory-Huggins equation with the local compositions. The
equation provides better representations of the non-ideal behavior of real systems rather
than that proposed by Wohl type with the same number of parameters and it is also
capable of representing multicomponent behavior with binary parameters. The main
disadvantage of Wilson’s equation is that it can not handle liquid-liquid immiscibility.
Wang (1996) noted that Wilson equation fails to provide reasonable results for systems
with relatively high HE values.
In 1968-69, Renon and Prausnitz developed the Non-Random Two-Liquid (NRTL)
model based on the two-liquid theory. In this model, they assumed that in a binary system
the liquid has a structure made up of cells of molecules of 1 and 2 types, each surrounded
by assortments of the same molecules, with each of the surrounding molecules in turn
surrounded in a similar manner. The accuracies of this model, for the correlation and the
prediction are similar to the Wilson equation but the model can be used for liquid-liquid
immiscible systems. The main disadvantage of NRTL model over Wilson equation is that
it requires three parameters for each pair of constituents. In 1978, Cruz and Renon
extended this model to electrolyte solutions. It provided good results in the representation
of the molar excess enthalpies of alcohol solutions when the model was combined with
associated solution models (Nagata et al., 1984 and 1985).
In 1975, Abrams and Prausnitz developed the Universal Quasi-Chemical
(UNIQUAC) equation with the concept of two-liquid model and local compositions.
They assumed expression of activity coefficients has two parts, one is the combinatorial
part, which is due to differences in size and shape of the molecules and the second is the
17
residual part, due to energetic interactions. They also showed the Wohl type of equation
and the Wilson and NRTL equations are special cases of the UNIQUAC equation when
suitable values of the parameters are assigned. The major characteristic of the UNIQUAC
equation are:
• Applicable to multicomponent mixtures in terms of binary parameters only
• Applicable to liquid-liquid equilibria
• Temperature dependency is valid over a moderate range
• Superior representation of mixtures of different molecular sizes
The main disadvantages of this equation are in the algebraic complexity of the
equation and often the representation of data is poorer than some simpler equations.
The development of solution theories relies on basic understanding of the solution at
the molecular level. But this method demonstrated great potential and promising future
despite being ideal.
2.2.3 Group contribution methods
There is one other approach for the representation of experimental data which is
based on the concept of group contribution. This approach is based on the assumption
that a real solution is composed of the constituent groups of its components. In 1925,
Langmuir suggested this concept for the calculation of thermodynamic properties. A
systematic development known as the analytical solution of groups (ASOG) was
established by Wilson and Deal (1962), which has been modified by Vera and Vidal in
1984 by an analytical group solution method, known as Simplified Group Method
Analysis (SIGMA). Another method known as the Universal Functional Activity
Coefficient (UNIFAC) has been developed by Frendenslund et al. in 1975. This equation
18
or model is based on the UNIQUAC method, the difference being in the residual term,
which contributes to the interaction of groups in the UNIFAC method. By reducing the
interactions between molecules to the interactions between their functional groups,
UNIFAC allows one to represent a large variety of experimental data with a reduced set
of parameters and to predict with reasonable confidence the behavior of systems for
which experimental data are unavailable.
Another good group contribution model known as DISQUAC (Dispersive-Quasi-
Chemical) model is developed by using simple extension of the quasi-chemical theory.
This model uses the structure-dependent interaction parameters. Each contact, either
polar or non-polar, is characterized by dispersive interchange energy and the polar
contacts are characterized by two additional parameters, the quasi-chemical interchange
energy and the coordination number.
Any group-contribution model requires very basic information about the constituent
groups of each component, but on the other hand it requires more time for calculations.
For the representation of experimental HE data, both the solution theory-related models
and group contribution models are superior.
2.3 NRTL (Non-Random Two Liquid) model
As mentioned previously in this chapter, the Non-Random Two-Liquid model is
based on the local composition concept and two-fluid theory. Renon and Prausnitz
(1968a, 1968b, and 1969) extended the concept of local composition which was
developed by Wilson (1964) for the two fluid theory.
The original form of the NRTL model has the following form for an excess Gibbs
energy:
19
gE ⎛ τ G τ 12 G12 ⎞
= x1 x 2 ⎜⎜ 21 21 + ⎟⎟ (2.9)
RT ⎝ x1 + x 2 G21 x 2 + x1G12 ⎠
, τ 21 = a 21 + 21 , G12 = exp(− α 12τ 12 ) , and G21 = exp(− α 21τ 21 )

b12 b
Where, τ 12 = a12 +
T T
The value of the non-randomness parameter, α , is regressed between 0 and 1 to
obtain more reliable and precise values of the parameters. The subscripts 1 and 2 denote
liquid components alkanolamine and water, respectively. For a binary system there are
five parameters a12, b12, a21, b21 and α , where the b terms represent temperature
dependency. The molar excess enthalpy, which indicates the temperature dependence of
the Gibbs free energy, can be determined by using the Gibbs-Helmholtz relation.
⎛ g Ex ⎞
d ⎜⎜ ⎟
HE ⎝ RT ⎟⎠
= (2.10)
R ⎛1⎞
d⎜ ⎟
⎝T ⎠
From equation (2.9) and (2.10), we can obtain the NRTL model for the molar excess
enthalpy:
HE ⎛ G b ( x (1 − ατ 21 ) + x 2 G 21 ) G12 b12 ( x 2 (1 − ατ 12 ) + x1G12 ) ⎞

= x1 x 2 ⎜⎜ 21 21 1 + ⎟
⎟ (2.11)
R ⎝ ( x1 + x G
2 21 ) 2
( x 2 + x G
1 12 ) 2
⎠
Gow (1993) used the partial excess enthalpy data with NRTL model to predict VLE
data. Hanks et al. (1971) also predicted the VLE data with NRTL by using excess
enthalpy data. Hanks et al. (1978) also showed the prediction of VLE data at higher
temperature using lower temperature excess enthalpy data.
2.4 UNIQUAC (UNIversal QUAsi-Chemical theory) model
Due to the lack of binary experimental data, it is difficult to obtain precise and
meaningful values of three binary parameters in the NRTL equation. In 1975, Abrams
20
derived an equation that extends the quasichemical theory developed by Guggenheim
(1952) for non-random mixtures to the mixtures or solutions of different molecular size.
This extension was called the UNIversal QUAsi-Chemical theory or, in short,
UNIQUAC.
The UNIQUAC model consists of two parts, (1) Combinatorial and (2) Residual.
The combinatorial part accounts for a combinatorial effects due to differences in
molecular size and shape and contains mole fraction, the average area fraction, and the
average segment fraction. These fraction values can be calculated from the pure-
component molecular structure constants depending on molecular size and external
surface areas which are from the van der Waals volume and surface areas of the
molecule. No adjustable binary parameters appear in this part and therefore no data or
empirical correlations are required to calculate the combinatorial contribution.
The residual part contributes inter-molecular forces and is computed from mole
fractions, area fractions and the energy of interactions between components. There are
two parameters representing the energy of interactions which are not measured or
tabulated, but must be determined empirically from vapor-liquid or liquid-liquid
equilibrium data.
The UNIQUAC equation is,
gE ⎛ gE ⎞ ⎛ gE ⎞
= ⎜⎜ ⎟⎟ + ⎜⎜ ⎟ (2.12)
RT ⎝ RT ⎠ combinatorial ⎝ RT ⎟⎠ residual
For a binary mixture,
⎛ gE ⎞ Φ* Φ* z ⎛ θ θ ⎞
⎜⎜ ⎟⎟ = x1 ln 1 + x 2 ln 2 + ⎜⎜ x1 q1 ln 1* + x 2 q 2 ln 2* ⎟⎟ (2.13)
⎝ RT ⎠ combinatorial x1 x2 2 ⎝ Φ1 Φ2 ⎠
21
⎛ gE ⎞
⎜⎜ ⎟⎟ ( ) (
= − x1 q1' ln θ1' + θ 2' τ 21 − x 2 q 2' ln θ 2' + θ1'τ 12 ) (2.14)
⎝ RT ⎠ residual
Where the z is the coordination number, and segment fraction, Φ * , and area fractions, θ
and θ ' , are given by
x1 r1 x 2 r2
Φ1* = Φ *2 = (2.15)
x1 r1 + x 2 r2 x1 r1 + x 2 r2
x1 q1 x2 q2
θ1 = θ1 = (2.16)
x1 q1 + x 2 q 2 x1 q1 + x 2 q 2
x1 q1' x 2 q 2'
θ1' = θ 2' = (2.17)
x1 q1' + x 2 q 2' x1 q1' + x 2 q 2'
b12 b21
a12 + a21 +
τ 12 = e T
τ 21 = e T
(2.18)
Parameters r, q, and q’ are pure-component molecular-structure constants depending
on the molecular size and the external surface areas. In the original equation q = q’. In
1978, Anderson adjusted q’ values for water and alcohols to obtain the optimum fit for
the systems containing water and alcohol components. The surface area parameters of the
selected alkanolamines are listed in Table (B1) of Appendix B. τ 12 and τ 21 are two
adjustable parameters. To obtain the expression of UNIQUAC equation for the excess
enthalpy, equation (2.10) is used. Only the residual term (equation 2.14) is used to obtain
the UNIQUAC equation for excess enthalpy as it contains the temperature dependency
term. From equation (2.14) and equation (2.10), the following form of the UNIQUAC
equation is derived.
HE ⎛ θ b τ ⎞ ⎛ θb τ ⎞
− = q1 x1 ⎜⎜ 2 21 21 ⎟⎟ + q 2 x 2 ⎜⎜ 1 12 12 ⎟⎟ (2.19)
R ⎝ θ1 + θ 2τ 21 ⎠ ⎝ θ 2 + θ1τ 12 ⎠
22
2.5 Modified UNIFAC (Dortmund) model
UNIFAC (UNIversal Functional Activity Coefficient) is based on the quasichemical
theory of liquid solutions proposed by Guggenheim (1952). In 1975, Abrams and
Prausnitz generalized this theory and in 1975 Fredenslund et al. applied this method to
functional groups within the molecules. This method has already been used in many areas
e.g. (1) for calculating the vapor-liquid equilibria (Fredenslund et al., 1977), (2) for
calculating the liquid-liquid equilibria (Magnussen et al., 1981), (3) for calculating the
solid-liquid equilibria (Gmehling et al., 1978), (4) for determining the activities in
polymer solutions (Oishi and Prauxnitz, 1978; Gottlieb and Herskowitz, 1981), (5) for
determining the vapor pressures of pure components (Jensen et al., 1981), (6) for
determining the influence of solvent on reaction rate (Lo and Paulaitis, 1981), (7) for
determining the flash points of solvent mixtures (Gmehling and Rasmussen, 1982), (8)
for determining the solubilities of gases (Nocon et al., 1983; Sander et al., 1983). This
literature is cited from Weidlich et al. (1987). Weidlich et al. noted, by considering a
couple of publications, (Thomas and Eckert, 1984) the results obtained by the UNIFAC
method for the calculation of activity coefficients at infinite dilution are unsatisfactory,
particularly for the systems with different sizes of molecules. They also noted the original
UNIFAC model is not able to calculate the excess enthalpy and thus temperature
dependence of the Gibbs excess energy with sufficient accuracy. For these reasons,
Weidlich et al. (1987) made some modifications in the original UNIFAC equation so the
vapor-liquid equilibria, activity coefficients at infinite dilution, and enthalpies of mixing
or heats of mixing can be calculated with sufficient accuracy using only one set of
parameters. The description of the original UNIFAC equation is given elsewhere
23
(Fredenslund et al., 1977). Here, only the temperature dependent term of the modified
UNIFAC (Dortmund) equation is considered as heats of mixing or molar excess enthalpy
data depend on temperature i.e. residual part of the modified UNIFAC (Dortmund)
equation. One of the main differences between the original UNIFAC and modified
UNIFAC (Dortmund) is the introduction of temperature-dependent interaction parameters
as:
⎡ a ⎤
Original UNIFAC: Ψnm = exp ⎢− nm ⎥ (2.20)
⎣ T ⎦
⎡ a + bnmT + c nmT 2 ⎤
Modified UNIFAC (Dortmund): Ψnm = exp⎢− nm ⎥ (2.21)
⎣ T ⎦
To obtain the expression of the modified UNIFAC (Dortmund) equation for the heat
of mixing or excess enthalpy, the Gibbs-Helmholtz equation (2.10) is used. The
expression for the UNIFAC model is:
gE
RT
(
= ∑ xi ln γ iR + ln γ iC ) (2.22)
i
Since the combinatorial part is temperature independent, only the residual part is used for
the calculation of excess enthalpy.
ln γ iR = ∑ν k(i ) (ln Γk − ln Γk(i ) ) (2.23)

