Review
Vapor-Liquid Equilibrium in the Acetic Acid-Ethanol-Ethyl
Acetate-Water Quaternary System: Critical Literature Review
and Thermodynamic Consistency of the Experimental Data
Georgii Misikov, Maya Trofimova * and Igor Prikhodko
Citation: Misikov, G.; Trofimova, M.;
Prikhodko, I. Vapor-Liquid
Equilibrium in the Acetic
Acid-Ethanol-Ethyl Acetate-Water
Quaternary System: Critical
Literature Review and
Thermodynamic Consistency of the
Experimental Data. Chemistry 2023, 5,
2542–2565. https://doi.org/10.3390/
chemistry5040165
Academic Editor: Ryan
C. Fortenberry
Received: 22 October 2023
Revised: 10 November 2023
Accepted: 11 November 2023
Published: 13 November 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Chemistry 2023, 5, 2542–2565. https://doi.org/10.3390/chemistry5040165
Department of Chemical Thermodynamics and Kinetics, Institute of Chemistry, Saint Petersburg State University,
Saint Petersburg 198504, Russia
* Correspondence: m.trofimova@spbu.ru
Abstract: This study presents a critical review of the experimental vapor-liquid equilibrium (VLE)
data for the quaternary acetic acid-ethanol-ethyl acetate-water system and its subsystems that are
reported in the literature. The thermodynamic consistency of the VLE data were verified using
two integral tests: the Redlich–Kister test and the direct integration of the Gibbs–Duhem equation.
The VLE data were correlated using the NRTL equation for further integration. Additionally, the
reliable value of the integral derived from the direct integration of the Gibbs–Duhem equation for
multicomponent systems under isothermal-isobaric conditions was estimated. This integral can be
used for testing the thermodynamic consistency of experimental VLE data.
Keywords: vapor-liquid equilibrium; ethyl acetate; thermodynamic consistency
1. Introduction
The development of environmentally friendly chemical processes that should become
more cost-effective, energy-efficient, and resource-saving than currently existing methods
is of great current interest in light of the global trend to reduce greenhouse gas emissions
and prevent global warming. This aligns with the criteria for sustainable development [1]
and the Kyoto Protocol [2].
Coupled processes, where the phase transition is accompanied by a chemical reaction,
are emerging as a crucial component of new energy-efficient and resource-saving industrial
chemical technologies. The synergistic effect of integration into chemical production of
such coupled processes as reactive distillation (RD), which combines the stages of chemical
interaction and distillation separation of substances in one apparatus, includes increased
reagent conversion, reduced energy costs, and minimized environmental risks [3]. The
application of RD facilitates the implementation of industrial processes in which the course
of a chemical reaction is limited by the chemical equilibrium between the reactants and
products, necessitating the removal of products from the reaction mixture without the need
for additional equipment and the generation of a significant amount of wastewater.
Detailed information on phase equilibrium in reacting systems and on the structure
and topology of the phase diagrams of the systems with coupled (phase and chemical) pro-
cesses is essential for the development and optimization of industrial processes involving
reactive distillation.
Currently, the investigation of coupled processes, such as RD, in systems with the es-
terification reaction is of utmost importance in the context of industrial technologies for the
production of esters, for example, ethyl acetate. This ester is highly significant in industrial
applications, including the production of paints and varnishes, adhesive compositions,
and artificial leather (as a solvent); pharmaceutical production (as a reagent and a reaction
medium); aluminum foil production and electronic industry (as a degreasing agent); food
industry (as an extracting agent of organic substances from aqueous solutions and a food
https://www.mdpi.com/journal/chemistry
 Chemistry 2023, 5, FOR PEER
Chemistry
REVIEW 2023, 5, FOR PEER REVIEW

Chemistry 2023, 5, FOR PEER REVIEW 2

reaction medium); aluminum reaction medium); foil production aluminum and electronic
foil production industry and(as electr
ad
Chemistry 2023, 5 2543
agent); food industry (as agent);
an extracting
food industry agent(as of an
organic
extractingsubstances
agent of fromorganic
aqueoussub
reaction medium); aluminum foil production and electronic industry (as a degreasing
and a food additive); explosivesand a foodproduction additive); explosives
(as a gelling production
agent); and (asperfumery,
a gelling agc
agent); food industry (as an extracting agent of organic substances from aqueous solutions
and food industry (asand a component
food industry of fruit (as essences).
a component Furthermore,
of fruit essences). ethyl aceta Fur
and a food explosives
additive); additive); explosives
production production
(astoxicity
a gelling (asagent);
a gelling and agent); and perfumery,
perfumery, cosmetics, cosmetics,
acterized by low acterized
[4] comparedby low toxicity
to other[4] industrially
compared toand
important
otherfood industrial
solvents
and food (as
industry industry (as a component
a component of fruit of fruit essences). Furthermore, ethyl acetate is char-
importantly, is essences).
biodegradable Furthermore,
importantly, ethyl acetate
[5,6].is biodegradable is characterized
[5,6]. by
acterized
low toxicity by [4]
lowcompared
toxicity [4] to compared
other to other important
industrially industrially important
solvents and, solvents
most and, most
importantly,
Conventionally, ethylConventionally,acetate is obtained ethylbyacetatedirect isacid-catalyzed
obtained by direct esterifi
importantly,
is biodegradable is biodegradable
[5,6]. [5,6].
acetic acid with ethanol acetic
in the acid liquid
withphase
ethanol in in
batchthe liquid
or continuous
phase inreactors,batch orand co
Conventionally,
Conventionally, ethyl ethylacetate
acetateis is obtained
obtained by direct
by direct acid-catalyzed
acid-catalyzed esterification
esterification of acetic of
tion occurs at temperatures tion occurs of 363.15–423.15
at temperatures K [7],ofmaking363.15–423.15
it extremely K [7],energy
makin
acetic acidethanol
acid with with ethanol in thephase
in the liquid liquidinphase
batchin orbatch
continuous or continuous
reactors, reactors,
and the reaction and theoccurs reac-
However, employing However, technologies employing
such as RD technologies
for the productionsuch as RD of for
ethyltheaceta
pro
tion occurs at temperatures
at temperatures of 363.15–423.15of 363.15–423.15
K [7], making K [7], making it extremely
it extremely energy intensive. energy intensive.
However,
peratures of 343.15–383.15 peratures K can of significantly
343.15–383.15increase K can significantly
the conversion increase
of reag th
However,
employingemploying
technologies technologies
such as RDsuch as RD
for the for the production
production of ethyl acetate of ethyl acetate at tem-
at temperatures of
pared to synthesis in pared a conventional
to synthesis reactorin a (almost
conventional complete reactor conversion
(almost of com et
peratures
343.15–383.15 of 343.15–383.15
K can significantlyK canincrease
significantly increase of
the conversion thereagents
conversion compared of reagents
to synthesiscom-
be achieved with a moderate be achieved height with
of thea moderate
distillation height
column)of theand distillation
provide colu a hig
pared to synthesis reactor
in a conventional in a conventional
(almost complete reactor conversion
(almost complete of ethanol conversion
can be of ethanolwith
achieved can
target product containing targetalmost product nocontaining
ethanol [8].almost Therefore,no ethanolincorporating
[8]. Therefo eth
a moderate
be achieved with height of the distillation
a moderate height ofcolumn) and provide
the distillation column) a high-quality
and provide target product
a high-quality
synthesis using RD in synthesis
industrial using
production
RD in industrial
makes theproduction process more makes enviro
the
containing
target productalmost no ethanol
containing [8]. Therefore,
almost no ethanol incorporating
[8]. Therefore, ethylincorporating
acetate synthesis ethylusing acetateRD
friendly, energy-efficient, friendly,
and resource-efficient.
energy-efficient, and Significant
resource-efficient.
contributions Significa
to the
in industrial production makes the process more environmentally
synthesis using RD in industrial production makes the process more environmentally friendly, energy-efficient,
ment of fundamentalment aspects of fundamental
of RD important aspectsfor theof RD design
importantof industrial
for thepr de
and resource-efficient.
friendly, energy-efficient, Significant contributions toSignificant
and resource-efficient. the development of fundamental
contributions to the develop-aspects
chemical technology have chemical beentechnology
made in papers have [3,9–12].
been made in papers [3,9–12].
of RDof
ment important
fundamental for the designofofRD
aspects industrial
important processes
for the of chemical
design technology
of industrial have been
processes of
made in papers [3,9–12]. A pre-requisite for developing A pre-requisite precise formodels
developing and predictions
precise models of the and be
chemical technology have been made in papers [3,9–12].
A pre-requisite complex
pre-requisite for reacting
for developing systems
developing precise complex for
precise models thereacting
models and purposes systemsof
and predictions the
predictions offorchemical
the purposes
of the industry,
the behavior
behavior ofof the
including
of chemical o
A
complex reacting existing
reacting systems
systems for processes
for the and
the purposes
purposes ofexisting
creating
of the processes
new
thechemical ones and
chemicalindustry, for creating
the synthesis
industry, including new ones
of
including optimizing ethyl
for
optimizing the
acetate,
synthesi
such
complex
existing processes the
and thermodynamic
creating new consistency
ones thefor thermodynamic
the of preliminary
synthesis of consistency
ethyl experimental
acetate, of such
preliminary
data.
as RD,
RD, Thisexperime
is paper p
existing processes and creating new ones for the synthesis of ethyl acetate, such as is
the thermodynamic critical
thermodynamic consistency review
consistency of of the data
critical
of preliminary on review
VLE
preliminary experimental for
of the
the
experimental data. system
data on
data. This with
VLE
This paper ethyl
for the
acetate
paper presents system
presents aa synthesis
with eth(
the
critical review
review of binary
of the
the dataandon VLEternary
VLE for subsystems)
thebinary
system andwithavailable
ternary
ethylsubsystems)
in the literature.
acetate available
synthesis Two in
rigorous
(including the literature
therm
critical data on for the system with ethyl acetate synthesis (including
binary and
and ternary tests of
ternary subsystems) the accessible
subsystems) available
available intests
experimental
in theof the accessible
the literature. VLE
literature. Two data experimental
array
Two rigorous are carried
VLE
rigorous thermodynamic
thermodynamic data
out. array are car
binary
tests of
tests of the
the accessible
accessible experimental
experimental VLE VLE datadata array
array are are carried
carried out. out.
2. Thermodynamic Consistency 2. Thermodynamic Tests Consistency Tests
2. Thermodynamic Consistency Tests
Due to theTests fact that the Due relations
to the factof classical
that thethermodynamics
relations of classical mustthermod
hold t
2. Thermodynamic Consistency
Due to the fact thermodynamic
that the relations systems,
ofthermodynamic
regardless
classical ofsystems,
their nature
thermodynamics regardless
must andhold the oftrue
specific
theirfor nature
form and
all of theth
Due to the fact that the relations of classical thermodynamics must hold true for all
thermodynamic systems, of state regardless
(EoS), the thermodynamic
of state
of their nature (EoS), consistency
andthe the thermodynamic
specific testsformareofaconsistency
good
the method
equation testsforarevera
thermodynamic systems, regardless of their nature and the specific form of the equation
of state (EoS), the thermodynamic consistency
reliability of the experimental reliability testsof are
VLE the
dataaexperimental
good
[13]. method
The essenceVLE for data
verifying
of all[13]. the
the Thetestsessence
is the
of state (EoS), the thermodynamic consistency tests are a good method for verifying the
reliability of the experimental
of the agreementVLE data [13].
between
of the Thethe essence
agreement
obtained ofbetween
all
data theand tests
thetheisobtained
the validation
thermodynamic data and of differen
the the
reliability of the experimental VLE data [13]. The essence of all the tests is the validation
the agreement between tions. the
Theobtained
most popular data and
tions.
tests the
The thermodynamic
aremost
based popular
on the tests differential
are basedequations.
Gibbs–Duhem on
equation
the Gibbs–Duh
[14–16]:
of the agreement between the obtained data and the thermodynamic differential equa-
The most popular tests are based on the Gibbs–Duhem equation [14–16]:
tions. The most popular tests are based on the Gibbs–Duhem 𝑠𝑑𝑇 − 𝑣𝑑𝑝 equation + ∑ 𝑥 𝑑𝜇 𝑠𝑑𝑇= 0,
[14–16]: − 𝑣𝑑𝑝 + ∑ 𝑥 𝑑𝜇 =
n
where s is thesdT 𝑠𝑑𝑇
molar−− vdp𝑣𝑑𝑝 +∑
entropy,
where+ ∑ sT 𝑥the
xisiis
dµ 𝑑𝜇
the =0, 0, entropy,vTisisthe
molar
temperature, themolar
temperature,
volume,(1)
(1) vpisisthethe
i =
xi is the mole fraction xof i is
thethe
i =1component
mole fraction i (inofterms
the component
of thermodynamics, i (in termseach of therco
where s is the molar entropy, T is the temperature, v is the molar volume, p is the pressure,
variable may be used here, variable i.e.,may
mass, beamount
used here, of substance,
i.e., mass, mass amount fraction,
of substance
etc.; in
i is thes mole
xwhere is thefraction
molar entropy, T is the temperature,
of the component i (in terms vofisthermodynamics,
the molar volume,each p is composition
the pressure,
xi is the mole
we
fraction
will
of the
use mole
component
fractions
we willto
i (in terms
use
make molefurther
fractions
of thermodynamics,
calculations
to make more
further convenient),
calculations µi st m
variable may be used here, i.e., mass, amount of substance, mass fraction,each etc.; composition
in this work
variable may chemical
be used here, potential of the
chemical
component potential i, andof n
theis component
a number of i,components.
and n is a number
Since to
we will use mole fractions toi.e.,
make mass,
furtheramount of substance,
calculations mass fraction,
more convenient), etc.; infor
µi stands thisa
work we potential Duhem
will use mole equation is the
Duhemconsequence
equation of is
thethefirst
consequence
and second oflaws
the first
of thermodyn
and secon
chemical of thefractions
component to make
i, andfurther calculations
n is a number more convenient),
of components. Since the stands
µiGibbs–
rived by applying therived
Euler bytheorem
applying to the
internal
Euler energy,
theorem it to
is an
internal
identical
the energy,equa
for a chemical
Duhem equation potential of the component
is the consequence of the i,firstandand n issecond
a number lawsofofcomponents.
thermodynamics Since de-
Gibbs–Duhem identical
equation is thenature of theidentical
consequence Gibbs–Duhem
of the firstnature and equation
ofsecond
the Gibbs–Duhem
makes of itthermodynamics
possible
equationto verify
makes theit rel
po
rived by applying the Euler theorem to internal energy, it is an laws identical equation. The
derived by applying different experimental different
data sets experimental
(isobaric VLE data
data setsand(isobaric
isothermal VLE VLE
data data).
and is
identical nature of thethe Euler theorem
Gibbs–Duhem to internal
equation makes energy, it is an
it possible toidentical
verify theequation.reliabilityThe of
identical experimental The
nature of the Gibbs–Duhem chemical potential
equation Theof a
chemical
makes component potential
it isothermal of
possible to VLE a solution
of a component
verifydata). can be represented
the reliability ofof a solution in ct
different data sets (isobaric VLE data and
different experimental ing form
data of[16]:
sets ing
(isobaric VLE form [16]:
The chemical potential a component of adata
solutionand isothermal
can be representedVLE data). in the follow-
○solution can be represented ○ ○
The chemical
ing form [16]: potential of a component of a
𝜇 = 𝜇 𝑇, 𝑝 + 𝑅𝑇 ln 𝜇 𝑎= = 𝜇𝜇 𝑝in
𝑇, 𝑇, 𝑝+the + 𝑎 𝑥=𝛾𝜇, ○ 𝑇, 𝑝
𝑅𝑇following
𝑅𝑇ln ln
form [16]:
𝜇µi == 𝜇𝜇µi○○(𝑇,
where T, 𝑝𝑝
𝑇, p) ++ 𝑅𝑇
is RTln ln
thewhere a𝑎
i =𝜇
standard =µi𝜇○(○𝑇,T, 𝑇,
𝑝p)𝑝+
part is +
of RTln
the𝑅𝑇standard
xln 𝑥 𝛾 , potential
i γi ,
chemical part of the (2)
(2) compon
of chemical
the po
○ function of the temperature functionand of the
pressure,
temperature
R is theand gaspressure,
constant,Raiisisthe thegas
activ c
where 𝜇
where µi (𝑇,
T, 𝑝p) is the standard part of the chemical potential potential of of the component ii as
the component as aa
component i, and γi iscomponent the activityi, coefficient
and γi is the of activity
the component coefficient i. Substitute
of the comp Eq
function of
function of the
the temperature
temperature and and pressure,
pressure, R R isis the constant, aaii is
the gas constant, is the
the activity
activity of of the
the
into Equation (1) and into rewrite Equation
the Gibbs–Duhem
(1) and rewrite equation
the Gibbs–Duhem
in the following equation
form
component i, and is the activity coefficient of the component
component i, and γii is the activity coefficient of the component i. Substitute Equation (2)
γ i. Substitute Equation (2)
into Equation
into Equation (1) (1) and rewrite the Gibbs–Duhem equation in the following form:
n
s v
dT − dp + ∑ xi dln ai = 0 (3)
RT RT i =1
Chemistry 2023, 5 2544

