TOPIC :

Calculation of High-Pressure Chemical

Equilibrium: Case of ammonia synthesis

INTRODUCTION:

LITERATURE SURVEY:
SR. TITLE Author Year of Summary
NO Publication
1 Development and O.Siddhiqui 2000 In the present study, a new ammonia
evaluation of a I Dincer synthesis and fuel cell system
solar-based integrated with solar energy is
developed. The excess energy from a
integrated
solar photo-voltaic power plant is
ammonia utilized for ammonia synthesis as an
synthesis and fuel energy storage medium. Two different
cell system locations in Canada are considered for
system modelling and simulation. The
thermodynamic performance of the
developed system is analyzed on a
transient basis taking into account the
variations in solar intensities across
the year.
2 Electrochemical 2019 Ammonia is important feedstock for
synthesis of both fertilizer production and carbon-
Jiarong Yang free liquid fuel. Many techniques for
ammonia in
ammonia formation have been
molten salts
Wei Weng developed, hoping to replace the
industrial energy-intensive Haber–
Bosch route. Electrochemical
synthesis of ammonia in molten salts
is one promising alternative method
due to the strong solubility of N3− ions,
a wide potential window of molten salt
electrolytes and tunable electrode
reactions. Generally, electrochemical
synthesis of ammonia in molten salts
begins with the electro-cleavage of
N2/hydrogen sources on electrode
 surfaces, followed by diffusion of
N3−/H+-containing ions towards each
other for NH3 formation.
3 Highly selective Baochen Cui 2019 Ammonia production via
and efficient Zhongjun Yu electroreduction of N2 and water
ammonia under mild conditions is emerging as
a promising alternative to the fossil
synthesis from
fuels-reliance and CO2 emitting
N2 and H2O via an Haber-Bosch process. However, the
iron-based achievement of high Faradaic
electrolytic- efficiency and high ammonia
chemical cycle formation rate is still challenging.
Here, we demonstrate how ammonia
can be selectively produced from
N2 and H2O via a two-step iron-based
cyclic process using a molten
hydroxide electrolyte. 
4 Photocatalytic Shuai Zhang 2019 Ammonia (NH3) is one of the most
ammonia Run Shi important commodity chemicals in
synthesis: Recent today's chemical industry.
Industrially, ammonia is
progress and
synthesized via the Haber-Bosch
future process at high temperature and
pressure (typically 400 °C and
200 atm). In nature, the nitrogenase
enzyme can convert N2 to NH3 at
ambient conditions, motivating the
search for similar sustainable
technologies for industrial-scale
NH3 production. Over the past few
years, photocatalytic ammonia
production using sunlight and
photocatalysts has attracted much
attention, allowing the reduction of
N2 to NH3 under very mild reaction
conditions. 
5 Recent progress Qianru Wang 2018 Ammonia is essential for food and
towards mild- Jianping Guo energy. Industrial ammonia synthesis
condition via Haber–Bosch process  is energy-
intensive and releases large amount of
ammonia
CO2. Increasing research efforts are
synthesis devoted to “green” ammonia
synthesis. The present article reviews
the recent progress in the fields of
thermocatalytic, electrocatalytic,
photocatalytic and chemical looping
processes for dinitrogen reduction
towards ammonia formation and
discusses the challenges borne for
mild-condition synthesis
6 A comparison of A.Daisley 2018 The present study presents an
the activities of J.S.J.Hargreaves empirical screening study of the
various supported catalytic performance of a variety of
R. Herman
supported materials for ammonia
catalysts for
synthesis at 400 and 500 °C. Amongst
ammonia the materials tested, those derived
 synthesis from Ru/Al2O3 exhibited the best
performance. Supported Os and CoRe
catalysts also demonstrated
comparatively high activities
indicating them to be potentially
worthy of further investigation.
7 A theoretical study Yijing Gao 2016 Electrocatalytic ammonia
of electrocatalytic Han Zhuo synthesis under mild conditions is an
ammonia attractive and challenging process in
the earth's nitrogen cycle, which
synthesis on single
requires efficient and stable catalysts
metal to reduce the overpotential. the
atom/MXene overpotential of electrolytic ammonia
synthesis is determined by the Gibbs
free energies of two potential-limiting
steps
N2 + H+ → NNH (ΔG1)
and
NH2 + H+ → NH3 (ΔG2).
8 Recent progress in Runbo Zhao 2019 Ammonia not only serves as a
the Le Chang building block for nitrogen-rich
electrochemical fertilizer, but offers a carbon-free
energy carrier. At present, industrial
ammonia
ammonia synthesis is dominated by
synthesis under the Hablocker-Bosch process under
ambient high temperature and pressure,
conditions resulting in high energy consumption
and serious environmental issues.
Considerable recent at tention has
focused on designing electrocatalysts
for the N2 reduction reaction (NRR).
However, the ammonia synthesis
through electrocatalytic N2 reduction
is still far from practical applications.
In this review, recent theoretical and
experiment investigations on various
catalysts for the ammonia synthesis
under mild conditions are highlighted.
9 A new synthesis Ankur Jain 2017 Recently ammonia  has emerged as a
route of ammonia Sanjay Kumar potential hydrogen storage  material
production because it contains 17.8 wt%
hydrogen. Here, we propose a new
through hydrolysis
synthesis route of ammonia
of metal – Nitrides production
using hydrolysis of nitrides, which is
based on the conversion technique
using thermal energy, solar  heat or
exhaust heat to form NH3 directly.
Lithium metal has been tested as a
starting material for the above
purpose. We present the detailed
results on room temperature
nitridation of lithium metal, it is
found that the nitridation properties
are strongly affected by the surface
state of lithium metal. The ammonia
 synthesis via hydrolysis of lithium
nitride succeeds and it is strongly
dependent on the reaction rate and
temperature
10 Kinetics of Kazuya Imamura 2019 It investigates the kinetics of
ammonia Yuta Nakasaka NH3 synthesis over a catalyst
synthesis over consisting of low-crystalline Ru nano-
layers supported on Pr2O3. We
Ru/Pr2O3
determined the reaction orders with
respect to N2, H2, and NH3 at various
temperatures and pressures over
Ru/Pr2O3, as well as Ru/CeO2 and
Ru/MgO. The reaction orders with
respect to N2 were always almost unity
for all the catalysts under all the
reaction conditions, indicating that