k
⎛ ⎞
⎜ ⎛ ⎞ θ Ψ ⎟
ln Γk = Qk ⎜1 − ln⎜ ∑ θ m Ψmk ⎟ − ∑ m km ⎟ (2.24)
⎜ ⎝ m ⎠ m ∑ θ n Ψnm ⎟
⎝ n ⎠
From equation (2.10), (2.22), (2.23) and (2.24), we can obtain the following relations
⎡ ⎛ ∂ ln Γ ⎞ ⎛ ∂ ln Γk(i ) ⎞ ⎤
H E = − RT ∑∑ xiν k(i ) ⎢T ⎜ k
⎟ − T ⎜⎜ ⎟⎟ ⎥ (2.25)
i k ⎢⎣ ⎝ ∂T ⎠ P , x ⎝ ∂T ⎠ P , x ⎥⎦
24
Γk is the group activity coefficient of group k in the mixture and Γk(i ) is the group activity
coefficient of group k in the pure substance.
⎡ ⎤
⎢ Ψkm ∑ θ n Ψnm ⎥
⎛ ∂ ln Γk ⎞ (b + ln Ψmk + 2cmk T )Ψmk ⎡ ⎛ Ψkm ⎞ ⎤
T⎜ ⎟ = Qk ∑ θ m ⎢ mk + n
⎢bkm − bnm + ln⎜⎜ ⎟⎟ + (c km − c nm )2T ⎥ ⎥
⎝ ∂T ⎠ P , x m
⎢
⎢ ∑n n nk
θ Ψ ⎛ ⎞
⎜ ∑ θ n Ψnm ⎟
2
⎣ ⎝ Ψnm ⎠ ⎦⎥
⎥
⎢⎣ ⎝ n ⎠ ⎥⎦
(2.26)
where,
⎡ a + bnmT + c nmT ⎤ 2
Qm X m
∑ν j
m xj
Ψnm = exp⎢− nm ⎥ , θm = , and X m =
j
⎣ T ⎦ ∑ Qn X n n
∑∑ν
j n
n
j
xj
⎛ ∂ ln Γk( i ) ⎞
The above statement equation (2.26) also supplies to the expression T ⎜⎜ ⎟⎟
⎝ ∂T ⎠ P , x
van der Waals group parameters for the Modified UNIFAC (Dortmund) Method are
listed in Table (B2) of Appendix B.
2.6 Determination of the parameters
The parameters of the selected three models have been determined by using the
ASPEN PLUS software package, which has built in algorithms for the fitting of the
experimental data called the Data Regression System. ASPEN basically performs a non-
linear optimization by varying the parameters to minimize the value of Q in the following
objective function.
⎛
⎜ ⎛ ⎛Z −Z ⎞
2
⎞ ⎞⎟
Q = ∑k ⎜ ∑ j ⎜ ∑i ⎜⎜ e m
⎟⎟ ⎟ (2.27)
⎜ ⎜ σ ⎠i ⎟ ⎟⎟
⎝ ⎝ ⎝ Z
⎠ j ⎠k
where,
Q: Objective function to be minimized by data regression
25
Z: Variables
i: Number of variable
j: Number of data points
k: Number of data sets
e: Estimated data
m: Measured data
σZ : Standard deviation of the indicated data
The standard deviations are entered for every variable in each data set. In general, the
standard deviations were set to 0.05 for temperature, 0.1 % for mole fractions and 2 % for
the molar excess enthalpy values. To obtain the optimized values of the parameters, Britt-
Luecke’s algorithm was selected in ASPEN PLUS software.
26
3. EXPERIMENTAL STUDIES
This Chapter is an overview of the experimental apparatus i.e. Setaram C80
calorimeter, calibration of the C80 calorimeter, experimental procedures for measuring
the molar heat capacity and molar excess enthalpy, and verification of the C80
calorimeter along with the possible sources of error during the measurements. The
conclusion describes a calculation method for the preparation of the aqueous
alkanolamine solutions in terms of mole fractions.
3.1 Experimental apparatus
Measurements of the molar heat capacity and molar excess enthalpy were carried out
with “C80 Calvet Calorimeter” manufactured by Setaram Instrumentation (France). The
C80 calorimeter works on Tian-Calvet heat flow principles which were described in
detail by Calvet and Part (1963).
C80 calorimeter measures the rate at which the heat flows into a sample as a function
of temperature. The rate at which heat flows into the sample is the power required to keep
the temperature of the sample rising at a set-heating rate or scanning rate. The actual
measurement is the difference in power supplied to the cells and the calorimetric block.
The measured signal is the power required by the sample heater to maintain the
isothermal condition in both the sample and the reference cells. This signal reflects either
the specific heat or the heat of mixing of the sample.
3.1.1 Overview of the C80 calorimeter
Figures (3.1) and (3.2) show the block diagram and sectional view of the C-80
calorimeter, respectively. As shown in Figure (3.2), the massive aluminium block
27
Power TCP Disk Plotter
Supply Drives
3456A Computer
DVM
PT1
Amplifier DVM Printer

PT2
C1
C2
C1, C2: Calorimetric cells

PT1, PT2: Platinum temperature measuring and controlling probes
DVM: Digital voltmeter
TCP: Temperature controller and programmer
Figure (3.1) Block diagram of C80 heat flow calorimeter
28
Figure (3.2) Sectional view of the C-80 heat flow calorimeter
29
is placed at the center of the cylindrical calorimeter shell, which acts as a calorimetric
thermostat. Two cells identical in design (C1 and C2) are placed separately into two
identical cavities located symmetrically from the centerline of the calorimeter. One cell
acts as a sample or measurement cell and the other as a reference cell. Standard cells and
membrane mixing cells were used for the measurement of the molar heat capacity and
molar excess enthalpy respectively. Detailed descriptions along with the figures of both
these cells are given later in this chapter.
Each cell is surrounded by a separate thermopile known as fluxmeter. Both
fluxmeters are identical in design and are connected in opposition to give a differential
thermopile output. This arrangement cancels interfering signal disturbances caused by the
presence of residual temperature instability or temperature programming. The fluxmeters
thermally connect the two cells to the calorimetric block. Hence, any thermal exchange
between the cells and the calorimetric block leads the fluxmeter to output a proportional
signal, which is channeled to a digital voltmeter.
To measure and to control the temperatures of the two cells, two separate platinum
resistance probes are placed within the calorimeter. They are labeled PT1 and PT2. The
measuring probe PT1 is used to obtain the temperature of the cells within the calorimeter.
It is placed between the measurement cell and the reference cell. This probe has about
100 Ω of resistance at 0 °C and is connected to the temperature safety unit (Setaram
TS1). This unit converts the measured voltage and the current across PT1 into a resistance
and then to a temperature. If the temperature exceeds the set safety temperature, the
power to the calorimeter would be cut off automatically. The controlling probe PT2 is
used to control the temperature of the calorimetric block. This probe has about 20 Ω of
30
resistance at 0 °C and is connected to the temperature controller unit. The temperature
controller unit is also connected with the heater of the aluminum block to maintain the set
experimental temperature of the calorimeter. For cooling and thermal insulation, an air
gap is provided following a layer of insulating material surrounding the block. The C80
calorimeter is equipped with state of the art software (Setsoft 2000) for data collection
and processing.
3.2 Calibration of the C80 calorimeter
For the precise measurement of the molar heat capacity and the molar excess enthalpy
of a sample, the sensitivity and the temperature scales of the C80 calorimeter must first
be calibrated. Calibration verifies the validity of the instrument with the help of well
defined and tested standard procedures. For the C80 calorimeter, the International
Confederation for Thermal Analysis and Calorimetry (ICTAC) has recommended
standard procedures for the sensitivity as well as for the temperature calibration.
3.2.1 Sensitivity calibration
Sensitivity calibration of C80 calorimeter was performed by Joule Effect. The
calibration was performed for the entire temperature range of the C80 calorimeter i.e. 30
o
C to 300 oC at the scanning rate of 0.1 K/minute. Specially designed two Joule effect
calibration cells and a calibration unit (EJ3) supplied by the Setaram, with all the
necessary accessories were used for the calibration. Both cells are identical in design and
composed of a metal cylinder adjusted to fit inside the heat flux transducer.
Before starting the calibration, a measurement cell was connected to the calibration
unit (EJ3) using a Joule Effect cable. The main aim of this Joule Effect calibration
procedure was to supply a constant power to the calibration resistance heater for a known
31
period of time. The first step in this calibration procedure was to allow the calorimeter,
by giving the sufficient period of time (approximately 3 hours), to reach the thermal
equilibrium at the specified temperature. After the sufficient period of time the joule
effect calibration was initiated by pressing the impulsion start button on the EJ3 unit. The
set power in the EJ3 unit was then automatically supplied to the resistance heater of the
joule effect calibration cell. The usual values that were used for calibration for power (P)
is 10 mW, for the time of the joule effect (TEJ) is 2100 sec and for the total time (Ttotal)
is 4500 sec. The power supply setting of 10 mW was examined by measuring the voltage
and current and was found to be 9.998 mW. After initiation of the experiment, the
differential fluxmeter signal increased and eventually leveled off with time. The
sensitivity constants given in Table (3.1) were obtained from the results of the sensitivity
calibration experiment and were entered in the Setsoft 2000 software. Figure (3.3) shows
the sensitivity curve and the calculated sensitivity constants.
Table (3.1) Sensitivity constants
Sensitivity Constants Values ( μ V/mW)

a(0) +3.152393E+001
a(1) -2.194865E-003
a(2) -1.631050E-004
a(3) +3.116455E-007
a(4) -1.950394E-010
3.2.2 Temperature calibration
The temperature scale of the C80 calorimeter must be calibrated to compensate the
lag of actual temperature of the sample with that of the displayed temperature. This lag
occurs due to the time necessary for the heat to transfer from the heater into the sample.
32
Figure (3.3) Sensitivity calibration curve
33
Temperature calibration is done by measuring the display temperature of a phase
change of substance, which has a well documented precise transition temperature.
Sample of the pure substance was encapsulated in aluminum foil and placed inside the
cell. The melting point was found by measuring the rate of heat flow into the sample as a
function of temperature at the melting time. The difference between the observed
transition temperature and the actual transition temperature determines the amount of
adjustment necessary to determine an unknown temperature accurately.
In this experimental study, pure Tin and Indium were used for the purpose of the
temperature calibration. Before placing the sample inside the cell, both the measurement
and reference cells were filled to one third of their height with calcined aluminum oxide
(Al2O3). Since the Al2O3 does not have any phase transitions in the temperature range of
the C80 Calorimeter, the effect of Al2O3 is only to add thermal mass to the cells and
thereby increasing the total molar heat capacity of the loaded sample. The total amount of
heat absorbed by the sample during melting was calculated by measuring the area under
the peak as shown in Figure (3.4). The melting point is the temperature at which the
extrapolated baseline under the peak and the line describing the initial rise in heat flow
during melting, cross each other. When this temperature is expressed in terms of the
displayed temperature on the calorimeter during melting, the temperature is referred to as
the apparent melting temperature. The value obtained for the apparent melting point
depends on the heating rate. This temperature is measured for several heating rates (e.g.
0.4 K/min, 0.8 K/min & 1 K/min) for both Indium & Tin. The software is used to
calculate the temperature difference between the apparent temperature and the actual
temperature to the heating rate, to give the value of b0, b1, b2, and b3, which are the
34
Figure (3.4) Temperature calibration with Indium at 0.4 K/min of scanning rate
35
temperature correction coefficients. Temperature calibration data along with the
temperature correction coefficients are listed in Table (3.2).
Table (3.2) Temperature correction coefficients
Scanning Temperature
Theoretical Experimental Calculated
Sample rate Correction
Temp (°C ) Temp ( °C ) Temp (°C )
(K/min) Coefficients
Indium 0.4 156.598 158.5219 156.418

Indium 0.8 156.598 160.8989 156.671 b0 = 1.19235E+00
Indium 1.0 156.598 161.9948 156.706 b1 = -7.79682E-03
Tin 0.4 231.928 233.6261 232.108 b2 = 5.37130E+00
Tin 0.8 231.928 235.5007 231.855
b3 = -1.13404E-02
Tin 1.0 231.928 236.5286 231.820
3.3 Molar heat capacity (Cp) measurements
The C-80 heat flow calorimeter is capable of measuring heat capacities in the
temperature range from ambient (298.15 K) to 573.15 K. The measurements of the molar
heat capacity data were conducted using the standard cells and in the temperature range
from (303.15 to 353.15) K.
The standard cells used for the molar heat capacity measurements, illustrated in
Figure (3.5), consist of concentric stainless steel cylinders. The diameter and the height of
both cells are 17 mm and 80 mm respectively. The top portion of the cells is closed by a
lid with tapered bearing surface, which is supported by an O-ring.
3.3.1 Methods of molar heat capacity (Cp) measurement
There are two generally accepted methods in C80 Calorimeter to determine the molar
heat capacity at specific temperature.
36
Figure (3.5) Standard cell for the molar heat capacity (Cp) measurement
37
3.3.1.1 Continuous two steps method
In this method, prior to the molar heat capacity measurement of the sample, it is
necessary to conduct a reference run with both cells empty. The main purpose of this run
is to correct the minor asymmetry between the reference cell and the measurement cell
and also between the fluxmeters. For the measurement of the molar heat capacity data, a
sample weighting about 5.5 to 6 grams was placed inside the measurement or sample cell.
The sample cell was placed into the measurement chamber (C1) of the calorimeter. The
reference cell placed in the reference chamber (C2) of the calorimeter remained empty.
Both the measurement cell and the reference cell were allowed to come in isothermal
condition over a period of 3-4 hours. The scanning rate was set at 0.1 K/min for all
sample runs. After allowing a sufficient period of time to reach the isothermal condition
at 298.15 K, the temperature of both cells is increased at the scanning rate of 0.1 K/min.
During this time the calorimetric signal increases as a function of time. On attainment of
the higher set temperature, the calorimeter automatically reverted to an isothermal mode,
causing the calorimetric signal to return to the baseline. The calorimetric signal of the
sample under study can be obtained from this data by subtracting the reference signal
from the measurement signal.
3.3.1.2 Continuous three steps method
This method is widely used for the measurement of the molar heat capacity of liquids.
Becker et al. (2000), and Becker and Gmehling (2001) have applied this method to the
measurement of the molar heat capacity for nine and twelve organic substances
respectively. The scanning rate for the temperature was set at 0.1 K/min. The main
difference in this method, compared to the two steps method, is the addition of one more
38
run for the reference substance (e.g. Sapphire) i.e. the measurements of the molar heat
capacity were conducted with a sample run, a blank run and a third step as a reference
run. The remaining procedure was the same as in the two steps method. In all three steps,
the experimental condition was identical. Figure (3.6) shows the heat flow signals from
the blank, reference and sample runs. Molar heat capacity data were calculated by using
the following equation:
⎛ H sample
F
− H blank
F
⎞⎛ mreference ⎞
C p (T ) = ⎜ ⎟⎜ ⎟C (T ) (3.1)
⎜HF ⎟⎜ m sample ⎟ p ,reference
⎝ reference − H blank
F
⎠⎝ ⎠
where,
C p (T ) : Molar heat capacity of the substance at temperature T
F
H sample : Heat flow for the sample
F
H reference : Heat flow for the reference material (sapphire)
F
H blank : Heat flow for the blank cells
msample : Mass of the sample
mreference : Mass of the reference material (sapphire)
C p, reference (T ) : Molar heat capacity of the reference material (sapphire) at temperature T
3.4 Molar excess enthalpy (HE) measurements
The C-80 heat flow calorimeter is also used for the measurement of the molar excess
enthalpy or heat of mixing, heats of reactions and heats of solution.
In these experimental findings, the heat of mixing data were measured at three
different temperatures (298.15, 313.15, and 323.15) K. A membrane mixing cell was
used for the molar excess enthalpy measurements. Similar to the standard cells, two
39
Figure (3.6) Three steps method for determination of molar heat capacity signals
40
identical mixing cells are required for the measurements of heats of mixing, one is for the
measurement chamber in the calorimeter and another is for the reference chamber. In the
sample or measurement cell, both the amine and water were placed into the separate,
sealed compartments on either side of the membrane (aluminum foil) and were not mixed
until the experiment began. In the reference cell, the amine and water were premixed to
their final desired composition, separated into equal volumes and placed in the two
compartments, separated by an aluminum foil membrane. The reference cell serves to
cancel the heat supplied to maintain isothermal conditions and the negligible heat of
stirring. Both cells were lowered into the calorimeter block to heat to the temperature of
the experiment. Once both vessels have reached the experimental temperature, the
membrane was broken and the solutions were stirred lightly for one minute. Fluxmeters
measured the difference in heat flow between the vessels and the calorimetric block. The
calorimetric block had sufficient thermal mass to supply or receive heat to the vessels
without changing temperature. A curve was generated of differential heat flow versus
time as shown in Figure (3.7). The area under this curve was then integrated by the
computer to calculate the total molar excess enthalpy of the sample solution.
3.4.1 Membrane mixing cell
A membrane mixing cell, illustrated in Figure (3.8), is made from stainless steel. It is
made up of a body containing a shoulder in the centre and fitted with two threaded ends.
The lower part of the cell is used to house a container into which one of the reactive
agents is placed. The container is closed by a captive circular membrane between two
Teflon sealing rings. These dovetail into each other clamping the membrane and closing
the container.
41
Figure (3.7) Molar excess enthalpy graph
42
Figure (3.8) Membrane mixing cell for the molar excess enthalpy measurement
43
When the latter is screwed into the lower part of the body, the ring is pressed onto the
shoulder which seals the lower compartment of the container. The membrane is generally
made up of a 0.015 mm thick aluminum disc. The upper part is used to house the second
sample and a perforated lid, threaded with a Teflon (O) ring, closes this part. A moveable
rod crosses the lid, which can be maneuvered from outside the calorimeter, screws on to
the end of the rod and enables it to be pushed into the cell through the membrane and
turned. The bottom of the rod is threaded; it is used to take a sharp-edged impeller, which
enables the membrane to be torn, making it possible to agitate the reactive agents.
3.5 Sources of error
There are two sources which may cause errors during the experimental measurements
of the molar excess enthalpy: (1) Solvent sticks to the walls of the cell and never mixes
with the solution, and (2) Absorption of CO2 takes place during the weighing process of
the solvents and generates the heat of reaction in addition to the heat generated during the
mixing of the two components.
3.6 Verification of the C80 heat flow calorimeter
3.6.1 Molar heat capacity measurements
The purpose of testing the calorimeter before using it is to determine its reliability. In
this study to verify the reliability of C80 Calorimeter in the molar heat capacity
measurement, two well known alkanolamines: MEA (99 % pure) and MDEA (99+ %
pure) were used. Both solvents were purchased from Sigma Aldrich and were used
without further purification. The heat capacities of both solvents were measured in the
temperature range of (303.15 to 353.15) K at a scanning rate of 0.1 K/min and compared
with the available literature data.
44
Chiu et al. (1999) and Chen et al. (2001) measured the heat capacities of MEA (99 %
pure) and MDEA (99+ % pure) respectively from 303.15 K to 353.15 K using a
differential scanning calorimeter (DSC). They reported their data for 0.1 K/min scanning
rate intervals. As shown in Table (3.3), Figure (3.9) and Figure (3.10) the heat capacities
of MEA and MDEA measured with a C-80 calorimeter are in agreement with those
measured with a differential scanning calorimeter (DSC) by Chiu et al. (1999) and Chen
et al. (2001). The percentage absolute average deviation for the molar heat capacity data
of MEA and MDEA measured in this study is 0.23 % when compared to the values
measured by Chiu et al. (1999) and Chen et al. (2001). The estimated uncertainty of the
measured molar heat capacity data is ± 2 % over the entire range of mole fractions.
3.6.2 Molar excess enthalpy measurements
To verify the reliability of C80 heat flow calorimeter for molar excess enthalpy
measurements, two systems have been chosen from the literature to be investigated.
These systems are methyldiethanolamin + water, and diethanolamine + water. HE
measurements for the systems of MDEA + water, and DEA + water were reported by
Maham et al. (1997) for mole fractions from almost 0.05 to 0.9 at T = 298.15 K for DEA
and 313.15 K for MDEA. As shown in Table (3.4), Figure (3.11), and Figure (3.12), the
molar excess enthalpy values of these systems are in agreement with those measured by
Maham et al. (1997). The estimated uncertainty of the measured molar excess enthalpy
data is ± 2 % over the entire range of mole fractions.
45
Table (3.3) Molar heat capacity data of MEA and MDEA
MEA MDEA
Cp/(J·mole-1·K-1) Cp/( J·mole-1·K-1)
Temperature Temperature
(K) Chiu et al., Present (K) Chen et al., Present
(1999) Study (2001) Study
303.15 167 168 303.15 272 273