Given that the Gibbs–Duhem Equation (3) holds true for every state of a system, it can
be integrated along with every variation of the parameters of the system:
n
s v
Z Z Z
dT − dp + ∑ xi dln ai = 0 (4)
RT RT i =1

or in the case of isothermal-isobaric conditions (T, p = const):

n Z
∑ xi dln ai = 0 (5)
i =1

It should be noted that such integration of a real experimental data set does not
generally lead to the strong conditions (4) and (5). The values of the integrals can differ
from zero due to the uncertainties of experimental methods and numerical calculations.
The reliable values of integrals cannot be obtained by means of thermodynamics, which
is why they should be evaluated based on the analysis of a large amount of experimental
data. However, in most cases, this method is not used by researchers, so the more popular
methods are applied. In our work, we will test VLE data reported by authors on the system
acetic acid-ethanol-ethyl acetate-water by integrating relation (5) and estimating the reliable
value of the integral for a real VLE data set.
The relations of classical thermodynamics are well known to hold true both for the
thermodynamic functions themselves and for the corresponding excess functions. Thus,
rewrite Equation (3) for the excess functions:
n
se ve
dT − dp + ∑ xi dln γi = 0, (6)
RT RT i =1

where se is the molar excess entropy and ve is the molar excess volume. The consequence of
the Gibbs–Duhem equation in this form will be used for the thermodynamic consistency tests.

2.1. The Redlich–Kister Consistency Test

For the Redlich–Kister method (also called the Herington test), the excess Gibbs energy
is used. In integral form, the following equation can be written [13,17]:

gE n
RT
= ∑i=1 xi ln γi = 0, (7)

where gE is a molar excess Gibbs energy. After the differentiation of Equation (7), we have:

gE n n
d
RT
= ∑i=1 xi dln γi + ∑i=1 ln γi dxi . (8)

The first term in the right part of Equation (8) can be rewritten using Equation (6), and
for the second term, we can take into account the relation between mole fractions in the
system (8):
gE sE vE n −1 γ
d =− dT + dp + ∑i=1 ln i dxi . (9)
RT RT RT γn
Integrating the Equation (9), we obtained the following relation [13,17]:

B B
Zxi
B
B ZT Zp n −1
gE sE vE γi
=− dT + dp + ∑ ln dx (10)
RT A RT RT i =1
γn i
TA pA xiA

or
B Z TB E Z pB E Z xB
gE h v n −1 γi
dp + ∑i=1
i
=− dT + ln dx = 0, (11)
RT A TA RT 2 pA RT xiA γn i
 synthesis using RD in industrial chemical productionhave
technology makes been themadeprocess more [3,9–12].
in papers environmentally
ment of fundamental aspects of RD important for the design of industria
friendly, energy-efficient, andAresource-efficient. Significant contributions to the develop-
chemicalpre-requisite
technology have for developing
been made in precise
papers models
[3,9–12]. and predictions of th
ment of fundamental aspects complex of RD reactingimportant
systems forfor the thedesign
purposes of industrial
of the processes
chemical of includ
industry,
A pre-requisite for developing precise models and predictions of th
chemical technology have been made
existing processes in papersand [3,9–12].new ones for the synthesis of ethyl acetate,
creating
complex reacting systems for the purposes of the chemical industry, includin
A pre-requisite for the developing
thermodynamic precise models andofpredictions of the behaviordata. of This pa
Chemistry 2023, 5 existing processes andconsistency creating new preliminary ones for the experimental
synthesis of ethyl 2545 acetate,
complex reacting systems for thereview
critical purposes of of the
the data chemical
on VLE industry,
for the including
system with optimizing
ethyl acetate synth
the thermodynamic consistency of preliminary experimental data. This pap
existing processes and creating binaryreview new ones
and ternary for the synthesis of ethyl acetate, such as RD, is
critical of thesubsystems)
data on VLEavailable for the system in the literature.
with ethylTwo acetate rigorous
synthe th
the thermodynamic consistency tests of of preliminary
the accessible experimental
experimental VLE data.data Thisarraypaperare presents
carried a
out.
binary and ternary subsystems) available in the literature. Two rigorous th
critical TA andof
wherereview TBthe
aredata
the temperatures
on VLE for the ofsystem
the system within the states
ethyl and B, pA(including
acetateAsynthesis and pB are
tests of the accessible experimental VLE data array are carried out.
the pressures
binary and ternaryof the system in the
2. Thermodynamic
subsystems) states A
available in and B, xiA andTests
Consistency
the literature. xiB are
Two the mole
rigorous fractions of the
thermodynamic
component
tests i of the system
of the accessible in
experimentalDue theto states
VLEthe data A and
fact array
that B,the
respectively.
are carried
relations Itclassical
out. has beenthermodynamics
shown that the must h
2. Thermodynamic Consistency Tests of
relation (10) holds true thermodynamic
for integration under systems, any curve
regardless in phase
of space; however, it seems
2.toThermodynamic
be the most convenient Consistency Due to
way to choose
Teststhe fact thatlimits
the the relations
so that of their
the classical
left
nature
part of
and the
thermodynamics
Equations
specific
(10) mustformhoo
of state
thermodynamic (EoS), the thermodynamic
systems, regardless consistency
of their tests
nature is and are a good
the specific method
form fo o
andDue(11) to
equals zero.
the fact The
that the molar
relations
reliability excess
of the of Gibbs
classical
experimental energy of
thermodynamics a pure
VLEconsistency substance
data [13]. The must hold
essenceknown
true for toallbe
of allmethod
the testsfor is
equal to zero; therefore, of state (EoS), the thermodynamic tests are a good
thermodynamic systems,ofthe following
regardless
the agreement of relation
theirbetween
is true
nature and
the
forthea binary
obtainedspecific mixture:
data form ofthe
andessence thethermodynamic
equation
reliability of the experimental VLE data [13]. The of all the tests diff is
of state (EoS), the thermodynamic tions. The consistency
most popularx = 1tests
tests are
are a good
based method
on the for verifying
Gibbs–Duhem the
equation [14–
of the agreementg Ebetween 1 the obtained data and the thermodynamic diff
reliability of the experimental VLE data [13]. The=essence 0. are 𝑠𝑑𝑇 of all the tests is the validation (12)
tions. The most popular tests based − 𝑣𝑑𝑝on the +∑ 𝑥 𝑑𝜇 = 0, equation
Gibbs–Duhem [14–
of the agreement between the obtainedRT data x1 =and0 the thermodynamic differential equa-
tions. The most popular where tests are s isbased
the molar on the Gibbs–Duhem
entropy, 𝑠𝑑𝑇 𝑣𝑑𝑝 + ∑ [14–16]:
−temperature,
equation 𝑥v𝑑𝜇 = 0,
Hence, under isothermal-isobaric conditions (T,Tp is = the
const), the Redlich–Kister is the molar
consis- volume, p
tency test is based on the x i is the mole fraction∑of the component i (in terms of thermodynamics, eac
where s is𝑠𝑑𝑇
equation −molar
thebelow 𝑣𝑑𝑝[13,17]:
+entropy, 𝑥 𝑑𝜇 T is=the 0, temperature, v is the molar(1) volume, p is
variable may
xi is the mole fraction be used here, i.e.,
of the component mass, amount
i (in terms of substance, mass fraction,
of thermodynamics, et
each
Z 1
where s is the molar entropy, we T isuse
will the mole
temperature,
fractions
γ 1 v to
is the
make molarfurthervolume, p is the pressure,
calculations more convenient),
variable may be used ln here, dx1 = i.e.,0.mass, amount of substance, mass(13) fraction, etc
xi is the mole fraction of chemical
the component potential 0 i fractions
(inofγterms of thermodynamics,
2 the component n is aeach
i, and calculations number composition
of components.
we will use mole to make further more convenient),Siµ
variable may be used here, Duhem i.e., mass,
equationamount is of substance, mass fraction, etc.; second
in this work
It use
should notedchemical
befractions that for potential
a real ofthe
experimentalthe consequence
componentdata set,i,of
and
the
then first
calculated
and
is a number value of
laws of therm
of components.
such Sin
we will mole rived to make
by further
applying calculations
the Euler more
theorem convenient),
to internal µ
energy,
i stands it for
is ana identical
an integral differsof from Duhem
zero, equation
which is the consequence of theoffirst and second laws of thermo
chemical potential theidentical
component naturei,may
and ofbenthe caused
is by a of
aGibbs–Duhem
number number
components.
equation purposes,
Since itfor
makes the instance,
Gibbs–to verify th
possible
experimental uncertaintiesrived by applying
of empirical the
data, Euler
errors theorem
of numerical to internal
procedures energy, duringit is an identical
calcu-
Duhem equation is the consequence
different of the
experimental first and sets
data second laws of
(isobaric VLE thermodynamics
data and isothermal de- VLE da
lations, identical nature of the Gibbs–Duhem equation makes it possible toofverify th
rived by etc. The value
applying of thatThe
the Euler integral
theorem chemical less than
to internal
potential 0.02 isofreported
energy, it is an
a(isobaric
component to be a sufficient
identical
of criterion
equation.
a solution can be The represented
thermodynamic different experimental data sets VLE data and isothermal VLE dat
identical nature ofconsistency.
the Gibbs–Duhem
ing form [16]: equation makes it possible to verify the reliability of
Forexperimental
isothermal conditions The chemical
(T = const), potential of a component ofmolar
a solution canvolume
be represented
different data sets (isobaric VLEthe data contribution
and isothermal of the VLE data).excess
should be taken into account ing form [16]:
[13,17]: 𝜇 = 𝜇 ○ 𝑇, 𝑝 + 𝑅𝑇 ln 𝑎 = 𝜇 ○ 𝑇, 𝑝 + 𝑅𝑇 ln 𝑥 𝛾 ,
The chemical potential of a component of a solution can be represented in the follow-
ing form [16]: whereZ𝜇p○1 𝑇, 𝜇Z = 𝜇γ○ 𝑇, 𝑝 part
v E𝑝 is the1 standard
+ 𝑅𝑇 of lnthe = 𝜇 ○ 𝑇,potential
𝑎 chemical 𝑝 + 𝑅𝑇 ln of 𝑥the𝛾 ,com
1
dp + ln dx 1 = 0, (14)
𝜇 = 𝜇 ○ 𝑇,𝜇p𝑝○2of𝑇,
function
where +
RTthe
𝑝𝑅𝑇is temperature
lnthe 𝑎0 = 𝜇γ○2 and
standard pressure,
𝑇, 𝑝part + 𝑅𝑇 of theln 𝑥Rchemical
𝛾is, the gas constant,
potential (2)of athe
i is the
com
component
function of i,
the and γ i is the activity coefficient of the component i. Substitu
temperature and pressure, R is the gas constant, ai is the a
where𝜇p○i is
where 𝑇,the
𝑝 is vapor pressure
the standard
into Equation in
partequilibrium
of
(1)theand with the
chemical
rewrite pure
potential
the component
Gibbs–Duhem of the component i. However,
equation as for
ini the afollowing
component i, and γ i is the activity coefficient of the component i. Substitute
most solutions,
function if the pressure
of the temperature and variation
pressure, is notR issothe high,gasthe value ofaithis
constant, is thecontribution
activity ofisthe not
into Equation (1) and rewrite the Gibbs–Duhem equation in the following f
significant (i,≈and
component 0.0001)
γi isand
the can be neglected,
activity coefficient so of thattheEquation
component (13) i.can be used as
Substitute well [13,17].
Equation (2)
For an isobaric data set (p = const), the
into Equation (1) and rewrite the Gibbs–Duhem equation in the following form: contribution of the molar excess enthalpy
should be taken into account [13,17]:

1 hE
Z T Z 1
γ1
− dp + ln dx = 0. (15)
T2 RT 2 0 γ2 1

The value of the first term in Equation (15) may reach 0.01 and usually cannot be
neglected. Thus, information about the molar enthalpies of mixing, which can be obtained
by means of calorimetry, is needed for testing an isobaric data set.
For multicomponent systems (ternary, quaternary, etc.), the use of isothermal-isobaric
conditions is preferred to avoid the necessity of estimating the molar excess enthalpies, too.
As for a binary system, the way of the composition variation could be chosen so that the
limits of the integration should be pure components, therefore the integral would be equal
to zero [13,17]:
Z xB
n −1 γ
∑i=1 x A ln γni dxi = 0.
i
(16)
i

The second convenient option is to choose the curve so that the initial and final
compositions are the same and the integral around a closed curve equals zero as well [13,17]:
I
n −1 γi
∑ i =1
ln dx = 0.
γn i
(17)
 importantly, importantly,
is biodegradable
importantly,is biodegradable [5,6].
is biodegradable
importantly, [5,6]. [5,6]. is biodegradable [5,6].
reaction medium); aluminum foil production and ele
Conventionally,
Conventionally,ethyl
Conventionally,
acetate ethylis acetate obtained
ethyl
Conventionally,
acetate
is obtained
by direct is obtainedethyl
by
acid-catalyzed
direct
acetate
byacid-catalyz
direct
is obtain
esteri
acid
agent); food industry (as an extracting agent of organic
acetic acidaceticwith acid
ethanol
acetic with acid
inethanol
thewith liquidethanol
in
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the
phase liquid
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phase
liquid ethanol
orinphasecontinuous
batch in inthe
orbatch
continuous
liquid
reactors,
orphase
contin anrei
and a food additive); explosives production (as a gelling
tion occurs tionat temperatures
occurs
tion at occurs
temperatures
ofat363.15–423.15
temperatures
tionofoccurs 363.15–423.15
Kofat[7],
363.15–423.15
temperatures
making K [7],itmaking extremely
K
of[7],363.15–423.15
making
it extreme
energy it
and food industry (as a component of fruit essences).
Chemistry 2023, 5 However,However,
employing However,
employing
technologies employing
technologies
However,
suchtechnologies
as RD such
employing
for as the such
RD production
technologies
for
as the RD production
forof the
2546 ethyl
suchproduc aceta
asofRe
acterized by low toxicity [4] compared to other industr
peratures peratures
of 343.15–383.15
peratures
of 343.15–383.15 K
of can343.15–383.15
significantly
peratures
K can significantly
K
of canincrease
343.15–383.15
significantly the
increase conversion
K canincrease
thesignificant
conversio
ofthe reag c
importantly, is biodegradable [5,6].
pared to synthesis
pared topared synthesis
in a conventional
to synthesis
in a conventional
paredinreactor
a conventional
to synthesis
(almost
reactorcomplete inreactor
(almost
a conventional(almost
complete
conversion complet
reactor
conve
of e
Conventionally, ethyl acetate is obtained by dire
be achieved
2.2. The Van Ness Consistency Test be with
achievedbe
a moderate
achieved
with a moderate
height
with be
a of
moderate
achieved
the
height distillation
of
height
with
the distillation
a of
column)
moderate
the distillation
and
column)
heightprovide of
column)
and
the apr di
hi
acetic acid with ethanol in the liquid phase in batch or
target producttarget containing
product
target product containing
almostcontaining target
noalmostethanolproductno
almost
[8].
ethanol
containing
Therefore,
no ethanol [8]. Therefore,
almost
incorporating
[8]. Therefore,
noincorpo
ethano eth
First, we will consider a binary system tion occurs temperature
at constant at temperatures and of pressure363.15–423.15 for better K [7], mak
synthesis synthesis
using RD synthesis
using
in industrialRD using in industrial
RDproduction
synthesisin industrialproduction
using
makes RD
production
the inmakes
process
industrial the
makesmore
process
productio
theenviropro
mo
clarity. For a binary solution, the following However, relations can employing
be written technologies
[13]: such as RD for the p
friendly, energy-efficient,
friendly,friendly,
energy-efficient, and
energy-efficient,
resource-efficient.
friendly,
and resource-efficient.
and
energy-efficient,
resource-efficient.
SignificantSignificant contributions
and resource-effici
Significant
contribut to th co
peratures of 343.15–383.15 K can significantly increas
ment of fundamental
mentgof E ment
fundamental
aspects
of fundamental ofaspects
RD ment important
aspects
of
of RD fundamental
important
of
forRD theimportant
design
aspects
for the ofof for
design
industrial
RD theimport
of
desig indpr
=technology
xhave pared + xto lnsynthesis in a conventional reactor (almost co
chemical technology
chemical 1 ln γ1been 2 , in
γbeen (18)
RT chemical technologyhave
2made chemical havepapers
made been
technology
in
[3,9–12].
made
papers in
have [3,9–12].
papers been[3,9–12].
made in pap
be achieved with a moderate height of the distillation c
A pre-requisite
A pre-requisite
for
A pre-requisite
developing for developing precise
for
A pre-requisite
developing
models
preciseand precise
models
forpredictions
developing
models
and predictions of
andprecise
thepre b
complex reacting
complex
 E complex  target
systems
reacting for
reacting
systems
product containing almost no ethanol [8]. Ther
the purposes
complex
systems
for the purposes
of
for
reacting
thethe chemical
purposes
systems
of the industry,
chemical
of
forthethe chemical
purposes
industry,
including ind oin
o
∂ g /RT synthesis using RD in industrial production makes t
existing processes
existing = ln γ − ln γ . (19)
∂x1existing
processes
and creating processes
andnew creating
existing
and
onescreating
new
forprocesses
the
ones new
synthesis
for and
onesthecreating
synthesis
of
forethyl
the synthesis
new
acetate,
of ethyl
onessuc of
for
ac
1 2
T,pfriendly, energy-efficient, and resource-efficient. Signifi
the thermodynamic
the thermodynamic
the consistency
thermodynamic consistency
ofthe preliminary
consistency
thermodynamic
of preliminary
experimental
of preliminaryconsistency
experimental
data. experimental
of
This prelimin
data.
paper Th
After substituting Equations (19) and ment
(8) into ofEquation
fundamental (18), aspects
we have of RD important for the
critical review
critical ofreview
critical
the data of
review
ontheVLE data
of critical
the
foronthe data
VLE review
system
onfor VLE
the of
with the[13]:
system
for ethyl
the
datasystemwith
acetate
on VLE ethylwithsynthesis
foracetate
ethyl
the sysa
chemical technology have been made in papers [3,9–12
binary and binary
ternary and
binary
subsystems)
ternary andternary
subsystems)
available
binary
subsystems) and
in
available
theternary
literature.
available
in subsystems)
the literature.
Two
in the rigorous
literature.
available
Two therm rigor Tw
in
E
g accessible A pre-requisite
∂ gEexperimental
/RTtests for developing precise models a
tests of the tests
accessible
ln γ1 =of tests
the experimental
of
+ x2 the accessible VLE experimental
ofdata the VLE
array
accessible
data
areVLE
, systems for the purposes (20) carried
array
experimental
data are
out.
array
carried areVLE carried
out. data
RT complex ∂x1reacting T,p
of the chemi
existing processes and creating new ones for the synth
2. Thermodynamic
2. Thermodynamic
2. Thermodynamic
Consistency  Consistency
Tests
2.Thermodynamic
Consistency Tests TestsConsistency Tests
g E the thermodynamic ∂ gE/RT consistency of preliminary experim
Due tolnthe γDue
2 fact
= tothat the
Due the
xfact
1torelations
−critical the
that fact
review thethat of
relations
Due
of. classical
the
the todata
relations
the
ofthermodynamics
classical
fact
on VLE that
of classical
thermodynamics
thethe
for relations
thermodyna
must of
(21)
system hold clas
with mt
thermodynamic thermodynamic RT
systems,
thermodynamic regardless
systems, ∂x1 systems,
thermodynamic
regardless
ofT,ptheir regardless
nature
of theirsystems,
and of
naturethe
their specific
regardless
and
nature the form
and
specific
of the
of
their thspf
binary and ternary subsystems) available in the literatu
Here, we use theof state (EoS),
of state
following theof(EoS),
thermodynamic
notation: statetests the(EoS),
thermodynamic
the of consistency
thermodynamic
state (EoS),
consistency
tests
the
of the accessible experimental VLE data array are consistency
are
thermodynamic
a tests
good are method
tests
a good consisten
are fora
methgoo
ver
reliabilityreliability
of the experimental
reliability
of the experimental
of the VLEexperimental
reliability
data VLE [13].of data
The the
VLE essence
[13].
experimental
data The [13].
ofessence
allThethe
VLE essence
tests
of data
allisthe the
[13]
oftea
g E
of the agreement
of the agreement
ofbetween
the agreement the
between
2. Thermodynamicobtained
of between
the
the obtained
data
agreement
theand obtained
data
the
Consistency Tests betweenthermodynamic
and data thetheand
thermodynam
obtained
the differen
thermo dat
g= , (22)
tions. Thetions.
most The popular
tions.
most Thetests
popular
RT mostare popular
based
tests
tions.are on
The tests
the
based
mostGibbs–Duhem
areon popular
based
the Gibbs–Duhem
ontests theequation
Gibbs–Duhem
are based [14–16]:
equatioon th
Due to the fact that the relations of classical therm
 E  thermodynamic 𝑠𝑑𝑇  − 𝑣𝑑𝑝 𝑠𝑑𝑇+ ∑− 𝑣𝑑𝑝
systems, 𝑠𝑑𝑇
𝑥 𝑑𝜇 +−∑=
regardless 𝑣𝑑𝑝 0,𝑥+ 𝑑𝜇
of∑their =𝑠𝑑𝑇
𝑥0,nature
𝑑𝜇− = 𝑣𝑑𝑝 an+
0,
∂ g /RT ∂g
gi = of state = (EoS), the. thermodynamic consistency (23) tests ar
where s iswherethe molar swhere
is∂xthe
entropy,
i molarsreliability
is the
T,p Tentropy,
is
molar
the
∂xwhere
ofi temperature,
entropy,
the T is
T,p s isthe the
experimentaltemperature,
T ismolar
vtheis the
temperature,
entropy,
VLE molar v is the
data T
volume,
ismolar
[13]. vtheisThe
the
tempera
pvolum
ismol
essenthe
x x
i is the mole i is fraction
the
Combine Equations (20) and (21) with of xmole
i is theof fraction
the
mole component
fraction
of
the agreement
Equations x
the i iscomponent
the
ofi (in
(22) andbetweenthemoleterms
component
fraction
i of
(in thermodynamics,
terms ofi
(23) [13]:the obtained data and the (in
theofterms
component
thermodynamic
of thermod
each i (inco
variable may variable
be usedvariable
mayhere, be may
used
i.e., be
mass,
here,used
variable
i.e.,
amount
here,
mass, may
i.e.,
of amount
substance,
tions. The most popular tests are based on the Gibbs–Dbe
mass, used amount
of here,
substance,
mass i.e.,
of fraction,
substance,
mass, mass amoun
etc.;
fracti
ma in
we will use wemolewill we use
fractions
will
mole
ln γ1 = g + x2 g1 ,useto
fractions
mole
make wefractions
further
to will
make use
calculations
to further
mole
make fractions
further
calculations
more calculations
to
convenient),
make
more
(24) further
conven
moreµ i stc
chemical potential
chemical chemical
of
potential
the component
potential
of the chemical
component
ofi, and
the component
npotential
is i,a and
number nof i,isand𝑠𝑑𝑇
the
aofnumber − 𝑣𝑑𝑝
components.
component
n is a number + ∑
of componen 𝑥
i, Since
and 𝑑𝜇
of co nt
Duhem equationDuhem Duhem is
equation
the consequence
equation
is the consequence
Duhem
is of thethe consequence
equation
firstofand theis second
first
of
thethe and
consequence
laws
first
secondand
of thermodyn
second
lawsof the of la tfi
where s is the molar entropy, T is the temperature, v is t
rived by applying
rived byrived γ2 =
lnapplying
the Euler −the
byg applying x1 g1Euler
theorem . rivedthe to
theorem
Euler
byinternal
applying
theorem
toenergy,
internal
the toEuler
itinternal
energy,
is an (25)
theorem
identical
energy,
it is an to equ
it
iden
inte is
xi is the mole fraction of the component i (in terms of th
The main point identical nature
of the vanidentical
Ness ofidentical
the
nature
method Gibbs–Duhem
of
nature
isthetheGibbs–Duhem
of identical
the equation
representationGibbs–Duhem
naturemakes
equation
ofof the the
itequation
possible
makes
Gibbs–Duhem
dependence itmakes
topossible
verify itequatio
possib
the
to ve re
variable may be used here, i.e., mass, amountofof substan