the rate-determining step was N

N bond cleavage. In contrast, the
reaction orders with respect to
H2 differed among the catalysts and
decreased with increasing pressure
and increased with increasing
temperature.
11 High-Pressure Mohamed 2000 The first part of this paper is a review
M. Elbaccouch of experimental methods and the
Vapor−Liquid And high-pressure phase behavior of
Equilibrium for J. Richard dimethyl ether systems for which
Dimethyl Ether + Elliott data have been published between
1932 and 1999. For the systems
Ethanol and investigated, the references,
Dimethyl Ether + temperatures, pressures, cell
Ethanol + Water volumes, and experimental
procedures are reported. The second
part of this paper is high-pressure
vapor−liquid equilibrium (VLE) data
for the systems dimethyl ether (DME)
+ ethanol at (332.95, 353.25, and
373.15) K and dimethyl ether +
ethanol + water at (333.55, 353.55,
and 373.65) K. The experimental data
are correlated using the
Elliott−Suresh−Donohue (ESD-EOS)
and Peng Robinson (PR-EOS)
equations of state.
12 Mariana 2001 Isothermal (P, T, x, y) data have been
High-Pressure measured for the binary and ternary
Teodorescu
Vapor−Liquid systems nitrogen + dimethyl ether at
And
15, 35, and 45 °C, dimethyl ether +
Equilibria in the Peter methanol at 80 °C, carbon dioxide +
Systems Nitrogen Rasmussen dimethyl ether + methanol at 40 and
60 °C, and nitrogen + dimethyl ether
 + methanol at 40 and 15 °C. The
+ Dimethyl Ether, pressure range under investigation
Methanol + was up to 9.5 MPa. The experimental
data for the binary systems were
Dimethyl Ether, correlated with the SRK equation of
Carbon Dioxide + state using the MHV2 mixing rule
combined with the UNIFAC or
Dimethyl Ether + UNIQUAC model for the expression of
the excess Gibbs energy. The
Methanol, and
experimental data for the ternary
Nitrogen + systems have been compared with
those predicted by means of the same
Dimethyl Ether + models, and the results are discussed
Methanol by comparison. The binary system of
nitrogen + dimethyl ether as well as
the two ternary systems have not
previously been studied.
Modeling Phase 
13 Selva 2019 In this work, we extend the Group
Contribution with Association
Pereda
Equilibria of Equation of State (GCA-EOS) to
Francisco model the phase behavior of mixtures
Ethers and A. Sánchez comprising ethers and alcohols. The
Alcohols with  model parametrization was done
using few binary vapor–liquid
GCA-EOS for equilibrium data sets of linear
monoethers. We also model the
Assessing the
behavior of branched ethers,
Coblending of traditionally used as fuel additives, as
well as that of polyethers, which are
Advanced nowadays being proposed as potential
Biofuels biofuels. Therefore, we investigate not
only the phase equilibria but also
excess enthalpies of these three types
of ethers in mixtures with alcohols.
Finally, we show that the GCA-EOS is
able to predict the phase behavior of
polyethers, as well as that of branched
ethers, using a group contribution
approach. This work is part of a
broader project for the development
of a robust and predictive
thermodynamic model for process and
product design in the context of
biomass valorization
Vapor−Liquid and
14 Oleg S. 2000 Isobaric vapor−liquid equilibrium
(VLE) data (T−x−y) for the binary
Pavlov
Chemical systems methanol/2-methoxy-2-
 Juha methylbutane (TAME), methanol/2-
Reaction Lineosi methyl-2-butene, and methanol/2-
Equilibria in the methylbutane were obtained at 101.3
kPa. All systems showed a positive
Synthesis of 2- deviation from ideality with a
minimum-boiling-point azeotrope.
Methoxy-2-