308.15 169 169 308.15 275 276
313.15 170 169 313.15 278 279
318.15 172 171 318.15 281 282
323.15 173 173 323.15 285 285
328.15 175 174 328.15 288 288
333.15 176 175 333.15 291 290
338.15 178 178 338.15 295 294
343.15 179 179 343.15 298 298
348.15 180 180 348.15 301 301
353.15 182 182 353.15 304 304
46
184
182
180
178
Cp /(J.mole-1.K-1)
176
174
172
170
168 Chiu et al. (1999)

Present study
166
300 310 320 330 340 350 360
T /K
Figure (3.9) Comparison of the molar heat capacity data of pure MEA
310
305
300
Cp /J mole-1 K-1
295
290
285
280
275 Chen et al. (2001)

Present study
270
300 310 320 330 340 350 360
T /K
Figure (3.10) Comparison of the molar heat capacity data of pure MDEA
47
Table (3.4) Molar excess enthalpies of (DEA + water) and (MDEA + water) systems
DEA + water at 298.15 K MDEA + water at 313.15 K

Maham et al. (1997) Present study Maham et al. (1997) Present study
HE HE HE HE
xDEA xDEA xMDEA xMDEA
(J·mole-1) ( J·mole-1) ( J·mole-1) ( J·mole-1)
0.0529 -678 0.0553 -685 0.0964 -1379 0.1004 -1409
0.0609 -768 0.0732 -896 0.1413 -1762 0.1501 -1803
0.0947 -1099 0.1001 -1141 0.2238 -2178 0.1986 -2074
0.3009 -2041 0.2005 -1780 0.2703 -2327 0.2593 -2271
0.3388 -2086 0.2943 -2079 0.3468 -2326 0.3681 -2308
0.3703 -2070 0.3400 -2135 0.4274 -2252 0.4312 -2237
0.3971 -2077 0.4007 -2082 0.5151 -1942 0.4941 -2072
0.4962 -1920 0.4969 -1916 0.6360 -1609 0.5930 -1743
0.5869 -1629 0.5945 -1609 0.7412 -1143 0.7778 -1048
0.6615 -1372 0.6597 -1389 0.8177 -838 0.8203 -869
0.7425 -1097 0.7421 -1091
0.8362 -712 0.8312 -721
0.9180 -355 0.9283 -302
48
0
-500
-1000
HE /J.mole-1
-1500
-2000
Maham et al. (1997)
Present study
-2500
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (3.11) Molar excess enthalpies of DEA (1) + water (2) system at 298.15 K
-500
HE /(J mole-1)
-1000
-1500
-2000
Maham et al. (1997)
Present study
-2500
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (3.12) Molar excess enthalpies of MDEA (1) + water (2) system at 313.15 K
49
3.7 Solution preparation
The solutions were prepared on the basis of mole fractions. An analytical balance
Ohaus (Model AP250D, Florham Park, NJ) was used to prepare gravimetrically the
binary mixtures of alkanolamine and deionized water with a precision of ± 0.1 mg. The
overall possible uncertainty in the mole fractions is around ± 0.0001. Amount of water
required for the specific mole fractions of solvent was determined as:
M Solvent
MWSolvent
Mole Fraction x = (3.2)
M Solvent M Water
+
MWSolvent MWWater
Where,
x: mole fraction of alkanolamine
M Solvent : Mass of alkanolamine
M Water : Mass of water
MWSolvent : Molecular weight of alkanolamine
MWWater : Molecular weight of water
N Solvent
x= (3.3)
N Solvent + N Water
Where,
N: Number of moles
M Solvent M Water
N Solvent = , and N Water = (3.4)
MWSolvent MWWater
x( N Solvent + N Water ) = N Solvent (3.5)
N Solvent
N Water = − N Solvent (3.6)
x
50
⎛1 ⎞
N Water = N Solvent ⎜ − 1⎟ (3.7)
⎝x ⎠
M Water M Solvent ⎛ 1 ⎞
= ⎜ − 1⎟ (3.8)
MWWater MWSolvent ⎝ x ⎠
M Solvent ⎛ 1 ⎞
M Water = MWWater ⎜ − 1⎟ (3.9)
MWSolvent ⎝ x ⎠
Equation (3.9) was used to calculate the required amount of water for the specific amount
of solvent for particular mole fraction (x).
51
4. EXPERIMENTAL RESULTS AND DISCUSSION
The molar heat capacities of the aqueous 2-((2-Aminoethyl)amino)ethanol (AEEA),
3-Amino-1-Propanol (AP), 2-(Methylamino)ethanol (MAE), 1-Amino-2-Propanol
(MIPA), and N-N-Dimethylethanolamine (DMEA) solutions were measured at eleven
temperatures ranging from (303.15 to 353.15) K and over the entire range of mole
fractions. The molar excess enthalpies of 2-((2-Aminoethyl)amino)ethanol (AEEA), 3-
Amino-1-Propanol (AP), 2-(Methylamino)ethanol (MAE), 1-Amino-2-Propanol (MIPA),
and N-N-Dimethylethanolamine (DMEA) in water were measured at three temperatures
(298.15, 313.15 and 323.15) K and over the entire range of mole fractions. As mentioned
earlier, the uncertainty in the measured Cp and HE values was found to be ± 2 %.
4.1 Materials
The alkanolamines used in this study were purchased from Sigma-Aldrich with purity
of 99 % for AEEA, ≥ 98 % for AP, 98+ % for MAE, ≥ 98 % for MIPA and 99.5+ % for
DMEA, and were used without further purification. The purity of all alkanolamines used
was based on mass %. A standard reference material, synthetic sapphire (α-Al2O3, 99.99
% pure by mass) was purchased from the National Institute of Standards and Technology
(Gaithersburg, USA).
4.2 Molar Heat Capacity Measurements
Experimentally measured values of the molar heat capacities of the five aqueous
alkanolamine solutions at (303.15, 308.15, 313.15, 318.15, 323.15, 328.15, 333.15,
338.15, 343.15, 348.15, and 353.15) K and for the entire range of mole fractions are
listed in Table (A1), Table (A2), Table (A3), Table (A4) and Table (A5), respectively.
52
4.2.1 2-((2-Aminoethyl)amino)ethanol (AEEA)
As shown in Figure (4.1), the molar heat capacity increases with increasing
temperature. Also the molar heat capacity increases with increasing mole fractions of
AEEA. Molar heat capacities of pure AEEA are represented as a linear function of the
temperature in the range from (303.15 to 353.15) K by:
C p , AEEA / J·mole-1 ·K -1 = 0.31 × T (K ) + 187 (4.1)
In equation (4.1), C p , AEEA represents the molar heat capacity of pure AEEA. The
percentage average absolute deviation (% AAD) for equation (4.1) is found to be 0.18.
The maximum value of C p , AEEA is found at 353.15 K.
The molar excess heat capacities ( C pE ) are calculated from the experimental molar
heat capacity values by:
C pE / J·mole-1 ·K -1 = C p − (x1C p ,1 + x2 C p , 2 ) (4.2)
where C p is the molar heat capacity of the mixture, C p ,1 and C p , 2 are the molar heat
capacities of pure alkanolamine and water respectively, and x1 and x2 are the mole
fractions of alkanolamine and water respectively. The molar heat capacity ( C p , 2 ) values
for water are taken from Osborne et al. (1939). Calculated values of the molar excess heat
capacity of AEEA (1) + water (2) mixtures are listed in Table (A6). Figure (4.2) shows
the concentration dependency of the molar excess heat capacities at various temperatures.
At all temperatures the molar excess heat capacity curves are positive with a maximum
around x1 = 0.2. The C pE value increases with increasing temperature for the entire range
of the mole fractions of AEEA. Figure (4.2) shows sharp changes in the values of the
molar excess heat capacity in water-rich regions.
53
350
300
0.1
250 0.2
Cp/(J mole-1 K-1)
0.3
0.4
200 0.5
0.6
0.7
150 0.8
0.9
Pure
100 AEEA
50
300 310 320 330 340 350 360
T /K
Figure (4.1) Molar heat capacity of AEEA in aqueous solution at various temperatures
50
40
CpE/(J mole-1 K-1)
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.2) Molar excess heat capacity of AEEA in aqueous solution
54
Redlich-Kister relation is employed to correlate the molar excess heat capacity
values:
n
C pE / J·mole -1 ·K -1 = x1 x 2 ∑ a i ( x1 − x 2 )
i
(4.3)
i =0
The coefficients and the standard deviations for AEEA (1) + water (2) system are
presented in Table (4.1). All the fitting polynomials are examined by the F-test
(Bevington, 1969; Shoemaker et al., 1989; Harris, 1991).
55
capacity ( C pE ) (equation (4.3)), for AEEA (1) + water (2) mixtures from
(303.15 to 353.15) K
T/K a0 a1 a2 a3 a4 σ / J·mole-1·K-1
303.15 15.4 -5.61 25.7 -33.0 -15.6 0.15
308.15 23.5 -7.51 36.5 -50.3 -13.6 0.31
313.15 29.1 -13.0 42.6 -51.6 -14.1 0.31
318.15 34.7 -17.5 52.7 -57.3 -20.5 0.34
323.15 40.7 -24.0 61.0 -62.1 -22.2 0.38
328.15 48.7 -31.3 66.0 -66.8 -13.1 0.36
333.15 56.7 -37.8 73.9 -79.1 -6.5 0.38
338.15 66.7 -44.1 82.9 -98.9 3.1 0.45
343.15 78.0 -50.9 97.4 -120 12.1 0.47
348.15 91.0 -59.0 115 -151 24.1 0.52
353.15 106 -70.7 131 -185 54.2 0.50
56
4.2.2 3-Amino-1-Propanol (AP)
As shown in Figure (4.3), the molar heat capacity increases for the entire range of the
mole fractions of AP as well as for pure AP with increasing temperature. The molar heat
capacity values of pure AP are represented as a linear function of the temperature in the
range from (303.15 to 353.15) K by:
C p , AP /J·mole-1 ·K -1 = 0.23 × T (K ) + 134 (4.4)
In equation (4.4), C p , AP represents the molar heat capacity of pure AP. The percentage
average absolute deviation (% AAD) for equation (4.4) is found to be 0.26. The
maximum value of C p , AP is found at 353.15 K.
The molar excess heat capacity ( C pE ) values are calculated from the measured molar
heat capacity values using the equation (4.2) and correlated as function of the mole
fractions employing the Redlich-Kister equation (4.3). The molar excess heat capacity
values and coefficients and the standard deviations for AP (1) + water (2) system are
presented in Table (A7) and Table (4.2) respectively. Figure (4.4) shows the
concentration dependency of the molar excess heat capacities at various temperatures. At
all temperatures the molar excess heat capacity curves are positive with a maximum
around x1 = 0.2. These C pE values increase with increasing temperature for the entire
range of mole fractions of AP.
57
240
220
200 0.1
0.2
0.3
Cp/(J mole-1K-1)
180 0.4
0.5
160 0.6
0.7
0.8
140 0.9
Pure
120 AP
100
80
300 310 320 330 340 350 360
T /K
Figure (4.3) Molar heat capacity of AP in aqueous solution at various temperatures
35
30
25
CpE/(J mole-1 K-1)
20
15
10
0
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.4) Molar excess heat capacity of AP in aqueous solution
58
capacity ( C pE ) (equation (4.3)), for AP (1) + water (2) mixtures from
(303.15 to 353.15) K
T/K a0 a1 a2 a3 a4 a5 σ /J·mol-1·K-1
303.15 12.9 -22.2 35.7 -7.19 9.26 -- 0.19
308.15 20.4 -24.7 35.8 -18.4 25.2 -- 0.14
313.15 25.6 -27.3 34.5 -18.6 31.7 -- 0.16
318.15 31.6 -29.2 32.8 -22.7 40.7 -- 0.18
323.15 37.6 -31.0 31.0 -29.5 50.6 -- 0.21
328.15 46.5 -33.1 23.5 -32.9 75.2 -7.57 0.17
333.15 54.2 -35.5 20.7 -39.3 93.1 -17.8 0.18
338.15 63.8 -38.6 20.1 -49.7 114 -28.4 0.20
343.15 75.1 -40.1 15.8 -66.7 148 -37.0 0.26
348.15 87.7 -45.3 12.2 -84.2 185 -54.1 0.32
353.15 103 -50.4 8.2 -108 237 -77.4 0.44
59
4.2.3 2-(Methylamino)ethanol (MAE)
As shown in Figure (4.5), the molar heat capacities increase for all mole fractions of
MAE as well as for pure MAE with increasing temperature. The molar heat capacities of
pure MAE are represented as a linear function of temperature in the range from (303.15
to 353.15) K by:
C p , MAE / J·mole-1 ·K -1 = 0.31 × T (K ) + 102 (4.5)
In equation (4.5), C p , MAE represents the molar heat capacity of pure MAE. The
The maximum value of C p , MAE is found at 353.15 K.
Maham et al. (1997) have measured the molar heat capacities of pure MAE (99 %
pure) at (299.1, 322.8, 348.5, 373.2, and 397.8) K. The Cp values, measured in this
present study at (303.15, 323.15, and 348.15) K, are compared with the values measured
by Maham et al. (1997) in Table (4.3). Values measured in this study are in agreement
with those measured by Maham et al. (1997).
The molar excess heat capacity ( C pE ) values are calculated from the experimental
molar heat capacity values using the equation (4.2) and correlated as function of mole
fractions employing Redlich-Kister equation (4.3). The molar excess heat capacity values
and coefficients and the standard deviations for MAE (1) + water (2) are presented in
Table (A8) and Table (4.4) respectively. Figure (4.6) shows the concentration
dependency of the molar excess heat capacities at various temperatures. At all
temperatures, the molar excess heat capacity curves are positive except for 303.15 K at x1
= 0.9, where it became a little bit negative. The maximum values of molar excess heat
60
220
200
0.1
180 0.2
Cp /(J mole-1 K-1)
0.3
160 0.4
0.5
0.6
140 0.7
0.8
0.9
120
Pure
MAE
100
80
300 310 320 330 340 350 360
T /K
Figure (4.5) Molar heat capacity of MAE in aqueous solution at various temperatures
40
30
CpE/(J mole-1K-1)
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.6) Molar excess heat capacity of MAE in aqueous solution
61
capacity occurs between x1 = 0.1 and x1 = 0.3. For the temperatures (303.15, 308.15,
313.15, and 318.15) K, the maximum values of C pE are found between x1 = 0.1 and x1 =
0.2, while for the remaining temperatures, the maximum values of C pE occurred between
x1 = 0.2 and x1 = 0.3. These C pE values increase with increasing temperature.
62
Table (4.3) Comparison of the molar heat capacity (Cp) values for pure MAE
Maham et al., (1997) Present study