different experimental
different different
experimental g values on composition as a function experimental
data experimental
sets (isobaric
data differentsets data
VLE
(isobaric
experimental
sets
data (isobaric
VLE
and isothermal
datadata
VLE and
sets
dataisothermal
(isobaric
VLE and data).
isothe VLVL
we will of use the mole fractions g(x
composition to 1make ), for example,
further calculation a
polynomial, a Margules The chemical
equation, The
a van potential
chemical
The equation,
Laar chemical
of
potential
a component
chemical potential
potential
etc.ofThea component
Then, chemical
ofof
of the
a asolution
assume component
component
potential
of
that acan solution
thebe ofofrepresented
a asolution
i,vapor
and n in
can
component
be repres
is a numbe
can inbto
ing form [16]:
ing form
equilibrium with the liquid phase is the ideal ing[16]:form [16]:
gas. In ing form
this case, [16]:
the consequence
vapor pressure can first be and se
Duhem equation is the of the
○ ○ ○ ○ ○ ○
calculated by means of Raoult’s law in 𝜇 its = 𝜇 𝜇𝑇,
particular
rived by𝑝 =applying
𝜇+ 𝜇𝑅𝑇
statement =ln
𝑇, 𝑝𝜇the
𝑎+=
[13]: 𝑅𝑇𝜇𝑝ln+theorem
𝑇,
Euler 𝑎𝑇,𝜇𝑅𝑇 𝑝==ln 𝜇+𝜇𝑎𝑅𝑇 to =
𝑇, 𝑇,𝑝𝜇𝑝𝑥○+𝛾+𝑇,
ln
internal 𝑅𝑇,𝑅𝑇𝑝energ
lnln+𝑥𝑎
identical nature of the Gibbs–Duhem equation makes it
= x1 γ1𝜇p○1where
pcalcwhere + p○2the
𝜇where
𝑇,x𝑝2 γ2is =𝑇, 𝑝 1𝜇pis
○ e g( x1 )+ x2 g1 + x p○ e g( x1 )− x1 g1 ,
1 𝑇,
xstandard
different the 𝑝 standard
iswhere
part the
experimental 2𝜇part
of standard
the 𝑇,data
𝑝 part
2 chemical
of the
issetsthe chemical
potential
of(isobaric
standard
the chemical (26)
potential
ofVLE the
part compon
potenti
data ofofand
the th
function of function
the temperature
function
of the temperatureof Theand
the chemical
temperature
pressure,
function andpotential
pressure,
of
R is and
the the temperature
pressure,
gasR isconstant,
the Rgas
of a component of a solutio is
and the
constant,
a i pressure,
isgasthe consta
activi iR
where pcalc is the calculated
component value
component of the
i, andcomponent vapor
γi isi, the and pressure. The activity coefficients can be
γi,
ingactivityi is
form andthe component
[16]: γactivity
coefficient
i is the activity i, and
coefficient
of γi is
the coefficient
componentof the the activity
component
ofi. the
Substitute
coefficien
compone i. Sub Eq
calculated with theinto Equations
Equation
into (24)
(1)and
and(25).
Equation
into (1) With
Equation
rewrite and the the
(1)
rewrite calculated
Gibbs–Duhem
into
and Equation
rewrite
the Gibbs–Duhem values
theequation
(1)Gibbs–Duhem
and ofrewrite
pressure
in
equation
the following
the and
equation
inGibbs–Duh
the follow
form
in th
activity coefficients, we can estimate the composition of the vapor: 𝜇 = 𝜇 ○ 𝑇, 𝑝 + 𝑅𝑇 ln 𝑎 = 𝜇 ○ 𝑇
xi γi,calc𝜇p○i 𝑇, 𝑝 is the standard part of the chemical
where
, yi,calc = (27)
function
pcalc of the temperature and pressure, R is the ga
component i, and γi is the activity coefficient of the com
where yi,calc is the calculated mole fraction ofinto
the Equation
component (1)i and
in the vapor the
rewrite phase, and γi,calc equati
Gibbs–Duhem
is the calculated activity coefficient of the component i. The difference between calculated
and experimental mole fractions of less than 1% is reported to be a sufficient criterion for
the thermodynamic consistency of experimental data, according to the van Ness test.
In a general case of a multicomponent system, the molar excess Gibbs energy is
presented as a function of the composition of the mixture g(x1 , x2 , . . ., xn −1 ). The van Ness
method gives the following relations for a multicomponent mixture:
n −1
ln γn = g − ∑i=1 xi gi , (28)
 target product containing reactionalmost
andmedium); no ethanol
reaction
friendly,
a food aluminum
energy-efficient,
additive); x[8].
medium); i is Therefore,
reaction
the
explosives foil
aluminum
mole medium);
production
and incorporating
fraction foil of
resource-efficient.
production aluminum
production
and
the aethyl
electronic
(ascomponent gelling foil acetate
and production
Significant industry
i electronic
agent); (in terms contri
and (asan
pe oi
synthesis
Chemistry 2023, 5,using RD2023,
Chemistry
FOR PEER inagent);
industrial
food
5, FORand
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agent);
mentindustry
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PEER of food peratures of 343.15–383.15 K can significantly increase the conve
makes
(asvariable
industry
an
fundamental
industry
REVIEW (as the
agent);mayprocess
food
extracting
(as an
beagent
aspects
a component used more
industry
extracting
of of
RDof (asenvironmentally
here, an extracting
organic
agent
i.e.,
important
fruit offor
essences). theagent
substances
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mass, ofof
from
amount org
substance
designaque
subs
Furthermore, ofe
reaction
friendly,medium); aluminum foilpared production
to synthesis and electronic
in a[4] conventional industry (astoathe degreasing
energy-efficient, andand a food resource-efficient.
acterized additive);
andby
chemical a food technology
low weand
explosives
additive);
toxicity Significant
will ahavefood
production
use explosives
mole
been
comparedcontributions
additive); (as
fractions
made toreactor
productionaexplosives
in gelling
other to make
papers (almost
(as develop-
agent);
industrially production
afurther
[3,9–12].gellingcomplete
andimportant perfume(as con
agent);
calculatio a ga
agent); food industry
ment of fundamental aspects (as an extracting
of be RD agent
achieved
important ofwith organic for a moderate
the substances
design heightof from of
industrial aqueous
the distillation solutions
processes column)
of and
and food industry
importantly, and A food (asbiodegradable
pre-requisite
is industry
achemical and for
component food a industry
(aspotential component
of fruit
developing
[5,6]. (as
ofessences).
the a component
of
precise fruitmodels
component Furthermore,
essences). i, and of
and fruit
nFurtherm aessen
isethyl
predicti num a
and a foodtechnology
chemical additive); explosives
have beenproduction
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[16]:
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Equation is
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ing ixform (𝜇𝑇,
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different function function of the of temperature
the data
temperature sets (isobaric
and pressure,
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pressure, dataR is andR
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using
function of RD
the of
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in chemical
industrial
temperature
the temperature
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papers
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the activity coefficient coefficient Significant
of the thecontributio
of component compone i.
phases and may be referred to of ing
as fundamental
the form
into
generalized
identical [16]:
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into nature Equation
complex (1)the
Raoult’s
of and (1) rewrite
and
law,
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reacting rewrite
including
systems the Gibbs–Duhem the Gibbs–Duhem
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have existing =data
processes
made 𝜇gas, in 𝑇,Equation
sets 𝑝(isobaric
and
papers +creating𝑅𝑇 (41)
lnVLE
[3,9–12]. 𝑎 new can
=data be
𝜇ones 𝑇, 𝑝isoth +
th
reduced to: A pre-requisite The chemical for thedeveloping potentialprecise
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models and ofofa predictions
solution can
preliminary
○x γ
complex reacting where py
ingiform = 𝜇 p 𝑇,
i [16]:
systems 𝑝
i critical
i is
for the the reviewstandard
purposes of theofdata part of
the chemical the
on VLE for chemical (42)
industry, thepotent syste inc
function of the binary temperature and ternary ○and pressure,
subsystems) R is the
available gas
○ in cons the
For an ideal solution, we existing
have the processes classic and formcreating of Raoult’s 𝜇new = law: 𝜇ones𝑇,for 𝑝 the + 𝑅𝑇 synthesisln 𝑎 =of𝜇 ethyl 𝑇, 𝑝ace+
the thermodynamic componentconsistency i, tests
and γofi isthe the activity coefficient
ofaccessible
preliminary experimental
experimental of the VLE compone
data.dataTh ar
into Equation ○
𝜇pi xdata 𝑇, (1) and rewrite the Gibbs–Duhem equation in t
critical review where pyiof=the i 𝑝 on is the VLEstandard for the system part ofwith the chemical ethyl (43)acetate poten sy
binary andfunction ternary subsystems) 2.
of the temperature Thermodynamic available and Consistency
in pressure,
the literature. Tests
R is the Twogas rigoro con
In the case of the system tests acetic
of the acid-ethanol-ethyl
component
accessible experimental i, andDue acetate-water,
γi isto the the
VLE fact
activity data the
that non-ideality
coefficient
array the are relations of the
carried ofofcompon
out.classic
the alcohol, ester, and water in the vapor intophase Equation can be neglected
thermodynamic
(1) and rewrite insystems,
quite
the a wide
Gibbs–Duhem regardless pressure of their na
equation in
range. As for the acetic acid, due to the
2. Thermodynamic Consistency strong association,
of state (EoS), the deviations
Teststhe thermodynamic consistency from an ideal
gas are significant even under low pressures [17]. The reliability non-ideal of the behavior of the acetic VLEacid
Due to the fact that the relations ofexperimental
classical thermodynamics data [13].mu Th
vapor may be taken into account by applying the relation of the (41);
agreement however, between it is necessary
the obtained to data a
thermodynamic systems, regardless of their nature and the specific fo
additionally use an EoS for the corresponding vapor. tions. The The alternative most way is to
popular tests consider are the
of state (EoS), the thermodynamic consistency tests are based a goodonmetho the G
dimerization process of the acetic acid in vapor:
reliability of the experimental VLE data [13]. The essence 𝑠𝑑𝑇of−all 𝑣𝑑𝑝 the+ tes ∑
of the agreement2AcOH between
(AcOH)2 the obtained data and the thermodynamic
(44)
tions. The most popularwhere tests are s is the based molar on the entropy, Gibbs–Duhem T is the temperatu equation
For the equilibrium (44) the following relationxican is the be mole written: fraction of the component i (in ter
𝑠𝑑𝑇 − 𝑣𝑑𝑝 + ∑ 𝑥 𝑑𝜇 = 0,
variable may be used here, i.e., mass, amount of
pd
where s is theKmolar a = 2entropy, , we will T use is the mole temperature, fractions to v ismake the molar further
(45) volum calc
pm
chemical
xi is the mole fraction of the component i (in terms of thermodynamics potential of the component i, and n is a
where Ka is the association constant, variable may pd isbe theused vapor here, Duhem
pressure i.e., mass, equation
of the amount is theof
dimer formconsequence
substance, of the acid, mass of the fractio first
and pm stands for the vapor wepressure
will useofmole the monomer fractions toform rived bymake applying
offurther
the acid. the Euler
calculations
The association theorem more convenie to interna
constant is assumed to be independent chemical potential of composition. of the identical Thus,nature
component the vapor i, and of the Gibbs–Duhem
n isequilibrium
in a number of with equation m
component
the quaternary system can be considered
Duhem equation an ideal is the gas,different containing five
consequence experimental of the components: data
first and second sets (isobaric
alcohol, lawsVLE of thd
ester, water, monomers, and dimers
rived of the acid.
by applying theThe Euler The
implementation chemical
theorem to internal potential
of this energy, of
approach a component it to is an iden of a
Equation (40) gives the relations identical for the nature calculation
of the Gibbs–Duhem ingof activity form [16]: coefficients
equation [13,17,19]: makes it possible to veri
different experimental
p data sets (isobaric VLE 𝜇 = 𝜇 ○and
data 𝑇, 𝑝isothermal
+ 𝑅𝑇 ln 𝑎VLE
=
− 1
The + 1 +
chemical 4K Py
potential
a AcOH ( 2
of −
a y )
component
AcOH of a solution can be represe
γAcOH = ○