The activity coefficients were
methylbutane calculated with the use of the Wilson
equation where the parameters of the
 binary systems were determined on
(TAME) the basis of the experimental data.
Other VLE data relevant to TAME
synthesis were collected from the
literature, and the respective
parameters were adjusted. Earlier
reported results of the reaction
equilibrium experiments on the
liquid-phase formation of TAME were
reanalyzed. On the basis of the
experimental reaction equilibrium, a
value of −109.6 kJ·mol-1 is presented
for the Gibbs energy of formation for
TAME in the gas phase at 298 K.
15 A modified Patel– Luis A. 2013 In this work, the parameters of the
Teja cubic Forero G equation of state formed by the Patel–
equation of state. Teja pressure–volume–temperature
relationship and the alpha function of
Part II: Parameters
Heyen have been estimated for 184
for polar polar substances. To obtain the
substances and its parameters of the proposed model,
mixtures pseudo-experimental data have been
generated using the DIPPR
correlations for vapor pressure and
liquid density. The proposed model in
conjunction with the Wong–Sandler
mixing rules and the NRTL activity
model have been used to describe the
vapor liquid equilibria of some
complex mixtures.
16 Isothermal Seol A. Ki 2012 Isothermal vapor-liquid equilibrium
vapor-liquid m data for the binary mixture of
equilibria for the Joon Hyu dimethyl ether (CH3OCH3)+methanol
binary system of k Yim (CH3OH) were measured within the
temperature range of 308.15–328.15
dimethyl ether
K. The data in the two-phase region
(CH3OCH3)+ were measured by using a
methanol circulation-type equilibrium
(CH3OH) apparatus in which both vapor and
liquid phases are continuously
recirculated. The experimental data
were correlated with the Peng-
Robinson equation of state (PR-EoS)
using the Wong-Sandler mixing rules
combined with the NRTL excess
Gibbs free energy model. The values
calculated by the PR-EOS with the
W-S mixing rules show good
agreement with our experimental
data.
17 Vapor-Liquid P. L. Chueh and 1967 Thermodynamics reduction and
J. M. Prausnitz correlation of vapour liquid
Equilibria at equilibrium data common at low
High Pressures. pressure but despite a general supply
Vapor-Phase of equilibrium data at high pressure
 Fugacity little attempt has been made to
reduce such data with
Coefficients in thermodynamically significant
Nonpolar and functions. In high pressure phase
Quantum-Gas equilibrium it is not possible to make
various simplifying assumption
Mixtures commonly made at low pressure and
as a result thermo dynamic analysis
has only rarely been applied to high
pressure systems.
18 CALCULATION P. L. Chueh and 1968 Although it has been common
J. M. Prausnitz practice for many years to subject
OF HIGH- vapour liquid equilibrium data to
PRESSURE thermodynamics analysis in the past
VAPOR-LIQUID this practice has been largely
confined to system at low or
EQUILIBRIA moderate pressure. While many
experimental studies of high pressure
and vapour liquid equilibrium has
been published little work has been
reported on the reduction of such
data to thermodynamics function.
19 Estimation Alberto 1995 This paper considers the calculation
Bertucco of homogeneous chemical equilibria
of Chemical Equil Massimili in high pressure gaseous system.A
ibria In High- ano Barolo and modified Redlich Kwong Soave
Giorgio equation of state which represent
Pressure Gaseous Soave satisfactorily single phase fugacity
Systems by a coefficients of pure fluids is extended
Modified Redlich- to mixtures. Mixtures parameter are
Kwong-Soave derived from the corresponding pure