Temperature /K Cp / J·mol-1·K-1 Temperature /K Cp / J·mol-1·K-1
299.1 191.6 299.11 193
322.8 198.1 322.80 200
348.5 209.4 348.50 210
capacity ( C pE ) (equation (4.3)), for MAE (1) + water (2) mixtures from
(303.15 to 353.15) K
T/K a0 a1 a2 a3 a4 σ /J·mol-1·K-1
303.15 17.4 -22.5 29.4 -62.7 30.3 0.16
308.15 25.4 -25.0 33.5 -68.5 34.7 0.23
313.15 31.2 -27.1 34.7 -68.4 35.1 0.23
318.15 38.5 -27.0 36.7 -72.8 33.5 0.21
323.15 45.7 -28.5 40.0 -74.8 34.3 0.16
328.15 54.0 -31.6 40.9 -78.2 44.3 0.24
333.15 64.4 -34.1 37.2 -82.1 60.4 0.32
338.15 77.2 -33.5 41.2 -99.4 65.2 0.44
343.15 92.5 -33.9 40.0 -110 94.9 0.45
348.15 109 -33.5 43.2 -128 130 0.54
353.15 123 -37.0 68.9 -162 133 0.66
63
4.2.4 1-Amino-2-Propanol (MIPA)
As shown in Figure (4.7), the molar heat capacities increase for all mole fractions of
MIPA as well as for pure MIPA with increasing temperature. The molar heat capacity
values of pure MIPA are represented as a linear function of temperature in the range from
(303.15 to 353.15) K by:
C p , MIPA / J·mole-1 ·K -1 = 0.39 ×T (K ) + 90.4 (4.6)
In equation (4.6), C p , MIPA represents the molar heat capacity of pure MIPA. The
The maximum value of C p, MIPA is found at 353.15 K.
The molar excess heat capacity ( C pE ) values are calculated from the measured molar
heat capacity values using the equation (4.2) and correlated as function of the mole
fractions employing Redlich-Kister equation (4.3). The molar excess heat capacity values
and the coefficients and the standard deviations for MIPA (1) + water (2) are presented in
Table (A9) and Table (4.5) respectively. Figure (4.8) shows the concentration
dependency of the molar excess heat capacities at various temperatures. For the
temperatures (298.15, 308.15, 313.15, 318.15 and 323.15) K, the molar excess heat
capacity curves are positive with a maximum at around x1 = 0.2, and for the remaining
temperatures, the molar excess heat capacity values become maximum around x2 = 0.3.
These C pE values increase with increasing temperature. Figure (4.8) shows sharp changes
in the molar excess heat capacities in water-rich region.
64
240
220
200 0.1
0.2
Cp /(J mole-1 K-1)
180 0.3
0.4
0.5
160
0.6
0.7
140 0.8
0.9
120 Pure
MIPA
100
80
300 310 320 330 340 350 360
T /K
Figure (4.7) Molar heat capacity of MIPA in aqueous solution at various temperatures
35
30
25
CpE/(J mole-1 K-1)
20
15
10
0
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.8) Molar excess heat capacity of MIPA in aqueous solution
65
capacity ( C pE ) (equation (4.3)), for MIPA (1) + water (2) mixtures from
(303.15 to 353.15) K
T/K a0 a1 a2 a3 a4 a5 σ /J·mol-1·K-1
303.15 12.1 -25.8 37.4 -29.8 4.65 0.31
308.15 20.2 -30.1 31.6 -34.8 26.6 0.30
313.15 26.9 -31.7 21.6 -36.4 43.1 0.29
318.15 33.3 -35.3 16.3 -36.7 52.0 0.25
323.15 40.8 -35.8 10.4 -48.8 63.2 12.6 0.21
328.15 49.2 -42.6 6.69 -32.0 74.5 -8.97 0.11
333.15 57.5 -51.5 5.52 -7.07 80.5 -45.5 0.01
338.15 67.6 -60.9 8.84 -1.82 85.0 -57.7 0.06
343.15 79.6 -75.1 7.46 15.6 96.1 -85.5 0.07
348.15 94.2 -92.3 -1.09 52.4 126 -148 0.06
353.15 112 -101 -8.32 25.9 156 -150 0.17
66
4.2.5 N-N-Dimethylethanolamine (DMEA)
As shown in Figure (4.9) the molar heat capacity values increase for all mole
fractions of DMEA as well as for pure DMEA as the temperature increases. The molar
heat capacity values of pure DMEA are represented as a function of the temperature in
the range from (303.15 to 353.15) K by:
C p , DMEA / J·mole-1 ·K -1 = 627 − 0.75 × T (K ) − 17261814 ÷ T 2 (K ) (4.7)
In equation (4.7), C p, DMEA represents the molar heat capacity of pure DMEA. The
The maximum value of C p , DMEA is found at 353.15 K.
Maham et al. (1997) have measured the molar heat capacity of pure DMEA (99 %
pure) at (299.1, 322.8, 348.5, 373.2, and 397.8) K. The Cp values measured in this study
at (303.15, 323.15, and 348.15) K are compared with the values measured by Maham et
al. (1997) in Table (4.6). Values measured in this study are in agreement with those
measured by Maham et al. (1997).
The molar excess heat capacities are calculated from the measured molar heat
capacities using the equation (4.2) and correlated as function of the mole fractions
employing Redlich-Kister equation (4.3). The molar excess heat capacity values and
coefficients and the standard deviations for DMEA (1) + water (2) are presented in Table
(A10) and Table (4.7) respectively. Figure (4.10) shows the concentration dependency of
the molar excess heat capacities at various temperatures. The maximum value of molar
excess heat capacity varies between x1 = 0.2 and x1 = 0.4 as temperature increases. At
303.15 K, maximum occurs at x1 = 0.2, for the temperatures ranging from (308.15 to
67
240
220
200 0.1
0.2
0.3
Cp/(J mole-1K-1)
180
0.4
0.5
160 0.6
0.7
140 0.8
0.9
120 Pure
DMEA
100
80
300 310 320 330 340 350 360
T /K
Figure (4.9) Molar heat capacity of DMEA in aqueous solution at various temperatures
60
50
40
CpE/(J mole-1K-1)
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.10) Molar excess heat capacity of DMEA in aqueous solution
68
333.15) K, maximum occurs at x1 = 0.3 and for the temperatures ranging from (333.15 to
353.15) K, maximum value of molar excess heat capacity occurs at x1 = 0.4. The C pE
value increases with increasing temperature.
69
Table (4.6) Comparison of the molar heat capacity (Cp) values for pure DMEA
Maham et al. (1997) Present study

Temperature /K Cp / J·mol-1·K-1 Temperature /K Cp / J·mol-1·K-1
299.1 205.1 299.11 204
322.8 218.0 322.80 220
348.5 228.8 348.50 225
capacity ( C pE ) (equation (4.3)), for DMEA (1) + water (2) mixtures from
(303.15 to 353.15) K
T/K a0 a1 a2 a3 a4 a5 σ /J·mol-1·K-1
303.15 48.9 -42.7 5.39 -8.12 111 -57.2 0.16
308.15 54.8 -43.5 9.56 -6.56 108 -49.0 0.17
313.15 62.1 -45.0 12.8 -6.77 106 -45.2 0.18
318.15 69.7 -45.9 20.7 4.91 93.9 -61.4 0.17
323.15 78.8 -45.8 24.2 8.36 91.4 -68.8 0.14
328.15 89.2 -42.6 33.9 6.80 81.2 -74.9 0.13
333.15 102 -41.0 48.6 18.2 65.6 -96.5 0.08
338.15 118 -39.2 62.9 39.0 60.3 -133 0.06
343.15 138 -42.2 78.9 89.7 61.1 -206 0.07
348.15 162 -44.4 86.0 129 60.4 -294 0.17
353.15 188 -48.7 101 160 46.8 -402 0.23
70
4.3 Comparison of Cp values of alkanolamines
As shown in Figure (4.11), among the five studied alkanolamines, AEEA + water
system has exhibited the maximum values of the molar heat capacity. Maham et al.
(1997) have analyzed by measuring the molar heat capacities of fourteen pure
alkanolamines and found the values of the molar heat capacity of alkanolamines are
dominated by –CH2 and –OH group contributions and the contributions increase with
increasing temperature. They also concluded that –NH group has exhibited its
contribution on the molar heat capacity in terms of the largest temperature dependency,
while the contribution of –N group is almost zero. In our study we concluded AEEA has
exhibited higher molar heat capacities because of the greater number of –CH2 group
present in the AEEA molecule and also because of the contribution of –NH group. If we
compare the values of the molar heat capacity of MAE and DMEA, we find that
additional methyl group present in DMEA has contributed towards the higher value of
the molar heat capacity of DMEA. This is also confirmed by comparing the molar heat
capacities of two primary amines AP and MIPA, as MIPA has exhibited higher values of
the molar heat capacities compared to AP because one methyl (–CH3) group is present in
MIPA molecule. Figure (4.11) shows that at temperature 338 K the values of the molar
heat capacity of DMEA and MIPA become very near and for higher temperatures the
values of molar excess heat capacity of MIPA exceeds the values of DMEA.
71
320
300
280
Cp /J mole-1K-1
AEEA
260 AP
MAE
240 MIPA
DMEA
220
200
180
300 310 320 330 340 350 360
T /K
Figure (4.11) Comparison of Cp values for the five selected alkanolamines
72
4.4 Molar excess enthalpy measurements
As mentioned earlier, the molar excess enthalpies were measured experimentally for
the five mentioned alkanolamines at three different temperatures (298.15, 313.15 and
323.15) K and over the entire mole fractions range of the alkanolamines. The
experimentally measured values are correlated as a function of the mole fractions using
Redlich-Kister equation. The enthalpies of alkanolamines and water at infinite dilutions
are also determined using the method proposed by Maham et al. (1997). Experimentally
measured molar excess enthalpies are modeled using both the “NRTL” and “UNIQUAC”
models. The molar excess enthalpies are also modeled using the modified functional
groups activity coefficient model: “Modified UNIFAC (Dortmund)”.
4.4.1 2-((2-aminoethyl)amino)ethanol (AEEA)
Molar excess enthalpies for (AEEA (1) + Water (2)) were measured experimentally at
three different temperatures (298.15, 313.15, and 323.15) K. The experimental values are
listed in Table (A11). Figure (4.12) shows the mole fractions dependency of the
experimental molar excess enthalpies at various temperatures. At all temperatures the
molar excess enthalpy curves are negative with a minimum around x1 = 0.35. Negative
molar excess enthalpies indicate a very strong exothermic mixing process between AEEA
and water. The exothermic mixing process between AEEA and water is due to the strong
interaction of the –OH group of water molecules with amine groups (–NH and –NH2) of
AEEA molecules.
The molar excess enthalpies are less negative at 298.15 K and 323.15 K compared to
the values at 313.15 K. Also as shown in the plots of molar excess enthalpy vs. mole
fractions at 298.15 K and 323.15 K in Figure (4.12), the molar excess enthalpies at
73
0
HE /(J mole-1) -1000
-2000
-3000
298.15 K
-4000
313.15 K
323.15 K
RK
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.12) Molar excess enthalpies for AEEA (1) + water (2) mixtures
-1000
HE /(J mole-1)
-2000
-3000
AEEA (Present study)