, (46)
1 + 4Ka𝜇PAcOH𝑇, 𝑝− is
p
xAcOH
ing − yAcOH ) where
form(2[16]: 1 the standard part of the ch
function of the temperature and pressure, R is
p 𝜇 = 𝜇 ○ (2𝑇,−𝑝y + 𝑅𝑇) ln 𝑎 = 𝜇 ○ 𝑇, 𝑝 + 𝑅𝑇 ln 𝑥 𝛾
1 + 4Ka P(2 − yAcOH ) − 1 + Ka Pycomponent
AcOH i, and γi is the activity coefficient of
AcOH
γi = y i , i 6= AcOH (47)
2 Equation (1) and rewrite the Gibbs–Duhem
where ○
2Ka𝜇Pi x𝑇,
i (2𝑝− is
yAcOH into
the )standard part of the chemical potential of the
function of the temperature and pressure, R is the gas constant, ai is
component i, and γi is the activity coefficient of the component i. Subs
into Equation (1) and rewrite the Gibbs–Duhem equation in the follow
Chemistry 2023, 5 2549

For further calculations, we used the value of the association constant of 0.375 mbar−1 [20].

3. VLE Data for Binary Subsystems

3.1. Ethanol-Water System
Navarro-Espinosa et al. [21] conducted a study of the VLE of nine binary mixtures
at 773 mbar, focusing on the ethanol-water binary mixture. A recirculation still was used
to measure the boiling temperatures of solutions at 773 mbar. The compositions of the
coexisting liquid and vapor phases were determined by means of refractometry and gas
chromatography. The Peng–Robinson Stryjek–Vera equation of state [22] together with the
Wong–Sandler mixing rules [23] (PRSV-WS) and the NRTL model were applied to correlate
the obtained VLE data for the studied systems. However, the authors did not perform any
thermodynamic consistency tests.
Iwakabe et al. [24] introduced a recirculating still for investigating vapor-liquid-liquid
equilibria (VLLE). The still was also applied for the experimental determination of the
boiling temperatures and equilibrium vapor compositions in the ethanol-water binary
system at 1013 mbar. The thermodynamic consistency was checked using the Herington’s
area test. It was found that the data were sufficiently consistent. The Equation (41) was
used for calculating the activity coefficients of the components. The non-ideal behavior of
the vapor phase was considered in terms of the virial equation of state. The second virial
coefficient was estimated by the Tsonopoulos method [25]. The Rackett equation, modified
by Spencer and Adler, was applied for the estimation of the molar volume of liquids.
Ueberfeld et al. [26] reported a variation of the static method for studying VLE in
binary mixtures. The partial pressure of ethanol in the vapor phase was determined
by a photoacoustic sensor. The experimental procedure included the measurement of
a photoacoustic signal of the vapor phase in equilibrium with the liquid of a certain
composition at a constant temperature under atmospheric pressure. The partial pressure of
ethanol in the vapor phase was calculated based on the obtained values of the photoacoustic
signal. Further processing of the VLE data were not conducted, and the thermodynamic
consistency was not checked.
Yang and Wang [27] determined the boiling temperatures and compositions of the
equilibrium liquid and vapor phases using a modified Rose still at 1013 mbar. It should
be noted that the authors proposed an unusual approach for the data correlation. They
did not use Equation (43) to calculate the activity coefficients of the components based on
the obtained VLE data. However, the activity coefficients were calculated with two model
equations (Wilson and UNIFAC). Based on the model calculations, the boiling temperatures
and vapor compositions were estimated and compared with the experimental ones. The
thermodynamic consistency was proven using Herington’s method.
Pemberton and Mash [28] presented a new apparatus for studying VLE with the static
method. Isothermal VLE data were obtained at four temperatures (303.15 K, 323.15 K,
343.15 K, and 363.15 K). The activity coefficients and, consequently, molar excess Gibbs
energy were calculated by Barker’s method [29]. The authors used literature informa-
tion about the molar excess enthalpy for the system [30] to check the reliability of the
obtained data and to calculate molar excess entropy values. However, the results of the
thermodynamic consistency tests were not presented.
Cui et al. [31] studied the compositions of the equilibrium liquid and vapor phases at
323.15 K using the dynamic flow method, which were in good agreement with data mea-
sured by Pemberton and Mash [28]. The equilibrium vapor pressure was not determined;
therefore, the activity coefficients could not be calculated from the obtained experimental
results. The calculation was performed using the NRTL equation. The Herington’s area
test was used to check the thermodynamic consistency of the data.
Dalmolin et al. [32] reported equilibrium vapor pressure for five compositions of the
ethanol-water system at four temperatures (288 K, 298 K, 308 K, and 323 K). However,
the vapor composition was not determined, and no thermodynamic consistency tests
were conducted.
Chemistry 2023, 5 2550

Vu et al. [33] obtained isothermal VLE data at 313.15 K using the static method with a
specially constructed still. Activity coefficients were calculated using the UNIQUAC equation.
The Hayden-O’Connell method for the evaluation of the second virial coefficients was applied,
allowing for correlation of the experimental P-x-y data. The thermodynamic consistency was
validated using the Redlich-Kister, point-to-point Van Ness, and Fredenslund methods.
Zhang et al. [34] reported several VLE data points at 1000 mbar measured using the
recirculating method with an ebulliometer. The vapor phase was considered an ideal gas for
the calculation of activity coefficients. The experimental data were correlated by applying
the NRTL equation. Various ways of predicting VLE were discussed. It was shown that the
prediction of the equilibrium vapor compositions based on the correlation of the T-x data gave
significantly smaller deviations than the prediction of the boiling temperatures based on the
correlation of the x-y data set. The correlation of the activity coefficients was observed to give
sufficient results as well. No thermodynamic consistency tests were conducted.
Orchillés et al. [35] investigated isobaric VLE at 1000 mbar using a modified Labodest
model recirculating still to measure T-x-y data. The NRTL model was applied for modeling
VLE and calculating activity coefficients. The Van Ness test in Fredenslund’s modification
was used to check for thermodynamic consistency.
Orjuela et al. [36] reported isobaric VLE data at 1013 mbar obtained by the static
method. The obtained results were compared with those presented in other papers and
were found to be in good agreement with most of them. Thermodynamic consistency was
not checked. The NRTL, UNIQUAC, and Hayden-O’Connell equations were applied for
VLE predictions. Good agreement between experimental and calculated values proved the
reliability of the data.

3.2. Acetic Acid-Water System

Miyamoto and Nakamura [37] utilized a flow-type apparatus to measure isothermal
VLE for the binary system of acetic acid and water at 343.2 K. Two tests (a point test and an
area test) were conducted to validate the thermodynamic consistency of the obtained data.
The correlation of the data were performed using the NRTL model. No azeotropes were
detected. Interaction parameters for the binary system under study were used to predict VLE
for ternary systems. For the correlation and prediction of VLE, the dimerization of acetic acid
in the vapor phase was taken into account. The values of enthalpy and entropy change of the
association were estimated to be −58.5 kJ/mol and −136.0 J/mol·K, respectively.
Navarro-Espinosa et al. [21] studied the VLE in the acetic acid-water system at
773 mbar, using similar experimental procedures and data processing as mentioned above
for the ethanol-water system. The thermodynamic consistency test was not conducted. The
NRTL and PRSV-WS equations were used for data correlation.
Vercher et al. [38] obtained isobaric VLE data for the binary systems of acetic acid
and water at 1000 mbar using the Labodest model recirculating still.. For further data
treatment and estimation of the activity coefficients, the authors suggested applying the
approach proposed by Marek [19] to take into account the dimerization process of acetic
acid in both the vapor and liquid phases. The experimental apparatus was previously
tested by studying pure acetic acid. The thermodynamic consistency was validated with the
modified point-to-point van Ness test. Because VLE was also studied for the ternary system
acetic acid-water-lithium acetate, the electrolyte NRTL model, proposed by Mock [39], was
used for correlating both the binary and ternary experimental data.
Chang et al. [40] investigated VLE in the acetic acid-water binary systems at
1013 mbar using a modified Rose-type recirculating still. The experimental data showed
good agreement with those obtained by Gilmont et al. [41]. The Equation (41) was uti-
lized for the estimation of activity coefficients. The Poynting term was neglected, and the
virial equation of state was applied for calculating fugacity coefficients. The second virial
coefficient was calculated with the Hayden-O’Connell approach [42]. The experimental
data successfully passed the Herington thermodynamic consistency test. The NRTL and
Chemistry 2023, 5 2551

UNIQUAC equations were used for data correlation and prediction of VLE in ternary acetic
acid-water-ester systems.
Bernatová et al. [43] conducted a study of isothermal VLE in the acetic acid-water system
at 323.15 K using a Dvorak–Boublík recirculating still. The NRTL equation was applied to
correlate activity coefficients. No thermodynamic consistency test results were reported.
Xie et al. [44] reported isobaric VLE data at 1013 mbar obtained using a modified Rose
recirculating still. Equation (41) was applied for calculating activity coefficients, neglecting
the Poynting term. Non-ideal behavior was accounted for by considering dimerization in
the vapor phase using chemical theory, as described earlier. The virial equation of state,
with the use of the Hayden-O’Connel method for the second virial coefficient evaluation,
was also applied for estimating the fugacity of components in the vapor phase. The authors
highlighted the significant contribution of acetic acid to deviations from ideal behavior.
Thermodynamic consistency of the data was proved using the Herington and Fredenslund
tests. The NRTL and UNIQUAC models were applied for correlating activity coefficients.
The NRTL equation proved to be more suitable.
Garner et al. [45] determined isobaric VLE for the acetic acid-water system using the
Ellis-type recirculation still. The total pressure of the experiment was not specified in the
article, but it appears to be atmospheric. The boiling temperatures and the compositions of
the equilibrium vapor and liquid phases were measured. Two data sets are presented: one
assuming both substances in the vapor phase are ideal gases (the molecular weight of the
acetic acid monomer was used in calculations), and the second considering the corrected
molecular weight of the acetic acid, which takes into account its’ association in the vapor
phase. The presented data indicates a significant influence of acetic acid’s association with
vapor on calculating activity coefficients, as well as its considerable deviations from ideal
gas behavior even at small pressures. The authors did not report any thermodynamic
consistency tests.