components one by one means of the
Equation of State classical mixture rules. Equilibirum
composition are predicted for the
ammonia synthesis, the water gas
shift reaction and methanol synthesis
20 Gas H. Frank 1976 This paper is concerned with an
Gibbard, aspect of chemical equilibrium in
phase chemical eq Michael the gas phase which is treated in
uilibria R. Emptage the most
physical chemistry textbooks: the
case when the pressure is
so high that partial pressures are
not a good approximation to
fugacities.
21 Using Computer- Zhao Li 2018 The application of the Reaction
and Monte Carlo (RxMC) algorithm to
Based
 “Experiments” in David S. standard textbook problems
Corti in chemical reaction equilibria is
the Analysis discussed. The RxMC method is a
of Chemical React molecular simulation algorithm for
ion Equilibria studying the equilibrium properties
of reactive systems, and therefore
provides the opportunity to
develop computer-based
“experiments” for the analysis of a
wide range of chemical reactions.
22 Physico-Chemical  Barnett 1932 For the design of the pressure
F.Dodge sustaining shell of such a equipment
Factors in High- data on the mechanical properties of
Pressure Design metal and alloys at various
temperature. Ultimate tensile
strength proportional limit creeps
stress modulus of elasticity are
among important properties in this
category. In addition to the data
there must be suitable formulas
based on the actual test to permit the
data to be applied to design.
23 Equations of State Leslie 2009 We present equations of state relating
Glasser the phases and a three-dimensional
and Phase phase diagram for ammonia with its
Diagrams solid, liquid, and vapor phases, based
on fitted authentic experimental data
of Ammonia and including recent information on
the high-pressure solid phases. This
presentation follows similar articles
on carbon dioxide and water
published in this Journal, where the
basics of multiple-phase equilibria are
described. Such an authentic diagram
for ammonia has not been presented
and may improve the understanding of
its phase relationships. Interactive
virtual 3D versions of these phase
diagrams, programmed in Jmol, are
also available.
24 High-Pressure Vap Rob M. 1997 Bubble-point and dew-point pressures
M. Stevens, and vapor−liquid critical points of the
or−Liquid Equilibr Arthur ternary system (x1)carbon dioxide +
ia of the Ternary Bakx, (x2)vinyl acetate + (x3)2-butanol were
Peter R. measured in the temperature range
System Carbon H. van der Neut, 278−510 K up to 14 MPa in a high-
Dioxide + Vinyl Theo W. pressure capillary glass tube
de Loos, and apparatus, using the synthetic method.
Acetate + 2-
Jakob de The system has been investigated for
 Butanol. Swaan Arons varying carbon dioxide compositions
at fixed ratios of vinyl acetate and 2-
butanol (x2/x3 = 1/3 and 3/1) and at
fixed 2-butanol composition (x3 =
0.15). Modeling of the
vapor−liquid equilibria of the ternary
system has been performed using two
equation of state (EOS) methods:  (1)
the Stryjek−Vera modification of the
Peng−Robinson EOS with the
Wong−Sandler mixing rules
(PRSV/WS) implementing the NRTL-
GE model; (2) the LCVM model,
which is the translated modified PR
EOS with the linear combination of
Vidal and Michelsen mixing rules
implementing the UNIFAC-GE model.
25 HIGH PRESSURE Viorel FEROIU, 2013 A single set of interaction
PHASE Sergiu SIMA, Dan parameters, representing well the
EQUILIBRIUM IN GEANĂ critical pressure maximum (CPM) was
CARBON used to model the global phase
DIOXIDE+ETHANO behavior of the carbon dioxide +
L SYSTEM ethanol system