-4000 DEtA (Copp & Everett, 1953)
MEA (Touhara et al., 1982)
DEA (Maham et al., 1997)
Ethanol (Larkin, 1975)
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.13) Molar excess enthalpies of binary mixtures AEEA, diethylamine, MEA,
diethanolamine and ethanol, in water at 298.15
74
298.15 K are less negative than the values at 323.15 K till x1 = 0.4, but after x1 = 0.4,
molar excess enthalpies at 323.15 K are becoming more negative than the values at
298.15 K.
Alkanolamines are multifunctional compounds with amine and hydroxyl groups.
Figure (4.13) shows the effect of such groups on the molar excess enthalpies by
comparing the molar excess enthalpies of AEEA + water with the molar excess
enthalpies of ethanol + water (Larkin, 1975), diethylamine + water (Copp and Everett,
1953), monoethanolamine + water (Touhara et al., 1982) and diethanolamine + water
(Maham et al., 1997). Maham et al. (1997) concluded by comparing the magnitude of the
molar excess enthalpies of water + ethanol and water + diethylamine the interaction
between water (–OH group) and diethylamine (–NH group) is more dominant than the
interactions between –OH groups from water and ethanol molecules. Thus, ethanol and
amine groups have the opposite effect on the molar excess enthalpies of aqueous binary
mixtures. This is also concluded by comparing the values between monoethanolamine
and diethanolamine, as diethanolamine has exhibited lower molar excess enthalpies on
the negative side compared to the values of monoethanolamine because the two
molecules of ethanol are present in diethanolamine. This is also proved in our study in the
case of AEEA + water as the molar excess enthalpies of this system are quite high in
negative side than the values of water + ethanol. The molar excess enthalpies of AEEA +
water system are even more negative than the values of water + diethylamine. This is
because the strong interaction of both primary and secondary amine groups are present in
the AEEA molecule with water.
A Redlich-Kister relation was used to correlate the molar excess enthalpy data:
75
n
H E / J·mol -1 = x1 x 2 ∑ ai ( x1 − x 2 )
i
(4.8)
i =0
The coefficients and the standard deviations are presented in Table (4.8a). The calculated
molar excess enthalpies, by using equation (4.8), are plotted in Figure (4.12) as solid lines
for all three temperatures. The percentage average absolute deviations (% AAD) are 0.9,
2.7, and 3.9 for the temperatures 298.15 K, 313.15 K and 323.15 K respectively. All the
fitting polynomials were examined by the F-test (Bevington, 1969; Shoemaker et al.,
1989; Harris, 1991).
Both the molar enthalpy of solution of AEEA at infinite dilution ( ΔH 1∞ ) in water and
the molar enthalpy of solution of water at infinite dilution ( ΔH 2∞ ) in AEEA were
obtained using the method proposed by Maham et al (1997). Enthalpies at infinite
dilution for AEEA and water are listed in Table (4.8b).
Figures (4.14), (4.15), and (4.16) show the experimental HE of AEEA + water system
for all three temperatures along with the fitted curves of NRTL, UNIQUAC and UNIFAC
models respectively. The % AAD from the experimental data for the three models are
4.9, 6.3, and 2.3 respectively. Parameters of the three models are listed in Table (4.9a)
and Table (4.9b). Parameters of the three models were regressed simultaneously for the
three temperatures using the built-in algorithm called the Data Regression System (DRS)
of Aspen Plus software. Among the three models, UNIFAC provided the best fitting to
the experimental HE values for this system. Compared to the other studied alkanolamine
+ water systems, AEEA + water system has exhibited higher negative values of HE which
might be considered one of the reasons why NRTL and UNIQUAC models are not well
regressed compared to UNIFAC model for AEEA + water system.
76
(HE) (equation 4.8), for AEEA (1) + water (2) mixtures for (298.15,
313.15, and 323.15) K
T/K a0 a1 a2 a3 a4 % AAD
298.15 -13843.3 10931.3 -4799.3 -1746.4 -494.1 0.9
313.15 -14920.2 8804.8 -5118.1 2439.7 -- 2.7
323.15 -14368.2 11724.4 -2428.0 -5773.8 -- 3.9
Table (4.8b) Molar enthalpies of AEEA at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in AEEA, ( ΔH 2∞ ), for (298.15, 313.15, and
323.15) K
T/K ΔH 1∞ /kJ·mole-1 ΔH 2∞ /kJ·mole-1
298.15 -28 -10
313.15 -31 -9
323.15 -23 -11
77
0
HE /(J mole-1) -1000
-2000
-3000
298.15 K
-4000
313.15 K
323.15 K
NRTL
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.14) Molar excess enthalpy of AEEA (1) + water (2) represented by the NRTL
Model
-1000
HE /(J mole-1)
-2000
-3000
298.15 K
-4000
313.15 K
323.15 K
UNIQUAC
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIQUAC Model
78
0
-1000
HE /(J mole-1)
-2000
-3000
298.15 K
-4000
313.15 K
323.15 K
UNIFAC
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIFAC Model
79
data of AEEA (1) + water (2) for (298.15, 313.15, and 323.15) K
NRTL UNIQUAC
Parameters values % AAD Parameters values % AAD
a12 0.405 a12 -2.738
a21 -1.736 a21 -0.455
6.3
b12 (K) -1305.53 4.9 b12 (K) 808.866
b21 (K) 252.226 b21 (K) 223.052
α 0.150
Table (4.9b) Modified UNIFAC (Dortmund) equation parameters for the molar excess
enthalpy data of AEEA (1) + water (2) for (298.15, 313.15, and 323.15) K
Groups (m)
CH2NH2 CH2NH CH2 H2O OH % AAD
(n)
anm/K 0.0000 -13653 313.37 -817.38 -75.630
CH2NH2 bnm 0.0000 -19.497 -2.7845 7.5325 -0.1511
-1
cnm/K 0.00000 0.17394 0.00815 -0.00414 0.00000
anm/K 18.080 0.0000 -1311.0 -988.51 -660.20
CH2NH bnm 10.114 0.0000 -1.5334 0.7069 1.7430
-1
cnm/K -0.01681 0.00000 0.02552 0.00429 0.00000
anm/K 1476.4 979.86 0.0000 2334.5 2777.0
CH2 bnm 2.2804 0.7340 0.0000 -3.6512 -4.6740 2.3
-1
cnm/K -0.02427 0.00427 0.00000 -0.00647 0.00155
anm/K 1283.5 10041 153.49 0.0000 1460.0
H2O bnm -5.7249 -8.9292 2.2779 0.0000 -8.6730
-1
cnm/K 0.00535 -0.06117 -0.00812 0.00000 0.01641
anm/K -923.70 -355.10 1606.0 -801.90 0.0000
OH bnm 2.4680 0.5800 -4.7460 3.8240 0.0000
-1
cnm/K 0.00000 0.00000 0.00092 -0.00751 0.00000
80
4.4.2 3-Amino-1-Propanol (AP)
Molar excess enthalpies for (AP (1) + water (2)) were measured experimentally at
molar excess enthalpies indicate an exothermic mixing process between AP and water.
The exothermic mixing process between AP and water is due to the strong interaction of
the –OH group of water molecules with amine (–NH2) group of AP molecules.
Figure (4.17) shows the molar excess enthalpies become less negative at lower
temperatures until x1 = 0.6. After x1 = 0.6 the values become less negative at higher
temperatures. The discussions of effects of the groups present in AP on molar excess
enthalpy are given in the later section of this chapter.
n
H E / J ⋅ mol -1 = x1 x 2 ∑ ai ( x1 − x 2 )
i
(4.9)
i =0
The coefficients and the standard deviations are presented in Table (4.10a). The
calculated molar excess enthalpies by equation (4.9) are plotted in Figure (4.17) as solid
lines for the three temperatures. The percentage average absolute deviations are 1.7, 1.9,
and 2.3 for the temperatures 298.15 K, 313.15 K and 323.15 K respectively. Both the
molar enthalpy of solution of AP at infinite dilution ( ΔH 1∞ ) in water and the molar
enthalpy of solution of water at infinite dilution ( ΔH 2∞ ) in AP were obtained using the
method proposed by Maham et al (1997), and are listed in Table (4.10b). Figure (4.18),
81
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
RK
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.17) Molar excess enthalpies for AP (1) + water (2) mixtures
82
(HE) (equation (4.9)), for AP (1) + water (2) mixtures for (298.15, 313.15,
and 323.15) K
T/K a0 a1 a2 a3 a4 % AAD
298.15 -9900.9 5380.2 -1555.2 -2449.5 -- 1.7
313.15 -9743.6 4953.8 -2613.9 -239.9 -- 1.9
323.15 -10396.5 4248.9 4940.6 2618.9 -12317.9 2.3
Table (4.10b) Molar enthalpies of AP at infinite dilution in water, ( ΔH 1∞ ), and of water

at infinite dilution in AP, ( ΔH 2∞ ), for (298.15, 313.15, and 323.15) K
298.15 -14 -9
313.15 -17 -8
323.15 -25 -11
83
Figure (4.19) and Figure (4.20) show the experimental values of molar excess enthalpy of
AP + water system for all three temperatures along with the fitted curves of NRTL,
UNIQUAC and UNIFAC models respectively. The percentage average absolute
deviations (% AAD) from the experimental data for all three models are 3.9, 4.9, and 1.8
respectively. Parameters of the three models are listed in Table (4.11a) and Table (4.11b).
As mentioned in the previous section, parameters of the three models were regressed
simultaneously for the three temperatures using the built-in algorithm called the Data
Regression System (DRS) of Aspen Plus software. Among the three models, modified
UNIFAC provided the best fitting to the experimental molar excess enthalpy values of
AP + water system.
84
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
NRTL
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.18) Molar excess enthalpy of AP (1) + water (2) represented by the NRTL
Model
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
UNIQUAC
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.19) Molar excess enthalpy of AP (1) + water (2) represented by the
UNIQUAC Model
85
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
UNIFAC
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.20) Molar excess enthalpy of AP (1) + water (2) represented by the UNIFAC
Model
86
Table (4.11a) NRTL and UNIQUAC equations’ parameters for the molar excess
enthalpy data of AP (1) + water (2) for (298.15, 313.15, and 323.15) K
NRTL UNIQUAC
a12 -38.653 a12 -0.383
a21 17.681 a21 -1.183
3.9 4.9
b12 (K) -234.450 b12 (K) 201.667
b21 (K) -1109.81 b21 (K) 466.078
α 0.021
molar excess enthalpy data of AP (1) + water (2) for (298.15, 313.15, and
323.15) K
Groups (m)
CH2 CH2NH2 H2O OH % AAD
(n)
anm/K 0.0000 2468.4 1519.4 2777.0
CH2 bnm 0.0000 19.247 -3.4654 -4.6740
cnm/K-1 0.00000 -0.08383 0.00111 0.00155
anm/K -466.48 0.0000 -935.70 -75.630
CH2NH2
bnm -3.2350 0.0000 4.0101 -0.1511
cnm/K-1 0.01949 0.00000 -0.00655 0.00000
1.8
anm/K -67.870 1997.5 0.0000 1460.0
H2O bnm -1.2059 -3.7534 0.0000 -8.6730
cnm/K-1 0.00756 0.00608 0.00000 0.01641
anm/K 1606.0 -923.70 -801.90 0.0000
OH bnm -4.7460 2.4680 3.8240 0.0000
cnm/K-1 0.00092 0.00000 -0.00751 0.00000
87
4.4.3 2-(Methylamino)ethanol (MAE)
Molar excess enthalpies for (MAE (1) + water (2)) were measured experimentally at
molar excess enthalpies indicate the exothermic mixing process between MAE and water
due to the strong interaction of the –OH group of water molecules with amine (–NH)
group of MAE molecules. Figure (4.21) shows, in the water rich region, the molar excess
enthalpies become slightly more negative at the higher temperatures. In the MAE rich
region there is no considerable difference between the values at higher and lower
temperatures except for a couple of values at 313.15 K for the x1 = 0.5833 and x1 =
0.6860, where molar excess enthalpies become higher than the values at 298.15 K and
323.15 K. Figure (4.22) shows the comparison of molar excess enthalpies measured in
this study at 298.15 K with that measured by Touhara et al. (1981). The measured values
are in agreement.
A Redlich-Kister relation was employed to correlate the molar excess enthalpies.
n
H E / J ⋅ mol -1 = x1 x 2 ∑ ai ( x1 − x 2 )
i
(4.10)
i =0
calculated molar excess enthalpies, by using equation (4.10), are plotted in Figure (4.21)
as solid lines for all three temperatures. The percentage average absolute deviations (%
AAD) are 1.9, 1.7, and 0.5 for the temperatures 298.15 K, 313.15 K and 323.15 K
respectively.
88
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
RK
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.21) Molar excess enthalpies for MAE (1) + water (2) mixtures
-500
-1000
HE/J mole-1
-1500
-2000
-2500
Present study
Touhara et al. (1982)
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.22) Molar excess enthalpies for MAE (1) + water (2) mixtures at 298.15 K
89
As displayed in Figure (4.21), the minimum value is shifted towards higher concentration
of MAE for higher temperatures. At 323.15 K, the minimum value of molar excess
enthalpy occurs at x1 = 0.4.
Both the molar enthalpy of solution of MAE at infinite dilution ( ΔH 1∞ ) in water and
the molar enthalpy of solution of water at infinite dilution ( ΔH 2∞ ) in MAE were obtained
using the method proposed by Maham et al. (1997), and are listed in Table (4.12c). Also
Table (4.12b) and Table (4.12c) show the comparison of both the molar enthalpy of
solution of MAE at infinite dilution ( ΔH 1∞ ) in water and the molar enthalpy of solution of
water at infinite dilution ( ΔH 2∞ ) in MAE at 298.15 K with the values obtained by
Touhara et al. (1981), and Maham et al. (1997) respectively.
Figure (4.23), Figure (4.24), and Figure (4.25) show the experimental values of molar
excess enthalpy of MAE + water system for all three temperatures along with the fitted
curves of NRTL, UNIQUAC and UNIFAC models respectively. The percentage average
absolute deviations (% AAD) from the experimental data for all three models are 3.5, 4.2,
and 2.1 respectively. Parameters of the three models are listed in Table (4.13a) and Table
(4.13b). Parameters of the three models were regressed simultaneously for the three
temperatures using the built-in algorithm called the Data Regression System (DRS) in
Aspen Plus software. Among the three models, UNIFAC (Dortmund) provided the best
fitting to the experimental molar excess enthalpy values of MAE + water system.
90
(HE) (equation (4.10)), for MAE (1) + water (2) mixtures for (298.15,
313.15, and 323.15) K
%
T/K a0 a1 a2 a3 a4
AAD
298.15 -9993.0 5291.6 -2972.1 1117.1 -- 1.9
313.15 -9939.4 4206.3 -5784.4 3188.3 -- 1.7
323.15 -10434.5 4010.5 6043.0 4465.1 -16348.3 2.4
Table (4.12b) Molar enthalpies of MAE at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in MAE, ( ΔH 2∞ ), for 298.15 K
This Study Touhara et al. (1981)