3.3. Acetic Acid-Ethanol System

The isobaric VLE data at 773 mbar for the acetic acid-ethanol mixture were presented
by Navarro-Espinosa et al. [21]. The data correlation were performed using the NRTL
and PRSV-WS equations. The authors note the potential application of their apparatus for
investigating VLE in reactive systems, depending on the rate of a chemical reaction. If the
rate is too high, the continuous shift of the compositions would hinder the setting of the
steady state in the recirculating still and, consequently, the VLE. That is why the possibility
of the still application for VLE investigation should be checked for every reacting system.
The authors did not perform any thermodynamic consistency tests. However, we will
presume that in this case, the chemical reaction does not affect the VLE in the still.
The isothermal VLE data for the acetic acid-ethanol binary mixture at 323.2 K were also
measured by Miyamoto and Nakamura [37]. It should be noted that the rate of esterification
reaction and its possible influence on the experimental results obtained with the flow-type
apparatus were not discussed by the authors. The thermodynamic consistency was checked
using a point-to-point and an area test. The NRTL model was used for data correlation,
and the optimized parameters were applied for VLE prediction on ternary systems. For the
acetic acid-ethanol system, the presence of both the dimer of acetic acid and the heterodimer
of acid and alcohol in the vapor phase was considered. The enthalpy change of the acid
and alcohol association was estimated to be −46.0 kJ/mol.
Reichl et al. [46] introduced a non-recycle flow still with a short equilibration time
that made it possible to conduct rapid measurements for VLE investigation in reacting
systems, specifically for thermally unstable compounds. The T-x-y VLE data were obtained
for the acetic acid-ethanol reacting mixture at 500 mbar and under atmospheric pressure.
The authors highlight the deviations between existent data on the system, which can
be caused by the complexity of the system and difficulties in VLE studies in mixtures
with chemical reactions. The experimental results were compared with the UNIFAC
Dortmund calculations. It was observed that the UNIFAC data qualitatively agreed with
Chemistry 2023, 5 2552

the experiment; however, quantitative prediction seemed to be insufficient. The results of

the data correlation with the NRTL equation were presented. The Wilson and UNIQUAC
equations were applied as well. These models were reported to give similar results.
Wagner et al. [47] conducted measurements of vapor pressure in equilibrium with
the liquid phase for the acetic acid-ethanol system at 308.15 K and 318.15 K using the
isoteniscope method. The stability of the measured pressure throughout the experiment led
to the neglect of its influence on chemical reactions. Activity coefficients and excess Gibbs
energy values were obtained through the integration of the Gibbs–Duhem equation. The
deviations from ideal gas were accounted for by considering the dimerization of acetic acid
in the vapor phase and introducing the virial equation of state. However, the association
between acid and alcohol was not considered. Thermodynamic consistency tests were not
performed; it should be noted that since the vapor compositions were not experimentally
determined but rather calculated through the integration of the Gibb-Duhem equation, the
tests based on this equation are not applicable.

3.4. Acetic Acid-Ethyl Acetate System

Miyamoto and Nakamura [37] also obtained experimental isobaric VLE data for the
acetic acid-ethyl acetate system at 323.2 K. The thermodynamic consistency of the data was
validated with area and point consistency tests. The NRTL equation interaction parameters
were estimated.
Navarro-Espinosa et al. [21] obtained the VLE data for the acetic acid-ethyl acetate
system at 773 mbar as well. However, the authors did not provide any results from
thermodynamic consistency tests. The experimental data were correlated with the NRTL
model and the PRSV-WS equation of state.
Kato [48] used a flow-type apparatus for measuring dew-point and bubble-point
temperatures in the system. The temperatures measured during the experiment were
corrected to the values at 987 mbar and smoothed. The composition of the vapor phase
was not determined. The Wilson equation was applied for data correlation and calculation
of VLE, while the association of the acetic acid in the vapor phase was taken into account.
Large deviations among experimental VLE data were observed for this system.
Garner et al. [45] applied an Ellis recirculation still to investigate isobaric VLE for
the acetic acid-ethyl acetate system as well. Two data sets were presented, one taking
into account the association of acetic acid in vapor and one without it. A significant
discrepancy among the obtained values of activity coefficients was observed, attributed
to the small deviations from ideality that led to a significant influence on the calculated
activity coefficients. The Margules equation was applied for correlating activity coefficients
even with small errors in determined compositions.
Macedo and Rasmussen [49] reported isothermal P-x-y VLE data for the binary acetic
acid-ethyl acetate system at 338 K and 346 K. The measurements were carried out on a
Dvorak–Boublik recirculating still. Pure substances were also studied to obtain the Antoine
equation parameters for further calculation. The relation (41) was applied for estimating
activity coefficients, neglecting the Poynting term. Acetic acid vapor was considered an
associated ideal gas, according to (46) and (47). The obtained data were processed using
the UNIQUAC equation and the two-, three-, and four-parameter Margules equation. The
results of all data reduction methods were reported to yield identical results. A good
correlation between experimental and calculated data was observed, with small deviations
believed to be evidence of thermodynamic consistency. No classical thermodynamic
consistency test based on the Gibbs–Duhem equation was conducted.
Furnas and Leighton [50] used the Othmer apparatus to measure the composition of
equilibrium vapor and liquid phases in the acetic acid-ethyl acetate system at atmospheric
pressure (995–1019 mbar). Boiling temperatures for the system were not measured. The x-y
diagram was plotted. No data reduction procedures were reported.
Chemistry 2023, 5 2553

3.5. Ethanol-Ethyl Acetate System

Figurski and Malanowski [51] found significant discrepancies, reaching 100%, among
the literature information on the VLE for the binary ethanol-ethyl acetate system. They
measured the boiling temperatures for the ethanol-ethyl acetate system at different pres-
sures, obtaining a total of 158 experimental points for pressures ranging from 35 mbar up to
1000 mbar, and the temperature range was from 294.15 K up to 350.15 K, both for pure sub-
stances and for several binary compositions. A van Ness ebulliometer was used for boiling
temperature measurements. The refractive index of liquids was measured to determine the
liquid phase composition. However, the compositions of equilibrium vapor phases were
not studied. The accuracy of the experimental procedure was tested by investigating pure
ethanol and comparing it with literature information reported by Ambrose and Sprake [52].
The AEOS equation [53,54] was used for data correlation. The authors assumed that the
good agreement between experimental values and calculated ones proved not only the
accuracy but also the thermodynamic consistency of the experimental data. However,
they did not conduct any thermodynamic consistency tests using the relations of classical
thermodynamics. Therefore, it can be assumed that the thermodynamic consistency of the
data has not been proved by the authors, but it has not been refuted either.
Navarro-Espinosa et al. [21] studied the ethanol-ethyl acetate system (isobaric VLE at
773 mbar). The NRTL model and the PRSV-WS equation were applied to correlating the
obtained VLE data for the studied system. Any thermodynamic consistency tests were not
performed by the authors.
Tu et al. [55] presented isobaric data on VLE for the ethanol-ethyl acetate system at
1013 mbar. The Hunsmann equilibrium, still with recirculation, was used for this study. Gas
chromatography was utilized for measuring the equilibrium liquid and vapor compositions.
The activity coefficient for the liquid phase was calculated using Raoult’s law. The Soave–
Redlich–Kwong equation of state [56] was used to estimate the fugacity coefficients of the
components in the vapor phase. The molar volumes of the liquid were calculated with the
modified Racket equation [57]. However, the thermodynamic consistency tests were not
provided as well.
Susial et al. [58,59] reported data on boiling temperatures and compositions of coexist-
ing liquid and vapor phases for the binary ethanol-ethyl acetate mixtures at 3000 mbar [58],
1000 mbar [59], 5000 mbar [59], and 7000 mbar [59]. A specially constructed stainless
steel ebulliometer for the high-pressure measurements was used. The activity coefficients
were calculated based on the experimental data obtained with the use of Raoult’s law.
The fugacities of the components in the vapor phase were also calculated using the virial
equation of state up to the second term. The second virial coefficients were evaluated
with the Hayden-O’Connell method [42]. The thermodynamic consistency of the data was
tested with the point-to-point van Ness method. Although the results of the test were not
provided, it was assumed to have been successfully passed. Additionally, the experimental
data were correlated with several model equations (Redlich-Kister, van Laar, Margules,
Wilson, NRTL, and UNIQUAC). Two group contribution models (UNIFAC and ASOG)
were applied to predict VLE in the system.
Furnas and Leighton [50] conducted research on the isobaric VLE for the ethanol-ethyl
acetate system at 1013 mbar, using Othmer apparatus to obtain the T-x-y data set. The x-y
curve was plotted, and the composition of the azeotrope was estimated. No consistency
tests were performed.
Kato et al. [60] proposed an apparatus for investigating isobaric VLE. The isobaric
VLE data set for the binary mixture of ethanol and ethyl acetate at 1013 mbar were collected
using the suggested apparatus. A substantial discrepancy was observed between their data
and Furnas and Leighton’s [50] results. Experimental data were smoothed and plotted on
phase diagrams. Thermodynamic consistency was not verified.
Orjuela et al. [61] reported VLE data for the ethanol-ethyl acetate system at 1013 mbar.
The experiment employed a recirculating apparatus (VLE 100D). The close agreement
Chemistry 2023, 5 2554

between the obtained data and the literature was reported. The UNIQUAC and Hayden-
O’Connell equations were used for data correlation with considerable accuracy.
Topphoff et al. [62] obtained isobaric VLE data for the ethanol-ethyl acetate mixture
at 1013 mbar using the recirculating method with a modified Scott ebulliometer. The data
were correlated and smoothed using the UNIQUAC equation to test data reliability, while
thermodynamic consistency was verified with the Redlich–Kister method.
Orchillés et al. [63] performed a study of the VLE for the ethanol-ethyl acetate system
at 1000 mbar using a modified Labodest model recirculating still (Pilodist). The pure
substances were studied as well, and the parameters of the Antoine equations were esti-
mated. Thermodynamic consistency was ascertained using the Van Ness test. The NRTL
model was applied to reduce experimental data. The activity coefficients were derived
using Raoult’s law in the form of Equation (42), considering the vapor of both ethanol and
ethyl acetate as ideal gases. The appropriate phase diagram and composition diagram
were plotted.
Li et al. [64] utilized a modified Othmer recirculating still to obtain isobaric the T-x-y
data set for the system ethanol-ethyl acetate at 1013 mbar. The obtained data were found to
be in good agreement with measurements taken by Tu et al. [55] and Orchillés et al. [63].
The relation (42) was used to calculate activity coefficients. The NRTL model was used for
data correlation. The relative volatility of ethyl acetate to ethanol was determined. The cor-
responding T-x-y phase diagram was plotted. However, the results of any thermodynamic
consistency tests were not presented.
Takamatsu and Ohe [65] determined the equilibrium compositions of the liquid and
vapor phases for the ethanol-ethyl acetate system at 313.15 K using the headspace gas
chromatography method. Thermodynamic consistency was verified by the Herrington area
test. The experimental results were correlated using the Wilson, UNIQUAC, and NRTL
equations. The x-y diagram was plotted, and the azeotrope composition was estimated.
Ashraf and Prasad [66] studied isothermal VLE in the ethanol-ethyl acetate system at
313.15 K. The infinite-dilution activity coefficients were evaluated. The Wilson equation
was used for the calculation of activity coefficients. Thus, the vapor compositions were
determined with Equation (42). Any thermodynamic consistency tests were not conducted.