26 Phase Equilibria Dan Geană, Liviu 2005 The importance and role of phase
Database and Rus equilibria are related to plant design,
Calculation safety, reliability, operation in
Program for Pure chemical and biochemical
Component engineering. For an effective and
Systems and efficient utilization of large amounts
of phase equilibrium data in chemical
Mixtures
and biochemical engineering, an
intelligent database program for
phase equilibrium (PHEQ) data
management and application was
developed.
27 Analysis of Hideyuki 2018 Ammonia is a potential hydrogen
influence of Matsumoto, carrier that contains 17.6 wt% of
operating Javaid Rahat, hydrogen. Moreover, as an energy
pressure on Yuichi Manaka, carrier, ammonia is thought to be a
dynamic behavior Mika Ishii, Tetsuya clean fuel as only water and nitrogen
of ammonia Nanba, are produced on direct combustion.
production over
ruthenium
catalyst under
high pressure
condition
28 Haber’s process Jayant M Modak 2002 Current Status of Ammonia
for ammonia Production and Haber’s Contributions
synthesis. to Ammonia Synthesis Process

29 Phase Equilibria in Yun-Yun Gao ,Lan- 2017 The phase equilibria of the ternary
the Ternary Rong Zhao ,Xiao- system were measured by the
System NaCl– Ping Li, Shi-Hua isothermal dissolution equilibrium
SrCl2–H2O (273 Sang method. The Pitzer model known as
and 308 K) and an ion-interaction model has been
Quaternary successfully used to calculate the
System LiCl–NaCl– solubilities of salts in water–salt
SrCl2–H2O (308 K). systems with an experimental
accuracy. Based on the Pitzer model
parameters from the literatures, the
Pitzer model was used to predict the
solubilities of salts in the ternary
system