T/K
ΔH 1∞ /kJ·mole-1 ΔH 2∞ /kJ·mole-1 ΔH 1∞ /kJ·mole-1 ΔH 2∞ /kJ·mole-1
298.15 -19 -6 -18.5 -6.2
Table (4.12c) Molar enthalpies of MAE at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in MAE, ( ΔH 2∞ ), for (298.15, 313.15, and
323.15) K
This Study Maham et al. (1997)

T/K
298.15 -19 -6 -18.4 -5.9
313.15 -19 -5 -- --
323.15 -29 -12 -- --
91
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
NRTL
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.23) Molar excess enthalpy of MAE (1) + water (2) represented by the NRTL
Model
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
UNIQUAC
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIQUAC Model
92
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
UNIFAC
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIFAC Model
93
data of MAE (1) + water (2) for (298.15, 313.15 and 323.15) K
NRTL UNIQUAC
Parameters Values % AAD Parameters values % AAD
a12 -67.695 a12 -0.092
a21 20.123 a21 -1.040
4.2
b12 (K) -159.767 3.5 b12 (K) 246.220
b21 (K) -1265.64 b21 (K) 418.965
α 0.019
molar excess enthalpy data of MAE (1) + water (2) for (298.15, 313.15
and 323.15) K
Groups (m)
CH3NH CH2 H2O OH % AAD
(n)
anm/K 0.0000 -189.01 1154.1 -660.20
CH3NH
bnm 0.0000 -2.6535 8.1353 1.7430
-1
cnm/K 0.00000 0.08071 -0.02946 0.00000
anm/K 3856.4 0.0000 585.75 2777.0
CH2
bnm 0.7340 0.0000 -6.8013 -4.6740
-1
cnm/K -0.04163 0.00000 0.01258 0.00155
2.1
anm/K 5497.7 -189.78 0.0000 1460.0
H2O bnm -17.132 0.8523 0.0000 -8.6730
-1
cnm/K 0.01081 0.00992 0.00000 0.01641
anm/K -355.10 1606.0 -801.90 0.0000
OH bnm 0.5800 -4.7460 3.8240 0.0000
-1
cnm/K 0.00000 0.00092 -0.00751 0.00000
94
4.4.4 1-Amino-2-Propanol or Monoisopropanolamine (MIPA)
Excess enthalpies for (MIPA (1) + water (2)) were measured experimentally at three
different temperatures (298.15, 313.15, and 323.15) K. The experimental values are listed
in Table (A14). Figure (4.26) shows the mole fractions dependency of the experimental
molar excess enthalpies at various temperatures. At all temperatures the molar excess
enthalpy curves are negative with a minimum around x1 = 0.35. Negative molar excess
enthalpy values indicate the exothermic mixing process between MIPA and water. The
exothermic mixing process between MIPA and water is due to the strong interaction of
the –OH group of water molecules with –NH2 group of the MIPA molecules. The MIPA
+ water system exhibited the lowest negative values of molar excess enthalpy among the
five studied alkanolamine + water systems. Figure (4.26) shows no considerable
difference in the values of excess enthalpies at higher and lower temperatures. As
displayed in Figure (4.26), the minimum value is shifted towards higher concentration of
MIPA for higher temperatures. At 323.15 K, the minimum value of molar excess
enthalpy occur at x1 = 0.4.
n
H E / J ⋅ mol -1 = x1 x 2 ∑ ai ( x1 − x 2 )
i
(4.11)
i =0
calculated values of molar excess enthalpy, by using equation (4.11), are plotted in Figure
(4.26) as solid lines for all three temperatures. The percentage average absolute
deviations (% AAD) are 1.7, 3.5, and 1.0 for the temperatures 298.15 K, 313.15 K and
323.15 K respectively.
95
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
RK
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.26) Molar excess enthalpies for MIPA (1) + water (2) mixtures
96
(HE) (equation 4.11), for MIPA (1) + water (2) mixtures for (298.15,
313.15, and 323.15) K
T/K a0 a1 a2 a3 a4 a5 % AAD
298.15 -9158.3 4306.8 -2723.1 1382.7 -- -- 1.7
313.15 -9176.0 3640.8 -2921.1 3411.9 -- -- 3.5
323.15 -9318.7 3907.3 -160.6 1409.3 -3175.2 -760.0 1.0
Table (4.14b) Molar enthalpies of MIPA at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in MIPA, ( ΔH 2∞ ), for (298.15, 313.15, and
323.15) K
298.15 -18 -6
313.15 -19 -5
323.15 -18 -7
97
Both the molar enthalpy of solution of MIPA at infinite dilution ( ΔH 1∞ ) in water and the
molar enthalpy of solution of water at infinite dilution ( ΔH 2∞ ) in MIPA were obtained
using the method proposed by Maham et al (1997), and are listed in Table (4.14b).
Figure (4.27), Figure (4.28), and Figure (4.29) show the experimental values of molar
excess enthalpy of MIPA + water system for all three temperatures along with the fitted
absolute deviations (% AAD) from the experimental data for the three models are 2.0,
2.3, and 1.4 respectively. Parameters of the three models are listed in Table (4.15a) and
Table (4.15b). Parameters of the three models were regressed simultaneously for the three
temperatures by using the built-in algorithm called the Data Regression System (DRS) of
Aspen Plus software. All three models have provided the best fit to the experimental
molar excess enthalpy values of MIPA + water system with the modified UNIFAC being
the best fit among them.
98
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
NRTL
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.27) Molar excess enthalpy of MIPA (1) + water (2) represented by the NRTL
Model
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
UNIQUAC
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIQUAC Model
99
0
-500
-1000
HE /(J mole-1)
-1500
-2000
298.15 K
-2500 313.15 K
323.15 K
UNIFAC
-3000
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIFAC Model
100
data of MIPA (1) + water (2) for (298.15, 313.15, and 323.15) K
NRTL UNIQUAC
Parameters values % AAD Parameters Values % AAD
a12 -2.4170 a12 -1.017
a21 -36.662 a21 -0.1920
2.3
b12 (K) -683.459 2.0 b12 (K) 401.318
b21 (K) -9.01700 b21 (K) 221.013
α 0.136
molar excess enthalpy data of MIPA (1) + water (2) for (298.15, 313.15,
and 323.15) K
Groups (m)
CH3 CH2NH2 H2O CH OH % AAD
(n)
anm/K 0.0000 1476.4 2927.2 0.0000 2777.0
CH3 bnm 0.0000 29.469 -6.9502 0.0000 -4.6740
cnm/K-1 0.00000 -0.11277 -0.00844 0.00000 0.00155
anm/K 598.39 0.0000 -1875.6 326.04 -75.630
CH2NH2 bnm 0.1121 0.0000 1.8385 -2.6348 -0.1511
cnm/K-1 0.03542 0.00000 0.01085 0.00336 0.00000
anm/K 155.28 6550.7 0.0000 -17.250 1460.0
H2O bnm 2.9069 -18.729 0.0000 0.8389 -8.6730 1.4
cnm/K-1 0.00562 -0.00790 0.00000 0.00090 0.01641
anm/K 0.0000 -164.04 1391.3 0.0000 2777.0
CH bnm 0.0000 4.9683 -3.6156 0.0000 -4.6740
cnm/K-1 0.00000 -0.01025 0.00114 0.00000 0.00155
anm/K 1606.0 -923.70 -801.90 1606.0 0.0000
OH bnm -4.7460 2.4680 3.8240 -4.7460 0.0000
cnm/K-1 0.00092 0.00000 -0.00751 0.00092 0.00000
101
4.4.5 N-N-Dimethylethanolamine (DMEA)
Molar excess enthalpies for (DMEA (1) + water (2)) were measured experimentally at
molar excess enthalpies indicate the exothermic mixing process between DMEA and
water due to the strong interaction of the –OH group of water molecules with –N group
of DMEA molecules. The DMEA + water system exhibited the second highest negative
values of molar excess enthalpy after AEEA + water system, among the five studied
alkanolamine + water systems. Figure (4.30) shows the molar excess enthalpies become
less negative as temperature increases.
n
H E / J ⋅ mol -1 = x1 x 2 ∑ ai ( x1 − x 2 )
i
(4.12)
i =0
calculated values, by using equation (4.12), are plotted in Figure (4.30) as solid lines for
all three temperatures. The percentage average absolute deviations (% AAD) are 0.8, 0.6,
and 3.4 for the temperatures 298.15 K, 313.15 K and 323.15 K respectively. Both the
molar enthalpy of solution of DMEA at infinite dilution ( ΔH 1∞ ) in water and the molar
enthalpy of solution of water at infinite dilution ( ΔH 2∞ ) in DMEA were obtained using
the method proposed by Maham et al. (1997), and are listed in Table (4.16b).
102
0
-500
-1000
HE /(J mole-1)
-1500
-2000
-2500
298.15 K
313.15 K
-3000
323.15 K
RK
-3500
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.30) Molar excess enthalpies for DMEA (1) + water (2) mixtures
-500
-1000
HE /J.mole-1
-1500
-2000
-2500
-3000
Present study
Touhara et al., (1982)
-3500
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.31) Molar excess enthalpies for DMEA (1) + water (2) mixtures at 298.15 K
103
Table (4.16a) Redlich-Kister equation fitting coefficients for the excess enthalpy (HE)
(equation 4.12), for DMEA (1) + water (2) mixtures for (298.15, 313.15,
and 323.15) K
T/K a0 a1 a2 a3 a4 a5 % AAD
298.15 -10779.8 5311.3 -1352.6 5657.0 -5167.8 -1793.3 0.8
313.15 -10230.0 6368.7 -1088.4 -1466.6 -5294.4 4615.4 0.6
323.15 -9603.1 4573.2 -4515.4 4998.2 -- -- 3.4
Table (4.16b) Molar enthalpies of DMEA at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in DMEA, ( ΔH 2∞ ), for 298.15 K
This Study Touhara et al. (1981)

T/K
298.15 -26 -8 -25.4 -6.3
Table (4.16c) Molar enthalpies of DMEA at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in DMEA, ( ΔH 2∞ ), for (298.15, 313.15, and
323.15) K
This Study Maham et al. (1997)