3.6. Ethyl Acetate-Water System

Garner et al. [45] note that the experimental determination of the VLE for the binary
mixture ethyl acetate-water causes significant challenges due to its wide splitting region of
liquid phase. This not only results in the splitting of the liquid phase for most compositions
but also causes the vapor phase condensate to be immiscible. The authors utilized two types
of recirculation stills, Ellis and Gillespie, to determine the isobaric VLE for the ethyl acetate-
water system. The composition of the heterogeneous azeotrope was determined. The
activity coefficients of the components in the liquid phase were calculated using Raoult’s
law (43) assuming both the substances in the vapor phase are ideal gases. The final values of
the activity coefficients of water and ethyl acetate were estimated using three methods. The
authors demonstrate that the van Laar equation is unsuitable for extrapolating the activity
coefficients from the homogeneous region into the immiscible region. The possibility of a
hydrolysis reaction between ethyl acetate and water and its influence on the experimental
data were not discussed. Any thermodynamic consistency tests were not reported.
Ellis and Garbett [67] obtained the isobaric VLE data for both homogeneous and
heterogeneous compositions of the binary ethyl acetate-water system at 1013 mbar. A
novel equilibrium still designed for investigating partially miscible systems was presented
by the authors. The azeotrope composition was measured. The activity coefficients were
calculated assuming the vapor phase behaved as an ideal gas. The possible impact of the
chemical reaction on experimental results was not reported.
Reichl et al. [46] reported VLE data at atmospheric pressure obtained with a non-
recirculating flow still. Good agreement with prior literature information was observed
for low and medium ethyl acetate concertation. At the same time, considerable deviations
Chemistry 2023, 5 2555

appeared for high concentrations of ethyl acetate, which were attributed to the composition
determination procedure. The NRTL model was applied for data correlation. Neither
the possible influence of the chemical reaction nor the thermodynamic consistency tests
were discussed.
Lee et al. [68] performed a study of isobaric VLE in a modified Othmer-type recircu-
lating still. Activity coefficients were determined with Equation (41) and molar volumes
of pure liquids were estimated with the Rackett equation. In order to take into account
fugacity coefficients, the virial equation of state was employed, with the second virial
coefficients evaluated using the Hayden-O’Connell method. The authors reported con-
siderable experimental difficulties when the concentration of water in the liquid phase
exceeded 0.988, attributed to the partial miscibility of the systems and resulting disturbed
recirculation. The authors used the van Ness and Abbot coexistence equation to predict
missing data. The enthalpies of vaporization were evaluated by the Watson relation and
the Viswanath–Kuloor method. The Vetere method was used to calculate the heat of va-
porization at the boiling temperature. The vapor phase was considered to be an ideal gas.
The NRTL and UNIQUAC models were utilized for data correlation and prediction. Two
correlation methods were applied: while the correlation based on experimental VLE data
showed good agreement with empirical information, the correlation based on LLE data
proved unsuitable for predicting VLE. Remarkably, no thermodynamic consistency tests
were performed, and the reacting nature of the system was not discussed.
Rajendran et al. [69] obtained isobaric VLE data at 1013 mbar with a Smith and Bonner
type still. The heterogeneous azeotropic composition was determined. No consistency tests
or correlations for this system were reported.

4. VLE Data for Ternary Subsystems

The ethanol-ethyl acetate-water ternary subsystem has been most extensively studied
in terms of VLE. The papers [68,70–74] include both isobaric and isothermal data.
Garner et al. [70] investigated VLE in the ternary acetic acid-ethyl acetate-water system
at atmospheric pressure. Experiments were carried out using the equilibrium still. The
acetic acid and water content in the samples were estimated by titration, while the ethyl
acetate content was determined by saponification. The authors provided a sizable VLE data
set but did not present any phase diagrams of these experimental outcomes. In addition,
an appropriate method for predicting ternary data from binary data based on the Margules
equation was suggested.
Griswold et al. [71] reported detailed experimental isobaric VLE data at 1013 mbar,
determined using a modified glass Colburn still. The measurement of specific gravity and
weight per cent of ethyl acetate by saponification was applied for sample analysis. Experi-
mental data were represented in a detailed concentration diagram. The authors confirmed
the previously obtained data [75,76] on the presence of ternary azeotrope at 343.45 K. The
“low boiling zone” in the ternary phase diagram, representative of a significant region
of minimum boiling temperature, was described. The authors obtained VLE data for the
binary ethanol-ethyl acetate and ethyl acetate-water subsystems.
Mertl [72] presented experimental isothermal VLE data for the ternary ethanol-ethyl
acetate-water system at 313.15 K, 328.15 K, and 343.15 K, and for the binary subsystems:
ethyl acetate-ethanol, ethyl acetate-water, and ethanol-water. The VLE was studied using a
modified Gillespie still. Samples were analyzed via refractometry (for water-rich mixtures
of ethyl acetate and water) and via density measurements (for the other solutions). The
author does not provide a visual interpretation of the obtained experimental data.
Van Zandijcke and Verhoeye [73] obtained a significant VLE data set at atmospheric
pressure for the ethanol-ethyl acetate-water system and its binary subsystems: ethyl acetate-
ethanol, ethyl acetate-water, and ethanol-water. The VLE was investigated using a modified
Gillespie still and a gas chromatography method. The experimental data were repre-
sented visually, including consideration of the “low boiling zone” [71] comprising ternary
azeotrope. The authors noted that the literature data regarding the ternary azeotrope
Chemistry 2023, 5 2556

composition in the ethanol-ethyl acetate-water system were inconsistent. According to

Van Zandijcke and Verhoeye [73], the boiling point of ternary azeotrope is 343.35 K. The
composition of the azeotropic mixture was determined graphically. Due to accurate boiling
point measurements, the authors clarified the boundaries of the «low boiling zone» and
nevertheless, all previously obtained data [71,75,76] were found to fall within this region.
Moreover, the ternary VLE data were predicted using the NRTL model and showed good
agreement with the experimental data. However, the authors confined themselves to root
mean square deviation (RMSD) values, not detailing the equilibrium data in the article.
Lee et al. [68] carried out both experimental investigation and thermodynamic model-
ing of VLE and vapor-liquid-liquid equilibrium (VLLE) of the ethanol-ethyl acetate-water
system and its constituent binary systems: ethanol-water, ethanol-ethyl acetate, and ethyl
acetate-water at atmospheric pressure. VLE and VLLE were measured using an Othmer-
type recirculating still and gas chromatography analysis. The authors chose three methods
to correlate experimental VLE results: UNIQUAC, NRTL, and the modified Wilson equa-
tion. Among these three models, the NRTL model provided the best estimation for the
ternary VLE. It was found that the NRTL model provided the best estimation of ternary VLE.
An extensive experimental data set were compared graphically with calculated data and
experimental data previously obtained by other researchers [60,77] for binary subsystems.
Gomis et al. [74] studied experimentally isobaric (1000 mbar) VLLE for the ethanol-
ethyl acetate-water system, utilizing a commercial all-glass dynamic recirculating still,
specifically the Labodest apparatus model 602, modified with an ultrasound homogenizer.
The subsequent sample analysis was carried out by GC. A comparison of the obtained
VLLE data with that reported by Mertl [72], Van Zandijcke [73], and Lee [68], including
phase diagrams, was presented. The authors note that their results generally agree with the
data of Mertl [72] and Lee [68]. However, they found significant discrepancies between the
data of Van Zandijcke [73] and the results of Lee [68] for the vapor curve. They concluded
that Lee’s data displayed considerable scatter, making it inadequate for constructing a
smooth vapor curve. It is noteworthy that Gomis et al. [74] did not provide explanations for
the discrepancies between their data and that of Van Zandijcke [73], especially considering
they only obtained five experimental data points, making their data set relatively sparse
compared to Van Zandijcke’s much more extensive data.

5. VLE Data for the Quaternary System

The results of the VLE study in the quaternary acetic acid-ethanol-ethyl acetate-water
system under isobaric conditions (atmospheric pressure) are presented in four works
only [78–80]. Notably, no isothermal data for VLE in this quaternary system has been found
in the scientific literature.
Kang [78] et al. investigated VLE in a chemically equilibrium quaternary acetic acid-
ethanol-ethyl acetate-water system at atmospheric pressure. Experiments were carried out
in recirculation. Samples were analyzed by the method of gas chromatography. Although
there is a significant volume of experimental VLE data obtained, the article does not present
a phase diagram. The phase equilibrium data were correlated using a modified UNIQUAC
method, and the calculated data were in good agreement with the experimental results.
Campanella and Mandagaran [79] made a theoretical study of VLE in the quaternary
system with an ethyl acetate synthesis reaction at atmospheric pressure. UNIQUAC and
NRTL models and the Wilson equation were applied to calculate azeotropic points, residue
curve maps, and distillation line diagrams for the conceptual design of RD. The authors
highlight that the presence of a reactive azeotrope in modeling the phase behavior of
the studied system depends on the value of the chemical equilibrium constant and is
not influenced by phase equilibrium parameter values. Calculations were made for both
reactive and non-reactive azeotropes.
Calvar et al. [80] presented detailed data on VLE in the system with the reaction of
acetic acid esterification with ethanol and its constituent binary systems: ethanol-ethyl
acetate, acetic acid-ethyl acetate, and acetic acid-water at 1013 mbar. The VLE study
Chemistry 2023, 5 2557

was carried out using a glass Fischer Labodest apparatus, model 602/D. Equilibrium
compositions were determined by density measurements for all binary subsystems, with
the exception of the acetic acid-water system, and by gas chromatography for the quaternary
system acetic acid-ethanol-ethyl acetate-water and for the binary acetic acid-water system.
The UNIQUAC method was utilized to correlate the experimental VLE data with the
quaternary system. Predicted and experimental data were found to be well-correlated.
ASOG and UNIFAC models were used to correlate binary data with ASOG, proving better
results. In addition, binary VLE data (for the ethanol-ethyl acetate and acetic acid-water
systems) were graphically compared with literature data [55,67,70] and they were found to
generally match well.

6. Thermodynamic Consistency of Experimental Data

In order to achieve the objective of our research, which is to estimate the reliable
value through the direct integration of the Gibbs–Duhem equation for a real experimental
data set, we applied two integral methods (the Redlich–Kister method and the direct
integration of the Gibbs–Duhem equation) for the thermodynamic consistency tests. The
NRTL equation was used to interpolate literature information for further processing and
integration. The NRTL [81] parameters were obtained by the optimization of the following
objective function (OF) to its minimum value:
v
u  2
u n E E
t ∑i=1 gi,exp − gi,calc
OF = , (48)
n−1
E
where gi,exp is the experimental value of the molar excess Gibbs energy for the composition
E
i, gi,calc is the calculated value of the molar excess Gibbs energy for the composition i, and
n is the number of experimental compositions. This procedure was used to estimate the
NRTL parameters for every experimental data set.
For both methods, relations for isothermal-isobaric (T, p = const) conditions (5) and
(17) were used. In the case of isothermal experimental VLE data, the pressure variation, as
previously mentioned, could be neglected in most cases. For the isobaric VLE data sets,
the temperature dependence of activity coefficients was taken into account with the NRTL
equations, and the consistency tests were conducted at a constant temperature (the mean
value over the temperature range studied by the authors).
For binary systems, integration was conducted over the whole composition range (the
limits of the integration are the pure components). The following integration paths were
chosen for ternary and quaternary systems, respectively:

(0.8, 0.1, 0.1)

. - , (49)
(0.1, 0.8, 0.1) −→ (0.1, 0.1, 0.8)

(0.2, 0.6, 0.1, 0.1) ←− (0.7, 0.1, 0.1, 0.1) ←− (0.3, 0.1, 0.1, 0.5)
& % , (50)
(0.2, 0.2, 0.5, 0.1) → (0.2, 0.2, 0.1, 0.5)
where (x1 , x2 , x3 ) and (x1 , x2 , x3 , x4 ) represent the compositions of ternary (acetic acid
(1)—ethyl acetate (2)—water (3) and ethanol (1)—ethyl acetate (2)—water (3)) and qua-
ternary (acetic acid (1)—ethanol (2)—ethyl acetate (3)—water (4)) mixtures; respectively.
The integration was performed numerically by the rectangle method. The results of the
consistency tests are summarized in Table 1.
Chemistry 2023, 5 2558

Table 1. Results of the thermodynamic consistency tests for VLE data of the acetic acid-ethanol-ethyl
acetate-water quaternary system and its’ subsystems using Redlich–Kister and Gibbs–Duhem equations.