30 High-pressure Wen Cao 2018 In this study, the Gibbs-Duhem

vapor-liquid Ning Wang equation was applied to make the
equilibrium thermodynamic consistency test and
studies for DME- thermodynamic model estimation for
CO2-CH3OH and systems of CO2-DME (dimethyl
DME-CO2- ether), DME-CH3OH, CO2-CH3OH and
C2H5OH systems C2H5OH systems on the basis of the
vapor-liquid equilibrium (VLE)
experimental data in published
reports.
31 Fluid phase W B Streett 2016 A vapor-recirculating equilibrium system
equilibria in the M E Pozzo has been used to study the fluid phase
system dimethyl behavior of the system dimethyl
ether/water from ether/water (DME/H2O). This system
exhibits a liquid-liquid phase separation
50 to 220 C and
and a mixture critical line that consists of
pressures to 500 two branches. One branch originates at
bar the critical point of DME (T = 126.6 C, P =
53.2 bar), and ends at a critical end point
(T = 157 C, P = 67.2 bar, xDME = 0.79)
where it intersects the three-phase
region liquid-liquid-vapor.
32 Calculation of high Chiaki Yokoyama 2016 An augmented van der Waals equation of
pressure vapour— KunioArai state based on a perturbation theory has
liquid equilibria ShozaburoSait been applied to the calculation of high
for systems pressure vapour—liquid equilibria for
systems containing polar substances. The
containing polar
equation of state comprises four terms,
substances with which imply the contributions from
 the use of an repulsion, symmetric, non-polar
augmented van asymmetric, and polar asymmetric
der Waals interactions. The characteristic
equation of state parameters of each pure substance have
been determined by three methods with
the use of vapour pressures and
saturated liquid densities.
33 Fluid phase M.E. Pozo de 2014 Vapour-liquid equilibrium data (P-T-x-y)
equilibria for the Fernández, J. Noles, for the binary system dimethyl ether/1-
binary system J.A. Zollweg, butene have been measured from 283 K
dimethyl ether / to 369 K. This region of vapour -liquid
coexistence has been explored for the
1-butene
first time. The experimental apparatus
and analysis system is described in detail.
Barker's method of data reduction has
been used to test the consistency, and
the ability of cubic equations of state to
represent the experimental results has
been examined.
34 High-pressure Michael L. 1990 Recent procedures developed by
Vapor-liquid Michelsen Heidemann (1990) and by Michelsen
Equilibrium with a Søren Dahl (1990a, b) enable us to formally
UNIFAC-based incorporate excess Gibbs energy
Equation of State model parameters into a fully
consistent equation of state, cith
accurate reproduction of the
behavior of the excess Gibbs energy
model at atmospheric pressure. This
paper investigates the ability of the
mixing rules proposed by Michelsen
to predict high-pressure phase
equilibrium, when used in
combination with the parameter
table of modified UNIFAC.
35 Calculation of Andrzej Anderko 1989 A previously proposed simple equation of
vapor—liquid state incorporating association is applied
equilibria at to calculate vapor—liqud equilibria (VLE)
elevated at elevated pressures for systems formed
by polar compounds and hydrocarbons.
pressures by
The pure-component parameters are
means of an calculated from experimental saturated
equation of state vapor pressure and liquid density data.
incorporating Such parameters are sufficient for the
association prediction of VLE with reasonable
accuracy in binary systems formed by
hydrogen sulfide, ammonia, carbon
dioxide, carbon monoxide or sulfur
dioxide with aliphatic hydrocarbons.
36 High-pressure R.M.M.StevensJ.C. 1997
vapour-liquid van
Bubble-point and some dew-point
equilibria in the RoermundM.D.Jag
 systems carbon erTh.W.de LoosJ.de pressures and vapour-liquid critical points
dioxide + 2- Swaan Arons of the binary systems carbon dioxide + 2-
butanol, + 2-butyl butanol, carbon dioxide + vinyl acetate
acetate, + vinyl and carbon dioxide + 2-butyl acetate
were measured in the temperature range
acetate and
of 278–520 K up to 15 MPa in a high-
calculations with pressure capillary glass tube apparatus,
three EOS using the synthetic method. For the
methods system [(1 − x) CO2 + (x) 2-butanol] data
of the three-phase line L2L1V for x =
0.1495 are given for a temperature range
of 249–252 K. The UCEP (L2L1 = V) is found
at P = 1.787 MPa and T = 251.39 K.

37 CALCULATION OF RAYMOND H. 2002 This paper will treat the thermo

CHEMICAL EWELL dynamics-i. e., equilibrium, of three
EQUILIBRIUM AT reactions: the methanol synthesis
HIGH PRESSURES reaction, the hydration of ethylene,
and the reac- tion of nitrogen and
acetylene to give hydrogen cyanide.
The knowledge of reaction rates and
catalysis in these reac- tions is a
separate field and will be given little
mention
38 A hundred years Mordechai An exercise that involves a process of
of chemical Shacham great historical importance - that of
equilibrium synthesizing ammonia from its elements -
calculations - The is presented. In the exercise, the students
are required to calculate the equilibrium
case of ammonia
conversion to ammonia using three
synthesis mathematical models: a regression model
which is based on experimental
equilibrium data obtained by Haber and
le Rossignol over a hundred years ago; a
model based on the Gibbs energy and
ideal gas conditions; and the Gibbs
energy model with gas phase non-ideality
included
39 High-pressure Wen Cao 2016 In this study, the Gibbs-Duhem
vapor-liquid Ning Wang equation was applied to make the
equilibrium thermodynamic consistency test and
studies for DME- thermodynamic model estimation for
CO2-CH3OH and systems of CO2-DME (dimethyl
DME-CO2- ether), DME-CH3OH, CO2-CH3OH and
C2H5OH systems C2H5OH systems on the basis of the
vapor-liquid equilibrium (VLE)
experimental data in published
reports.
40 CALCULATION P. L. Chueh 1968 Although it has been common
J. M. Prausnitz practice for many years to subject
 OF HIGH- vapour liquid equilibrium data to
thermodynamics analysis in the past
PRESSURE this practice has been largely
VAPOR-LIQUID confined to system at low or
EQUILIBRIA moderate pressure. While many
experimental studies of high pressure
and vapour liquid equilibrium has
been published little work has been
reported on the reduction of such
data to thermodynamics function.

RESULTS & DISCUSSION :