T/K
298.15 -26 -8 -24.1 -6.3
313.15 -26 -7 -- --
323.15 -24 -4 -- --
104
Figure (4.31) shows the comparison of molar excess enthalpies measured in this
study at 298.15 K with those measured by Touhara et al. (1981), values are in agreement.
Table (4.16b) and Table (4.16c) show the comparison of both the molar enthalpy of
solution of DMEA at infinite dilution ( ΔH 1∞ ) in water and the molar enthalpy of solution
of water at infinite dilution ( ΔH 2∞ ) in DMEA at 298.15 K with the values obtained by
Touhara et al. (1982) and Maham et al. (1997) respectively.
Figure (4.32), Figure (4.33), and Figure (4.34) show the experimental molar excess
enthalpies of DMEA + water system for all three temperatures along with the fitted
absolute deviations (% AAD) from the experimental data for the three models are 1.8,
2.0, and 1.4 respectively. The parameters of the three models are listed in Table (4.17a)
and Table (4.17b). The parameters of the three models were regressed simultaneously for
the three temperatures using the built-in algorithm called the Data Regression System
(DRS) in Aspen Plus software. All three models have provided good fitting to the
experimental molar excess enthalpy values of DMEA + water system and with modified
UNIFAC the fit was best.
105
0
-500
-1000
HE /(J mole-1)
-1500
-2000
-2500
298.15 K
313.15 K
-3000
323.15 K
NRTL
-3500
0.0 0.2 0.4 0.6 0.8 1.0
x1
Figure (4.32) Molar excess enthalpy of DMEA (1) + water (2) represented by the NRTL
Model
-500
-1000
HE /(J mole-1)
-1500
-2000
-2500
298.15 K
313.15 K
-3000
323.15 K
UNIQUAC
-3500
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIQUAC Model
106
0
-500
-1000
HE /(J mole-1)
-1500
-2000
-2500
298.15 K
313.15 K
-3000
323.15 K
UNIFAC
-3500
0.0 0.2 0.4 0.6 0.8 1.0
x1
UNIFAC Model
107
data of DMEA (1) + water (2) for (298.15, 313.15, and 323.15) K
NRTL UNIQUAC
a12 0.131 a12 0.401
a21 2.021 a21 -1.925
1.8 2.0
b12 (K) -393.889 b12 (K) 127.816
b21 (K) -567.127 b21 (K) 613.564
α 0.961
molar excess enthalpy data of DMEA (1) + water (2) for (298.15, 313.15,
and 323.15) K
Groups (m)
CH3N CH2 H2O CH3 OH % AAD
(n)
anm/K 0.0000 168.75 81.040 205.65 1876.0
CH3N bnm 0.0000 1.0201 -4.7503 -1.4436 11.500
-1
cnm/K 0.00000 0.03917 0.01136 0.00000 0.09000
anm/K -223.35 0.0000 2221.3 0.0000 2777.0
CH2 bnm 0.8103 0.0000 -1.2299 0.0000 -4.6740
-1
cnm/K -0.00206 0.00000 0.00803 0.00000 0.00155
anm/K 745.87 -189.78 0.0000 -17.250 1460.0
H2O bnm -3.4661 2.9399 0.0000 0.8389 -8.6730 1.4
-1
cnm/K -0.00012 0.00055 0.00000 0.00090 0.01641
anm/K -175.70 0.0000 1391.3 0.0000 2777.0
CH3 bnm 1.8570 0.0000 -3.6156 0.0000 -4.6740
-1
cnm/K 0.00000 0.00000 0.00114 0.00000 0.00155
anm/K 104.60 1606.0 -801.90 1606.0 0.0000
OH bnm -5.0140 -4.7460 3.8240 -4.7460 0.0000
-1
cnm/K 0.00885 0.00092 -0.00751 0.00092 0.00000
108
4.5 Comparison of HE values of alkanolamines
Figures (4.35), (4.36) and (4.37) show the comparison of molar excess enthalpies of
the five studied alkanolamines at 298.15 K, 313.15 K and 323.15 K respectively. Among
the five alkanolamines, AEEA + water system has exhibited the highest values of molar
excess enthalpy at 298.15 K on the negative side followed by DMEA + water, MAE +
water, AP + water and MIPA + water. At 313.15 K, AEEA + water system has also
exhibited the highest negative molar excess enthalpy values among the five studied
alkanolamines. As shown in Figure (4.36), MAE has exhibited slightly higher values of
molar excess enthalpies compared to DMEA in the amine rich region. Also at 313.15 K,
MIPA has exhibited slightly higher negative values of the molar excess enthalpies
compared to AP in the water rich region. As in the case of 323.15 K, AEEA + water
(Figure (4.37)) has exhibited the highest negative values of the molar excess enthalpies
and MAE has exhibited slightly higher negative values of molar excess enthalpies
compared to DMEA in both amine rich and water rich regions. At 323.15 K, AP has also
exhibited greater molar excess enthalpy values compared to MAE and DMEA in amine
rich region. An interesting observation in this study was the values of molar excess
enthalpy also depend upon the position of the –OH and -NH2 groups in the molecule of
alkanolamine, as in the case of AP and MIPA. According to Maham et al. (1997), –CH3
group contributes to the higher molar excess enthalpies but in this study we have
observed that MIPA, which contains one –CH3 group, has exhibited lower values of
molar excess enthalpies compared to AP. The reason could be the position of the –OH
group on the second carbon atom of the MIPA molecule, which has contributed to the
109
lower molar excess enthalpies on the negative side, compared to the contributions of the
position of the –OH group in AP on first carbon atom.
110
0
-1000
-2000
HE /J.mole-1
-3000
AEEA
AP
-4000
MAE
MIPA
DMEA
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
alkanolamines at 298.15 K
-1000
-2000
HE /J.mole-1
-3000
AEEA
AP
-4000
MAE
MIPA
DMEA
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
111
0
-1000
-2000
HE /J.mole-1
-3000
AEEA
AP
-4000
MAE
MIPA
DMEA
-5000
0.0 0.2 0.4 0.6 0.8 1.0
x1
112
5. CONCLUSION AND RECOMMENDATIONS
5.1 Conclusion:
The molar heat capacities of the aqueous AEEA, AP, MAE, MIPA and DMEA
solutions were measured over a range of temperatures from (303.15 to 353.15) K and
over the entire range of mole fractions. The molar excess heat capacity ( C pE ) values for
the aqueous AEEA, AP, MIPA and DMEA solutions were positive at all temperatures
and mole fractions. At 303.15 K for x1 = 0.9, aqueous MAE solution has exhibited
negative value of the molar excess heat capacity ( C pE ), while for all other temperatures
and mole fractions, the molar excess heat capacity ( C pE ) values of aqueous MAE
solutions were positive. The molar excess heat capacities were correlated as a function of
mole fractions employing Redlich-Kister equation. Among the five studied
alkanolamines, AEEA has exhibited the highest values of the molar heat capacity and
MAE has exhibited the lowest values of the molar heat capacity. This study confirms the
observation made by Maham et al. (1997) that the values of molar heat capacity of the
alkanolamines are dominated by –CH2 and –OH group contributions and these
contributions increase with increasing temperature.
The molar excess enthalpies of the AEEA, AP, MAE, MIPA, and DMEA in water
were measured at three different temperatures (298.15, 313.15 and 323.15) K and over
the entire range of mole fractions. Molar enthalpies at infinite dilution were calculated for
the selected five alkanolamine (1) + water (2) systems for all three temperatures (298.15,
313.15 and 323.15) K.
113
The molar excess enthalpies were correlated as a function of mole fractions
employing the Redlich-Kister equation. The experimental molar excess enthalpy values
were modeled successfully by using the solution theory models: NRTL, and UNIQUAC
models and by using the group contribution model: Modified UNIFAC (Dortmund)
model. Among the three models, Modified UNIFAC (Dortmund) has exhibited lowest
percentage average absolute deviations from the experimental molar excess enthalpies,
followed by NRTL and UNIQUAC.
Among five studied alkanolamines, AEEA + water system has exhibited the highest
values of molar excess enthalpy in the negative side followed by DMEA + water, MAE +
water, AP + water, and MIPA + water system. This study confirms the conclusion made
by Maham et al. (1997) that the interaction between water (–OH group) and diethylamine
(–NH group) is more dominant than the interactions between –OH groups from water and
alcohol molecules. This study also confirms that –CH3 group has contributed the higher
values of molar excess enthalpy. One important observation made in this study is that the
values of the molar excess enthalpy also depend upon the position of the –OH and -NH2
groups in the molecule of alkanolamines as observed in AP and MIPA.
5.2 Recommendations:
• Measurements of the molar heat capacity and the molar excess enthalpy for the
mixed (chemical and physical) solvents at various temperatures
• Measurements of the molar heat capacity and the molar excess enthalpy for the
CO2 loaded alkanolamines at various temperatures and pressures
114
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122
7. APPENDICES
7.1 APPENDIX A: Experimental data
This Appendix contains the experimental data of the molar heat capacity and the
molar excess enthalpy data for the five selected alkanolamine (1) + Water (2) systems.
This Appendix also contains the calculated values of the molar excess heat capacity for
the five selected alkanolamine (1) + water (2) systems.
Table (A1) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for AEEA (1) +
water (2) mixtures from (303.15 to 353.15) K
Mole fractions of AEEA (x1)
0.0999 0.1999 0.2995 0.4000 0.5002 0.5997 0.7011 0.8003 0.8979 1.0000
T/K Cp /J·mole-1·K-1
303.15 100 121 141 161 181 201 221 240 258 279
308.15 103 125 145 165 185 205 226 245 263 284
313.15 104 127 147 167 187 207 227 247 265 285
318.15 106 129 150 170 190 209 229 249 266 286
323.15 107 131 152 172 192 211 231 250 267 287
328.15 110 134 155 175 195 214 233 252 269 289
333.15 112 137 158 178 197 216 235 254 271 290
338.15 116 141 162 181 201 219 238 257 273 292
343.15 120 146 167 185 204 223 241 260 275 293
348.15 124 152 172 189 208 227 244 262 277 295
353.15 130 158 177 194 213 231 248 265 279 296
123
Table (A2) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for AP (1) +
Mole fractions of AP (x1)
0.0999 0.2001 0.3003 0.4015 0.4996 0.6006 0.7003 0.8003 0.8966 1.0000
303.15 94 108 120 131 143 155 168 180 193 204
308.15 96 111 123 135 147 159 171 184 196 207
313.15 97 112 124 136 148 160 172 185 197 208
318.15 98 113 126 138 150 162 173 186 198 208
323.15 99 115 128 140 152 163 175 187 199 209
328.15 101 117 130 142 154 166 177 189 200 210
333.15 103 119 132 145 157 169 179 191 202 211
338.15 106 122 135 148 160 172 182 193 204 213
343.15 110 126 139 151 163 175 185 196 206 214
348.15 114 130 143 155 167 179 188 198 208 216
353.15 119 135 147 160 172 183 192 201 210 217
124
Table (A3) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for MAE (1) +
Mole fractions of MAE (x1)
0.1000 0.1998 0.3003 0.3990 0.5002 0.6061 0.6987 0.8003 0.9004 1.0000
303.15 96 108 119 129 139 151 160 172 182 194
308.15 98 111 122 132 143 155 165 176 187 199
313.15 99 113 124 135 146 157 167 178 189 200
318.15 100 114 126 137 148 160 170 180 190 202
323.15 101 116 128 139 150 162 172 183 192 203
328.15 103 118 131 142 153 165 175 185 195 205
333.15 105 121 134 145 157 168 178 188 197 206
338.15 107 124 138 149 161 172 182 191 199 207
343.15 110 127 141 153 164 176 185 194 201 208
348.15 114 132 146 158 169 181 190 198 205 210
353.15 119 138 152 163 174 186 195 203 208 212
125
Table (A4) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for MIPA (1) +
Mole fractions of MIPA (x1)
0.1000 0.2007 0.2996 0.4001 0.4983 0.6013 0.6999 0.7996 0.8959 1.0000
303.15 95 110 121 133 145 158 170 183 196 209
308.15 97 113 124 137 149 162 174 187 200 213
313.15 98 114 126 139 151 164 176 188 201 214
318.15 99 116 128 141 154 166 177 190 202 215
323.15 100 117 130 144 156 168 180 192 204 217
328.15 102 119 133 147 159 171 182 194 206 218
333.15 104 121 136 150 162 174 185 197 209 221
338.15 106 125 140 154 166 178 188 200 211 223
343.15 109 128 144 158 170 181 192 203 214 225
348.15 112 133 149 163 175 185 195 206 216 228
353.15 117 138 155 169 180 190 199 209 219 230
126
Table (A5) Experimental molar heat capacity ( C p /J·mole-1·K-1) values, for DMEA (1) +
Mole fractions of DMEA (x1)
0.0997 0.1962 0.3003 0.3984 0.4983 0.6008 0.6980 0.7981 0.8938 1.0000
303.15 103 118 132 144 156 168 179 191 202 213
308.15 104 119 134 146 158 170 181 193 205 215
313.15 105 121 136 149 161 173 185 196 208 217
318.15 105 123 139 152 164 177 188 199 210 219
323.15 107 125 141 155 168 180 191 203 213 221
328.15 108 127 144 158 171 184 195 206 215 222
333.15 109 129 147 161 175 187 199 209 217 223
338.15 112 132 150 165 179 192 203 213 220 223
343.15 114 136 155 170 184 196 208 218 223 223
348.15 118 140 160 176 190 203 214 223 225 224
353.15 123 146 166 184 198 210 221 229 228 226
127
Table (A6) Molar excess heat capacity ( C pE /J·mole-1·K-1), for AEEA (1) + water (2)
mixtures from (303.15 to 353.15) K
Mole fractions of AEEA (x1)
0.0999 0.1999 0.2995 0.4000 0.5002 0.5997 0.7011 0.8003 0.8979
T/K C pE /J·mole-1·K-1
303.15 4.24 5.17 4.97 4.43 3.90 3.42 2.96 2.12 0.35
308.15 6.63 7.72 7.57 6.77 5.92 5.19 4.51 3.50 0.82
313.15 7.92 9.53 9.41 8.42 7.33 6.33 5.38 4.15 1.20
318.15 9.37 11.5 11.4 10.1 8.84 7.50 6.38 4.93 1.48
323.15 11.0 13.6 13.6 11.8 10.4 8.62 7.24 5.57 1.74
328.15 13.1 16.3 16.1 14.1 12.5 10.3 8.44 6.46 2.36
333.15 15.6 19.2 18.8 16.4 14.4 12.0 9.60 7.33 2.74
338.15 18.7 22.8 22.1 19.2 17.0 14.2 11.1 8.45 3.14
343.15 22.3 27.0 25.9 22.4 19.8 16.8 13.0 9.94 3.86
348.15 26.9 32.2 30.4 26.0 23.0 19.8 15.2 11.5 4.48
353.15 32.7 38.6 35.8 30.4 26.8 23.3 17.7 13.1 5.56
128
Table (A7) Molar excess heat capacity ( C pE /J·mole-1·K-1), for AP (1) + water (2)
Mole fractions of AP (x1)
0.0999 0.2001 0.3003 0.4015 0.4996 0.6006 0.7003 0.8003 0.8966
303.15 5.45 6.88 5.78 4.24 3.49 2.48 1.89 1.93 1.67
308.15 7.42 9.01 7.81 6.28 5.26 4.13 3.20 2.81 2.24
313.15 8.25 10.2 9.06 7.68 6.62 5.20 4.01 3.50 2.68
318.15 9.35 11.5 10.5 9.22 8.12 6.53 4.97 4.28 3.13
323.15 10.6 12.9 12.1 10.8 9.60 7.97 5.83 5.04 3.48
328.15 12.4 14.8 14.2 12.9 11.8 9.84 7.46 6.06 4.25
333.15 14.4 16.8 16.1 14.8 13.6 11.6 8.74 6.91 4.68
338.15 17.0 19.5 18.8 17.3 15.9 13.9 10.5 8.03 5.31
343.15 20.2 22.5 21.6 20.2 18.5 16.6 12.5 9.46 6.21
348.15 24.2 26.4 25.2 23.3 21.7 19.3 14.5 10.7 6.83
353.15 29.3 31.2 29.4 27.2 25.3 22.8 16.9 12.4 7.76
129
Table (A8) Molar excess heat capacity ( C pE /J·mole-1·K-1), for MAE (1) + water (2)
Mole fractions of MAE (x1)
0.1000 0.1998 0.3003 0.3990 0.5002 0.6061 0.6987 0.8003 0.9004
303.15 8.91 9.30 7.64 5.70 4.45 3.13 1.84 0.99 -0.17
308.15 10.5 11.2 9.84 7.95 6.41 4.88 3.36 2.26 0.48
313.15 11.2 12.4 11.3 9.42 7.87 6.10 4.50 3.04 0.93
318.15 12.2 13.8 13.0 11.2 9.59 7.99 6.03 4.11 1.46
323.15 13.2 15.4 14.7 13.0 11.4 9.65 7.67 5.16 2.15
328.15 14.8 17.3 17.0 15.1 13.3 11.5 9.31 6.26 2.93
333.15 16.5 19.4 19.5 17.9 15.9 13.5 11.2 7.75 3.86
338.15 18.8 22.2 22.6 21.2 19.1 16.4 13.9 9.66 4.65
343.15 21.8 25.5 26.2 24.8 22.7 20.2 17.2 12.1 6.54
348.15 25.5 29.6 30.3 28.7 26.5 24.3 20.9 14.9 8.73
353.15 30.2 34.7 34.9 32.9 30.2 27.2 23.8 17.5 9.72
130
Table (A9) Molar excess heat capacity ( C pE /J·mole-1·K-1), for MIPA (1) + water (2)
Mole fractions of MIPA (x1)
0.1000 0.2007 0.2996 0.4001 0.4983 0.6013 0.6999 0.7996 0.8959
303.15 6.57 8.12 5.90 4.44 3.17 2.21 1.26 0.51 0.25
308.15 8.31 10.1 7.94 6.55 5.27 3.83 2.34 1.43 0.90
313.15 9.15 11.1 9.27 8.21 7.02 5.17 3.36 2.12 1.35
318.15 10.0 12.3 10.9 9.89 8.66 6.42 4.18 2.76 1.66
323.15 11.0 13.5 12.6 11.8 10.5 7.96 5.48 3.59 2.18
328.15 12.4 15.2 14.8 14.1 12.4 9.68 6.86 4.54 2.81
333.15 13.8 16.9 17.2 16.4 14.4 11.4 8.17 5.46 3.19
338.15 15.9 19.7 20.2 19.3 16.9 13.5 9.62 6.51 3.68
343.15 18.3 22.9 23.8 22.8 19.9 15.7 11.1 7.45 4.08
348.15 21.6 26.5 27.8 26.9 23.7 18.2 13.0 8.76 4.64
353.15 25.8 31.2 32.8 31.6 27.9 22.0 15.6 9.93 5.04
131
Table (A10) Molar excess heat capacity ( C pE /J·mole-1·K-1), for DMEA (1) + water (2)
Mole fractions of DMEA (x1)
0.0997 0.1962 0.3003 0.3984 0.4983 0.6008 0.6980 0.7981 0.8938
303.15 14.0 15.4 15.1 13.8 12.2 9.71 7.47 5.29 3.83
308.15 14.3 16.4 16.5 15.3 13.6 11.2 8.78 6.48 4.75
313.15 15.1 17.8 18.3 17.1 15.4 13.0 10.2 7.70 5.54
318.15 15.8 19.1 20.0 19.0 17.4 14.8 12.0 9.31 6.30
323.15 16.8 20.7 22.0 21.2 19.7 17.1 14.0 11.0 7.23
328.15 17.9 22.5 24.2 23.7 22.3 19.8 16.7 13.2 8.41
333.15 19.3 24.8 26.9 26.8 25.6 23.0 20.1 16.0 9.93
338.15 21.4 27.7 30.4 30.7 29.5 27.2 24.3 19.8 12.2
343.15 24.2 31.2 34.8 35.8 34.5 32.1 29.2 24.6 15.1
348.15 27.6 35.5 39.7 41.8 40.7 38.0 34.5 29.0 16.9
353.15 32.4 40.9 45.5 48.3 47.1 44.0 40.2 33.0 17.7
132
Table (A11) Molar excess enthalpy (HE/J·mole-1), for AEEA (1) + water (2) mixtures
for (298.15, 313.15, and 323.15) K
298.15 K 313.15 K 323.15 K
x1 HE/J·mole-1 x1 HE/J·mole-1 x1 HE/J·mole-1
0.0298 -771 0.0299 -936 0.0301 -617
0.0496 -1273 0.0498 -1317 0.0498 -1029
0.0699 -1713 0.0701 -1720 0.0697 -1594
0.0992 -2241 0.1000 -2338 0.0992 -2037
0.1503 -3000 0.1495 -3051 0.1491 -2915
0.2015 -3447 0.2002 -3620 0.1988 -3414
0.2962 -3909 0.2956 -4119 0.3014 -3815
0.2982 -3918 0.3547 -4234 0.3527 -3938
0.3484 -4009 0.4001 -4150 0.3958 -3916
0.3994 -3955 0.4461 -3976 0.4971 -3600
0.4454 -3771 0.4893 -3784 0.5908 -3027
0.4962 -3489 0.6009 -3148 0.7056 -2241
0.5050 -3433 0.6723 -2669 0.7484 -1939
0.5922 -2865 0.7961 -1714 0.8999 -820
0.6969 -2192 0.9041 -888 -- --
0.7700 -1711 -- -- -- --
0.9077 -779 -- -- -- --
133
Table (A12) Molar excess enthalpy (HE/J·mole-1), for AP (1) + water (2) mixtures for
(298.15, 313.15, and 323.15) K
298.15 K 313.15 K 323.15 K
0.0299 -404 0.0297 -483 0.0298 -643
0.0705 -927 0.0702 -1026 0.0718 -1213
0.1203 -1525 0.1200 -1569 0.1192 -1660
0.2000 -2130 0.2007 -2108 0.1996 -2144
0.2982 -2501 0.3015 -2541 0.3018 -2542
0.3452 -2595 0.3458 -2632 0.3493 -2645
0.4067 -2613 0.3982 -2647 0.3947 -2667
0.4989 -2462 0.5034 -2499 0.5038 -2498
0.5930 -2171 0.6045 -2125 0.6050 -2163
0.7515 -1531 0.7564 -1375 0.7594 -1423
0.8969 -711 0.9333 -481 0.8801 -753
134
Table (A13) Molar excess enthalpy (HE/J·mole-1), for MAE (1) + water (2) mixtures for
(298.15, 313.15, and 323.15) K
298.15 K 313.15 K 323.15 K
0.0302 -530 0.0310 -535 0.0299 -742
0.0514 -902 0.0500 -902 0.0501 -1114
0.0695 -1163 0.0704 -1182 0.0700 -1359
0.1002 -1480 0.1011 -1591 0.1008 -1655
0.1485 -1919 0.1488 -1987 0.1504 -1975
0.1992 -2243 0.2003 -2302 0.2004 -2220
0.3021 -2671 0.2983 -2639 0.2985 -2568
0.3471 -2750 0.3491 -2678 0.3492 -2642
0.3996 -2732 0.3986 -2668 0.4023 -2650
0.4471 -2667 0.5035 -2513 0.5108 -2478
0.5017 -2508 0.5833 -2289 0.6095 -2142
0.5992 -2148 0.6860 -1919 0.6956 -1732
0.6960 -1707 0.8053 -1277 0.8039 -1169
0.7988 -1219 0.8956 -679 0.8815 -749
0.8939 -688 -- -- -- --
135
Table (A14) Molar excess enthalpy (HE/J·mole-1), for MIPA (1) + water (2) mixtures
for (298.15, 313.15, and 323.15) K
298.15 K 313.15 K 323.15 K
0.0300 -497 0.0304 -560 0.0301 -478
0.0501 -777 0.0701 -1057 0.0500 -714
0.0697 -1010 0.1001 -1364 0.0705 -1022
0.1002 -1357 0.1500 -1761 0.0999 -1289
0.1505 -1755 0.1999 -2054 0.1507 -1679
0.2012 -2040 0.3021 -2443 0.1993 -1979
0.2994 -2393 0.3520 -2516 0.2999 -2304
0.3496 -2482 0.4015 -2502 0.3533 -2415
0.3993 -2478 0.5022 -2327 0.4045 -2454
0.4465 -2423 0.5910 -2039 0.5070 -2318
0.4940 -2320 0.6920 -1640 0.5849 -2081
0.6033 -2012 0.7864 -1184 0.6741 -1756
0.7155 -1527 0.8808 -730 0.8125 -1092
0.7954 -1130 -- -- 0.9073 -601
0.8847 -725 -- -- -- --
136
Table (A15) Molar excess enthalpy (HE/J·mole-1), for DMEA (1) + water (2) mixtures
for (298.15, 313.15, and 323.15) K
298.15 K 313.15 K 323.15 K
0.0299 -701 0.0307 -701 0.0301 -661
0.0705 -1452 0.0695 -1314 0.0705 -1317
0.1008 -1854 0.1196 -1923 0.1217 -1823
0.1501 -2282 0.2038 -2444 0.2027 -2328
0.2052 -2587 0.2979 -2727 0.3001 -2631
0.3010 -2847 0.3490 -2782 0.3486 -2692
0.3490 -2895 0.4063 -2772 0.4001 -2682
0.4106 -2888 0.4925 -2584 0.4995 -2497
0.4544 -2816 0.5885 -2202 0.6093 -2046
0.5365 -2575 0.7046 -1686 0.7618 -1291
0.6599 -2008 0.7891 -1235 0.9197 -464
0.7996 -1247 0.9076 -607 -- --
0.9156 -557 -- -- -- --
137
7.2 APPENDIX B: Molecular area and volume parameters
Appendix B contains pure-component molecular-structure constants depending on the
molecular size and the external surface areas. Molecular surface area and volume
parameters for the UNIQUAC Model are listed in Table (B1). Table (B2) lists the
functional group area (Q) and volume (R) parameters for the Modified UNIFAC
(Dortmund) Model. The parameters in Table (B1) and Table (B2) were retrieved from the
ASPEN PLUS Data Regression Tool.
Table (B1) Molecular surface area and volume parameters for the UNIQUAC model
Surface area Surface area Volume