Reference T, K R-K 1 G-D 2

Ethanol-water system
[21] 346.15 +3 0.023
[24] 356.15 + 0.024
[26] NC 4 NC NC
[27] 361.85 + 0.024
[28] 303.15 + 0.025
[28] 323.15 + 0.024
[28] 343.15 + 0.024
[28] 363.15 + 0.023
[31] NC NC NC
[32] NC NC NC
[33] 313.15 + 0.024
[34] 351.15 + 0.024
[35] 356.35 + 0.025
[36] 359.95 + 0.026
[72] 343.15 + 0.022
[72] 328.15 + 0.024
[72] 313.15 + 0.026
[73] 354.65 + 0.024
Acetic acid-water system
[37] 343.15 + 0.033
[21] 368.15 + 0.028
[38] 378.65 + 0.030
[40] 379.15 + 0.031
[41] D 5 D D
[43] 323.15 + 0.032
[44] 378.45 + 0.029
[45] 380.15 + 0.029
[80] 377.15 + 0.032
Acetic acid-ethanol system
[21] 358.65 SD(+) 6 0.045
[37] 323.15 SD(+) 0.046
[46] 352.65 SD(+) 0.049
[47] 308.15 + 0.054
[47] 318.15 + 0.054
Acetic acid-ethyl acetate
[21] 361.15 + 0.200
[37] 323.15 + 0.033
[45] 368.95 SD(+) 0.040
Chemistry 2023, 5 2559

Table 1. Cont.

Reference T, K R-K 1 G-D 2

[48] 367.65 + 0.037
[49] 338.25 + 0.040
[49] 346.15 + 0.040
[50] NC NC NC
[80] 368.15 + 0.042
Ethanol-ethyl acetate system
[21] 338.15 + 0.028
[49] 313.15 + 0.025
[50] 347.55 + 0.032
[51] NC NC NC
[55] 347.55 + 0.033
[58] 381.65 + 0.036
[59] 347.15 + 0.033
[59] 400.45 + 0.038
[59] 423.15 + 0.052
[60] 347.15 + 0.031
[61] 347.15 + 0.032
[62] 347.15 + 0.031
[63] 347.15 + 0.031
[64] 347.15 + 0.033
[65] NC NC NC
[68] 347.15 + 0.032
[71] 347.15 + 0.032
[72] 343.15 D D
[72] 328.15 D D
[72] 313.15 D D
[73] 347.15 + 0.032
Ethyl acetate-water system
[45] NC NC NC
[46] 351.20 + 0.014
[60] 349.60 + 0.056
[67] 358.85 + 0.061
[68] 346.80 + 0.013
[69] 344.15 + 0.002
[71] NC NC NC
[72] 343.15 + 0.032
[72] 328.15 + 0.032
[72] 313.15 + 0.024
[73] 344.75 + 0.006
Chemistry 2023, 5 2560

Table 1. Cont.

Reference T, K R-K 1 G-D 2

Acetic acid-ethyl acetate-water system
[70] 361.15 + 0.042
Ethanol-ethyl acetate-water
[68] 347.15 + 0.056
[71] 346.15 + 0.046
[72] 343.15 + 0.048
[73] 347.15 + 0.050
[74] NC NC NC
Acetic acid-ethanol-ethyl acetate-water system
[78] 357.15 + 0.032
[80] 352.00 D 0.065
1The value obtained by the Redlich–Kister test (Equation (13) for binary mixtures, Equation (16) for ternary and
quaternary systems); 2 : The value obtained by the integration of the Gibbs–Duhem equation (Equation (5)); 3 Tests
passed; 4 NC-Tests not conducted; 5 Doubtful results; 6 Significant dispersion of data.

7. Results and Discussion

As for the binary subsystems, they have been extensively studied compared to ternary
and quaternary mixtures. The majority of works have focused on the study of VLE in four
binary subsystems of the quaternary system: ethanol-water, acetic acid-water, ethanol-
ethyl acetate, and acetic acid-ethyl acetate. Among observed mixtures, these systems
are the easiest to study in terms of VLE because they are not reacting and do not have
a heterogeneous area. Much less data on the VLE for the binary mixtures acetic acid-
ethanol and ethyl acetate-water is available. For the acetic acid-ethanol system, the possible
esterification should be taken into account during VLE studies, while the ethyl acetate-water
system is not only reacting but also partially miscible, which leads to several difficulties in
both experimental procedures and data analysis.
Most of the literature data sets passed the Redlich–Kister test and the point-to-point
van Ness consistency test successfully (see the corresponding commentary in the above
text), which makes it possible to consider the VLE information to be thermodynamically
consistent. However, for the ethanol-water mixture, these tests were not performed for the
data from works [26,31,32]. Ueberfeld et al. [26] did not provide a full set of parameters
(p-T-x-y), so their results were not tested. Cui et al. [31] did not measure equilibrium vapor
pressure for the isothermal data set, and vapor composition was not determined for the
liquid mixtures in [32].
Isobaric VLE data were presented at 1013 mbar [24,27,36,73], 1000 mbar [34,35]
and 773 mbar [21], while isothermal VLE was studied at 288.15 K [32], 298.15 K [32],
303.15 K [28], 308.15 K [32], 313.15 K [33,72], 323.15 K [28,31,32], 328.15 K [72],
343.15 K [28,72] and 363.15 K [28]. It can be observed that isobaric data were only reported
for pressures close to atmospheric; thus, even isobaric VLE data for different pressures for
the acetic acid-ethanol-ethyl acetate-water systems are rather limited. The temperature
range for isothermal data tends to be wider, but most temperatures were studied in only
one or two works, making it difficult to compare and test the reliability and reproducibility
of different data.
Isobaric VLE data for the acetic acid-water system are reported at 1013 mbar [40,41,44,45,80],
1000 mbar [38], 773 mbar [21], 667 mbar [41], 333 mbar [41], and 167 mbar [41]. Data
obtained by Gilmont et al. [41] are considered doubtful due to discrepancies because the
dependence of the molar excess Gibbs energy gE on composition at 1013 mbar qualitatively
differs from those obtained by other researchers. Based on the data reported by Gilmont
et al. [41], the gE curve should have both positive and negative values, with one maximum
Chemistry 2023, 5 2561

and one minimum. However, calculations according to other literature data give the gE
curve only positive values with one maximum. Isothermal data sets are presented in two
works only at 343.15 K [37] and 323.15 K [43].
The reactive binary acetic acid-ethanol subsystem was studied under pressures of
773 mbar [21], 500 mbar [46], and at three temperatures: 323.15 K [37], 318.15 K [47], and
308.15 K [47]. It should be noted that the possible influence of the esterification reaction
on the obtained VLE data are almost not discussed. At the same time, considerable dis-
persion in gE values for this system was observed for results reported in works [21,37,46].
The consistency tests were performed for smoothed dependencies obtained using the
NRTL equation. The dispersion could be caused by the temperature shift or by the in-
fluence of the chemical reactions; however, further studies are necessary to make more
detailed conclusions.
For the binary acetic acid-ethyl acetate system, isobaric VLE data are presented at
1013 mbar [45,50,80], 987 mbar [48], and 773 mbar [21]. The values of the integral obtained
using both the Redlich–Kister method and the integration of the Gibbs–Duhem equation
for data produced by Navarro-Espinosa et al. [21] were greater than those obtained for
other data sets (0.2 against 0.04 for other data sets). Such findings may be a result of the
limited range of experimental compositions used for the approximation with the NRTL
model. Boiling temperatures were not provided by Furnas et al. [50], hence these data
were not tested. Significant dispersion of the gE values was observed for the results
reported in [45]. The isothermal VLE has been studied at 323.15 K [37], 338.15 K [49], and
346.15 K [49]. All the data satisfactorily passed the consistency test.
The ethanol-ethyl acetate system is one of the most extensively studied. Isobaric
VLE data sets are available at 7000 mbar [59], 5000 mbar [59], 3000 mbar [58], 1013 mbar
[50,55,60–62,64,71,73,80], 1000 mbar [59,63], and 773 mbar [21]. All these data sets passed
the consistency test. The isothermal VLE data are reported at 313.15 K [49,65,72],
328.15 K [72], and 343.15 K [72]. A substantial amount of VLE data in the temperature
range of 294.15–350.15 K is presented in a paper [51]. However, these data were not tested
due to the omission of the vapor composition. The equilibrium vapor pressures were
not measured by Takamatsu et al. [65]. Data for the ethanol-ethyl acetate system in the
paper [72] are considered doubtful since the calculated curve of gE dependence on com-
position has two minimums and one maximum with negative values of gE . Meanwhile,
the corresponding curve by Ashraf et al. [66] has a similar form with one maximum and
positive values of gE . This discrepancy could be attributed to a systematic error in data
processing and representation.
For the ethyl acetate-water system, isobaric VLE data are solely reported at atmo-
spheric pressure [45,46,60,67–69,71,73]. Isothermal VLE was studied at 315.15 K, 328.15 K,
and 343.15 K exclusively in this work [72]. Due to the limited number of studied composi-
tions, the results obtained by Garner et al. [45] and Griswold et al. [71] were not subjected
to thermodynamic consistency tests. However, other data sets successfully passed the
consistency test.
It is evident that VLE in ternary and quaternary systems is studied less extensively
than that in binary ones, with only a few works focusing on the VLE investigation in ternary
and quaternary mixtures. The majority of these studies were carried out at atmospheric
pressure [68,70,71,73,80]. The results of the isothermal VLE study at 313.15 K, 328.15 K, and
343.15 K for the system ethanol-ethyl acetate-water are only presented in a single paper [72].
The data obtained by Calvar et al. [80] were considered doubtful due to the existence of
numerous compositions with a significant mole fraction of acetic acid in the liquid phase
and its absence in the vapor phase. We are not sure whether such a tendency is reliable.
Moreover, the values of the integral (5) for this data set at 352.15 K were significantly
higher than the mean value for all the observed systems (0.065 against the mean value of
0.03–0.04).
The mean value of the integral (5) across the data sets under review were calculated to
be 0.04 (0.024 for the ethanol-water system, 0.031 for the acetic acid-water system, 0.050 for
Chemistry 2023, 5 2562

the acetic acid-ethanol system, 0.039 for the acetic acid-ethyl acetate system, 0.033 for the
ethanol-ethyl acetate system, 0.027 for the ethyl acetate-water system, 0.042 for the acetic
acid-ethyl acetate-water system, 0.050 for the ethanol-ethyl acetate-water system, 0.032 for
the quaternary system). We assume that this value can be used to test the thermodynamic
consistency of VLE data in multicomponent systems through the direct integration of the
Gibbs–Duhem equation.

8. Conclusions
A comprehensive review of both isobaric and isothermal VLE data presented in the
literature for the quaternary acetic acid-ethanol-ethyl acetate-water system, along with its
ternary and binary subsystems, was carried out. An analysis revealed that the majority of
literature information on the VLE in this system predominantly consists of isobaric data
sets obtained at pressures close to atmospheric. Compared to isobaric data, the isothermal
VLE data set appeared more restricted. It was found that binary, non-reacting systems
without any miscibility gaps were the most investigated. Furthermore, it was established
that VLE data concerning the quaternary system and its ternary subsystems are markedly
scarce. Therefore, the investigation of VLE in multicomponent reacting systems (including
the system with the reaction of ethyl acetate synthesis) presents a promising direction for
future research.
The thermodynamic consistency of the observed literature VLE data was examined
using two integral area tests: the Redlich–Kister test and the direct integration of the Gibbs–
Duhem equation. The major part of the data proved to be thermodynamically consistent.
Concurrently, several works containing potentially doubtful information were found. The
reliable value of the integral in condition (5) for a real experimental VLE data set was
estimated to be 0.04. This value can be used for testing the thermodynamic consistency of
the VLE data in multicomponent systems.

Author Contributions: Conceptualization, G.M. and M.T.; methodology, G.M.; validation, G.M. and
I.P.; formal analysis, G.M., M.T. and I.P.; data curation, I.P.; writing-original draft preparation, G.M.
and M.T.; writing—review and editing, I.P.; supervision, M.T.; project administration, M.T.; funding
acquisition, M.T. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Russian Science Foundation, grant number 23-23-00227.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: Maya Trofimova thanks the Russian Science Foundation (grant № 23-23-00227)
for the financial support of this research.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of this study, in the collection, analysis, or interpretation of data, in the writing of this manuscript, or
in the decision to publish these results.

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