Alkanolamines
parameter (q) parameter (q’) parameter (r)
2-((2-Aminoethyl)amino)ethanol 3.836 3.836 4.45485
3-Amino-1-Propanol 2.900 2.900 3.24786
2-(Methylamino)ethanol 2.908 2.908 3.31246
1-Amino-2-Propanol 2.896 2.896 3.24984
N-N-Dimethylethanolamine 3.452 3.452 3.96638
Water 1.400 1.000 0.92000
138
Table (B2) Main groups and subgroups and the corresponding van der Waals quantities
for the modified UNIFAC (Dortmund) model
Main Group Subgroup R Q

CH3 0.6325 1.0608
CH2 0.6325 0.7081
CH2
CH 0.6325 0.3554
C 0.6325 0.0000
OH (prim) 1.2302 0.8927
OH OH (sec) 1.0630 0.8663
OH (tert) 0.6895 0.8345
Water H2O 1.7334 2.4561
CH3NH2 1.6607 1.6904
CH2NH2 1.6607 1.3377
CNH2
CHNH2 1.6607 0.9850
CNH2 1.6607 0.9850
CH3NH 1.3680 1.4332
CNH CH2NH 1.3680 1.0805
CHNH 1.3680 0.7278
CH3N 1.0746 1.1760
(C)3N
CH2N 1.0746 0.8240
Gmehling et al. (1993) have also published the van der Waals quantities for the
modified UNIFAC (Dortmund) model.
139

Calorimetric Measurements of The Molar H

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Calorimetric Measurements of The Molar H

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CALORIMETRIC MEASUREMENTS OF THE MOLAR

HEAT CAPACITY AND THE MOLAR EXCESS

ENTHALPY FOR VARIOUS ALKANOLAMINES IN

Submitted to the Faculty of Graduate Studies and Research

In Partial Fulfillment of the Requirements

for the Degree of

Master of Applied Science

in Industrial Systems Engineering

Copyright © 2007: M. Mundhwa

for 2-((2-Aminoethyl)amino)ethanol, 3-Amino-1-Propanol, 2-(Methylamino)ethanol, 1-

Amino-2-Propanol, and N-N-Dimethylethanolamine in water were carried in a C80 heat

excess enthalpy was found to be ± 2 %.

Among the five studied alkanolamines, 2-((2-Aminoethyl)amino)ethanol exhibited

side (exothermic mixing process), followed by N-N-Dimethylethanolamine, 2-

(Methylamino)ethanol, 3-Amino-1-Propanol, and 1-Amino-2-Propanol.

calculated at infinite dilution.

contribution model: modified UNIFAC (UNIversal quasi chemical Functional group

molar excess enthalpy values on the negative side.

I would like to express my gratitude to my supervisor, Dr. Amr Henni, whose

guidance, thought provoking suggestions, encouragement and financial assistance

different ways helped me with my work on this Master’s thesis.

its own sake. This thesis is also dedicated to my brother Himanshu.

2.1 Calorimetric methods 10

3.1 Experimental apparatus 27

4. EXPERIMENTAL RESULTS AND DISCUSSION 52

5. CONCLUSION AND RECOMMENDATIONS 113

5.1 Conclusion 113

7.1 APPENDIX-A: Experimental data 123

Table (3.1) Sensitivity constants…………………………………………………………….…………………...32

(303.15 to 353.15) K……………………………………………………………….………………..56

(303.15 to 353.15) K………………………………………………………………….……………..59

(303.15 to 353.15) K………………………………………………………….……………………..63

(303.15 to 353.15) K…………………………………………………………………….…………..66

(303.15 to 353.15) K……………………………………………………….………………………..70

water at infinite dilution in AEEA, ( ΔH 2∞ ), for (298.15, 313.15, and

at infinite dilution in AP, ( ΔH 2∞ ), for (298.15, 313.15, and 323.15) K…...83

water at infinite dilution in MAE, ( ΔH 2∞ ), for 298.15 K……………….………...91

Table (4.12c) Molar enthalpies of MAE at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in MAE, ( ΔH 2∞ ), for (298.15, 313.15, and

water at infinite dilution in MIPA, ( ΔH 2∞ ), for (298.15, 313.15, and

water at infinite dilution in DMEA, ( ΔH 2∞ ), for 298.15 K………...…………..104

Table (4.16c) Molar enthalpies of DMEA at infinite dilution in water, ( ΔH 1∞ ), and of

water at infinite dilution in DMEA, ( ΔH 2∞ ), for (298.15, 313.15, and

+ water (2) mixtures from (303.15 to 353.15) K……………………...…………….123

water (2) mixtures from (303.15 to 353.15) K……………………………………….124

water (2) mixtures from (303.15 to 353.15) K……………………………………….125

+ water (2) mixtures from (303.15 to 353.15) K…………………………...……….126

+ water (2) mixtures from (303.15 to 353.15) K…………………………...……….127

mixtures from (303.15 to 353.15) K………………………………………………………129

mixtures from (303.15 to 353.15) K………………………………………………………129

mixtures from (303.15 to 353.15) K………………………………………………………130

mixtures from (303.15 to 353.15) K………………………………………………………131

mixtures from (303.15 to 353.15) K………………………………………………………132

Figure (1.1) Chemical structures of the selected alkanolamines……………………………...…….7

a NRTL and UNIQUAC energy interaction parameter

ai Redlich-Kister equation parameters

anm UNIFAC group interaction parameter between groups n and m, K

b NRTL and UNIQUAC energy interaction parameter, K

bnm UNIFAC group interaction parameter between groups n and m

cnm UNIFAC group interaction parameter between groups n and m, K-1

Cp molar heat capacity, J/mole/K

C p (T ) molar heat capacity of the substance at the desired temperature T,

C pE molar excess heat capacity, J/mole/K